Enscm 2022 Cuminet

THESE POUR OBTENIR LE GRADE DE DOCTEUR DE
L’ECOLE NATIONALE SUPERIEURE DE CHIMIE DE MONTPELLIER
En Chimie et Physico-Chimie des Matériaux
École doctorale Sciences Chimiques Balard (ED459)
Unité de recherche Institut Charles Gerhardt Montpellier UMR 5253
Synthèse et caractérisation de vitrimères de

transestérification sans catalyseur
Présentée par Florian CUMINET

le 11 octobre 2022
Sous la direction de Sylvain CAILLOL et Éric DANTRAS

Et co-encadrée par Vincent LADMIRAL et Éric LECLERC
Devant le jury composé de
Tatiana BESSET, Directrice de recherche CNRS, INSA Rouen Normandie Rapporteure

François TOURNILHAC, Directeur de recherche CNRS, ESPCI-Paris Rapporteur
Frédéric PERUCH, Directeur de recherche CNRS, LCPO (CNRS/Bx INP-ENSCBP/ Univ. Bx) Président
Rinaldo POLI, Professeur des Universités, Institut National Polytechnique de Toulouse Invité
Sylvain CAILLOL, Directeur de recherche CNRS, ICGM Co-directeur de thèse
Éric DANTRAS, Maître de conférences, Université Toulouse 3 Paul Sabatier Co-directeur de thèse
Vincent LADMIRAL, Directeur de recherche CNRS, ICGM Co-encadrant
Éric LECLERC, Chargé de recherche CNRS, ICGM Co-encadrant
Remerciements
REMERCIEMENTS
i
Remerciements
Je tiens d’abord à remercier Patrick Lacroix-Desmazes, directeur du département Chimie et Matériaux

MacroMoléculaires de l’Institut Charles Gerhardt de Montpellier, de m’avoir accueilli au sein de l’équipe
pour la majeure partie de ma thèse. Merci à Marc Taillefer, directeur de l’ex-équipe Architectures
Moléculaires et Matériaux Nanostructurés au sein de laquelle j’ai travaillé pendant les trois premiers
mois de ma thèse, et tout particulièrement à Jean-Marc Campagne, pour m’avoir accueilli dans son
groupe. Merci également à Christophe Laurent, directeur du Centre Inter-universitaire de Recherche et
d’Ingéniérie des Matériaux de Toulouse, et à Éric Dantras, responsable de l’équipe Physique des
Polymères, de m’avoir également accueilli dans leurs locaux.
Merci à l’Institut Carnot Chimie Balard – CIRIMAT d’avoir financé mon projet de thèse.
Je remercie Mme Tatiana Besset et M. François Tournilhac, en leurs qualités de rapporteure et

rapporteur, ainsi que M. Frédéric Peruch, en qualité d’examinateur, d’avoir accepté d’évaluer ces
travaux de thèse.
Je tiens à exprimer toute ma reconnaissance et ma gratitude envers mes directeurs et encadrants de

thèse : Sylvain Caillol, Éric Dantras, Vincent Ladmiral et Éric Leclerc. Merci à tous pour votre aide, votre
attention, vos nombreux conseils, votre soutien et votre bienveillance. Merci Sylvain pour les nombreux
conseils stratégiques affutés, pour ta présence dans les moments de tension, et pour m’avoir transmis
ta vision très appliquée de la science des polymères. Merci Vincent pour m’avoir appris la rigueur, le
souci du détail et du mot juste, et la gestion de son temps (« on dormira quand on sera morts », Vincent
Ladmiral, 2019), mais également pour l’indulgence dont tu sais faire preuve. Et merci à tous les deux
d’avoir souvent illustré cette phrase qui vous va si bien « Ici on fait des choses sérieuses, sans se prendre
au sérieux » (Sylvain Caillol, 2021). Merci Éric (Dantras) pour m’avoir appris les rudiments de la physique
des polymères, la rigueur en analyse mécanique et la prudence dans les interprétations de résultats.
Expliquer la physique à un chimiste n’a pas dû être facile, merci pour ta patience. Tu as trouvé la formule
parfaite pour résumer ces trois ans : « Les vitrimères, c’est l’école de la patience » (Éric Dantras, 2021).
Merci Éric (Leclerc) pour les 3 mois passés à travailler avec toi, j’ai découvert et appris beaucoup en très
peu de temps. Merci pour ta bienveillance, et d’avoir veillé tout au long du projet à corriger mes
hypothèses de chimie organique, parfois farfelues. J’ai beaucoup appris au contact de chacun d’entre
vous, bien plus que ces quelques lignes ne sauraient le résumer. Vos compétences dans des domaines
très variés et vos visions complémentaires de la recherche ont fait la force de cette équipe et ont permis
de mener ce projet à son terme. Sans chacun d’entre vous, tout cela n’aurait pas été possible.
Je tiens également à remercier toutes les personnes avec qui j’ai pu collaborer, sur mes travaux de thèse
ou sur des sujets transversaux : Jennifer « Jenn », Romain, Anne-Sophie, David, Rinaldo Poli, Sébastien
Lemouzy, Cédric Totée, Gilles Silly, Sabine Devautour-Vinot, Paul Iacomi, Maxinne, Baptiste, Julien et
ii
Remerciements
Dimitri. Merci à Marc Guerre et François Tournilhac pour les discussions sur les vitrimères qui ont permis
de me faire avancer dans mes questionnements. Merci à Lise Reymond pour son aide sur la synthèse
de monomères.
Merci à tous les membres du département C3M « D2 », que j’ai croisé au quotidien, permanents et non-
permanents. Merci en particulier à Abdou, Caroline, Christine (J-D), Claire, qui est restée bienveillante à
mon égard malgré que j’ai refusé son sujet de thèse, Ghis, que je n’ai pas épargné non plus, Julien,
Maxime, Patrick, Rémi et Sylvain Catrouillet, qui s’entête à venir me parler, malgré le peu d’informations
utiles que je lui apporte. Merci à Aliénor, Fabien, Gaëlle et Zoé pour la bonne ambiance au bureau et au
labo.
Merci aux membres du groupe Jean-Marc Campagne de l’ex-équipe AM2N : Chayma, Eleonora, pour ton
intarissable bonne humeur et ton énergie, Emmanuel, Éric, Georg, Jean-Marc, Liyan, Pierre et Renata,
merci pour ta gentillesse. Merci à Pascale pour nos échanges non dénués d’un grain de folie, souvent
brefs au détour d’un couloir, mais toujours très agréables.
Merci aux membre de l’équipe Phypol de m’avoir accueilli pendant un mois, et en particulier à Éric et
Antoine, pour votre aide et vos conseils sur l’analyse mécanique.
« Une thèse, c’est un marathon de 3 ans » m’a dit un jour un certain Vincent Bouad. Et comme pour un
marathon, il est plus facile de tenir sur la durée lorsqu’on est bien entourés. J’ai eu la chance de partager
un magnifique appartement pendant 2 ans avec « mes loulous » Maxinne et Guilhem. Je vois dois
énormément à tous les deux, pour avoir mis tant de gaîté dans mon quotidien et pour avoir été présents
dans les meilleurs moments comme dans les pires. Merci aussi pour tous les supers moments que je ne
compte plus, les apéros sur la terrasse à refaire le monde (et surtout le labo !), les vacances incroyables
organisées par notre tour-op’ de compétition Maxinne, bref, pour ces années incroyables à vos côtés.
Merci à Dimitri et à Sébastien pour l’aide précieuse qu’ils m’ont apporté au moment où j’en avait le plus
besoin, et dans un autre registre, pour les sessions de course à pied avec Dimitri qui nous ont mené
jusqu’au semi-marathon de Montpellier. Merci à Camille et Baptiste d’avoir été nos coachs pendant nos
WOD clandestins sur le parking, et à Baptiste pour les « vrais » WOD partagés, après que tu aies passé
presque 2 ans à essayer de me convaincre que le CrossFit me plairait. On dirait que tu avais raison !
Merci Elena pour ton énergie (encore une italienne survitaminée, ça fait plaisir !). Merci à Léo, Lorelei,
Joshua, Philibert et Camille pour avoir énormément contribué à la bonne ambiance qui règne au labo.
Et bien-sûr à Maxime et Morgane, on se voit trop peu, mais c’est toujours avec grand plaisir.
Bien-sûr je n’oublie pas les « anciens », de la génération IAM, ceux qui n’ont connus que les vieux locaux
rue de l’Ecole Normale. Heureusement que vous étiez là, pour supporter ces vieux labos vétustes et pas
iii
Remerciements
très rassurants. Merci à tous les membres du « bureau des garçons + Mélanie + Camille » : Fabien, notre
Caliméro à nous, que j’ai grand plaisir à retrouver dans mon labo aujourd’hui, Camille, Benjamin, Vincent
et bien sûr Romain. Tu as été mon premier chef, et j’ai beaucoup apprécié de travailler à tes côtés. Tu
m’as beaucoup appris et c’est toujours un plaisir de se revoir, même en terre hostile, à des centaines
de kilomètres de Montpellier ! Je n’oublie pas Anne-Sophie, qui m’a légué la responsabilité des DSC,
sur lesquelles j’ai veillé pendant 2 ans et demi… J’espère avoir été à la hauteur de la tâche. J’ai toujours
ton « héritage » dans sa boite, tout neuf, il faudra que je le transmette à Philibert pour poursuivre la
lignée. Je pense également à David, avec qui on a échangé pendant des heures sur les vitrimères (ou
pas), avec généralement plus de questions sans réponse à la fin qu’au début. A Yvan et Eline, pour les
très bonnes soirées avec des chorégraphies parfois… approximatives, un peu comme les souvenirs que
j’en ai d’ailleurs ! A Céline pour ta gentillesse et pour ton énergie positive. Enfin, à Mélanie, bien qu’on
se soit peu croisés. J’ai gardé en tête cette phrase que tu as dit la première fois qu’on s’est rencontrés :
« c’est mon poulain ! ». L’air de rien, elle a fait son chemin dans ma tête et m’a aidé à rentrer plus
sereinement dans le projet au début de ma thèse.
Je tiens également à remercier mes deux stagiaires Chloé et Nathan, pour tout le travail accompli. Je
finirai par le valoriser, bientôt, c’est promis ! Vous m’avez apporté et appris beaucoup, sans doute plus
que vous ne l’imaginez, et je vous en remercie.
Je remercie également tous ceux que j’ai connu avant la thèse et qui ont continué à me suivre de plus
ou moins loin pendant ces trois années. Je pense bien sûr à Péroline, Clothilde, Anna, Antoine, Lucas,
Sophie et les autres membres des « Kékos » et de la « basse-cour de l’ENSCM », qui se reconnaitront.
Un grand merci également à Giovanna, après 12 ans c’est toujours un grand plaisir de se revoir (on
devrait faire ça plus souvent !).
Enfin, un énorme merci à ma famille, en particulier à mes parents et à Océane, pour m’avoir soutenu
depuis toutes ces années. Je n’en serais pas là si vous n’aviez pas été là, derrière moi. Merci pour votre
soutien dans les moments de doutes, de stress, dans les petites galères du quotidien et les galères tout
court. Et puis merci de m’avoir supporté aussi… un thésard sous pression ça n’est pas tous les jours
facile à vivre. Merci pour les supers moments partagés en vacances, en Normandie, en week-end. Bref,
merci pour tout. Je vous aime. D’ailleurs en parlant de vacances… Chat-Wane, on part où pour les
prochaines ? J’ai aussi une pensée pour Zen, elle aussi m’a soutenu à sa façon.
Je pense avoir fait le tour. Ces trois années auront été riches en rencontres, malgré les confinements et
autres restrictions, et j’espère sincèrement n’avoir oublié personne !
iv
Sommaire
SOMMAIRE
v
Sommaire
Remerciements ........................................................................................................................................ i
Sommaire .................................................................................................................................................v
Liste des abréviations .............................................................................................................................. ix
Introduction générale.............................................................................................................................. 1
Chapitre I : Etat de l’art sur les réactions d’échange employées dans les vitrimères et les stratégies pour
les activer ................................................................................................................................................ 7
Introduction du chapitre I ................................................................................................................. 10
Neighboring Group Participation and Internal Catalysis Effects on Exchangeable Covalent Bonds:
Application to the Thriving Field of Vitrimer Chemistry.................................................................... 12
1. Abstract ................................................................................................................................. 12
1. Introduction ........................................................................................................................... 12
2. Exchangeable Bonds with an Associative Mechanism .......................................................... 17
3. Internal Catalysis, Sterics, and Neighboring Groups Effects on Exchangeable Bonds .......... 35
Conclusion and Outlook ................................................................................................................ 61
References ..................................................................................................................................... 62
Conclusion du chapitre I .................................................................................................................... 79
Chapitre II : Synthèse et caractérisation d’un vitrimère de transestérification sans catalyseur activé par
des α,α-difluoroesters ........................................................................................................................... 81
Introduction du chapitre 2 ................................................................................................................ 83
Catalyst-free transesterification vitrimers: activation via α-difluoroesters ...................................... 86
1. Abstract ................................................................................................................................. 86
2. Introduction ........................................................................................................................... 86
3. Results and discussion ........................................................................................................... 88
Vitrimer characterization .............................................................................................................. 91
Conclusion ..................................................................................................................................... 97
Experimental section ..................................................................................................................... 98
Notes and references .................................................................................................................. 101
Conclusion du chapitre II ................................................................................................................. 105
vi
Sommaire
Chapitre III : Synthèse d’un vitrimère à partir d’époxy et d’α,α-difluoroacides difonctionnels ......... 107
Introduction du chapitre III ............................................................................................................. 109
Synthesis of a transesterification vitrimer activated by fluorine from an α,α-difluoro carboxylic acid

and a diepoxy .................................................................................................................................. 111
Abstract ....................................................................................................................................... 111
Introduction ................................................................................................................................. 111
Results and Discussion ................................................................................................................ 113
Conclusion ................................................................................................................................... 122
Experimental Section................................................................................................................... 123
Acknowledgements ..................................................................................................................... 126
References ................................................................................................................................... 126
Conclusion du chapitre III ................................................................................................................ 129
Chapitre IV : Transposition de la synthèse d’α,α-difluoroacides au resvératrol pour la synthèse de

vitrimères biosourcés sans catalyseur................................................................................................. 131
Introduction du chapitre IV ............................................................................................................. 133
From vineyards to 100 % resveratrol materials: α-CF2 activation in biobased catalyst-free vitrimers
......................................................................................................................................................... 135
Abstract ....................................................................................................................................... 135
Introduction ................................................................................................................................. 135
Conclusion ................................................................................................................................... 144
Experimental section ................................................................................................................... 145
References ................................................................................................................................... 148
Conclusion du chapitre IV................................................................................................................ 153
Conclusion générale ............................................................................................................................ 155
Annexes A : annexes au chapitre II...................................................................................................... 163
Annexes B : annexes au chapitre III ..................................................................................................... 191
vii
Sommaire
Annexes C : annexes au chapitre IV..................................................................................................... 211
Production scientifique ................................................................................................................... 225
Articles publiés............................................................................................................................. 225
Articles à soumettre prochainement ........................................................................................... 225
Participations à des congrès scientifiques ...................................................................................... 226
viii
Liste des abréviations
LISTE DES ABREVIATIONS
ix
ATR attenuated total reflectance - réflectance totale atténuée

BADGE bisphenol A diglycidyl ether- diglycidyl éther de bisphénol A
DGEBA diglycidyl éther de bisphénol A
3D three-dimensional - tridimensionnel
BDE bond dissociation energy - énergie de dissociation d'une liaison
BDGE butanediol diglycidyl ether- diglycidyl éther de butanediol
BMSC bis-(methylsalicyl)carbonate
BPA bisphenol A - bisphénol A
CAN covalent adaptable network - réseau covalent adaptable
CIRIMAT Centre Inter-universitaire de Recherche et d'Ingénierie des MATériaux
CNRS Centre National de la Recherche Scientifique
COSY (NMR) correlated spectroscopy - RMN bidimensionnelle par corrélation homonucléaire
CX1 complex 1 - complexe 1
CX2 complex 2 - complexe 2
DBTL / DBTDL dibutyltin dilaurate - dilaurate de dibutylétain
DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene - 1,8-Diazabicyclo[5.4.0]undéc-7-ène
DCM dichloromethane- dichlorométhane
DMA dynamic mechanical analysis - analyse mécanique dynamique
DMF dimethylformamide- diméthylformamide
DMSO dimethylsulfoxide - diméthylsulfoxyde
DMTDA dimethylthiotoluenediamine- diméthylthiotoluènediamine
DPC diphenyl carbonate - diphényl carbonate
DSC differential scanning calorimetry - calorimétrie différentielle à balayage
EDG electron donating group - groupe électrodonneur
EEW epoxy equivalent weight - masse équivalente pour une mole de fonction époxy
EG-AA ethylene glycol–bisacetoacetate - bis(acétoacétate) d'éthylène glycol
EN en anglais
ESI- negative electrospray ionization - ionisation négative par électronébuliseur
ESI+ positive electrospray ionization - ionisation positive par électronébuliseur
Et2O diethyl ether - éther diéthylique
EWG electron withdrawing group - groupe électroattracteur
FR en français
FTIR Fourier transform infrared spectroscopy - spectroscopie infrarouge à
transformée de Fourier
HRMS high resolution mass spectroscopy - spectroscopie de masse à haute résolution
HSQC (NMR) heteronuclear single quantum coherence
ICGM Institut Charles Gerhardt de Montpellier
INP-ENSCBP Institut National Polytechnique - École Nationale Supérieure de Chimie, de
Biologie et de Physique
INSA Institut National des Sciences Appliquées
KWW Kohlrausch-Williams-Watts (fonction de) ou fonction exponentielle étirée
LCPO Laboratoire de Chimie des Polymères Organiques
MDI methylene diphenyl diisocyanate - 4,4'-diisocyanate de diphénylméthylène
MeCN acetonitrile - acétonitrile
MOCA 4,4′-methylenebis(2-chlorobenzenamine)- 4,4'-méthylènebis(2-chloroaniline)
NaOH sodium hydroxide - hydroxyde de sodium
NGP neighboring group participation - participation des groupes voisins ou
assistance anchimérique
x
NMR nuclear magnetic resonnance - résonnance magnétique nucléaire (RMN)

P-DAF 2,2'-(1,4-phenylene)bis(2,2-difluoroacetic acid) - acide 2,2'-(1,4-
phénylène)bis(2,2-difluoroacétique)
P-DAF/BDGE vitrimère fluoré issu du P-DAF et du BDGE
P-DE diethyl 2,2'-(1,4-phenylene)bis(2,2-difluoroacetate) - 2,2'-(1,4-
phénylène)bis(2,2-difluoroacétate) de diéthyle
PDMS polydimethylsiloxane - polydiméthylsiloxane
PEEK polyetherketoneketone - polyéthercétonecétone
PEEKK polyetheretherketoneketone - polyétheréthercétonecétone
PEG polyethylene glycol - polyéthylène glycol
PEK polyetherketone - polyéthercétone
PET poly(ethylene terephthalate) - poly(téréphtalate d'éthylène)
PHU polyhydroxyurethane - polyhydroxyuréthane
PTFE polytetrafluoroethylene - polytétrafluoroéthylène
PTMG poly(tetramethylene ether)glycol or polytetrahydrofuran
PTU polythiourethane - polythiouréthane
PU polyurethane - polyuréthane
ROP ring opening polymerization - polymérisation par ouverture de cycle
RT room temperature - température ambiante
RvOEt triester α,α-difluoré issu du resvératrol
RvOGly resvératrol époxydé
RvOH-TAF triacide α,α-difluoré issu du resvératrol
TBD triazabicyclodecene - triazabicyclodécène
TEA triethanolamine - triéthanolamine
TBAB tetrabutylammonium bromide - bromure de tétrabutylammonium
TGA thermogravimetric analysis - analyse thermogravimétrique
TGDDM tetraglycidyl methylenedianiline- tétraglycidyléther de 4,4′-
diaminodiphénylméthane
THF tetrahydrofuran - tétrahydrofurane
TMS tetramethylsilane - tétraméthylsilane
TPE 1,1,1-Tris(4-hydroxyphenyl)ethane - 1,1,1-Tris(4-hydroxyphényl)éthane
TPE-TAF triacide α,α-difluoré issu du 1,1,1-Tris(4-hydroxyphényl)éthane
TPE-TAF/BDGE vitrimère fluoré issu du TPE-TAF et du BDGE
TPE-TE triester α,α-difluoré issu du 1,1,1-Tris(4-hydroxyphényl)éthane
TPP triphenylphosphine - triphénylphosphine
TREN tris(2-aminoethyl)amine- tris(2-aminoéthyl)amine
TTS transition state - état de transition
Vm-RvOH vitrimère fluoré issu du resvératrol (RvOH-TAF et RvOGly)
VU vinylogous urethane or enaminone
xi
Introduction générale
INTRODUCTION GENERALE
1
Depuis l’essor des polymères de synthèse dans les années 1930 jusqu’au début des années 2000, la
communauté des polyméristes classifiait les architectures polymères en deux groupes : soit le
matériau polymère était formé par un réseau macromoléculaire trimensionnel, soit constitué de
chaînes linéaires enchevêtrées. Dans l’industrie, ces deux types d’architecture ont été qualifiées
respectivement de thermodurcissable ou de thermoplastique, en fonction de leurs propriétés,
notamment de mise en oeuvre. En effet, les thermodurcissables ont une morphologie fixée une fois
leur polymérisation achevée. Leur mise en forme se fait à partir du prépolymère, et la morphologie
obtenue est fixée après réticulation. Les thermoplastiques, en revanche, sont généralement fusibles
après polymérisation, à quelques exceptions près (aramides, PTFE). Cette propriété permet des
procédés de mise en œuvre à l’état fondu, par exemple par extrusion, par injection ou encore par
calandrage. Les propriétés différentes des thermodurcissables et des thermoplastiques dépendent
directement de leur structure macromoléculaire. Un thermodurcissable forme en théorie une seule
macromolécule qui occupe tout le volume du matériau, la cohésion du réseau étant liée
principalement aux liaisons covalentes qui le composent. Dans le cas d’un thermoplastique, il n’y a pas
de liaison covalente entre les chaînes, la cohésion est assurée par les enchevêtrements et les liaisons
faibles pouvant intervenir entre ces chaînes (liaisons hydrogènes, liaisons de Van der Waals). Les
propriétés de ces deux types de matériaux, qui découlent de leur architecture, sont de ce fait très
différentes. Les thermodurcissables permettent d’obtenir de hautes performances mécaniques, et
sont généralement plus résistants en température et aux agents chimiques que les thermoplastiques.
En revanche ils ne sont pas recyclables par des méthodes mécaniques (extrusion, moulage par
compression, etc.) et restent des défis pour le recyclage chimique (dépolymérisation, solvolyse). Les
thermoplastiques, à l’inverse, sont la plupart du temps recyclables par procédés mécaniques lorsque
la température dépasse leur température de transition vitreuse (Tg), et dans le cas des semi-cristallins
leurs températures de fusion. En revanche, leur résistance aux solvants ainsi que leurs propriétés
mécaniques et de tenue en température sont généralement plus limitées, à l’exception toutefois de
quelques cas particuliers (aramides, PEK, PEEK, PEEKK…).
La vision binaire historique scindant thermodurcissables et thermoplastiques a commencé à être mise

à mal avec l’apparition1 des réseaux covalents adaptables (CAN). Ce type de matériaux est basé sur un
réseau tridimensionnel de liaisons covalentes, à l’instar des thermodurcissables. La différence réside
dans la capacité de certaines de ces liaisons à s’échanger d’une séquence du réseau polymère à une
autre, lorsque le matériau est chauffé à une température suffisante pour activer cet échange. Cette
propriété rend le réseau dynamique par chauffage, et permet de remettre en forme ces matériaux. En
1
Kloxin, C. J.; Bowman, C. N. Chem. Soc. Rev. 2013, 42 (17), 7161–7173.
2
particulier, l’équipe de Leibler a théorisé en 2011 le concept de vitrimère,2 un cas particulier de CAN
dans lequel l’échange se fait par un mécanisme associatif. Ce mécanisme confère au matériau des
propriétés particulières, en particulier rhéologiques et de résistance aux solvants. Cette découverte,
basée sur l’échange de liaisons par transestérification, a suscité l’engouement de la communauté des
polyméristes. En effet, ce nouveau type de matériaux polymères permet d’envisager l’utilisation de
procédés de mise en œuvre traditionnellement réservés aux thermoplastiques, pour des applications
pour lesquelles les thermodurcissables sont préférentiellement utilisés. De plus, les réactions
d’échange rendent possible la remise en oeuvre de ces matériaux, et propose une solution au
problème du recyclage des thermodurcissables, qui reste limité à l’heure actuelle. Suite à la découverte
des vitrimères, d’autres réactions d’échange ont été étudiées pour élargir la gamme des propriétés
des vitrimères. Un des objectifs principaux a été de trouver des systèmes qui soient dynamiques sans
avoir à recourir à des catalyseurs « externes » (non liés au réseau) au sein du matériau. En effet, les
vitrimères de transestérification nécessitent l’emploi de catalyseurs en grande quantité (jusqu’à 10 %
molaire) afin d’activer la réaction d’échange et rendre les nœuds de réticulation dynamiques.
L’utilisation de catalyseurs externes induit un risque de lixiviation de ces espèces chimiques lorsque le
matériau est en usage, et un risque de vieillissement prématuré du matériau au moment de son
recyclage mécanique. Outre l’utilisation de réactions d’échange qui ne nécessitent pas de catalyseur,
une autre stratégie est d’activer des réactions telles que la transestérification, par des groupements
disposés sur la macromolécule. Cette stratégie d’activation est l’objet de la présente étude.
2
Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Science 2011, 334 (6058), 965–968.
3
Figure A. Représentation schématique de la structure de (a) réseaux 3D (thermodurcissables), (b) linéaires

(thermoplastiques) et (c) CANs avec des nœuds de réticulation échangeables
La transestérification est une réaction de substitution. Elle a lieu par l’attaque d’un groupement
hydroxyle nucléophile sur le carbone électrophile du carbonyle de l’ester. Pour activer cette réaction,
il est donc possible d’augmenter le caractère nucléophile du groupe hydroxyle, ou d’augmenter le
caractère électrophile du carbonyle. C’est cette dernière stratégie qui a été retenue pour ce projet. En
particulier, l’objectif est de démontrer la possibilité d’utiliser le fluor comme activateur de
transestérification dans des vitrimères polyester. En effet, le fluor, de par sa forte électronégativité,
confère aux groupements fluorés des effets inductifs électroattracteur intenses. Ce projet est basé sur
le postulat que des atomes de fluor placés à proximité du carbonyle d’un ester vont exercer un effet
inductif électroattracteur de manière à diminuer la densité électronique sur le carbone de ce
carbonyle, et le rendre plus électrophile (Figure B).
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Figure B. Activation de la réaction de transestérification par effet inductif d’atomes de fluor en position α- par rapport au
carbonyle de l’ester. L’effet inductif électroattracteur des atomes de fluor augmente le caractère électrophile du carbonyle.
Dans un premier temps, les travaux décrits dans ce manuscrit avaient pour but l’obtention de la preuve
de concept à partir d’un premier monomère. Par la suite, des solutions ont été envisagées pour
simplifier les synthèses de monomères activés par rapport à la première génération. Enfin, l’utilisation
de synthons biosourcés et l’élargissement de la gamme de propriétés des matériaux obtenus ont été
étudiés.
Ces travaux ont été menés au sein des départements Chimie et Matériaux Moléculaires (C2M, ex-
AM2N) et Chimie et Matériaux MacroMoléculaires (C3M, ex-IAM) de l’Institut Charles Gerhardt de
Montpellier (ICGM) et de l’équipe Physique des Polymères du Centre Interuniversitaire de Recherche
et Ingénierie des Matériaux de Toulouse (CIRIMAT). Ils s’inscrivent dans le cadre du projet
16CARN000801 financé par l’institut Carnot Chimie Balard Cirimat.
Dans un premier temps, nous passerons en revue les stratégies d’activation décrites dans la littérature
pour les réactions d’échanges employées dans les vitrimères jusqu’à présent. Nous verrons ensuite
qu’il est possible d’activer la réaction de transestérification grâce à l’introduction de groupements α,α-
difluoroesters afin de synthétiser des vitrimères sans catalyseur. Nous nous attarderons ensuite sur
l’étude de la formation de réseaux tridimensionnels à partir de monomères difonctionnels dans ce
type de vitrimères. Enfin, nous discuterons de la possibilité d’utiliser des synthons d’origine naturelle
pour la synthèse de monomères α,α-difluoro acides carboxylique, et des vitrimères associés.
Ce manuscrit de thèse est essentiellement rédigé sous forme d’une compilation d’articles scientifiques
acceptés ou soumis dans des revues internationales à comité de lecture.
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Chapitre I : Etat de l’art sur les réactions d’échange employées dans les vitrimères et les stratégies
pour les activer
CHAPITRE I : ETAT DE L’ART SUR LES REACTIONS
D’ECHANGE EMPLOYEES DANS LES VITRIMERES ET LES
STRATEGIES POUR LES ACTIVER
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Introduction du chapitre I ................................................................................................................. 10
Neighboring Group Participation and Internal Catalysis Effects on Exchangeable Covalent Bonds:
Application to the Thriving Field of Vitrimer Chemistry.................................................................... 12
1. Abstract ................................................................................................................................. 12
2. Introduction ........................................................................................................................... 12
3. EXCHANGEABLE BONDS WITH AN ASSOCIATIVE MECHANISM............................................. 17
Esters. ........................................................................................................................................ 17
Carbonates. ............................................................................................................................... 19
Boronic Esters. ........................................................................................................................... 20
Sulfur-Containing Bonds. ........................................................................................................... 21
Disulfides. .............................................................................................................................. 21
Thioesters. ............................................................................................................................. 22
Meldrum’s Acids. ................................................................................................................... 22
Trialkylsulfonium Salts. .......................................................................................................... 22
Silyl Ether Transalkoxylation and Metathesis............................................................................ 23
Urethanes, Ureas, Thiourethanes, and Hydroxyurethanes....................................................... 24
Olefin Metathesis. ..................................................................................................................... 27
Imines. ....................................................................................................................................... 29
Vinylogous Urethanes, Ureas, and Amides. .............................................................................. 30
Diketoenamines......................................................................................................................... 33
4. INTERNAL CATALYSIS, STERICS, AND NEIGHBORING GROUPS EFFECTS ON EXCHANGEABLE

BONDS ........................................................................................................................................... 35
Transesterification Enhancement by Neighboring Groups: Influence on the Exchange

