Block and Graft Copolymers

11
CONTeNTs
11.1 11.2
Block and Graft Copolymers

Ali E. Muftuoglu, M. Atilla Tasdelen, Yusuf Yagci, and Munmaya K. Mishra
Introduction .................................................................................................307 Synthesis of Block Copolymers ..................................................................308 11.2.1 Block Copolymers via Conventional Radical Polymerization ......309 11.2.2 Block Copolymers via Controlled Radical Polymerization Routes ............................................................................................ 310 11.2.3 Block Copolymers via Nitroxide Mediated Polymerization (NMP)............................................................................................ 314 11.2.4 Block Copolymers via Atom Transfer Radical Polymerization (ATRP) .......................................................................................... 317 11.2.5 Block Copolymers via Reversible Addition Fragmentation Chain Transfer Polymerization (RAFT) ....................................... 325 11.3 Synthesis of Graft Copolymers ................................................................... 329 11.3.1 Synthesis of Graft Copolymers via Conventional Radical Polymerization Methods................................................................ 329 11.3.1.1 Graft Copolymers by Grafting onto Method ............. 329 11.3.1.2 Graft Copolymers by Grafting from Method ............ 330 11.3.1.3 Graft Copolymer Synthesis via Macromonomers ......... 330 11.3.2 Synthesis of Graft Copolymers via Controlled/Living Radical Polymerization Methods................................................................ 333 11.4 Conclusion ................................................................................................... 337 References .............................................................................................................. 337
11.1 INTRODUCTION
Synthesis of materials with novel properties has attracted growing scientific interest in recent years. A great deal of research activity has been devoted to this fundamental issue due to endless demands of the industry for high-tech applications. A number of strategies have been sought by polymer researchers as well as many others, in need of preparing new materials displaying improved physical and chemical properties. Such improved properties might be achieved by combining a number of physical and chemical properties and can usually be adopted by either blending homopolymers
307
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Handbook of Vinyl Polymers: Radical Polymerization and Technology
or by chemically linking different polymer chains. When two homopolymers are mechanically mixed, formation of an immiscible blend is often the case encountered. Microphase-separated heterogeneous mixtures arising from the incompatibility of the blended polymers can successfully be avoided by the latter strategy, which involves preparation of block and graft copolymers. Thus, engineering macromolecules of various block and graft structures appears to be an elegant approach in achieving polymers with improved physical and chemical properties. Preparation of block copolymers using living polymerization techniques has been known for quite a long time. Anionic polymerization [1], which provides endgroup control and permits the synthesis of polymers with a narrow polydispersity index, is a noteworthy example of these techniques. Yet, it does not offer full-control over the molecular weight of the synthesized macromolecules. The limited choice of monomers and the extremely severe reaction conditions lower its applicability. Recently, advances in controlled polymerization techniques [25], such as radical, cationic, metathesis, and group transfer, have allowed for the synthesis of polymers with predetermined molecular weights and low polydispersities. A variety of block copolymers has been prepared by cationic, group transfer, metallocene, and metathesis routes. Among others, controlled radical polymerization routes have been studied extensively, because it can be employed for the polymerization of numerous vinyl monomers under mild reaction conditions. These are atom transfer radical polymerization (ATRP) [68], nitroxide-mediated polymerization (NMP) [911], and reversible addition-fragmentation chain transfer polymerization (RAFT) [12, 13]. The significant advance in the block and graft copolymer synthesis has come with the advent of controlled radical polymerization (CRP) techniques [14, 15]. One way to prepare block and graft copolymers is by using main chain and side chain macroinitiators, respectively. In this method, reactive sites are produced at the chain ends or side chains, which serve as initiating moieties in the polymerization of a second monomer. In another approach, separately synthesized macromolecular chains having antagonist groups or latent active sites are made to react with each other. If these groups are located at the chain ends, the resulting polymer is a block copolymer. In a similar way, the chains bearing the reactive end-functions can be interacted with pendant moieties of a backbone yielding a graft copolymer. This chapter covers the synthetic strategies to prepare block and graft copolymers via radical polymerization routes, focusing on the latest, state-of-the-art studies.
11.2 sYNTHesIs OF BLOCK COPOLYMeRs

Normally, block copolymers cannot be synthesized by classical free radical copolymerization technique. Spontaneous block copolymer formation upon free radical copolymerization of A and B monomers would only occur when both reactivity ratios ra and r b are far larger than unity. Such system has never been found. Generally, one can get access to block copolymers by the following strategies. According to the most common methodology, monomer A is polymerized completely, after which, monomer B is introduced in the mixture and its polymerization proceeds upon initiation by the active site of the first block. This approach is referred to as sequential monomer addition in controlled/living polymerization methods. For obtaining a
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well-defined block copolymer, the living site of the first monomer must be effective in initiating the polymerization of the second monomer. That is, simultaneous initiation of all growing B chains must be ensured and the rate of the crossover reaction must be higher than the rate of propagation of monomer B. Another route involves the use of a difunctional initiator and has been employed in the preparation of ABA symmetric triblock copolymers. In this methodology, a compound possessing two initiating sites is utilized in the formation of the middle block first, followed by the polymerization of the second monomer to synthesize the first and the third blocks. This allows the preparation of the ABA blocks in two, instead of three steps without fractionation or other purification steps. The difunctional initiator must be chosen to initiate the polymerization with the same rate from either direction. Moreover, AB diblock or ABA triblock copolymers can be prepared by coupling two appropriately end-functionalized chains of A and B homopolymers or AB blocks, respectively. In the latter case, block B should initially contain half the molecular weight of the final desired block B. The efficiency of coupling will be high if the reaction is rapid and the living diblock copolymer is used in excess.
11.2.1 Block copolymers via conventional radical polymerization

The most widely employed method for the preparation of block copolymers by using conventional radical polymerization route is the macroinitiator technique. This technique has several advantages. First, macroinitiators can be fully characterized before their use in the free radical step to obtain block copolymers. Moreover, the macroinitiators can be prepared practically by all polymerization methods. In living polymerizations, it is possible to introduce the free radical initiating functionalities into polymers at both initiation and termination steps as presented in Scheme 11.1. Azo or peroxy groups are incorporated into the free-radical initiating sites of the polymers. Typical examples of such methodology by using living anionic and cationic polymerizations are given in Schemes 11.2 [16] and 11.3 [17], respectively. Tables 11.1 and 11.2 give the compilation of block copolymers prepared by using macroinitiators possessing thermolabile azo and peroxy groups, respectively.
Initiation Functionalization Macroinitiator Termination Functionalization
= Initiator for Monomer 1 = Initiator for Monomer 2
= Monomer 1 = Monomer 2
sCHeMe 11.1
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O NH2 NH C O N O O CH3 CN CH3 N C CN O O R n CH3 CN
CH2 CH2 C N
2
R 2n H O R n O
NH CH C NH NH C CH2 CH2 C N
CH2 CH2 C NH NH C CH NH
sCHeMe 11.2
11.2.2 Block copolymers via controlled radical polymerization routes

Well-defined block copolymers can be synthesized by using well-known anionic polymerization technique and the first study dates back to as early as 1956, in which styrene and isoprene were successfully blocked anionically [95]. In tailoring welldefined blocks, it is essential that the polymerization be performed in the absence of undesired transfer and termination, which can be provided quite successfully with anionic polymerization. However, it has several drawbacks, such as limited choice of monomers and the extremely severe reaction conditions. Radical polymerization is the most widely used method in the polymerization of numerous vinyl monomers without the need to provide special reaction conditions required for ionic polymerization systems. It can be employed with ease in industrial applications. However, owing to its inadequacy in the control of chain lengths and in the preparation of block copolymers, it has been a major goal for researchers to establish a controlled mechanism in conjunction with a free radical route. Only after the early works of Otsu [96], Solomon [97], and Georges [98], it was realized that radical polymerizations could be conducted in a controlled manner. This breakthrough opened new pathways in the preparation of tailor-made polymers with desired properties. Among the controlled radical routes, nitroxide mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) have been studied extensively. In all these methods, the controlled/living character is maintained due to the existence of a dynamic equilibrium between a dormant species present in great amount and a low concentration of active radical sites. Consequently, transfer and termination are minimized. In the absence of chain breaking reactions, the system possesses a living nature, as a result
O Cl CH3 CN 2AgBF4 THF 2 BF4 O O CH3 CN CH3 N C CN O BF4 O
C CH2 CH2 C N
C CH2 CH2 C N
CH2 CH2 C
sCHeMe 11.3
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TaBLe 11.1 Block Copolymers Prepared from Macroperoxyinitiators

