Construction and Building Materials 301 (2021) 124065

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Construction and Building Materials

journal homepage: www.elsevier.com/locate/conbuildmat

Review

Origin and industrial applications of lignosulfonates with a focus on their

use as superplasticizers in concrete
Damien Breilly a,b, Sami Fadlallah a, Vincent Froidevaux b, Antoine Colas b, Florent Allais a,⇑
a
URD Agro-Biotechnologies Industrielles (ABI), CEBB, AgroParisTech, 51110 Pomacle, France
b
CHRYSO, 7 rue de l’Europe, Z.I. 45300 Sermaises du Loiret, France

h i g h l i g h t s

Superplasticizers are used as dispersants to alter the properties of fresh and hardened concrete.

Superplasticizers modify concrete properties such as workability, fluidity, and setting time.

Current superplasticizers are fossil-based and do not comply with the green chemistry principles.

Lignosulfonates are promising materials for the production of sustainable superplasticizers.

Chemical functionalities of lignosulfonates offer a wide range of structural modifications.

a r t i c l e i n f o a b s t r a c t

Article history: In concrete technology, superplasticizers (SPs) are commonly used to reduce water content in concrete
Received 29 December 2020 admixtures. Although most of them are fossil fuel-based, some derive from lignosulfonates (LS), that
Received in revised form 20 June 2021 are sustainable and environmentally-friendly polyphenolic crosslinked polymers. Indeed, LS are an inex-
Accepted 21 June 2021
pensive and abundant raw material that contains a variety of functional groups including hydroxyls
which can be involved in a wide range of chemical modifications to finely tune the physico-chemical
properties of the material. This review presents: (1) the current SPs and their mechanism of adsorption
Keywords:
and dispersion as admixtures to improve the properties of fresh concrete (e.g., workability, fluidity, set-
Lignosulfonate
Superplasticizer
ting time and water reducing ability) and that of hardened concrete (e.g., compressive and flexural
Cement strength), (2) LS origin and structure, (3) the various LS functionalization methods reported in the liter-
Concrete ature since 2000, and (4) their corresponding applications in the different fields such as water depollu-
Green chemistry tion, dispersant, superadsorbant, antioxidant, material replacement, and more specifically as water
Biorefinery reducers for concrete. A special focus is made on the cement-SPs interactions and the impact of the
modified-LS structures on the efficiency of concrete. This review aims at demonstrating that, in the con-
text of green chemistry, biorefinery and bioeconomy, sustainable chemical modification of low cost and
abundant LS is a worthwhile approach to design materials that find applications in critical industries such
as the concrete sector.
Ó 2021 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Action mechanisms of SPs and interaction with concrete . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
3. Evolution of superplasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
4. Structure, characterization and production of lignin derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
4.1. Methylolation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.2. Sulfonation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.3. Esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.4. Etherification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

⇑ Corresponding author.
E-mail address: [email protected] (F. Allais).

https://doi.org/10.1016/j.conbuildmat.2021.124065
0950-0618/Ó 2021 Elsevier Ltd. All rights reserved.
D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

4.5. Polyurethane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.6. Radical activation for free radical polymerization, enzymatic reaction and radical grafting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
4.7. Pegylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
4.8. Grafting via nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
5. Modified LS and their application in concrete industries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
6. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

1. Introduction state-of-the-art is given on the most common SPs employed for

building applications.
High-range water reducers, better known as superplasticizers
(SPs), are concrete admixtures used in construction industries as 2. Action mechanisms of SPs and interaction with concrete
dispersants for aqueous mineral suspensions in order to alter the
properties of fresh and hardened materials. SPs affect the physical The main role of SPs is to reduce the amount of mixing water,
properties of these materials such as rheology, workability, com- known as water reduction, while improving or maintaining the
pressive and flexural strength. Moreover, their chemical structures workability of concrete by retarding agglomeration. Having an
impact the adsorption, conductivity and zeta potential of the fresh excess amount of water during the concrete hardening leads to
concrete. A number of reviews have described the research carried the creation of porosity after partial water consumption/evapora-
out in the development of concrete admixtures and the structure- tion. This can limit the strength and durability of the concrete. Con-
properties relationships [1–3]. For instance, Khudhair et al. [1] cisely, SPs adsorb on the surface of the cement particles due to the
described the various chemical admixtures used as formulations presence of calcium ions at the interface between the cement par-
for building materials. Houst et al. [2] discussed the several param- ticles and the interstitial solution (Fig. 1a). Firstly, thanks to their
eters considered in the calculation of interparticle forces in cemen- negative charges, the attractive forces between the aggregates
titious suspensions. Furthermore, Mollah et al. [3] covered the are reduced, and flocculation is limited (electrostatic hindrance).
interfacial structure, properties and effects of SPs structure on Moreover, the newly formed layer of SP hinders the diffusion of
the cement-SPs interactions. All these reviews explained the action calcium ions into the matrix by complexation - an important step
of SPs admixtures during the hydration of cement particles, i.e., the of cement hydration - thus retarding the entire process and chang-
setting phase of cement where the concrete turns from fluid to ing the setting time. Secondly, with the most recent generations of
hard. However, due to the rise of environmental awareness caused SPs, hydrosoluble side chains such as polyethylene oxide (PEO) are
by the continuous use of fossil fuel resources, the demand of grafted on the polymers in order to achieve a better dispersion.
renewable and natural products is greatly increasing. Indeed, the Indeed, the added side chains can be deployed in water due to their
vast majority of SPs used as concrete admixture are fossil fuel- affinity and interpenetrate each other. Such interpenetration
derived (e.g., polycarboxylate ether). Thus, the transition from cur- increases the repulsive force of the ‘‘hairy”-like chains which
rent non-renewable SPs to new sustainable materials is highly improves the dispersion of cement-SPs aggregates in the system
needed. In this context, lignosulfonat (LS), renewable byproducts while avoiding flocculation. This is called the steric (or entropic)
of wood pulp production, holds tremendous potential for the syn- effect (Fig. 1b). All these changes brought by efficient SPs improve
thesis of biobased SPs. the rheological behavior of the fresh concrete and allow good
The scope of this review is mainly focused on the reported mod- workability without the need for an excess amount of water.
ifications of LS since 2000 with a special attention to the applica-
tions of these modifications in the field of concrete industry. For 3. Evolution of superplasticizers
a better understanding of the structure-properties relationships,
the action of SPs is described while explaining the interaction SPs and simple plasticizers are hydrosoluble polymers that can
between concrete and SPs molecular structures. Furthermore, a be natural, such as LS, or synthetic such as polynaphtalene

Fig. 1. a) Classical adsorption of SPs on the cement surface, b) entropic effect.