Mechanism and Vitrimer Properties. ........................................................................................ 36
The Case of Oxime−Esters. ........................................................................................................ 42
Carbonate Activation by Electron-Withdrawing Groups. ......................................................... 43
Dioxaborolane Transesterification Acceleration ....................................................................... 46
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Disulfide Metathesis: Effect of Aromatic Substituents ............................................................. 49
Internal Catalysis of Silyl Ether Transalkoxylation by Amines, Urethanes, and Ureas .............. 52
Case of Urethanes and Hydroxyurethanes................................................................................ 54
Ureas Exchange ......................................................................................................................... 55
Transimination Acceleration by Activating Groups ................................................................... 56
Vinylogous Urethanes and Amides, an Efficient Exchange Chemistry without Catalyst .......... 58
Hints for Diketoenamine Activation .......................................................................................... 60
Effect of the Alkylating Agent on Trialkylsulfonium Salt Exchange ........................................... 60
Conclusion and Outlook ................................................................................................................ 61
References ..................................................................................................................................... 62
Conclusion du chapitre I .................................................................................................................... 79
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Introduction du chapitre I
Les travaux de thèse décrits dans ce manuscrit portent sur des systèmes vitrimère dont le caractère
dynamique nécessite habituellement l’emploi de catalyseurs externes. Ces catalyseurs externes sont
emprisonnés dans le réseau, mais n’y sont pas liés directement. Ces espèces chimiques peuvent donc
migrer vers l’extérieur du polymère. Pour palier ce problème, il est possible d’utiliser des « catalyseurs
internes », c’est-à-dire des groupements liés au réseau polymère capables d’activer les fonctions
échangeables à proximité. Afin de circonscrire les objectifs du projet, une étude bibliographique a été
menée. Elle s’articule autour de deux axes. Le premier consiste en un inventaire des réactions
d’échange décrites dans la littérature afin de synthétiser des matériaux vitrimères. Un intérêt
particulier a été apporté aux mécanismes d’échanges mis en jeu, connus ou postulés, pour mieux
comprendre les leviers existants afin d’activer les échanges dans chaque cas. La nature du mécanisme
d’échange, associatif ou dissociatif, a également une influence primordiale sur les propriétés
rhéologiques des matériaux obtenus, ce qui a également été développé dans ce chapitre. Le second
axe est consacré aux outils déjà décrits pour activer les différentes réactions détaillées auparavant. En
particulier, un inventaire des groupements activant les échanges lorsqu’ils sont à proximité a été
réalisé. Certains de ces groupements ont été décrits dans des vitrimères et leur influence sur les
propriétés dynamiques des matériaux a été étudiée. Cependant, beaucoup de ces groupements ont
été utilisés dans d’autres domaines de la chimie, organique notamment, et souvent en solution.
L’inventaire de ces groupements a donc pour but de mettre en lumière des possibilités encore
inexploitées pour activer les échanges, et potentiellement les mettre à profit dans de futures études
dans le domaine des vitrimères.
Au-delà du simple inventaire des groupements activateurs, cette étude a permis de comprendre par
quels mécanismes ces groupes activent les échanges (effets inductifs, assistance anchimérique, effets
stériques, cyclisation pour stabiliser l’intermédiaire réactionnel, etc.).
Cette étude a permis la publication d’un article de perspective3 dans le journal Macromolecules en
mars 2021, qui constitue ce chapitre (Figure C).
3
Cuminet, F.; Caillol, S.; Dantras, É.; Leclerc, É.; Ladmiral, V. Macromolecules 2021, 54 (9), 3927–3961.
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Figure C. Activation of bond exchanges in vitrimers by external catalysis or internal catalysis and neighboring group
participation
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Neighboring Group Participation and Internal Catalysis Effects on
Exchangeable Covalent Bonds: Application to the Thriving Field of
Vitrimer Chemistry
Florian Cuminet,a,b Sylvain Caillol,a Éric Dantras,b Éric Leclerca and Vincent Ladmirala
a
ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France
b
CIRIMAT Physique des Polymères, Université de Toulouse, CNRS, Université Toulouse 3 - Paul Sabatier,
31062 Toulouse, France
1. Abstract
Vitrimers constitute a fascinating class of polymer materials that make the link between the historically
opposed 3D networks (thermosets) and linear polymers (thermoplastics). Their chemical resistance,
reshaping ability, and unique rheological behavior upon heating make them promising for future
applications in industry. However, many vitrimers require the use of high catalyst loadings, which
raises concerns for their durability and limits their potential applications. To cope with this issue,
internal catalysis and neighboring group participation (NGP) can be used to enhance the reshaping
ability of such materials. A few studies report the effect of activating groups on the exchange reactions
in vitrimers. Nevertheless, knowledge on this topic remains scarce, although research on vitrimers
would greatly benefit from NGP already known in organic chemistry. The present Perspective presents
the different types of exchangeable bonds implemented in vitrimers and discusses chemical groups
known to have or potentially capable of an enhancing effect on exchange reactions. This analysis is
underpinned by a thorough mechanistic discussion of the various exchangeable bonds presented.
1. Introduction
Since the team of L. Leibler discovered and described the first vitrimer in 2011,1 these materials have
attracted tremendous attention in the polymer and materials communities. This enthusiasm is not
surprising given the amazing properties of these materials. Nevertheless, though the definition of this
concept seems easy to handle at first glance, caution should be taken when classifying new materials
as vitrimers. To understand well what a vitrimer is, the usual classification of polymer materials must
be clearly recalled. Historically, polymers have been categorized in two main classes: thermoplastics
and thermosets. Thermoplastics consist of entangled linear polymer chains that are free one from
another. In contrast, in thermosets, polymer chains are linked by covalent bonds that cannot be
cleaved without destroying the network.2 This difference at the molecular scale has consequences on
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the macroscopical behavior of these materials. Most thermoplastics are soluble provided that a
convenient solvent is used (or exists). In thermosets the solvent is not able to set the chains apart, and
the material does not dissolve. Besides this different behavior toward solvents, the other main
difference lies in the thermal behavior of these materials. In most cases when thermoplastics are
heated, the relative movement of the chains becomes easier. Macroscopically this phenomenon is
visible when the material flows.2 Thermosets cannot flow when heated.2,3 Reversible reactions
involving covalent bonds have been known for many decades, and their possible use in polymers had
already been inferred in the 1960s.4,5 The concept of reversible covalent bonds implemented in
polymers led to a new class of materials called CANs, short for covalent adaptable networks. In CANs,
polymer chains are covalently cross-linked as in thermosets, but these cross-linking bonds are
reversibly cleavable, which leads to properties such as malleability in response to an external stimulus
such as temperature or light irradiation.6 The most iconic reversible reaction used in such materials is
probably the Diels−Alder reaction.7−13 This reaction is reversible upon heating. When this reaction is
used to make cross-linked materials, the crosslinking bonds can break upon heating and re-form at
lower temperature, thus leading to reshapability (Figure 1C).6
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Figure 1. Schematic representations of the mechanisms at work in (A) associative CANs (vitrimers), (B) vitrimer-like
dissociative CANs, and (C) dissociative CANs. Vitrimer-like dissociative CANs (B) exhibit a constant Keq over the vitrimer-like
temperature regime and a short lifetime of the dissociated state.
Most CANs designed before the year 2010 were based on the dissociative mechanism whereby a bond
has to be cleaved before another bond is formed between the dissociated moieties. In 2005, Bowman
et al. reported the first CAN based on an associative exchange reaction.14 Allyl sulfides were used as
addition−fragmentation chain transfer agents. The exchange proceeded via a photoinduced radical
mechanism allowing constant cross-linking density and network connectivity even though the topology
changed.14 Later, in 2011, Leibler et al.1 described the first thermally triggered associative CAN, based
on transesterification as the exchange reaction. This material exhibited a novel rheological behavior
with its viscosity decreasing linearly with increasing temperature. Because this behavior is common in
inorganic materials and especially strong glass, this new kind of polymer was coined “vitrimer”. On the
one hand, vitrimers are often insoluble like thermosets, except for specific cases such as very fast
vitrimers for instance.15,16 On the other hand, they can be reshaped and recycled by heating without
precise control over temperature, like glass. Their singular rheological behavior was attributed to the
associative mechanism of the bond exchange. In contrast to the majority of dissociative CANs, because
vitrimers keep a constant connectivity regardless of the temperature (even the reshaping
temperatures), their viscosity only depends on the rate of the exchange reaction. Therefore, the
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viscosity and stress−relaxation profiles as a function of temperature follow the Arrhenius law. These
behaviors are often considered specific to vitrimers,1,17−19 although this point has recently been
questioned and is debatable. Two visions of what a vitrimer is coexist, depending on whether the
chemist’s or the physicist’s point of view is adopted. The chemist’s definition focuses on the exchange
mechanism. In consequence, only a CAN based on an associative mechanism is a vitrimer (Figure 1A).
In contrast, the physicist defines a vitrimer according to the physical properties. For example,
Drockenmuller et al.20 described a material based on a dissociative mechanism that exhibits an
Arrhenius viscosity dependence with temperature. Such materials were designated as “vitrimer-like”.21
The hypothesis to explain such vitrimer-like behavior in dissociative CANs lies in the thermodynamic
and kinetic of the exchanges. When the equilibrium constant of dissociative bonds is displaced toward
the associated state, though the dissociation−association happens, the overall number of bonds and
cross-link density is barely reduced. Kinetically, this happens when the association reaction is much
faster than the dissociation reaction. The dissociated state is thus transitory, globally the number of
bonds hardly changes, and the network integrity remains virtually unchanged (Figure 1B).22,23 The
Arrhenian rheological behavior can also be observed in a range of temperatures over which the
equilibrium constant does not vary much. For instance, Konkolewicz et al. made vitrimer-like
dissociative CANs out of anilinium salts. They reported for the adduct formation a ΔH value of −2.8 ±
0.2 kJ mol−1 and compared it with the case of Diels−Alder adduct formation with a ΔH value of −157 ±
14 kJ mol−1.21 Because ΔH is very low for their system, the dependence of Keq with temperature is
considered negligible. In this case, the ratio of dissociated and associated bonds over this temperature
range is constant (Figure 1B), and the network connectivity does not change.21,24 With the increasing
number of chemical platforms able to undergo exchange discovered, some particular cases of
dissociative CANs somewhat blur the boundary with vitrimers.20,21,25,26 In addition, networks featuring
both permanent and exchangeable cross-links are reported to exhibit vitrimer-like stress−relaxation,
but within a certain limit as the permanent cross-links induced a residual stress plateau.27 Such
borderline materials indicate that the definition of a vitrimer still remains debatable, depending on the
viewpoint adopted. Vitrimers address the problem of thermoset recyclability and thermoplastic
vulnerability toward solvents. Therefore, the interest for these materials is growing in industry, as
highlighted in recent reviews.22,28,29 Nonetheless, some characteristics may limit their industrialization.
They often display high relaxation times and high viscosity during reprocessing, making them
unsuitable for the recycling processes usually found for thermoplastics in industry. Furthermore, most
vitrimers rely on catalysts and in some cases on high catalyst loadings.1 The use of catalysts may
generate problems such as limited number of recycling/reshaping cycles due to premature
degradation or migration and loss of the catalyst.30−32 A solution to this issue is the design of vitrimers
that do not rely on catalysis. This can be done by using a large excess of exchanging functional
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groups32−34 or by using exchange reactions that do not require any catalyst.18,35−42 Another strategy,
inspired by organic chemistry in solutions, relies on chemical functions near the exchangeable bond to
enhance the reaction rate. This effect is called either neighboring group participation (NGP) when the
accelerating substituents are at some point covalently bonded to the reaction center during the
exchange or internal catalysis for effects at longer distance such as electrostatic interactions, steric
effects, or weak bonds.43 Guan et al.44 implemented this strategy in boronic ester CANs and enhanced
the transesterification rate thanks to neighboring tertiary amines. This effect was later implemented
in other kinds of vitrimers featuring ester or silyl ether exchangeable bonds, for instance.38,45 In their
review, Guerre et al.43 highlighted the few examples of internal catalysis in vitrimers reported so far
and the strong potential of this strategy to tune the properties of vitrimers. More recently, Van
Lijsebetten et al.46 also emphasized the power of NGP in dynamic covalent chemistry, especially in
polymeric materials, in a very clear and useful tutorial review. To proceed further with this concept, a
general outline of the activating groups potentially beneficial to vitrimers would give useful insight for
further research on this fast rising topic. Nevertheless, caution should be taken when using NGP as this
strategy can sometimes drastically modify the exchange mechanism.24,43 For instance,
transesterification, which usually proceeds via an associative exchange, was reported to follow a
dissociative pathway in the presence of specific activating groups.47,48 Activating groups are a very
powerful yet complex tool. Because the case of vitrimer-like dissociative CANs is still debated in the
vitrimer community, this Perspective focuses on internal catalysis and NGP in associative exchange
reactions, to follow the strict definition of vitrimers. The first part is dedicated to the description of the
associative exchange reactions implemented in vitrimers, their mechanisms, and some of the pitfalls a
vitrimer scientist should be aware of (Figure 2). Then, in light of this mechanistic discussion, the
activating groups potentially useful to tune the properties of vitrimers are briefly presented and
discussed. Insights into the activating groups proven to be beneficial on small molecules but not yet
implemented in vitrimers are also given. For each kind of exchangeable bond the influence on the
kinetics of exchange reactions is discussed as well.
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Figure 2. Associative exchangeable bonds for vitrimers’ design.
2. Exchangeable Bonds with an Associative Mechanism

Esters.
Scheme 1. Ester Exchange Mechanisms: (a) Alcoholysis, (b) Acidolysis, and (c) Direct Ester−Ester Exchange
Esters are probably one of the oldest known exchangeable bonds, as Friedel and Craft, famous for the
eponymous reaction, also discovered in 1865 the exchange reaction occurring between two ester
groups.49 Several terms such as ester exchange, ester−ester interchange, interesterification or the
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nowadays most commonly used transesterification are considered as synonymous, though they
actually encompass several reactions.50 Actually, three reactions are reported to happen in what is
commonly considered as the transesterification equilibrium,51 namely, alcoholysis, acidolysis, and the
genuine transesterification.49,52−54 Alcoholysis is the main reaction55 although the direct ester−ester
exchange prevails for esters synthesized from aromatic acids over 300 °C.56 The alcoholysis mechanism
proceeds by the attack of the alcohol onto the carbon of the carboxylate. A tetrahedral intermediate
is thus formed prior to the elimination of an alkoxy group, leading either to the starting ester or to
the exchanged one (Scheme 1a). The mechanism of acidolysis is similar: the nucleophilic oxygen of
the acid attacks the electrophilic carbon of the carbonyl moiety of the ester and forms a tetrahedral
intermediate, prior to the elimination of the attacking acid, or the exchanged one. Elimination of the
alkoxy group on the intermediate can also occur. This produces an anhydride intermediate which
reacts immediately with the released alcohol (Scheme 1b).53,57 The third mechanism is less usual and
is described as a concerted interchange (Scheme 1c). This reaction was reported experimentally thanks
to kinetics experiment at temperatures over 300 °C.56 Kotliar et al. pointed out that the enthalpy
change during this reaction is near zero, suggesting an associative pathway.53 Anyway, these three
mechanisms are associative. Catalysis does not seem to change this feature as acid-catalyzed
transesterification is reported to proceed through an addition/elimination mechanism.58 Additionally,
base catalysis only changes the nucleophile from an alcohol to its more reactive alkoxide
counterpart.59 Transesterification was studied in polymers in the second half of the 20th century, as
the exchange reaction is more significant in bulk materials;49,52,55,60 then this reaction regained
popularity among scientists with the development of biodiesel and biofuels. Recently, the interest in
biomass valorization and greener fuels has grown, and catalysts such as N-heterocyclic carbenes,61
calcium oxide,62 ZrO2/SO4,59 silicates and clays,63,64 or aluminum chloride65 were (re)- discovered.
Metal-based catalysis (such as Sn, Ti, or Mg51,54 for instance) draws particular attention as zinc-based
catalysts were recently used in the first reported vitrimer.1 The mechanism involves a Zn2+ species,
which coordinates to the ester carbonyl group and activates it with respect to the nucleophilic attack
of the alcohol or alkoxide and then proceeds via the pathway previously described.66 In summary, all
the catalytic mechanisms encountered so far were associative.
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Carbonates.
Scheme 2. Exchange Reactions on Carbonates (a) Transcarbonation and (b) Carbonate Interchange
Owing to their structural similarity, carbonates and esters are often compared, and their chemistries
are considered very close. As in the case of esters, several names are used for the exchange reactions
of carbonate. The exchange between an alcohol and a carbonate is called transcarbonation, carbonate
transesterification, or carbonate alcoholysis when the exchange occurs on polycarbonate chains and
small alcohols (Scheme 2a). Carbonate interchange refers to the exchange between two carbonates
(Scheme 2b). The interest for transcarbonation rose when scientists aimed at synthesizing
polycarbonate materials without the use of highly toxic phosgene.67 The exchange between diphenyl
carbonate and bisphenol A was used as a safer pathway to produce polycarbonates. The mechanism
involved was similar to ester transesterification68 and was proven quite recently. In the absence of
catalyst, there is a prototropy between the phenol and the carbonate. The deprotonated counterpart
(phenolate) is the reactive species toward the electrophilic carbon of the carbonate carbonyl moiety.
The reaction proceeds through a tetrahedral intermediate before the elimination of a phenolate (from
the starting carbonate or from the reactant).69,70 However, this exchange is very slow.67
Transcarbonation is known to be catalyzed by metal-derived catalysts such as tin salts,71−73 zinc
acetate,74 copper salts,72 and even a dimetallic iron−manganese cyanide catalyst.75 Bases are also
common catalysts, for instance, magnesium hydroxide,76 calcium salts,77,78 or sodium alkoxides.74,79 All
the catalyzed mechanisms described are associative,69,71,74,76−80 though they are slightly different
depending on the type of catalysis employed (Scheme 3). When a base catalyst is used, the carbonate
and the alcohol moiety form a prereaction complex (CX1). Then the reaction proceeds via a tetrahedral
transition state (TTS) yielding a postreaction complex (CX2) and ultimately the free exchanged species
(Scheme 3b).74 The overall reaction follows an “addition−elimination” mechanism. When a Lewis acid
catalyst is employed, such as zinc acetate, a cyclic transition state involving a ternary complex between
the carbonate, the alcohol, and the catalyst is formed. Then, the reaction proceeds through a
concerted mechanism to generate a postreaction complex, following an addition−elimination
mechanism.74 Direct ester−carbonate interchange has also been reported81 and described as following
an associative pathway as well.
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Scheme 3. (a) Transcarbonation Pathway and (b) Catalytic Effect by Bases and Metal Ions
Boronic Esters.
Cyclic boronic esters, also known as dioxaborolanes, are synthesized by condensation of boronic acids
with 1,2- and 1,3-diols leading to 5- and 6-membered rings, respectively.82−84 Boronic acids are used
in a wide range of reactions in organic chemistry, as catalysts, pronucleophiles (cross-coupling
reactions), or reaction intermediates.82,85 In carbohydrate chemistry, they are also useful as protective
groups for diols and diamines.82,85,86 Besides, their ability to bond with diols makes boronic esters
particularly useful in biology, biochemistry, or chromatography for sugars and diol bearing
compounds purification or carbohydrate sensors, for example.85,87−89 In medicine they are also
proposed for drug delivery90−92 and glucose sensing for diagnostic purposes.93,94 The key feature of
boronic esters is their reversible formation from diols and boronic acids, resulting in dynamic systems
with tunable properties. In biological media, this reactivity results in a dissociative mechanism, as
boronic esters in aqueous conditions are prone to hydrolysis yielding boronic acids.95,96 The
equilibrium between dissociated boronic acid−diol and associated boronic ester (Scheme 4) was
exploited to prepare covalently cross-linked self-healing hydrogels, for example.97−99
Scheme 4. Equilibrium between Boronic Acid and 1,2-Diol
Over the past few years, growing interest for this functionality has spread in the polymer science
community, in particular for the preparation of self-healing polymers.100,101 Interestingly, Sumerlin et
al.101 showed that two different mechanisms are involved in the exchange reactions occurring in
boronic ester-based cross-linked materials. The exchange occurs either via classical boronic ester
dissociation and reesterification or via an associative mechanism similar to transesterification,
provided that free diol functions are available in the material. As the dissociative mechanism requires
water to cleave the boronic ester, it is assumed that in a completely dry environment only the
associative transesterification mechanism occurs.85,102 Guan et al. implemented this associative
mechanism in the first boronic ester cross-linked vitrimers.44 Eventually, Nicolaÿ and Leibler et al.103
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reported a vitrimer based on a third kind of exchange reaction, namely, the direct metathesis between
two boronic ester moieties. Although the exact mechanism of this reaction remains uncertain, the
hypothesized transition states and intermediates are expected to have a higher connectivity,104 as
expected for an associative mechanism. Raynaud et al. investigated the mechanism at work in dynamic
polymer networks based on pinacol boronates. The experimental and theoretical results corroborate
the hypothesis of an associative mechanism as suggested and that the reaction is triggered by
adventitious traces of nucleophiles trapped in the medium.105 Nevertheless, mechanistic studies
would be very useful to confirm the associative pathways of boronic ester exchange reactions in
anhydrous conditions and to acquire the knowledge required to harness this type of exchange reaction
more efficiently.
Sulfur-Containing Bonds.
Disulfides.
For a long time, disulfide bonds have been known to feature an interesting reversible behavior.
Historically, this behavior has been used in personal care products. Disulfide bonds naturally occurring
in keratin were cleaved by a reducing agent before new bonds were generated by using an oxidant to
perform so-called “permanent wave” on hair.106 This process can be considered as an early chemically
reshapable material and was implemented after several decades in reversibly cross-linked
polymers.107,108 Disulfide bonds are also involved in the rubber vulcanization process. Hence, in 1946,
Stern and Tobolsky already discussed possible mechanisms for the reshuffling of these bonds to
explain stress−relaxation in these materials.109 The mechanism remained uncertain but usually
admitted to be associative.104 Two possible mechanisms have been discussed: (1) a [2 + 2] metathesis
mechanism and (2) a radical mediated [2 + 1] mechanism, where a S−S bond would be homolytically
cleaved prior to a radical attack of another S−S bond to yield a three-membered intermediate (Scheme
5).
Scheme 5. Disulfide Exchange [2 + 1] Radical Mechanism
To elucidate which mechanism was involved, in silico studies were carried out and concluded that the
radical mechanism was more likely to occur.110−112 This conclusion was verified experimentally by
model exchange reactions in the presence of radical traps or radical sources.113 However, when a
nucleophilic catalyst is used, two mechanisms occur simultaneously: the radical mechanism described
previously and a thiol-mediated exchange due to the formation of thiolate anions. Moreover, UV light
can advantageously activate disulfide metathesis. Thus, materials exhibiting self-healing behavior
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upon 5 min exposure to 320−390 nm UV light were synthesized.114 Although this reaction is convenient
to yield self-healing materials,114−116 its dissociative mechanism may not be suitable to obtain vitrimer
properties. Additionally, disulfide metathesis is not always the only mechanism involved. Hence,
depending on the synthetic pathways for disulfide-containing polymers and on the stoichiometry
chosen, dangling thiol moieties enable thiol/disulfide exchanges. For this reaction the exchange
proceeds through an associative mechanism, whereby a disulfide bond is attacked by a thiolate,
yielding a new disulfide bond through a three membered transition state (Scheme 6).111,117 Thus,
attention should be paid to stoichiometry when designing a disulfide containing vitrimer or self-
healing material.
Scheme 6. Thiol−Disulfide Exchange Mechanism
Thioesters.
Recently, Bowman et al. reported thioester dynamic networks.118 Without neighboring groups the
exchange takes place via a purely associative pathway. Nevertheless, when NGP were present, two
competitive mechanisms were discussed: a mechanism involving an equilibrium between the
associated thioester form and the dissociated thiol/anhydride form and the associative
transthioesterification mechanism requiring free thiol moieties.
Meldrum’s Acids.
Scheme 7. Mechanism of Meldrum’s Acid Exchange with a Thiol as an Example
Sulfur-bearing Meldrum’s acids were also described as exchangeable cross-linkers in PDMS vitrimers
through an associative mechanism involving thiol moieties (Scheme 7).119
Trialkylsulfonium Salts.
In the 1970s, a group at Ghent got interested in poly(propylene sulfide) and the mechanism of its
degradation upon incorporation of oxonium salts to introduce sulfonium groups in the material. They
reported an exchange reaction between thioethers and trialkylsulfonium likely proceeding through an
associative mechanism whereby the sulfur atom of the thioether attacks the α-carbon atom of a
sulfonium salt prior to the elimination of the exchanged thioether following an associative pathway
(Scheme 8).120−123
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Scheme 8. Proposed Mechanism for Thioether−Sulfonium
The fact that sulfides react with electrophiles (brosylates for instance) and the positively charged
sulfonium is a good leaving group comfort the hypothesis of a SN2 mechanism, while a SN1 is unlikely
considering this pathway would involve a highly unstable primary carbocation. Four decades later, the
group of Du Prez studied and updated this forgotten chemistry and implemented it in polythioether
networks to prepare catalyst-free vitrimers.40 Knowledge on this bond exchange chemistry remains
scarce, but the promising opportunities offered in rubber recycling124 might favor more in-depth
studies.
Silyl Ether Transalkoxylation and Metathesis.

Silicones represent an $11 billion industry, and production of formulated silicones exceeded 2 Mt in
2013.125 Silicones are made from silicon, which is also the main component of glass. In the 1950s,
polydimethylsiloxanes (PDMS) were reported to exhibit stress−relaxation behavior thanks to a
chemical phenomenon of chain exchange, catalyzed by either an acid or a base.126,127 The acid-
catalyzed mechanism was supposed to involve a protonated oxygen atom on the Si−O−Si bond as an
intermediate,127 but this mechanism still seems unclear. The base-catalyzed mechanism was supposed
to involve the attack of the basic species onto a silicon atom, consequently cleaving a Si−O−Si bond
and yielding an anionic −O−Si group.127 However, the mechanism leading to the exchange between
two polymer chains was not fully elucidated. Surprisingly, the self-healing properties of these
materials were somehow forgotten, except for a patent reporting thermally reversible silicone
rubbers catalyzed by strong acids, becoming malleable at 150 °C but remaining insoluble and
dimensionally stable at room temperature.128 The self-healing behavior of polysiloxanes was
rediscovered in 2012 by McCarthy et al.129 after the concept of vitrimer was first defined. They studied
tetramethylammonium dimethylsilanolate-terminated polysiloxane chains and emphasized that any
cross-linked PDMS elastomer could be converted into a self-healable polymer by addition of basic
catalysts. The mechanism involved is an associative transsiloxanation. The first step of this mechanism
would be the dissociation of the chain-end silanolate−counterion ion pair followed by the attack of
the silanolate anion onto a silicon atom and simultaneous cleavage of a Si−O bond (Scheme 9).130,131
Thus, the ion pair would behave as a dormant species and the silanolate anion as the active one,
enabling chain exchange.
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Scheme 9. Trans-Siloxanation Mechanism130
Other strong bases can be used to generate living chain ends such as the most effective potassium
hydroxide and cesium hydroxide, but a major flaw at high temperature is the formation of volatile
cyclic oligomers leading to decreases of connectivity and average molar mass.131 In 2017, Guan et al.
used a silyl ether as the exchangeable moiety in cross-linkers to make polystyrene networks, where
the exchange reaction involved free hydroxyl groups without ion pairs.45 Finally, the same group
reported an exchange reaction in the absence of free hydroxyl moieties and hypothesized a direct silyl
ether metathesis mechanism catalyzed by acids, but the mechanism still remains unclear and further
investigations are needed to fully understand the behavior of this material.132
Urethanes, Ureas, Thiourethanes, and Hydroxyurethanes.

Polyurethanes (PU) are the fifth largest production of industrial polymers with a global production
reaching 20 Mt/y.133 The urethane bond, alternatively called carbamate, is usually obtained by
reaction between an isocyanate and an alcohol and has been known to be reversible at high
temperatures for a long time. Ureas are obtained by reaction between isocyanate and amine, and the
direct condensation of ureas leads to biuret functions. In the 1950s, PU materials were shown to
exhibit stress−relaxation thanks to urethane cleavage.134 Furthermore, relaxation times were shorter
when the material included ureas and biuret bonds,135 highlighting the increased reactivity of nitrogen
in exchange reactions. Catalyst-free vitrimers based on exchangeable urea bonds were also made
thanks to bulky groups, which enhances their reactivity toward urea−urea exchange without the need
of any catalyst.136 Nevertheless, the mechanism involved in this process is uncertain. In the early
studies on urethane cleavage, the mechanism was suggested to be dissociative, involving the
dissociation of the urethane to its initial isocyanate and alcohol moieties,137 as no free hydroxyl groups
was available for transurethanization reaction.138,139 Even when a free alcohol is available next to a
urethane bond, the dissociative pathway occurs most of the time, in some cases along with an
associative pathway similar to transesterification (Scheme 1), depending on the system composition
and temperature. A low temperature favors the associative mechanism, and reversely, high
temperatures favor the dissociative one.137 In solution, external catalysts such as phosphoryl chloride
were shown to favor the associative mechanism between a urethane and a phenol over the
dissociative one (Scheme 10).140 The direct exchange between two urethane moieties via an associative
mechanism has been ruled out.139
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Scheme 10. Phosphoryl Chloride as a Catalyst Favors the Associative Mechanism of Transcarbamoylation with Phenols 140
Ureas seem to be promising bonds to implement in selfhealing materials as the exchange reaction is
much faster.135 However, the exchange mechanism is similar, with first a dissociation (which rate
depends on the steric hindrance of the amine) yielding the starting isocyanate and amine.141−143 Thus,
based on their apparent dissociative mechanism, polyurethanes and polyureas do not seem to be
suitable to obtain vitrimer properties. Recently, polythiourethanes (PTU) started to be investigated to
make self-healing materials. PTU vitrimers catalyzed by dibutyltin dilaurate were synthesized by
reaction of a trithiol with different diisocyanates: isophorone diisocyanate, 1,6- diisocyanatohexane,
or tolylene-2,6-diisocyanate. In these materials, the structure of the isocyanate precursor influenced
the relaxation time. Aliphatic isocyanate-derived networks displayed much higher relaxation times at
180 °C than their aromatic analogues. The relaxation times of the isophorone diisocyanate- or 1,6-
diisocyanatohexane-derived network were 11.1 and 10.7 min, respectively, whereas it was only 2.9
min for the aromatic tolylene-2,6-diisocyanate-based material. Both associative and dissociative
exchange mechanisms were reported to be involved in their reprocessability (Scheme 11).144,145
Scheme 11. Associative and Dissociative Exchange Pathways for Polythiourethanes144,145
Compared to traditional PU, the case of polyhydroxyurethanes (PHU) prepared from cyclic carbonates
and amines may be different. PHU contain hydroxyurethane bonds, which are carbamate bonds with
a hydroxyl group at the β-position (Scheme 12) or γ-position. The synthesis of these materials is
advantageously greener compared to PU, as it does not involve the use of isocyanates which are toxic
substances.
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Scheme 12. Synthesis of Polyhydroxyurethanes (PHU) from (a) Five- and (b) Six-Membered Cyclocarbonates Featuring a
Substituent at the β-Position
Fortman et al. studied PHU vitrimers and suggested that transcarbamoylation occurred, albeit slowly,
and that decomposition and side reactions occurred more easily at high temperatures.146 In particular,
side reactions were observed at 160 °C and over, whereas the decomposition of the urethane linkage
to an isocyanate and an alcohol usually occurs over 250 °C. These observations were highly dependent
on the type of PHU: five-membered cyclocarbonate-derived PHU (5-CC PHU, Scheme 12a) were more
prone to decomposition via dissociative reactions at 180 °C. 5-CC PHU were shown to decompose back
to their 5CC amine precursors (Scheme 13a). Several decomposition reactions were hypothesized:
reaction of amine with cyclic carbonates by the irreversible decarboxylative mechanism (Scheme
13b), addition of amines to carbamates to form ureas (Scheme 13c), decarboxylative reaction of free
hydroxyl groups with cyclic carbonate to form ethers (Scheme 13d) or carbonates (Scheme 13e), and
oxazolidone formation, to name a few. These irreversible reactions are responsible for the loss of
mechanical properties of the reprocessed materials. On the contrary, the dissociative reversion
reaction leading to the starting amine and cyclocarbonate was not observed for 6-CC PHU (Scheme
12b), thus limiting the decomposition reactions. This suggests that the associative
transcarbamoylation may be responsible for the stress−relaxation behavior observed for these 6-CC
PHU materials.139,147
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Scheme 13. (a) Reversion of 5-CC PHU to the Original 5-CC and Amine and Hypothesized Decomposition Reactions (b) by
Decarboxylation, (c) by Formation of Urea, (d) by Formation of Ether, and (e) by Formation of Carbonate 147
Chen et al. also pointed out that two simultaneous mechanisms were responsible for the network
rearrangement of their 5-CC PHU, the associative transcarbamoylation and the dissociative reversible
cyclocarbonate aminolysis, yielding back the initial cyclocarbonate and amine.148 Because two main
reactions seem to be accountable for the stress−relaxation behavior of PHU and PTU and because one
is associative whereas the other is dissociative, one can rule out this chemistry for associative CANs.
However, more research could be done to favor the associative mechanism over the dissociative one,
investigating the effects of catalysts, the network morphology, or the monomer structure, for example.
Olefin Metathesis.
In the early days of petrochemistry, investigations led on propane cracking revealed that cracking of
propylene at 752 °C under 0.2 atm yielded 23−24 mol % of butylene and ethylene.149 The overall
reaction equation is similar to a metathesis. However, this reaction is inexploitable under such
conditions that do not allow any control. Olefin metathesis was then developed in the 1960s by
chemists working for DuPont and has been extensively studied for both industrial production and
research purposes.150−152 Olefin metathesis requires metal catalysts to occur quantitatively. An in-
depth discussion on these catalysts is out of the scope of this article, but a rich literature and very
relevant books are available.150,152 At first glance, the overall reaction seems to be rather simple and
can be summarized as a carbene exchange between two olefins. Nevertheless, the underlying
mechanism involved is complex. Yves Chauvin, Richard Schrock, and Robert Grubbs were awarded the
Nobel Prize in Chemistry in 2005 for elucidating this mechanism, developing the first catalysts, and
synthesizing more convenient catalysts, respectively.153−155 Their studies deepened the knowledge of
this exchange reaction, which was useful to develop new catalysts. Indeed this reaction fully relies on
metal−carbene catalysts.
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Scheme 14. Olefin Metathesis Mechanism150
The mechanism of olefin metathesis is detailed in Scheme 14.150,156−159 All the steps for this reaction
are equilibria, so if the reactants and desired exchanged products have a similar enthalpy, the reaction
is degenerate. This property is convenient to make exchangeable cross-links in vitrimers. In contrast,
when metathesis is used for organic synthesis, aiming at efficient synthesis of a desired exchanged
olefin product, the equilibrium can be easily displaced by using a R−CH=CH2 olefin as the substrate.
Thereby, the direct reaction yields the desired product, and easy removal of ethylene from the reaction
vessel provides the necessary driving force for the reaction to happen preferentially in the desired
direction. An example of polybutadiene vitrimers implementing olefin metathesis as the exchange
reaction was reported.160,161 These materials were made of cross-linked polybutadiene by reaction of
butadiene with benzoyl peroxide. The interest of polybutadiene is the presence of insaturations in the
network after cross-linking. These insaturations can undergo olefin metathesis in the presence of a
Grubbs catalyst. Therefore, it is possible to make a vitrimer by adding a Grubbs second generation
catalyst before the polymerization, but a much more original approach is to make a vitrimer out of a
thermoset by swelling it with a solution of the catalyst after the cross-linking process. Such a strategy
to make vitrimers has so far been specific to olefin metathesis vitrimers. These vitrimers exhibited self-
healing at ambient temperature and below. Selfhealing behavior was also observed for thermoset
materials after the catalyst was only applied on the surface where healing was required. When no
catalyst was used, no effective selfhealing was observed. In summary, olefin metathesis allows original
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strategies to make vitrimers, which is not possible with other chemistries. However, the use of a metal
catalyst seems unavoidable and could be seen as the major drawback of this exchange reaction.
Imines.
Imines result from the condensation of an aldehyde or a ketone and a primary amine to obtain a C=N
bond. Imines were investigated in the field of biochemistry, as their reversible covalent bond is known
to be involved in enzymatic reactions,162 and more recently in the field of materials chemistry,163−175
with the growing interest in dynamic covalent networks. Actually three exchange reactions are known
for imines: a dissociative hydrolysis followed by reaction with another amine; an associative exchange
between an imine bond and a free amino moiety called transimination; and a direct associative
imine−imine exchange termed imine metathesis.166,170 Obviously, only the latter two associative
reactions are interesting for associative CANs design. Although dissociative hydrolysis may happen in
imine-based vitrimers, if the amount of water in the polymer matrix remains low, this reaction is
unlikely to influence significantly the properties of the material. Therefore, the focus here is put on
transimination, which requires residual amines, and on imine metathesis, which does not.
Transimination has been known to occur through an equilibrated associative pathway for several
decades.176,177 Three successive steps were described. The first and rate-determining step consists in
the attack of a free primary amine on the imine carbon atom to form a geminal diamine tetrahedral
intermediate.162,178−181 Then, two protons transfer from the nitrogen atom of the formerly attacking
amino moiety to the nitrogen atom of the former imine moiety.162,179,181 Finally the exchanged amino
moiety dissociates and leads to the formation of the new imine162 (Scheme 15a). The mechanism of
imine metathesis is less extensively studied but is described as a nucleophilic addition of a neutral
imine to a protonated one. The reaction proceeds through a 1,3-diazetidinium intermediate, yielding
the exchanged imines or the initial reactants179,182 (Scheme 15b). Transimination and imine metathesis
have already been implemented in various polymeric materials to make vitrimers directly from
polyimines163,165,167,169 or by using imine bonds to cross-link polyesters,166,172,173,175 polybutadienes,164,168
polydimethylsiloxanes,171 and polyethers.174
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Scheme 15. (a) Transimination and (b) Imine Metathesis Mechanisms
Vinylogous Urethanes, Ureas, and Amides.

