1 s2.0 S0079670010001139 Main

Progress in Polymer Science 36 (2011) 455567
Contents lists available at ScienceDirect
Progress in Polymer Science

journal homepage: www.elsevier.com/locate/ppolysci
Telechelic polymers by living and controlled/living polymerization methods

Mehmet Atilla Tasdelen, Muhammet U. Kahveci, Yusuf Yagci
Istanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469 Istanbul, Turkey
a r t i c l e
i n f o
a b s t r a c t
Telechelic polymers, dened as macromolecules that contain two reactive end groups, are used as cross-linkers, chain extenders, and important building blocks for various macromolecular structures, including block and graft copolymers, star, hyperbranched or dendritic polymers. This review article describes the general techniques for the preparation of telechelic polymers by living and controlled/living polymerization methods; namely atom transfer radical polymerization, nitroxide mediated radical polymerization, reversible addition-fragmentation chain transfer polymerization, iniferters, iodine transfer polymerization, cobalt mediated radical polymerization, organotellurium-, organostibine-, organobismuthine-mediated living radical polymerization, living anionic polymerization, living cationic polymerization, and ring opening metathesis polymerization. The efcient click reactions for the synthesis of telechelic polymers are also presented. 2010 Elsevier Ltd. All rights reserved.
Article history: Available online 20 October 2010 Keywords: Telechelic polymers End-functionalized polymers Living polymerization Controlled/living polymerization Click chemistry
Corresponding author. Tel.: +90 212 285 3241; fax: +90 212 285 6389. E-mail address: yusuf@itu.edu.tr (Y. Yagci). Abbreviations: PAA, poly(acrylic acid); PAAL, poly(N-acryloylalanine); PAEPC, poly(2-acryloyloxyethyl phosphorylcholine); PAEL, poly(2acryloyloxyethyl lactoside); PAGA, poly(acryloyl glucosamine); PAM, polyacrylamide; PAMA, poly(2-aminoethyl methacrylate hydrochloride); PAMBA, poly(sodium 3-acrylamido-3-methylbutanoate); PAMPS, poly(2-acrylamido-2-methylpropanesulfonate); PAMMA, poly(9-anthracenylmethyl methacrylate); PAN, polyacrylonitrile; PAzPMA, poly(3-azidopropyl methacrylate); PBA, poly(butyl acrylate); PtBA, poly(tert-butyl acrylate); PtBAM, poly(tert-butyl acrylamide); PBd, poy(1,3-butadiene); PBMA, poly(butyl methacrylate); PtBMA, poly(tert-butyl methacrylate); PBONBI, poly(N-butyloxanorbornenimide); PtBSt, poly(tert-butyl styrene); PnBuOx, poly(2-n-butyl-2-oxazolines); PbzMA, poly(benzyl methacrylate); PChA, poly(cholesteryl acrylate); PChMA, poly(cholesteryl methacrylate); PCO, poly(cyclooctene); PCOD, poly(1,5-cyclooctadiene); PCOT, poly(1,3,5,7-cyclooctatetraene); PDADMAC, poly(diallyldimethylammonium chloride); PDDMA, poly(2,2-dimethyl-1,3-dioxolane)methyl acrylate; PDDMAA, poly((2,2-dimethyl-1,3dioxolane)methyl acrylamide); PDEAEMA, poly(2-(diethylamino)ethyl methacrylate); PDEAM, poly(N,N-diethylacrylamide); PDEGMA, poly(diethylene glycol monomethyl ether methacrylate); PDEVBA, poly(N,N-diethyl vinylbenzylamine); PDLLA, poly(d,l-lactide); PDMA, poly(N,N-dimethyl acrylamide); PDMAEMA, poly(2-dimethylaminoethyl methacrylate); PDMAPAA, poly(N,N-dimethylaminopropyl acrylamide); PDMAPMA, poly(N[3-(dimethylamino)propyl] methacrylamide); PDMS, polydimethylsiloxane; PDPAEMA, poly(2-(diisopropylamino) ethyl methacrylate); PDVB, poly(divinylbenzene); PEA, poly(ethyl acrylate); PECH, polyepichlorohydrin; PEEA, poly(1-ethoxyethyl acrylate); PEEGE, poly(1-ethoxyethyl glycidyl ether); PEHA, poly(2-ethylhexyl acrylate); PEMA, poly(ethyl methacrylate); PEMAM, poly(N-ethyl-N-methyl acrylamide); PEO, poly(ethylene oxide); PEtOx, poly(2-ethyl-2-oxazoline); PFABu, poly(butyl 2-uoroacrylate); PFMA, poly(pentauorophenyl methacrylate); PGalEMA, poly(2-(b-d-galactosyloxy)ethyl methacrylate); PGAMA, poly(d-gluconamidoethyl methacrylate); PGME, poly(glycidyl methyl ether); PGlMA, poly(glycerol monomethacrylate); PHFDA, poly(heptadecauorodecyl acrylate); PHEA, poly(2-hydroxyethyl acrylate); PHEMA, poly(2-hydroxyethyl methacrylate); PHMA, poly(hostasol methacrylate); PHMS, poly(4-(hydroxymethyl) styrene); PHPA, poly(2-hydroxypropyl acrylate); PHPMA, poly(2-hydroxypropyl methacrylate);
0079-6700/$ see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.progpolymsci.2010.10.002
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M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567
Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Telechelic polymers by controlled/living radical polymerization (C/LRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Iniferters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Atom transfer radical polymerization (ATRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Protected initiator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Atom transfer radical addition and coupling (ATRA/C) reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. Postmodication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.5. Macromonomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Nitroxide mediated radical polymerization (NMRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.1. Functional nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3.2. Postmodication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Reversible addition-fragmentation chain transfer polymerization (RAFT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1. Functional chain transfer agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2. Postmodication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5. Other controlled radical polymerization techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.1. Iodine transfer polymerization (ITP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.2. Cobalt mediated radical polymerization (CMRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5.3. Organometallic radical polymerization (OMRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Telechelic polymers by anionic polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Functionalization by using functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Functionalization by termination with suitable electrophile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.1. Direct functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2.2. Derivatization of functional groups by postmodication processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Telechelic polymers by cationic polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1. Telechelic polymers by cationic polymerization of vinylic monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.1. Functionalization by using functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.2. Functionalization by using termination with suitable nucleophile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.3. Functionalization by post-modication processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.1.4. New cationic polymerization techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2. Telechelic polymers by cationic polymerization of cyclic monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.1. Functionalization by using functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.2.2. Functionalization by using termination agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Telechelic polymers by metathesis polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.1. ADMET polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2. Ring-opening metathesis polymerization (ROMP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Telechelic polymers by the combination of click chemistry and C/LRP methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457 457 458 459 459 460 467 471 471 471 471 473 484 484 494 496 496 496 497 497 497 499 499 508 511 511 513 514 517 520 522 522 522 525 527 527 531 538 538
3.
4.
5.
6. 7.
PHPMAM, poly(N-(2-hydroxypropyl) methacrylamide); PIB, polyisobutylene; PIBVE, poly(isobutylvinyl ether); PIP, polyisoprene; PKSPMA, poly(potassium 3-sulfopropyl methacrylate); PLA, poly(lauryl acrylate); PLAMA, poly(2-lactobionamidoethyl methacrylate); PLMA, poly(lauryl methacrylate); PMA, poly(methyl acrylate); PMAGA, poly(methacryloyl N-acetyl-d-glucosamine); PMAIpGlc, poly(3-O-methacryloyl-1,2,5,6-di-O-isopropylidened-glucofuranose); PMAIpGpc, poly(6-O-methacryloyl-1,2,3,4-di-O-isopropylidene- -d-galactopyranose); PMAM, poly(methacryl amide); PMAMGlc, poly(methyl 6-O-methacryloyl- -d-glucoside); PMAMMns, poly(6-O-methacryloyl mannose); PMAn, poly(maleic anhydride); PMEEMA, poly(2-(2methoxyethoxy)ethyl methacrylate); PMeOx, poly(2-methyl-2-oxazoline); PMM, poly(methylidene malonate); PMMA, poly(methyl methacrylate); PMnsTzMA, poly(mannose triazole methacrylate); PMPC, poly(2-methacryloyloxyethyl phosphorylcholine); PMVK, poly(methyl vinyl ketone); PNaA, poly(sodium acrylate); PNIPAM, poly(N-isopropylacrylamide); PNaMA, poly(sodium methacrylate); PNAm, poly(N-acryloyl morpholine); PNAS, poly(N-acryloyloxysuccinimide); PNaVBz, poly(sodium 4-vinylbenzoate); PNB, poly(norbornene); PNBFer, polymer of norbornene derivative containing ferrocene; PNBPhT, polymer of norbornene derivative containing phenothiazine; PNBOE, poly(norbornene octyl ester); PNIPAM, poly(N-isopropyl acrylamide); PNIPMA, poly(N-isopropylmethacrylamide); PNHSMA, poly(N-hydroxysuccinimidyl methacrylate); PNSVB, poly(Nsuccinimide-p-vinylbenzoate); PNVCL, poly(N-vinylcaprolactam); PNVP, poly(N-vinyl pyrrolidone); PNVPh, poly(N-vinylphthalimide); POEGA, poly(oligo (ethylene glycol) acrylate); POEGMA, poly(oligo (ethylene glycol) methacrylate); POx, polyoxazoline; PPAA, poly(propylacrylic acid); PPAM, poly(N-propyl acrylamide); PPATS, poly((3-acryloxypropyl)-trimethoxysilane); PPBA, poly(1-pyrenebutyl acrylate); PPDSM, poly((2-(2-pyridyldisulde)ethyl methacrylate)); PPhOx, poly(2-phenyl-2-oxazoline); PPrOx, poly(2-propyl-2-oxazoline); PiPrOx, poly(2-isopropyl-2-oxazoline); PPVK, poly(phenyl vinyl ketone); PQDMA, poly(quaternized 2-(dimethylamino)ethyl methacrylate); PRhBMA, poly(rhodamine B methacrylate); PTMS-PgMA, poly(trimethylsilyl-protected propargyl methacrylate); PNBDHMA, poly(7-nitrobenz-2-oxa-1,3-diazole hexyl methacrylate); PMMA, poly(methyl methacrylate); PMeSt, poly(alphamethyl styrene); PPO, poly(propylene oxide); PSMA, poly(solketal methacrylate); PSt, polystyrene; PSTA, poly(stearyl acrylate); PSSS, poly(sodium 4-styrene sulfonate); PTHF, polytetrahydrofuran; PTHPA, poly(tetrahydropyran acrylate); PTyMA, poly(thymine methacrylate); PVAc, poly(vinyl acetate); PVAGP, poly(6-O-vinyladipoly-d-glucopyranose); PVBA, poly(vinylbenzyl alcohol); PVBC, poly(vinylbenzyl chloride); PVK, poly(vinyl carbazole); PVP, poly(4-vinyl pyridine); PVPGVG, poly(valine-proline-glycine-valine-glycine methacrylate).