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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Fig. 2. Structural representation of a) LS, b) PNS, c) PMS, d) PCE.

sulfonate (PNS), polymelamine sulfonate (PMS) and polycarboxy- the hydration process. In fact, the performance of PCE depends on
late ether (PCE), the most common polymers used for this purpose many parameters including the length, chemical nature, distribu-
(Fig. 2). According to the NF EN 934 French regulation, SPs - such as tion, anionic charge density of both backbone and side-chains
PCE - reduce water by more than 12%, whereas the range of water [13,14]. Several reviews on PCE have been published in the last
reduction for simple plasticizers such as LS is 5–12%. few years and show how rapidly this field has been evolving
LS was the first tested polymer exhibiting good adsorption, i.e., [15,16]. Nevertheless, PCEs, as well as PNS and PMS, are mainly
an electrostatic repulsion effect. This natural polymer was used obtained from non-renewable fossil fuel feedstocks which necessi-
without any modification in the 1930 s owing to its high availabil- tate their replacement by new biomass-derived substitutes.
ity and low cost [4–6]. However, LS showed a limited water reduc- Indeed, in the context of the revolution of circular economy, special
tion capability of 8–10% [4]. Although LS is among the cheapest considerations are being directed to make products from biomass
admixtures present in the market, such low water reduction pre- by-products such as LS. Nonetheless, in most cases, such renewable
vented its usage to design high-performance concrete. Conse- materials suffer from the poor properties that need to be improved
quently, constant investigations showed that increasing the to comply with the applications sought in the industrial sectors
molecular weight (Mw) of LS to 80 kDa leads to an increase in the such as concrete. For instance, although LS was used previously
water reduction to reach 20% and improves the workability reten- for the presence of sulfonate groups that enhance its solubility in
tion [4]. aqueous solution, unmodified LS does not provide concrete with
In the same period, PNS was developed for textile chemicals and efficient properties due to the lack of entropic effect [2]. For this
synthetic rubbers. PNS was later found suitable for their use as a reason, various research groups have dedicated great efforts to
water reducer in the 1960s [6] due to their dispersing effect [7]. modify the LS through the functionalization of the reactive groups
Aside from improving the workability and water reduction, PNS present in their structure (e.g., phenolic groups, alcohols)
brings a certain resistance to freeze–thaw cycle for concrete [8]. [32,33,70,79,88,89,92,93]. Such an approach can improve the prop-
Later, PMS was discovered in the 1970s. Although the plasticiz- erties of LS and widen its range of applications as a cheap and
ing ability and water reduction of PMS are comparable to that of abundant biobased product.
PNS, PMS provides higher slump loss, i.e., a decrease in fluidity,
while bringing less retardation during cement hydration [9]. Nev-
ertheless, because of the negative impact on the environment 4. Structure, characterization and production of lignin
due to the residual formaldehyde (Volatile Organic Chemical, derivatives
VOC) liberated during the hardening [10] and the lack of diversity
in the number and types of the monomers used, these synthetic Lignocellulosic biomass is the most abundant natural resource
polymers were replaced. on Earth. It contains lignin that can be extracted by the wood-
In the late 1980 s, polyacrylate-based polymers appeared as pulp industries for industrial and academic use [17]. Lignin, and
interesting candidates due to the large variety of the constituting all its technical derivatives such as LS, have very complex and
monomers [6,11,12], and led to the development of polycarboxy- heterogeneous structures that are not only based on three consti-
late ether (PCE). PCE is composed of: (1) a backbone chain assem- tuting phenolic monomers (monolignols: coniferyl alcohol, cou-
bled through the radical polymerization of vinylic acid such as maryl alcohol, and sinapyl alcohol; Fig. 3), but also strongly
acrylic acid, maleic acid or methacryclic acid, and (2) side-chains depends on the plants/tree species and environment. As repre-
such as polyethylene oxide (PEO) or polypropylene oxide (PPO). sented in Fig. 4, monolignols can connect to each other through
The dispersing abilities of these polymers principally come from various covalent linkages, namely a-O-4, b-5, b-O-4, 5-5, 4-O-5,
the non-adsorbing side chains that create an entropic effect and b-1 and b-b bonds. The proportions of the monomers and that of
lead, in the case of PCE, to a water reduction of around 40%. More- the different strong C–C and labile C-O-C linkages greatly depend
over, PCE improves the slump life, in addition to the retardation of on the origin of lignin (e.g., softwood or hardwood) [18]. The char-
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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Fig. 3. The three constituting monolignols in lignins.

Fig. 4. Possible linkages of lignin.

Scheme 1. Mechanism of the sulfite process.

acterization of lignin was thus a great challenge to tackle due to the (SEC) that provide crucial insights on the structure and MW, respec-
complexity of the crosslinked structure of lignin and the diverse tively [19,20,21,22].
occurrence of monomers and linkages. Continuous investigations LS are obtained through the sulfite pulping process (Scheme 1)
showed how lignin main structure can be more precisely deter- [23], that was integrated into a biorefinery for the first time in the
mined through spectroscopy (UV, FTIR, 31P NMR, 1H NMR, 13C 1990s [24]. The degradation mechanism of lignin into LS starts
NMR and 2D-HSQC-NMR) and size exclusion chromatography with the acid-catalyzed cleavage of the b-O-4 linkage that creates
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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 2. (a) Methylolation of LS, (b) synthesis of resin phenol-LS.