1st segment PAm polyacrylate copolymer PBA-co-PAAc PEHA PEHMA PEHA-co-PHEMA PEHMA-co-PBMA PPFOEA-co-PTFEMA PHEA-co-PNMeAm PHEA-co-PHEMA PHEA-co-PDEGMA PLMA PLMA-co-PAAc PSMA PSMA-co-PNMeAm PSt-co-PBA PSt-co-PMMA PVAc PVC-co-PVAc PEA PEMA PDFCE PPFOEA 2nd segment polyacrylate copolymer References [18, 19] [1823] [23] [24] [22, 24] [24] [24] [25] [21] [21] [21, 26] [27] [22, 24] [18, 22, 24] [28] [23, 25] [18] [26] [18, 22] [20] [20] [28] [25] [25] [25] [21, 26] [21, 26, 27] [29, 30] [31] [32] [25, 28] [28] [25] [28] [28] [33] [34] [35] [36] [31] [31] [30, 32, 3640] [31] (Continued)
PHEA PHEMA PMMA
PHEMA-co-PEHMA PEHMA-co-PBMA PEMA PBMA PMMA-co-PBA PMMA-co-PHEMA Polyacrylate copolymer PVAc PHEMA PPFOEA PFHEA PSMA-co-PEFS PBMA-co-PPFOEA PFHEA-co-PPFOEA PEGMA-co-PPMA PAN PBVE PBA-co-PHE PBMA-co-PHE PHPMQA PHEMA PMMA PNaAMPS
PMMA-co-PSMA PMMA-co-PBA PMMA-co-PEA PFHVE PSt
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TaBLe 11.1 (CONTINUeD) Block Copolymers Prepared from Macroperoxyinitiators

1st segment 2nd segment PVAc PVAc-co-PAC PVAC-co-PMAc PVAc-co-PBA PVAc-co-PBA PBA PBA-co-PEHA PBMA PSt-co-PMAc PSt-co-PMMA PMMA-co-PMFS PSt, PMMA, PVAc PSt References [21, 29, 32, 36, 37, 41, 42] [35] [43] [28] [28] [27, 44] [44] [18, 22] [42] [43] [25] [45] [46]
PENS PVAc
PVC PDMS PEO
PAm: polyacrylamide; PBA: poly(butyl acrylate); PAAc: poly(acrylic acid); PEHA: poly(ethyl hydroxyacrylate); PHEMA: poly(hydroxylethyl methacrylate); PEHMA: poly(ethylhexyl methacrylate); PBMA: poly(butyl methacrylate); PPFOEA: perfluorodecylacrylate; PTFEMA: poly(trifluoroethyl methacrylate); PNMeAm: poly(N-methylol acrylamide) PDEGMA: poly(diethyleneglycol monomethacrylate) PLMA: poly(lauryl methacrylate) PSMA: poly(stearyl methacrylate); PSt: polystyrene; PVAc: poly(vinyl acetate); PVC: polyvinylchloride; PEMA: poly(ethyl methacrylate); PDFCE: poly(difluorochloro ethylene) PMMA: poly(methyl methacrylate); PPFOA: perfluorooctylacrylate; PFHEA: perfluorooctylacrylate; PFHVE: perfluoroheptylvinylether; PEGMA: poly(ethyleneglycol monomethacrylate); PPMA: poly(propyl methacrylate); PAN: polyacrylonitrile; PBVE: poly(butylvinyl ether) PHE:methacryloyloxyethyl-t-butyl-peroxycarbonate; PHPMQA: 2-hydroxyl-3-methacyloxypropyltrimethlammonium; PNaAMPS: 2-acrylamide-2-methylpropane sodium sulfonate; PAC: allyl-t-butylperoxycarbonate; PMAc: poly(methacrylic acid); PMFS: N-methyl-N-(B-methacryloxyethyl)-perfluorooctyl sulfonamide; PDMS: polydimethylsilonxane; PEO: poly(ethylene oxide).
of which, a variety of macromolecular architectures, such as block, graft, star, and hyperbranched (co)polymers with low polydispersities can be achieved. Decreasing the number of active species present in the medium, polymers with predetermined molecular weights can be obtained. Additionally, a successful controlled polymerization system requires that all chains be initiated early and simultaneously, and the exchange between species should be rapid enough to allow only a certain number of monomers to be added each time the chain is active. Block copolymers can be prepared by controlled polymerization routes as described previously. In the sequential monomer addition strategy, certain experimental conditions governing the growth of the first block should be handled carefully to increase the blocking efficiency. It is essentially important to stop the polymerization of the first monomer before it is used up completely for the fact that end functionalities might be lost, resulting in the formation of dead blocks. Another feature to be considered, as in all sequential monomer additions, is the order of introducing
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TaBLe 11.2 Block Copolymers Prepared from Macroazoinitiators

1st segment PAN polyacrylate copolymer PB PMMA PSt PB, PVP polyacrylate copolymer polyfluoroacrylate copolymer PDMI PB, PBA PAN PB PBA PMAc PMA PMMA PMMA-co-PBMA PNMeVAc polyolefin PSt-co-PSSSt, VPy PSt-co-PB PAm PB PSt, PMMA, PMA PAN PMMA PMMA-co-PVAc PSt PSt-co-PAN PSt-co-PIB PVAc-co-PAAc PVIBE-co-PVPp PBMA PHEMA PVAc PEO PPO polyacrylate copolymer PMMA PSt PB PVP PAm PAN polyacrylate copolymer PMMA PSt 2nd segment [47] [48] [28],[49] [50] [47] [47] [47] [51,52] [53] [54] [34,47,55] [56] [54] [57] [47] [58] [59] [47] [60] [61] [34,47,6265] [61] [34,47,51,6368] [61] [61] [61] [61] [65] [65] [65] [62] [62] [48,6972] [34,7383] [45,63,67,7681,8385,8792] [47,84] [47] [80,85] [85] [48,69,70,72] [48,61,86] [48,86] (Continued) References
PSt-co-PAN PVAc Poly(dibenzazepine) Polyamide
Polyester
polyurethane
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TaBLe 11.2 (CONTINUeD) Block Copolymers Prepared from Macroazoinitiators