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1. Introduction A major concern of polymer and material science is designing functional materials with physical features tuned to match the needs of expanding technology. In particular, end-functional polymers have an important economic position because of their possible applications as components in the synthesis of block copolymers, thermoplastic elastomers, polymer networks, surfactants, macromonomers, etc. [1]. According to the IUPAC, telechelic polymers are dened as polymeric molecules with reactive end groups that have the capacity to enter into further polymerization or other reactions. Reactive end-groups in telechelic polymers come from the initiator or the terminating or chain-transfer agents in chain polymerizations, but not from monomer(s) as in polycondensations and polyadditions [2]. Functionalization of polymer chain ends can also take place in postpolymerization reactions. Pioneering work on the synthesis of telechelic polymers and their conversion to the nal products with specic properties by reacting with functional groups may be dated to 1947 [3]. However, the concept was not fully recognized until 1960 [4]. Signicant contributions to the development of this class of polymeric materials continue in the current literature [46]. In the last decade there has been a rapid growth in the development and understanding of new controlled/living radical polymerizations (C/LRP) [7]. Precise control of functionality, molecular weight, and uniformity (molecular weight distribution) can now be made not only by living ionic polymerization routes but also by newly developed controlled/living radical polymerization techniques. Another striking development has been achieved in metathesis polymerization and click chemistry. In addition, many new catalysts have been developed and applied to prepare advanced materials [811]. The range of monomers and functional groups used in the preparation of telechelic polymers has been expanded in recent years as a result of such developments. This article describes the general techniques for the preparation of telechelics with special emphasis on living and controlled/living polymerization methods. A polymer can be considered to be telechelic if it contains end groups that react selectively to give a bond with another molecule. Depending on the functionality, which must be distinguished from the functionality of the end group itself, telechelics can be classied as mono- or semi, di-, tri-, and multifunctional telechelics (polytelechelics) [5]. The functionality is dened as: f = Number of functional groups Number of polymer chains
kyklo-, multicyclic, etc.), new classications and notations are needed. Telechelic polymers can be used as cross-linkers, chain extenders, and pre-cursors for block and graft copolymers [1214]. Moreover, star and hyper-branched or dendritic (or hyper-branched) are obtained by coupling reactions of monofunctional and multifunctional telechelics with appropriate reagents. Various macromolecular architectures obtained by the reactions of telechelics are represented in Fig. 1. The functionality of the end group is important. When such groups are bifunctional (e.g., vinyl groups) they can participate in polymerization reactions, yielding graft copolymers or networks; such telechelic polymers are called macromolecular monomers, macromonomers, or macromers. Industrial interest in telechelics was stimulated by the development of thermoplastic elastomers, which consist of ABA block and multiblock copolymers. Liquid telechelic polymers are the basis for reaction injection molding. Liquid telechelics that can be used for network formation offer processing advantages and may result in materials with improved properties [6]. For example, alcohol and carboxylic acid functional telechelic polymers can be used to make their respective polyesters via polycondensation. Hydroxyl telechelic functional polymers are also reacted with difunctional isocyanates to form polyurethanes. When telechelic polymers are designed for use in synthesizing networks, they are stoichiometrically reacted with multifunctional cross-linkers containing a complimentary antagonist group. This leads to a welldened polymer network, which can be very important for commercial applications. 2. Telechelic polymers by controlled/living radical polymerization (C/LRP) Accurate control of polymerization process is an important aspect for the preparation of well-dened telechelics and end-functionalized macromolecules [15]. Such control of chain ends was traditionally accomplished using living ionic polymerization techniques. But it is well known that the ionic processes suffer from rigorous synthetic requirements and in some cases they are sensitive to the functional groups to be incorporated. On the other hand, free radical polymerization is exible and less sensitive to the polymerization conditions and functional groups. However, conventional free radical processes yield polymers without control of molecular weight and chain end. Competing coupling and disproportionation steps and the inefciency of the initiation step lead to functionalities less than or greater than those theoretically expected. Recent developments in controlled/living radical polymerization provided the possibility to synthesize well-dened telechelic polymers with controlled functionality [16]. As described below, all the controlled/living radical polymerization methods, namely atom transfer radical polymerization (ATRP) [17,18], nitroxide mediated radical polymerization (NMRP) also called as stable free radical mediated polymerization (SFRP) [19], reversible addition-fragmentation chain transfer polymerization (RAFT) [20], iniferters [21], iodine transfer polymerization (ITP) [22], cobalt mediated rad-
In the polymer science community, the term telechelic commonly refers to a linear polymer having the same functionality at both chain-ends. When the polymer chain contains two different functional groups at the ends, it is called heterotelechelic. As the concept of telechelics is now expanding from classical linear bifunctional polymers toward many other types varying the number and positions of functional groups (semi-, eso-, etc.) and more importantly the topology of polymer chains (star-, dendritic-,
458
Fig. 1. Various architectures obtained by the reactions of telechelics.
ical polymerization (CMRP) [23], and organotellurium-, organostibine-, organobismuthine-mediated polymerization (OMRP) [24] have been used for the preparation of telechelic polymers. There are two strategies for synthesizing telechelic polymers using the widely used C/LRP methods including ATRP, RAFT, or NMRP processes [25,26]. Functionality can be incorporated onto the initiating segment of ATRP, RAFT, or NMRP initiators which afford -functional telechelic polymer. Equally, functionality can be afxed to the terminating portion of initiators which provides -functional telechelic polymer (Scheme 1). Polymers can be functionalized at one end (semi-telechelic), both ends (telechelic), or possess differing functionality at the ends (heterotelechelic). As an alternative, functionalization of polymer chain ends can be achieved by post-polymerization reactions. 2.1. Iniferters Iniferter is a useful and convenient method for the synthesis of vinyl polymers under mild reaction conditions, although the polymerization is quasiliving radical polymerization [21]. Photochemically or thermally activated polymerization can proceed in the presence of radically polymerizable vinyl monomers under appropriate reaction conditions through radical pair generation, monomer addition, and rapid recombination [27]. The peculiar behavior
of thiuram disuldes in free radical polymerization was rst identied by Ferington and Tobolsky [28,29]. These molecules can act simultaneously as an initiator, chain transfer agent, and terminator in a polymerization reaction and generally referred as iniferters by anomy to their role [30,31]. So far, many iniferters have been reported and utilized for the synthesis of telechelic polymers. Telechelic preparation is based on the concept of locating the required function on the alkyl group of the thiuram disulde and using it in the photo or thermal polymerization. Since end groups are introduced via initiation and transfer and common bimolecular termination between two growing chains are negligible, perfect bifunctional telechelics are available along this route. Several functional disuldes and substituted tetraphenylethylenes were also used as iniferters in free radical polymerization. The functionalities of the telechelics prepared by iniferter method were reported to be close to 2, within experimental error. The formation of the nonfunctional polymers was claimed to be negligible because of the triple function of the iniferter. For example, carboxylic acid and amino functionalities were introduced to polystyrene using the corresponding disuldes [32]. Diamino functional poly (t-butyl acrylate) was also prepared [33]. In this case, polymers were readily hydrolyzed to polyacrylic acid possessing amino terminal groups, which is a useful material for the application of polyelectrolytes. The photochemically and thermally induced
459
Scheme 1. General synthesis strategies for telechelic polymers by ATRP, NMRP and RAFT methods.
iniferter properties of the tetraalkylthiuram disuldes during free radical polymerization were also exploited to end functionalize poly(methyl methacrylate) and polystyrene (Scheme 2) [30,34]. Table 1 summarizes the functional iniferters used for obtaining telechelic polymers. 2.2. Atom transfer radical polymerization (ATRP) Among the C/LRP strategies, ATRP, coined by Wang and Matyjaszewski [45] and Sawamoto and co-workers [46] in 1995, has turned out to be the most promising method allowing good control on the molecular weight and microstructure of the polymers in a targeted manner. In this method, control is achieved by the equilibrium maintained between an active (Pn ) and a dormant chain (Pn X). The mechanism involves reversible homolytic cleavage of a carbonhalogen bond by a redox reaction between an dormant species and a metal/ligand complex, such as copper (I) complexes with 2,2-bipyridine, as illustrated in Scheme 3. Several monomers are added at each activation step. In a well-adjusted slow activation and a fast deactivation, transfer and termination reactions have mostly been eliminated. As illustrated in Scheme 4, several strategies can be employed for the synthesis of telechelic polymers using ATRP. (I) The most convenient strategy is based on the use of initiators carrying reactive functional groups (e.g., alcohol, ester, epoxide) that do not require any protection. (II) Conversely, initiators containing specic functional groups such as thiol or carboxylic acid can be used only after an initial protection step, because of their participation in the polymerization process. (III) Atom transfer radical addition or coupling (ATRA/C) reaction relies on the same mechanism as ATRP,
but instead of polyadditions, only a single molecule is added. Functionalization by ATRA/C reaction was demonstrated with a co-monomer which does not homopolymerize in radical polymerization or a chain transfer agents or a stable radical or a combination of low molecular weight or polymeric radicals. (IV) Finally, an alternative route to reach telechelic polymers is to transform the terminal halide groups to the desired functionality by postmodication reactions such as nucleophilic substitutions. 2.2.1. Functional initiators Telechelic polymers are easily accessible with ATRP using functional initiators. To date, well-dened styrene and acrylate type telechelic polymers have been successfully prepared with functional groups such as amine, ester, nitro, hydroxyl, aldehyde, phenyl and acid via the corresponding functional initiator (Table 2). It should be pointed out that besides the desired functionality, the initiators need to be equipped with a radical stabilizing group on the -carbon atom such as aryl, carbonyl, nitrile, and multiple halogens to ensue successful ATRP. Notably, direct bonding of halogen to aryl or carbonyl group does not facilitate radical generation. For example, ATRP of methyl methacrylate with copper/ligand complex in the presence of hydroxy functional alkyl bromide initiator leads to -hydroxy functional PMMA with controlled architecture without the use of protecting group chemistry (Scheme 5) [47]. Like ATRP, reverse atom transfer radical polymerization, RATRP, has been shown to produce similarly telechelic polymers suitable for continued polymerization. RATRP involves initiation by conventional azo or peroxy initiators in the presence of appropriate transition-metal complexes in a higher oxidation state [48]. Monotelechelic polystyrenes with cyano, carboxylic acid, and hydroxyl terminal groups can be prepared via RATRP using corresponding azo initiators in conjunction with metal/ligand complexes (Scheme 6) [49].
Scheme 2. Synthesis of telechelic polymers by iniferter method.