a benzylic carbocation intermediate while reducing native lignin phenomenon. This parameter can be improved according to three
Mw. The transient carbocation then undergoes a nucleophilic attack main approaches.
by a sulfite to provide LS. The spent sulfite liquor obtained through The first one was developed to turn classical lignin into sodium
this process contains lignosulfonate as well as mono/oligosaccha- LS in the presence of Na2SO3 at high temperature and high pressure
rides and acetic acid. Finally, the process ends with extraction to (Scheme 3a). This approach is similar to the sulfite process previ-
provide pure LS. ously described in Scheme 1, except that the Mw is not affected
because the sulfonate groups are grafted on the benzylic double
4.1. Methylolation bond in the presence of Na2SO3 rather than breaking it.
The second sulfonation approach relies on the new hydroxyl
Methylolation, also known as hydroxymethylation, is an old and groups formed by methylolation. These groups can be employed
classical way to functionalize LS. The Lederer Manasse reaction is to access LS having higher sulfonate content compared to the syn-
used to add new aliphatic hydroxyl groups on the phenolic struc- thesis reported in the first strategy thanks to the increased number
tures in presence of formaldehyde under basic conditions of hydroxyl groups (Scheme 3b). For example, Yu et al. [32] and Wu
(Scheme 2a). Alonso et al. [25] reported that softwood LS is prefer- et al. [33] performed such modification of LS to produce LS-based
able for an efficient methylolation reaction to occur due to the SP. Furthermore, Yanhua et al. [29] and Li et al. [34] studied the
higher number of aromatic protons and phenolic hydroxyl groups effect of sulfonate content on the surface activity, and showed that
compared to hardwood LS. This reaction was employed by differ- the latter increases when LS was used instead of kraft lignin.
ent research groups to access a wide variety of products. For Recently, Qiu et al. [35,36] developed a third approach to signif-
instance, Yamini et al. [26] used it to prepare epoxy resins, Bai icantly improve the sulfonate content and studied the dispersion
et al. [27] for urea–formaldehyde polymer, Wang et al. [28] for properties of the resulting material. In this reaction, cyclic 1,4-
phenolic resin, and Yanhua et al. [29] for grafting aliphatic polya- butanesultone is opened by the phenolic and aliphatic hydroxyl
mine by a one-pot reaction on LS in the presence of sodium groups of the LS in the presence of sodium hydroxide
hydroxide and formaldehyde. Other researchers such as Wang (Scheme 3c). It is noteworthy to mention that no formaldehyde,
et al. [30], used a dialdehyde (e.g., glutaraldehyde) instead of which is a highly toxic and volatile, is required in this approach.
formaldehyde to crosslink triethylenetetramine and LS in order Lee et al. [37] found a method to obtain a sulfonated material
to create an adsorbent for dye molecule. from LS by treating it with a large excess of sulfuric acid at high
This formaldehyde-mediated reaction can be useful to create temperature (<200 °C). The resulting product is represented in
nanosphere by crosslinking LS with other molecules. Pandey et al. Fig. 5. It was tested as a catalyst for classical esterification reactions
[31] synthesized a nanosphere for biomedical and environmental [37].
use by crosslinking LS and chitosan in presence of formaldehyde
and sulfuric acid. Wang et al. [28] reported the crosslinking of phe- 4.3. Esterification
nol with LS to prepare core–shell microspheres for highly efficient
removal of cationic dyes from aqueous solution (Scheme 2b). One of the best methods to improve LS properties is to perform
the esterification of the aliphatic and phenolic hydroxyl groups, as
4.2. Sulfonation well as the carboxylic acids.
LS can be used as a biomass-derived building block to prepare
The sulfonate content is an important parameter to consider if renewable materials, such as hydrogels, by grafting prepolymers
one wants to improve some properties related to the adsorption on it. Wang et al. [38,39] used maleic anhydride under basic condi-
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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 3. (a) Classical way for modification of lignin into sodium lignosulfonate, (b) sulfomethylation, (c) sulfobutylation.

dride. This newly formed acrylate was then subjected to radical

polymerization (Scheme 4b).
Polyethylene terephtalate (PET), which is produced from the
esterification of ethylene glycol (EG) and terephtalic acid (TA)
using Sb2O3 as a catalyst, is one of the most used commodity poly-
mers. Ma et al. [42] reported a novel family of PET/LS copolymers
containing 0.5%w/w to reinforce the mechanical and dielectric
properties of PET. Nevertheless, they showed that the amount of
LS must be kept as low as 0.5%w/w otherwise an excessive amount
of LS would have a detrimental effect on the mechanical properties
of PET. The molecule is represented in Scheme 4c.
Moreover, Ismail et al. [43] developed adhesives through the
esterification of succinic anhydride, EG and LS to prepare a prepoly-
Fig. 5. The resulting product from LS under concentrated sulfuric acid (<200 °C). mer to which glycerol diglycidyl or ethylene glycol diglycidyl ether
were subsequently added to crosslink the structure (Scheme 4d).
Li et al. [44] replaced sodium alkanoate, a hazardous catalyst, by
tions to improve mechanical and thermal properties of LS in LS/p a greener natural catalyst, i.e., choline chloride, in the esterification
oly(e-caprolactone) blends. Similarly, Panzarasa et al. [40] used a of LS with butyric anhydride[45]. Choline chloride disrupts the
copolymer - poly(ethylene-alt-maleic anhydride) - allowing to hydrogen bonds in the LS structure thus increasing its solubility
graft different functions in a one-pot reaction (Scheme 4a). and catalyzing the esterification reaction. This reaction can be
Another way to obtain hydrogels through the esterification of LS considered as a green method for the esterification of a natural
was explored by Jin et al. [41] who used esterification to graft polymer, such as LS, as it uses cheap and environmentally friendly
chemical groups bearing a double bond such as methacrylic anhy- reagents (Scheme 4e).

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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 4. (a) Esterification of LS and poly(ethylene-alt-maleic anhydride), (b) esterification of LS with methacrylic anhydride, (c) PET with LS as diol, (d) synthesis of LS-
based adhesives, (e) the mechanism of the green butyration of LS.