1th segment polysiloxane 2nd segment polyacrylate copolymer PMMA PSt PVAc PVC PSt PSt [87,88] [83,89] [89] [89] [90] [91] [9294] References
polyimide polycarbonate
PAN: polyacrylonitrile; PB: polybutadiene; PVP: poly(1-vinyl-2-pyrrolidone); PDMI: poly(dimethylitaconate); PBA: poly(butyl acrylate); PMAc: poly(methacrylic acid); PMA: poly(methyl acrylate); PSt: polystyrene; PMMA: poly(methyl methacrylate); PBMA: poly(butyl methacrylate); PNMeVAc: poly(N-methyl-N-vinylacetate); PSSSt: poly(styrene sodium sulfonate); PAm: polyacrylamide; PVAc: poly(vinyl acetate); PIB: polyisobutylene; PAAc: poly(acrylic acid); PVIBE: poly(vinyl isobutyl ether); PVPp: poly(vinyl propionate); PEO: poly(ethylene oxide); PPO: poly(propylene oxide); PVC: polyvinylchloride.
each monomer. Along with the rate constant of cross-addition ka and the rate constant of propagation kp of the second monomer, the equilibrium constants Ka and Kb between active and dormant species for the two kinds of monomer units should be taken into consideration. Apparently, the very active monomer should be polymerized first, which is valid for either of the controlled polymerization mechanisms. Different from sequential monomer addition technique utilized in anionic living polymerization, controlled routes allow for the polymerization of monomers A and B to be performed separately in two distinct steps, allowing chain functionalities to be preserved. The first block functions as a macromolecular initiator, a so-called macroinitiator, in the preparation of the second block. The first block can alternatively be synthesized via any of the conventional chain-growth and step-growth polymerization methods. When the monomers to be assembled in a targeted diblock structure do not polymerize by the same mechanism, a need for changing the active site arises and this synthetic approach is referred to as site transformation. In cases where a bifunctional macroinitiator is employed, the resulting copolymer will be an ABA triblock copolymer.
11.2.3 Block copolymers via nitroxide mediated polymerization (nmp)

In NMP systems, stable free radicals, such as nitroxides, are used as reversible terminating agents to control the polymerization process. Dormant chains are generated by reversible deactivation of the growing chains through covalent bond formation. At high temperatures, the bond undergoes a homolytic cleavage to produce the active growing chain and the nitroxide radical. Activation is followed by a rapid deactivation, whereby a few monomer units are incorporated to the propagating chain (Scheme 11.4). The counter radicals should be quite stable (i.e., they should be inert
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ka kd kp +M
315
Pn X
Pn + X
sCHeMe 11.4
towards each other, monomers, or side reactions [e.g., H-abstraction]). Bimolecular initiating systems comprising a thermal initiator, such as an azo compound or a peroxide, and a stable free radical, TEMPO, have been utilized in the polymerization of styrene and its derivatives. However, several drawbacks associated with the use of TEMPO limited its utility. These involve its unsuitability for the polymerization of acrylates and its high temperature requirement. These drawbacks could be overcome by the use of unimolecular nitroxide initiators containing both the initiating radical and the alkoxyamine counter radical [10, 99]. Diaz et al. [100] reported the synthesis of poly(N,N-dimethylacrylamide-b-4vinylpyridine) [poly(DMAA-b-4VP)] by using a b-phosphonylated nitroxide (Ntert-butyl-N-(1-diethylphosphono-2,2-dimethylpropyl) nitroxide, DEPN) as a control agent. The hydrophilic poly(DMAA) block was prepared by polymerizing the monomer along with the initiator (AIBN) and the nitroxide at 110C, after which the reaction was stopped by cooling the flask and excess monomer was evaporated under reduced pressure (0.5 mmHg). The polymer, recovered as a powder, was used as a macroinitiator in the polymerization of 4VP (Scheme 11.4). The controlled nature of the polymerization was confirmed by the linear plots of both in ([M]0/[M]) versus time and Mn versus conversion, where [M]0, [M], and Mn respectively stand for
O N
P(OEt)2 O
Initiator 110C N
O N
n
P(OEt)2
110C
4 VP P(OEt)2 O
O
n
P(OEt)2 EtOH, 70C O CH3(CH2)pBr p = 7, 11, 15 N
O N
n
O N
O N
N Br (CH2)p CH3
sCHeMe 11.5
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316
monomer original and current concentration in the bulk and polymer number-average molar weight. It was found that DEPN provided good control in the homopolymerization of 4VP and DMAA with polymerization rates and conversions (~ 60 %) that were much higher than those observed with TEMPO. Consequently, poly(DMAA-b4VP) with desired lengths of each block was obtained quantitatively. A variety of block copolymers derived using NMP is given in Table 11.3.
TaBLe 11.3 sequential addition synthesis of Block Copolymers by NMP

1st segment CMS (St-co-CMI), (St-co-NVC) tBOSt 4VP, CMS EBPBB (St-alt-MAh) BrSt and St St St 2nd segment References [101103] [104,105] [106] [107] [108] [109] [110] [111] [112] [113] [114] [115] [116] [117,118] [119] [120] [121] [122] [123] [124] [125] [126] [127] [128] [129] [130] [131] [10] [132] [133] [134] [47] [135]
St and BrSt tBuSt PIMS MPCS (St-co-AN) MA DMA BD, IP PES multifunctional acryl- and methacryl derivatives PFDS, PFDA StSA BA MPVB DMAM, SSC 4VN Po NVC St HEA (BA-co-St) BA, St St, MA, MMA (St-co-CMS) BA Si2St, Si2CSt, OSi2St, St, AcOSt MA
AcOSt SSt
nBA
St, nBA IP PPV DMAEA St, AcOSt, OSi2St AA, St
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TaBLe 11.3 (CONTINUeD) sequential addition synthesis of Block Copolymers by NMP

1st segment DMA St, CMS nBA CMS, St 2nd segment References [136] [137]
St: styrene; CMS: chloromethyl styrene; CMI: N-cyclohexylmaleimide; NVC: N-vinylcarbazole; tBOSt: p-tert-butoxystyrene; 4VP:4-vinylpyridine; EBPBB: 4-ethylbiphenyl-4-(4-propenoyloxybutyloxy)benzoate; MAh: maleic anhydride; BrSt: p-bromostyrene; PIMS: phthalimide methylstyrene; MPCS: 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene; AN: acrylonitrile; MA: methyl acrylate; DMA: N,N-dimethylacrylamide; BD: 1,3-butadiene; IP: isoprene; PES: 4-(phenylethynyl)styrene; PFDS: (perfluorooctyl-ethylenoxymethylstyrene); PFDA: (1,1,2,2-tetrahydroperfluorodecyl acrylate) acrylate); StSA: styrene sulfonic acid; AcOSt: 4-acetoxystyrene; MPVB: [(49-Methoxyphenyl) 4-oxybenzoate]-6-hexyl (4-vinylbenzoate); tBuSt: p-tert-butylstyrene; SSt: sodium 4-styrene-sulfonate; DMAM: 4-(dimethylamino)methylstyrene; AAc: acrylic acid; SSC: sodium 4-styrenecarboxylate; VN: vinylnaphthalene; Po: (5-(4-acryloyloxyphenyl)-10,15,20-tritolylporphyrin); BA: n-butyl acrylate; HEA: 2-hydroxyethyl acrylate; PPV: 2,5-dioctyloxy-1,4-phenylenevinylene; DMAEA:2(dimethylamino)ethyl acrylate; OSi2St: 4-(pentamethyldisiloxymethyl) styrene; Si2St: 4-(pentamethyldisilyl) styrene; Si2CSt: 4-(bis(trimethylsilyl)methyl) styrene.
11.2.4 Block copolymers via atom transfer radical polymerization (atrp)