In the late 1970s, the exchange of amine moieties on enaminone structures was reported.183 Later in
the 1990s, similar exchanges between dialkylamine-derived enaminones and aromatic primary amines
were discussed.184,185 However, this exchangeable bond was not implemented in polymers until
2014.186 Moreover, the mechanism involved in this first example was based on a reversible hydrolysis
to the amine and carbonyl components, although a possible “component exchange” (amine direct
exchange) was evoked by the authors. In this field of chemistry, enaminones are commonly termed
vinylogous urethanes, vinylogous ureas, and vinylogous amides depending on their structure. These
structures are easily prepared by acetoacetylation of polyols followed by reaction with a primary
amine.18 In 2015, Denissen et al.18 reported the first vinylogous urethane vitrimer, exhibiting relaxation
times as short as 85 s at 170 °C without the need of any catalyst. The exchange mechanism was later
described by the same team187 and depends on whether the medium is acidic, neutral, or basic. In
neutral and acidic conditions, the free primary amine is protonated to form an ammonium, and the
ammonium−enamine couple is in equilibrium with the amine−iminium couple. The latter couple can
evolve by reaction of the nitrogen atom of the amine with the iminium to form a geminal
amine−ammonium tetrahedral adduct similar to the intermediate described earlier for transimination.
Then, dissociation occurs, yielding either the exchanged products or the reactants (Scheme 16a). The
amine−iminium pathway written in Scheme 16a (bottom) for a Brønstedt acid can be extended to
Lewis acids. Under these conditions, the reaction can proceed through a zwitterionic intermediate.
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Scheme 16. Vinylogous Urethane Transamination Mechanism (a) in Acidic and Neutral Conditions and (b) in Basic Conditions
For instance, Friary et al.184 studied the transamination of an enaminone bearing alkyl substituents
with an aromatic primary amine in solution. The exchanged enaminone was then able to cyclize. When
1 equiv of toluenesulfonic acid was added, the overall yield increased from 29 to 56%. The authors
suggested that the acid accelerated the enaminone transamination step (Scheme 17).
Scheme 17. Diketoenamine Transamination Catalyzed by p-Toluenesulfonic Acid (p-TsOH)
The catalyst protonates the oxygen atom of the enaminone and generates an iminium tosylate, more
electrophilic toward the attack of the amine. The exchange kinetics can be tuned by using simple
additives. Brønsted and Lewis acids such as sulfuric acid, dibultyltin dilaurate (DBTL), or zinc(II)
accelerate the reaction. The use of 1 mol % p-toluenesulfonic acid was reported to reduce the time to
reach equilibrium from >1 h to <10 min at 100 °C. On the contrary, non-nucleophilic bases such as
triazabicyclodecene (TBD) were reported to increase the equilibration time.187,188 In a basic
environment the exchange reaction happens but is slower and involves a direct Michael-like addition
of a neutral amine on a neutral vinylogous urethane (Scheme 16b).187,189 These mechanisms are all
associative and thus suitable to obtain vitrimer properties. Some vitrimers exhibit a dual temperature
response.189,190 Interestingly, their dual behavior was explained by possibly concomitant mechanisms
a and b (Scheme 16), which are usually independent as they require different pH conditions. The
iminium pathway would be dominant at low temperatures whereas the neutral Michael-type pathway
would prevail at high temperatures. Catalysts also have an impact on the behavior of vitrimers. The
relaxation time of vinylogous urethane materials was reported to decrease from 10 min at 120 °C in
the absence of catalysts to 2 min with 0.5 mol % of p-TsOH.187 A recent study by Haida and Abetz191
studied the impact of p-TsOH in vinylogous urethane vitrimers with different stoichiometries. The
networks were synthesized from hexane-1,6-diylbis(3- oxobutanoate) and tris(2-aminoethyl)amine
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(TREN). When an excess of amine was used, the relaxation time decreased from 29 s without p-TsOH
to 0.3 s with 0.05 wt % p-TsOH. Similarly, with an excess of the acetoacetate the relaxation time
decreased from >46800 s to only 134 s (Figure 3).191 DBTL and sulfuric acid were shown to be less
effective. In the case of sulfuric acid, the sulfate anions probably form salts with the ammonium ions.
In consequence, the ammonium species are less available and thus less reactive.
Figure 3. Impact of the stoichiometry and p-TsOH catalysis on vinylogous urethane properties. aRatio acetoacetate/amine.
bRelaxation time at 110 °C. cActivation energy (VU-E stands for an equal ratio of amines and acetoacetates, VU-A an excess
of acetoacetates, and VU-NA an excess of amines).191
Similarly, carboxylate anions are also known to be proton scavengers for ammonium species in
nonaqueous solutions, for instance.187 When DBTL was used, the reaction activation energy dropped
from 74 to 45 kJ mol−1, suggesting a different mechanism, probably via the carbonyl moiety activation
of the vinylogous urethane. On the contrary, TBD increased the activation energy up to 103 kJ mol−1
because of proton scavenging. Interestingly, Spiesschaert et al.192 managed to incorporate acidic or
basic functionalized fillers in PDMS-vinylogous urethane matrices. When 10 wt % kaolin bearing acidic
groups was incorporated, the relaxation time of the resulting material decreased from 5725 to 4650 s
at 150 °C, whereas nonfunctional fillers were shown to increase relaxation time. Acid, basic, or neutral
alumina fillers were also studied. When the relaxation time for the matrix was 4000 s, the material
containing neutral alumina or basic alumina displayed relaxation times of 4650 and 4500 s,
respectively. On the contrary, the material made from acid alumina showed a shorter relaxation time
(3600 s), in agreement with the results observed in solution (Figure 4).192
Figure 4. Effect of different functionalization of alumina fillers on vinylogous urethane vitrimer composites’ relaxation time.
Other kinds of catalysis were also reported, and not surprisingly an excess of free primary amines in a
vinylogous urethane vitrimer accelerates transamination.189 Eventually, it is important to highlight the
crucial role of the backbone and cross-linking density on the behavior of vitrimers, as already
mentioned for imine vitrimers. Spiesschaert et al.190 recently disclosed in a detailed study that the
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relaxation rate of various vinylogous urethane-cross-linked polyether vitrimers decreased with
increasing cross-linking density. An effect on the activation energy was also reported even if a clear
trend was not identified. A dual temperature behavior was reported for polytetrahydrofuran,
poly(propylene glycol), and poly(ethylene glycol) backbones, as reported previously in
perfluoropolyether.189,190 Nonetheless, this effect was not observed on a polypropanediol backbone,
emphasizing the influence of both the matrix type and the molar mass of the spacers. The dual
mechanism discussed earlier is probably the cause for this dual behavior.190 Because they are versatile
and they allow short reprocessing times, vinylogous urethanes have already been implemented in
various polymers networks. Many examples were reported such as polysaccharide hydrogels,193
polysiloxanes,188,190,192,194,195 polybutadienes,190,196 perfluoropolyethers,189 methyl methacrylate-(2-
acetoacetoxy)ethyl methacrylate copolymers,197 polystyrenes,198 polydimethylsiloxane (PDMS)−kaolin,
PDMS−alumina and PDMS-aminated silica composites,188,192 epoxy−amine copolymers,199
polyethers,190 and vinylogous urethane polymers bearing photodimerizable anthracene units.200
Diketoenamines.
Scheme 18. Dde Protection Group Exchange on Amines (a) by Direct Electrophilic Attack and (b) Mediated by Piperidine 201
Diketoenamines are known as a Dde protecting group for amines in peptide synthesis.201,202 This
protecting group is formed by reaction between 2-acetyl-5,5-dimethyl-1,3-cyclohexanedione (also
known as 2-acetyldimedone) and primary amines.203 In 2009, the behavior of Dde was studied in detail
on lysine in solid-phase synthesis. Lysine is an interesting amino acid bearing two amino moieties in
the α- and ε-positions.201 This study reported the ability of ε-NH2 to attack a Dde-protected ε-NH2 or
α-NH2, leading to an amine exchange. According to the authors,201 the mechanism involves a direct
nucleophilic attack of the free amine on the Dde group via a Michael addition, before a retro-Michael
addition yielding either the original structure or the amine exchanged one (Schemes 18a and 19).
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Scheme 19. Mechanism of Diketoenamine Exchange
Another mechanism involving piperidine as catalyst was also described. Piperidine acts as a mediator
to pick up the Dde group from the originally protected amine before attack of another primary amino
group. The overall reaction is composed of two successive exchanges: first between the originally
protected amine and piperidine and then between the protected piperidine and a free amine (Scheme
18b). In all cases, the mechanism of amine exchange is associative. This chemistry was implemented
in materials synthesis by Christensen et al. to make vitrimers;204,205 they reported the synthesis of a
network by click polycondensation between β-triketones and primary amines (Scheme 20).
Scheme 20. Example of Synthesis of Diketoenamine Vitrimer; Alternatively, Various Diketones and Mixes of Primary
Triamines and Diamines Were Also Used204,205
Triketones were synthesized from polytopic carboxylic acids and 1,3-diketones and the final materials
simply by ball-milling of the reactants at room temperature. The materials obtained were
reprocessable without requiring a catalyst and followed an Arrhenius behavior. These materials
areeasily hydrolyzed. While this feature is often considered as a flaw, it can be beneficial for specific
applications. In particular, as the materials are fully hydrolyzed in a few hours at room temperature in
sulfuric acid (<12 h in 5 M H2SO4), the monomers can be easily recovered. Amines are separated from
the triketones thanks to an ion exchange resin, with a recovery above 90%. The recovered monomers
can be reused to make new poly(diketoenamines). This feature affords a convenient and efficient
chemical recycling by hydrolysis at room temperature, while other hydrolyzable vitrimers require
heating and more demanding conditions. The range of exchange reactions suitable for the design of
vitrimers is already large (Figure 2), and new exchange chemistries occurring via associative pathways
are still to be implemented in such materials,206 although proving the associative character of an
exchange reaction is often challenging and remains uncertain in some cases. In addition, a survey of
the activation energies of the associative exchange reactions implemented in vitrimers (Figure 5)
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shows that these energies can be distributed over relatively large ranges. This is certainly an asset for
chemists and materials scientists who want to tune the reshaping ability of vitrimers.
Figure 5. Activation energy ranges for exchangeable bonds implemented in vitrimers.
3. Internal Catalysis, Sterics, and Neighboring Groups Effects on Exchangeable

Bonds
Figure 6. Examples of effects to activate bond exchanges.
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Many parameters influence the properties of vitrimers: the cross-link density, the nature of the
network backbone, and obviously the type of exchangeable bonds, for instance. For the exchange
reaction to be efficient, many vitrimers rely on external catalysts. These compounds often come with
some risks of leaching out of the material or premature aging limiting the recycling abilities of the
materials. To address these problems, internal catalysis, steric effects, and neighboring group
participation (NGP) are valuable. For a given exchange reaction, well-designed chemical modification
of the exchangeable bonds surroundings is a way to accelerate the exchange, without resorting to any
external catalyst. Different effects at the molecular scale are gathered in these three concepts (Figure
6). In light of the reaction mechanisms discussed, some relevant activating groups, either already
implemented in bulk vitrimer networks or only in solution, are presented below. This should give new
insights for further research in such dynamic materials.
Transesterification Enhancement by Neighboring Groups: Influence on the Exchange

Mechanism and Vitrimer Properties.
Figure 7. Main examples of activating groups activating transesterification. The temperature range 25 for stress−relaxation
experiments and the range of calculated activation energies24 of the exchange reaction in vitrimers are given.
A few activating groups have been reported to influence the reactivity of esters toward
transesterification and/or hydrolysis in solution (Figure 7). For instance, on phenyl esters, a
neighboring hydroxymethyl group on the ortho position increases the transesterification rate.
However, the mechanism involves a cyclization after the attack on the ester by the −OH group, leading
to a transient lactone (Scheme 21).207
Scheme 21. Catalytic Effect of an Ortho Hydroxymethyl Group on Phenyl Ester Transesterification by Transient Lactone
Formation
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This chemistry if it were implemented in a CAN would proceed through a dissociative mechanism. A
regioselectivity effect is also reported on pyridine triesters as one of the ester groups possesses an
ortho hydroxyl group. Interestingly the transesterification reaction was reported to be regioselective
on the ortho hydroxy ester, highlighting a reactivity increase (Scheme 22).208
Scheme 22. Regioselective Transesterification: (a) 10 mol % EtNiPr2, ROH, 60 °C; (b) 5 mol % Sc(OTf)3, ROH, cat. H2O, 60 °C208
Nevertheless, in this case the regioselectivity is due to the hydrogen-bonding ability of the hydroxyl
group, and the mechanism is associative, contrary to the previous example. The same kind of
regioselectivity was reported with 3-benzamidophthalates. The ester group located ortho to the
amide moiety undergoes transesterification whereas that located in the meta position does not
(Scheme 23).209
Scheme 23. Regioselectivity of 3-Benzamidophtalates Transesterification
Two mechanisms were discussed depending on the substituent: the first one is the regular attack of
the alcohol on the ester groups activated by hydrogen bonding with the proton of the amide (Scheme
24a), and the second one is the formation of a more reactive 3,1-benzoxazin-4-one intermediate
(Scheme 24b).
Scheme 24. Regioselective Transesterification of 3-Benzamidophtalates: (a) Direct Pathway and (b) Pathway with 3,1-
Benzoxazin-4-one Intermediate
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In contrast, neighboring thioether groups stabilize the ester bond,210 hence decreasing its reactivity
toward transesterification. Fluorene structures (Figure 8) bearing a methyl carboxylate substituent on
the 1-position were studied. When one ethylthio group was present on the central five membered
ring, the rate constant of transesterification (using methanol-d4) was 0.29 times the rate of the
unsubstituted fluorene ester. Interestingly, on the fluorene ester bearing two ethylthio groups, the
effect was shown to be opposite. This ester was more prone to transesterification.
Figure 8. Effect of substitution by ethylsulfane groups on fluorene esters’ transesterification rate.210
According to the authors of this study,210 this phenomenon is likely due to at least two different causes,
resulting in opposite effects on the transesterification rate. On one hand, the steric hindrance induced
by one ethylthio group would decrease the transesterification rate, as the reactive site is less
accessible. On the other hand, ethylthio groups induce a stabilizing electronic effect on the protonated
ester intermediate (Scheme 25).
Scheme 25. Stabilizing Effect of Sulfur on Protonated Esters210
The authors hypothesized that the electronic effect were low compared to the steric effect when only
one ethylthio substituent was present. On the contrary, when two ethylthio groups were present, the
resulting electronic effect is significant and exceeds the steric effect, even though this effect is stronger
than in the monosubstituted counterpart. β-Ketoesters as well as esters derived from malonates or
oxalates, for example, are also more prone to transesterification reactions in solution.211 Indeed,
acetoacetic acid is 10 times stronger than acetic acid, so its conjugated base is more stable and the
corresponding ester bond is weaker, leading to easier transesterification.211 Oxalates’ reactivity toward
transesterification is explained exclusively by inductive effects. For β-ketoesters and malonates, a
stabilized cyclic intermediate was proposed to explain the reactivity of the other aforementioned
species, though inductive effects also play a significant role (Scheme 26).
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Scheme 26. Proposed Stabilization by Cyclic Intermediate for the Transesterification of β-Ketoesters211
Recently, diethylmalonate was used as cross-linker in a polyester vitrimer, disclosing the enhancing
effect of β-activated esters.212 Phthalate monoesters also displayed enhanced transesterification
similarly to the previously discussed o-hydroxymethyl phenyl esters,207 as demonstrated by Du Prez et
al.47 The neighboring carboxylic acid can indeed attack the carbonyl of the ester to yield a cyclic
anhydride and an alcohol (Scheme 27a). Recently the same team enhanced this effect by using a β-
aminodiol with a dianhydride to make networks (Scheme 27b).
Scheme 27. Dissociative Transesterification Pathway Involving a Cyclization (a) by an o-Carboxylic Acid,47 (b) by an o-
Carboxylic Acid with an Inductive Effect of the β-Amino Alcohol,214 and (c) by an o-Sulfonic Acid48
The enhancing effect of β-amines had already been described for ester hydrolysis in 1962.213 The
tertiary amine at the β-position of the hydroxyl groups induced a dual activation: the neighboring
group participation of the dangling −COOH and the internal catalysis effect of the tertiary amine. The
stress−relaxation times decreased by a factor 500 compared to the amine-free analogous network.214
However, it should be noted that the mechanism was dissociative in these cases, highlighting that
great care should be taken when considering neighboring groups participation as they potentially
change the bond exchange mechanistic pathway.47,214 The same mechanism was also recently reported
with 2,5-bis(methoxycarbonyl)benzenesulfonic acid, a benzoester bearing an o-sulfonic acid moiety
(Scheme 27c).48 These materials showed a faster stress−relaxation than their carboxylic acid
analogues. Amines were also shown to be efficient catalysts for transesterification vitrimers.17
Triazabicyclodecene (TBD) in particular has often been used. Strategies have been designed to
integrate tertiary amine groups into the polymer network. For example, bisphenol A diglycidyl ether
(BADGE) was mixed with primary or secondary amines to generate epoxy terminated tertiary amines
oligomers. In a second step, the oligomers were reacted with polyacids to obtain a network bearing
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covalently bonded tertiary amines (Figure 9a).38 The exchange reaction activation energy (Ea) for this
network was 93.6 kJ mol−1, very close to the 80−90 kJ mol−1 range observed for the Zn-catalyzed epoxy
vitrimers.
Figure 9. Strategies to embed tertiary amines in polyester networks using (a) epoxy-ended tertiary amines (two steps),38 (b)
ethanolamine as coreactant,216 and (c) a commercial tetraepoxide bearing tertiary amines.217
Alternatively, triethanolamine was added as coreactant in a BADGE−(methyl nadic anhydride) system

for the same purpose (Figure 9b).216 The relaxation time at 190 °C decreased from 19460 to 4200 s
when the triethanolamine content increased from 5 to 10 mol % (Figure 11).216 Recently, catalyst-free
transesterification vitrimers were synthesized from a hydrogenated dimerized acid derived from
vegetable oil and tetraglycidyl-4,4’-diaminodiphenylmethane (TGDDM), a tetrafunctional epoxide
bearing two tertiary amino groups (Figure 9c).217 These tertiary amines were shown to act as internal
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catalysts. The effect was reported to be enhanced by the flexibility induced by the vegetable oil
structure. Instead of increasing monomers’ flexibility, dangling chains which can plasticize the material
were also shown to promote similar enhancement as tertiary amines’ internal catalytic effect.218
However, a similar internal catalysis was also reported in systems based on shorter, more rigid acids
and which did not contain any plasticizer.219 These examples of internal catalysis emphasize the role
of tertiary amines as promising activating groups to increase the transesterification rate. Interestingly,
a chemistry similar to the first vitrimer1 featuring β-hydroxyesters pointed out the participation of the
hydroxyl moiety in transesterification.34,220,221 A six-membered ring with a hydrogen bond between the
hydroxyl and the ester groups was hypothesized (Figure 10). The hydrogen bond is assumed to weaken
the ester bond as previously discussed for the 3-benzamido group.
Figure 10. Hypothesized activating effect of the β-hydroxyl groups for transesterification. The hydrogen bond (dashed bond)
increases the carbonyl C electrophilicity, facilitating the attack of an electrophile such as an alcohol (first step of the
transesterification).
Besides, increasing the amount of free hydroxyl moieties was used to prepare catalyst-free
transesterification vitrimers.29,222 Although this effect cannot be considered as neighboring group
activation or internal catalysis, it remains significant in transesterification vitrimers, was often reported
in the vitrimer literature, and therefore deserves to be mentioned. The acceleration of the exchange
reaction can be explained by the large amount of hydroxyl groups, facilitating the transesterification
by a concentration effect.33,219 In addition, a catalytic effect is also likely caused by hydrogen bonding,
as in the case of oxime−esters (vide infra). Accordingly, the addition of glycerol to an epoxy−anhydride
vitrimer matrix increases the concentration of free hydroxyl groups. The concentration effect is clear
as the relaxation time of the materials at 180 °C dropped from 204 min to 86 and 66 min for 25, 50,
and 75 mol % of glycerol, respectively (Figure 11).33
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Figure 11. Effect of various enhancing strategies on stress−relaxation time: hyperbranched epoxy prepolymers (HBE),
network-embedded triethanolamine (TEA), and free oxime hydroxyl group in the oxime−ester network. 33,216,233 Note that
comparison between these three systems should be exerted with caution since structural parameters (backbone, cross-
linking density, etc.) differ from one system to another.
The Case of Oxime−Esters.

Oxime−ester bonds can be considered as a subgroup of the ester family or as a specific type of bond.
The most important difference between the oxime−ester and ester is the nucleophile (an oxime
instead of an alcohol). Heat-induced transesterification of the oxime−ester enabled the synthesis of
catalyst-free vitrimers (Scheme 28),233 with relaxation times ranging from 5102 to 2725 s at only
100 °C, depending on the free oxime−OH available and their concentrations ranging from 0 to 5 mol
% (Figure 11). The acceleration of the exchange reaction is caused mainly by the high concentration
of exchangeable bonds. However, part of the enhancing effect can be explained by the higher
nucleophilicity of the oxime (exchangeable moiety) compared to hydroxyl groups. This would allow to
decrease relaxation temperatures and times. Nevertheless, considering the scarcity of reports
dedicated to oxime−ester vitrimers, it would be unwary to compare the relaxation parameters with
transesterification vitrimers, as many parameters are varying between the systems reported in the
literature, such as the backbone or the cross-linking density, for example.
Scheme 28. Transesterification of Oxime−Ester Bonds233
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Carbonate Activation by Electron-Withdrawing Groups.
Figure 12. Examples of activating groups enhancing transcarbonation rate in solution and characteristics of reported
transcarbonation vitrimers.225−228
Transcarbonation (Scheme 3) is used to synthesize polycarbonates, but this reaction requires a catalyst
(Figure 12). Basic catalysts are probably the most used. Indeed, the generation of a more nucleophilic
alkoxide increases the rate of addition onto the electrophilic carbon of the carbonate.69,70,74,77−80
Activation of the carbonate with Lewis acids has also been reported but is less common.74 Besides,
some metal catalysts (such as tin or calcium salts, for instance) that may combine Lewis acid activation
of the carbonate67,71,73,76−78 and activation of the nucleophilic alcohol71,73,75,77−79 have been also used.
The formation of metal complexes coordinating both reacting partners increases the electrophilicity
of the carbonyl67,71,74,77−79 and also has a templating effect that accelerates the reaction. Nevertheless,
neighboring group effects on transcarbonation are still relatively unknown (Figure 12). Inspired by a
similar study on esters, Tillett and Wiggins investigated the effect of hydroxy- and methoxy-substituted
phenylethylcarbonates on their hydrolysis rate (Figure 13a).224
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Figure 13. (a) Structures investigated by Tillett and Wiggins.224 (b) Effect of the electron-withdrawing group (EWG) position
on the exchange rate.225 (c) Polymerization rate of nitrophenylcarbonates with bisphenol A depending on the substituent
position.226 (d) Effect of CF3 substituent on the exchange rate.229
An influence on the hydrolysis rate could be extrapolated to transcarbonation reactions due to the
strong mechanistic similarities between these reactions. At high pH, the hydrolysis rates of o-hydroxy-
, p-hydroxy-, and o-methoxy-substituted compounds were not significantly different. However, in
neutral conditions the o-hydroxy-substituted phenylethylcarbonate was hydrolyzed 10 times faster
than the two other compounds. General principles for transcarbonation were given in a very complete
review on carbonates in 1996.225 Generally, the more nucleophilic alcohol displaces the less
nucleophilic one, and in the case of equal nucleophilicity, the less volatile alcohol displaces the more
volatile one. This rule does not apply to phenols, as dialkylcarbonates react with phenols to make
diarylcarbonates. In addition, alcohols bearing bulky groups or electron-withdrawing groups are poorly
reactive. On the contrary, when the carbonate contains electron-withdrawing groups, the alcohol
exchange is accelerated. For instance, fluorinated dialkylcarbonates and diarylcarbonates bearing
−NO2, −CN, or −Cl groups on the ortho position undergo much faster alcohol exchange (Figure 13b).
The activation is less noticeable when the substituents are on the para position. Brunelle et al.
harnessed this effect with the use of a catalyst. Hence, they successfully polymerized o-
nitrophenylcarbonates with bisphenol A at room temperature and even below,226 whereas high
temperatures (up to 200−300 °C) are usually required to prepare polycarbonates.227 The exchange
between nitrophenylcarbonates and phenol was twice faster with the ortho-substituted carbonate
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than with the parasubstituted homologue (Figure 13c). Similarly, bis-(trifluoroethyl)carbonates were
shown to exchange with various alcohols and phenols in refluxing heptane or toluene (at 98 and 111
°C, respectively) in the presence of a base,225,228 and their reactivity was reported to be between the
very reactive dimethylcarbonate and the less reactive diphenylcarbonate (Figure 13d).229 Kamps et al.
studied bis(methylsalicyl)carbonate (BMSC, Figure 14) as an activated carbonate to lower the
temperature for melt transcarbonation synthesis of polycarbonate.227 BMSC was polymerized with
bisphenol A (BPA), and this polymerization was compared to that of diphenylcarbonate (DPC) and BPA.
DPC−BPA polymerization was achieved in 135 min, whereas for the BMSC−BPA system, 40 min was
sufficient to reach similar molar masses (Figure 14).
Figure 14. Polymerization of bis(methylsalicyl)carbonate (BMSC) and diphenylcarbonate (DPC) with bisphenol A (BPA).227
This polymerization is composed of two successive substitutions. The rates of the first and second
substitutions were reported to be 30 and 9 times higher for the BMSC−BPA system, respectively.
Although this study focused on the direct overall two-step reaction, the rate of the reverse reaction
for the first substitution was determined for both BMSC and DPC. Indeed, the rate of the first step
reverse reaction for DPC was half that of the direct reaction, whereas for BMSC it was 3 decades lower.
The overall two-step reaction is an equilibrium. When this equilibrium was reached for the DPC−BPA
system, the main product was the monosubstituted compound, and the same amounts of starting
carbonate and disubstituted product were observed. In contrast, for the BMSC−BPA system, the
disubstituted carbonate was the main product and the monosubstituted product was also present as
byproduct, whereas no starting material remained, suggesting that the equilibrium was more displaced
toward the products in this case. Such observation is significant for the design of vitrimers based on
exchangeable carbonate bonds. Groups containing nitrogen seem to exert a significant activating
group effect on carbonates. Amine-modified mesoporous silica prepared from amine-terminated
silanes showed a catalytic effect on the transcarbonation between ethylene carbonate and methanol
to produce dimethylcarbonate.80 Thus, an amino neighboring group might have interesting effects on
the transcarbonation reaction, too. Examples of vitrimers based on carbonate exchange are very
scarce,230,231 and they rely on Ti(IV) catalysts; they thus exhibit similar flaws to metal-catalyzed
transesterification vitrimers discussed earlier. Smart molecular design based on the knowledge on
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activating groups effects on transcarbonation might help the development of such transcarbonation
vitrimers.
Dioxaborolane Transesterification Acceleration
Figure 15. Reported activating groups enhancing dioxaborolanes’ exchange rate and range of stress–relaxation experiment
temperatures25 and activation energies.24
As discussed previously, boronic esters were mainly used in aqueous media. Therefore, the effects of
activating groups on boronic esters were mainly described under such conditions. Although the
behavior of an exchangeable bond is very different in solution and in the bulk of a material, especially
with a peculiar solvent such as water, it may still be possible to draw general conclusions on the effects
of activating groups (Figure 15). In aqueous solution, there is an equilibrium between the dissociated
boronic acid–diol couple and the corresponding boronic ester. The formation of a boronic ester by
reaction between a boronic acid and a diol must be performed at a pH higher than the pKa of the
acid.232,233 Interestingly, the pKa of boronic acids can easily be tuned by chemical modification. For
instance, compared to the pKa value of 8.8 of phenylboronic acid, the pKa of methylboronic acid is
10.4, whereas the pKa of the very electron-withdrawing 3-pyridylboronic acid is 4.0.84 This shift of the
esterification equilibrium gives a glimpse of the possible electronic and internal catalysis effects. An
early study showed that arylboronic acids bearing ortho neighboring groups containing oxygen, sulfur,
or fluorine do not enhance the esterification or the transesterification.234 Nevertheless, electron-
withdrawing groups decrease the boronic acid pKa, whereas electron-donating groups increase it83,84
and destabilize the ester bond. For instance, the boron atom of phenylboronic acids is reported to be
highly electron deficient, which reduces the pKa and facilitates ester formation.84,233,235 Recently,
benzoxaborole-cross-linked poly(ethylene glycol) (PEG) networks were synthesized out of 4-carboxy-
3-fluorophenylboronic acid along with its non-fluorinated counterpart (Figure 16). Four-arm amine-
terminated PEG was modified with 4-carboxy-3-fluorophenylboronic acid or 4-carboxyphenylboronic
acid to afford tetrafunctional boronic acids. The same procedure was applied to d-glucolactone to
obtain a tetrafunctional diol. Each tetrafunctional acid was then reacted with the tetrafunctional diol
to make a network (Figure 16). This study showed that the resulting partially fluorinated material had
a higher dynamic modulus and a faster relaxation time than the non-fluorinated analogue.236
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Figure 16. Synthesis of a network based on boronic esters: (a) poly(ethylene glycol) (PEG) monomers functionalized by
boronic acids (blue) and diols (red) and their equilibrium with the boronic ester form; (b) schematic representation of the
network.236
Nevertheless, the most studied and most promising activating groups so far are nitrogen-containing
groups. Aminomethyl-substituted arylboronic acids were shown to be esterified several orders of
magnitude faster than nonsubstituted phenylboronic acids.237 Their transesterification was also
accelerated compared to unsubstituted boronic acids or such acids bearing substituents containing
oxygen, sulfur, or fluorine.234,238 In solution, the addition of a dimethylaminomethyl group on a
phenylboronic ester was shown to accelerate the rate of transesterification by 5 orders of magnitude.44
The amino group on the ortho or para position decreases the pKa of phenylboronic acid233 and
facilitates the formation of the ester.239 This is due to electronic substituent effects on the aromatic
ring. Even when the amino moiety is not directly attached to the aromatic ring, the acceleration effect
is noticeable. In this case, the effect is caused by the formation of B–N dative bonds (a proper example
of neighboring group participation, Figure 17a).83,85,233,239
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Figure 17. (a) Example of coordinative B–N bond.239 (b) Slow exchange cross-linker and (c) fast exchange cross-linker (bottom)
studied by Guan et al.44
Interestingly, amino activating groups have been implemented in vitrimers.44 They demonstrated an
accelerating effect on boronic esters transesterification in bulk, which enabled the tuning of the
properties of dioxaborolane vitrimers. Indeed, materials containing amino activating groups relaxed
stress within 5 min while the reference dioxaborolane material required more than 20 min (Figures
17b and 18).
Figure 18. Effect of amine activating groups on the relaxation time of vitrimers with different kinds of exchangeable bonds
(NG stands for neighboring group and TEA for triethanolamine).
Other kinds of effects such as steric interactions and ring strain also play a role in the ester stability, as
functional groups attached or adjacent to the boron atom on a boronic acid decrease the association
constant with diols.83,232,240 Steric hindrance is particularly relevant in polymers. Sumerlin et al.
reported higher pKa and lower binding affinity of boronic acid-containing polymers compared to small
molecules. The monomer pKa was 7.2 whereas the polymer had a pKa of 8.2. In the polymer, the low
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mobility of the chains limited the availability of the binding sites.87,232 Great care should be taken in the
design of the exchangeable bond as the effect obtained can be opposite to the expected one in some
cases. For instance, in a recent study, vitrimers based on nitrogen-coordinating cyclic boronic diesters
were synthesized, with a dative B → N bond embedded in the cyclic diester (Figure 19).241 This
particular structure not only offered an improved resistance to hydrolysis but also lowered the
exchange rate compared to other cyclic boronic esters. In this particular case the effect on
transesterification is somewhat counterintuitive. In summary, boronic esters in polymers allow the
fine-tuning of materials properties thanks to activating groups84 with electronic and/or steric effects.
This feature is interesting for vitrimers design. However, the knowledge on these effects in bulk
remains scarce and deserves further investigations.236
Figure 19. Nitrogen-coordinating cyclic boronic diester exchange.241
Disulfide Metathesis: Effect of Aromatic Substituents
Figure 20. Disulfide exchange enhancement by activating groups (activation energy from Jourdain et al. 24).
Neighboring group participation (NGP) in the exchange of disulfide bonds has hardly been probed yet,
and the data readily available on this topic focus on the dissociative [2 + 1] radical assisted mechanism
previously discussed in the Disulfides subsection (Figure 20). However, this general knowledge on
disulfide bonds strength is useful to understand how to tune their dynamic behavior. Aromatic
disulfides were mainly investigated, as the exchange reaction does not require the use of a catalyst to
occur significantly contrary to exchange between alkyl disulfides usually catalyzed by triethylamine or
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tributyl phosphate, for instance.110-113,242,243 The metathesis of alkyl disulfides is a very slow reaction
and even considered as not spontaneous in the absence of a catalyst, especially in solid state.115 Adding
6% of triethylamine is, however, sufficient for the reaction to happen.244 Phosphines are also good
catalyst candidates, and 5 mol % tricyclohexylphosphine was reported to accelerate the reaction 240
times in solution at room temperature, whereas the same amount of tri(dimethylamino)phosphine
accelerated it 520 times, although some degradation products were observed in that case. 245
Nevertheless, a catalyst-free self-healable hydrogel based on alkyl disulfide was reported.246 The
network was formed by harnessing the thiol–disulfide exchange reaction of a telechelic thiol-ended
PEG with telechelic PEG bearing cyclic five-membered disulfide (Scheme 29). This network formation
did not require any catalyst, as the tension of the five-membered disulfide ring favors its opening and
enhances the exchange reaction. This design also allowed self-healing in slightly acidic condition,
whereas such behavior is usually observed only in neutral and alkaline mediums, in the presence of
nucleophilic thiolates.
Scheme 29. Hydrogel Polymerization by Thiol–Disulfide Exchange on Strained Five-Membered Ring Disulfides246
Nitrogen has an enhancing effect110 in different kinds of activating groups such as tertiary amines on
phenyl disulfides,111,247 thiuram disulfides,248 or sulfenamides.243 For instance aromatic sulfenamide-
derived disulfides (Figure 21) exhibited a bond dissociation energy (BDE) of around 35 kcal mol–1,
whereas their nitrogen-free counterpart exhibited a BDE around 50 kcal mol–1.243 The lower is the BDE,
the more radicals are generated, and the easier is the exchange reaction. Thanks to the enhancement
of the exchange reaction, some catalyst-free materials based on aromatic disulfides exhibited self-
healing at room temperature.116 In those materials bis(4-aminophenyl) disulfides were used as
dynamic cross-linkers to make poly(urethane–urea) systems.
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Figure 21. Structures of aromatic sulfenamide-derived disulfides and the associated bond dissociation energies (BDE)
calculated by DFT.243
4-Hydroxyphenyl disulfides are known to undergo faster radical generation than their 4-aminophenyl
homologues,113 but this effect is still poorly documented. 4-Hydroxyphenyl disulfide exchange reaction
with diphenyl disulfide reached 60% conversion in only 2 h, whereas 12 h was necessary for the 4-
aminophenyl disulfide with diphenyl disulfide under UV radiation. Matxain et al. published a thorough
computational reactivity study of the disulfide bonds dissociation energy.110 They pointed out that
electron-donating groups lower the disulfide BDE and that electron-withdrawing groups (EWG)
increase this BDE. Compared to the 48 kcal mol–1 BDE value of unsubstituted aromatic disulfides, the
p-sulfonic acid substituent increased this value to 55.6 kcal mol–1 whereas an amino derivative in the
para position decreased the BDE to 41.3 kcal mol–1 and even to 30.1 kcal mol–1 with the trisubstituted
bis(2,4,6-triaminephenyl) disulfide (Figure 22a). They also reported that dendralene and thiuram
disulfides (Figures 22b and 22c) have a low BDE, which may allow self-healing at room temperature
and provide a good alternative to aryl disulfides. Though disulfide bonds have been known for a long
time, there is still much research needed to understand how to better tune the exchange reaction in
materials, especially in the case of the associative thiol–disulfide reaction about which literature
remains scarce.
Figure 22. Structures of (a) bis(2,4,6-triaminephenyl) disulfide, (b) dendralene disulfide, and (c) thiuram disulfide.
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Internal Catalysis of Silyl Ether Transalkoxylation by Amines, Urethanes, and Ureas
Figure 23. Examples of activating groups enhancing silyl ether exchange and range of stress–relaxation experiment
temperatures25 and activation energies.24
When implementing the previously discussed ion pair dissociation-triggered mechanism in silyl ethers,
the main parameters to tune the exchange reactivity are obviously the nature131 and concentration130
of the ion pairs. The environment of the counterion influences its ability to dissociate and thus the rate
of the exchange reaction (Figure 23). For instance, cation complexation by oxygen atoms on
neighboring siloxane chains was reported to increase the electrophilic behavior of silicon atoms and
the nucleophilic behavior of silanolate moieties, facilitating trans-siloxanation.131 In 1970, Wright et al.
studied the equilibrium between chains and rings in [R(CH3)SiO]x structures, showing that for x = 2 or
4 bulkier R led to favored cyclization. However, the opposite effect was shown for x > 10.249 Catalysis
by triphenylphosphine (TPP) and triazabicyclodecene (TBD) in silicone materials was also reported. TPP
led to materials with a temperature of plastic flow around 240 °C whereas the materials containing
TBD flowed at 120 °C.250 In 2014, tertiary and secondary amines, urea, and carbamate groups on α-
and γ-silanes (Figure 24) were reported to interact with the alkoxy leaving group or the attacking
nucleophile, thus increasing the hydrolysis rate of the alkoxy group. This study performed both in
solution and in silico showed the significant influence of several activating groups. For instance,
secondary amines accelerated the hydrolysis reaction from 5 to 50 times and tertiary amines at least
40 times. Carbamate groups accelerated the reaction from 6 to 80 times, depending on their position
and structure.251
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Figure 24. Structure of (a) α-silanes and (b) γ-silanes. The effects of various −X substituents on the hydrolysis rate of the
alkoxy group were studied (c) in basic conditions and (d) in acidic conditions. 251
This result was later successfully implemented in malleable materials with activating amino moieties
accelerating the exchange rate of silyl ethers.45,252 A copolymer of styrene and 2-((4-
vinylbenzyl)oxy)ethan-1-ol was synthesized by free radical copolymerization. Then the resulting
copolymer was cross-linked either with N,N’-bis(3-(trimethoxysilyl)propyl)ethane-1,2-diamine or with
1,10-bis(trichlorosilyl)decane (Scheme 30). Both cross-linked structures were similar, and the cross-
linkers used had the same length. The relaxation time for the structure incorporating secondary amines
was 260 s at 180 °C, 3 times less than the 779 s needed for the amine-free structure (Scheme 30).45
Variations of the silyl ether bulkiness and the polymer backbone are suggested to tune the properties
of these materials.132
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Scheme 30. Synthesis of Styrene-Derived Networks Cross-Linked by Silyl Ethersa
aTwo cross-linkers were used, one bearing secondary amines (top) and the other not (bottom). The reprocessabilities of the
obtained materials were compared.45
Case of Urethanes and Hydroxyurethanes