4.4. Etherification conditions such as high pressure, high temperature, and strong
acidic and basic media. Generally, halogenated compounds are
Etherification is also a common way to functionalize LS by used to easily create ether bonds with phenolic and aliphatic
creating a strong carbon–oxygen bond that can withstand harsh hydroxyl groups through Williamson etherification. Barhpaima

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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 5. (a) carboxyethylation of LS, (b) synthesis of a two-component adhesive (A and B), (c) epoxidation of LS, (d) oxypropylation of LS, (e) etherification of LS by
epichlorohydrin under hard conditions.

et al. [46] etherified phenol-protected LS with 2-chloropropionic urethane (PU) (Scheme 6c). De Oliveira et al. [49] also used epoxide
acid to obtain carboxyethylated LS and thus extended the possible to prepare PU by oxypropylation of LS as depicted in Scheme 5d.
applications of the modified LS by replacing the aliphatic groups In an attempt to reduce the adsorption capacity of LS to use it as
with reactive carboxylic acid (Scheme 5a). Empire Technology a dye dispersant, Yu et al. [50] used epichlorohydrin at 90 °C and
Development LLC [47] developed LS-based adhesives by etherify- under basic conditions (pH 11–12) to etherify the phenols
ing LS with propargyl bromide and 2-bromoethanol to form mole- (Scheme 5e). Other research groups focused their work on lignin
cules A and B, respectively (Scheme 5b). The latter was reacted at a lower temperature (70 °C) [51], to obtain epoxidized lignin
with phosphorus tribromide and sodium azide to transform the which can be compared with Yu’s results who assumed that when
primary alcohol into an azide. A and B can react through click- a relatively small amount of epichlorohydrin was added at low pH,
chemistry under mild pressure conditions (Scheme 6b). the reaction between lignin and epichlorohydrin yielded product C
A well-explored approach to etherify LS is the functionalization (Scheme 5e). On the other hand, increasing the pH and amount of
of LS through glycidylation, followed by the opening of the result- epichlorohydrin led predominantly to product D (Scheme 5e) [50].
ing epoxide with different molecules. It is a two-step reaction: first,
a phase-transfer catalyst (e.g., tetrabutylammonium bromide) is 4.5. Polyurethane
added to LS and epichlorohydrin to generate phenolates in solu-
tion, thus allowing the ring-opening of epichlorohydrin. Finally, PU is an efficient material used in many applications such as
in a second step, sodium hydroxide is added to close the opened thermal isolation or foams. PU can be prepared by the reaction of
oxirane on LS. A SN2 mechanism on the carbon bearing the chloride two reactive monomers, a diol and a diisocyanate, as illustrated
is also possible to directly obtain the resulting oxirane. Yamini in Scheme 6a(i). Interestingly, Leitner et al. [52] used LS as a polyol
et al. [26,48] reported the glycidylation on LS to to synthesize poly- to synthesize PU by mixing LS with toluene-2,4-diisocyanate (TDI)
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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 6. (a) (i) Classic polyurethanization, (ii) polyurethanization from LS, (b) polyutheranization of LS and LDH via MDI using blocking agent (acetanilide).

at 60 °C for 24 h (Scheme 6a(ii)). It was observed that not only the a blocking agent such as acetanilide, and changed the reaction
reaction is favored on phenols compared to aliphatic alcohols, but temperature to lock or unlock the diisocyanate in order to obtain
also the sulfonate groups act as a catalyst for the reaction. Through control of the polymerization, thus facilitating the study of the
this approach, they built nanosized salt crystals as well as PU- properties (Scheme 6b).
based hydrogels for water absorption. Due to their toxicity for humans and the environment, iso-
The reaction between various ethylene glycols (EG) (e.g., cyanates need to be replaced in PU synthesis. Many research
diethylene gycol (DEG), triethylene glycol (TEG), or polyethylene groups have been looking for greener synthetic methods and sub-
glycol (PEG)) as a diol with a common diisocyanate (e.g., methy- stitutes. For example, a safer and more sustainable alternative to
lene diphenyl 4,40 -diisocyanate (MDI)) was studied by Hatakeyama the classical urethane bond formation was developed [57]. This
et al. [53,54] to improve the properties of the newly formed mate- strategy relies on the glycidylation of a diol, followed by the
rials such as glass transition temperature. Moreover, Lu et al. [55] lithium bromide-catalyzed opening of the resulting oxirane by
used a mixture of LS, DEG and MDI to obtain flame retardant build- CO2 to obtain cyclic carbonate. Then, the latter is opened by a dia-
ing on Hatakeyama’s previous work. They observed that, by limit- mine to obtain non-isocyanate polyurethane (NIPU) (Scheme 7a).
ing the oxygen content in the matrix, phenols prevent the This reaction presents the advantages of being isocyanate-free,
formation of flames. De Oliveira et al. [49] combined crude and and avoids the dispersion of toxic unreacted molecules into the
oxypropylated-LS with OH-containing vegetable oil, such as castor environment. Also, it uses CO2 as a sustainable reagent. Unfortu-
oil, before reacting it with MDI. They showed that oxypropylation nately, this method is not readily industrialized as it requires pres-
and such association with castor oil allow a fine-tuning of PU prop- sure reactors; moreover, only a few developments were performed
erties based on a difference in reactivity between crude and for this method on lignocellulosic materials, specifically on LS
oxypropylated LS. This was due to a lower diversity and a better [58,59].
accessibility of hydroxyl groups for the polyurethanization of the This method was applied by Yamini et al. [48,26] using biobased
latter. After prepolymer formation, the final polymerization - materials such as LS to transform lignin-based industrial waste
called ‘‘cure cycle” - required a lower temperature compared to into a value-added reinforcing agent for epoxy matrix composites.
classical polyurethanization of LS, which is a great advantage for To increase the hydroxyl content and thus that of carbonate
industrial purposes. groups, they methylolated, glycidylated, and carbonated LS before
An interesting strategy for PU synthesis was developed by He proceeding to the polyurethanization (Scheme 7b). The obtained
et al. [56] who grafted LS with layer double hydroxides (LDH, inor- resin, completely cured - which means the reaction is total after
ganic materials) via MDI, TDI or isophorone diisocyanate (IPDI) to the formation of prepolymers - are eco-efficient materials with
obtain UV additives for bitumen. They controlled the reaction with higher mechanical properties compared to classical NIPU.

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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 7. (a) Example of synthesis of NIPU, (b) synthesis of LS-based NIPU with DGEBA and DETA, (c) alternative synthetic pathway to LS-NIPU.