Atom transfer radical polymerization (ATRP), pioneered by Wang and Matyjaszewski [138] and Kato et al. [139], is based on a continuous and reversible halogen transfer (pseudo halogen) between a dormant propagating species, Pn, and a transiAu: Is bipy cor- tion-metal (e.g., Cu), complexed by a ligand (e.g., bipy), in its lower oxidation state rect? Should be bipyridine? (Scheme 11.6). Halogen transfer is accompanied by a one-electron oxidation of the transition metal, whereby propagation takes place by the addition of monomers to the activated chains. Homogeneity of the polymeric chains is controlled by the fast and simultaneous initiation as well as rapid deactivation of the growing chains. Here, the rate of deactivation should be faster than the propagation rate for an effective control. Low concentration of the active centers, maintained by deactivation, suppresses termination and chain transfer reactions at later stages. Transition metals involving copper [138], ruthenium [139], nickel [140], iron [141143], rhodium [144], rhenium [145], and palladium [146] have been employed in conjunction with nitrogen- and phosphorus-based ligands. It was also found that
ka kd +M kp
Pn X + CuX/bipy
Pn + CuX2/bipy kt Polymer
sCHeMe 11.6
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318
nitrogen-based ligands were effective in copper mediated systems, whereas phosphorus-based ligands, particularly PPh3, were successfully applied with the previously mentioned transition metals. Halogenated compounds possessing activating b-carbonyl, vinyl, phenyl, and cyano groups have been shown to be good ATRP initiators [147149]. ATRP allows for the facile preparation of di-, tri-, or multi-block copolymers as well as star polymers using bi- or multi-functional initiators carrying the active halogen atoms. Pyun et al. reported the synthesis of ABA triblock copolymers containing polyhedral oligomeric silsesquioxane (POSS) groups via ATRP [150]. The middle (B) and outer segments (A) were poly(n-butyl acrylate) (pBA) and poly(3-(3,5,7,9,11,13,15-heptaisobutyl-pentacyclo [9.5.1.13,9.15,15.17,13]-octasiloxane-1-yl)propyl methacrylate (p(MA-POSS)), respectively. Bromo-difunctional poly(n-butyl acrylate), with a number-average molecular weight of 61,700 g/mol, was prepared by the ATRP of BA from a dimethyl 2,6-dibromoheptanedioate initiator and used in the next step as a macroinitiator in the polymerization of MA-POSS to achieve the desired ABA triblock copolymer as depicted in Scheme 11.7. The macroinitiators prepared by various other routes such as ring-opening, anionic, cationic, and conventional radical processes can also be used in the chainextensions through ATRP to get diblock or triblock copolymers. For this purpose, a modification reaction from one or both ends of the precursor polymer is usually necessary to incorporate the desired halogen functionality to the chain. A diblock copolymer is produced if an -functional telechelic is used as the macroinitiator, whereas an ABA triblock copolymer can be obtained from an ,-functional telechelic. For example, a poly(-caprolactone) macroinitiator was prepared via ringopening polymerization of -caprolactone, followed by a modification reaction on the hydroxyl end group, and used subsequently for the ATRP of 2,5-bis[(4-metho xyphenyl)oxycarbonyl]styrene (MPCS). Finally, diblock copolymers consisting of crystallizable poly(-caprolactone) and PMPCS [151] were achieved with relatively narrow polydispersity indices (PDI <1.11) (Scheme 11.8). Polarized optical microscopy (POM) and DSC results confirmed that the diblock copolymer showed liquid
O O CH3O Br Br O OCH3 O(CH2)3CH3 Cu(I)Br/PMDETA Br O O(CH2)3CH3 CH CH2 CH2 CH O Br
Macroinitiator
O(CH2)3CH3
o-xylene
Cu(I)Br/PMDETA
O MA-POSS
p(MA-POSS)-b-pBA-b-p(MA-POSS)
sCHeMe 11.7
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O O 1. Al(OiPr)3, toluene, 0C 2. HCl O O O
n
319
O O OH
n
Br O NEt3 O O
Br
Br Cu(I)Br, PMDETA O
m
O
n
Br O
PCL-b-PMPCS O = CH3O O C O C O
OCH3
sCHeMe 11.8
crystalline behavior when the degree of polymerization (DP) of PMPCS block was higher than 44. Other work, by Kurjata, et al. [152] involves the synthesis of a polydimethylsiloxane (PDMS)-macroinitiator via anionic polymerization of hexamethylcyclotrisiloxane (D3) followed by reaction with 3-(chlorodimethylsilyl) propyl 2-bromo-2-methylpropanoate propyldimethylchlorosilane. Subsequent use of this macromolecular initiator for the ATRP of oligo[ethylene glycol] methyl ether methacrylate afforded AB type amphiphilic comb-like block copolymers of poly(oligo[ethylene glycol] methyl ether methacrylate) and polydimethylsiloxane (Scheme 11.9). Another strategy combining two distinct polymerization mechanisms for the synthesis of diblock copolymers is the use of dual initiators. In this approach, a compound possessing two functional groups is employed to initiate two polymerizations based on different mechanisms. This strategy has the advantage of eliminating the need for transformation of the active chain-end. In a recent work [153], we reported the use of N,N-dimethylaniline end-functional polystyrenes in the preparation of poly(St-b-MMA) via photoinduced radical polymerization of MMA and poly(St-b-CHO) via radical promoted cationic polymerization of cyclohexene oxide (CHO). For this purpose, 4-(dimethylamino)-benzyl 4-(bromomethyl) benzoate, a dual initiator, was synthesized first by the esterification of 4-(bromomethyl)-benzoyl chloride and [4-(dimethylamino)phenyl]methanol in diethyl ether. In the second step, ATRP of styrene was performed using this initiator
CH3 n-BuLi THF CH3 CH3(CH2)2 SiO CH3
n
O CH3 (CH2)3O C C Br CH3 CH3 CH3 CH3(CH2)2 SiO Si

n+1
CH3 SiO Li CH3
CI
Si CH3
O CH3 (CH2)3O C C Br CH3 Cu(I)Br, Ligand
m D3
CH3 CH3
O 4.5 O
PDMS-b-POEGMA
sCHeMe 11.9
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CH3 CH3 O N ATRP Initiator St CuBr/bpy CH3 CH3 O N CH2 O C Polymeric Co-initiator CH2 CH2 CH
n
CH2 O C
CH2Br
Br
O C
O C Polymeric Co-initiator
CH3 CH2
O N CH2 O C CH2 CH2 CH n Br +
OH C
MMA . PSt-b-PMMA
sCHeMe 11.10
in the presence of CuBr/bipyridine complex. The polymer bearing end-chain N,Ndimethyl amino moiety was finally used as a macromolecular coinitiator in the photopolymerization of MMA and CHO via radical and radical promoted cationic polymerization routes, respectively, as depicted in Schemes 11.10 and 11.11. In the former case, macroradical generation was achieved with benzophenone sensitizer by photoexcitation followed by hydrogen abstraction from amino end groups. A visible light initiating system has been utilized in the radical promoted cationic polymerization of CHO. The system involves a xanthene dye (Erythrosin B) as the sensitizer, an aromatic N,N-dimethyl amino group and diphenyl iodo- Au: InitialIscap correct? this nium hexafluorophosphate as the radical source and radical oxidizer, respectively. a product/ brand name Although pure block copolymers were obtained via the free radical route, the free that requires a trademark radical promoted cationic polymerization, yielding both block and homopolymers. or registered symbol? Au: Ref. 154 is Du Prez and co-workers reported the sequential two-step synthesis of wellauthor Bernaerts et al., not defined block copolymers of polystyrene (PSt) and poly(tetrahydrofuran) (PTHF) by Du Prez. Please verify. ATRP and cationic ring-opening polymerization (CROP) using 4-hydroxy-butyl-2bromoisobutyrate as a dual initiator [154]. The bromoisobutyrate group contained in the initiator effectively initiates the ATRP of styrene in conjunction with the Cu(0)/ Cu(II)/N,N,N,N,N-pentamethyldiethylenetriamine catalyst, whereas the triflate ester group obtained from the in situ reaction of the hydroxyl groups of the initiator with trifluoromethane sulfonic anhydride initiates the CROP of tetrahydrofuran
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Dye h Dye* Polymeric Co-initiator H2C H3C
321
Dye +
CH2
O CO
CH2
CH2
CH n Br
+ I
P F6
+
H2C H3C
PF6 N CH2 O CO CH2 CH2 CH n Br +
I + + Dye
PF6 O
H2C H3C
CH2
O CO
CH2
CH2
CH n
Br
O PF6
O m H2C H3C
CH2 O CO
CH2
CH2
CH
Br
sCHeMe 11.11
(THF). In this manner, both the PSt-OH and PTHF-Br homopolymers were prepared and used as macroinitiators for the CROP of THF and the ATRP of styrene, respectively, to afford PTHF-b-PS block copolymers, as depicted in Scheme 11.12. CROP of THF using PSt-OH as a macroinitiator produced a mixture of the PSt-b-PTHF block copolymer and the remaining PSt macroinitiator due to nonquantitative initiation. On the other hand, PTHF-Br was found to initiate the ATRP of styrene quantitatively, eventually yielding well-defined PTHF-b-PSt block copolymers. Preparation of block copolymers comprising monomers of distinct reactivities requires that the monomers be introduced in a specific sequence if one desires to obtain good control over the polydispersities. The addition should be handled in a manner favoring the cross-propagation (i.e., the initiation of the second block by the first one) over propagation. For instance, a PMMA block should precede the growth of a PSt block, and not the reverse. In this case, the cross-propagation is rather fast,
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322