As discussed previously, the mechanism involved in polyhydroxyurethane exchange reaction remains
uncertain. Hence, the determination of the effects of activating groups on transcarbamoylation is
intricate as they were mainly studied for the dissociative decomposition reaction discussed in section
I (Figure 25).254-256 It should be mentioned that an important activation reported is the oxime-promoted
transcarbamoylation, similar to the effect on esters previously discussed. It was implemented in
dissociative covalent adaptable networks since the mechanism is purely dissociative in this case.253
Figure 25. Characteristics of polyurethanes, polyhydroxyurethanes, polythiourethanes, and poly(oxime–urethanes): range of

stress–relaxation experiments temperatures25 or reprocessing temperatures and activation energies.24,253
For thiourethanes solvolysis by thiols, secondary amines or alcohols, the suggested reaction pathway
was an associative addition/elimination mechanism257 instead of the dissociative elimination/addition
commonly accepted. Nonetheless, as previously pointed out, the recent implementation of
thiourethane bonds in materials highlighted a dual associative and dissociative mechanism.258
Knowledge on the effects of activating groups on hydroxyurethane-based vitrimers is very limited.
Nevertheless, an excess of free exchanging dangling groups, namely alcohol groups for polyurethanes
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and thiol groups for polythiourethanes, was shown to favor the associative pathway and decrease
degradation reactions. Furthermore, this excess of dangling exchanging groups allows a better control
over the reprocessing temperature and shorter reprocessing time.144,258 After 70 min at 140 °C a PU
network without free −OH group exhibited 83% recovery of cross-link density in the presence of 1 mol
% dibutyltin dilaurate (DBTDL) as catalyst. In contrast, only 15 min at 120 °C was sufficient to reprocess
a PU containing 20% of free −OH.258 In contrast, an increase of the relaxation time was observed in the
case of thiourethane-based networks (Scheme 11) containing free thiols compared to the thiol-free
analogue. This counterintuitive result was explained by a change from a dissociative to a slower
associative mechanism.144 In conclusion, the chemistry of polyhydroxyurethanes is much more
complex that it seems at first glance. Dissociative and associative exchange mechanisms compete and
are influenced by many parameters such as the availability of exchangeable group, the presence of
activating group or internal catalysts, or the temperature. Therefore, much caution should be taken
when designing covalent adaptable networks out of polyhydroxyurethanes.
Ureas Exchange
Scheme 31. Synthesis of Polyurethane–Urea Self-Healable Elastomers259
Recently, a polyurethane–urea elastomer was claimed to be a vitrimer.259 The authors first synthesized
a PU prepolymer out of poly(oxatetramethylene) glycol (PTMG) and 4,4’-diphenylmethane
diisocyanate (MDI). Then this prepolymer was mixed either with 3,5-dimethylthio-2,4-toluenediamine
(DMTDA) or with 3,3’-dichloro-4,4’-diaminodiphenylmethane (MOCA) to form exchangeable biuret
groups (N,N’-diarylurea) (Scheme 31). Because the diamines used are primary, each amine can react
twice, thus ensuring the formation of a cross-linked materials (primary diamines can be considered as
hidden tetrafunctional reactants). The amines used possessed either electron-donating methylthio
substituents or electron-withdrawing chlorine atoms. The stress–relaxation time of the methylthio
group-containing network was 3–4 times shorter than that of the chlorinated analogue, depending on
the temperature (100–120 °C). The relaxation was assigned to urea–urea exchanges, and the
mechanism was reported as associative.259 Nevertheless, there is little proof to support this claim.
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Transimination Acceleration by Activating Groups
Figure 26. Characteristics of transimination: reported range of stress–relaxation experiments temperatures25 and activation
energies.260 Two examples of potentially active neighboring groups are given.
The success of imine-derived vitrimers (Figure 26) may be explained by the versatility of this linkage
but also because these vitrimers can be reprocessed without the need for a catalyst.163-174 When used
in organic chemistry or biochemistry, transimination was reported to be catalyzed by thiourea–metal
complexes (2 orders of magnitude rate acceleration),177 triflate salts of scandium, terbium, samarium,
and other lanthanides (up to 5 orders of magnitude acceleration),178,261 zinc bromide,262 iron chloride,
copper chloride, and magnesium chloride.263 Besides, acidic and basic catalyses are known to be
efficient as well in aqueous175,264 or organic solutions.175,265 In particular, interesting examples of
internal basic catalysis in solution were reported in the 1980s by using primary amines featuring an
internal tertiary amine function.264,265 Ciaccia et al.180 reported a study on aromatic imines in organic
solvents at room temperature. Part of this work dealt with the exchange between N-
benzylideneanilines and p-toluidine (Figure 27). The exchange reaction exhibited low equilibrium
constants (Keq < 10); thus, the results could have been carefully extrapolated to degenerate system
such as those encountered in vitrimers. The authors showed that the rate of the forward
transimination reaction was almost unaffected by EWG and EDG on the imine aromatic ring but that
the reverse reaction was mildly affected by these substituents. The electron-donating −OCH3 group
slightly increased the reverse reaction rate, whereas electron-withdrawing −CN and −NO2 groups
decreased this rate (Figure 27). Similarly, Schaufelberger et al.262 studied the impact of substituents on
the exchange of aromatic imines with benzylamines in the presence of zinc bromide as catalyst in
acetonitrile. Nevertheless, in this system, two simultaneous reactions were involved: imine
isomerization and transimination. Thus, it would be dubious to draw general conclusions on internal
catalysis based on this study.
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Figure 27. Transimination reaction between N-benzylideneanilines and p-toluidine and kinetic parameters studied by Ciaccia
et al.180
Because the first step of the amine–imine exchange reaction is associative, it occurs at room
temperature without catalyst in solvents only with unhindered reactants.179 This idea underlines the
fact that the environment of the exchangeable bond likely plays a major role in the reaction. For
instance, the solvent used to make dynamic covalent gels had an influence—acetonitrile allowing
faster imine exchange than toluene.266 Additionally, imine metathesis is catalyzed by zirconium,
molybdenum, rhenium, and niobium in organic solvents if the temperature reaches 100 °C179 and by
hafnium imido complexes at 80 °C as well.267 An interesting strategy involving minute amounts of
primary amines was also reported to accelerate this reaction in solution at room temperature. 179 The
effect of primary amines on imine metathesis was investigated in terms of mechanism and
thermodynamics. Mechanistically speaking, the overall reaction can be seen as two concomitant
transimination reactions (Scheme 32). Thus, it is not stricto sensu an imine metathesis, but the overall
result is the same. Minute amounts of an imine A bearing an isobutyl group exchange with the minute
amount of n-butylamine, leading to the release of minute amounts of the exchanged imine C and
isobutylamine. This amine then undergoes transimination with an imine B bearing a n-butyl group. This
second step releases the exchanged imine D and n-butylamine able to react with A and so on. The
overall reaction is an equilibrium between amines A and B, on one hand, and between C and D, on the
other. Thermodynamically speaking, the overall reaction is an imine metathesis.179 This effect was
implemented in imine-cross-linked PEG networks. A slight excess of dangling primary amines enabled
self-healing at 50 °C within 5 min.266 Thus, choosing carefully the stoichiometry for the synthesis of
imine-derived vitrimers would enable the tuning of their properties.
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Scheme 32. Imine Metathesis Catalysis by Minute Amounts of Primary Amines179
Recently the effect of hydrogen bonds was also emphasized. Indeed, hydrogen bond donors such as
thioureas and squaramides catalyzed both imine metathesis and transimination in solution and their
efficiencies depended on their structures.268 Similarly imines derived from salicylaldehyde were
reported to be stabilized by hydrogen bonding with −OH or −NHR substituents on the ortho position.269
Once again, this effect could be used in the molecular design of imines to tune the exchangeable bond
properties.
Vinylogous Urethanes and Amides, an Efficient Exchange Chemistry without Catalyst
Scheme 33. Characteristics of Vinylogous Urethane Transamination: Reported Range of Stress–Relaxation Experiment
Temperatures25 and Activation Energies;24 Dangling Hydroxyl Groups Accelerate the Relaxation Time of VU Materials
Transamination of vinylogous urethane is a very effective exchange reaction and enables chemists to
design easily reprocessable catalyst-free vitrimers (Schemes 16 and 33). This observation might be the
cause for the rarity of reports on such effects on vinylogous urethanes. Although the exchange is so
efficient that many catalyst-free vitrimers were synthesized, vinylogous urethane-based CANs would
still benefit from activating group participation or internal catalysis to lower reprocessing
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temperatures. Actually, an example of internal catalysis was recently reported in vinylogous urethane-
cross-linked epoxy–amine materials.199 Tri- and difunctional amines were reacted with a
bisacetoacetate to prepare a vinylogous urethane bond-containing hardener for an industrial epoxy
resin. Two synthesis methods were compared. On the one hand, the amines, the bisacetoacetate, and
the epoxy resin were mixed in one pot. On the other, the amines and the bisacetoacetate reacted in a
first step to yield a vinylogous urethane curing agent bearing free primary amines. Then the curing
agent was mixed with the epoxy resin in a second step (Figure 28). The difference lies in the water
release when amines and the bisacetoacetate reacted together. In the one-pot strategy, this water
was trapped in the material, whereas in the two-step strategy the water produced during the first step
was removed prior to the second step to yield a water-free material. The materials exhibited a
relaxation time at 160 °C of 3.5 s for the one-pot material and of 5.5 s for the two-step synthesis,
showing no significant difference between the two preparation procedures. These values must be
compared with the 25.5 s relaxation time observed in epoxy-free vinylogous urethanes vitrimers with
a similar structure, although having a higher vinylogous urethane bond concentration. Certainly, the
network structure influences the relaxation time, and thus direct comparison of these values might be
adventurous, but an internal catalytic effect from the dangling hydroxyl groups is likely responsible for
the shorter relaxation times.199 To support this idea, the authors performed model reaction on small
molecules. They studied the disappearance of propyl-3-(octylamino)but-2-enoate (octyl VU) with
benzylamine in 2-hexanol or dodecane at 100 °C. The reaction was faster in 2-hexanol, showing the
accelerating effect of hydroxyl moieties on the exchange reaction, independently of any matrix effect.
As the study of vinylogous urethane vitrimers is popular, numerous tuning possibilities might emerge
in the future not only by implementation of internal catalysis in these networks but also by variation
of the backbones nature and length.
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Scheme 34. Two strategies to synthesize VU networks were reported by Spiesschaert et al.199 The one-pot strategy traps the
water released by the reaction. The two-step strategy allows to remove water from the VU curing agent after the first step,
allowing water-free network. TREN = tris(2-aminoethyl)amine; BAC = 1,3-bis(aminomethyl)cyclohexane; EG-AA = ethylene
glycol–bisacetoacetate.
Hints for Diketoenamine Activation

As previously mentioned, diketoenamines were essentially studied as protecting groups, and there is
no extensive knowledge on a potential effect of neighboring groups. Nevertheless, in the work of
Augustyns et al.201 already discussed earlier, a few interesting trends on reactivity were gathered. The
two amino groups on lysine did not have the same reactivity toward the exchange of the Dde group.
Unprotected ε-NH2 groups could exchange with protected ε-NH2 and α-NH2 groups, but free α-NH2
groups could not exchange Dde with ε-NH2. This was probably because α-NH2 groups were too
sterically hindered and not nucleophilic enough due to the neighboring electron-withdrawing
carboxylic acid. In addition, when 2-acetyldimedone was reacted with polyamine, primary amines were
selectively protected.201 The use of diketoenamines in vitrimers is just starting to emerge, and there is
undoubtedly a lot to discover on this chemistry based on the encouraging proof of concept recently
disclosed.204,205
Effect of the Alkylating Agent on Trialkylsulfonium Salt Exchange

As mentioned before, the knowledge on trialkylsulfonium exchange with thioethers is poor except for
the proof-of-concept disclosed by Du Prez’s group.40 Of course, the most obvious parameters to tune
the material reprocessability are the nature and quantity of the alkylating agent. Without an alkylating
agent, no stress–relaxation was observed in polythioether.40 Conversely increasing the concentration
of the butyl brosylate alkylating agent from 1 to 10 mol % decreased relaxation time at 150 °C from 75
to 10 min.40 The same behavior was observed by using trimethylsulfonium iodide as an alkylating
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agent.124 Once again, there might be room for internal catalysis studies with this kind of chemistry.
Indeed, this exchange reaction was studied on small arylalkyl sulfides in solution. If no change in the
kinetics was observed with electron-rich aromatic groups, electron-poor aromatic groups slowed the
conversion rate. The alkyl substituent bulkiness also played a role. Phenylalkyl sulfides bearing various
alkyl groups were transalkylated with methyl iodide. tert-Butylphenyl sulfides reached full conversion
in 25 h, whereas the butyl-, 3-pentyl- and 2,2-dimethylpropyl analogues only reached 70, 60, and 8%
conversion, respectively. Diphenyl sulfide showed no conversion at all.270 This effect has never been
studied in materials but underlines the importance of the exchangeable group and might bring useful
insights. These articles also underline the effect of the counteranions which nucleophilicity likely plays
a role as seen in the transalkylation of triazolium salts.271-273
Conclusion and Outlook

Since the invention of vitrimers ten years ago, this class of organic materials has triggered an
undeniable enthusiasm in the polymer scientists’ community. These materials have not only aroused
scientists’ curiosity, but their implications for industrial applications are also potentially
transformative. Indeed, the rheological behavior of these materials allows a precise control of the
viscosity upon heating. This property is central to processing and reprocessing issues. One drawback
of these materials is that many vitrimers require catalysts, sometimes at high loadings, which raise
concerns for the risks of leaching and premature aging of the materials. Consequently, further work
on vitrimers will likely focus on designing catalyst-free vitrimers and on the tuning of the vitrimers’
properties, especially the reshaping ability, for the associative systems already known. Parameters
such as the cross-linking density, the concentration and availability of exchanging moieties, or the
structure and chemical groups of the backbone are already known to influence the behavior of
vitrimers. A few studies on the effect of activating groups on the exchange reactions and consequently
on materials reshaping are already available. Nonetheless, the use of this strategy to tune the rheologic
profile of associative CANs is still in infancy. Beyond the sole tuning of the reshaping parameters, the
study of activating group and internal catalysis would be significant progress for understanding how
the exchange reactions in vitrimers works, and it would give access to the scientists’ community to
more intimate knowledge of this innovative class of polymer materials. At the moment knowledge on
the phenomena occurring at the molecular scale in vitrimers is still poor. In addition, the mechanistic
studies on the exchange mechanisms involved are sometimes only preliminary or even inexistent.
Moreover, activating groups can have an influence on the exchange mechanism at work in CANs. They
may change an associative exchange into a dissociative one. Mechanistic studies are thus fundamental
for the development of CANs. A better comprehension of the phenomena at the molecular scale would
indeed allow scientists to design materials with original properties by exploiting such mechanism
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changes. Broadening the pool of techniques used to characterize CANs would also undoubtedly help
to understand their behavior and contribute to a better and more purposeful design. For example,
molecular mobility studies using dielectric spectroscopy or dynamic mechanical analysis could enrich
knowledge on these fascinating materials.
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Conclusion du chapitre I
Dans ce chapitre bibliographique, un état de l’art des réactions d’échange mises en œuvre dans des
vitrimères a été dressé. Les mécanismes d’échanges ont été discutés, ainsi que leurs implications sur
les propriétés du matériau, rhéologiques notamment. D’autre part, cette étude a permis de mettre en
lumière les différentes manières d’activer ces réactions d’échange, pour chacune d’entre elles. En
outre, ces stratégies n’ont pas été limitées à celles décrites dans la synthèse de matériaux activés, mais
ont été élargies à des effets observés dans d’autres domaines de la chimie, organique notamment.
L’objectif ne se limite pas à un catalogue de l’existant dans le domaine des vitrimères, il est de proposer
des stratégies encore inutilisées, pour de futures études, afin d’approfondir la connaissance de ce type
de matériaux et de leur caractère dynamique.
Les premiers vitrimères décrits étaient basés sur des réseaux polyesters. Bien que de nombreuses
autres réactions aient été utilisées depuis, les polyesters présentent l’avantage d’être facilement
produits en quantités importantes. En effet, ils peuvent être synthétisés à partir d’époxy et d’acides
carboxyliques polyfonctionnels, et beaucoup de ces monomères existent dans le commerce pour des
utilisations à l’échelle industrielle.
Cependant, l’utilisation de catalyseurs tels que le zinc (II) ou le triazabicyclodecene (TBD) en grande
quantités pose un problème pour l’industrialisation de tels matériaux, et leur stabilité, en usage et au
moment de leur recyclage.
La précédente étude bibliographique a permis également d’identifier des moyens d’activer les
réactions d’échange. Dans le cas de la transestérification qui a lieu dans les vitrimères polyesters, les
effets inductifs peuvent diminuer la force de la liaison ester et rendre le carbone du carbonyle plus
électrophile vis-à-vis du –OH nucléophile à l’origine de l’échange.
Le fluor a été identifié comme un candidat prometteur afin de créer un effet inductif suffisamment
intense pour transestérifier sans catalyseur. En effet, le fluor est l’atome le plus électronégatif, il
devrait donc fortement augmenter le caractère électrophile du carbonyle. De plus, la chimie des
polymères fluorés est une compétence historique de l’équipe polymères de l’ICGM, c’est donc tout
naturellement que cette idée d’activation par le fluor a germé.
Dans la suite de ce manuscrit, nous détaillerons la stratégie définie en termes de structures de

monomères et de position des atomes de fluor, afin d’obtenir un réseau tridimensionnel, de garantir
l’effet d’activation escompté sur la liaison ester, et de veiller à former des fonctions –OH lors de la
polymérisation, qui sont indispensables à la réaction de transestérification.
79
des α,α-difluoroesters
CHAPITRE II : SYNTHESE ET CARACTERISATION D’UN
VITRIMERE DE TRANSESTERIFICATION SANS CATALYSEUR
ACTIVE PAR DES α,α-DIFLUOROESTERS
81
Chapitre II : Synthèse et caractérisation d’un vitrimère de transestérification sans catalyseur activé
par des α,α-difluoroesters
Introduction du chapitre 2 ................................................................................................................ 83
Catalyst-free transesterification vitrimers: activation via α-difluoroesters ...................................... 86
1. Abstract ................................................................................................................................. 86
2. Introduction ........................................................................................................................... 86
3. Results and discussion ........................................................................................................... 88
α-Difluoro carboxylic acid monomer synthesis ......................................................................... 88
Polymerization and curing ......................................................................................................... 89
Vitrimer characterization .............................................................................................................. 91
Conclusion ..................................................................................................................................... 97
Experimental section ..................................................................................................................... 98
Materials.................................................................................................................................... 98
Synthetic procedures................................................................................................................. 98
Determination of the epoxy equivalent weight (EEW) ............................................................. 99
“TPE-TAF/BDGE” vitrimer ........................................................................................................ 100
Instrumentation ...................................................................................................................... 100
Notes and references .................................................................................................................. 101
Conclusion du chapitre II ................................................................................................................. 105
82
Introduction du chapitre 2
Dans le premier volet de ces travaux, l’objectif est de démontrer que l’effet inductif des atomes de
fluor sur la liaison ester a pour effet de favoriser la transestérification dans des matériaux polyester. A
cette fin, le système de monomères utilisé doit être conçu en respectant plusieurs contraintes, qui
constituent le cahier des charges.
Tout d’abord, la question de la position de l’atome de fluor par rapport à la liaison ester s’est posée.
La fonctionnalisation peut se faire du côté du groupe partant (R1-COO-R2) ou du côté du carbonyle (R1-
COO-R2). Dans le premier cas, le groupement fluoré va diminuer la densité électronique de l’oxygène
du groupe partant (HO-R2). Ainsi, lorsque ce groupe se retrouvera à l’état « libre » (OH libre), le
caractère nucléophile de l’oxygène sera diminué. Par suite, la réactivité du groupe hydroxyle vis-à-vis
de la transestérification s’en trouvera diminuée. En revanche, sous la forme ester, le groupe partant
sera meilleur. L’effet sur la vitesse de transestérification sera donc vraisemblablement limité. En
revanche, si le groupement fluoré est placé du côté du carbonyle, la densité électronique sur l’atome
de carbone va diminuer et le rendre plus nucléophile, favorisant la transestérification. La
fonctionnalisation doit donc se faire du côté du carbonyle (Figure D). De plus, afin de maximiser l’effet
inductif du fluor, et comme les effets inductifs sont très localisés, le choix de placer les atomes de fluor
au plus prés du carbonyle a été fait. Ainsi, les travaux décrits porteront sur des α,α-difluoro esters.
Figure D. a. réaction de transestérification b. désactivation par des atomes de fluor sur le nucléophile et c. activation par des
atomes de fluor sur l’électrophile
83
Il convient de choisir les fonctions chimiques qui conduiront au matériau polyester. La synthèse peut
impliquer la condensation d’acides carboxyliques et de polyols, la transestérification d’esters
plurifonctionnels avec un polyol, ou encore l’ouverture de fonction époxyde avec des acides
carboxyliques. La voie par condensation est souvent difficile à mettre en œuvre, requiert des
températures élevées, au-delà de 200 °C, et un montage permettant une élimination efficace de l’eau.
Cette voie est utilisée industriellement dans la synthèse de résines alkydes (ou glycéro-phtaliques)
utilisées dans les peintures,4 mais le contrôle de ces réactions est difficile et les polymères obtenus
présentent généralement une importante variabilité (distribution de masses molaires, variabilité d’un
lot à l‘autre). La voie par transestérification est utilisée pour la synthèse industrielle du poly(éthylène
téréphtalate) (PET) à partir de téréphtalate de diméthyle et de l’éthylène glycol.5 Là encore, la réaction
a lieu à haute température et nécessite l’élimination en continu du méthanol formé. La dernière voie
envisagée semble la plus avantageuse. En effet, l’ouverture d’un cycle oxirane par un acide
carboxylique conduit à la formation de β-hydroxyesters. Ces fonctions –OH formées sont d’un intérêt
majeur, puisqu’elles sont à l’origine de la réaction de transestérification, qui ne peut avoir lieu en leur
absence. De plus, beaucoup de prépolymères époxy sont disponibles dans le commerce. Cette dernière
voie a donc été retenue pour ce projet.
Compte-tenu des choix de former des α,α-difluoro esters et de l’utilisation de la réaction époxy-acide
pour former le réseau, il est nécessaire de synthétiser des α,α-difluoro acides carboxyliques. Les
monomères utilisés doivent être de fonctionnalité moyenne supérieure à 2, afin de créer un réseau
tridimensionnel et non des chaînes linéaires. La première voie envisagée a été la synthèse d’acides
α,α-difluorés difonctionnels, et de les faire réagir sur des époxy commerciaux tri- ou tétrafonctionnels.
Cependant, après étude du marché des époxy, plusieurs écueils potentiels ont été identifiés. Tout
d’abord, beaucoup des prépolymères époxy commerciaux vendus sont solides, et la plupart des acides
carboxyliques polyfonctionnels sont solides également, ce qui peut poser des problèmes au moment
du mélange, et provoquer la formation de matériaux inhomogènes. D’autre part, ces références
commerciales sont souvent des mélanges de structures chimiques différentes difficiles à distinguer, ce
qui peut nuire à la rigueur nécessaire à l’obtention d’une preuve de concept solide et indiscutable.
Enfin, du fait de ces mélanges, la fonctionnalité moyenne observée est souvent à peine supérieure à
4
Chardon, F.; Denis, M.; Negrell, C.; Caillol, S. Hybrid Alkyds, the Glowing Route to Reach Cutting-Edge
Properties? Prog. Org. Coatings 2021, 151, 106025.
5
De Vos, L.; Van de Voorde, B.; Van Daele, L.; Dubruel, P.; Van Vlierberghe, S. Poly(Alkylene Terephthalate)s: From
Current Developments in Synthetic Strategies towards Applications. Eur. Polym. J. 2021, 161, 110840.
84
2. Cette faible fonctionnalité peut remettre en cause la formation d’un réseau tridimensionnel, et le
caractère vitrimère du matériau final peut être mis en doute.
Afin de palier ces préoccupations, une stratégie différente a finalement été adoptée. Le choix s’est
porté sur la synthèse d’un acide α,α-difluoré trifonctionnel, qu’il est possible de faire réagir avec un
époxy difonctionnel pour former un réseau covalent. L’intérêt est qu’il existe des époxy difonctionnels
dont la pureté est suffisamment élevée pour ne pas nuire au caractère tridimensionnel du réseau. De
plus, certains de ces époxy sont des liquides, ce qui simplifie le procédé de synthèse du polymère. Le
diglycidyléther de butanediol (BDGE) a été identifié comme un candidat intéressant. En effet il est
vendu avec une pureté supérieure à 95 %, il est liquide à température ambiante et présente une faible
viscosité (16,65 mPa.s à 20 °C).
Ce chapitre décrit la synthèse d’un acide α,α-difluoré trifonctionnel, sa caractérisation, sa

polymérisation avec le BDGE, et les caractérisations du matériau dynamique obtenu. Ces travaux ont
été décrits dans une publication dans le journal Polymer Chemistry.6
6
Cuminet, F.; Berne, D.; Lemouzy, S.; Dantras, E.; Joly-Duhamel, C.; Caillol, S.; Leclerc, E.; Ladmiral, V. Polym.
Chem. 2022, 8, 5255–5446.
85
Catalyst-free transesterification vitrimers: activation via α-
difluoroesters
Florian Cuminet,a Dimitri Berne,a Sébastien Lemouzy,a Éric Dantras,b Christine Joly-Duhamel,a
Sylvain Caillol,a Éric Leclerca and Vincent Ladmirala
a
b
CIRIMAT Physique des Polymères, Université de Toulouse, CNRS, Université Toulouse 3 - Paul Sabatier,
1. Abstract
Transesterification vitrimers often require high catalyst loadings to achieve 3D networks reprocessable
at moderately high temperature. The addition of an activating group close to the ester bonds allows
to synthesize catalyst-free transesterification vitrimers. Here, we unveil the effect of the α-
difluoromethylene group as a novel activating group for such materials. Fluorine features exceptional
properties, in particular a strong electronegativity enabling CF2 groups to activate the epoxy-acid
polymerization, and more interestingly also the transesterification reaction on adjacent esters.
Consequently, this fluorinated group affords the easy synthesis of a highly crosslinked reprocessable
material that do not require any metallic or organic catalyst. This vitrimer is endowed with
advantageous reprocessing abilities and underwent 10 consecutive cycles without loss of mechanical
properties. In brief, the vitrimer combines durability, recyclability and is catalyst-free. This discovery is
one step further towards recyclable greener polymers.
2. Introduction
For decades, polymer materials have been classified depending on their macromolecular structure. On
the one hand are amorphous thermoplastics, composed of entangled linear chains. In these materials,
polymer chains are not covalently bonded, and are able to slide on one another.1 This translates, at
the macroscopical scale, in their solubility in suitable solvents and in their ability to be reshaped upon
heating. On the other hand are thermosets, composed of a 3D network. Theoretically, a thermoset is
a single infinite macromolecule forming a covalently crosslinked network. This permanent structure
leads to insolubility in solvents, and prevents recycling by simple thermal methods.1,2 In the pursuit of
greener, more sustainable polymers, thermosets remain a challenge for recycling.3 Yet, they are assets
in many applications for which thermal and chemical resistances are required. A third class of polymer
materials consisting in a covalent crosslinked network in which the covalent bonds can be exchanged
by reversible chemical reactions was proposed. They were called CANs, short for Covalent Adaptable
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Networks. In 2005, Bowman et al.4 synthesized a covalently bonded 3D network alike thermosets,
endowed with covalent bonds able to exchange via an associative mechanism upon irradiation with
visible light. This concept was further developed by Leibler et al.5 in 2011 with a material based on
transesterification activated upon heating. This material was insoluble in common organic solvents
even at high temperature, but able to flow and to be reshaped upon heating. Interestingly, this new
kind of material exhibited an Arrhenian viscosity decrease with increasing temperature, a feature
usually observed for inorganic glasses, or more generally for “strong” glasses in accordance with the
work of Angell.6 This analogy inspired the name vitrimers for such materials. Since this discovery, other
kinds of exchangeable bonds such as carbonates,7 boronic esters,8,9 disulfides,10,11 silyl
ethers,12,13 urethanes,14–18 olefins,19 imines,20–23 vinylogous urethanes,24–26 diketoenamines,27 acylated
acetals,28,29 and trialkylsulfonium salts30,31 have been investigated. Despite the success of vitrimers in
materials research, they have yet to be implemented in industrial and commercial applications as they
are not adapted to the recycling processes existing for thermoplastics.32 Moreover, long reprocessing
times at high temperatures can trigger premature degradation of the vitrimer after repeated reshaping
processes.33 To accelerate the reshaping process, one solution is the use of catalysts. However, some
exchange reactions such as transesterification are so slow that they often require high loadings.5 Yet,
the use of catalysts raise concerns about the materials ageing or the risk of leaching,34,35 which is
undesirable for application such as food-contact materials for example. The first catalyst-free vitrimer
was based on vinylogous urethanes exchange. This reaction is fast enough to afford short reprocessing
times without catalyst.25 Since this seminal article, other examples of catalyst-free vitrimers based on
fast exchange reactions were proposed, such as hydroxyurethanes,16 hemiacetal
esters,28 trialkylsulfonium salts,31 oxime-esters33 and imines.36 Lowering the crosslinking density and
increasing the number of exchangeable moieties were proven to enhance the reshaping abilities of
catalyst-free materials.37–41 However, since these parameters also influence the materials mechanical
properties, this strategy may not be suitable to a wide range of applications. To overcome the risk of
catalyst leaching, some vitrimers were also synthesized with a catalyst (amines for instance) embedded
in the network.42–44
In 2015, Guan et al. proposed to implement in vitrimers the concept of neighboring group participation
(NGP), well-known in the field of organic chemistry but new to the field of vitrimers.45 Materials
crosslinked using difunctional dioxaborolane and possessing neighboring amino groups relaxed faster
than the one deprived of such groups. The potential of internal catalysis or internal activation and
neighboring group participation (NGP) to tune CANs has recently been reviewed.46,47 In their review,
Van Lijsebetten et al.46 made a clear distinction between NGP for which the neighboring group is
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involved with a covalent bond at some point of the reaction, and the broader concept of internal
catalysis including effects such as inductive effects.
The present work focuses on transesterification vitrimers, as they usually require a catalyst. To address
the concerns raised by the use of external catalysts, some functional groups were reported to be
efficient for NGP, such as phthalate monoesters48 or benzenesulfonic acid groups.49 Such groups
modify the transesterification mechanism and facilitate the exchange. Examples of activation by
inductive effect were reported on Meldrum's acids in PDMS50 or in polyimine vitrimers for instance.51 In
transesterification vitrimers, malonates were used to activate the exchange reaction.52 Because of its
high electronegativity, fluorine has a strong potential to activate bond exchanges. Indeed, the carbonyl
group of fluorinated esters is known to be very electrophilic,53 which facilitates hydrolysis and
nucleophilic attack.54,55 Fluorine substitution thus appear as a good strategy to activate
transesterification reactions. Recently, a CF3 group positionned on the α carbon of esters was
demonstrated to have a significant activating effect on transesterification in polyester networks.56 In
the present work, fluorine atoms were added one atom closer to the ester bond and α-diflluoro esters
are implemented for the first time to design a catalyst-free transesterification vitrimer. A trifunctional
α-difluoro carboxylic acid was prepared and used in combination with a commercial diepoxide
(butanediol diglycidyl ether, BDGE) to prepare an epoxy-acid network which displayed insolubility in
organic solvents, but was able to be reshaped under relatively mild conditions without catalyst.
3. Results and discussion

α-Difluoro carboxylic acid monomer synthesis
Transesterification vitrimers require dangling hydroxy groups for the exchange reactions to happen.
Fortunately, the epoxy opening by a carboxylic acid produces such groups in beta position to the ester.
The strategy developed here therefore relies on the use of a trifunctional carboxylic acid monomer,
and a commercial diepoxide to obtain a 3D network. To maximize the inductive effect of fluorine on
the ester bond, the strongest fluorinated activating group (CF2) should be positioned as close as
possible to the exchangeable bond. A trifunctional monomer bearing three α-difluorocarboxylic acids
was thus designed and synthesized in two steps from a commercial triphenol (1,1,1-tris(4-
hydroxyphenyl)ethane, “TPE”). TPE was reacted with ethyl bromodifluoroacetate at 70 °C for 40 hours
to obtain by nucleophilic substitution a mixture of the di- and trisubstituted esters (15 and 60 mol%
respectively). After column chromatography, the resulting α-difluoro triester then underwent facile
saponification to yield, after appropriate workup, the desired α-difluoro triacid (TPE-TAF) as a white
waxy solid with an overall yield of 50% (Scheme 1).
88
Scheme 1. 2-Step synthesis of the trifunctional α-difluoro carboxylic acid TPE-TAF.
Polymerization and curing

Butanediol diglycidyl ether (BDGE, Annexes A Figures S14, S15 and sections A, B) was identified as a
promising commercial epoxy resin, as its viscosity is very low and because it can dissolve TPE-TAF
before gelation happens. In addition, its structure advantageously adds flexibility to the network, may
counterbalance the rigidity of the TPE-TAF structure, and might prevent a high Tg which would make
the reprocessability of the material more difficult (Scheme 2).
Scheme 2. (a) Network synthesis from TPE-TAF and BDGE and (b) schematic representation of the network.
TPE-TAF was dissolved in BDGE at room temperature (ca. 20 °C). The mixing time needed to be reduced
to a few minutes only, to avoid the gelation caused by the fast reaction between the α-difluoro acids
and the epoxides (even at room temperature) and ensure the homogeneity of the mixture. The mixture
was then left at room temperature for at least 8 h, resulting into a brittle gel, which was then cured at
150 °C.
The gel time observed visually was consistent with the gel time determined by rheological analysis
(Annexes A Figure S17). At 20 °C, a gel time of 1.3 h was estimated at the crossover of loss and storage
moduli, confirming that the epoxy opening by the α-difluoro carboxylic acid readily happens at room
temperature. This behavior is highly unusual for epoxy-acid systems, which usually require catalysis
and relatively high temperatures (80–120 °C).57 For catalyst-free systems, even higher temperatures
(around 200 °C) are required.58 This fast polymerization reaction at low temperature strongly suggests
the activating inductive effect of fluorine atoms on the carboxylic acid towards the epoxy-opening
reaction.
The polymerization kinetics at room temperature were monitored via FTIR. The disappearance of the
epoxy band at 908 cm−1 was clearly observed but the conversion of acid functions at 1758 cm−1 into
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esters at 1761 cm−1 could not be determined, because the acid and ester bands overlapped too much
(Annexes A Figure S22). The epoxy band decreased significantly for the first 6 h of reaction, and then
decreased at a much lower rate until the end of the acquisition after 64 h (Figure 1). This rate change
was probably due to the gelation of the mixture which slowed down the reaction between the
remaining reactive species.
Figure 1. Evolution of the epoxy FTIR band at 908 cm−1 of the TPE-TAF/BDGE binary mixture versus time at room
temperature (ca. 20 °C).
The material obtained after 4 days at room temperature was left for 3 h in an oven at 150 °C to ensure
complete polymerization. Three consecutive DSC ramps were carried out on the resulting material.
The thermograms overlaid perfectly, did not show any residual exotherm and revealed a Tg of 47 °C
which did not evolve after any of these heating ramps (Annexes A Figure S18). The curing of the
material was thus deemed complete.
Solubility tests were performed in acetone, THF, toluene, cyclohexane, DMSO, DCM and acetonitrile
(Annexes A Table S1). The highest values were found for acetone and THF. In particular, after 24 h
under agitation, an insoluble fraction of 94 ± 2% was measured in acetone (the best solvent for BDGE
and TPE-TAF), thus proving that the curing process led to the formation of a 3D crosslinked material,
as expected.
90
Vitrimer characterization
TGA under air showed that no significant mass loss was observed up to 200 °C, with a 2% and 5%
degradation temperatures Td2% and Td5% of 205 °C and 262 °C respectively (Annexes A Figure
S20 and Table 1). The Tg of the TPE-TAF/BDGE material was determined to be 47 °C (Annexes A Figure
S18 and Table 1). TPE-TAF contains three aromatic cycles which bring rigidity to the polymer structure,
whereas the linear structure of BDGE adds flexibility. This balance explains the moderate Tg value
observed.
Table 1. Table of the vitrimer properties
Gel contenta (%) Td2% (°C) Mass lossb (4 h, %) Mass lossb (16 h, %) Tg (°C) Tα (°C) E′Gc (GPa) E′Rd (MPa)
94 ± 2 205 4.3 4.4 47 39 3.7 18.1
a
Gel content in acetone at 20 °C for 24 h. b T = 100 °C. c Value at Tα −50 °C. d Value at Tα +50 °C.
A few preliminary reshaping trials allowed to set the reshaping temperature value at 100 °C. The
material stability to reprocessing cycles was then determined by isothermal TGA experiments
performed at 100 °C for 16 h under air, to simulate the oxidative environment during reprocessing
(Figure 2 and Table 1). After 4 h, a mass loss of 4.3% was observed. The value stabilized to 4.4% after
5 h and did not evolve afterwards. This loss might be due to the evaporation of remaining unreacted
monomers trapped in the TPE-TAF after synthesis.
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Figure 2. Isothermal TGA thermogram of TPE-TAF/BDGE material under air at 100 °C (% mass loss).
The kinetics of the flow behavior of the material was studied using stress-relaxation experiments. The
relaxation modulus was monitored with time between 170 and 210 °C with 10 °C steps (Figure 3). It is
important to state here that analogous non fluorinated polyester epoxy network prepared using
0.1 mol% Zn catalyst by Leibler et al. did not show vitrimer properties.5
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Figure 3. Normalized stress–relaxation curves from 170 to 210 °C with 10 °C steps fitted with the Kohlrausch–Williams–
Watts equation (KWW) and τKWW relaxation times reported in the Arrhenius diagram (inset, R2 = 0.98985).
Normalized stress-relaxation experimental curves shown in Figure 3 reveal that, in the 170 °C–210 °C
temperature range, the TPE-TAF/BDGE network relaxed the stress applied. This behavior is expected
only if the network is able to reorganise. The fact that this material flowed on the rubbery plateau
proves that fluorine atoms activated the transesterification. A contribution from minute amounts of
unreacted carboxylic acid function might as well favor the transesterification.60 Furthermore, the
relaxation rate depended on the temperature, as expected for a vitrimer.
The usual fitting model for such experiments is the exponential decay (Maxwell model). Nevertheless,
this model did not fit well the experimental data obtained in the logarithmic time scale (R2 between
0.934 and 0.989). A Kohlrausch–Williams–Watts “stretched exponential” equation was found to better
fit (see Annexes A Table S2 for the equation and the fitting parameters) the stress relaxation
dataset1 (R2 between 0.995 and 0.99975, depending on the temperature). In KWW model, a stretch
parameter β is added to the exponential decay. The closer to 1 is β, the closer to the Maxwell model
are the data. From 170 °C to 210 °C, the value of β was about 0.56 ± 0.02, indicating that the flow
93
kinetics was associated with a distribution of relaxations rather than with a single relaxation time
kinetics.1
The relaxation time values obtained from the KWW fitting equations were plotted in an Arrhenius
diagram (Figure 3 inset) to determine the value of the flow activation energy Ea. This Ea was
determined to be 77 kJ mol−1, in good agreement with the 29–163 kJ mol−1 range reported so far for
transesterification vitrimers,47 especially for catalyst-free vitrimers activated by neighboring groups for
which the activation energy values are ranging from 78 to 94 kJ mol−1.42,59–61
The material relaxation observed in the absence of external catalyst demonstrated the activating effect
on the transesterification of the two fluorine atoms located on the α-carbon of the esters, as non-
catalyzed epoxy-acid networks usually exhibit no relaxation on a measurable time scale. As previously
mentioned, tiny amounts of unreacted carboxylic acid, if present, could also add a contribution on this
effect. A slight contribution from the phenoxy group is plausible, but would be much weaker than the
contributions of the two fluorine atoms given the relative electronegativities of these elements (χF =
4.2, χO = 3.6). This is well illustrated by the pKas of acetic acid 4.7, glycolic acid 3.8, phenoxyacetic acid
3.2 and difluoroacetic acid 1.2.63,64 This range stresses out the difference in electron-withdrawing
ability of two fluorine vs. one oxygen atom. The material behavior in temperature followed an
Arrhenius law, as expected for a vitrimer. α-Difluoro esters are thus efficient activated esters for the
design of catalyst-free transesterification vitrimers.
The discrepancy between the sluggishness in stress-relaxation experiments and the mild reprocessing
conditions observed is striking. This difference can be explained by the pressure applied to the
material,65,66 which is an important and often overlooked parameter. The force applied onto the
material during reprocessing is 8.8 times the force applied during relaxation experiments. The
reprocessing experiments are thus carried out at high pressure value in compression, which explains
the difference in the behavior observed.
Reprocessing classical thermosets by compression molding is impossible, in contrast to vitrimers which

possess exchangeable bonds. The TPE-TAF/BDGE material was successfully reprocessed using
compression-molding further demonstrating its vitrimer character. 1 mm3 pieces of the material were
reassembled into a small ribbon after 1.5 h at 100 °C under a 6 ton load. The required reprocessing
conditions were relatively mild compared to transesterification vitrimers reported in literature,
whether they are catalyzed or not (Figure 4).5,37,40,44,48,52,62,67–72
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Figure 4. Comparison of TPE-TAF/BDGE reprocessing temperature, pressure and time with various catalyzed and catalyst-
free transesterification vitrimers reported so far.5,37,40,44,48,52,62,67–72
Ten successive reprocessing cycles were successfully performed and each time homogeneous
transparent samples were recovered. The color of the material did not significantly change with the
successive reshaping cycles (Figure 5). To quantitatively assess the material evolution with
reprocessing, thermomechanical analyses were performed.
95
Figure 5. TPE-TAF/BDGE aspect after several reprocessing cycles.
The TPE-TAF/BDGE material evolution with reprocessing was studied using DMA experiments. The
values of the storage modulus E′ in the glassy plateau and in the rubbery plateau regions, and the
evolution of Tα allow to detect whether the TPE-TAF/BDGE material mechanical properties decrease
after several reprocessing cycles. A ramp from −100 to +150 °C was performed after each reprocessing
cycle to check whether the mechanical properties were fully recovered.
96
The pristine material exhibited a glassy plateau storage modulus E′G = 3.7 GPa, a rubbery plateau
storage modulus E′R = 18 MPa and a Tα = 39 °C, which is consistent with the values reported in the
literature37,70,72–74 for epoxy-acid and epoxy-anhydride vitrimers (Table 2 and Annexes A Figure S19).
Table 2. Evolution of DMA characteristic values before and after 10 reprocessing cycles
Reprocessing cycle Tα (°C) E′Ga (GPa) E′Rb (MPa)
Pristine 39 3.7 18.1
10 49 3.9 18.7
a
Value at Tα −50 °C. b Value at Tα +50 °C.
Upon the first three reprocessing cycles, the Tα increased from 39 °C to 41, 47 and 49 °C respectively,
suggesting that the crosslink density slightly increased after each reshaping step, which is consistent
with the increase of the rubbery plateau modulus (Table 2). After this 3rd reshaping process,
the Tα value did not change with further reprocessing cycles up to the tenth cycle (Table 3).
Table 3. Evolution of Tα with the successive reprocessing cycles
Reprocessing cycle Pristine 1 2 3–10