Mimini et al. [60] used directly cyclic carbonate to build LS- merization of LS. An old method is the use of Fenton reagent (i.e.,
based NIPU following another method without using epichlorohy- ferrous ion such as FeSO4 or FeCl2) as an initiator, in the presence
drin which is considered a toxic compound. They performed a of hydrogen peroxide, to generate a radical as depicted in
direct esterification reaction on LS with glycerol carbonate in the Scheme 8b [61].
presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a catalyst. Ye et al. [61] used Fenton reagent with acrylic acid to initiate a
This step was followed by the polymerization with hexam- growing acrylic chain on LS. The Texaco company [62] used a LS-
ethylenediamine (Scheme 7c). co-poly(acrylic acid) to prepare a sacrificial agent for carbon diox-
ide foaming agents. Moreover, seeking an adjuvant to control the
4.6. Radical activation for free radical polymerization, enzymatic viscosity of water-based mud systems for deflocculation, Akzo
reaction and radical grafting Nobel Chemicals International [63] used Fenton-type polymeriza-
tion to prepare a copolymer based on LS, monomethylmaleate,
The use of a radical initiator to grow up chains or to graft acrylic acid and hydroxymethylmetacrylate (Scheme 8c). Similarly,
molecules on LS is another functionalization strategy Liu et al. [64] made a dust depressor based on LS-co-poly(acrylic
(Scheme 8a). LS could be used as an initiator by deprotonating acid) using FeSO4. Although this method was industrialized thanks
phenols as illustrated below in this review. Several initiation to its efficiency, it cannot be considered green because of the use of
methods were explored in the literature for the free radical poly- ferrous ions which can be released in the environment.

10
D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 8. (a) Classic free radical polymerization mechanism, (b) mechanism of initiation via Fenton reagent, (c) example of one-pot free radical polymerization of LS via
Fenton reagent for various monomers, (d) initiation of radical polymerization with LS via ascorbic acid, (e) mechanism of radical polymerization of LS and vinylic monomers
via thermally-induced initiation with KPS.

11
D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

In a greener process, Zhao et al. [65] replaced Fenton reagent by 2-methylpropane sulfonic acid (AMPS) via KPS at 60 °C. The sul-
a system composed of safe and naturally occurring ascorbic acid fonic acid and carboxylic acid moieties grafted on a chain grown
and hydrogen peroxide to synthesize LS-based hydrogels and from LS through AMPS improve concrete properties by retarding
acrylic acid with N,N0 -methylenebisacrylamide (MBAAm) as a the setting time.
crosslinking agent. Ascorbic acid/hydrogen peroxide initiation Jin et al. [41] made pH-responsive hydrogels through a two-step
mechanism is illustrated in Scheme 8d. reaction: esterification followed by radical polymerization. In a
Abdollahi et al. [66] compared two methods of initiation: a first step, they esterified LS with methacryclic anhydride to graft
redox system using calcium chloride and hydrogen peroxide, and a double bond as described in Scheme 4b. Then, they thermally
a thermally-induced initiation system using persulfate potassium. activated this double bond via KPS to grow up the pH-responsive
They synthesized environmentally friendly additive for high salty copolymer of itaconic acid and N-isopropylacrylamide (NIPAM).
water-based drilling fluid with a copolymer of LS and acrylamide Kunpeng et al. [71] thermally activated both chitosan and LS
where 13.3% of conversion was recorded for the thermal system with KPS and sodium thiosulfate to create a crosslinked matrix that
vs. 3.38% for the redox system. They concluded that the proved a good agent of deflocculation for water depollution. Liu
thermally-induced initiation system is both more efficient and et al. [72] grafted N,N-dimethylacrylamide and c-
more environmentally friendly for the radical polymerization of methacryloxypropyl trimethoxy silane on LS via KPS and sodium
LS in comparison to a redox system using ferrous ion or chloride bisulfite to obtain filtration reducer for water-based drilling fluid.
ions. Another way to green up the radical polymerization of LS with
Concerning the radical formation by thermal activation, many vinyl monomer (e.g., acrylamide, acrylic acid) consists of using
researchers used potassium persulfate (KPS) to initiate classical microwave or ultrasounds-activated new technology that signifi-
polymerization. For instance, Xu et al. [67] made hydrogels in order cantly reduces the reaction time while increasing yields. The Initia-
to remove dyes from water by copolymerizing acrylic acid, LS and tor is activated by irradiation instead of heating (Scheme 9a).
ethylene glycol dimethacrylate in a mixture of dioxane and water Zhang et al. [73] chose microwave for copolymerizing acrylamide,
by thermal activation and UV (Scheme 8e). Yao et al. [68,69] also dimethyldiethylammonium chloride on LS, thus creating polymers
followed this method to create composite adsorbing Pb2+ in con- with better flocculation performances useful for dye removal. They
taminated water by copolymerizing LS with acrylamide (AM)/ added ethylenediaminetetraacetic acid (EDTA) into the reaction to
NMBA, then acrylamide/maleic anhydride. chelate any traces of metal ions, as well as ammonium persulfate
Thermal activation can be useful to obtain industrial products (APS) and sodium bisulfite (NaHSO3) as thermal initiator. Zhang
such as retarders for phosphoaluminate cement. Ma et al. [70] opti- et al. [73] were able to produce the modified LS in 14 min com-
mized the copolymerization of LS, itaconic acid and 2-acrylamido- pared to several hours for a reaction without microwave activation.

Scheme 9. (a) Microwave-assisted initiation of radical polymerization of LS, (b) example of ultrasound-assisted radical copolymerization for hydrogels synthesis.