O O CH3 CH3 Toluene S OH O O CH3 Br + H2O CH3
HOCH2CH2CH2CH2OH + HO
C C
Br
HOCH2CH2CH2CH2OC C
CH3
Cu(0)/Cu(II)Br2 PMDETA, nSt
ATRP
CROP
1) (CF3SO2)2O, 2) mTHF 3) MeOH
, CH2Cl2
O CH3 HOCH2CH2CH2CH2OC C CH2 CH Br CH3 1) (CF 3SO2)2O, 2) mTHF 3) MeOH Ph

n m
O CH3 MeO CH2CH2CH2CH2O CH2CH2CH2CH2OC C Cu(0)/Cu(II)Br2 PMDETA, nSt Br CH3
ATRP
O CH3 MeO CH2CH2CH2CH2O CH2CH2CH2CH2OC C CH2 CH Br

m
CH3
Ph
sCHeMe 11.12
for the fact that the equilibrium between active and dormant chains lies more to the active side. On the other hand, the rate of propagation of the St monomer is comparatively slow. As a result, nearly all the chains of the second PSt block are initiated before the propagation takes place. Evidently, this results in a low polydispersity. Alternatively, a technique, so called the halogen exchange [140, 155159], can be employed to change this sequence of blocking. In this methodology, the first block (e.g., PSt) is formed using a bromine-functional initiator in combination with a copper (I) bromide catalyst. In the next step, the second monomer (e.g., MMA) is added together with copper (I) chloride. Here, the activation of bromine-functional chain is followed by deactivation with CuCl2 (or CuClBr). Because the carbon-chlorine bond is stronger than that of carbon-bromine, formation of a carbon-chlorine bond predominates in this mixed halogen system, and thereby retards the propagation in comparison to the cross-propagation. An ABCBA-type pentablock terpolymer was prepared using a bromo-terminated PtBuA-b-PSt-b-PtBuA triblock as a macroinitiator in the chain-extension with MMA [160]. The triblock copolymer with Mn = 13,600 and PDI = 1.23 was synthesized beforehand from a bifunctional PSt using the CuBr/PMDETA catalyst system. Subsequent chain-extension with MMA, using the system CuCl/HMTETA afforded the desired PMMA-b-PtBuA-b-PSt-b-PtBuA-b-PMMA terpolymer with Mn = 48,500 and PDI = 1.21. An increase in the PDI was avoided due to the halogen exchange mechanism, which enhanced the rate of cross-propagation relative to the rate of propagation.
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323
TaBLe 11.4 summary of Block Copolymers Prepared Using aTRP

1st Block BMA 2nd Block MMA St St-BMA BMA MA, BA BA St DMAEMA HEMA VP BzMA AN BEMA ArIt tBMA, MMA, DMAEMA PMPCS MMA DMAEMA DMA BMDO MMA HPMA St TMS-HEA MA MA-POSS HEMA NPMA MMA BA tBA MA MAA, tBMA MAIpGlc AcGEA HEMA-co-DMAEMA 4VP DMAA PFA DHPA St, MA (MA-b-tBA) MA References [161,162] [163,164] [165] [166] [167] [168,169] [170,171] [172] [170,173] [174] [175] [176] [177] [54] [172,178] [179] [168] [172] [180] [181] [140,168,182] [180] [183,184] [185] [186] [187] [170] [188] [67] [170,189191] [192196] [138,197] [198,199] [200] [201] [202] [203] [204] [205] [206] [194,207] [207] [193] (Continued)
Au: Provide callout in text.
MMA
MA
nBA
St
tBA (tBA-b-St)
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324
TaBLe 4 (CONTINUeD) summary of Block Copolymers Prepared Using aTRP

1st Block TMS-HEA LC2 OEGMA FOMA MMA, BA AmS iBMA 4VP LC11 BA, LA DMEMA SPMA LMA AN PEO-b-PMMA PDECVP PFS MPC nBA NaVB MMA MMA and DMAEMA BA, BMA ,St St 2nd Block References [185] [208] [209] [210] [211] [184] [212] [213,214] [215] [216] [217] [218] [219] [220] [221] [222] [223] [224] [225] [226] [227] [228] [229] [230] [231] [232] [233] [234]
MMA, iBOA, St MMA
DEA styrene-based DEAEMA POEM tBMA, nBMA, OMA,
St BA PMPCS St St, PDECVP, MMA St MMA DMA, DPA DMA,DEA, DPA, HEMA, HPMA, GMM HEMA semifluorinated tBMA BMA OMA, tBA
BMA: butyl methacrylate; MMA: methyl methacrylate; St: styrene; MA: methyl acrylate; BA: butyl acrylate; DMAEMA: (N,N-dimethylamino)ethyl methacrylate; DEAEMA: 2-(diethylamino)ethyl methacrylate; HEMA: hydroxylethyl methacrylate; 2VP:2-vinylpyridine; 4VP: 4-vinylpyridine; BzMA: benzyl methacrylate; AN: acrylonitrile; BEMA: 1-(butoxy)ethyl methacrylate; ArIt: N-aryl itaconimide; tBMA: tert-butyl methacrylate; PMPCS: 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene; DMA: 2(dimethylamino)ethyl methacrylate; BMDO: (5,6-benzo-2-methylene-1,3-dioxepane); HPMA: hydroxypropyl methacrylate; TMS-HEA: 2-trimethylsilyloxyethyl acrylate; MA-POSS: 3-(3,5,7,9,11,13,15-heptacyclopentyl-pentacyclo[9.5.1.1.3,91.5,1517,13]-octasiloxane-1-yl)propyl methacrylate; NPMA: p-nitrophenyl methacrylate; MAAc: methacrylic acid; MAIpGlc: 3-O-methacryloyl-1,2 : 5,6-diO-isopropylidene-D-glucofuranose; AcGEA: 2-(2,3,4,6- tetra-O-acetyl-beta-D-glucopyranosyloxy) ethyl acrylate; DMAA: N,N-dimethylacrylamide; PFA: perfluorooctyl ethyl acrylate; DHPA: 2,3-dihydroxypropyl acrylate; PFA: 2-perfluorooctyl ethyl acrylate; LC2: 2- [2-(4-cyano-azobenzene-4oxy)ethylene-oxy] ethyl methacrylate; NaVB: sodium 4-vinylbenzoate.
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325
Au: Please insert spell-out for PDECVP.
OEGMA: oligo(ethylene glycol) methacrylate; FOMA: fluorinated (meth)acrylates; AmS: p(4-amino styrene); iBOA: isobornyl acrylate; iBMA: i-butyl methacrylate; LC11:11-[4-(3-ethoxycarbonyl-coumarin-7-oxy)-carbonylphenyloxy]-undecyl methacrylate; LMA: lauryl methacrylate; LA: lauryl acrylate; SPMA: potassium 3-sulfopropyl methacrylate; PEO: poly(ethylene oxide); PDECVP: PFS: pentafluorostyrene; DEA: 2-(diethylamino)ethyl methacrylate; DPA: 2-(diisopropylamino)ethyl methacrylate; GMM: glycerol monomethacrylate; MPC: (2-methacryloyloxyethyl phosphorylcholine; POEM: (oxyethylene)-9-methacrylate); OMA: octadecyl methacrylate; PMPCS: 2,5-bis[(4-methoxyph enyl)oxycarbonyl] styrene.
11.2.5 Block copolymers via reversiBle addition fragmentation chain transfer polymerization (raft)
Au: Ref. 12 is author Chiefari et al., not Rizzardo. Please verify.
RAFT, developed by Rizzardo and co-workers in the late 1990s, utilizes a chaintransfer-active thiocarbonylthio moiety for the exchange between active and dormant chains [12]. The mechanism is illustrated in Scheme 11.13. The active species, such as the radicals stemming from the decomposition of the initiator and propagating radicals (Pn), are transferred to the RAFT-agents (e.g., the thiocarbonylthio moiety). Meanwhile, an intermediate radical is formed and undergoes a fast fragmentation reaction, giving a polymeric RAFT agent and a new radical. The radical reinitiates the polymerization. The equilibrium is established by successive chain transfer-fragmentation stages. Z and R groups in the thiocarbonylthio compound represent the activating group and homolytically leaving group, respectively. These, in turn, determine the rates of addition and fragmentation. In fact, the choice of RAFT agent for a specified monomer is rather significant and affects the degree of control.
Initiation and Propagation Initiator + Monomer Addition to RAFT Agent Pn S C S R Pn S C Z Pm S R Pn S C Z S + R Pn
Z Reinitiation R + Monomer
Chain Equilibration by Reversible Addition Fragmentation Pm + S M Overall Initiator + Monomer + S C Z S R R Pm S C Z S C Z S Pn Pm S C Z S Pn Pm S C Z S + Pn M
sCHeMe 11.13
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326