460
2.2.2. Protected initiator Protection of the functional groups of initiators susceptible to ATRP process has proven to be a general method enabling the preparation of functional polymers with well-
dened architecture. The functional group in the ATRP initiators can be an aldehyde, an amine, a hydroxyl, a phenyl, a nitro, or an acid. Unfortunately, to obtain an aliphatic acid and an amine or an anhydride functions, it
Table 1 Functional iniferters. Functionality Iniferter Polymers
S
OH
HO
S
2
PMMA [35]
OH
Si O C
2
PMMA [36]
S
COOH
S HOOC HOOC
PMMA [37]
COOH
PSt [38]
COOH
COOH
O
NH2
S N
S
N C
PIP [39]
OH and COOH
HO
S COOH
PSt [40], PDMA [40]
S
OH and COOH
HO
S O
OH
PSt [40], PDMA [40]
S
NH2 and COOH
HOOC N
NH2
PSt [40], PDMA [40]
Cl
chloride
NC C
2
PSt [41,42], PMMA [41,42]
Cl
S O
phosphorylamide
P O
S
2
PSt [43], PMMA [43]
R
furanyl
Si O C
2
R: -phenyl, -tolyl, -mestyl
PSt [44], PMMA [44], PBA [44], PSTA [44]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 2 Functional initiators for ATRP. Functionality OH Initiator Polymers
461
HO
ClCl Cl
PMMA [50]
Cl
OH
Cl OH
HO
HO N
SO2 Cl
SO2Cl
Cl
PSt [51], PMMA [51,52]
OH
PSt [51], PMMA [51]
OH
PSt [53,54], PMMA [55]
O
OH
HO
Br
PSt [47,5660], PMMA [47,56,5862], PFOMA [63], PtBMA [64], PBA [65,66], PtBA [66], PMMA-b-PBA [67], POEGMA [68], PNaMA [69]
O
OH
HO
HO
O
Br
Br Br Br
Br
PSt [70]
OH
PMMA [71], PBA [71]
OH
HO
PSt [72], PMMA [50,71,73], PHEMA [71,73], PBA [71,73]
O
OH
HO
O
O O
Cl Ph
PMMA [74]
OH
HO
Br
PSt [75]
O
OH
HO
4N
O Br
PSt [76]
OH
HO HO
N O
O O Br
PDMAEMA [77]
O
OH
HO
HO
O Cl
Cl
PMMA [62]
OH
PSt [78]
N
HO
OH
N
O
Br
PMMA [78]
N
OH
O Br
O CN N N N NC H O
PTyMA [79]
N OH H
HO
H N
OH
OH
PSt [49]
COOH COOH
HOOC Cl
HOOC Br
PSt [80], PAM [81] PSt [80], PMMA [71,82], PBA [71]
462 Table 2 (Continued) Functionality
Initiator
Polymers
COOH
HOOC
HOOC
HOOC
Cl
PSt [38,75,80,8385], PMMA [84,85]
COOH
SO2Cl
O
O
PSt [51], PMMA [51], PBMA [51]
O O
O O
COOH
Br
PSt [80]
COOH
HOOC
Br
PSt [76]
COOH
HOOC
Br
PSt [80,86]
COOH
HO
O
NC
N
O N
CN
OH
PMMA [48], PSt [49]
CHO
OHC
O O O Br
PSt [75]
CHO
OHC
Br
PSt [75,87], PMMA [87]
O
CHO
OHC HO
Cl
PSt [88]
OH and CHO
OHC
H2N
Cl
O
PSt [88]
NH2
Br
PSt [87], PMMA [87]
Br
NH2
H2N Ph
X
Ph
PSt [89]
Y X,Y :(NO2, H), (NH2, H)

NH2
(H,NH 2), (H,NO 2)
Y O
O O
2
Br O
PMMA [90]
N
N(CH3 )2
SO2Cl
O
PMMA [51]
N(CH3 )2
Br
PtBA [91], PMMA [62]
N(CH3 )2
O O
O N H
Br
Br
POEGMA [92,93], PMMA [62]
N(CH3 )2
Br
PGlMA [94]
N(CH3 )2
N Ph
Ph
PSt [95]
N
N(CH3 )2
O O Br
PSt [75,96]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 2 (Continued) Functionality Initiator Polymers
463
O
N(CH3 )2
O N O Br
PHEMA [97], PHEMA-co-PGlMA [97], PHEMA-co-PHPMA [97]
O
N(CH3 )2
O Cl
SO2Cl
O O
PMMA [62]
NO2
O2N
O2N
PSt [98], PMMA [99]
NO2
Br
PSt [87], PMMA [87], PBA [100]
O
N3
N3
O
O
O
Br
Br
PDMAEMA [101103]
N3
N3
nO
n: 2,3,4,6
PMMA [104,105], PNIPAM [106], PAMA [107], PDEAEMA [107], PMPC [107], PDMAEMA [107], PHEMA [107], PGlMA [107], PHPMA [107], PKSPMA [107], PQDMA [107], PMMA-co-PHMA [108],
O
N3
N3 N3
N3
N
O
Cl
PNIPAM [106]
N3
N H
Cl
PNIPAM [109,110]
O
N3
N3
3N
O O
O Br
PSt [76]
CN
NC
Br
PSt [60,92,93], PMMA [60,92,93]
CN
NC Br
N N
PSt [111], PMMA [111], PAN [112]
CN
CN
NC
R: -CH2(C6H5) or -CH(CH3)COOCH3
PSt [49]
amide
O N H Br
PBMA [113], PbzMA [113], PSt [113], PDMAEMA [113], POEGMA [113]
amide
O N H Cl
PMMA [62]
O
phthalic anhydride
O O
O
Br
PSt [86]
phthalimide
N O
O O
Br
PMMA [114]
O
acetal
O O Br
PtBA [115]
O
O
succinimide
N O O O
Br
PMMA [114], POEGMA [116], PMAIpGlc [117], PMAIpGpc [117], POEGMA-co-PHMA [118],
Initiator
Polymers
triazine
H3 CO
Cl O O Br
PMMA [114]
N N HN
CH3
coumarine
O O O
O O
O
O O
Br
PSt [119], PMMA [120]
Br
PMMA [120]
coumarine
O
alkyne
O
O O
Br
O
O
PSt [121124], PMMA [57,124126], PtBA [57,127], PbzMA [128], PDMAEMA [103]
O Br
PSt [76]
alkyne
NH
O O Br
O
alkyne
PSt [129]
alkyne
Br
O
PSt [130], PNIPAM [131,132], PEEA [133], PMMA-co-PHMA [108],
benzoyl
O O
Br
PSt [134,135]
O O O
benzoyl
Br
PMMA [136], PSt [137]
O
benzophenone
O O Br
PSt [138], PMMA [138]
SO2 Cl
naphthalene PMMA [51]
Br
uorene PSt [139]
carbazole
N Br
PVK [140], PVK-b-PMMA [140]
O
anthracene
Br
PMMA [141,142], PSt [143146]
Br
pyrene PSt [147150], PBA [151], POEGMA [151], PNIPAM [152], PAM [153], PDMAPAA [153], PHEMA [154]
N
fullerene
O O Br
PSt [155]
465
trimethylsilyl
Si
O
11
NC N O
N CN
PSt [156]
imidazolium
N +N
O O Br
PMMA [157]
PF6-
O
adamantyl
O
N S
X
Br
O
PDMAEMA [131]
pyridine
S
X
Br
PHEMA [158], PMAGA [159]
bipyridine
PSt [160], PMMA [161]
X : -H, -CH2Cl, -CH2OCOC(CH3)2Cl
O
amino acid
N O H
O O
Br
PtBA [162], PtBA-b-PSt [162]
nucleoside and oligosaccharides
X: -nucleosideor
Br -oligosaccharide
PSt [163,164], PMMA [163,164], POEGMA [164], PMAIpGlc [164], PDMAEMA [164]
O
naphthyridine
3
O N N N N H H O O Br
PBA [128]
ureido pyrimidinone
NHO O N N N H H
O O
Br
PbzMA [128], PBA [128]
oligopeptide
Ph O O
Ph n: 0, 1, 3
N n H
O H N O
Br
PtBMA [165], PDEAEMA [165]
biotin
O X: -Br, -ClR: -CH3, -H HN NH O O H H O R N 3 2 X S H
PMAGA [166], PtBA [167], PNIPAM [168170], PtBA-b-PMA [167]
S
azobenzene
O azobenzene O
PMMA [171]
O
azobenzene
azobenzene
Br
PSt [172], PMMA [172174]
azobenzene
azobenzene SO2 Cl
porphyrin
PMMA [51]
porphyrin
O O
Br
PSt [175]
Ph
diphenyloxazole
O N
Br
PMMA [132]
Ph
Initiator
Polymers
O
estrone
H H H O
PSt [176], PMMA [176]
Br
O
naphthopyran
O O O
O O
O O
Br
PBA [177]
spirooxazine
N NO
S Br
Cl
PSt [178]
benzothiazole
N
Br
PSt [179]
HO
Br
PSt [60,92,93], PMMA [60,92,93]
halide
halide
SO2 Cl
X: -F, -Cl
PSt [98,180], PMMA [99,180]
ouro
Cl Cl F3 C Cl
FF O O
n = 7,8
PSt [181]
ouro
Br
PSt [182], PMMA [183,184], PBMA [182], POEGMA [183,184]
FF
ouro
O
6
Br O
PMEA [185], POEGMA [185], PMMA [183185],
C8F 17H6H3 CO
ouro
C8F 17H6H3 CO
C8F 17H6H3 CO X
ouro
Br
PSt [186], PMMA [186]
C8F 17H6H3 CO
O
PSt [186], PMMA [186]
X: H or OCH 3H6 C8F 17
Br
Scheme 3. General mechanism for ATRP.
467
Scheme 4. General strategies for the synthesis of telechelic polymers by ATRP.
is necessary to protect such groups in order to circumvent complexation with the copper catalyst during the polymerization. Ketal, acetal and phthalate functional ATRP initiator can be used in the polymerization as protecting groups for the following functional groups: diol, aldehyde, and phthalic anhydride, respectively [187]. A trimethysilyl group and isobutyrate in initiator are efcient protecting group of alkyne and maleimide functionalities with simple deprotection steps. Table 3 gives some examples of protected initiators used in ATRP. Previously, Zhang and Matyjaszewski have reported the use of protected and unprotected -halocarboxylic acids as initiators for the ATRP of styrene [188]. The unprotected initiator efciency was quite low and was not effective for the ATRP of styrene. Protection of the carboxylic acid group by a trimethylsilyl, tert-butyldimethylsilyl, or tert-
butyl group led to high initiator efciencies for the ATRP of styrene. Subsequent hydrolysis of the protecting groups can provide well-dened PSt with terminal carboxylic acid groups (Scheme 7). The advantages of these techniques include quantitative functionality and the ability to produce telechelics as well as asymmetric telechelics. 2.2.3. Atom transfer radical addition and coupling (ATRA/C) reactions Atom transfer radical addition and coupling (ATRA/C) reactions can also be utilized in the functionalization of end halogenated polymers readily prepared via ATRP. The reaction mechanism is mechanistically similar to ATRP with the exception that the reaction conditions are modied in such a way that only one addition step occurs. This mechanism can be subdivided into four sections accord-
Scheme 5. Synthesis of hydroxy-telechelic PMMA by ATRP using functional initiator.
Scheme 6. Synthesis of hydroxy-telechelic PSt by RATRP using functional initiator.