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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

4.7. Pegylation

Polyethylene glycol (PEG) chains are generally helpful for differ-

ent applications as they provide hydrophilicity and create entropic
effect, two key properties for specific applications such as concrete.
Pegylation consists of grafting PEG on synthetic or natural mole-
cules such as LS. While different pegylation strategies have been
reported in the literature, only a few were applied to LS [82,83,84].
Teng et al. [85] synthesized PEG-LS-based hydrogels using a
two-step reaction: Mannich reaction using formaldehyde and
diethylenetriamine (DETA) to graft amine groups on the aromatic
cycle, and grafting of polyethylenediglycidylether (PEGDE). In this
example, both diamine and phenol can open the oxirane, thus lead-
ing to a crosslinked network (Scheme 10a).
Generally, epoxidized PEG was mainly used to be grafted on the
phenol moiety (Ar-OH) through etherification. Lin et al. [82] stud-
ied the effect of LS-PEG on enzymatic hydrolysis of lignocellulose.
They observed that cellulose adsorbs on lignin, thus limiting its
hydrolysis. To overcome this, they proposed using LS-PEG to favor
hydrolysis by preventing cellulose adsorption. To do so, they syn-
thesized diepoxide-PEG in presence of epichlorohydrin, and BF3.
Et2O as a catalyst, and grafted the latter on LS at pH 13 at 80 °C dur-
ing 3 h. Ou et al. [86] prepared LS-based polypropylene glycol
diglycidyl ether, by grafting polypropylene glycol diglycidyl ether
(PPGDE) on LS at 70 °C for 5 h at pH 11, to evaluate its performance
as a detergent builder and more generally as surfactant by studying
their emulsifying and dispersing ability.
Another possible route for the pegylation is to use directly the
sulfonate groups of sulfonated lignin. Empire Technology Develop-
ment LLC [83] synthesized an adhesive based on pegylated LS. Mit-
sunobu reaction with triphenyl phosphine and diethyl
azodicarboxylate was used to add PEG on LS (Scheme 10b).
Finally, Gupta et al. [84] wanted to obtain a LS-PEG plasticizer
for concrete by creating a hybrid between LS and PCE which is
Fig. 6. Mechanism of enzymatic grafting of LS on starch. Copyright [81]
the actual SP used in industry. To synthesize it, tosylated PEG
was prepared and then grafted on LS (Scheme 10c). The perfor-
Other researchers, such as Hao, Zhang, Wang et al. mance of the new SP will be discussed later in this review.
[74,75,76,77,78] used ultrasonic reactors to copolymerize LS. Such
a polymerization method is considered green and fast as it helps 4.8. Grafting via nitrogen
with the dispersion of molecules into the solvent and favors the
radical activation of LS. They obtained superabsorbent hydrogels As previously shown in the section devoted to methylolation,
using ammonium or potassium persulfate as initiator, N,N0 - formaldehyde can be used to graft new aliphatic hydroxyl groups
methylenebisacrylamide (NMBA) as a crosslinker and acrylic acid, on phenolic structures. By combining formaldehyde and amine,
maleic acid, vinyl alcohol, and acrylamide as monomers. The reac- other possibilities to functionalize LS were reported. Using Man-
tion was heated at 53 °C and 70 °C for 2 and 3 h, respectively, both nich reaction with formaldehyde and tetraethylenepentamine,
at a power of 250 W, and at a frequency of 40 kHz. They also made Gao et al. [87] synthesized polycatecholamine-based hydrogels
hydrogels for drug delivery by copolymerizing LS, acrylic acid and able to remove dyes from water through a two-step reaction: graft-
polyvinylpyrrolidone (PVP) also under ultrasounds at 100 W and ing of aliphatic polyamine onto LS with formaldehyde (5 h, 90 °C),
40 kHz (Scheme 9b). and addition of the catechol in the reaction to allow polymeriza-
Radical polymerization can be useful for the grafting of different tion (48 h, room temperature) (Scheme 11a). This functionalization
chemical moieties. For example, Sun et al. [79] grafted methacrylic strategy was also used by Teng et al. [85] and Yanhua et al. [29] to
acid (MAA), methoxy polyethylene glycol methacrylate graft PEG and polyamine on LS, respectively.
(MPEGMA), sodium methyl acryl sulfonate (SMAS), PEG, sulfonate Then, Bai et al. [27] applied the same concept to create urea–
and carboxylic acid groups on LS to create functional polymers for formaldehyde-LS microcapsules from hydroxymethylated pre-
the concrete industry as it will be further discussed in this review. polymers to encapsulate acetochlor, a phytosanitary product
Furthermore, Sudrajat et al. [80] simply added PEG on LS after (Scheme 11b).
using KPS. Starting from triethylenetetramine and glutaraldehyde, Wang
LS-based free radicals can be formed by enzymes as well. Shog- et al. [30] also obtained aminated LS to adsorb on dyes for water
ren et al. [81] grafted LS on starch using Trametes versicolor laccase depollution. It is worthy to note that the use of glutaraldehyde -
catalysis in an aqueous solution. 1-Hydroxybenzotriazole (HBT) a dialdehyde - instead of formaldehyde further increased crosslink-
was added into the solution as a mediator to both facilitate the ini- ing (Scheme 11c).
tiation and reduce hydrogen peroxide content (Fig. 6). The combi- In order to study the mechanical properties of the concrete mix-
nation of starch, LS, and an enzyme is a great strategy to green up ture with modified LS as a water reducer, another nitrogen-based
the production of an adjuvant, such as an antioxidant, as it replaces linkage was tested by Li et al. [88,89] They grafted p-
a non-environmentally friendly catalyst system by natural aminobenzene sulphonic acid on LS under chlorohydric acid and
enzymes while employing natural polymers. sodium nitrite (Scheme 11d). Also, Zhang et al. [90,91] developed
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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 10. (a) Creation of network with PEG and Mannich reaction, (b) Mitsonubu conditions for pegylation of LS, (c) pegylation of LS via tosylation.