Tα (°C) 39 41 47 49
The storage modulus (E′) value in the glassy plateau region slightly changed from 3.7 to 3.9 GPa for
the pristine network and after the tenth reprocessing respectively. Similarly, the value of E′ in the
rubbery plateau region increased by a mere 0.6 MPa (Table 2) (from 18.1 to 18.7 MPa for the pristine
and 10th reprocessing cycle). These results show that there is no significant evolution of the network
after 10 cycles.
Conclusion
In summary, polyester vitrimers were prepared out of a synthesized trifunctional α-difluoroacid and a
commercially available difunctional epoxy resin. Thanks to the activation of the acid by the fluorine
atoms, the epoxy-acid polymerization reaction happened readily at room temperature, whereas
catalysts and high temperatures are usually needed for non-fluorinated systems. The resulting TPE-
TAF/BDGE material was insoluble yet able to be reprocessed under mild conditions (100 °C, 1.5 h, 6 t).
As expected, α-difluoro ester underwent significantly accelerated transesterification. This activation
was such that no external catalyst was needed, in contrast to most other transesterification vitrimers.
The flow activation energy Ea was evaluated to be 77 kJ mol−1 which is consistent with the values
reported for transesterification vitrimers catalysed by internal amines for instance, but also very close
to the value (67–72 kJ mol−1) obtained for α-CF3 activation.56 This polymer proved highly stable over
97
repeated reprocessing cycles, with very little degradation of the mechanical properties observed after
10 cycles. The proof-of-concept based on the high electron withdrawing effect of fluorinated groups
and exposed here is very promising to tune vitrimers properties and address the concerns related to
the use of external catalysts, such as premature ageing, leaching of the catalyst or limited reprocessing
abilities.34,35,75
Experimental section
Materials
1,4-Butanediol diglycidyl ether (BDGE, Aldrich, ≥95%, NMR spectra, FTIR spectrum and EEW
calculations in Annexes A Figures S14, S15 and sections A, B), 1,1,1-Tris(4-hydroxyphenyl)ethane
(“TPE”, Sigma-Aldrich, 99%), 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU, Fluorochem, 98%), ethyl
bromodifluoroacetate (Fluorochem, 98%), benzophenone (Avocado Research Chemicals Ltd, 99%),
succinic acid (ABCR, 99%) were used as received. Solvents were supplied by VWR Chemicals.
Deuterated solvents were supplied by Eurisotop (99.8%).
Synthetic procedures
“TPE-TE” compound: 1,1,1-Tris(4-hydroxyphenyl) ethane (6.13 g, 20 mmol, 1 equiv.) was dissolved in
dry DMF (120 mL, 0.16 M). 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU, 15 mL, 100 mmol, 5 equiv.) was
added in one portion and the reaction was heated to 70 °C. Ethyl bromodifluoroacetate (12.8 mL, 100
mmol, 5 equiv.) was then added via a syringe pump at a rate of 5.0 mL h−1 and the reaction was stirred
at 70 °C for 40 h. The resulting reaction mixture was very dark due to the probable oxidation of some
of the phenol reagents, which could not be prevented even under argon atmosphere or protection
from light. The crude mixture was cooled to room temperature, diluted with H2O (600 mL), and
extracted 5 times with Et2O (5 × 100 mL). The combined organic layers were washed with 2 × 150 mL
water and with 150 mL of brine, dried with Na2SO4, filtered, and concentrated under reduced pressure.
The dark-brown crude mixture was purified by column chromatography on silica gel using
pentane/ethyl acetate mixtures (5/1, 3/1 and finally 1/1) as eluent to afford the pure triester (F1: 8.2
g, 61%, white solid) and diester (F2: 1.8 g, 16%, off-yellow viscous oil).
Triester TPE-TE characterizations (NMR spectra in Annexes A Figures S1 to S3): 1H NMR 400MHz
CDCl3: δ 7.15–7.10 (m, 6H, aromatic protons, m-OCF2), 7.07–7.02 (m, 6H, aromatic protons, o-OCF2),
4.39 (q, 3J = 7.2 Hz, 6H, OCH2CH3), 2.15 (s, 3H, Ar3C-CH3), 1.36 (t, 3J = 7.1 Hz, 9H, OCH2CH3). 19F NMR
377 MHz, CDCl3: δ −76.41. 13C NMR 101 MHz, CDCl3: δ 159.9 (CO2Et, t, 2JC–F = 41.5 Hz), 148.0 (ipso-ArC-
O, t, 3JC–F = 2.0 Hz), 146.5 (ortho-ArC-O, t, 4JC–F = 2.0 Hz), 129.9 (ipso-ArC-C-CH3), 121.2 (ortho-ArC-C-CH3),
114.1 (OCF2, t, 1JC–F = 272.5 Hz), 63.8 (O-CH2CH3), 51.7 (Ar-C-CH3), 30.9 (Ar-C-CH3), 14.0 (O-
98
CH2CH3). Rf (petroleum ether : ethyl acetate 5 : 1) = 0.42. HRMS (ESI+) Calc. for [M + Na]+ 695.1686,
found 695.1677.
Disubstituted ester characterizations (NMR spectra in Annexes A Figures S4 to S8): 1H NMR 400MHz
CDCl3: δ 7.14–7.08 (m, 4H, aromatic protons, m-OCF2), 7.07–7.03 (m, 4H aromatic protons, o-OCF2),
6.95–6.89 (m, 2H aromatic protons, m-OH), 6.79–6.72 (m, 2H, aromatic protons, o-OH), 5.06 (s, 1H,
OH), 4.39 (q, 3J = 7.1 Hz, 4H, OCH2CH3), 2.12 (s, 3H, Ar3C-CH3), 1.36 (t, 3J = 7.2 Hz, 6H, OCH2CH3). 19F
NMR 377 MHz, CDCl3: δ −76.34. 13C NMR 101 MHz, CDCl3: δ 160.0 (CO2Et, t, 2JC–F = 41.2 Hz), 154.1,
147.7 (ipso-ArC-O, t, 3JC–F = 2.0 Hz), 147.2, 140.6, 129.9, 129.9, 121.1 (ortho-ArC-O t, 4JC–F = 0.7 Hz), 115.0,
114.1 (OCF2, t, 1JC–F = 272.4 Hz), 63.8 (O-CH2CH3), 51.4 (Ar-C-CH3), 30.9 (Ar-C-CH3), 14.0 (O-
CH2CH3). Rf (petroleum ether : ethyl acetate 5 : 1) = 0.30.
“TPE-TAF” compound: In a 250 mL round bottom flask, 7 g of triester were dissolved in acetonitrile
(90 mL). Then, a 5 M aqueous solution of NaOH (12.5 g in 62 mL) was added slowly at room
temperature, and the mixture was stirred for 3 h. 200 mL of a saturated NaHCO3 solution was added
to the mixture and the aqueous layer was washed with 100 mL of diethyl ether. The organic layer was
extracted with 50 mL of saturated NaHCO3 solution, and the gathered aqueous layers were acidified
to pH = 1 using 2 M HCl. Finally, the acidified aqueous layer was extracted with 3 × 100 ml of diethyl
ether, and the solvent was removed under high vacuum to afford the desired triacid as a white waxy
solid (yield over the two steps η = 50%, purity >98% estimated from 1H NMR spectrum). Up to 9 grams
per batch could be obtained.
Trifunctional acid TPE-TAF characterizations (NMR spectra, FTIR spectrum and TGA thermogram in
Annexes A Figures S9 to S13): 1H NMR 400MHz d6-acetone: δ 7.89 (br s, 3H, COOH), 7.20 (m, 12H,
aromatic protons), 2.22 (s, 3H, C-CH3). 19F NMR 377 MHz, d6-acetone: δ −77.50. 13C NMR 101 MHz, d6-
acetone: δ 160.9 (COOH, t, 2JC–F = 40.7 Hz), 148.9 (ipso-ArC-O, t, 3JC–F = 2.0 Hz), 147.6, 130.8, 121.8,
115.3 (OCF2, t, 1JC–F = 270.9 Hz), 52.4 (C-CH3), 30.9 (C-CH3). HRMS (ESI+) Calc. for [M + Na]+ 611.0747,
found 611.0750.
Determination of the epoxy equivalent weight (EEW)

The EEW of the BDGE was evaluated by NMR titration using benzophenone as standard in deuterated
chloroform (experimental details are given in Annexes A section A). This value was confirmed by DSC
studies using succinic acid as the curing agent (experimental details are given in Annexes A section B).
The procedure was described in a previous article.76 Several BDGE/succinic acid ratios were used to
make a series of thermosets. The highest Tg was achieved for a 1 : 1 stoichiometry, from which the EEW
was calculated.
99
“TPE-TAF/BDGE” vitrimer
Typically, 1.156 g (5.90 meq COOH) of TPE-TAF was quickly mixed manually in a 10 mL beaker with
0.682 g (5.93 meq epoxy) of BDGE at room temperature (ca. 20 °C) until the acid was fully dissolved. A
clear yellowish viscous liquid was obtained and quickly cast in PTFE molds. The mixture was left at least
8 h at room temperature for gelation. The resulting material (TPE-TAF/BDGE) was then removed from
the molds and cured 3 h at 150 °C.
Instrumentation
NMR: 1H, 13C and 19F were acquired on a Bruker Avance 400 MHz spectrometer at 23 °C. External
reference was tetramethylsilane (TMS) with chemical shifts given in ppm. Samples were diluted in
0.5 mL of CDCl3 or DMSO-d6 depending on their solubility.
FTIR: FTIR spectra and single wavenumber measurements were acquired on a ThermoScientific Nicolet
iS50 FT-IR equipped with an attenuated total reflectance cell (ATR). The data were analyzed using the
software OMNIC Series 8.2 from Thermo Scientific.
Mechanical characterizations: Gel time experiment was performed at 1 Hz with a 20 mm plane-plane

geometry on a ThermoScientific Haake Mars 60 rheometer equipped with a Peltier heating cell. A
30 mL h−1 nitrogen flux was applied. Stress relaxation experiments were performed on the same
apparatus equipped with a textured 8 mm plane-plane geometry. A 10% torsional strain was applied
on 8 mm diameter and 2 mm thickness circular samples, and the rubbery modulus evolution with time
was monitored.
DMA: Dynamic Mechanical Analyses were carried out on Metravib DMA 25 with Dynatest 6.8 software.
Uniaxial stretching of samples (1 × 5 × 12 mm3) was performed while heating at a rate of 3 °C min−1 from
−90 °C to 150 °C, keeping the frequency at 1 Hz.
TGA: Thermogravimetric thermograms were recorded on a TA TGA G50 instrument using a 40

mL min−1 flux of synthetic air as purge gas. Approximately 10 mg of sample were used for each analysis.
Ramps from 20 to 500 °C were applied at a rate of 20 °C min−1.
DSC: Analyses were carried out using a NETZSCH DSC200F3 calorimeter. The calibration was performed
using adamantane, biphenyl, indium, tin, bismuth and zinc standards. Nitrogen was used as purge gas.
Approximately 10 mg of sample were placed in perforated aluminum pans and the thermal properties
were recorded between −100 °C and the temperature of 2% degradation Td2% at 20 °C min−1. The
reported values are the values measured during the second heating ramp.
100
Reprocessing: the material was cut into 1 × 1 × 1 mm3 pieces and then pressed in a PTFE mold for 1.5 h
at 100 °C under a 6 tons load using a Carver 3960 manual heating press.
Notes and references

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Conclusion du chapitre II
Le premier volet des travaux décrits dans ce chapitre a conduit à la synthèse d’un acide carboxylique
α,α-difluoré trifonctionnel (TPE-TAF) dont la structure était inédite dans la littérature au moment de
la publication de ces travaux. Ce monomère a été engagé dans une réaction de polymérisation par
ouverture de cycle avec le BDGE, afin de former un matériau à la structure tridimensionnelle. Le
matériau obtenu TPE-TAF/ BDGE possède de très bonnes propriétés de remise en forme, dans des
conditions douces comparées à celles décrites dans la littérature sur les vitrimères de
transestérification avec catalyse interne par des céto-esters,7 des amines tertiaires8 ou encore des
hydroxyles surnuméraires.9,10,11 (1,5 h à 100 °C sous 15 bars). Après 10 cycles de remise en oeuvre,
l’aspect du matériau et ses propriétés mécaniques ont très peu varié, ce qui montre sa très bonne
tenue au recyclage.
Les propriétés rhéologiques du matériau ont été étudiées. L’écoulement depuis le plateau
caoutchoutique, un comportement associé aux CAN, a été démontré. De plus, le temps de relaxation,
temps caractéristique associé à cet écoulement, évolue avec la température en suivant la loi
d’Arrhénius, un comportement observé en général pour les CAN associatifs, aussi appelés vitrimères.
En résumé, ce premier monomère a conduit à la synthèse d’un vitrimère de transestérification sans

catalyseur grâce à l’effet inductif des atomes de fluor qui active les liaisons ester. La preuve de concept
sur l’idée originale de ce projet a donc été validée.
Néanmoins, le système décrit présente des imperfections. En particulier, la voie de synthèse du

monomère TPE-TAF nécessite une purification sur colonne de silice. Cette opération, très courante en
synthèse organique, présente des inconvénients : elle est fastidieuse, et ne permet pas de traiter des
quantités importantes de monomère. Ces limitations ont déjà engendré des difficultés pour les travaux
décrits dans ce chapitre. En effet, l’analyse mécanique des polymères nécessite des échantillons de
taille suffisante, avec des géométries contrôlées, et suffisamment de matière afin d’établir des
protocoles optimisés et vérifier la répétabilité des analyses sur plusieurs échantillons d’un même
matériau. Une voie de synthèse et une purification plus simples permettraient de faciliter les
expériences d’analyse mécanique.
7
Debnath, S.; Kaushal, S.; Ojha, U. ACS Appl. Polym. Mater. 2020, 2, 1006-1013.
8
Li, Y.; Liu, T.; Zhang, S.; Shao, L.; Fei, M.; Yu, H.; Zhang, J. Green Chem. 2020, 22 (3), 870–881.
9
Wang, S.; Teng, N.; Dai, J.; Liu, J.; Cao, L.; Zhao, W.; Liu, X. Polymer 2020, 210, 123004.
10
Liu, Y.; Ma, S.; Li, Q.; Wang, S.; Huang, K.; Xu, X.; Wang, B.; Zhu, J. Eur. Polym. J. 2020, 135, 109881.
11
Han, J.; Liu, T.; Hao, C.; Zhang, S.; Guo, B.; Zhang, J. Macromolecules, 2018, 51, 6789–6799.
105
Dans la suite de ces travaux, l’objectif a été de simplifier la synthèse de monomères acides
carboxyliques α,α-difluorés, pour pouvoir la mener sur de plus grandes échelles (de quelques grammes
par lot à quelques dizaines de grammes par lot). De plus, des méthodes de purifications adaptées à
des lots de plus grande échelle ont été testées et développées.
106
Chapitre III : Synthèse d’un vitrimère à partir d’époxy et d’α,α-difluoroacides difonctionnels
CHAPITRE III : SYNTHESE D’UN VITRIMERE A PARTIR
D’EPOXY ET D’α,α-DIFLUOROACIDES DIFONCTIONNELS
107
Chapitre III : Synthèse d’un vitrimère à partir d’époxy et d’α,α-difluoroacides difonctionnels ......... 107
Introduction du chapitre III ............................................................................................................. 109
Synthesis of a transesterification vitrimer activated by fluorine from an α,α-difluoro carboxylic acid

and a diepoxy .................................................................................................................................. 111
Abstract ....................................................................................................................................... 111
Introduction ................................................................................................................................. 111
Monomer Synthesis................................................................................................................. 113
Vitrimer Network Synthesis..................................................................................................... 114
Vitrimer Characterization ........................................................................................................ 118
Conclusion ................................................................................................................................... 122
Experimental Section................................................................................................................... 123
Materials.................................................................................................................................. 123
Synthetic Procedures............................................................................................................... 123
References ................................................................................................................................... 126
Conclusion du chapitre III ................................................................................................................ 129
108
Introduction du chapitre III
L’objectif de ce deuxième volet de travaux est de faciliter l’obtention de monomères α,α-difluoro

acides carboxyliques, notamment à une échelle supérieure à la synthèse du TPE-TAF, qui a permis la
validation de la preuve de concept. La purification éventuelle du monomère devra également être
adaptée à des lots de l’ordre de la dizaine de grammes, ceci dans le but d’obtenir des quantités
d’échantillons suffisants afin de faciliter les études mécaniques.
La voie de synthèse décrite au chapitre précédent à partir d’un triphénol conduit à un mélange des
composés trisubstitués, disubstitués, monosubstitués et probablement de produits d’oxydation au
regard de la couleur très sombre et de l’opacité du mélange réactionnel, caractéristiques de
l’oxydation de phénols. Ce mélange ne peut pas être utilisé en l’état et nécessite une purification par
chromatographie sur silice. Bien que ce procédé soit usuel au laboratoire, il ne permet pas de purifier
de grandes quantités de matière.
Afin d’éviter ces problèmes d’oxydation et de limiter les produits de substitution partielle, une autre
voie de synthèse à partir de iodoaryles a été identifiée.12,13 Cette synthèse a été décrite sur des aryles
monoiodés, mais jamais sur des di- ou tri-iodés. L’autre inconvénient est que le triiodobenzene, bien
que disponible commercialement, est vendu à des tarifs prohibitifs pour des applications industrielles.
En revanche le diiodobenzene est accessible mais implique l’utilisation d’un époxy de fonctionnalité
bien supérieure à 2, avec les limitations discutées au chapitre précédent.
Cependant, dans le cas de systèmes époxy-acide carboxylique, la réaction d’ouverture de l’époxy par
l’acide n’est pas la seule mise en jeu dans la formation du réseau.14 La transestérification peut être
concomitante à la polymérisation par ouverture de cycle, ce qui conduit à des chaînes liées entre elles,
c’est-à-dire un réseau tridimensionnel, et à la formation d’oligomères libres au sein du réseau
macromoléculaire, mais non liés à cette structure. La transestérification est liée à la présence de
catalyseur (TBD) dans les matériaux décrits. Ces considérations, ainsi que les travaux de Poutrel et al.15
publiés en juin 2020 sur des vitrimères époxy-acide carboxylique ont amené à reconsidérer cette voie
de synthèse.
12
Eto, H.; Kaneko, Y.; Sakamoto, T. Chem. Pharm. Bull. 2000, 48 (7), 982–990.
13
Mizuta, S.; Stenhagen, I. S. R.; O’Duill, M.; Wolstenhulme, J.; Kirjavainen, A. K.; Forsback, S. J.; Tredwell, M.;
Sandford, G.; Moore, P. R.; Huiban, M.; Luthra, S. K.; Passchier, J.; Solin, O.; Gouverneur, V. Org. Lett. 2013, 15
(11), 2648–2651.
14
Steinmann, B. Polym. Bull. 1989, 22 (5–6), 637–644.
15
Poutrel, Q.-A.; Blaker, J. J.; Soutis, C.; Tournilhac, F.; Gresil, M. Polym. Chem. 2020, 11 (33), 5327–5338.
109
Dans le cas de polyesters sans catalyseur activés par le fluor, la question de la formation ou non d’un
réseau tridimensionnel se pose. En effet, les conditions de polymérisation sont différentes, avec un
traitement à 150 °C pendant 3 h après une polymérisationà température ambiante pendant 8 h dans
le cas des acides fluorés,16 contre un traitement de 8 h à 145 °C suivi de 8 h à 160 °C pour les vitrimères
avec catalyseur.17 Ce traitement thermique dans des conditions plus douces dans le cas des matériaux
fluorés peut avoir des conséquences différentes sur les réactions mises en jeu au moment de la
polymérisation, et donc sur la structure macromoléculaire des matériaux formés.
Afin de vérifier la faisabilité d’une telle structure, un monomère difonctionnel α,α-difluoro acide
carboxylique a été synthétisé à partir de 1,4-diiodobenzene. La purification de ce monomère a pu été
optimisée pour pouvoir être adaptée à grande échelle. Un échantillon a été synthétisé par réaction
avec le BDGE. Ce matériau présente une structure tridimensionnelle, et des propriétés vitrimères à
l’instar du premier système étudié (Figure E).
Cette étude inédite a été rédigée sous la forme d’une publication qui sera prochainement soumise
dans le journal European Polymer Journal.
Figure E. Synthèse d’une macromolécule tridimensionnelle à partir d’un diacide fluoré et d’un diépoxy par transestérification
activée par des groupements α-CF2
16
Cuminet, F.; Berne, D.; Lemouzy, S.; Dantras, E.; Joly-Duhamel, C.; Caillol, S.; Leclerc, E.; Ladmiral, V. Polym.
Chem. 2022, 8, 5255–5446.
17
110
Synthesis of a transesterification vitrimer activated by fluorine from an
α,α-difluoro carboxylic acid and a diepoxy
Florian Cuminet,a Sylvain Caillol,a Éric Dantras,b Éric Leclerc,a Cédric Totée,c Olivier Guille,d and
Vincent Ladmirala
a ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France

b CIRIMAT, Université Toulouse 3 Paul Sabatier, Physique des Polymères, 118 Route de Narbonne,
c ICGM, PAC, Univ Montpellier, CNRS, ENSCM, Montpellier, France
d Institut d’Electronique et Systèmes (IES) UMR 5214, Université de Montpellier/CNRS, 34095,
Montpellier, France
Abstract
An α,α-difluorodicarboxylic acid (P-DAF) was easily synthesized in two steps from diiodobenzene and
reacted with a commercial diepoxy (BDGE). The electron-withdrawing effect of the fluorinated group
activated the polymerization and gelation readily happened at room temperature. After curing at
150 °C a novel dynamic material was obtained. The P-DAF/BDGE material exhibited a high gel content
(94 %) and was able to flow when heated. This material could be successfully reshaped by compression
molding under mild conditions (1.5 h at 150 °C). This new material demonstrates that catalyst-free
transesterification vitrimers can be prepared from difunctional monomers.
Introduction
Thermosets are polymers made of a network of covalent bonds. Thanks to this structure, they are
endowed with high chemical resistance, as they do not solubilize in organic solvents, and high thermal
resistance, as they do not flow upon heating.1 In the current context of pursuit for greener and more
sustainable polymers, thermosets are raising concerns as they cannot be easily recycled.2 An answer
to this issue is the use of reversible covalent bonds to prepare the network, since such bonds can be
broken into reactive species able to re-associate with similar partners elsewhere in the network and
form new bonds of the same nature.3–7 At low temperatures, the bonds are unreactive and the network
is permanent, whereas upon heating exchange reactions between reversible bonds can take place.
This feature allows the polymer chains to rearrange at the local scale, and the material to flow at the
macroscopic scale and be recycled. The most extensively studied chemistry for such materials is
probably the Diels-Alder and retro-Diels-Alder reactions.8,9 However, the dissociative nature of this
reaction often induces a dramatic loss of the network integrity during the reprocessing steps.10 In 2005,
Bowman et al. introduced a dynamic network in which covalent bonds exchanges proceeded via an
associative mechanism triggered by visible light.11 In such exchange mechanisms the crosslinking
111
density does not decrease, as a new bond is formed when another is broken, simultaneously. Thereby,
the number of crosslinks remains the same even when the network rearranges. Later, in 2011, the
same idea was implemented in polyester networks, using transesterification reactions triggered by
heat.12 The exchange reaction was promoted by a ZnII catalyst so that the rearrangements at high
temperature were fast enough to induce a flow of the material. Because the viscosity of these polymers
evolves linearly with temperature as silica glasses, and because they can be shaped the same way, they
were called vitrimers. This discovery generated a strong emulation within the polymer scientists
community, leading to the discovery of many other exchange reactions and their implementation in
vitrimers: carbonates,13 dioxaborolanes,14,15 olefins,16 vinylogous urethanes17–19 and imines20–23 are just
a few examples of exchangeable functions that have been reported in vitrimers thus far. The major
drawback of the polyester vitrimers is the use of an external catalyst, usually Zn2+, triazabicyclodecene
or phosphines.24 However, these catalysts are suspected to leach out of the material or to induce
premature ageing upon reprocessing.25–27 To overcome this issue, some strategies were developed to
synthesize catalyst-free transesterification vitrimers. Hyperbranched epoxy monomers were
synthesized from BADGE and a trifunctional alcohol before curing with succinic anhydride. The
resulting relatively loose network and the high content of free hydroxy groups favored the mobility
and the catalyst-free transesterification.28 The effect of high hydroxy group concentration alone was
also reported.29,30 Another strategy is to embed a catalytic function in the network. For example,
tertiary amines integrated in a polyester network were proved to act as an internal catalyst and
activate the material flow.31 Finally, the addition of activating groups in the direct vicinity of the ester
links can also promote the transesterification reaction.32 Oxime-esters are a representative example
of this strategy.27 Recently, the activation of the transesterification reaction thanks to vicinal
fluorinated groups was demonstrated.33 In particular, the careful design of ,,-trifluoro and α,α-
difluoro polycarboxylic acids, from a tetrathiol and a triphenol respectively, allowed the synthesis of
catalyst-free polyester vitrimers.34,35 The present work aimed at the diversification of such fluorinated
monomers and of the properties of the materials obtained thereof. Inspired by the work of Poutrel et
al. on the synthesis of crosslinked vitrimers from a mix of diepoxides and sebacic acid,10 a catalyst-free
transesterification vitrimer was synthesized from a simple difunctional α,α-difluorodicarboxylic acid
and a commercially available difunctional epoxy. The gelation of diepoxy-diacid “2+2” systems for
classical thermosets is well known36 and was also reported for vitrimers.10 In 2+2 systems, the ring
opening of the epoxy by the acid cannot explain the gelation alone. Side reactions, such as direct
esterification and epoxy homopolymerization also occur as the curing is done at high temperatures,
thus inducing the crosslinking.1 The goal of this work is to study the feasibility of a crosslinked network
at lower temperature with fluorinated dicarboxylic acids. The activation of the transesterification by
fluorine is expected to be beneficial for the crosslinking density. In this context, a novel
112
α,α-difluorodiacid (P-DAF) was synthesized in two scalable steps from 1,4-diiodobenzene. P-DAF was
reacted with commercial butanediol diglycidylether (BDGE) to obtain an insoluble crosslinked material
which resistance to solvents, mechanical properties and flow properties were studied. The
P-DAF/BDGE vitrimer ability to be reprocessed was also assessed.
Results and Discussion

Monomer Synthesis
A novel α,α-difluorinated bis-carboxylic acid (P-DAF, Figure 1) was synthesized for the first time,
following procedures described for monofunctional analogues.37,38 The conditions for this reaction
feature several advantages. First, the corresponding diester is synthetized in DMSO, which is a non-
toxic solvent. The temperature of the reaction is 60 °C, which is relatively mild. In addition, the
purification procedure is much easier and more convenient than the silica gel chromatography
previously reported, especially for large-scale syntheses.34 Indeed, the reaction conditions used to
prepare α,α-difluorinated carboxylic acids from a tri-phenol induce a partial oxidation of the latter,
thus requiring a purification on silica gel to obtain the pure target monomer. Here, the purification of
the crude product is easily scalable, as the desired compound is isolated by a simple recrystallization
in ethanol. The overall yield after the first recrystallization was 42 %. Nevertheless, this yield was
improved by removing the solvent and performing a second recrystallization to reach an overall yield
of 54 %. Finally, a straightforward saponification using a potassium carbonate aqueous solution in
methanol led to the pure desired diacid P-DAF as a white powder, without further purification (Scheme
1).
Scheme 1. 2-step synthesis of P-DAF from 1,4-diiodobenzene
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Vitrimer Network Synthesis
Figure 1. a. Vitrimer synthesis from P-DAF and BDGE and b. schematic representation of the structure
P-DAF was mixed with BDGE at room temperature (ca. 20°C) and a gel formed after after 8 h. The
resulting gel was then cured at 150 °C for 3 h (Figure 1 and 3a). As previously described,34,35 fluorine
atoms enhance the acid reactivity towards the epoxy, allowing the ring opening to happen significantly
at room temperature (RT). A FTIR monitoring was performed over the first two hours of reaction at RT
(Annexes B Figure S1). The shift of the acid C=O band to the ester around 1761 cm-1 was too narrow to
follow the conversion of these functions. Nevertheless, the intensity of the epoxy band at 914 cm-1
clearly decreased over time, which indicates that the opening of the epoxy by the acid occurs at RT
(Annexes B Figure S2). Additionally, this reaction could also be observed using 13C high resolution magic
angle spinning (HRMAS) NMR spectroscopy. No deuterated solvent was used, which is common in solid
state NMR, but rather uncommon for HRMAS NMR experiments. The high resolution obtained in 13C
allowed to acquire spectra without lock, and calibrate them using the peaks at 26 and 71 ppm of the
butanediol core of BDGE. In addition, the outstandingly fast acquisition (256 scans, 0.1 s per scan) of
these 13C spectra allowed to qualitatively monitor the reaction by this technique. The progressive
disappearance of the epoxy signals at 44 ppm (R-CH-O-CH2) and 51 ppm (R-CH-O-CH2) was easily
followed over the course of 6 h, when they completely disappeared (Figure 2 and Annexes B Figure
S3). Attempts to follow the reaction by 1H HRMAS NMR failed because the signal resolution was too
poor. 19F HRMAS NMR could not be used either to follow the ester formation. Indeed the difference in
chemical shifts of the α-difluoroacids and α-difluoroesters was too small (-102.1 ppm for P-DE
and -103.0 ppm for P-DAF in solution 19F NMR, Annexes B Figures S4 and S5).
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Figure 2. Monitoring of the P-DAF / BDGE polymerization reaction by 13C HRMAS NMR over time a. full spectrum and b.
zoom on the 55-40 ppm zone.
After gelation at room temperature, a DSC of the resulting material was performed to check whether
the polymerization was complete. Two consecutive heating ramp from -100 °C to +250 °C were applied
(Annexes B Figure S6). On the first heating ramp a Tg is visible at 13 °C, and a small endothermic peak
can be observed between the Tg and the maximum temperature. On the second heating ramp, this
endothermic phenomenon is absent and the Tg increased to 27 °C. This result suggests that a curing
step at higher temperature is necessary to finish the polymerization reaction. This was confirmed by
the relatively low gel content observed after the polymerization at room temperature (50-60 % in polar
solvents, Annexes B Table S1). The end of the polymerization was also followed by monitoring the
evolution of the dynamic storage modulus E’ of the material with time, first at 150 °C (Annexes B Figure
S7) and then at 170 °C (Annexes B Figure S8). At 150 °C, the storage modulus increased during 80
minutes from 0.5 to 3.7 MPa, before reaching a plateau. The analysis was stopped after 100 min. Then,
a second step at 170 °C was applied, to check whether the polymerization was over or if a higher
temperature would extend it again. No significant evolution of the modulus (which ranged between
4.0 and 4.5 MPa at this temperature) was observed. This result suggested that a curing step of 80 min
at 150 °C was sufficient to finish the polymerization. This curing time was nonetheless doubled to
ensure a complete curing; and the BDGE/P-DAF gel obtained at room temperature was cured for 3 h
at 150 °C. This treatment produced a flexible light brown material (Figure 3b).
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Figure 3. a. Crosslinked material after 8 h at room temperature (ca.20 °C); and b. after 3 h at 150 °C
The swelling index (SI) and gel content (GC) of the BDGE/P-DAF material were determined in a series
of solvents (Annexes B Table S2). Polar solvents showed the highest affinity with the polymer, as the
swelling index was 237, 148, 159 and 136 % in dimethylsulfoxide (DMSO), dichloromethane (DCM),
water and tetrahydrofuran (THF), respectively. This is not surprising since the network contains many
polar functions such as esters, hydroxyl and -CF2 groups. The material exhibited a gel content of 96 %
in THF, the best solvent for both monomers, thus confirming the crosslinked structure of the material.
The morphology of the C=O FTIR band in the 1780-1710 cm-1 area (Annexes B Figure S9) did change
form a single band at 1760 cm-1 with a shoulder towards low wavenumbers, to two bands at 1765 and
1730 cm-1 after the curing step at 150 °C. Unfortunately, the bands of the acid and of the ester are
hardly distinguishable. Nevertheless, a very weak band centered on 2631 cm-1 which can be ascribed
to the O-H stretching of carboxylic acid disappeared after the curing at 150 °C (Annexes B Figure S10).
This confirmed that a small amount of unreacted carboxylic acid remained in the material after the
polymerization at room temperature. This residual unreacted –COOH groups are probably due to the
lack of mobility of the reactive species after the gelation occurred.
Obtaining a crosslinked network from a difunctional epoxy and a difunctional carboxylic acid seems
counterintuitive if only the reaction of epoxide opening by acids is considered. In this case, the
polymerization would indeed lead to linear polymer chains and the material would be a thermoplastic.
However, if other reactions happen concomitantly to the epoxy ring-opening, in particular
transesterification, then 3D network can be formed.36 The epoxy opening by a carboxylic acid leads to
primary and secondary β-hydroxyl esters (Scheme 1).
Scheme 1. Epoxide opening by a carboxylic acid leads to a. secondary or b. primary β-hydroxyl ester.
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Then, the dangling hydroxy groups can undergo transesterification with an ester of another
chain/segment. This leads to crosslinks and to the formation of free polyol oligomers, disconnected
from the network, in the sol fraction (Figure 4). This mechanism was clearly explained and theorized
recently for non-fluorinated epoxy-acid vitrimers made from difunctional acids and is represented for
the present system in Figure 4.10
Figure 4. Expected structures of a diepoxy-diacid “2+2” polymer (a). if only epoxy opening by the acid is considered (b). if
transesterification and Fisher esterification are taken into account (crosslinked network: blue, orange and pink segments
and oligomers in the sol fraction in red).
In addition, other minor side reactions could increase the degree of crosslinking of the network:
1) Fisher esterification with the remaining traces of carboxylic acid groups (Figure 5a), and
2) irreversible formation of ether bonds (Figure 5b).1,10Although these reactions only happen to a small
extent, they generate crosslinks which can be beneficial to the formation of 3D network.
117
Figure 5. Possible side reactions during the curing step at 150 °C a. Fisher esterification, b. etherification by epoxy opening by
an alcohol
Vitrimer Characterization
The thermal stability of the BDGE/P-DAF vitrimer was assessed by TGA under air. The temperature of
2 % mass loss was 262 °C whereas 5 % mass loss was attained at 321 °C (Annexes B Figure S11, Table
1). The Tg measured by DSC was 27 °C (Annexes B Figure S6). This value is rather low considering the
aromatic nature of the diacid, and shows that BDGE brings flexibility to the network, as expected. This
feature also translates on the DMA experiment, with Tα = 47 °C. The values of the storage modulus
were E’G = 1.9 GPa and E’R = 11 MPa on the glassy plateau and on the rubbery plateau respectively
(Annexes B Figure S12, Table 1), which is consistent with similar networks reported
previously.28,29,34,39,40
Table 4. Thermal properties of the BDGE/P-DAF vitrimer
T2% loss (°C) T5% loss (°C) Tg (°C) Tα (°C) E’G (GPa)a E’R (MPa)b SI (%)c GC (%)c
262 321 27 47 1.9 11 136 96±1
a
at Tα–50 °C │ at Tα+50 °C │ in THF
b c
The flow properties of the BDGE/P-DAF vitrimer were studied by stress-relaxation in the time domain.
To assess the role of fluorine in the flow properties, a non-fluorinated counterpart called BDGE/P-DA
was prepared by reaction of 1,4-phenylenediacetic acid and BDGE at 120 °C overnight and at 180 °C
for 1 h. As no catalyst was used the polymerization of the non-fluorinated system required higher
temperatures and longer polyùerization times, which might have an influence on the macromolecular
structure. Nevertheless, this material is useful for the direct comparison of the dynamic properties of
two uncatalysed systems, fluorinated and non-fluorinated. A 10 % torsionnal strain was applied and
full stress relaxation was observed for the fluorinated BDGE/P-DAF material at 210 °C after 45900 s (12
h 45 min, the end of the curve is noisy because of the apparatus technical limitations to keep the
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applied strain constant at low torque). The same experiment was performed on the non-fluorinated
BDGE/P-DA counterpart. The relaxation was much slower, as only 37 % of the applied stress was
relaxed after the same duration. This proves the significant effect of the α,α-difluoro group to activate
transesterification and allow the material to flow (Figure 6).
Figure 6. Stress relaxation experiments on fluorinated P-DAF/BDGE and non-fluorinated P-DA/BDGE at 210 °C with a 10 %
strain.
The modulus behavior was monitored for isotherms ranging from 170 to 210 °C (Figure 7). The stress
relaxation data were fitted with a Kohlraush-Williams-Watts equation and the obtained relaxation
times τKWW were plotted in an Arrhenius diagram (Figure 7 inset). The value obtained from the curve
at 170 °C was discarded, because the data at this temperature was considered inaccurate. Indeed, the
relaxation seemed faster than expected compared to the other isotherms. This is likely due to a slow
slipping of the sample at lower temperatures for long experiment times, in spite of the experimental
efforts implemented to overcome this issue. This translates clearly on the Arrhenius plot when the 5
isotherms values are plotted. Thus, only the isotherms from 180 °C to 210 °C were considered. The
τKWW values followed a linear fit, proving the vitrimer follows the Arrhenius law, and the activation
energy was determined to be Ea = 118±8 kJ mol-1 (Figure 7 inset).
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Figure 7. Normalized stress-relaxation experiments from 170 to 210 °C for BDGE/P-DAF vitrimer fitted with the Kohlraush-
Williams-Watts equation (KWW) and Arrhenius plot of the τKWW relaxation times obtained.
The reprocessing ability of the vitrimer was successfully assessed by compression molding. Samples
were diced into ≈ 1 mm3 pieces and reprocessed by compression molding for 1.5 h at 150 °C under a 6
ton load (Figure 8).
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Figure 8. P-DAF/BDGE vitrimer before and after reprocessing by compression molding, front lighting (center) and backlit
(right)
Table 5. Properties of P-DAF/BDGE vitrimer pristine, after reprocessing and after subsequent annealing
Pristine Reprocessedb Annealedc