AN N CN N CN S Ph CH3 CN Pn S Ph S CH3 CN Pn S Ph S + CH3 CN AN Pn
Pn + S AN
sCHeMe 11.14
Matyjaszewski and co-workers reported the preparation of block copolymers of acrylonitrile (AN) and n-butyl acrylate (n-BA) with low polydispersity and controlled molecular weight using a novel RAFT agent, 2-cyanoethyl dithiobenzoate (CED) (Scheme 11.14) [235]. Polymerizations of AN were performed with two different ratios of initiator and RAFT agent at 60C, and the best results were achieved. That is, a 40.2% conversion was achieved in 7 h with Mw/Mn = 1.05, upon selectOK ing a monomer/initiator/RAFT agent mol ratio of 500:1:3. Attempts to control the Au: Editstwo in these sentences? polymerization of AN failed when cumyl dithiobenzoate (CDB) was used as the RAFT agent. Moreover, chain extension from poly(n-butyl acrylate) (PBA) to AN yielded multimodal GPC traces with high polydispersity signifying a low blocking efficiency. Consequently, PAN macroinitiators were shown to crosspropagate more easily, allowing the preparation of PAN-b-PBA block copolymers by chain extension from PAN to n-BA. Convertine et al. [236], were first to polymerize water-soluble vinylpyridine (VP) monomers, specifically 2-vinylpyridine (2VP) and 4-vinylpyridine (4VP), via RAFT, which might be helpful in preparing novel block copolymers with monomers not suitable with other controlled routes. They also showed the ability to synthesize 2VP-4VP and 4VP-2VP block copolymers in a controlled manner by using RAFT (Scheme 11.15). In another work, PEO containing a xanthate end group was used as a macro RAFT agent in the polymerization of N-vinylformamide (NVF) to yield polyethylene-b-polyN-vinylformamide (PEO-b-PNVF) (Scheme 11.16) [237].
2VP or 4VP CH3 C CH2 CH CH3
m
CDB AIBN
1 or 2 S S C 4VP AIBN CH3 C CH2 CH CH3