468 Table 3 Protected initators for ATRP. Functionality
Initiators
Polymers
O
OH
O O
O
O
Br
PSt [189]
OH
O O
Br
PBA [190]
O
COOH
Br
PSt [60,80,191], PMMA [60]
O
COOH
O O
O O O
Br
PMMA PSt [192], PNBDHMA [193], PMMA-co-PAMMA [193]
CH3OOC
COOH
O CH3OOC
O Br
PSt [194,195]
Br
PSt [195]
COOH
O
O O Br
COOH
PSt [195]
O
COOH
Br
PSt [195]
O
COOH
PBA [196]
Br
O
CHO
O O O Br
POEGMA [197]
NH2
Boc
H N
H N
O N H
O O O
Br
O O 4 Br
PSt [191], PMMA [198,199]
NH2
Boc
PNIPAM [200], PHEMA [200], POEGMA [200]
NH2
Boc
H N
O O O O
4O
Cl
PNIPAM [200], PHEMA [200], POEGMA [200]
Boc
NH2
O N H O
n = 1,2 n
Br
PBA [100], PSt [201], POEGMA [202]
O
NH2
N O O O O
Br
PSt [203]
NH2
N O
2
Br O
PtBA [204]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 3 (Continued) Functionality Initiators Polymers
469
O
NH2
N O
Br O O O
PSt [205]
O
NH2
N O
Br
O O N H O
5O
PSt [203]
Br
PMPC-b-PDMAEMA [206], PMPC-b-PDPAEMA [206]
NH2
NH2
O OH O O N Br H O O
PHEMA [207]
NH2
H O O N Cl
PSt [207]
O N H
O O N H O N O H
NH2
O Br
PSt [76]
O
alkyne
O TMS O O TIPS
O O
Br
PSt [80,189,208,209], PMMA [208,210,211], PHEMA [212], PtBA [189,210], PSt-co-PMI [213], PiBA [214]
alkyne
Br
O O Br
PSt [80,215], PMA [80,215], PtBA [80,215], PS-b-PtBA [80,215], PMA-b-PSt-b-PtBA [80,215]
maleimide
N O
PMMA [143146,216218], PSt [219], POEGMA [202], PHMA [220], PtBA [144,145,218], PSMA-co-PPgMA-co-PTMS-co-PgMA [221], PMnsTzMA [221], PRhBMA [221],
O
maleimide
N O
O
O O Br
PSt [219]
O O Br
O O Br
PMMA [222] PSt [205]
maleimide
N O O
S
SH
O2N
NO2
O
SH
N S S
n: 1, 2
Br
O
PMMA [223], PNHSMA [223], PNIPAM [224]
O
SH
Br
Br
PSt [225], PEEA [226]
O
SH
O S S O Br
PMMA [227], PtBMA [227], PBMA [227]
Br
Initiators
Polymers
O O
sugar
O O O
Br
POEGMA [228], PbzMA [228]
sugar
O O
O O
POEGMA [228], PbzMA [228]
O O
Br
ing to the molecules used for end-group functionalization (Scheme 8): a) Functional monomers, that is, monomers including desired functionality such as allyl alcohol, ethene, C60 fullerene, and maleic anhydride, which is unable to undergo homopolymerization under the polymerization conditions. They are mainly added one unit without further propagation. b) Functional addition-fragmentation transfer agents (AFTs). AFTs lose a radical fragment after addition to the polymer radical, producing an irreversibly terminated polymer chain and a small radical. This radical could be terminated by the deactivating copper (II) species present in the reactive system during a classical ATRA experiment to give a stable product. c) Functional stable radicals, such as nitroxides, that can be added to the polymerization medium to terminate
all produced polymer radicals as well as introduce dened end groups. For styrenes and acrylates, the process mainly takes places through combination. When a methacrylate is used, trapping via disproportionation is competitive with coupling with nitroxides. The combination is the main process at low temperatures. On the other hand, disproportionation via hydrogen abstraction from an -hydrogen atom of the polymeric radical leads to introduce vinyl end groups at high temperatures. Also, tetraphenylethane derivatives can be used as a stable radical to trap polymeric radicals. d) Termination by combination of radicals (atom transfer radical coupling (ATRC)). When the polymers terminated by combination, telechelic polymers can be prepared with increasing radical concentration that in the absence of monomer to increase the probability of termination events. Thus, utilizing a functional ATRP initiator to produce the polymer and coupling of the
Scheme 7. Synthesis of hydroxyl telechelic polymers by ATRP using protected and unprotected -halocarboxylic acids.
Scheme 8. End-group modication of polystyrenes by ATRA/C with a functional monomer (a), or a functional chain transfer agent (b), or a functional stable radical (c), or by ATRC process (d).
471
halogen chain ends is an alternate pathway to telechelic polymer. If the main termination reaction consists of disproportionation, this scheme cannot be followed, and small amount of second monomer such as styrene should be added to promote the combination mechanism by reacting with two polymer radicals. The method was rstly applied by Fukuda and co-workers [229] The technical term atom transfer radical coupling was established by Yagci who was the rst to recognize the synthetic potential of ATRC for the preparation of , telechelic polystyrene containing variety of functional groups at both ends, including alcohols, carboxylic acids and aldehydes [75]. Other groups also reported the successful syntheses of telechelics with various functional groups by ATRC including phenol [75], aniline [75], aldehyde [75,230], hydroxyl [49,231,232], carboxylic acid [49,75,233], ester [234236], phthalimide [205], dimethylfulvene-protected maleimide [219], NBoc [201], and trimethylsilyl [233,237] groups [238]. Moreover, Matyjaszewski et al. performed the successful ATRC of hydroxy-terminated poly(methyl acrylate)s by introducing small amounts of styrene to provide efcient coupling [231]. Combination of ATRP and ATRA/C strategy could be useful in designing the reactive groups at one or both ends of the polymer chains by polymerizing styrenes, acrylates and methacrylates from a functional initiator and then coupling. Telechelic polymers prepared by these reactions are summarized in Table 4. 2.2.4. Postmodication Obviously, polymer chain prepared by ATRP always contains terminal halogen due to the fast deactivation process. Therefore, -mono- and -, -telechelics can be prepared by transformation of the halide end group by means of postpolymerization reactions such as nucleophilic substitution or electrophilic addition of catalyzed by Lewis acids. Different compounds including sodium azide, n-butylamine, and n-butylphosphine have been tested. A representative example is the successive transformation of a halogen into an azide and then to an amine functionality to afford , -amino functional polystyrene (Scheme 9). Quantitative conversion of the end groups was observed in each transformation reaction [259261]. The resulting polymer was further reacted with terephthaloyl chloride in a polycondensation process to yield chain extended polystyrenes with internal amide linkages. The halide displacement reaction is particularly important in the preparation of , -hydroxy telechelics, which nd application in the preparation of segmented polyester and polyurethanes [190,241,262,263]. In such applications the rst hydroxyl group can be incorporated by using hydroxy-functional initiator derivatives [56]. The second hydroxyl group functionalization can then be achieved by direct displacement of halogen group with an amino alcohol or utilizing allyl alcohol (Scheme 10). Recently, Hilborn and co-workers reported a versatile method for the transformation of terminal halide of polystyrene into thiol [264]. Well-dened bromo end-functional polystyrene was prepared by ATRP and con-
verted into thiol end-groups by reaction with thiourea followed by treatment with NaOH (Scheme 11). Table 5 reviews some of the postmodication reactions. 2.2.5. Macromonomer Among the controlled radical polymerization techniques, perhaps ATRP has received remarkable attention with regard to macromonomer synthesis (Scheme 12). ATRP has been utilized for the synthesis of a number of macromonomers containing pyrrole, thiophene, lactone, vinyl ester, epoxy, vinyl ether, allyl, and norbornene, polymerizable end groups by means of which each of these groups exhibits a low susceptibility to polymerization under ATRP conditions (Table 6). Incorporation of unsaturated end groups to polymers by ATRP is limited to certain groups. In order to produce polymers with a more reactive unsaturated end groups such as methacrylates, a combined ATRP and catalytic chain transfer (CCT) process was proposed [335]. In this methodology, the CCT agent was added to the ATRP of MMA near to the end of polymerization, leading to the formation of -unsaturated PMMA macromonomer with low polydispersity and controlled molecular weight (Scheme 13). Here, the CCT agent acts as a chain transfer terminator but does not initiate new chain in the classical manner. Similarly, Haddleton and co-workers used methyl(2bromomethyl) acrylate in transition-metal-mediated controlled radical polymerization to replace the -halogen end group via addition-fragmentation to yield a methacrylatebased macromonomer [250]. More recently, a convenient, one-pot synthesis of telechelic polymers with unsaturated end groups was developed [251]. Addition of excess ethyl(2bromomethyl)acrylate to ATRP of acrylate monomers after 8090% conversion resulted in the formation of mono-and bifunctional polymers (Scheme 14). The average degree of end functionality was almost quantitative (f = 1 for a monofunctional and f = 2 for a bifunctional initiator). 2.3. Nitroxide mediated radical polymerization (NMRP) Another C/LRP method developed in recent years is NMRP, also called SFRP by some authors [19,336]. This type polymerization can be realized through reversible deactivation of propagating chain end by relatively stable radical nitroxides such as 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) (Scheme 15). 2.3.1. Functional nitroxides It is possible to prepare telechelic polymers by NMRP procedure since it tolerates a wide variety of functional groups [19]. The presence of the terminal nitroxide species in the nal products has introduced several strategies for synthesizing telechelic polymers. The simplest method is incorporation of desired functionality onto initiator or nitroxide molecules. For the synthesis of , -telechelic polymers may be reached either through a unimolecular or bimolecular process. The unimolecular procedure for the synthesis of telechelic polymers relies on the use of active species carrying both the desired functional groups
472
Table 4 Summary of telechelic polymers obtained by ATRA/C reactions. Functionality a Polymers PMMA [56,74,190,239242], PMA [56,74,190,239242], PBA [56,74,190,239242], PEO-b-PEA [56,74,190,239242] PMMA [243]
HO
HO
O
a a
PMA [239] PMMA [234]
O
a
N O H
PMMA [74]
PMMA [234]
O
a
PMMA [234]
PMMA [244246], PSt [244246]
O O O Si O
O
PMMA [234], PSt [247]
X -OSi(CH3)3
Si O
X: -F, -Cl,
PMMA [234,240,248,249], PBA [234,240,248,249]
Si
PMMA [249]
O O
Br
PMMA [250], PSt [251], PBA [251], PMA [251]
PSt [252]
X
S
N O X: -OH, -COOH,
-NH2, -OCH2CCH
PSt [240,253255], PMMA [234], PBA [240,253,254],
S S S
Ph Ph C OSi(CH3)3 Ph
Br
ATRC
PMMA [256], PDMAEMA [256]
(H3C)3SiO C Ph
X
PSt [257]
X: -COOH,-CHO, -OH,-N(CH 3)2, -CH2COOH,-Si(CH 3)3
PSt [75,233,237]
X
d
O O Br
ATRC X
O O
O O
X
PSt [201,231233,258], PMA [235], PMMA [231,232], PBA [235], PtBA [235], PFABu [236]
X: -(CH2)3Si(CH3)3, -CH3, -(CH2)2OH,-(CH2)3NHBoc
O
d
O Br
ATRC
O N O
O N O
N O
O
N O
O
PSt [205]
N O
Br ATRC
N O
PSt [219]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 4 (Continued) Functionality Polymers
473
X
O
Br
ATRC
X
O O
ATRC
PSt [49]
X: -CN, -COOH, -OH

d
Br + Br
O O
ATRC
PMMA [234]
Br + Br
CHO
O O
CHO
PSt [230]
Scheme 9. Successive postfunctionalization of halogen end-functionalized polystyrene.