drilling fluid additives from LS after nitration and oxidation of phe- ments to understand the impact of grafting PEG on the affinity of
nol. Furthermore, after methylolation, Lignotech USA [92] ammox- LS for cement particles (Fig. 7). A plateau was observed at
idized LS under high pressure and temperature with ammonium concentrations  4 mg/mL which is similar to that of PCE SPs. On
hydroxide to obtain LS possessing free nitrogen as amide, nitrile the other hand, when unmodified LS was employed, a continuous
and/or amine functional groups. The final modified LS was used increase in adsorption with respect to concentration was observed
as a dispersant for concrete. (Fig. 7). This difference in behavior towards the cement particles
can be explained by the absence of multilayer structure when
grafted PEG chains are added in the mixture, even at low PEG graft-
5. Modified LS and their application in concrete industries
ing content. Indeed, the repulsion generated by PEG chains limits
the possibility to form a new layer that increases both the disper-
In this section, a special focus will be given to the use of LS as
sion and water reduction capacity of the SP. Furthermore, the
SPs for concrete and how chemical modifications impact concrete
slump spread was increased by 20% which is dependent on the
physico-chemical properties. As explained previously, LS acts as a
water reduction found as 20–25%. A lower value of water reduction
plasticizer through electrostatic repulsion. However, no steric
was observed in the case of unmodified LS, commonly<12%. Con-
effect was observed, thus leading to the formation of multilayers
cerning the viscosity of the obtained concrete using pegylated LS
on the cement particles that reduce drastically its performance
as a superplasticizer, they also demonstrated that LS-PEG provides
[2]. This results in low water reduction, high setting retardation,
an effective plasticization by measuring both the storage modulus
or/and high air-entraining which creates bubbles in the matrix.
and loss modulus (i.e., viscoelastic responses of the materials).
These drawbacks can be minimized by adding chemical functions
Yu et al. [32] and Wu et al. [33] reported strategies based on the
on LS to trigger the steric effect, and to further improve the prop-
oxidation, methylation and sulfonation reaction methods to
erties of the fresh and hardened concrete. As discussed above,
improve the properties, especially, fluidity of the fresh concrete.
grafting PEG onto LS improved the separation of cement aggregates
Two general effects were observed: (1) the increase of the number
by increasing the steric repulsion between SPs triggered by the
of hydrophilic groups, such as sulfonate groups which chelate cal-
interpenetrated ‘‘hairy”-like PEG chains [84]. They compared three
cium ions, and modify the adsorption of LS on the surface of
mixtures of cement: without plasticizer, with LS and with LS-PEG
cement particles, (2) the narrowing of the Mw of LS which increases
using PEG of 900 Da. They demonstrated that PEG-grafted LS cre-
the repulsion potential energy between the particles. They studied
ates a steric effect and provides better plasticization of cement
the fluidity of the resulting materials with regards to different
compared to unmodified LS. They performed adsorption measure-
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D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

Scheme 11. (a) Copolymerization of LS and catechol, (b) creation of urea–formaldehyde-LS prepolymer, (c) crosslinking of LS-glutaraldehyde-triethylenetetramine, (d) LS
grafting via azo groups.

reaction conditions such as stoichiometric ratio, temperature and By employing the Mannich reaction, Jiangsu TMS Group[93]
reaction time for each step of the process. They demonstrated that prepared LS-based water reducer by growing aliphatic carbonyl
adding sulfonate groups improved the dispersing ability due to the compounds onto LS such as sulphite-acetone-formaldehyde (SAF)
increased content of hydrophilic groups, resulting in better fluidity. to enhance the properties of LS (Fig. 8). The aliphatic carbonyl
Also, they both observed a change in Mw and especially a reduction groups led to high water reduction despite the use of a large
in the dispersity (Ð) which enhances the repulsion between the amount of formaldehyde which is toxic for humans and the
particles. environment. Furthermore, a strong red coloration of the concrete

15
D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

However, the adsorption kept in increasing when the LS bearing

sulfonate groups was considered.
The influence of the copolymer of LS, AMPS and itaconic acid
was tested by Ma et al. [70] for application in phosphoaluminate
cement, a cement known for its rapid solidification, rapid harden-
ing and good CO2 resistance. They compared the properties - such
as thickening time which represents the duration where the slurry
remains fluid, rheology and compressive strength - of cement by
adding 3% LS or 0.5% grafted LS, both with a water/cement ratio
(w/c) of 0.5. The thickening time was measured with a consistome-
ter under high pressure and temperature, using the evolution of
consistency specifically used to study retarding effects for alumi-
nate cement [94], until it reached a limit of 75 Bearden units. They
observed that the limit was reached in 245 min at 90 °C and 3000
Fig. 7. Adsorption of LS and LS-PEG onto cement particles [84] psi and in 274 min at 75 °C and 1500 psi. As the preferential thick-
ening time should be generally between 4 and 6 h, these results
proved to be very promising. Rheology measurements demon-
strated that the grafted LS led to a good rheological behavior of
the concrete thanks to the good adsorption of molecules onto
cement particles which led to an increase in the flow. Finally, the
compressive strength at 75 °C under 1500 psi, and at 90 °C under
Fig. 8. Typical SAF molecule. 3000 psi, for grafted LS was much better than that for ‘‘neat” LS
but similar to that of cement alone. The grafted LS showed good
mixture was observed which is a critical issue for commercial use. potential to replace LS for fresh and hardened concrete.
Therefore, they decided to graft carbonyl aliphatic chains onto LS Sun et al. [79] prepared copolymers of polycarboxylate and LS
to reduce its carbonyl groups/Mw ratio in the general polymer by using MPEGMA, MAA, LS, and sodium methyl acryl sulfonate
matrix while preserving its properties. Then, they compared prop- (SMAS) to be used as SPs for concrete. They compared the resulting
erties of concretes (1) without water reducer, (2) with the aliphatic copolymers with cold combinations of LS and polycarboxylate (PC)
carbonyl alone, (3) with the newly grafted LS, and (4) with the cold at the same ratios, with a w/c about 0.29 and a quantity of water
combination of aliphatic carbonyl and unmodified LS. The viscosity reducer about 0.2%. Fluidity was measured to obtain plasticizing
was reduced in the presence of the grafted LS and the fluidity of the properties. It was demonstrated that LS-based copolymer offers
mixture was similar to the aliphatic product but higher than that of better plasticization of concrete compared to cold combinations
the cold combination. Furthermore, the water reducing ability was of LS with PC. Also, at a ratio of 5 or 10% w/w of LS in the copoly-
increased by 15% by using an aliphatic or grafted product. How- mer, compressive strength obtained for the solid concrete at
ever, the compressive strength of the concrete containing grafted 28 days was similar to the one with PC alone. Finally, those ratios
LS was inferior to that enclosing the aliphatic carbonyl but higher of 5 and 10% w/w of LS resulted in water-reducing rates higher
than the value obtained for the cold combination. Therefore, graft- than 30%, this is similar to the one obtained for common PC.
ing aliphatic carbonyl compounds on LS avoids both the strong red
coloration and the use of non-environmentally friendly reagents,
while keeping similar properties. The Mannich reaction was also 6. Conclusion
used by Lignotech USA [92] using polyamine with formaldehyde.
All the obtained formulations showed better performance in set- In this review, we defined SP - hydrophilic molecules used in
ting retardation, water reducing ability, and air-entraining limita- the field of building materials as high-range water reducers for
tion compared to commercial LS. concrete - and their sought properties. Through various examples
As shown previously in this review, sulfonate groups are con- on the commercially available SPs (i.e., LS, PMS, PNS and PCE),
sidered good hydrophilic moieties for the complexation of calcium. we demonstrated how LS, the non-expensive and abundant bypro-
Under such considerations, Li et al. [88] and Pei et al. [89] explored duct of pulp and paper industry and the only commercial SP
another way to add hydrophilic groups, such as sulfonate or car- derived from renewable resources, despite being not optimal yet,
boxylate groups, on LS structure by using diazonium salt could be a good starting point for the development of new sustain-
(Scheme 11d). Pei et al. [89] grafted a hydrophobic aromatic group able SPs via specific chemical modifications to enhance its perfor-
bearing sulfonate moiety to reduce the surface activity of LS, and mance as a concrete admixture. In many applications such as
thus decreased both air entrainment and foaming ability. The flex- hydrogels for water depollution, dispersant, superadsorbant,
ural and compressive strength of the (non-)grafted LS were mea- antioxidant, or as alternatives to some existing materials such as
sured after 7 or 28 days. The results showed that in the case of PU, PET, or epoxy resin, modifications of LS (e.g., etherification,
grafted-LS, higher dispersing ability and lower air entrainment esterification and free radical polymerization of LS) were investi-
were obtained, thus leading to higher compressive and flexural gated and proved successful, owing to the diverse active functional
strength compared to the of unmodified LS. Li et al. [88], from groups grafted. A special focus has been made on the concrete
the same laboratory, investigated this strategy but by using car- application, and the importance of adsorption and dispersion
boxylic group instead of sulfonate. They also observed a lower sur- mechanisms in the hydration process was highlighted. It has been
face activity and better mechanical properties of the concrete than concluded from the literature survey that the cement-SPs interac-
with ‘‘neat” LS. Moreover, they observed a plateau in the adsorp- tions are largely affected by the modified-LS structure, especially
tion for the functionalized LS compared to ‘‘neat” LS which showed by preventing the multilayer structure formation. Researchers
a growing adsorption profile, indicating the absence of the creation demonstrated that many chemical groups such as PEG or sulfonate
of multilayer structure. It is worthy to note that the LS-based plas- groups can significantly impact concrete properties such as
ticizer possessing carboxylates displayed better performance in adsorption, fluidity, mechanical strength, water-reducing ability
terms of adsorption where a saturation plateau was registered. or setting retardation. In order to replace the current petroleum-
16
D. Breilly, S. Fadlallah, V. Froidevaux et al. Construction and Building Materials 301 (2021) 124065