m
S CH2 CH
n
N 1
N N 3 S
n
CH3 C CH2 CH CH3 N

n
S S C
2VP, DMF AIBN
CH3 C CH2 CH CH3 N CH2 CH

m
sCHeMe 11.15
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Initiation/Propagation I NVF
327
S S
CH3 C CN
O (CH2)2 C O PEG
PNVFn + EtO C
Addition-Fragmentation PNVFn S C EtO S + CH3 C CN Block Copolymer Formation CH3 m NVF + C CN O (CH2)2 C O PEG PEG b PNVFm O (CH2)2 C O PEG PNVFn S C S CH3 C CN O (CH2)2 C O PEG
sCHeMe 11.16
More recently, hydroxy functionalities of PEOs were converted to dithiobenzoyl groups and used as macro RAFT agent in RAFT polymerization of N-isopropylacrylamide (NIPAa) (Scheme 11.17). Depending on the functionality of the initial polymers, AB and ABA type block copolymers with well-defined structures were prepared [238, 239]. In some cases, different controlled polymerization systems are combined to produce block copolymers (see Table 11.6). For example, mechanistic transformations involving ATRP and NMP were performed.
HO
PEG OH
O HOOC CH2 O C CH CH C O PEG C
O PEG C CH2 CH S C S CH CH COOH
C S
SH C S S
CH COOH
HOOC C O NH CH(CH3)2 O
AIBN
O CH2 C C S S PNIPAM CH COOH
PEG C CH2 HOOC CH PNIPAM S C S
sCHeMe 11.17
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328
Au: provide callout in text.
TaBLe 11.5 synthesis of Block Copolymers by RaFT Using sequential addition strategy
1st segment StCo AGA St 2nd segment MA NIPAM, HEA AA VBCl E3VC MMA BA Mah MA SA NAPy, SB, nBA, VB, DMA MMA EEA DMAEMA St, (St-co-CMS) St AOEPCl, HEA AA NAS tBA HEMA PBA MMA, AEMA, BMA, BA, NiPAM 4VP PEA SBz, DMVBA DMA, MeSt, AA, EA, MAA, St, DMAMEA, BzMA References [240] [241] [242] [243] [244] [245] [246248] [249] [250] [251] [252] [253] [254] [255] [256] [257] [258] [259] [260] [261] [262] [235] [263] [236] [264] [265] [266]
DMA nBA, EOA, EOMA, DMA, NAPy, NIPAM, SSt GMPS MA, nBA, MMA, DMA MMA VAc BA NIPAM DMA 4VP MMAGl AN AEMA, PMMA 2VP MMA, BMA, MA, EA, BA, St SSt, VBTMACl St, BA, MA, MMA, BzMA, EO
StCo: Styrene-Coumarin; MA: methyl acrylate; AGA: acryloyl glucosamine; NIPAM: N-isopropylacrylamide; St: styrene; AA: acrylic acid; HEA: hydroxyethyl acrylate; VBCl: 4-vinylbenzyl chloride; Mah: maleic anhydride; E3VC: N-ethyl-3-vinylcarbazole; MMA: methyl methacrylate; BA: n-butyl acrylate; DMA: N,N-dimethylacrylamide; SA:sodium acrylate; EOA:poly(ethylene glycol) acrylate; EOMA:poly(ethylene glycol) methacrylate; NAPy:N-acryloylpyrrolidine; SSt: sodium 4-styrene-sulfonate; SB:sulfobetaine; VB:vinylbenzoic acid; GMPS:gamma-methacryloxypropyltrimethoxysilane; EEA:1-ethoxyethyl acrylate; DMAEMA: 2-(dimethylamino)ethyl methacrylate; CMS: chloromethyl styrene; VAc:vinyl acetate; AOEPCl:(2-acryloyloxyethyl phosphorylcholine); NAS: Nacryloxysuccinimide; MMAGl:(methyl 6-O-methacryloyl-alpha-D-glucoside); AN:acrylonitrile; HEMA: 2-hydroxyethyl methacrylate; AEMA:2-(acetoacetoxy)ethyl methacrylate; BMA:butyl methacrylate; 4VP:4-vinylpyridine; 2VP:2-vinylpyridine; EA: ethyl acrylate; VBTMACl:(ar-vinylbenzyl)tri methylammonium chloride; BzMA:benzyl methacrylate; SBz:sodium 4-vinylbenzoate; DMVBA:N,Ndimethylvinylbenzylamine; EO:ethylene oxide; MeSt: para-methylstyrene; MAA:methacrylic acid.
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329
TaBLe 11.6 some examples of Polymers Obtained by Combination of Different Controlled Radical Polymerization Mechanisms
Combined Controlled Radical Polymerizations NMP-ATRP Cobalt Mediated - ATRP DT-ATRP NMP-RAFT FRP-ATRP ATRP-Telomer References [66,267270] [271] [272] [273] [274,275] [276278]
NMP: nitroxide-mediated radical polymerization; ATRP: atom transfer radical polymerization DT: degenerative transfer polymerization; RAFT: reversible addition fragmentation chain transfer polymerization.
11.3 sYNTHesIs OF GRaFT COPOLYMeRs 11.3.1 synthesis of graft copolymers via conventional radical polymerization methods
Graft copolymers are another class of segmented copolymers. As stated previously, no major difference exists between block copolymer synthesis and graft copolymer synthesis. The location of the sites and functions are at the chain ends or on the chains, respectively. Graft copolymers can be obtained with three general methods: (1) grafting-onto, in which side chains are preformed, and then attached to the backbone; (2) grafting-from, in which the monomer is grafted from the backbone; and (3) grafting-through, in which the macromonomers are copolymerized. 11.3.1.1 Graft Copolymers by Grafting onto Method Grafting onto methods involve reaction of functional groups (Y) located at the chain ends of one kind of polymer with another functional groups (X) which distributed randomly on the main chain of the other polymer (Scheme 11.18). The method is most suited for the reaction of living anionic and cationic polymers onto electrophilic and nucleophilic functions carried by a polymer backbone,
Y X X X
sCHeMe 11.18
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330
respectively. Corresponding radical grafting method has been used. In reported studies, usually functional backbone polymers prepared by radical mechanism are reacted with terminally functionalized polymers. The functionalization of polymers by free radical vinyl polymerization has been discussed in detail in another chapter Au: Please of the book. specify the 11.3.1.2 Graft Copolymers by Grafting from Method Initiating radicals can be formed on a polymer chain upon irradiation with -rays, electron beams [279, 280] and UV light [76, 281, 282]. Grafting is usually performed by irradiation of a polymer swollen by a monomer. The method has found number of applications to modify the properties of the polymers for special uses. For example, surface modification, which is often required to broaden the applicability of plastics, can be achieved by photografting. Surface modification by photografting can bring about improvements in dyeability, adhesiveness, printabilty, paintabilty, biocompatibility, antifogging, antistatic, and antistainabilty properties. Regarding textiles, an increase in wrinkle and flame resistance of fibers may be of commercial importance. Typical examples of photografting are given in Table 11.7. In this connection, the readers attention is also directed towards previously published review articles solely devoted to photografting [287, 297304]. Chemical initiation has also been used in grafting from method. In this case, a polymer backbone containing some thermally cleavable bonds such as azo and peroxide linkages (Scheme 11.19). If the polymers are heated in the presence of a second monomer, initiation takes places. In such systems, homopolymer formation is unavoidable because of the concomitant formation of low molar mass radicals. A wide range of side chain macroinitiators by which graft copolymers can be synthesized via grafting from method, are available and their chemistry has been studied in detail [305]. Side chain polymeric photoinitiators are also suitable precursors for this type of graft copolymerization. Both cleavage [306] (Scheme 11.20) and hydrogen abstraction [307] (Scheme 11.21) type photoinitiation have been successfully employed. In this connection, it should be emphasized that the hydrogen abstraction type photoinitiation has the advantage of producing graft copolymers free from the homopolymer contamination as the process yields only macroradicals. It is well known that certain cerric salts such as nitrate and sulfate form very effective redox system in the presence of organic reducing agents such as alcohols, aldehydes, and amines. Application of this technique to polymers with pendant reducing group provides a versatile method for the grafting from strategy [308] (Scheme 11.22). 11.3.1.3 Graft Copolymer synthesis via Macromonomers Macromonomers are short polymer chains possessing a polymerizable group at the one termini. A great variety of methods involving living polymerization techniques, chain transfer reactions, and end chain modifications have been developed to synthesize such species. Details of these methods have been discussed in earlier reviews and books [167, 290, 305, 309, 310], and are beyond the scope of this book.
chapter to which you are referring.
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331
TaBLe 11.7 Typical examples of Photografting

Polymer Backbone PMVK PMIK, PBVK PSt-co-PVBP, PSt-DEASt ABME, PDAA BMEA PSt-co-PVBB Pst PAm, PAN PAN PVC Cl-MeSt PDMS PPVS PVA PVTClAc, PSt, PC, PA, PPp D-OH PTFE Grafted Chain AN, MMA, VAc St, MMA, AN, VAc EHMA, DEA AA, MA St, MMA MMA MMA AN, Am MEPM MEPM, DAEM MEPM, DAEM HEMA, Am, MAEMA, MAc MMA Am, AAc, AN, St St, MMA, CP HEMA, Am, AAc St, MMA Reference [283] [48] [284] [285] [286] [287] [246] [7] [288] [289] [290] [89,291] [292] [38] [293295] [296] [60]
PMVK: poly(methyl vinyl ketone); PMIK: poly(3-methyl-3-buten-2-one); PBVK: pol(4,4-dimethyl-1penten-3-one; AN: acrylonitrile; MMA: methyl methacrylate; VAc: vinyl acetate; St: styrene; EHMA: 2-ethylhexyl methacrylate; DEA: diethylaniline; PSt-co-PVBP:poly(styrene-co-vinylbenzophenone); PSt-co-DEASt: poly(styrene-co-p-N,N-diethylaminostyrene); ABME: allylbenzoin methyl ether; PDAA: propyldiallylamine hydrochloride, diethylaniline; BMEA: poly(-methylol benzoin methyl ether acrylate); MA: methyl acrylate; AA: acrylic acid; PVBB: poly(styrene-co-p-vinylbenzophenonep-t-butyl perbenzoate); Am: acrylamide; Cl-MeSt: chloro methylated styrene; MEPM: methoxy polyethylene-glycol monomethacrylate; DAEM: 2-(N,N-dimethylamino)ethyl methacrylate; HEMA: 2-hydroxyethyl methacrylate; MAEMA: 2-methylaminoethyl methacrylate; PPVS: poly(phenyl vinyl sulfide); PDMS: polydimethylsiloxane; PVA: polyvinylamine; PVTClAc: poly(vinyl trichloroacetate); PC: polycarbonate; PA: polyamide; PPp:polypeptide; CP: chloroprene; D-OH: dextran; PTFE: polytetrafluoroethylene.
+ R
R = Cleavable Bonds Graft Copolymer Homopolymer
sCHeMe 11.19
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332