and a nitroxide unit. The alternative bimolecular process is based on a combination of functional nitroxide and radical initiators. Functional groups can be placed at the initiating chain end, F1 , or the nitroxide mediated chain end, F2 (Scheme 16). Telechelics with a variety of functional groups can essentially be prepared by using functional nitroxides (Table 7). For example, nitroxides carrying many useful reactive groups such as OH, COOH groups were readily used for the creation of controlled molecular architectures by NMRP. A recent study has shown that high degree of functionalization, i.e., greater than 95%, is possible even at molecular weights up to 50,00075,000 by
NMRP method [337]. This elegant method provides high level of functionalization without using postpolymerization strategies.Functional groups such as primary amines or alkynes, which react with radicals during the polymerization, may interfere with NMRP process and require chemical protection prior to polymerization (Scheme 17) [21]. 2.3.2. Postmodication A wide variety of functional groups including polynuclear aromatic groups such as pyrene can also be introduced by taking advantage of monoadditioin of maleic anhydrides and maleimide derivatives to N-alkoxyamine
Scheme 10. Synthesis of - -hydroxy telechelics by combination of functional initiator and postmodication strategies.
Scheme 11. Synthesis of thiol end-functionalized polystyrene by ATRP and postmodication reaction.
Scheme 12. Synthesis of -caprolactone functionalized macromonomer by ATRP.
474
Table 5 Summary of telechelic polymers obtained by postmodication reactions. Functionality Reactions Polymers
OH
Br
NH2(CH2)nOH Et3N (n: 2, 4)

SH(CH2)nOH
OH
PSt [56,261], PMA [56,261]
OH
Br
OH
PBA [240]
OH
HO
HOOC
Br
NH2(CH2)5OH 25 oC
i) tBuONa
HO
OH
HOOC COOH
PMMA-b-PBA [67]
COOH
Br
ii)
COOH
PSt [38]
O O O
COOH
HO
Br
i) Et3N, DMF ii) %10 aq HCl
HOOC
Br
POEGMA [68]
O Cl
COOH
HO
Br
Et3N 4-methoxyphenol
HOOC
Br
PBA [65]
O
COOC2 H5
OC2H5 OC2H5 HOOC O O OC 2H 5 OC 2H 5

PSt [38]
HOOC
Br O
KOH
Br
B(OH)2 OHC Br
2 OHC Pd(PPh3)4, Na2CO3 aq./THF
CHO
Br
Br OHC
PSt [265,266]
N3
Br
NaN3 DMF
N3
PSt [70,121,122,130,137,146,189,215,259,267275], PtBA [70,125,189,209,259,267,272,276], PBA [128,260,269], PMMA [259,277], PMA [70,215,259,260,269,278], PNIPAM [132], PSt-b-POEGMA [279], PEO-b-PSt [280,281], PSt-co-PMI [213] PSt [208,282284], PBA [260], PMMA [260], PiBA [133]
N3
Br
Me3SiN3 TBAF
N3
N3
Br
Br
NaN3 DMSO
N3
N3
PSt [68,121,189,274,285], PtBA [126,286], PSMA-b-PPO-b-PSMA [287,288] PSt [208]
N3
Br
Br
Me3SiN3 TBAF
O N-K+
N3
N3
NH2
Br
O
DMF, reflux
O N O
KOH tBuOH, reflux
PSt [203], PtBA [289]
NH2
Br
NH2
Me3SiN3 TBAF
N3 N3
i. Ph3P ii.H2O
Br
NaN3 DMF
NH2
PBA [260], PMMA [260]
NH2
Br
NaN3 DMF
N3
LiAlH4 Et2O
NH2
PSt [283]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 5 (Continued) Functionality Reactions Polymers
475
Br
NaN3 DMF
1/2 H2SO4,
N3
NH4HCO2, Pd/C DMF
NH2
PSt [290]
Br
NH2
B(OH)2 H 2N Br H 2N
PSt [265,291293]
Br Br
2 H2 N Pd(PPh3)4, NaHCO3 aq./THF
NH2
Br
Br
i) N-Boc-1, TEA/THF, r.t. 4-diaminobutane
H2 N
NH2
PAEL [294]
ii) TFA (20%, v/v)/ CHCl3, r.t
S
SH
Br
Br
H 2N NH2 NaOH
DMF
Bu3P / H2O Oxidation
SH
2
PSt [38,264,295]
SH
S S
Br
SH
PMMA [227], PbzMA [227], PtBMA [227]
cyclopentadiene
Br
NiCp2/NaI/PBu3 THF, r.t.

PSt [296], PMMA [296], PMA [296], PiBA [296]
cyclopentadiene
Br
NaCp THF, r.t.

PSt [297,298]
O OH
acrylate or methacrylate
Br
R
DBU, EtOAc
O O
+ DBUH
PBA [299,300]
SnBu3
allyl
Br
PMA [301,302]
Benzene
BBr2
Si
Br
BBr3
Br
PSt [237]
phosphonium
R
O O
Br
Ph3P
Ph3P Br
O
R : -H, -CH3, -(C6H5), -C4H9,

Nucleophile
PMA [303], PSt [303]
Nu HO
PSt [304]
OH and OH, NH2 , piperidine
Nu: piperidine,butyl alcohol, NaOH, N,N-dimethyl-1,3-propanediamine
O
benzodioxinone
HO Br
O Ph O Ph
O O O Ph O Ph
PSt [305]
K2CO3, 60 oC acetone,
O
dithiocarbamate
Br
Br
N S- Na+ S
DMF,48h, r.t.
O N S S S N S
PSt [306]
476 Table 6 Macromonomers prepared by ATRP. Functionality
Initiator
Polymers
oxazoline
O N
O
O O
O Cl N O H
O
Br
PSt [86]
thiophene
Cl Cl
PMMA [307,308]
pyrrole
Br
PSt [308,309], PMMA [309], PtBA [309], PDMAEMA [309], POEGMA [309], PBA [309], PMEEMA [309]
caprolactone
O O
O
PMMA [310]
Br
O
caprolactone
O
O
Br
PSt [304]
butyrolactone
Br
O
PSt [60], PMMA [60]
vinyl acetate
Br
PSt [60,311], PMMA [60,311]
O
vinyl acetate
O N O Br Br
PNaVBz [312], POEGMA [92,93]
O
epoxy
O O
Br
O
PSt [60,91], PMMA [60,91]
epoxy
Br
PSt [313]
vinyloxy
O Cl N H Cl Cl
O O
PMMA [314], PDAEMA [314]
vinyloxy
Br
PSt [314,315], PMMA [314,315], PDAEMA [314,315]
oxazoline
O N
Br
PSt [316]
oxazoline
O N
O N
O
Br
Br
PSt [316]
oxazoline
O O
PSt [316]
allyl
O
Br
Br
PSt [273,315], PMMA [273,315], PDMAEMA [317]
allyl
PSt [284,318], PMMA [318]
O
allyl
9O
Br
PSt [273], PMMA [273]
477
O
norbornene
O
O
O
Br
Br
PSt [319], PMMA [319], PtBA [319], PtBMA [319], PMA [319]
norbornene
N H
PMMA [320]
O
acetylene
Br
PSt [321323], PMMA [321323]
Br
halide
Br
Br
PSt [265,266,292,293,324327]
Br
halide
Br
PSt [265,292,293,327331]
Br
Br
O B O Br O B O
halide
PSt [332]
Br
halide
O B O Br
O B O
PSt [333,334]
end group followed by elimination of mediating nitroxide radical (Scheme 18) [401]. The thermal stability of the telechelics was increased as the alkoxyamine group was removed.
Another postmodication methodology of chain end functionalization relies on the stability of N-alkoxyamine radicals. In this methodology, the precursor polymer prepared with any N-alkoxyamine initiator can be exchanged
Scheme 13. Synthesis of -methacrylate end-functionalized polymers by ATRP and CCT processes.
Scheme 14. Synthesis of -, -methacrylate end-functionalized polymers by ATRP and CCT processes.
Scheme 15. General scheme for NMRP process.