Tg (°C) 27 -2 20
Tα (°C) 47 30 40
a
SI (%) 136 308 -
GC (%)a 96±1 93±1 -
E’R (MPa) 11 7 6
a
in THF │b1.5 h, 150 °C, 6 tons in press│c3 h, 150 °C in oven
The vitrimer chemical stability upon reshaping was checked by FTIR (Figure 9). A slight increase of the
–OH band and the appearance of a weak band at 1630 cm-1 were observed. These may be caused by
a slight water intake of the material from ambient moisture before reprocessing. The value of Tg
obtained by DSC dropped from 27 °C for the pristine material to -2 °C for the reprocessed material
(Table 2 and Annexes B Figure S13). The swelling index of 136 % before reprocessing increased to 308 %
after reprocessing, whereas the gel content slightly decreased from 96±1 % to 93±1 % (Table 2). The
water intake could lead to plasticization, or to some hydrolysis at high temperature in the heating
press. By DMA the Tα shifted from 47 °C to 30 °C before and after reprocessing, respectively and the
modulus on the rubbery plateau decreased from 11 to 7 MPa (Table 2 and Annexes B Figure S14). The
Tα ascribes for the effects of both plasticization and possible hydrolysis, whereas the modulus on the
rubbery plateau depends only on the crosslinking density, thus the decrease observed can be ascribed
to hydrolysis during reprocessing. This hypothesis of a plasticization effect after hot pressing remains
plausible, as the sample is constrained between two plates which hinder water evaporation. When a
121
reprocessed sample underwent an annealing treatment in an oven for 3 h at 150 °C, in which water is
free to escape from the material, the Tg and the Tα reached values (Tg = 20 °C, Tα = 40 °C) close to those
of the material before reprocessing. This results are consistent with a water plasticizing effect.
Nevertheless, the modulus on the rubbery plateau was not recovered (6 MPa) which suggests partial
hydrolysis. The change in the gel content, though very limited, also supports this hypothesis.
Therefore, the behaviour of the material is most likely due to a combination of both plasticization and
hydrolysis (Table 2).
Figure 9. FTIR spectra of the P-DAF/BDGE vitrimer before and after reprocessing by compression molding
Conclusion
Catalyst-free transesterification vitrimers were synthesized from P-DAF, an α,α-difluorodicarboxylic
acid and a commercially available diepoxy. P-DAF was easily synthesized in two steps and purified by
recrystallization. The α,α-difluoro groups proved to activate P-DAF reactivity towards epoxy ring
opening, as the reaction with the diepoxy BDGE readily happened at room temperature. This bulk
polymerization resulted in a gelled material. After completion of the curing at 150 °C for 3 h, an
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insoluble thermosetting material was obtained. Transesterification concomitant to the epoxy-acid

reaction during the curing was responsible for the crosslinking of the network. The P-DAF/BDGE
material relaxed stress when a constant strain was applied at temperatures ranging from 170 to 210 °C.
The dynamic properties of this material are due to bond exchanges by transesterification activated by
the inductive effect of the α-CF2 groups to the ester bonds. The relaxation times at different isotherms
followed the Arrhenius equation, which is consistent with the behavior of a vitrimer. The P-DAF/BDGE
vitrimer was then successfully reprocessed by compression molding for 1.5 h at 150 °C under a 6-ton
load to give homogeneous reshaped samples, without the need for any added catalyst. The feasibility
of such α,α-difluoro activated vitrimers from difunctional monomers will simplify the synthesis of other
similar materials, as difunctional species are more available than tri- or tetra-functional ones. This
could benefit in the future to a better understanding of the structure/properties relationship in such
materials, but also to their potential synthesis on larger scales.
Experimental Section
Materials
Copper powder (Aldrich, 99 %), 1,4-diiodobenzene (Fluorochem, 98 %), 1,4-butanediol diglycidyl ether
(BDGE, Aldrich, ≥ 95 %, 1,1,1-Tris(4-hydroxyphenyl)ethane (“TPE”, Sigma-Aldrich, 99 %),
1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU, Fluorochem, 98 %), ethyl bromodifluoroacetate
(Fluorochem, 98 %), 1,4-phenylenediacetic acid (ABCR, 97 %) were used as received. Solvents were
supplied by VWR Chemicals. Deuterated solvents were supplied by Eurisotop (99.8 %).
Synthetic Procedures
Synthesis of diethyl 2,2'-(1,4-phenylene)bis(2,2-difluoroacetate) (P-DE): 1,4-diiodobenzene (41.3 g,
125 mmol, 1 equiv.) was dissolved in DMSO (300 mL) in a 500-mL round-bottom flask. Copper powder
(42.17 g, 664 mmol, 5.3 equiv.) was added under vigorous stirring to obtain a suspension. Ethyl
bromodifluoroacetate (51.0 g, 251 mmol, 2 equiv.) was then added. The flask was sealed with a septum
and heated to 60 °C for 7 hours. The crude mixture was cooled to room temperature, poured in a
mixture of ice and saturated ammonium chloride aqueous solution (1.5 L) under vigorous magnetic
stirring. The aqueous solution was extracted 4 times with ethyl acetate (4 x 500 mL). The combined
organic layers were washed 4 times with saturated aqueous ammonium chloride (4 x 400 mL) and
twice with brine (2 x 400 mL), dried with MgSO4 and concentrated under reduced pressure. The solvent
was removed under high vacuum to afford 38 grams of an orange solid-and-oil mixture. The crude
product was taken in a minimum of cold ethanol, inducing a crystallization of 17 grams of the pure
diester (white solid, 42 %). The filtrate was concentrated under reduced pressure and the same
operation was repeated to afford another 4.9 grams of the diester (off white solid, 12 %). 1H NMR
123
400MHz DMSO-d6 (Annexes B Figure S15): δ (ppm) 7.80 (s, 4 H, aromatic protons), 4.31 (quad, 4 H,
CH2), 2.50 (DMSO), 1.21 (t, 6 H, CH3). 19F NMR 377 MHz, DMSO-d6 (Annexes B Figure S16): δ (ppm) -
102.1. 13C NMR 101 MHz, DMSO-d6 (Annexes B Figure S17): δ (ppm) 163.2 (RCOOR, JC-F = 36 Hz), 135.4
(CIV aromatic, JC-F = 26 Hz), 126.6 (CH aromatic, JC-F = 6 Hz), 113.3 (CF2, JC-F = 252 Hz), 64.2 (CH2), 40.0
(DMSO), 14.0 (CH3). HRMS (ESI+) Calc. for [M+H]+ 323.0901, found 323.0902. FTIR spectrum: Annexes
B Figure S18.
Synthesis of 2,2'-(1,4-phenylene)bis(2,2-difluoroacetic acid) (P-DAF): In a 250-mL round-bottom

flask, 9.4 g of diester P-DE were dissolved in 80 mL of methanol. Then, 80 mL of a 1M potassium
carbonate aqueous solution was added under magnetic stirring and the reaction was left to proceed
overnight at room temperature. The crude mixture was then precipitated in 300 mL of 1M HCl,
extracted with ethyl acetate (3 x 200 mL), washed twice with brine (2 x 150 mL), dried over Na2SO4 and
the solvent was removed under reduced pressure to afford 7.7 g of the pure diacid (white solid).
1
H NMR 400MHz DMSO-d6 (Annexes B Figure S19): δ (ppm) 7.76 (s, 4 H, aromatic protons). 19F NMR
377 MHz, DMSO-d6 (Annexes B Figure S20): δ (ppm) -103.0. 13C NMR 101 MHz, DMSO-d6 (Annexes B
Figure S21) : δ (ppm) 165.1 (RCOOR, JC-F = 33 Hz), 135.9 (CIV aromatic, JC-F = 27 Hz), 125.6 (CH aromatic,
JC-F = 168 Hz), 113.5 (CF2, JC-F = 250 Hz), 40.0 (DMSO). HRMS (ESI-) Calc. for [M-H]- 265.0129, found
265.0135. FTIR spectrum: Annexes B Figure S22.
Synthesis of BDGE/P-DA reference material: 0.97 g (10 meq ; EEW=97 g/eq) of 1,4-phenylenediacetic
acid was mixed with 1.19 g of BDGE at 90 °C to obtain a homogeneous light brown mixture. The mixture
was cast in aluminum molds and left overnight in an oven at 120 °C. The mixture was not cured and a
subsequent 1 h step at 180 °C was applied. The curing was checked by DSC and no remaining
exothermic phenomenon was observed.
Synthesis of BDGE/P-DAF vitrimer: 1 g (7.5 meq COOH, HEW=133) of P-DAF and 1.067 g (7.5 meq
epoxy, EEW=142) of butanediol diglycidyl ether (BDGE) were mixed together manually at room
temperature until P-DAF was totally dissolved. A viscous clear yellowish solution was obtained and
quickly cast in PTFE molds. The solution was left to gel at room temperature, typically for 8 hours.
Then, a brittle gel was obtained, unmolded and left for 3 h in an oven at 150 °C.
Instrumentation
reference was tetramethylsilane (TMS) with chemical shifts given in ppm. Samples were dissolved or
diluted in 0.5mL of CDCl3 or DMSO-d6 depending on their solubility.
124
FTIR: FTIR spectra were acquired on a ThermoScientific Nicolet iS50 FT-IR equipped with an attenuated
total reflectance cell (ATR). The data were analyzed using the software OMNIC Series 8.2 from Thermo
Scientific.
HRMAS: High resolution MAS NMR experiments were carried out on a Varian VNMRS 600 MHz
spectrometer equipped with a wide bore magnet (B0 = 14.1 T). Prior to HRMAS NMR experiments, the
BDGE and the P-DAF were manually mixed together in a beaker, and injected in a 4 mm quartz zirconia
HRMAS rotor insert with a 1 mL syringe. No solvent was added and the calibration was made using the
peaks at 72 and 26 ppm of the BDGE, as observed in liquid NMR. Experiments were performed at room
13
temperature. The sample spinning rate was 5 kHz. C NMR spectra were recorded at 20 °C, 38 kHz for
spectral width, 15 kHz for transmitter frequency offset, 0.1 s for acquisition time, 256 scans (NS) with
a 45 ° pulse (5.5 µs) and a relaxation delay at 1 s . 1H decoupling was applied during the whole
sequence. The outstandingly short overall acquisition time compared to usual 13C experiments allowed
to obtain spectra within a few minutes and to monitor qualitatively the polymerization reaction for
several hours.
Mechanical analysis: Dynamic Mechanical Analyses were carried out on Metravib DMA 25 with
Dynatest 6.8 software. Uniaxial stretching of samples (1 × 2 × 6 mm 3) was performed while heating at
a rate of 3 °C min−1 from −90 °C to 150 °C, at a f=1 Hz frequency. Relaxation experiments were
performed on a ThermoScientific Haake Mars 60 rheometer equipped with a electric heating cell and
a textured 8-mm plane-plane geometry. A 10 % torsional strain was applied on 8 mm diameter and
2 mm thickness circular samples, and the relaxation modulus evolution with time was monitored. The
curing checking experiment was performed on a TA Ares G2 at a given temperature (150 or 170 °C) by
applying a 0.1 % deformation at ω = 1 rad.s-1 under a normal force of 100 grams every 2 minutes, and
monitoring G’.
TGA: Thermogravimetric thermograms were recorded on a TA TGA G50 appliance using a 40 mL min-1
flux of synthetic air as purge gas. Approximately 10 mg of sample were used for each analysis. Ramps
from 20 to 500 °C were applied at a rate of 20 °C min-1.
DSC: Analyses were carried out using a NETZSCH DSC200F3 calorimeter. The calibration was performed
were recorded between -100 °C and the temperature of 2% mass loss Td2% at 20 °C min-1. The reported
values are the values measured during the second heating ramp.
125
Reprocessing: the material was cut into 1 x 1 x 1 mm3 pieces and then pressed in a PTFE mold for 1.5 h
at 150 °C under a 6 tons load using a Carver 3960 manual heating press.
Acknowledgements
This work was funded by the Institut Carnot Chimie Balard CIRIMAT (16CARN000801). The authors
would like to thank Dr. Marc Guerre and Dr. François Tournilhac for fruitful discussions.
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128
Conclusion du chapitre III
Dans ce chapitre, un vitrimère de transestérification activé par le fluor a été synthétisé à partir d’un
acide carboxylique difonctionnel et d’un époxy commercial difonctionnel. La formation d’un réseau
macromoléculaire tridimensionnel est liée à la réaction de transestérification, qui a lieu en même
temps que la polymérisation par ouverture de cycle de l’époxy par l’acide carboxylique. Grâce à la
transestérification, les macromolécules théoriquement linéaires se lient entre elles en libérant des
oligomères diglycol (tetraol) qui ne sont plus liés au réseau, que nous avons nommés « oligomères
sacrificiels ». Si la formation d’un tel réseau a déjà été décrite pour des thermodurcissables18 et pour
des vitrimères polyester catalysés,19 leur faisabilité à partir d’acides α,α-difluorés a été démontrée
dans ces travaux.
D’une part, un des intérêts majeurs de la synthèse du diacide α,α-difluorés P-DAF décrite est sa facilité
à être adaptée sur de plus grandes échelles. Cette synthèse permet déjà d’obtenir plusieurs dizaines
de grammes par lot (environ 40 g) à l’échelle du laboratoire, et les conditions de synthèse employées
ne présentent pas d’obstacle a priori à une montée en échelle pour produire de plus grandes quantités.
De plus, la méthode de purification par cristallisations et lavages successifs est également adaptée à
une production à grande échelle : elle est peu énergivore et est économe en solvants, en comparaison
d’une chromatographie sur colonne de silice par exemple.
D’autre part, la réaction mise en jeu présente des conditions de réaction plus vertueuses. En
particulier, le solvant employé est le DMSO, qui est non-toxique contrairement au DMF utilisé
précédemment (voir Chapitre II). Le temps et la température de réaction sont aussi plus faibles, 7 h à
60 °C, contre 40 h à 70 °C, ce qui permet un gain d’énergie. De plus, la réaction est plus robuste, les
réactifs sont introduits en même temps dans le réacteur et la réaction ne nécessite pas de précaution
particulière, contrairement à la synthèse du TPE-TAF (voir Chapitre II) qui nécessite un ajout progressif
du bromodifluoroacétate d’éthyle pour limiter les réactions secondaires. Toutefois, l’utilisation de
cuivre (0) en grande quantité reste un inconvénient majeur pour envisager une éventuelle production
industrielle. En effet, le cuivre utilisé lors de la réaction n’est pas totalement récupéré en fin de
réaction, ce qui entraîne un coût important en matières premières. De plus, les sels formés peuvent
être toxiques.20 Des travaux d’optimisation pourraient être envisagés afin de réduire la quantité de
18
19
20
Bisson, M.; Boulevert, E.; Marliere, M.; Oberson Geneste, D. Cuivre et Ses Composés - Fiche de Données
Toxicologiques et Environnementales Des Substances Chimiques; INERIS 2019.
129
cuivre nécessaire pour cette réaction et de réutiliser au maximum les effluents de cette réaction. Le
recours à d’autres métaux en quantités catalytique peut aussi être envisagé.
Pour finir, la disponibilité et la diversité des synthons difonctionnels est plus importante que celle des
synthons trifonctionnels ou de fonctionnalité supérieure. La possibilité de former des structures
tridimensionnelles à partir d’acides α,α-difluorés difonctionnels permet d’envisager l’utilisation de ces
synthons difonctionnels voire le recours à d’autres voies de synthèse, ce qui permettrait de diversifier
les structures des monomères accessibles et d’étudier leur influence sur les propriétés des matériaux
qui en sont issus.
130
vitrimères biosourcés sans catalyseur
CHAPITRE IV : TRANSPOSITION DE LA SYNTHESE D’α,α-
DIFLUOROACIDES AU RESVERATROL POUR LA SYNTHESE
DE VITRIMERES BIOSOURCES SANS CATALYSEUR
131
vitrimères biosourcés sans catalyseur................................................................................................. 131
Introduction du chapitre IV ............................................................................................................. 133
From vineyards to 100 % resveratrol materials: α-CF2 activation in biobased catalyst-free vitrimers
......................................................................................................................................................... 135
Abstract ....................................................................................................................................... 135
Introduction................................................................................................................................. 135
α,α-Difluoro Carboxylic Acid Monomer Synthesis .................................................................. 137
Trifunctional Epoxy Synthesis .................................................................................................. 138
Polymerization and Curing ...................................................................................................... 138
Vitrimer Characterization ........................................................................................................ 139
Conclusion ................................................................................................................................... 144
Experimental section ................................................................................................................... 145
Materials.................................................................................................................................. 145
Synthetic Procedures............................................................................................................... 145
References ................................................................................................................................... 148
Conclusion du chapitre IV................................................................................................................ 153
132
Introduction du chapitre IV
Dans le contexte actuel d’intérêt croissant pour la préservation de l’environnement, l’utilisation de

matériaux polymères soulève de plus en plus d’inquiétudes quant à la gestion de leur fin de vie. Les
vitrimères présentent un élément de réponse original au problème de recyclage des matériaux
thermodurcissables, puisque leur remise en œuvre est possible par certaines techniques de recyclage
mécanique. En revanche, l’utilisation de catalyseurs dans ces matériaux n’est pas souhaitable.
L’utilisation de groupements activants α,α-difluorés a permis de synthétiser un vitrimère de
transestérification sans catalyseur, capable d’être remodelé plusieurs fois (voir Chapitre II). Par la suite,
des monomères acide difonctionnel et époxy difonctionnel ont également permis d’obtenir un
matériau de type vitrimère sans catalyseur, et d’ouvrir la voie à d’autres structures potentielles.
Si l’anticipation de la fin de vie des matériaux polymères est extrêmement importante, la question des
ressources utilisées dans leur fabrication n’en demeure pas moins primordiale. Aujourd’hui, 99 % des
polymères sont fabriqués à partir de matières premières d’origine fossile, en particulier du pétrole.21
Cette dépendance au pétrole pose deux problèmes majeurs. D’une part, les filières de production de
polymères sont dépendantes du prix du pétrole, qui fluctue en fonction de l’offre et de la demande,
mais aussi d’évènements géopolitiques. D’autre part, les réserves fossiles sont par définition finies, ce
qui implique que d’autres sources de matières premières devront être trouvées à échéance. Par
conséquent, la recherche dans le domaine des polymères synthétisés à partir de synthons biosourcés
s’est fortement développée ces dernières années. 22 , 23 Les vitrimères n’échappent pas à cette
tendance, et de nombreux exemples de vitrimères biosourcés ont été décrits et publiés dans des
articles scientifiques, dans le but de synthétiser des polymères toujours plus vertueux, de la matière
première utilisée jusqu’à leur fin de vie.24
Un des enjeux actuels des vitrimères est d’obtenir de hautes Tg avec des propriétés mécaniques
adaptées à des applications structurales, tout en conservant la capacité de ces matériaux à être remis
en œuvre.12 Ce contexte a amené l’idée de réutiliser la réaction de synthèse du TPE-TAF et de l’adapter
à un polyphénol biosourcé. Le resvératrol, un triphénol extrait de la vigne, a été choisi pour ses
similitudes structurales avec le TPE, et pour sa disponibilité. La forte densité en cycle aromatique a été
mise à profit afin d’obtenir un matériau avec une haute Tg. Pour favoriser encore plus cette propriété,
l’époxy utilisé a lui aussi été synthétisé à partir du resvératrol, pour obtenir un monomère
21
Avérous, L. ; Caillol, S. L'Actualité Chimique, Société chimique de France, 2021, 95-100.
22
Avérous, L. L'Actualité Chimique, Société chimique de France, 2013, 375-376, 83-90.
23
Nakajima, H.; Dijkstra, P.; Loos, K. Polymers 2017, 9, 523.
24
Vidil, T.; Llevot, A. Macromol. Chem. Phys. 2022, 223, 2100494.
133
trifonctionnel. La haute fonctionnalité moyenne des deux monomères, de l’ordre de 3, a permis la
formation d’un réseau dense et d’un matériau rigide, qui pourrait être adapté à des applications telles
que les composites par exemple (Figure F).
Figure F. Synthèse d’un vitrimère de transestérification sans catalyseur à base de resvératrol
134
From vineyards to 100 % resveratrol materials:
α-CF2 activation in biobased catalyst-free vitrimers
Florian Cuminet,a,b Sébastien Lemouzy,a Éric Dantras,b Sylvain Caillol,a Éric Leclerca and Vincent
Ladmiral*a
a
b
CIRIMAT, Université Toulouse 3 Paul Sabatier, Physique des Polymères, 118 Route de Narbonne, 31062
Toulouse, France
Abstract
Vitrimers are a class of polymers bridging the gap between resistant crosslinked thermosets and
recyclable linear thermoplastics. The first vitrimer was a polyester network requiring relatively high
catalyst loadings to be reshaped. This feature raises concerns about catalyst potentially leaching out
of the materials and accelerated ageing upon reprocessing cycles. Recently, strategies such as
activation of the exchange reaction by inductive effects or neighboring group participation were
implemented in vitrimers allowing to produce reshapable materials which do not require catalysts.
Hence, α,α-difluoro esters proved to be very prone to transesterification thanks to fluorine exceptional
properties, in particular its very high electronegativity. This feature implemented in polyester vitrimers
permitted to synthesize reshapable catalyst-free highly crosslinked networks. Moreover, this principle
initially designed on petrosourced monomers is here successfully adapted to resveratrol, a biobased
polyphenol found in particular in grapes. The material presented here is fully bio-based, catalyst-free,
durable and recyclable and features a high Tg.
Introduction
Vitrimers are a class of polymer materials which exhibits excellent mechanical properties and the
ability to be recycled mechanically.1,2 Ideally, they combine the best of thermoplastics, which are often
easily recyclable, and thermosets, which are endowed with very good mechanical properties and
resistance at high temperature. These exceptional properties come from their structure. While
thermoplastics are essentially a network of entangled linear chains which cohesion is due to weak
bonds, thermosets are a tridimensional network made of strong covalent bonds.3 Vitrimers are also
3D networks made of covalent bonds, but these bonds feature a singular property: they can exchange
with each other, or with free reactive groups on the polymer segments, by a degenerate chemical
equilibrium.4–7 These exchanges usually activated by heat are accountable for the vitrimers flow and
recyclability at high temperature. Vitrimers were invented a decade ago, and first illustrated with
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polyesters able to flow thanks to a transesterification reaction.8 They are of particular interest in the
field of composites, in which the polymer matrix needs high mechanical performances and thermal
resistance.9,10 Indeed, composites are difficult to recycle, in particular for thermoset-based composites,
but the recovery of the valuable fibers without destroying them remains a challenge.11,12 Vitrimers,
because they can be reshaped, or in some cases, can undergo solvolysis, bring a solution to this issue.13–
15
However, one of the main obstacles to the implementation of vitrimers in composites is the difficulty
to obtain rigid materials with high Tg, which remain reprocessable on reasonable time and temperature
scales.16–18 Such materials with excellent mechanical properties are desirable in structural application,
for instance in aerospace, automotive or engineering applications.19 Epoxy-anhydride vitrimers
catalyzed by zinc (II) with Tg values upto 140 °C were described, but they required hard reprocessing
conditions, at 250 °C under 500 bars.20 A epoxy-acid system catalyzed by Sn(II) with 2 equivalent of
epoxy compared to the acid allowed to reach a Tg at 231 °C thanks to the homopolymerization of the
epoxy.21 However, the resulting ether bonds are permanent and might decrease the material
reprocessability. Furthermore, in the case of transesterification vitrimers, an external catalyst is usually
required to accelerate the transesterification reaction, so that the material may flow at a measurable
timescale and be recycled.22 The use of catalysts such as zinc(II) and triazabicyclodecene (TBD) raises
concerns about potential leaching of the catalyst out of the material, and premature ageing of the
vitrimer after several recycling/reshaping cycles.23–25 For these reasons, the use of catalyst-free
vitrimers is preferable. A first strategy is to use other exchange reactions. For instance, vinylogous
urethanes were used to make vinyl-based vitrimers with a Tg at 110 °C.26 Gamardella et al. synthesized
vitrimers based on polythiourethanes transcarbamoylation, with a Tg at 130 °C. Disulfides were used
to make vitrimers with Tg at 129 °C27 and recently at 175 °C for aerospace applications.28 However, the
dynamic behaviour of this last material was low, as a plateau at 20 % is visible at the end of stress
relaxation experiments. Imine bonds were also used to make catalyst-free vitrimers with high Tg,
between 100 and 150 °C29–31 and even upto 274 °C with high thermal resistance.32 Nishimura et al.
reached a Tg at 125 °C with a silyl ether-based vitrimer.33 Dynamic Si-O-Ph bonds were also used in a
polybenzoxazine vitrimer with a Tα around 280-300 °C. Several other strategies were described to make
catalyst-free vitrimers, in particular in the case of transesterification vitrimers. Hyperbranched
vitrimers featuring a loose network allowed catalyst-free reprocessing, but their mechanical properties
were fairly limited.34 A high concentration of free hydroxyl groups in the network also accelerates the
transesterification, but it implies limitations in terms of accessible monomers and network structures
and properties, and may increase the water intake of such materials.35,36 The kinetics of the exchange
reaction can also be increased by an activating group, linked to the network, in proximity to the
exchangeable bonds.37,38 In particular, fluorinated esters were recently proven to undergo fast
transesterification without the recourse to an external catalyst, both in solution39 and in vitrimers.40,41
136
Furthermore, in a context of increasing tension on crude oil supply and price volatility, the pursuit of
biobased materials is of booming interest to increase polymers sustainability.42–44 The first vitrimer was
partly biobased as the polyfunctional carboxylic acid used was made from dimers and trimers of fatty
acids.8 Many naturally occurring building blocks can be used in the synthesis of vitrimers, such as
lignins, phenols, furans, oils, polysaccharides, carboxylic acids or natural rubber.45 In particular, several
examples of biobased vitrimers based on natural phenols such as vanillin,46–48 eugenol49,50 or cardanol51
for instance have been reported. However, only few of them exhibit a Tg over 100 °C and high thermal
stability, two precious properties for biobased vitrimers.52 Liu et al. reported a biobased vitrimer
synthesized from succinic acid and a trifunctional epoxy based on vanillin and guaiacol.53 This
transesterification vitrimer was catalyzed by Zn(II). Protocatechuic acid, was used as an alternative to
BADGE to make a Zn(II)-catalyzed vitrimer by reaction with succinic anhydride, with a Tg of 157 °C.
Finally, two examples of high-Tg catalyst-free biobased vitrimers were reported. The first example is
based on acetal exchange, with a Tg up to 121 °C.54 The other example is based on transesterification
activated by tertiary amines in polybenzoxazines, with Tg ranging from 143 to 193 °C. Many of the high-
Tg vitrimers reported so far are based on monomers featuring aromatic structures. Biobased phenols
and furans,45 thanks to their aromatic cycles and often compact structures, can provide high
crosslinking density, rigidity, high Tg and thermal resistance to vitrimers.
In the work presented here, a catalyst-free, high Tg biobased transesterification vitrimer was
synthesized from resveratrol, a biobased triphenol mainly found in grapes, peanuts and a plant called
Japanese knotweed (Reynoutria japonica).55,56 The goal was to achieve high mechanical properties and
reach high Tg thanks to the high aromatic carbon content of this bioresource. Resveratrol was
functionalized to prepare two building blocks: a trifunctional epoxy, and a trifunctional α,α-
difluorocarboxylic acid. The rationale was that the ring-opening polyaddition of these building blocks
would lead to a dense network, endowed with high Tg and transesterification capability via fluorine
group activation.
Results and Discussion

α,α-Difluoro Carboxylic Acid Monomer Synthesis
α,α-Difluoro carboxylic acids were proven to activate the transesterification reaction in polyester
networks, without the need for any catalyst, thus enabling the synthesis of catalyst-free
transesterification vitrimers.39,41 A biobased tris α,α-difluoro carboxylic acid was synthesized from
resveratrol (a biobased compound extracted from grapes). Starting from the triphenol, a 2-step
synthesis lead to the desired monomer. Resveratrol underwent nucleophilic substitution with ethyl
bromodifluoroacetate at 70 °C for 40 hours. After a filtration on silica gel, the expected α,α-difluoro
137
triester (RvOEt) was obtained in 87 % yield. The isolated product then underwent facile saponification
to yield, after appropriate workup, the desired α,α-difluoro triacid (RvOH-TAF) as a brown waxy solid
with an overall yield of 85 % and a biobased carbon content of 70 % (Scheme).
Scheme 1. 2-step synthesis of RvOH-TAF from resveratrol
Trifunctional Epoxy Synthesis

In parallel to the modification of resveratrol into an activated trifunctional acid, the triphenol was
functionalized with epichlorohydrin to yield a trifunctional epoxy (Scheme 2). The glycidylation of
phenols is very efficient, easily scalable and was extensively described already on biobased phenols
including resveratrol.57–60 The targeted building block RvOGly was prepared in large quantities (> 40g)
by simple reaction of resveratrol with epichlorohydrin and tetrabutylammonium bromide (TBAB).
RvOGly features high functionality (EEW = 185 g/eq) and a 52 % aromatic carbon content, close to the
57 % value of bisphenol A diglycidyl ether (BADGE). These properties are interesting to obtain materials
with high Tg.
Scheme 2. Synthesis of epoxydized resveratrol RvOGly
Polymerization and Curing

RvOGly and RvOH-TAF were mixed at room temperature (ca. 20 °C) in PTFE molds to avoid any transfer
step, because of the fast gelation of the mixture even at room temperature (ca. 20°C). The reaction
between both monomers was exothermic and the mixing step needed to be performed on small scale,
typically 1-2 g, to better control the heat transfer and to avoid gelation before complete mixing. This
fast gelation is caused by the strong activation of the carboxylic acids toward the epoxy opening by the
fluorine atoms. A reaction on larger scales may benefit from the addition of a solvent to control the
heat release. This pathway was not explored in this study though, to avoid the plasticizing effect of
138
potential residual solvent and its effect on mechanical properties. The mixture formed a material
within a few minutes, and was left at room temperature for 3 h.
Figure 1. Polymerization of RvOGly and RvOH-TAF resulting into the Vm-RvOH material, insert : optical image of Vm-RvOH
(1 cm x 4.5 cm x 0.3 cm)
The curing was checked by DSC (Annexes C Figure S9). On the first heating ramp, an exothermic
enthalpy is visible starting from 150 °C. On the second ramp this phenomenon does not appear and a
Tg is visible in the 100-130 °C range. The exothermic phenomenon was attributed to a residual
polymerization occuring when the material is heated higher than 150 °C. Thus, a 1 h curing step at 150
°C was applied and the DSC analysis was repeated (Annexes C Figure S10). After this curing step, two
consecutive heating ramps overlaid almost perfectly. There was no sign of ongoing polymerization by
DSC. The curing was also checked by mechanical analysis. The evolution of the modulus was monitored
with time at 150 °C. The stabilization of the value happened after 7 h (Annexes C Figure S11). Therefore,
the materials were left 10 h at 150 °C to ensure complete polymerization, resulting into a hard brittle
dark brown material (Vm-RvOH, Figure 1). The resulting material exhibits a 85 % biobased carbon
content.
Vitrimer Characterization
After complete polymerization three consecutive DSC ramps were carried out on the resulting
material. The first ramp was meant to erase the thermal history of the material, then the thermograms
of the second and third ramps overlaid perfectly, and no residual exotherm was observed. The T g is
visible in the 92-125 °C range, but the transition is broad and the ΔCp is low (0.241 J.g-1.K-1). Therefore,
the Tg was determined as the minimum of the heat flow derivative, at 117 °C (Annexes C Figure S12
and Table 1). The high Tg compared to previously reported covalent adaptable networks40,41 was
expected because of the high aromatic carbon content of the polymer (52 % aromatic carbon content).
This value of Tg is comparable to the value of the catalyst-free biobased vitrimer synthesized from lignin
by Moreno et al.54 (Tg = 121 °C), but lower than the value of the catalyst-free biobased polybenzoxazine
139
vitrimers recently reported by Adjaoud et al. (Tg from 143 to 193 °C).17 This last case benefits from a
50 % aromatic carbon content, close to the 52 % value reported here, but also a 17 % cycloaliphatic
carbon content caused by the isosorbide core of its monomer, which brings additional rigidity. Thus,
the performance of Vm-RvOH in term of Tg is consistent with its structure.
A DMA analysis was also performed to confirm the results observed by DSC, and to characterize the
mechanical properties of the material (Annexes C Figure S13). Tα was determined as the maximum of
the loss modulus E” at 94 °C. As observed by DSC, the mechanical relaxation was broad and the
temperature of the maximum of tan(δ) was 117 °C, which is consistent with the Tg measured by DSC.
The moduli on the glassy plateau and on the rubbery plateau were respectively E’G = 2.1 GPa and E’R =
46 MPa. The modulus on the glassy plateau is comparable to values reported for a material made from
epoxydized resveratrol and 4,4’-diaminodicyclohexylmethane (PACM),60 and with the value of a lignin-
based catalyst-free vitrimer.54 For the modulus on the rubbery plateau, the value for Vm-RvOH is 14
times lower than the epoxydized resveratrol-PACM thermoset,60 but still in the 11-73 MPa range
reported for other high-Tg vitrimers,18,21 included for aerospace applications.28 Additionally, this value
is 2.5 times higher than the value reported on the similar α,α-difluoro vitrimer previously reported.41
At temperatures over 200 °C, the modulus decreases from the rubbery plateau. This could be the
mechanical manifestation of a beginning of flow.
The thermal stability of Vm-RvOH was assessed by TGA under nitrogen. The 2 % and 5 % degradation
temperatures Td2% and Td5% were 237 °C and 275 °C respectively (Annexes C Figure S14 and Table ). The
residue at 900 °C under nitrogen was 28.9 % of the initial weight. The Td5% value is low compared to
the values superior to 300 °C reported for other high-Tg vitrimers,18,31,32,61–63 but still higher than the
value at 224 °C for a lignin-based catalyst-free vitrimer.54. The residue (char yield) was comparable with
an epoxy vitrimer in the same range of Tg.30 The relatively high char yields depends essentially on the
monomers structures, thanks to the high aromatic carbon content (52 %).
Solubility tests were performed in THF (a good solvent for both resveratrol-based precursors). After
24 h under agitation, a swelling of 278 % and an insoluble fraction of 73 ± 2 % were measured (Table
1). These results prove the formation of a 3D crosslinked material.
Table 1. Physicochemical main properties of Vm-RvOH
Max Gel Swelling Residue Weight