hv C O
n
C O O
C OCH3
St
n
+ PSt
PSt
C O R C OCH3
C O
Graft Copolymer Homopolymer
sCHeMe 11.20
Macromonomers can be copolymerized with low molecular weight monomers in homogeneous and heterogeneous systems to yield graft copolymers (Scheme 11.23). In some cases, the copolymerization reactivity of a macromonomer is nearly identical to that of low molecular weight analogue [12, 273]. Their reactivity can be you predicted by intristic reactivity of the polymerizable end group, which is related to Au: Dointrinmean
sic?
O C
hv
O C
* + CH2 CH
m
CH2 CH
CH2 CH2 CH3 OH C + N CH3 CH2 CH
CH2 CH
CH2 CH
CH2 CH
CH2 CH
mk
CH2 MMA CH2 CH2 N CH3
CH2 CH3 C CH2 C O OCH3 x CH2 CH2 N CH3 CH3
CH2 CH2 N CH3
sCHeMe 11.21
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4+ + Ce + 3+ + H + Ce
333
OH
OH
OH
Monomer
sCHeMe 11.22
the electronic and steric factors. On the other hand, in some cases macromonomer reactivites are lower due to the thermodynamic repulsion or incompatability of the macromonomer and the trunk polymer from the comonomer. By using macromonomer method, various kinds of graft copolymers can be prepared. At least in principle, no limitation exists in the selection of both macromonomers and comonomers. Moreover, the molecular structure of the produced graft copolymer is well-defined compared with those obtained with other methods. For example, the grafted chain length is controlled by the molecular weight of the macromonomer, and the number of grafted chains and the copolymer composition is controlled by the feed composition and the other copolymerization compositions. Therefore, many applications are promising and literature contains a huge number of reports.
11.3.2 synthesis of graft copolymers via controlled/ living radical polymerization methods
Preparation of graft copolymers by using controlled/living radical polymerization methods also follows the same synthetic strategy that described previously for the conventional radical polymerization. Obviously, graft copolymers obtained by using controlled/living radical polymerizations exhibit high structural control. Although earlier studies only concerned with ATRP and NMP, today it is possible to synthesize graft copolymers with all the controlled methods. Typical recent examples of graft copolymers prepared by using these methods are presented in Schemes 11.24 and
= Second Monomer = Macromonomer
sCHeMe 11.23
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334

BPO/HTEMPO 130C
n m
CH2 Cl CFPA/Solvent
CH2 Cl CuCl/bpy
CH2 CH2 CH
C O
Cl
OCH2(CF2)3CF2H
sCHeMe 11.24
11.25. A compilation of literature data on these systems is provided in Tables 11.8 and 11.9. An interesting example which combines two different controlled radical polymerization methods, namely NMP and ATRP, via Click Chemistry strategy between anthracene and maleimide [346] has been given at the end of the chapter. Using these Diels-Alder (DA) functional groups, well-defined polystyrene-g-poly(methyl methacrylate) (PS-g-PMMA) copolymers were successfully prepared. The whole process was divided into two stages; (1) preparation of anthracene and maleimide functional polymers and (2) the use of Diels-Alder reaction of these groups. First, random copolymers of styrene (S) and chloromethyl styrene (CMS) with various CMS contents were prepared by nitroxide mediated radical polymerization (NMP) process. Then,
CH2 C COCl + AgClO4 CH3 C C+ ClO4 CH3 CROP THF CH3
x y n
CH2
ATRP CH2 St
O C C O(CH2)4 OH CH3
n
C O(CH2)4 OH O
sCHeMe 11.25
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335
TaBLe 11.8 Graft Copolymers Prepared by Grafting from Technique

Backbone Grafts Methods References St St, St-co-EOEA, St FRP/NMP [311, 312] DAMA-co-MMA, PMI, St FRP/NMP [34, 313] MVISC St-CMS St, EMA, MMA, AMO FRP/ATRP [314, 315] HEA, MAOETMACl St FRP/ATRP [316] PFS-b-PGMA PtBA FRP/ATRP [317] PP St, BMA Commercial/NMP [116, 249, 318, 319] PVC St, MA, BA, MMA Commercial/ATRP [8] p(IB-co-St) St Commercial/ATRP [320, 321] PSEP EMA Commercial/ATRP [188] Polyethylene St, MMA Commercial/ATRP [157, 188, 322] St St, BA, MMA NMP/ATRP [323] St-CMS OFPA NMP/ATRP [324] St, MMA St ATRP/NMP [325] St-CMS MMA, BMA, DDMA DPE/ATRP [326] HEMA BA ATRP/ATRP [327] St: styrene; EOEA: 2-ethoxyethyl acrylate; DAMA: 2-(dimethylamino)ethyl methacrylate; PMI: phenylmaleimide MVISC: methylvinylisocyanate; CMS: p-chloromethylstyrene; MMA: methyl methacrylate; EMA: ethyl methacrylate; AMO: acryloylmorpholine; HEA: hydroxyethyl acrylate; MAOETMACl: 2-(methyacryloyloxy) ethyl trimethylammonium chloride; PFS: pentafluoro styrene; PGMA: glycidyl methyacrylate; tBA: t-butyl acrylate; BA: n-butyl acrylate; BMA: n-butyl methacrylate; PP: polypropylene PVC: polyvinyl chloride; IB: isobutylene; PSEP: poly(styrene-b-ethylene-co-propylene); OFPA: 2,2,3,3,4,4,5,5-octafluoropentyl acrylate; DDMA: n-dodecyl methacrylate; HEMA: 2hydroxyethyl methacrylate.
TaBLe 11.9 Graft Copolymers Prepared by Macromonomer Technique

Macromonomer PDMS PCL PEO Comonomer MMA St MMA ODMA, ODA BA MMA, St MMA BA MMA, St NVP BA Mechanism AROP/ATRP AROP/ATRP References [328330]/ [331] [332,333]/ [334]/ [334]/ [335] [106,336] [106,337] [338,339] [175] [340] [341] (Continued)
St, tBA PAAc, PIBVE, PTHF PE St, MMA St PMMA
ATRP/FRP CROP/ATRP ROMP/ATRP RAFT/ATRP ATRP/FRP GTP/ATRP-FRP
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336
TaBLe 11.9 (CONTINUeD) Graft Copolymers Prepared by Macromonomer Technique

Macromonomer PDMS, PEO PLA PEO 2VP Comonomer MMA St St NIPAM Mechanism AROP/RAFT AROP/NMP AROP/NMP NMP/FRP References [328, 330, 342, 343] [344] [113] [345]
PDMS: polydimethylsiloxane; PCL: poly(-caprolactone); MMA: methyl methacrylate; PEO: poly(ethylene oxide); St: styrene; ODA: poly(octadecyl methacrylate); ODMA: poly(octadecyl methacrylate); BA: butyl acrylate; tBA: t-butyl acrylate; PAAc: poly(acrylic acid); PIBVE: PTHF: polytetrahydrofurane; PE: polyethylene; NVP: N-vinyl vinylpyrrolidinone; PLA: polylactide; 2VP: 2-vinylpyridine NIPAM: N-ispopropylacrylamide.
O N O
+
m nm
PMMA
n O
DA CLICK CHEMISTRY Toluene, Reux
n m
n
O
O N O
PMMA
sCHeMe 11.26
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337
the chloromethyl groups were converted to anthryl groups via etherifaction with 9anthracene methanol. The other component of the click reaction, namely protected maleimide functional poly(methyl methacrylate) (PMMA) obtained by atom transfer radical polymerization (ATRP) using the corresponding functional initiator. Then, in the final stage, PMMA prepolymer was deprotected by retro Diels-Alder in situ reaction by heating at 110C in toluene. The recovered maleimide groups and added anthryl functional polystyrene underwent Diels-Alder reaction to form respective (PS-g-PMMA) copolymers (Scheme 11.26).
11.4 CONCLUsION
Free-radical polymerization is still a very important process in view of its wide utility in terms of designing various block and graft copolymers is described in this chapter. The design of block and graft copolymers can be achieved via different pathways. Very rapid developments on the area of controlled radical polymerizations in recent years certainly helped to explore the new ways of making block and graft copolymers.
ReFeReNCes
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342 236. 237. 238. 239. 240. 241. 242. 243. 244. 245. 246. 247. 248. 249. 250. 251. 252. 253. 254. 255. 256. 257. 258. 259. 260. 261. 262. 263. 264. 265. 266. 267. 268. 269. 270. 271. 272. 273. 274. 275. 276. 277. 278. 279. 280. 281. 282. 283.
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343
Au: Is a1 correct?
Au: Is RMC correct?
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