478
Table 7 Some functional unimolecular and bimolecular nitroxides for NMRP. Functionality Nitroxide structure Polymers
OH
HO
N O
PSt [338342], PBA [342]
HO
OH
N O HO
HO OH
PSt [343], PBA [343]
OH
HO
N O Ph
O O O O N O
PSt [344,345], PBA [344], PIP [344], PDMA [344]
OH
HO
PSt [346]
OH
HO
N O
PSt [347], PBA [348]
OH
HO
N O
PSt [347,349], PBA [348]
OH
HO
N O
PSt [349]
HO
OH
O N
HO
PSt [350,351], PSt-co-PMMA [352,353], PSt-co-PBA [352,353]
OH
O N
OH
PSt [338,352]
HO
OH
O N
NH O O N
PSt [354]
HO
OH
P(O)(OEt)2
PSt [355], PBA [356]
O N
OH
HO
PSt [357], PtBA [357]
HO
OH
N O
PSt [342,345,358], PBA [342,358]
HO
OH
(EtO)2(O)P
N O
PSt [345]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 7 (Continued) Functionality Nitroxide structure Polymers
479
HO
OH
O N
PSt [359], PNIPAM [359], PDMA [359]
HO
OH
N O
PSt [360]
O
OH
HO
N H
N
2
+ O N
PSt-co-PVK [361]
HOOC
COOH
O N
PSt [362,363]
HOOC
COOH
N O
PSt [364]
COOH
O N HOOC
HOOC O O
COOH
PSSS [365]
COOH
N O
PSt [360], PtBA [360]
COOH
HOOC O N
P(O)(OEt)2
PSt [366369], PMMA [370], PtBA [367,371], PFSt [368], PHPA [372], PDMA [372], PNAM [372], PtBMA [373], PtBA [374], POEGA [375], PSt-co-PtBMA [376], PGMA-co-PMMA-co-PSt [376378], PMMA-co-PAN [379], PMMA-co-PAN-b-PBA [379], PMMA-co-PAN-b-PSt [379], PSt-co-PtBA [380], PSt-co-PAA [381], PtBMA-b-PSt [373], PtBMA-b-PtBSt [373], PSt-alt-PMAn, PtBMA-b-PNIPAM [373], PSt-alt-PMAn-b-PSt, PtBA-b-PSt [374], PSt-b-PAA [374], PMMA-co-PSt [369], PEMA-co-PSt [369], PBMA-co-PSt, PSt-co-PAA [382], PSt-co-PNaA [382]
O
COOH
HO
N CN
+ O N
2
PSt-co-PAN [383]
HO
COOH and OH
O N
COOH
PSt [365]
O
protected COOH and OH
O O O
O N
PSt [354]
Si O
protected OH
N O Si O
PSt [343,384], PBA [343]
Si O
protected OH
N O
PSt [342,358], PBA [342,358]
Nitroxide structure
Polymers
BocHN
protected NH2
O N
PSt [357], PtBA [357]
O
protected NH2
O N
PSt [357], PtBA [357]
Boc
NH
Boc
protected NH2
N O O N
PSt [385]
protected NH2
O BocHN
O N
PSt [359]
protected NH2
Ph OH Ph BocHN
O
BocHN
O N
PSt [359]
protected NH2
O N
PSt [351]
Cl
halide
O N
PSt [357,359,386388], PtBA [357], PNIPAM [389], PBA [389]
Cl
halide
O N
PSt [390]
Br
halide
O N
PSt [362,363]
N3
N3
O N
PSt [357], PtBA [357], PBA [389], PNIPAM [389]
protected alkyne
Si
O N
PSt [357]
quaternized ammonium
N O
PSSS [391]
quaternized ammonium
N O N
PSSS [391]
sulfonate
Na -O3S
N O
PSSS [391]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 7 (Continued) Functionality Nitroxide structure Polymers
481
triuoromethyl
F3C
N O
PSt [342], PBA [342]
O N O
PSt [337], PtBA [337]
pyrene
4O
pyrene
O N
PSt [337], PtBA [337]
pyrene
O N
PSt-co-PMMA [352,353], PSt-co-PBA [352,353]
pyrene
O O N CN
2
+ O N
PSt [392]
uorene
O N
PSt [393]
O
naphthalene
O
O S N O H N(CH3)2
N O
PSt [346]
dansyl
PSt [337], PtBA [337]
perylene diimide
O N
perylene diimide
PSt [394,395], PBA [394,395], PIP [394,395], PB [394,395]
terpyridine
O N
terpyridine O
PSt [396,397]
R1O
terpyridine and ureido pyrimidinone
O N
R1:terpyridine, R2:ureidopyrimidinone
HN O O
R2
6
PSt [398]
O N
barbituric acid
R
R:1,2-dihydroxyalkyl orbarbituricacid
PBA [389], PNIPAM [389]
uracil
O HN O N H
O N
PSt [399], PBA [399]
Nitroxide structure
Polymers
O
uracil
HN O N H
O
O N
P(O)(OEt)2
PSt [399], PBA [399]
succinimide
N O O
O N N
2
O N
P(O)(OEt)2
PSt [376], PBA [376]
oxazoline
+ O N
PSt [400]
by addition of a large excess of functional nitroxides under heating. At this temperature the equilibrium between nonfunctional nitroxide and the polymer chain is established and the exchange of nonfunctional nitroxide with the functional nitroxide can lead to the desired end functionalized polymer. Turro et al. have elegantly taken advantage of this nitroxide mediated free radical procedures to develop a strategy for the facile preparation photoactive telechelic polymers (Scheme 19) [346]. This strategy presents a number of advantages, reactive functional groups can be introduced under mild conditions and from the same precursor polymer a variety of functional group can be incorporated [402]. Schubert et al. used the terpyridine-nitroxide initiator to synthesize semitelechelic terpyridine polystyrene. With the chain end functionalization methodology of the maleimide unit, they were able to synthesize telechelic terpyridine polystyrene. They utilized a terpyridinefunctionalized maleimide that replaced the nitroxide chain end of semitelechelic polystyrene (Scheme 20). The telechelic polymers would be signicant value to prepare ABA metallo-supramolecular triblock copolymers [396,397]. Hemery and co-workers described synthesis of heterotelechelic polystyrene containing -hydroxy- -carboxylic acid end groups and their intramolecular cyclization (Scheme 21) [403]. The nitroxide mediated radical polymerization of styrene was carried out using 4,4-azobis(4-
cyanovaleric acid) as the initiator with 4-hydroxy-TEMPO as the mediator to prepare heterotelechelic polystyrene [383]. The intramolecular cyclization was performed by esterication reaction. Although the cyclization efciency was greatly reduced in the case of high molecular weight polymers due to the formation of various polycondensate by-products, the yield of cyclization was close to 95% for the low molecular weight polymers. Another method involves the combination of NMRP and reduction processes. In the rst step, the polymerization of styrene in the presence of a hydroxyl-functional alkoxyamine yielded -hydroxy functional polystyrene with an alkoxyamine group in the position [404,405]. By the same strategy, -hydroxy, -carboxylic acid telechelic polymer can also be prepared [366]. In the second postpolymerization step, the reduction of the alkoxyamine group into an alcohol using an acetic acid/zinc mixture, allows in principle the preparation of well-dened , telechelic polystyrene (Scheme 22). In a similar way, Hawker and Hedrick synthesized -amino, -aminoxyl polystyrene using tert-butyloxycarbonyl protected azo initiator. The tertbutyloxycarbonyl protected group was replaced by an amino group with triuoroacetic acid (Scheme 23) [351]. Recently, telechelic nucleobase functional polymers have gathered attention due to the thermally reversible hydrogen bonding associations that play a part in the interesting rheological and mechanical properties they impart
Scheme 16. General strategies for the synthesizing telechelic polymers by NMRP.
483
Scheme 17. Synthesis of amino-functionalized telechelic polymers by protected nitroxide.
Scheme 18. Functionalization of N-alkoxyamine terminated polymers with maleic anhydrides and maleimides.
Scheme 19. Preparation photoactive telechelic polymers by nitroxide exchange process.
Scheme 20. Synthesis of -, -terpyridine telechelic polystyrene by NMRP.
Scheme 21. Synthesis of -hydroxy- -carboxylic acid functional PSt and intramolecular cyclization.
Scheme 22. Synthesis of telechelic polymers via NMRP followed by a reduction of the alkoxyamine.
484
Scheme 23. Synthesis of -amino telechelic polymers by NMRP using protected initiator.
Scheme 24. Hydrogen bonding network of uracil functionalized PSt prepared by NMRP.
when combined with polymers. Long and co-workers developed uracil functional alkoxyamines to afford multiple hydrogen bonding at the polymer chain ends of the polymer chains (Scheme 24) [399]. Such functionalization leads to increase in Tg and melt viscosity of polymers. 2.4. Reversible addition-fragmentation chain transfer polymerization (RAFT) Reversible addition-fragmentation chain transfer (RAFT) polymerization is one of the most recent entrants and one of the most efcient methods in C/LRP techniques [20,406409]. A major advantage of the RAFT process over other controlled radical polymerization techniques is its tolerance of protic and other functionalities that can be incorporated into the chain transfer agent [407,410412]. In this technique, after the initiation, the RAFT agents reversibly deactivate the polymer chains as the rate constant of chain transfer is faster than the rate constant of propagation (Scheme 25). 2.4.1. Functional chain transfer agent In the RAFT polymerization, the functional group present on the chain transfer agent (CTA) is retained at the end of the polymerization. This enables the incorporation a wide range of functional end-groups such as OH, COOH, NR2 , CONR2 , SCO3 Na, etc. -Functional groups can be introduced via the R group while the Z group of the
CTA contribute to the incorporation of -functional groups (Scheme 26). A number of RAFT agents that could be used for the synthesis of novel - and/or -telechelic polymers are available (see Table 8). For example, Scheme 27 shows how Lai et al. [413] and Lui et al. [414] used appropriate trithiocarbonate transfer agents and conventional free radical initiator (2,2 azobis (isobutyronitrile)) to prepare polymers capped with functional groups (carboxylic, hydroxyl, etc.). 1,3-Dipolar cycloaddition reaction between an azide and an alkyne has received a great deal of attention due to its high specicity and nearly quantitative yields in the presence of many functional groups [415]. Therefore, the use of simple RAFT process to directly generate polymers that bear either azide or alkyne units has gained considerable importance (Scheme 28) [416]. Various functional RAFT agents that have been successfully utilized in this context are listed in Table 8. Recently, a unique functionalization strategy that relies on hetero-Diels-Alder reactions of dienes with terminal thiocarbonylthio groups on RAFT polymers was introduced by Barner-Kowollik and co-workers [297,298,417420]. RAFT agents with electronwithdrawing Z groups such as, diethoxyphosphoryl, benzyl pyridinyl and sulfonyl dithioformates result in polymers capable of highly efcient hetero-Diels-Alder cycloaddition reactions [421427]. At the present time, primary and secondary amine endfunctionalized polymers are not directly accessible through