Tg Tα E’G E’R Td 2% Td 5%
tan(δ) content index (char) loss
(°C) (°C)a (GPa)b (MPa)c (°C)e (°C)e
(°C) (%)d (%)d (%)f (%)g
117 94 117 2.1 46 73±2 278 237 275 28.9 2.9
a
determined as the maximum of E” | at Tα – 50 °C | at Tα + 50 °C | in THF | N2 atmosphere | f at
b c d e
900 °C, N2 atmosphere | g after 6 h at 170 °C, air atmosphere
140
Reprocessing trials were performed on Vm-RvOH by compression molding. In a previous study on a
similar system, the reprocessing temperature was set at 100 °C, 50 °C above the T g , under 16 bars.41
At 170 °C, the material could be reprocessed in 2 h under 80 bars (Figure 3). The reprocessing
temperature is 50 °C above the Tg, like the previous system. The pressure applied is lower than for
many high-Tg vitrimers, which often require a pressure of at least 100 bars.27,31,62–64
Figure 2. Vm-RvOH reprocessing for 2 h at 170 °C under 80 bars (scale of pristine material: 1 cm x 4.5 cm x 0.3 cm, diameter
of recycled materials: 1 cm)
The thermal stability of the material at this reprocessing temperature was assessed. An isothermal
experiment at 170 °C was performed in air atmosphere, to simulate the reprocessing conditions
(Annexes C Figure S15). After 2 h, the relative mass loss was 2.48 %. Between 2 h and 4 h the additional
mass loss was 0.29 % and between 4 h and 6 h, 0.47 % to attain an overall mass loss after 6 h around
3 %. This value is small, but cannot be ignored. Reprocessing trials were made at 150 °C under 80 bars
to lower the risk of potential degradation, but the resulting materials remained very inhomogeneous
after 4 h. Therefore, the DMA analysis of the material need to be assessed and compared before and
after reprocessing at 170 °C, to monitor a possible degradation. Two consecutive reprocessing cycles
at 170 °C were made, and the mechanical properties after each cycle were studied by DMA (Figure 3).
141
Figure 3. DMA thermograms (a) E', (b) E" and (c) tan (δ) of Vm-RvOH pristine, after one reprocessing cycle and after two
reprocessing cycles
142
The value of the modulus on the glassy plateau remains quasi-constant. The value of Tα decreased from
94 to 75 °C after the first reprocessing cycle, and remained at 76 °C after the second cycle (Table 2).
Similarly, the values of the modulus on the rubbery plateau E’R decreased from 46 to 23 MPa with the
first reprocessing, and then remained the same after the second cycle. These results suggest a
decrease of the crosslinking density upon the first cycle, which might be due to a slight hydrolysis at
the reprocessing temperature. Then the crosslinking density remains constant for the subsequent
cycle, thus the hydrolysis remains very limited. This is likely due to the aromatic carbon content (56 %
aromatic carbon) which brings a hydrophobic behavior to the material and balances the hydrophilic
behavior brought by the esters and hydroxyl groups. Moreover, the high Tg probably plays an
important role, as the water uptake is very limited when the material is in the glassy state, but much
easier in the rubbery state. Indeed, in the rubbery state, the mobility of the polymer makes easier the
penetration of water in the network. Finally, the results obtained by DMA were confirmed by DSC, with
a Tg of 117 °C for the pristine material, 97 °C after the first reprocessing and 91 °C after the second
cycle.
Table 2. Evolution of the thermomechanical properties of Vm-RvOH with reprocessing cycles.
Tg Tα Max tan(δ) E’G E’R

Reprocessing Cycle a
(°C) (°C) (°C) (GPa) (MPa)c
b
Pristine 117 94 117 2.1 46

Reprocessed once 97 75 101 2.4 23
Reprocessed twice 91 76 104 2.7 23
a
determined as the maximum of E” | b at Tα – 50 °C | c at Tα + 50 °C
The flow from the rubbery plateau was studied by isothermal stress-relaxation experiments to
evaluate the kinetics of this phenomenon (Annexes C Figure S16). The modulus of the material was
monitored under a 0.3 % strain between 170 and 210 °C. For all temperatures, a plateau around 5 %
was reached at the end of the relaxation experiment. This is likely due to a proportion of non-
exchangeable crosslinks in the network. The presence of such permanent crosslinks can be explained
by a minor homopolymerization of the epoxy.21 Indeed, the strong acidity of α,α-difluoro acids may
favor this reaction.21
The stress-relaxation experiments were normalized, and a Kohlrausch-Williams-Watts “stretched

exponential” equation with an added constant y0 was used to fit the experimental data (Figure 4 and
Annexes C Table S1). The constant y0 shifts the final plateau of the relaxation, and the stretch
parameter β describes the width of the distribution around the value of the relaxation time τKWW. The
closer to 1 β is, the narrower the distribution is. This parameter describes the heterogeneity in the
vicinity of the exchangeable bond. Here, the values of β ranged between 0.486 at 170 °C and 0.797 at
210 °C and increased with the temperature. With the increase of the temperature, the environment is
143
more homogeneous, the values of beta tend towards 1.The constant added y0 allowed a better
accuracy on the fitting, with 0.99264≤R²≤0.99639 without constant and R² = 0.99937 to 0.99979 with
a constant. The mean value of this constant y0 (Annexes C Table S1) is 0.054 (values between 0.043
and 0.064). Thus, a mere 5 % of the applied stress is not relaxed because of the permanent crosslinks,
which does not impede the reprocessing of the material.
Figure 4. Normalized stress–relaxation curves from 170 to 210 °C with 10 °C steps fitted with the Kohlrausch–Williams–
Watts equation (KWW) and τKWW relaxation times reported in the Arrhenius diagram (inset, R² = 0.983)
The relaxation times τKWW obtained for each temperature were plotted in an Arrhenius diagram (Figure
4 inset). A linear fit was obtained (R² = 0.983) and the flow activation was calculated from the slope Ea
= 107 kJ mol-1, in accordance with the 29-163 kJ mol-1 range reported for transesterification vitrimers.38
This Ea is higher than that reported in previous studies of transesterification vitrimers activated by
fluorinated groups (67-77 kJ mol-1).40,41 It is likely caused by the higher crosslinking density and lower
mobility at the local scale of Vm-RvOH.
Conclusion
A catalyst-free polyester vitrimer was synthesized from resveratrol, a biobased triphenol found mainly
in grapes. This material exhibits a high biobased carbon content of 85 %. A trifunctional epoxy and a
trifunctional α,α-difluoro carboxylic acid were synthesized by functionalization of resveratrol with
epichlorohydrin and ethyl bromodifluoroacetate, respectively. When these two resveratrol derivatives
were mixed together, the ring opening polymerization of the epoxy by the acid occurred at room
temperature due the activation of the acid by the fluorine atoms. After a curing step at 150 °C, a rigid
144
slightly brittle material was obtained. This material exhibited a high Tg (117 °C), comparabled to other
high-Tg vitrimers,27,30,65,66 which makes it relevant for composite application for instance. The synthesis
described could be adapted to other biobased compounds with similar structures and higher
functionality, such as quercetin, to reach even higher Tg values. Moreover, the α,α-difluoro esters can
exchange with free hydroxyl groups without any added catalyst. This feature allows the efficient
reprocessing of the material at 170 °C for 2 h by compression molding. Two recycling cycles were
achieved and the mechanical performance remained worthwhile for structural applications This
material is one of the first high-Tg catalyst-free biobased vitrimers.17,54
Experimental section
Materials
Trans-Resveratrol (Fluorochem, 98 %), 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU, Fluorochem, 98 %),
ethyl bromodifluoroacetate (Fluorochem, 98 %), epichlorohydrin (Sigma-Aldrich, ≥ 99 %),
tetrabutylammonium bromide (TCI, > 98 %), benzophenone (Avocado Research Chemicals Ltd, 99 %),
were used as received. Dimethylformamide (DMF), tetrahydrofuran (THF) and NaHCO3 were supplied
by VWR Chemicals, diethyl ether and pentane were supplied by Carlo Erba, ethyl acetate was supplied
by Fisher Chemicals, acetonitrile was supplied by Acros Organics, sodium hydroxide and chlorhydric
acid ≥ 37 % were supplied by Honeywell Fluka. Deuterated solvents were supplied by Eurisotop (99.8
%).
Synthetic Procedures
“RvOEt” compound: Trans-Resveratrol (3,5,4′-trihydroxy-trans-stilbene, 2.3 g, 10 mmol, 1 eq) was
dissolved in dry DMF (60 mL, 0.16 M). 1,8-Diazabicyclo [5.4.0] undec-7-ene (DBU, 7.5 mL, 50 mmol, 5
eq) was added in one portion and the reaction was heated to 70 °C. Ethyl bromodifluoroacetate (6.4
mL, 50 mmol, 5 eq) was then added via a syringe pump at a rate of 5.0 mL.h -1 and the reaction was
stirred at 70 °C for 40 h. The crude mixture was cooled to room temperature, diluted with H2O (300
mL), and extracted 5 times with Et2O (5 x 50 mL). The combined organic layers were washed twice with
water and once with brine, dried with Na2SO4, filtered, and concentrated under reduced pressure to
obtain a dark red oil. The crude mixture was purified by filtration on silica gel using pentane/ethyl
acetate (1:1) to afford the pure triester (6 g, 87 %, clear brown viscous liquid).
Triester RvOEt characterizations (NMR spectra in Annexes C Figures S1 to S3: 1H NMR 400MHz CDCl3:
δ 7.50 (m, 2H, aromatic protons), 7.25 – 7.21 (m, 4H, aromatic protons and C=C), 7.11 – 6.95 (m, 3H,
aromatic protons), 4.40 (2q, 3J = 8 Hz, 6H, OCH2CH3), 1.37 (2t, 3J = 8 Hz, 9H, OCH2CH3). 19F NMR 377
MHz, CDCl3: δ -76.30, -76.53. 13C NMR 101 MHz, CDCl3 : δ 159.9 (m, CO2Et), 150.3 (m), 150.2 (m), 140.1,
134.7, 130.3, 128.1, 127.1, 122.0, 117.4, 114.1 (t, 1JC-F = 1021 Hz, OCF2), ), 114.0 (t, 1JC-F = 1025 Hz, OCF2),
145
64.0 (O-CH2CH3), 63.9 (O-CH2CH3), 14.0 (O-CH2CH3), 14.0 (O-CH2CH3). HRMS (ESI+) Calc. for [M+H]+
595.1397, found 595.1394.
“RvOH-TAF” compound: In a 250 mL round bottom flask, 6 g of triester were dissolved in acetonitrile
(90 mL). Then, a 5M aqueous solution of NaOH (12.5 g in 62 mL) was added slowly at room
temperature, and the mixture was stirred for 3 h. 200 mL of a saturated NaHCO3 solution was added
to the mixture and the aqueous layer was washed with 100 mL of diethyl ether. The organic layer was
extracted with 50 mL of saturated NaHCO3 solution, and the gathered aqueous layers were acidified
to pH=1 using 2M HCl. Finally, the acidified aqueous layer was extracted with 3 x 100 mL of diethyl
ether, and the solvent was removed under high vacuum to afford 5 g of the desired triacid as a brown
waxy solid (yield 98 %, yield over the two steps η = 85 %, purity > 98 % estimated from 1H NMR
spectrum).
Trifunctional acid TPE-TAF characterizations (NMR spectra in Annexes C Figures S4 to S6): 1H NMR
400MHz d6-DMSO: δ 7.72 (d, 2H), 7.59-7.13 (m, 5H, aromatic protons and C=C), 7.00 (s, 1H). 19F NMR
377 MHz, d6-DMSO: δ -76.16, -76.50. 13C NMR 101 MHz, d6-DMSO: δ 161.0 (COOH, t, 2JC-F = 39.0 Hz),
160.7 (COOH, t, 2JC-F = 39.0 Hz), 150.4 (ipso-ArC-O), 149.4, 140.8, 135.0, 130.6, 128.7, 127.1, 121.8,
117.3, 114.64 (OCF2, t, 1JC-F = 272 Hz), 114.56 (OCF2, t, 1JC-F = 274 Hz), 113.4. HRMS (ESI+) Calc. for
[M+H]+ 511.0458, found 511.0468. HRMS (ESI-) Calc. for [M-H]- 509.0313, found 509.0319.
“RvOGly” compound (glycidylation of resveratrol): In a 500 mL round bottom flask, 20.56 g (90 mmol,
1 eq) of resveratrol was dissolved in 82 mL (96 g, 1.04 mol, 12 eq) epichlorohydrin at room temperature
under magnetic stirring. The flask was then equipped with a condenser and heated to 100 °C. 1.56 g
(4.8 mmol, 0.05 eq) of tetrabutylammonium bromide “TEBAB” was added and the reaction was left to
proceed under stirring at 100 °C for 4 h. Then, the reaction medium was cooled to room temperature
and 20 wt% aqueous solution of NaOH and TEBAB was added (21 g NaOH + 1.56 g TEBAB in 106 mL
deionized water). The mixture was left 1.5 h under vigorous stirring. The mixture was then diluted with
600 mL of water and extracted with 3 x 300 mL ethyl acetate. The organic layers were gathered,
washed with 2 x 200 mL brine, dried on magnesium sulfate. The solvent was evaporated under reduced
pressure to afford 42.3 g of a clear yellow viscous oil.
Epoxydized resveratrol RvOGly characterizations (NMR spectra in Annexes C Figures S7 and S8): 1H
NMR 400MHz d6-acetone: δ 7.52 (d, 2H), 7.29-6.99 (dd, 2H, C=C), 6.97 (m, 2H), 6.81 (d, 2H), 6.51 (t,
1H), 4.34 and 3.86 (3+3H), 3.33 (3H), 2.86 and 2.73 (3+3H). 13C NMR 101 MHz, d6-acetone: δ 160.9,
159.3, 140.7, 131.0, 129.5, 128.6, 127.1, 115.5, 106.0, 101.3, 70.1, 50.6, 44.4.
146
Determination of the Epoxy Equivalent Weight (EEW): The EEW of the RvOGly was evaluated by NMR
titration using benzophenone as standard in deuterated chloroform (experimental details are given in
Annexes C Section A).
“TPE-TAF/BDGE” vitrimer: Typically, 1 g (2.0 mmol, 5.9 meq COOH, HEW = 170 g/eq) of RvOH-TAF was
quickly mixed manually directly in a PTFE mold with 1.07 g (5.9 meq epoxy, EEW = 185 g/eq) of RvOGly
at room temperature (ca. 20 °C) until a light brown viscous homogeneous mixture was obtained. The
mixture was left at least 3 h at room temperature for gelation. The resulting material (TPE-TAF/BDGE)
was then removed from the molds and cured 10 h at 150 °C.
Instrumentation
reference was tetramethylsilane (TMS) with chemical shifts given in ppm. Samples were diluted in
0.5 mL of CDCl3, DMSO-d6 or acetone-d6 depending on their solubility.
Mechanical characterizations: temperature ramps in elongation mode were carried out on Netzsch
DMA 242 E Artemis cooled by liquid nitrogen. Uniaxial stretching of samples (1 × 3.5 × 12 mm 3) was
applied while heating at a rate of 3 °C min−1 from −50 °C to 270 °C, keeping the frequency at 1 Hz.
Curing monitoring experiments were performed on a ThermoScientific Haake Mars 60 rheometer
equipped with a Peltier heating cell and a 8-mm plane-plane geometry. A 0.1 % deformation was
applied to 8 mm diameter and 2 mm thickness circular samples at ω = 1 rad.s-1 under a normal force
of 100 grams every 2 minutes, and G’ evolution over time was monitored. Stress relaxation
experiments were performed with a 0.3 % torsional strain applied on 8 mm diameter and 2 mm
thickness circular samples, and the rubbery modulus evolution with time was monitored.
TGA: thermogravimetric thermograms were recorded on a TA TGA G50 instrument using a 40 mL min-1
flux of nitrogen or synthetic air as purge gas. Approximately 10 mg of sample were used for each
analysis. Ramps were applied at a rate of 20 °C min-1.
DSC: analyses were carried out using a NETZSCH DSC200F3 calorimeter. The calibration was performed
were recorded at 20 °C min-1. The reported values are the values measured during the second heating
ramp.
Reprocessing: the material was grinded with a manual stainless steel coffee grinder (for DSC and DMA)
or cut into 6 to 9 mm3 pieces (for pictures) and then pressed in stainless steel molds for 2 h at 170 °C
under 200 bars of pressure using a manual heating press.
147
Acknowledgements
This work was funded by the Institut Carnot Chimie Balard CIRIMAT (16CARN000801).
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Conclusion du chapitre IV
L’étude décrite dans ce chapitre porte sur la fonctionnalisation du resvératrol, un triphénol naturel
extrait de la vigne. D’une part, ce triphénol a été transformé en acide α,α-difluoré trifonctionnel par
réaction avec le bromodifluoroacétate d’éthyle. D’autre part, le resvératrol a également été
transformé en époxy trifonctionnel par réaction avec l’épichlorhydrine, qui peut être biosourcée. La
réaction de ces deux composés à température ambiante a conduit à la formation d’un matériau brun,
fragile et rigide après cuisson à 150 °C pendant 10 h. L’utilisation de monomères avec une forte densité
en carbones aromatiques et d’une fonctionnalité moyenne élevée a permis l’obtention d’une Tg élevée
de l’ordre de 100 à 120 °C.
L’obtention d’une Tg élevée permet d’envisager une utilisation dans des applications telles que des
composites plus structuraux, pour lesquelles le recyclage reste un défi à l’heure actuelle. Les atomes
de fluor en position alpha de l’ester on encore une fois montré leur capacité d’activation pour rendre
ce matériau dynamique. En effet, deux cycles de remise en œuvre ont été effectués. Si le premier cycle
engendre une légère diminution des propriétés mécaniques, notamment de la Tα, celle-ci reste
contenue et ne semble pas affecter le matériau après un deuxième cycle de remise en œuvre. Une
telle capacité de remise en œuvre permettrait d’envisager le recyclage de composites par des
techniques jusqu’ici réservées aux thermoplastiques, comme par exemple le moulage par
compression.
Le resvératrol représente 50 % de la masse du matériau Vm-RvOH. Dans le cas où l’épichlorhydrine

employée est biosourcée, le taux de carbone renouvelable dans ce matériau atteint 86 %. Ce matériau
est donc hautement biosourcé, peut être remis en œuvre, ne contient pas de catalyseur externe, et
présente des propriétés mécaniques intéressantes.
La structure du matériau Vm-RvOH peut également apporter des avantages en termes de

vieillissement des matériaux. En effet, après plusieurs mois, les matériaux TPE-TAF/BDGE (Chapitre II)
et dans une moindre mesure P-DAF/BDGE (Chapitre III) montrent une nette sensibilité à l’humidité
ambiante, voire à l’hydrolyse. La structure de ces matériaux est riche en groupements hydrophiles
(esters, éthers et hydroxyles), et le diépoxy employé présente une structure aliphatique très courte,
qui favorise l’hydrophilie, à l’instar du polyéthylène glycol (PEG). Cette propriété entraîne une
pénétration d’eau dans le matériau, limitée à l’état vitreux, mais importante à l’état caoutchoutique.
De plus, l’activation recherchée de l’ester vis-à-vis de l’attaque nucléophile d’un alcool le rend
également plus vulnérable à l’attaque nucléophile non souhaitée de l’eau, donc à l’hydrolyse du
matériau. Bien qu’une étude approfondie soit nécessaire pour caractériser et quantifier ces
153
phénomènes de prise en eau, le matériau Vm-RvOH semble moins sensible à ce phénomène. En effet,
la pénétration d’eau étant plus rapide à l’état caoutchoutique, une Tg supérieure à 100 °C limite
fortement cette pénétration. De plus, le taux élevé de carbones aromatiques dans le réseau
macromoléculaire augmente vraisemblablement son caractère hydrophobe, et limite également la
pénétration de l’eau et, par conséquent l’hydrolyse.
154
Conclusion générale
CONCLUSION GENERALE
155
Les vitrimères, à l’interface entre les thermoplastiques et les thermodurcissables, présentent de

nombreux intérêts par leurs propriétés originales. Ces matériaux sont résistants aux solvants et
permettent d’obtenir des propriétés mécaniques parfois comparables aux thermodurcissables, ce qui
peut être utile pour des applications structurales, par exemple dans des composites. De plus, leur
caractère dynamique peut permettre une mise en œuvre par des techniques habituellement réservées
aux thermoplastiques, par exemple le moulage par compression ou l’extrusion. Enfin, toujours grâce à
leur caractère dynamique, ils peuvent être remis en œuvre en fin de vie, pour être réutilisés. Ainsi, leur
durée de vie est accrue. Cependant, plusieurs facteurs limitants entravent leur développement dans
des applications industrielles. En particulier, les vitrimères les plus étudiés, basés sur la réaction de
transestérification, nécessitent la plupart du temps l’emploi de catalyseurs incorporés en quantité
importante au sein même du réseau macromoléculaire. Les vitrimères encourent plusieurs risques liés
à l’utilisation de catalyseurs. Au cours de leur utilisation, les catalyseurs peuvent s’échapper du
polymère par lixiviation. Ce phénomène peut poser des risques pour la santé selon le catalyseur
employé, mais il peut également réduire la capacité des matériaux à se remettre en forme. De plus,
les catalyseurs externes peuvent induire un vieillissement prématuré qui limite également leur
capacité de remise en œuvre. Ainsi, l’obtention de vitrimères sans catalyseur est devenue un des
objectifs majeurs de la recherche dans ce domaine.
Plusieurs stratégies sont possibles pour éviter l’utilisation d’un catalyseur. La première est d’utiliser
d’autres réactions d’échange, dont la vitesse de réaction intrinsèque est suffisamment rapide à la
température de remise en œuvre. L’autre stratégie est de placer à proximité de la liaison échangeable
un groupement activant, par des effets inductifs, stériques ou par assistance anchimérique.
Le premier chapitre de ce manuscrit passe en revue les différentes réactions d’échange qui ont été
décrites dans la littérature sur les vitrimères. Les mécanismes mis en jeu ont été discutés, en particulier
leur caractère associatif ou dissociatif. En effet, le caractère associatif d’une réaction est une condition
suffisante (bien que pas toujours nécessaire) pour s’assurer que la vitesse d’écoulement du matériau
suive une loi d’Arrhénius en fonction de la température. Cette propriété traduit la capacité de ces
matériaux à être mis en forme par des techniques utilisées pour les verres inorganique, grâce à une
diminution progressive de la viscosité, ce qui a inspiré le terme vitrimère. Ces considérations sur les
différents mécanismes d’échange permettent de comprendre par quels leviers il est possible de les
activer, et donc quels groupements utiliser à quelles positions. C’est l’objet de la deuxième partie de
cette étude bibliographique. Pour chaque réaction décrite auparavant, les stratégies d’activation
existantes dans la littérature sur les vitrimères ont été décrites. De plus, certaines stratégies et certains
groupements utilisés dans d’autres domaines de la chimie, la chimie organique notamment, ont
156
également été rapportés. L’objectif est de donner des pistes de stratégies d’activation innovantes pour
les futures études sur les vitrimères, en particulier les vitrimères sans catalyseur.
Suite à l’inventaire des stratégies d’activation connues, le choix de la réaction d’échange s’est porté
sur la transestérification. En effet, les premiers vitrimères décrits sont basés sur cette réaction,25 et les
travaux sur les vitrimères de transestérification sont les plus nombreux, bien que beaucoup reste à
faire sur la compréhension de ces systèmes. De plus, le mécanisme de transestérification a été
largement étudié et il est aujourd’hui bien connu. La stratégie adoptée pour activer la liaison ester est
basée sur des effets inductifs électroattracteurs pour diminuer la densité électronique sur le carbonyle,
et le rendre plus réactif vis-à-vis d’une attaque nucléophile par une fonction alcool. Afin d’obtenir
l’effet inductif le plus intense possible, le choix s’est porté sur l’atome de fluor, puisqu’il est l’élément
le plus électronégatif (3.96 sur l’échelle de Pauling). De même, toujours dans le même but de
maximiser l’effet inductif, le choix a été fait de placer les atomes de fluor au plus près de la liaison
ester, en position α, tout en ayant le maximum de substituants fluor à cette position, donc un groupe
α-CF2.
Le premier volet de travaux expérimentaux, décrits dans le chapitre II, a un objectif double. Il est d’une
part d’obtenir une preuve de concept sur la possibilité d’activer la transestérification par des
groupements α-CF2 à proximité des liaisons ester, et d’autre part de montrer son efficacité pour former
des matériaux polyester dynamiques sans catalyseur. A partir d’un triphénol, un composé α,α-difluoro
acide carboxylique trifonctionnel original a été synthétisé. Ce composé a été utilisé dans la
polymérisation par ouverture de cycle d’un époxy difonctionnel, le BDGE, afin de former un matériau
dont la structure est un réseau macromoléculaire tridimensionnel. Ce matériau est insoluble dans les
solvants organiques aprotiques, et il peut être remis en forme jusqu’à 10 fois, dans des conditions
modérées (100 °C, 1h30min, 15 bars), tout en conservant ses propriétés mécaniques. De plus,
l’écoulement du matériau depuis le plateau caoutchoutique a été mis en évidence, et la vitesse de cet
écoulement suit une loi d’Arrhénius en fonction de la température. Le matériau TPE-TAF/BDGE se
comporte donc comme un vitrimère polyester, et son caractère dynamique ne nécessite pas d’ajout
de catalyseur. Suite à cette étude, la preuve de concept sur la faisabilité d’un vitrimère sans catalyseur
activé par le fluor a donc été validée.
Dans la continuité de ces travaux, l’objectif a été de se rapprocher d’éventuelles applications pratiques.
Pour cela, il est nécessaire de simplifier la synthèse des monomères α,α-difluoro acides. En effet, la
synthèse du TPE-TAF semble difficile à réaliser à grande échelle, et sa purification sur colonne de silice
peu adaptée pour d’éventuelles applications industrielles. Un deuxième monomère, le P-DAF, a été
25
Montarnal, D.; Capelot, M.; Tournilhac, F.; Leibler, L. Science 2011, 334 (6058), 965–968.
157
synthétisé à partir du diiodobenzène. La synthèse de ce composé est plus rapide, plus robuste et le
solvant utilisé est le DMSO, moins dangereux que le DMF utilisé précédemment. Cependant le
monomère obtenu est difonctionnel, ce qui ne garantit pas l’obtention d’un réseau tridimensionnel
par réaction avec un époxy difonctionnel. La possibilité d’utiliser des époxy de plus haute
fonctionnalité a été envisagée, mais présente de nombreuses limites. En effet, beaucoup de ces résines
époxy sont solides, et pour celles qui se présentent sous forme liquide leur faible miscibilité avec le
P-DAF pose problème. Une autre stratégie inspirée de la littérature a donc été choisie, dans laquelle le
P-DAF réagit avec un époxy difonctionnel, et la réticulation est permise par la réaction de
transestérification, conduisant à des liens entre les chaînes macromoléculaires, et à la formation
d’oligomères sacrificiels. Ce phénomène bien connu pour les thermodurcissables époxy-acide 26 et
27
décrit pour des vitrimères de transestérification catalysés, implique que la réaction de
transestérification a une cinétique dont l’ordre de grandeur est comparable à celle de la
polymérisation par ouverture de cycle de l’époxy par l’acide. Dans le cas des acides fluorés, sans
catalyseur, les conditions de polymérisation sont plus douces, puisque la réaction a lieu
essentiellement à température ambiante. Bien qu’une étape en température à 150 °C soit nécessaire
pour finir la polymérisation, la formation d’un réseau macromoléculaire ne semblait pas assurée. Le
P-DAF a donc été engagé avec le BDGE afin de former un matériau. Après l’étape de réticulation en
température, ce matériau s’est montré lui aussi insoluble dans les solvants aprotiques. Sa capacité à
se remettre en forme a également été étudiée, ainsi que son caractère dynamique, par analyse
mécanique.
Le développement de vitrimères sans catalyseur s’inscrit dans une démarche pour inventer des
matériaux polymères plus durables et plus respectueux de l’environnement. Le sujet des additifs est
au cœur des préoccupations qui ont amené à la réalisation de ces travaux. Le problème de la fin de vie
des matériaux polymères est l’essence même du concept de vitrimère. Cependant, la question de la
provenance des matières premières utilisées n’a pas encore été posée dans les travaux décrits aux
chapitres précédents. En effet, la grande majorité des polymères produits sont issus de matières
premières fossiles, dont les réserves sont finies. Afin d’anticiper de futures tensions croissantes pour
l’accès aux ressources fossiles, des polymères sont développés à partir de matière première d’origine
renouvelable. Cette tendance se confirme également dans le domaine des vitrimères. 28 Une autre
limite des vitrimères développés jusqu’à présent concerne leurs propriétés mécaniques souvent
insuffisantes pour certaines applications telles que les composites. En particulier les valeurs de Tg
26
27
28
Vidil, T.; Llevot, A. Macromol. Chem. Phys. 2022, 223 (13), 2100494.
158
rapportées sont généralement en-dessous de 100 °C. C’est également le cas des deux vitrimères décrits
précédemment. L’objectif de ce dernier volet de travaux a été d’obtenir un matériau avec une Tg
supérieure à 100 °C. Pour cela, un polyphénol biosourcé a été mis à profit, le resvératrol. Ce composé
est extrait de la vigne et comporte trois fonctions phénol qui peuvent être modifiées. De plus, il est
riche en carbones aromatiques, ce qui lui confère de la rigidité, qui est favorable à l’obtention de Tg
élévée. Le resvératrol a été fonctionnalisé de deux manières différentes. D’une part, les fonctions
phénol ont été modifiées pour obtenir un α,α-difluoro acide trifonctionnel. D’autre part, le resvératrol
a été transformé en époxy trifonctionnel par réaction avec l’épichlorhydrine. Le mélange des deux
monomères a une fonctionnalité moyenne de 3, ce qui permet d’obtenir un réseau plus dense et
d’augmenter la Tg du Vm-RvOH par rapport aux matériaux précédents. Ainsi, le Vm-RvOH a une Tg de
120 °C, tout en conservant sa capacité à être remis en œuvre, à 170 °C pendant 2 h. Ce matériau
présente un taux de carbone renouvelable de 86 %.
En conclusion, ces travaux de thèse ont permis de démontrer l’efficacité de groupements α-CF2 pour
activer la liaison ester vis-à-vis de la transestérification, et d’utiliser cet effet pour former des vitrimères
de transestérification sans catalyseur inédits, activés par le fluor. Des pistes ont été trouvées afin de
simplifier la synthèse de composés α,α-difluoro acides pour obtenir de tels matériaux. En particulier,
la faisabilité d’une structure macromoléculaire tridimensionnelle à partir de monomères acide et
époxy difonctionnels a été montrée. De plus, la synthèse de monomères α,α-difluoro acides a été
adaptée à un triphénol biosourcé, le resvératrol. Cette synthèse a permis d’obtenir un vitrimère
biosourcé, sans catalyseur, avec une Tg élevée.
Néanmoins de nombreuses pistes d’améliorations peuvent être envisagées pour la poursuite de ces
travaux. En termes de montée en échelle, la synthèse du TPE-TAF n’est pas adaptée, car impossible à
purifier avec des procédés industriels. Une optimisation des conditions de réactions pourrait être
envisagée afin de réduire la formation de composés disubstitués et monosubstitués. La synthèse du
P-DAF utilise des procédés beaucoup plus simples, et la purification par cristallisation-lavage est
adaptée à la production à grande échelle. Cependant, cette réaction fait intervenir du cuivre métallique
en grande quantité. Une partie de ce cuivre n’est pas récupéré après la réaction. Le cuivre consommé
doit donc être renouvelé, et les effluents, qui présentent un risque pour l’environnement et la santé,
doivent être traités, ce qui rend l’utilisation du cuivre très coûteuse. Là encore, une optimisation des
conditions de réaction pourrait permettre de réduire les quantités de cuivre utilisées. La synthèse du
RvOH-TAF semble finalement plus prometteuse, bien que proche de celle du TPE-TAF, car la
purification se fait par une simple filtration sur silice, et les rendements sont meilleurs.
159
Les propriétés mécaniques du Vm-RvOH le rendent intéressant pour des applications composites plus
structuraux. L’étude de divers procédés de mise en œuvre de ce matériau dans la fabrication de
composites pourrait être une suite intéressante à donner à ces travaux, par exemple par moulage par
compression ou par infusion d’une solution des deux monomères dans des fibres.
De plus, le phénomène d’hydrolyse des matériaux, qui n’avait pas été anticipé, mérite d’être étudié
afin de trouver des solutions à ce problème. En effet, le carbone du carbonyle de l’ester est activé vis-
à-vis de l’attaque nucléophile d’un alcool, mais cet effet a pour conséquence de l’activer également
vis-à-vis de l’attaque nucléophile néfaste d’eau. Ce phénomène se traduit par une hydrolyse des
matériaux après plusieurs mois, le TPE-TAF/BDGE étant le plus sujet à l’hydrolyse. Le matériau
Vm-RvOH semble moins sensible à l’hydrolyse, probablement du fait de sa haute Tg. En effet la
pénétration d’humidité au sein du matériau est plus importante à l’état caoutchoutique. Une Tg élevée
et des monomères plus hydrophobes limitent donc cette pénétration d’eau et par suite les risques
d’hydrolyse. Toutefois, ce phénomène d’hydrolyse nécessite d’être étudié en détail pour chacun des
matériaux formés. Bien que ce ne soit pas le but initial, l’activation de l’hydrolyse par le fluor pourrait
avoir une utilité, par exemple pour fabriquer des matériaux thermodurcissables dégradables.
Outre l’hydrolyse, les vitrimères subissent d’autres phénomènes de vieillissement, notamment le

vieillissement thermique au moment de la remise en œuvre. Ce phénomène n’est pas décrit dans la
littérature. Une étude approfondie du vieillissement des vitrimères avec catalyseur et sans catalyseur
activés par le fluor pourrait permettre de mettre en évidence et de quantifier l’effet bénéfique d’une
activation interne par rapport à un catalyseur externe sur la durée de vie du matériau.
Pour finir, les esters de phosphate présentent l’intérêt de s’échanger sans catalyseur, et quelques
vitrimères basés sur cet échange ont été décrits.29,30,31,32 Dans ce cas, la stratégie est différente puisqu’il
s’agit d’utiliser une réaction qui ne nécessite pas de catalyseur, et non plus de l’activer par des groupes
à proximité. Cependant ce type d’esters présente des avantages. Pour commencer, ils limitent les
étapes de synthèse car ils n’ont pas besoin d’être activés. De plus, ils peuvent être synthétisés à partir
d’acide phosphorique et d’époxy, de façon similaire aux esters d’acides carboxyliques. Quelques
travaux préliminaires ont été menés sur ces esters, qui ont permis de mettre en évidence deux limites
sur lesquelles travailler : la forte exothermie de la réaction d’ouverture de cycle des époxy par l’acide
29
Majumdar, S.; Zhang, H.; Soleimani, M.; A. T. M. van Benthem, R.; P. A. Heuts, J.; P. Sijbesma, R. ACS Macro
Lett. 2020, 9 (12), 1753–1758.
30
Feng, X.; Li, G. Chem. Eng. J. 2021, 417, 129132.
31
Huang, L.; Yang, Y.; Niu, Z.; Wu, R.; Fan, W.; Dai, Q.; He, J.; Bai, C. Macromol. Rapid Commun. 2021, 2100432.
32
Liu, Y.; Wang, B.; Ma, S.; Xu, X.; Qiu, J.; Li, Q.; Wang, S.; Lu, N.; Ye, J.; Zhu, J. Eur. Polym. J. 2021, 144, 110236.
160
phosphorique, qui doit être contenue, et la sensibilité importante de ces matériaux à l’hydrolyse. Ces
matériaux ont été peu étudiés à l’heure actuelle et semblent dignes d’intérêt pour de futurs travaux
161
Annexes A : annexes au chapitre II
ANNEXES A : ANNEXES AU CHAPITRE II
163
Catalyst-Free Transesterification Vitrimers: α-CF2 group activation of
the ester linkages: Supporting Information
Florian Cuminet,a Dimitri Berne,a Sébastien Lemouzy,a Éric Dantras,b Christine Joly-Duhamel,a
Sylvain Caillol,a Éric Leclerca and Vincent Ladmirala
a
b
CIRIMAT, Université Toulouse 3 Paul Sabatier, Physique des Polymères, 118 Route de
Narbonne, 31062 Toulouse, France
TPE-TE characterizations ............................................................................................................. 166
Figure S1. 1H NMR spectrum of the triester TPE-TE in CDCl3 .................................................. 166
Figure S2. 19F NMR spectrum of the triester TPE-TE in CDCl3.................................................. 167
Figure S3. 13C NMR spectrum of the triester TPE-TE in CDCl3 ................................................. 168
Figure S4. 1H NMR spectrum of the disubstituted byproduct in CDCl3 ................................... 169
Figure S5. 19F NMR spectrum of the disubstituted byproduct in CDCl3 .................................. 170
Figure S6. 13C NMR spectrum of the disubstituted byproduct in CDCl3 .................................. 171
Figure S7. COSY 1H NMR spectrum of the disubstituted byproduct in CDCl3.......................... 172
Figure S8. HSQC 1H-13C NMR spectrum of the disubstituted byproduct in CDCl3 ................... 173
TPE-TAF characterizations ........................................................................................................... 174
Figure S9. 1H NMR spectrum of the triacid TPE-TAF in acetone-d6. ........................................ 174
Figure S10. 19F NMR spectrum of the triacid TPE-TAF in acetone-d6 ...................................... 175
Figure S11. 13C NMR spectrum of the triacid TPE-TAF in acetone-d6 ...................................... 176
Figure S12. FTIR spectrum of the triacid TPE-TAF ................................................................... 177
Figure S13. TGA thermogram of the triacid TPE-TAF (air, 20 °C.min-1) ................................... 178
BDGE characterizations ............................................................................................................... 179
Figure S14. 1H NMR spectrum of the commercial BDGE in CDCl3 ........................................... 179
Figure S15. 13C NMR spectrum of the commercial BDGE in CDCl3 .......................................... 180
Figure S16. FTIR spectrum of the commercial BDGE............................................................... 181
A. Experimental procedure for the determination of BDGE epoxy equivalent weight (EEW) by
1
H NMR in CDCl3 ...................................................................................................................... 182
164
B. Experimental procedure for the determination of BDGE epoxy equivalent weight (EEW) by
DSC........................................................................................................................................... 183
TPE-TAF / BDGE vitrimer characterizations ................................................................................. 184
Figure S17. Determination of the gel time of the TPE-TAF/BDGE mixture at 20 °C by rheology
................................................................................................................................................. 184
Figure S18. DSC thermogram of the TPE-TAF/BDGE material after curing 3 h at 150 °C (nitrogen,
20 °C.min-1) ............................................................................................................................. 185
Table S1. Gel content of the pristine TPE-TAF/BDGE material after curing 3 h at 150 °C in various
solvents.................................................................................................................................... 186
Figure S19. DMA thermogram of the pristine TPE-TAF/BDGE material after curing 3 h at 150 °C
................................................................................................................................................. 186
Figure S20. TGA thermogram of the pristine TPE-TAF/BDGE material after curing 3 h at 150 °C
(air, 20 °C min-1) ....................................................................................................................... 187
Table S2. Equation and fitting parameters of the Kohlrausch-Williams-Watts stretched

exponential model for the stress relaxation experiments ...................................................... 187
Figure S21. FTIR spectrum of the cured TPE-TAF/BDGE material ........................................... 188
Figure S22. Stacked FTIR spectra of TPE-TAF, BDGE, material after gelation 4 days at room
temperature and TPE-TAF/BDGE material after curing 3 h at 150 °C ..................................... 189
165
TPE-TE characterizations
Figure S1. 1H NMR spectrum of the triester TPE-TE in CDCl3
166
Figure S2. 19F NMR spectrum of the triester TPE-TE in CDCl3
167
Figure S3. 13C NMR spectrum of the triester TPE-TE in CDCl3
168
Figure S4. 1H NMR spectrum of the disubstituted byproduct in CDCl3
169
Figure S5. 19F NMR spectrum of the disubstituted byproduct in CDCl3
170
Figure S6. 13C NMR spectrum of the disubstituted byproduct in CDCl3
171
Figure S7. COSY 1H NMR spectrum of the disubstituted byproduct in CDCl3
172
Figure S8. HSQC 1H-13C NMR spectrum of the disubstituted byproduct in CDCl3
173
TPE-TAF characterizations
Figure S9. 1H NMR spectrum of the triacid TPE-TAF in acetone-d6.