based SPs with renewable, non-toxic and environmentally friendly [18] G.E. Fredheim, S.M. Braaten, B.E. Christensen, Molecular weight determination
of lignosulfonates by size-exclusion chromatography and multi-angle laser
alternatives, concrete research needs further development and
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the production of adhesives: application to lignosulfonate, kraft, soda-
anthraquinone, organosolv and ethanol process lignins, Ind. Crops Prod. 24
Damien Breilly: Investigation, Data curation, Formal analysis,
(2006) 8–16, https://doi.org/10.1016/j.indcrop.2005.10.002.
Writing - original draft. Sami Fadlallah: Conceptualization, Visual- [21] A. Salanti, L. Zoia, M. Orlandi, F. Zanini, G. Elegir, Structural characterization
ization, Investigation, Data curation, Formal analysis, Supervision, and antioxidant activity evaluation of lignins from rice husk, J. Agric. Food
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[22] F. Oveissi, P. Fatehi, Characterization of four different lignins as a first step
tion, Supervision, Writing - review & editing. Antoine Colas: Con- toward the identification of suitable end-use applications, J. Appl. Polym. Sci.
ceptualization, Project administration, Funding acquisition, 132 (2015), https://doi.org/10.1002/app.42336.
Supervision, Validation, Resources, Writing - review & editing. [23] S. Van den Bosch, S.-F. Koelewijn, T. Renders, G. Van den Bossche, T. Vangeel,
W. Schutyser, B.F. Sels, Catalytic strategies towards lignin-derived chemicals,
Florent Allais: Conceptualization, Project administration, Funding Top. Curr. Chem. 376 (2018) 36, https://doi.org/10.1007/s41061-018-0214-3.
acquisition, Supervision, Validation, Resources, Writing - review [24] J.H. Clark, F.E.I. Deswarte, The Biorefinery Concept-An Integrated Approach, in:
& editing. Introd. Chem. Biomass, 2008: pp. 1–20.
[25] M.V. Alonso, J.J. Rodríguez, M. Oliet, F. Rodríguez, J. García, M.A. Gilarranz,
Characterization and structural modification of ammonic lignosulfonate by
Declaration of Competing Interest methylolation: modification of ammonic lignosulfonate by methylolation, J.
Appl. Polym. Sci. 82 (2001) 2661–2668, https://doi.org/10.1002/app.2119.
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The authors declare that they have no known competing finan- lignosulfonate as a bio-resourced reactive reinforcing agent for epoxy
cial interests or personal relationships that could have appeared biocomposite: from natural waste to value-added bio-additive, J. CO2 Util.
to influence the work reported in this paper. 24 (2018) 50–58, https://doi.org/10.1016/j.jcou.2017.12.007.
[27] W. Bai, Y. Wang, X. Song, X. Jin, X. Guo, Modification of urea-formaldehyde
microcapsules with lignosulfonate-Ca as Co-polymer for encapsulation of
Acknowledgement acetochlor, J. Macromol. Sci. Part A. 51 (2014) 737–742, https://doi.org/
10.1080/10601325.2014.936286.
[28] G. Wang, Q. Liu, M. Chang, J. Jang, W. Sui, C. Si, Y. Ni, Novel
D. Breilly, S. Fadlallah and F. Allais are grateful to CHRYSO, Fe3O4@lignosulfonate/phenolic core-shell microspheres for highly efficient
Grand Reims, Département de la Marne and Grand Est Region for removal of cationic dyes from aqueous solution, Ind. Crops Prod. 127 (2019)
financial support. 110–118, https://doi.org/10.1016/j.indcrop.2018.10.056.
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