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 8 Functional RAFT agents for the synthesis of telechelic polymers. Functionality RAFT agent Polymers
485
S
OH
HO
O O
S
S O
S
OH
PNIPAM [429], PMA [414], PSt [414]
HO
OH
N S O O
N S O O
OH
PMMA-co-PEA-co-PAA [430], PEA-co-PSt [430], PBA-co-PAA-co-PSt [430]
S
OH
HO
NC S
C
S
PMMA [20,431,432], PSt [419]
OH
HO
H N O
PMMA [432]
S
OH
HO
S
S CN C S O
PSt [433,434]
OH
HO HO
H N
PSt [435]
OH
HO
O O
S
S CN C S S
PHPMAM [436]
COOH
HOOC S
COOH S
PSt [413,437,438], PEA [413], PMMA [413], PHEA [413], PtBAm [413], PBA [413,431,439,440],PMA [440,441], PAA [413,442], P2VP [443], PNIPAAM [442,444447], PGAMA [448], PLAMA [448], PSt-co-PAzPMA [449], POEGMA-co-PDDMAA [450], POEGMA-co-PDDMA [450] PtBA [451], PDEHEA [451], PMA [452], PBA [452], PDA [452]
S
COOH
HOOC S
C S
S COOH
COOH
HOOC S
C12H25
PSt [413,453455], PMMA [433,456], PEA [413], PHEA [413], PtBAm [413,457], PAA [413,454],PHFDA [458], PBA [413,431,439], PNIPAAM [457,459465], PCMS [466], PHMS [466], PMA [467,468], PBMA [455], PDMA [457,462,469], PPAM [457,465], PDEAM [457,462], PEMAM [457,462], PIP [470], PNVP [471], PAN [472], PPVK [473], PMVK [473], PGAMA [448], PLAMA [448], PPAM [462,465], PDMAEMA [454], PChA [474], PChMA [475], PNIPAM [462,465], PChA-b-PSt [474], PtBA [476], PtBA-b-PIP [476], PtBA-b-PSt [476], PMAIpGlc-co-PAzPMA [449] PAAL [477,478], PDMA [477,479]
S
COOH
HOOC S
C S
COOH
HOOC S
S S
CH3
PSt [480], PBA [481]
NC
HOOC S
S
COOH
C4H9
PMMA [280]
HOOC S
C 4H9
PAA [453,482484], PBA [453], PAA-b-PBA [482484], PAA-b-PSt [482484]
486 Table 8 (Continued) Functionality RAFT agent
Polymers
S
COOH
HOOC S
C 12H 25
PAA [485], PBA [486], PSt [453]
S
COOH
HOOC S
NC HOOC NC HOOC
S
S
C12H25
PMMA [280]
COOH
C S
C 12H 25
PMMA [280,409], PNVPh [487], PMAA-co-PChMA [488]
COOH
PNIPAM [489], PDMAEMA [489,490], PDMAEMA-b-PPAA-co-PBMA [489,490]
S
COOH
NC HOOC S
PVAGP [491]
S
COOH
HOOC
PSt [433,492495], PBA [439,496], PAEPC [497], PAA [444,498], PNIPAM [212,444,493], PAGA [499], PVTEMP [500], POEGA [493,501], HPMA [501], PDMA [495], PStNa [502], PDADMAC [503], PSt-b-PDMA [495], PVTEMP-b-PNIPAM [500], PHEMA-co-PSt [504], POEGA-b-PSt-co-PMAm [501],PHPMAM-b-PSt-co-PMAm [501]
S
COOH
HOOC
C
S
COOH
PSt [438], PBA [439]
COOH
HOOC
PSt [438], PBA [439], PAm [505,506]
COOH
S
COOH
HOOC
PSt [438], PBA [439]
S COOH
S
COOH
HOOC
S
S
COOH
S
PSt [438,445]
COOH
HOOC S
PVAc [507]
4O
S COOH
HOOC
COOH
S O
S
S O
CH3
PVAc [508]
COOH
HOOC S
C
S
PVAc [507,509], PNVP [509]
COOH
HOOC S
PNAM [510]
S
COOH
HOOC S
C
S
PNAM [510], PAA [453]
COOH
S HOOC
PMMA [511,512], PSt [513,514], PMAA [515], PMAA-b-PSt [515]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 8 (Continued) Functionality RAFT agent Polymers
487
S
COOH
HOOC S
PSt [514,516], PMMA [516,517], PBA [515], PMAA [518], PNIPAM [518], PAm [517,519] PDEAM [517], PDMAM [517]
S
COOH
HOOC
S
S
PAA [520]
COOH
HOOC
S
S
PSt [514]
COOH
NC HOOC S
PSt [521523], PDMAEMA [20,524], PDPAEMA [525], PMAMGlc [526530], PGalEMA [530], POEGMA [531534], PDMA [477,531,535], PFMA [536], PPFA [537], PAM [538], PDMAPMA [539], PHPMAM [493,540,541], PMAM [542], PAMPS [543,544], PAMBA [543,544], PMMA [493,545547], PNIPAM [493,548,549], PMA [548], PMAA [550,551], PEILPMA [550], PMILEMA [550], PEILEMA [550], PBMA [552], PAMA [553555],PAMPA [555,556], PAAL [477], PDEGMA [545,546], PGAPMA [557], PGAEMA [557], PGAPMA [557], PMAG [558], PMAU [558], PNAS [559], PBPVBZ [560], PPFPVBZ [560], PBTVBZ [560], PStNa [502], PVPGVG [561,562], PPDSM [563], PHPMAM [564], POEGMA-co-PDDMAA [450], PHPMAM-b-PLMA [565], PBMA-b-PMPC [552,566], POEGMA-co-PDDMA [450], PPDSM-b-PHPMAM [567]
S
COOH
HOOC
S O
O O P O
PSt [568], PNIPAM [568], POEGA [568]
S
COOH
HOOC HOOC
S S S C
O S O
PEG
PINAM [569], POEGA [569]
COOH
PAA [453]
HOOC
O
PBA-co-PAA [570]
S
COOH
HOOC
PDADMAC [503]
S
COOH
HOOC
PNVCL [571]
S O
CHO
O OHC
O
3
S O
C12H25
PSt [572], PMMA [572], PIP [572]
S
NH2
H2N
O
6
S O
S
C12H25
PSt [572]
N3
N3
O O
C12 H25
PSt [416], PDMA [416], PNIPAM [573], PBA [574], PNIPAM [574], POEGA [574]
S
N3
N3
O O
NC S
PSt [416,575,576], PNIPAM [577], PDMA [416,577]
Polymers
S
N3
N3
O
3
S O
O S O
N S
PNIPAM [578,579], PSt [578], POEGA [578], PMMA [578], PHPMAM [578], PDMA [579]
S
N3
N3
O
3
S O
O S
PSt [575], PVAc [575,580]
N3
N3
O O
S S
PNIPAM [581]
N3
N3
O O
NC S
PSt [582]
S
N3
S N3
PVAc [583]
S
N3
N3
O O
PDMA [584], PNIPAM [584]
S
N3
N3
[585] PVAc
S
N3
N3
O O
S
S
PNIPAM [586]
TMS
alkyne
O O S
NC S
PSt [575], PMAMMns [587]
alkyne
O O
C12H25
PAM [123], PMMA [124], PSt [124]
S
alkyne
O O
PTHPA [357], PTHPA-b-PSt [357]
S
alkyne
O O
PSt [588], PSt-b-PMAH [588]
alkyne
O O
O O
S CN C S
S S S
POEGA [589], POEGA-b-PAPTS-co-PPBA [589]
alkyne
PSt [590]
489
S
alkyne
O O
S O
PVNP [591,592]
S F
pentauoro phenyl
F F F
F F
O FO
S C F F
NC S
C
POEGMA [593596], PLMA [593,596], PMMA [593,597], PDEGMA [593,598,599], PNIPMA [593]
pentauoro phenyl
S CN
PMMA [600]
F F
pentauoro phenyl
F S C S O
PSt [601], PODA [602], PtBA-co-PVAc [603], PODA-co-PAN [602], PODA-b-PNVP [602]
pyridyl
N S
PSt [298], PiBA [298,419]
S
pyridyl
N S
O O S
PBA [604,605], POEGA [604,605]
S
pyridyl
N S
N S
O O S
C
S
PEG
PNIPAM [569,606], PHEA [606], POEGA [569]
pyridyl
O O
POEGA [607]
S N
pyridyl
S
S
O O
C
2
POEGA [608,609], POEGA-b-PSt-b-POEGA [609]
pyridyl
C N
PSt [417,421,422]
phosphonyl
O O P S O S
S S NC S O C
PSt [298,417,418,421], PiBA [297]
thiazolidine-2-thione
S N
PHPMAM [564,610]
S
thiazolidine-2-thione
S O
4
S N
O
2
NC S O
PHPMAM [436]
S
tetrathiafulvalene
S S O O S
S C S
PSt [611], PBA [611], PNIPAM [611]
Polymers
S X
tertiary amine
N O
S S
X:-phenyl X: -CH3, -H
PSt [612], PMA [612], PDMA [612], PDMA [613,614]
tertiary amine
PMA [584], PSt [584]
S
protected amine
Boc
O N H O O
H N
2
S O
PNIPAM [615]
O
succinimide
N O O
O
S CN C S O
S C S
PNSVB [616]
phthalimido
N S O O
PSt [428], PBA [617], PNIPAM [617], PAA-co-PChPA [618], PAA-co-PPgA [618]
S C S
2
phthalimido
N S O
O
PSt [409,428], PBA [617], PNIPAM [617]
S C
O S N O
PSt [428], PBA [617], PNIPAM [617]
phthalimido
N S O O
S C O
PNVP [617,619], PVAc [617]
phthalimido
N S O
O
phthalimido
S C S C12 H25
PSt [433], PtBA [433]
N S O O O N O
S O O
S
maleimide
POEGA [620,621]
naphthalene
PSt [622,623]
S
anthracene
C
PSt [624], PMA [624]
S
anthracene
O O
NC S
PAcN [625]
491
S
anthracene
PSt [622]
S
pyrene
C
PSt [626]
CN S
coumarin
O O
C
PAcN [627]
S
benzodioxole
O O
O O
S S C
PSt [628]
terpyridine
N N N
PSt [629], PNIPAM [629]
S S
terpyridine
N N N
2
PSt [630], PBA [630]
S
allyl
PSt [631], PtBA [631], PtBA-b-PSt [631], PSt-b-PtBA [631]
S
S
allyl
O O
NC
S
PSt [632], PMMA [632], PMA [632]
S
norbornene
O O
NC S
PSt [632], PMMA [632], PMA [632]
S
cinnamate
O O O S O
NC S
PSt [632], PMMA [632], PMA [632]
epoxy
O O O
C12H25
PSt [633], PBA [633], PLA [633], PEHA [633], PBMA [633]
S O O S C S C12H25
PSt [633], PBA [633], PLA [633], PEHA [633], PBMA [633]
oxetane
Polymers
S
pincer ligand
S O O C S S C12H25
PMA [634], PMA-b-PtBA [634]
S
disulde
PEG
O S S O
O O
C 12H25
PSt [635]
S
boronic acid
(HO)2 B
O O
S
S
C12H25
PSt [636], PDMA [636], PNIPAM [636]
trimethoxysilyl
(H3 CO)3Si
S O
PSt [637], PMMA [637], PMA [637], PBA [637], PtBA [637], PDMA [637], PNIPAM [637], PNAM [637]
thymine
H O N O N O
9
S S O C O
PVAc [638]
cysteine
X: -H, -COOCH3 O O O N OH O O S S HO N NH2 H S X
PMA [639], PBA [639], NIPAM [639], PSt [639], PDMA [639], PMMA [639]
glutathione
HO O O N S S H S X
X: -H, -COOCH3
PMA [639], PBA [639], NIPAM [639], PSt [639], PDMA [639], PMMA [639]
carbohydrate
S O O H C N S O O O O
O S
2
PNAM [640,641]
O N H O
2
carbohydrate
N H
C S
PNAM [640,641], PNAM-co-PGalAm [642]
HN NH O
S
carbohydrate
H N O
O O S C S
X
PNIPAM [643,644], PHPMAM [643]
HN NH O
S
2
X: -C2H5, -C12H25
O R1 R2 O
carbohydrate
O S C
S
PNIPAM [645]
S HN NH O R1= NH or O, R2= O or SS
S
carbohydrate
PNVP [646]
oligosaccharide N
S
peptide
peptide S
C12H25
PNIPAM [647]
493
O
peptide
peptide N H
H peptide N
C S
PBA [648,649]
O O S C CN S
PBA [648]
peptide
S O
protein
BSA
POEGA [605]
S O
protein
S BSA
N O
O
2
C12H25
PNIPAM [650]
Scheme 25. The mechanism of RAFT polymerization.
Scheme 26. Functionalization of polymers by RAFT process: (i) functional RAFT agent and (ii) postpolymerization.
Scheme 27. Synthesis of telechelic polymers by using functional RAFT agents.
494
Scheme 28. Synthesis of azido-functionalized telechelic polymers by using functional RAFT agents.
Scheme 29. Synthesis of amino functionalized telechelic polymers by using protected RAFT agents.