Very small signals at 1.30 and 4.39 ppm correspond to residual ester functions (which amount to less
than 2 mol% compared to the acid groups).
174
Figure S10. 19F NMR spectrum of the triacid TPE-TAF in acetone-d6
175
Figure S11. 13C NMR spectrum of the triacid TPE-TAF in acetone-d6
176
Figure S12. FTIR spectrum of the triacid TPE-TAF
177
Figure S13. TGA thermogram of the triacid TPE-TAF (air, 20 °C.min-1)
178
BDGE characterizations
Figure S14. 1H NMR spectrum of the commercial BDGE in CDCl3
179
Figure S15. 13C NMR spectrum of the commercial BDGE in CDCl3
180
Figure S16. FTIR spectrum of the commercial BDGE
181
A. Experimental procedure for the determination of BDGE epoxy equivalent weight (EEW) by 1H
NMR in CDCl3
50 to 70 mg of BDGE and 50 to 80 mg of benzophenone were dissolved in deuterated chloroform. 1H

NMR spectra were integrated in the 7.87-7.28 ppm range for benzophenone protons (10 H), in the
3.19-2.97 ppm range for CH oxirane and in the 2.82-2.45 range for CH2 oxirane. EEW was calculated
as follows :
7.87
𝑚𝐵𝐷𝐺𝐸 × ∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × 𝑀𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒
𝐸𝐸𝑊𝐶𝐻 = 3.19
10 × 𝑚𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × ∫2.97 𝐶𝐻 𝑜𝑥𝑖𝑟𝑎𝑛𝑒
7.87
2 × 𝑚𝐵𝐷𝐺𝐸 × ∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × 𝑀𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒
𝐸𝐸𝑊𝐶𝐻2 = 2.82
10 × 𝑚𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × ∫2.45 𝐶𝐻2 𝑜𝑥𝑖𝑟𝑎𝑛𝑒
182
𝑚𝐵𝐷𝐺𝐸 𝑚𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 3.19 2.82 𝐸𝐸𝑊𝐶𝐻 𝐸𝐸𝑊𝐶𝐻2

∫2.97 𝐶𝐻 𝑜𝑥𝑖𝑟𝑎𝑛𝑒 ∫2.45 𝐶𝐻2 𝑜𝑥𝑖𝑟𝑎𝑛𝑒
(mg) (mg) 7.87 7.87
∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 ∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒
73.3 80.9 0.157 0.324 117 113

54.6 80.0 0.117 0.241 118 115
57.8 50.7 0.197 0.406 117 114
Average EEW 115 ± 4 g/eq
B. Experimental procedure for the determination of BDGE epoxy equivalent weight (EEW) by
DSC
To confirm the EEW value obtained by NMR, a DSC study was performed. Thermosets of BDGE and
succinic acid were made with different stoichiometric ratios. The Tg of the thermosets was measured
by DSC, the maximum value corresponding to a acid/epoxy function ratio of 1:1, allowing to calculate
the corresponding EEW, knowing the acid HEW (hydrogen equivalent weight). HEW of succinic acid is
59 g/eq.
The coarse acid powder was first crushed in a mortar to obtain a powder as thin as possible. Then it
was mixed manually with the right amount of BDGE in a tube. The tube was sealed with a septum
and cured overnight at 200 °C in an oven. The thermosets obtained were analysed by DSC (-100 to +
150 °C at 20 °C/min). The Tg was determined upon second heating ramp. The optimal ratio was 1:1,
which confirmed the EEW determined by NMR.
𝑚𝑠𝑢𝑐𝑐𝑖𝑛𝑖𝑐 𝑎𝑐𝑖𝑑 (mg) 𝑚𝐵𝐷𝐺𝐸 (mg) Ratio (based on NMR EEW) Tg (°C)
66.9 119 0.91 7.9
70.1 134.5 0.99 8
81.6 158.6 1.00 9.4
76.1 156 1.05 7.7
82.8 178.4 1.11 3.7
86.9 206.9 1.22 3.3
183
TPE-TAF / BDGE vitrimer characterizations
Figure S17. Determination of the gel time of the TPE-TAF/BDGE mixture at 20 °C by rheology
184
Figure S18. DSC thermogram of the TPE-TAF/BDGE material after curing 3 h at 150 °C (nitrogen,
20 °C.min-1)
185
Table S1. Gel content of the pristine TPE-TAF/BDGE material after curing 3 h at 150 °C in various
solvents
Solvent Acetone THF Toluene Cyclohexane DMSO CH2Cl2 Acetonitrile
GC (%) 94 94 99 99 96 97 96
Figure S19. DMA thermogram of the pristine TPE-TAF/BDGE material after curing 3 h at 150 °C
186
Figure S20. TGA thermogram of the pristine TPE-TAF/BDGE material after curing 3 h at 150 °C
(air, 20 °C min-1)

exponential model for the stress relaxation experiments
T (°C) 170 180 190 200 210
τ (s) 79692 43025 30376 20772 13097
β 0.57 0.58 0.58 0.53 0.56
R² 0.99513 0.99975 0.99906 0.99804 0.99923
Note: for β = 1 the KWW expression is a Maxwell
187
Figure S21. FTIR spectrum of the cured TPE-TAF/BDGE material
188
Figure S22. Stacked FTIR spectra of TPE-TAF, BDGE, material after gelation 4 days at room
temperature and TPE-TAF/BDGE material after curing 3 h at 150 °C
189
Annexes B : annexes au chapitre III
ANNEXES B : ANNEXES AU CHAPITRE III
191
Supplementary Material to “Synthesis of a transesterification vitrimer
activated by fluorine from an α,α-difluoro carboxylic acid and a
diepoxy”
Florian Cuminet,a Sylvain Caillol,a Éric Dantras,b Éric Leclerc,a Cédric Totée,c Olivier Guilled and
Vincent Ladmirala
a ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France

b CIRIMAT, Université Toulouse 3 Paul Sabatier, Physique des Polymères, 118 Route de Narbonne,
c ICGM, PAC, Univ Montpellier, CNRS, ENSCM, Montpellier, France
d Institut d’Electronique et Systèmes (IES) UMR 5214, Université de Montpellier/CNRS, 34095,
Montpellier, France
Figure S1. ATR-FTIR monitoring of the P-DAF/BDGE mixture reaction at room temperature over
time ............................................................................................................................................. 194
Figure S2. Evolution of the epoxy ATR-FTIR band at 914 cm-1 of the P-DAF/BDGE binary mixture
over time at room temperature (ca. 20 °C)................................................................................. 195
Figure S3. 13C NMR spectrum of commercial butanediol diglycidyl ether (BDGE) in CDCl3 ........ 196
Figure S4. 19F NMR spectrum of P-DE in DMSO-d6 ...................................................................... 197
Figure S5. 19F NMR spectrum of P-DAF in DMSO-d6 .................................................................... 198
Figure S6. DSC thermograms of the BDGE/P-DAF after gelation at room temperature. Two
consecutive ramps from -100 °C to +250 °C were applied.......................................................... 198
Table S1. Swelling Index and Gel Content of the BDGE/P-DAF gel after curing at room temperature
in various solvents ....................................................................................................................... 199
Figure S7. Monitoring of BDGE/P-DAF end of curing at 150 °C by dynamic mechanical analysis. A
0.1 % oscillation was applied every 2 minutes at an angular frequency of 1 rad/s and the storage
modulus G’ evolution with time was followed............................................................................ 199
Figure S8. Check of complete curing of BDGE/P-DAF at 170 °C by dynamic mechanical analysis,
after the curing step at 150 °C. A 0.1 % oscillation was applied every 2 minutes at an angular
frequency of 1 rad/s and the storage modulus G’ evolution with time was followed ............... 200
Table S2. Swelling Index and Gel Content of the BDGE/P-DAF vitrimer after 3 h at 150 °C in various
solvents........................................................................................................................................ 200
192
Figure S9. Comparison of the ATR-FTIR C=O bands of the P-DE (ester), the P-DAF (acid) and the
BDGE/P-DAF material before and after the curing step at 150 °C .............................................. 201
Figure S10. Zoom of the ATR-FTIR spectra on the 4000-2500 cm-1 area for BDGE/P-DAF before and
after the curing step at 150 °C .................................................................................................... 202
Figure S11. TGA thermogram of BDGE/P-DAF in air (20 °C/min) ................................................ 203
Figure S12. DMA thermograms of BDGE/P-DAF in air (3 °C/min, 1 Hz) ...................................... 204
Figure S13. DSC thermograms of BDGE/P-DAF pristine (black), after reprocessing 1.5 h at 150 °C
by compression molding (green), and after reprocessing by compression molding and annealing
3 h at 150 °C in an oven (red) ...................................................................................................... 205
Figure S14. DMA thermograms (3°/min, 1 Hz) of BDGE/P-DAF pristine (black), after reprocessing
1.5 h at 150 °C by compression molding (green), and after reprocessing by compression molding
and annealing 3 h at 150 °C in an oven (red) .............................................................................. 206
Figure S15. 1H NMR spectrum of P-DE in DMSO-d6..................................................................... 207
Figure S16. 19F NMR spectrum of P-DE in DMSO-d6 .................................................................... 207
Figure S17. 13C NMR spectrum of P-DE in DMSO-d6.................................................................... 208
Figure S18. ATR-FTIR spectrum of P-DE....................................................................................... 208
Figure S19. 1H NMR spectrum of P-DAF in DMSO-d6 .................................................................. 209
Figure S20. 19F NMR spectrum of P-DAF in DMSO-d6 .................................................................. 209
Figure S21. 13C NMR spectrum of P-DAF in DMSO-d6 ................................................................. 210
Figure S22. ATR-FTIR spectrum of P-DAF .................................................................................... 210
193
Figure S1. ATR-FTIR monitoring of the P-DAF/BDGE mixture reaction at room

temperature over time
194
Figure S2. Evolution of the epoxy ATR-FTIR band at 914 cm-1 of the P-DAF/BDGE
binary mixture over time at room temperature (ca. 20 °C)
195
Figure S3. 13C NMR spectrum of commercial butanediol diglycidyl ether (BDGE) in
CDCl3
196
Figure S4. 19F NMR spectrum of P-DE in DMSO-d6
197
Figure S5. 19F NMR spectrum of P-DAF in DMSO-d6
Figure S6. DSC thermograms of the BDGE/P-DAF after gelation at room

temperature. Two consecutive ramps from -100 °C to +250 °C were applied
198
Table S1. Swelling Index and Gel Content of the BDGE/P-DAF gel after curing at
room temperature in various solvents
SI (%) GC (%)
Acetone 99 54
Methanol 62 53
THF 162 59
Acetonitrile 35 55
DCM 168 80
Toluene 41 94
Cyclohexane 30 93
Figure S7. Monitoring of BDGE/P-DAF end of curing at 150 °C by dynamic

mechanical analysis. A 0.1 % oscillation was applied every 2 minutes at an angular
frequency of 1 rad/s and the storage modulus G’ evolution with time was followed
199
Figure S8. Check of complete curing of BDGE/P-DAF at 170 °C by dynamic

mechanical analysis, after the curing step at 150 °C. A 0.1 % oscillation was applied
every 2 minutes at an angular frequency of 1 rad/s and the storage modulus G’
evolution with time was followed
Table S2. Swelling Index and Gel Content of the BDGE/P-DAF vitrimer after 3 h at
150 °C in various solvents
SI (%) GC (%)
Acetone 115 ± 9 97 ± 1
Ethanol 99 ± 21 97 ± 1
Water 159 ± 61 95 ± 4
THF 136 ± 11 96 ± 1
DMSO 237 ± 29 95.9 ± 0.4
Acetonitrile 109 ± 26 96.5 ± 0.9
DCM 148 ± 22 97.3 ± 0.2
Toluene 86 ± 68 99.0 ± 0.3
Cyclohexane 45 ± 16 99.3 ± 0.5
200
Figure S9. Comparison of the ATR-FTIR C=O bands of the P-DE (ester), the P-DAF
(acid) and the BDGE/P-DAF material before and after the curing step at 150 °C
201
Figure S10. Zoom of the ATR-FTIR spectra on the 4000-2500 cm-1 area for BDGE/P-
DAF before and after the curing step at 150 °C
202
Figure S11. TGA thermogram of BDGE/P-DAF in air (20 °C/min)
203
Figure S12. DMA thermograms of BDGE/P-DAF in air (3 °C/min, 1 Hz)
204
Figure S13. DSC thermograms of BDGE/P-DAF pristine (black), after reprocessing

1.5 h at 150 °C by compression molding (green), and after reprocessing by
compression molding and annealing 3 h at 150 °C in an oven (red)
205
Figure S14. DMA thermograms (3°/min, 1 Hz) of BDGE/P-DAF pristine (black),

after reprocessing 1.5 h at 150 °C by compression molding (green), and after
reprocessing by compression molding and annealing 3 h at 150 °C in an oven (red)
206
Figure S15. 1H NMR spectrum of P-DE in DMSO-d6
Figure S16. 19F NMR spectrum of P-DE in DMSO-d6
207
Figure S17. 13C NMR spectrum of P-DE in DMSO-d6
Figure S18. ATR-FTIR spectrum of P-DE
208
Figure S19. 1H NMR spectrum of P-DAF in DMSO-d6
Figure S20. 19F NMR spectrum of P-DAF in DMSO-d6
209
Figure S21. 13C NMR spectrum of P-DAF in DMSO-d6
Figure S22. ATR-FTIR spectrum of P-DAF
210
Annexes C : annexes au chapitre IV
ANNEXES C : ANNEXES AU CHAPITRE IV
211
Supplementary information to “From vineyards to 100 % resveratrol
materials: α-CF2 activation in biobased catalyst-free vitrimers”
Florian Cuminet,a,b Sébastien Lemouzy,a Éric Dantras,b Sylvain Caillol,a Éric Leclerca and Vincent
Ladmirala
a
b
CIRIMAT, Université Toulouse 3 Paul Sabatier, Physique des Polymères, 118 Route de Narbonne,
Resveratrol α,α-difluorotriester “RvOEt” characterizations ........................................................... 213

Figure S1. 1H NMR spectrum of RvOEt in CDCl3 .................................................................................. 213
Figure S2. 19F NMR spectrum of RvOEt in CDCl3 .................................................................................. 213
Figure S3. 13C NMR spectrum of RvOEt in CDCl3 ................................................................................. 214
Resveratrol α,α-difluorotriacid “RvOH-TAF” characterizations ...................................................... 214
Figure S4. 1H NMR spectrum of RvOH-TAF in DMSO-d6 ...................................................................... 214
Figure S5. 19F NMR spectrum of RvOH-TAF in DMSO-d6 ..................................................................... 215
Figure S6. 13C NMR spectrum of RvOH-TAF in DMSO-d6 ..................................................................... 215
Figure S7. 1H NMR spectrum of RvOGly in acetone-d6........................................................................ 216
Figure S8. 13C NMR spectrum of RvOGly in acetone-d6 ....................................................................... 216
A. Experimental procedure for the determination of RvOGly epoxy equivalent weight (EEW) by 1H
NMR ..................................................................................................................................................... 217
Vitrimer characterizations (Vm-RvOH) ............................................................................................ 219
Figure S9. DSC thermogram of Vm-RvOH after curing 3 h at room temperature............................... 219
Figure S10. DSC thermogram of Vm-RvOH after curing 3 h at room temperature and 1 h at 150 °C 219
Figure S11. Curing step at 150 °C monitored by the evolution of the material storage modulus G'.. 220
Figure S12. DSC thermogram of Vm-RvOH after complete curing 10 h at 150 °C .............................. 220
Figure S13. DMA thermogram of Vm-RvOH after complete curing 10 h at 150 °C (0.1 % strain, 1 Hz, 3
°C/min) ................................................................................................................................................ 221
Figure S14. TGA thermogram under nitrogen of Vm-RvOH after complete curing 10 h at 150 °C..... 221
Figure S15. Isothermal TGA thermogram at 170 °C under air of Vm-RvOH after complete curing 10 h
at 150 °C .............................................................................................................................................. 222
Figure S16. Stress–relaxation curves of Vm-RvOH from 170 to 210 °C with 10 °C steps (0.3 % strain)
............................................................................................................................................................. 222
Table S1. Equation and fitting parameters of the Kohlrausch-Williams-Watts stretched exponential
model for the stress relaxation experiments ...................................................................................... 223
212
Resveratrol α,α-difluorotriester “RvOEt” characterizations
Figure S1. 1H NMR spectrum of RvOEt in CDCl3
Figure S2. 19F NMR spectrum of RvOEt in CDCl3
213
Figure S3. 13C NMR spectrum of RvOEt in CDCl3
Resveratrol α,α-difluorotriacid “RvOH-TAF” characterizations
Figure S4. 1H NMR spectrum of RvOH-TAF in DMSO-d6
214
Figure S5. 19F NMR spectrum of RvOH-TAF in DMSO-d6
Figure S6. 13C NMR spectrum of RvOH-TAF in DMSO-d6
215
Figure S7. 1H NMR spectrum of RvOGly in acetone-d6
Figure S8. 13C NMR spectrum of RvOGly in acetone-d6
216
A. Experimental procedure for the determination of RvOGly epoxy equivalent weight (EEW) by
1H NMR
50 to 70 mg of BDGE and 50 to 130 mg of RvOGly were dissolved in deuterated acetone. 1H NMR

spectra were integrated in the 7.87-7.28 ppm range for benzophenone protons (10 H), in the 3.46-
3.26 ppm range for CH oxirane and in the 3.0-2.65 range for CH2 oxirane. EEW was calculated as
follows :
7.87
𝑚𝐵𝐷𝐺𝐸 × ∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × 𝑀𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒
𝐸𝐸𝑊𝐶𝐻 = 3.46
10 × 𝑚𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × ∫3.26 𝐶𝐻 𝑜𝑥𝑖𝑟𝑎𝑛𝑒
7.87
2 × 𝑚𝐵𝐷𝐺𝐸 × ∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × 𝑀𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒
𝐸𝐸𝑊𝐶𝐻2 = 3.0
10 × 𝑚𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 × ∫2.65 𝐶𝐻2 𝑜𝑥𝑖𝑟𝑎𝑛𝑒
217
𝑚𝑒𝑝𝑜𝑥𝑦 𝑚𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 3.19 2.82 𝐸𝐸𝑊𝐶𝐻 𝐸𝐸𝑊𝐶𝐻2

∫2.97 𝐶𝐻 𝑜𝑥𝑖𝑟𝑎𝑛𝑒 ∫2.45 𝐶𝐻2 𝑜𝑥𝑖𝑟𝑎𝑛𝑒
(mg) (mg) 7.87 7.87
∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒 ∫7.28 𝑏𝑒𝑛𝑧𝑜𝑝ℎ𝑒𝑛𝑜𝑛𝑒
55.9 39.9 0.157 0.283 163 180

94.8 44.8 0.227 0.390 170 198
125.9 54.8 0.245 0.402 171 208
Average EEW 182 ± 8 g/eq
218
Vitrimer characterizations (Vm-RvOH)
Figure S9. DSC thermogram of Vm-RvOH after curing 3 h at room temperature
Figure S10. DSC thermogram of Vm-RvOH after curing 3 h at room temperature and 1 h at 150
°C
219
Figure S11. Curing step at 150 °C monitored by the evolution of the material storage modulus
G'
Figure S12. DSC thermogram of Vm-RvOH after complete curing 10 h at 150 °C.
220
Figure S13. DMA thermogram of Vm-RvOH after complete curing 10 h at 150 °C (0.1 % strain,
1 Hz, 3 °C/min)
Figure S14. TGA thermogram under nitrogen of Vm-RvOH after complete curing 10 h at 150 °C
221
Figure S15. Isothermal TGA thermogram at 170 °C under air of Vm-RvOH after complete curing
10 h at 150 °C
Figure S16. Stress–relaxation curves of Vm-RvOH from 170 to 210 °C with 10 °C steps (0.3 %
strain)
222

exponential for the stress relaxation experiments
T 170 180 190 200 210
(°C)
τ (s) 1827 1042 648 333 156
β 0.486 0.569 0.593 0.642 0.797
y0 0.043 0.049 0.060 0.064 0.053
R² 0.99962 0.99975 0.99937 0.99974 0.99979
Note: for β = 1 and y0 = 0, the KWW expression becomes a Maxwell
223
Production scientifique
Production scientifique
Articles publiés
(1) Cuminet, F.; Caillol, S.; Dantras, É.; Leclerc, É.; Ladmiral, V. Neighboring Group Participation
and Internal Catalysis Effects on Exchangeable Covalent Bonds: Application to the Thriving
Field of Vitrimer Chemistry. Macromolecules 2021, 54 (9), 3927–3961.
https://doi.org/10.1021/acs.macromol.0c02706
(2) Cuminet, F.; Berne, D.; Lemouzy, S.; Dantras, E.; Joly-Duhamel, C.; Caillol, S.; Leclerc, E.;
Ladmiral, V. Catalyst-Free Transesterification Vitrimers: Activation via α -Difluoroesters.
Polym. Chem. 2022, 8, 5255–5446. https://doi.org/10.1039/D2PY00124A.
(3) Berne, D.; Cuminet, F.; Lemouzy, S.; Joly-Duhamel, C.; Poli, R.; Caillol, S.; Leclerc, E.; Ladmiral,
V. Catalyst-Free Epoxy Vitrimers Based on Transesterification Internally Activated by an α–CF
3 Group . Macromolecules 2022, 55 (5), 1669–1679.
https://doi.org/10.1021/acs.macromol.1c02538.
(4) Quienne, B.; Cuminet, F.; Pinaud, J.; Semsarilar, M.; Cot, D.; Ladmiral, V.; Caillol, S. Upcycling
Biobased Polyurethane Foams into Thermosets: Toward the Closing of the Loop. ACS Sustain.
Chem. Eng. 2022, 10 (21), 7041–7049. https://doi.org/10.1021/ACSSUSCHEMENG.2C00950.
(5) Lemouzy, S.; Cuminet, F.; Berne, D.; Caillol, S.; Ladmiral, V.; Poli, R.; Leclerc, E. Understanding
the Reshaping of Fluorinated Polyester Vitrimers by Kinetic and DFT Studies of the
Transesterification Reaction. Chem. – A Eur. J. 2022.
https://doi.org/10.1002/CHEM.202201135
Articles à soumettre prochainement

(1) Cuminet, F.; Caillol, S.; Dantras, E. ; Leclerc, E. ; Totée, C. ; Guille, O. ; Ladmiral, V. Synthesis of
a transesterification vitrimer activated by fluorine from an α,α-difluoro carboxylic acid and a
diepoxy. To be submitted in Eur. Polym. J.
(2) Cuminet, F.; Lemouzy, S. ; Dantras, E.; Caillol, S.; Leclerc, E.; Ladmiral, V. From vineyards to
100 % resveratrol materials: α-CF2 activation in biobased catalyst-free vitrimers. To be
submitted in Green Chem.
225
Participations à des congrès scientifiques
Participations à des congrès scientifiques
• Balard Chemistry Conferences – Montpellier – Juin 2021 :

Communication orale (EN) et présentation d’un poster (EN) ”Catalyst-free transesterification
vitrimers: the power of fluorine to activate bond exchanges”
• 48èmes Journées d’Etudes des Polymères (JEPO) – Porquerolles – 2021 :

Communication orale (FR) “Vitrimères de transestérification sans catalyseur activés par des
groupements α-CF2”
• 9èmes Journées Méditerranéennes des Jeunes Chercheur(e)s (JMJC) – Montpellier – 2021 :

Communication orale (EN) “α-CF2 groups to activate the transesterification in catalyst-free
vitrimers”
• International Symposium on Green Chemistry 2022 (ISGC 2022) – La Rochelle – 2022 :

Communication orale (EN) “Biobased Catalyst-free Vitrimers: From Vineyards to Reprocessable
Networks”
• 26th Annual Green Chemistry and Engineering Conference (GC&E 2022) – Reston, VA, USA –
2022 :
Communication orale (EN) “Reprocessable biobased polyurethane foams:
an asset for circular economy, from biomass to multiple recycling steps” et présentation d’un
poster (EN) “From vineyards to 100 % resveratrol materials: α-CF2 activation in biobased catalyst-
free vitrimers”
• Bordeaux Polymer Conference (BPC 2022) – Bordeaux – 2022 :

Présentation d’un poster « From vineyards to 100 % resveratrol materials: α-CF2 activation in
biobased catalyst-free vitrimers”
226
Les vitrimères sont des matériaux polymères qui présentent une bonne résistance aux solvants, des
propriétés mécaniques qui peuvent se comparer à celles des thermodurcissables, et qui peuvent être remis
en œuvre par des techniques mécaniques, grâce à des liaisons échangeables au sein du réseau. En particulier,
les vitrimères polyesters ont été beaucoup étudiés, du fait de la disponibilité des résines époxy dont ils sont
issus. Néanmoins, un inconvénient majeur de ces vitrimères polyester réside dans l’utilisation de catalyseurs
en grande quantité au sein du réseau macromoléculaire. Ces catalyseurs peuvent subir des phénomènes de
lixiviation au cours de la vie du matériau, ce qui diminue sa capacité de remise en œuvre, et peut induire des
risques pour l’environnement voire la santé. De plus, ces catalyseurs peuvent provoquer un vieillissement
prématuré de ces matériaux au cours de leur remise en œuvre. L’objectif de cette étude a donc été de
réaliser des vitrimères sans catalyseur. Pour cela, deux stratégies sont possibles. La première est d’exploiter
des réactions d’échange intrinsèquement plus rapides. La deuxième stratégie est d’ajouter des groupements
à proximité des sites d’échange pour activer ces échanges. Après avoir dressé un état de l’art sur les réactions
d’échange disponibles et les stratégies d’activation existantes, le choix de travailler sur l’activation des
liaisons ester a été fait. Des groupements CF2 placés en α de la liaison ester ont permis d’activer la réaction
de transestérification. Une preuve de concept a ainsi été obtenue sur un vitrimère formé à partir d’un α,α-
difluoro acide trifonctionnel et d’un diépoxy. Un deuxième système 2+2 a été synthétisé par la suite,
permettant de montrer la faisabilité d’un réseau macromoléculaire tridimensionnel à partir de deux
composés difonctionnels, grâce à l’effet de la transestérification. Enfin, un troisième système a été formé à
partir de monomères issus de resvératrol, un triphénol naturel extrait de la vigne. Un vitrimère sans
catalyseur avec 85 % de carbone biosourcé a ainsi été synthétisé. Ces trois systèmes permettent de proposer
différentes solutions afin d’améliorer la durabilité des vitrimères, depuis le choix de la matière première
utilisée, jusqu’à leur remise en œuvre et leur fin de vie.
Vitrimers are a type of polymer materials featuring superior resistance to solvents, mechanical properties
comparable to thermosets, and the ability to be reprocessed. Their macromolecular network embeds
exchangeable bonds responsible for their ability to be reshaped upon heating. Polyester vitrimers are the
most studied as they are made from very available epoxy resins. Nonetheless, a major drawback of these
vitrimers is the need for large quantities of catalysts in the macromolecular network. They induce risks of
leaching when the material is in use, which decreases its ability to be reprocessed and induces risks for the
environment and the human health. They can also trigger a premature ageing of the material upon
reprocessing. The aim of this project was to create catalyst-free vitrimers. A first strategy is to implement
other exchange reactions which are faster, and do not require any catalyst. Another strategy is to accelerate
the exchange reaction by activating groups in close vicinity to the exchangeable bonds. The state-of-the-art
on the variety of exchangeable bonds and the activation strategies was summarized. Then, the choice to
work on transesterification vitrimers was made, with the idea to activate the ester carbonyl by
electroattractive inductive effects. In particular, a proof-of-concept of the activation of α-CF2 esters towards
transesterification was proven, in a catalyst-free vitrimer made of a trifunctional α,α-difluoro acid and a
diepoxy. Then, a 2+2 system led to the synthesis of a second vitrimer, showing the feasibility of a crosslinked
macromolecular network from difunctional monomers, thanks to the effect of the transesterification
reaction. Finally, a third vitrimer was made out of resveratrol, a biobased triphenol extracted from grapes,
after a 2-way functionalization. This catalyst-free vitrimer exhibited a 85 % biobased carbon content. These
three systems propose different solutions toward more sustainable vitrimers, taking into account their whole
life, from the sourcing of the raw materials, to their reshaping and the management of their end-of-life.

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THESE POUR OBTENIR LE GRADE DE DOCTEUR DE

L’ECOLE NATIONALE SUPERIEURE DE CHIMIE DE MONTPELLIER

En Chimie et Physico-Chimie des Matériaux

École doctorale Sciences Chimiques Balard (ED459)

Unité de recherche Institut Charles Gerhardt Montpellier UMR 5253

Synthèse et caractérisation de vitrimères de

Présentée par Florian CUMINET

Sous la direction de Sylvain CAILLOL et Éric DANTRAS

Devant le jury composé de

Tatiana BESSET, Directrice de recherche CNRS, INSA Rouen Normandie Rapporteure

Je tiens d’abord à remercier Patrick Lacroix-Desmazes, directeur du département Chimie et Matériaux

Je remercie Mme Tatiana Besset et M. François Tournilhac, en leurs qualités de rapporteure et

Je tiens à exprimer toute ma reconnaissance et ma gratitude envers mes directeurs et encadrants de

Liste des abréviations .............................................................................................................................. ix

Introduction du chapitre I ................................................................................................................. 10

2. Exchangeable Bonds with an Associative Mechanism .......................................................... 17

Conclusion and Outlook ................................................................................................................ 61

Conclusion du chapitre I .................................................................................................................... 79

Introduction du chapitre 2 ................................................................................................................ 83

Catalyst-free transesterification vitrimers: activation via α-difluoroesters ...................................... 86

3. Results and discussion ........................................................................................................... 88

Vitrimer characterization .............................................................................................................. 91

Experimental section ..................................................................................................................... 98

Notes and references .................................................................................................................. 101

Conclusion du chapitre II ................................................................................................................. 105

Introduction du chapitre III ............................................................................................................. 109

Synthesis of a transesterification vitrimer activated by fluorine from an α,α-difluoro carboxylic acid

Abstract ....................................................................................................................................... 111

Introduction ................................................................................................................................. 111

Results and Discussion ................................................................................................................ 113

Conclusion ................................................................................................................................... 122

Experimental Section................................................................................................................... 123

Acknowledgements ..................................................................................................................... 126

References ................................................................................................................................... 126

Conclusion du chapitre III ................................................................................................................ 129

Chapitre IV : Transposition de la synthèse d’α,α-difluoroacides au resvératrol pour la synthèse de

Introduction du chapitre IV ............................................................................................................. 133

Abstract ....................................................................................................................................... 135

Introduction ................................................................................................................................. 135

Results and Discussion ................................................................................................................ 137

Conclusion ................................................................................................................................... 144

Experimental section ................................................................................................................... 145

Acknowledgements ..................................................................................................................... 148

References ................................................................................................................................... 148

Conclusion du chapitre IV................................................................................................................ 153

Conclusion générale ............................................................................................................................ 155

Annexes A : annexes au chapitre II...................................................................................................... 163

Annexes B : annexes au chapitre III ..................................................................................................... 191

Annexes C : annexes au chapitre IV..................................................................................................... 211

Production scientifique ................................................................................................................... 225

Articles publiés............................................................................................................................. 225

Articles à soumettre prochainement ........................................................................................... 225

Participations à des congrès scientifiques ...................................................................................... 226

LISTE DES ABREVIATIONS

ATR attenuated total reflectance - réflectance totale atténuée

NMR nuclear magnetic resonnance - résonnance magnétique nucléaire (RMN)

La vision binaire historique scindant thermodurcissables et thermoplastiques a commencé à être mise

Figure A. Représentation schématique de la structure de (a) réseaux 3D (thermodurcissables), (b) linéaires

CHAPITRE I : ETAT DE L’ART SUR LES REACTIONS