RAFT polymerization due to the rapid reaction of trithiocarbonate group with the unprotected primary and secondary amine groups to form a thiol and a dithiocarbamate derivative [409]. It is, therefore, necessary to protect amine end groups during RAFT polymerization. Typical protection of the amine groups involves the use of phthalimido [428] or tert-butyloxycarbonate (t-Boc) [100] groups. This approach requires the removal of the thiocarbonylthio groups before the deprotection step (Scheme 29). Afterward, the phthalimido and t-Boc groups can be efciently converted to amine groups by deprotection in the presence of hydrazine and of triuoroacetic acid, respectively. 2.4.2. Postmodication One of the typical features of the RAFT polymerization is the incorporation of the dithiocarbonyl moiety from the CTA at the end of all the polymer chains. Such an end group facilitates to introduce the desired functionality in the polymer chain end by post-polymerization. Common postmodication reactions used for end group transformation of the dithiocarbonate group including hydrolysis [651656], aminolysis [20,409,431,459,480,651,657669], metal assisted [20,212,409,619,670672] and radical-induced reductions [409,593], are summarized in Scheme 30. Hydrolysis, under certain temperature and pH conditions, is a powerful method to convert the dithiocarbonate groups into thiols. Treatment of dithiocarbonyl group of polymers with a strong base such as sodium hydroxide yielded thiol functional telechelic polymers [652,655,673]. However, this method has some side reactions, such as formation of disulde bridges, elimination to form vinyl end groups and cyclizations [673]. On the other hand, the acidic hydrolysis of polymers containing a dithiocarbonate group can be catalyzed at 90 C using 35% hydrochloric acid. The nal hydrolyzed polymer contained thiol end groups corresponding to a quantitative reduction of the dithiocarbonyl groups [656]. An alternative approach for modication of the dithiocarbonate groups into thiols is aminolysis. Both primary and secondary amines, acting as nucleophiles, can transform the dithiocarbonyl function into a thiol, and this
method has been applied to synthesis of thiol telechelics (Scheme 31) [20,409,481,493,537,548,590,657,674,675]. Additionally, the reduction of dithiocarbonate group of RAFT synthesized polymers can be achieved by using suitable transition metal complex such as sodium borohydride or lithium aluminum hydride [671,672]. In a recent communication, Perrier et al. reported a simple technique to cleave the dithiocarbonyl end functionality of polymer by mixing the polymeric chains with an excess of thermal radical generators such as (4,4 -azobis(cyanovaleric acid) [676] and bis(2-(2,4-dinitrophenylthio)-ethyl) 4,4 -(diazene-1,2diyl)bis(4-cyanopentanoate) [677]). During the process of addition-fragmentation, the formation of the polymeric chain radical can be recombined irreversibly with one of the free radicals present in excess in solution, thus forming a dead polymeric chain. This method not only provides the elimination of the dithiocarbonate end group, but also pioneers a new functionality at the end of the polymer chain as shown in Scheme 32 [51]. This strategy was further expanded. Maynard et al. installed the maleimido functionality by a radical cross-coupling reaction between the trithiocarbonate chain-end and a protected-maleimide azo-initiator [644,645,678]. Amine end-functionalized polymers cannot be synthesized directly using RAFT due to the reactivity of the trithiocarbonyl compounds with primary and secondary amines. In such cases, polymers are indirectly prepared by using RAFT agents with protected amine functionality, such as phthalimido groups in RAFT agents. Upon removal of the trithiocarbonayl end groups, the phthalimido protecting group can be efciently removed through hydrazinolysis to reveal primary amine telechelic polymers (Scheme 33) [428,617]. Recently, Dichtel and co-workers [521] and Winnik and co-workers [581] investigated the one-pot transformations that achieve the removal of the dithioester moiety and the introduction of a functional group to a polymer chain end simultaneously (Scheme 34). In this process, the thiol group formed after the reduction of dithioester moiety either by hydrolysis or aminolysis is trapped through a Michael addition reaction with an acceptor such as an acrylate. This
495
Scheme 30. End group transformation reactions of dithiocarbonate terminated RAFT polymers.
Scheme 31. Synthetic pathway for the transformation of the polymer end groups via aminolysis.
Scheme 32. End group transformation of dithiocarbonate terminated RAFT polymer by radical-induced reaction.
method affords telechelic polymers with a variety of functionalities in high conversions. In a recent paper, Theato and Maynard groups [596,679,680] showed that combination of aminolysis and functional methane thiosulfonate addition can be used to attach not only methyl disuldes but also functional
groups onto various polymers. The polymers originating from different common chain transfer agents include polymethacrylates, poly(ethylene glycol) methyl ether acrylate, poly(N-isopropyl acrylamide) and polystyrene were successfully used (Scheme 35). The thiol released at the polymer end group prefers to react with the methyl-MTS.
Scheme 33. Indirect synthesis of amino telechelic polystyrene by RAFT polymerization.
Scheme 34. One-pot transformation of the polymer end groups via hydrolysis or aminolysis/Michael additions reactions.
496
Scheme 35. End group transformation of dithiocarbonate terminated RAFT polymers by combination of aminolysis and functional methane thiosulfonate addition.
Scheme 36. End group transformation of dithiocarbonate terminated RAFT polymers into a hydroperoxyl or hydroxyl end-groups.
Barner-Kowollik and co-workers demonstrated that one-pot transformation reactions of trithiocarbonate functional (meth)acrylate polymers into hydroxyl functional polymers proceeds with a very high efciency [681683]. In the reported procedure, dilute solution of the RAFT polymer and a radical initiator in THF is stirred at elevated temperatures (60 C) in the presence of atmospheric oxygen to yield hydroperoxide functional polymer. Subsequent reduction by triphenylphosphine leads to hydroxyl telechelic polymers in a one-pot manner (Scheme 36).
2.5. Other controlled radical polymerization techniques Invention of a new C/LRP methods such as iodine transfer polymerization [22,684,685] (ITP), cobalt mediated radical polymerization (CMRP) [686689] and organotellurium- [690,691], organostibine- [692,693], and organobismuthine-mediated [694], polymerization (OMRP) offers alternative routes to prepare well-dened polymer with predetermined molecular weights, low polydispersities, precisely controlled end-group functionalities, and chain topologies. Compared to the success of the three well-known C/LRP methods (ATRP, NMRP and RAFT), the new types of C/LRP techniques are less successful in telechelic synthesis. They are still under construction to optimize polymerization conditions with various monomers [16].
2.5.1. Iodine transfer polymerization (ITP) One of the new methods for preparing polymers with controlled molecular weights is the iodine transfer polymerization. Like RAFT, ITP is a degenerative transfer polymerization using alkyl iodides as the degenerative transfer agent. In the process, the iodine atom is exchanged between a polymeric radical and a dormant chain without formation of an intermediate radical. Polymerizations of styrene and certain uoro-monomers in the presence of alkyl iodides are the rst reported examples [684,695]. More recently, several post-functionalization studies have shown that ITP can also be used in the preparation of well-dened telechelic polymers. These are (i) direct functionalization, (ii) functionalization by substitution after ethylenation and (iii) radical coupling (Scheme 37) [696]. Telechelic uoropolymers having diol, diacid, diisocyanate, diamine, diene functionalities are very promising starting materials for the production of commercial polymers via condensation polymerizations or polyaddition polymerizations [697]. 2.5.2. Cobalt mediated radical polymerization (CMRP) Although, cobalt mediated radical polymerization is the rst example of C/LRP [686688], the method had not been established well, because it is limited to only acrylates. Recently, Jerome and co-workers reported the CMRP of a non-acrylic monomers, cobalt(II) acetylacetonate (Co(acac)2 ) complex provides the high efciency in controlled radical polymerization of vinyl acetate [689]. In
Scheme 37. Postfunctionalization of iodine terminal polymers.
497
Scheme 38. Synthesis of telechelic polymers by CMRP process.
this method, (Co(acac)2 ) reacts reversibly with the growing chains, which are accordingly involved in equilibrium between active and dormant species (Scheme 38). Functional organocobaloxime photoinitiators [698] have been reported for the synthesis of telechelic polyacrylates containing various functional groups, such as phenyl, bromide, hydroxyl, carboxyl and nitrile groups [699,700]. The fundamental characteristic of the CMRP process is all the polymer chains having terminal cobalt complex used as controlling agent. The modication of alkylcobalt complexes is well known, and a few methodologies have been applied to remove and modify this group into an alternative functional group. For example, photolysis of cobalt dimethylglyoximes pyridine end-functional poly(ethyl acrylate) (PEA-Co(DMG)2 (Py)) in the presence of bis(p-aminophenyl) disulde and methyl methacrylate yielded corresponding amino-functional PEA and well-dened PEA macromonomers via radical addition mechanism (Scheme 39) [700,701]. Growing PVAc chains can be quenched either by addition of functional non-polymerizable monomers (1,2epoxy-5-hexene and 3-butene-1-ol, fullerene C60 ) or by exchange of the Co(acac)2 moiety with a functional nitroxides (with epoxy, -bromo ketone and -bromo ester moieties) [702704]. This one-pot technique is an efcient strategy to prepare well-dened, cobalt free telechelic poly(vinyl acetate)s (Scheme 40). 2.5.3. Organometallic radical polymerization (OMRP) The most recent examples of CLRP involve the use of organotellurium [690,691], organostibine [692,693], and organobismuthine [694] compounds. The polymerization proceeds via a combination of degenerative chain transfer and thermal dissociation mechanisms [24,705]. The common feature of these methods is their high versatility for the polymerization of different monomers and good tolerance to functional groups. Despite these features it is difcult to obtain -functional polymers due to the fact that synthesis of the chain transfer agents requires specic conditions and heteroatom groups of the chain transfer agents are sensitive to oxygen. Therefore, an alternative route for the synthesis of functional chain transfer agents involving the reaction of azo-initiators with chain-transfer agents was described. As the reactions take place under neutral conditions, a variety of functional groups can be introduced from the corresponding functional azo-initiators (Scheme 41). Using in situ generated functional chaintransfer agents leads to the synthesis of -homotelechelic polymers [706]. Transformations of the organometallic end-groups of the polymers via radical and ionic reactions endow with a variety of telechelic polymers with dened structure with various functional groups. Thus, trapping of the grow-
ing polymeric radical with ethyl 2-(tributylstannyl)methyl acrylate afforded the well-dened macromonomer with quantitative yield [706,707]. Furthermore, the end-group of polymer could be transformed by ionic reactions through transmetalation reactions followed by esterication with pyrene butanol or treatment with aqueous HCl to give -pyrene and carboxylic acid telechelic polymers, respectively [708]. Organstibine-end functionalized polymers were also transformed into a number of different functional groups by radical-coupling, radical-addition, and oxidation reactions. For example, the reaction of functional diazo initiator with tetramethyldistibine terminated polystyrene gave , -diol functionalized telechelic polystyrene as the major product, but disproportionation product -hydroxyl PSt also formed as a side product [706]. 3. Telechelic polymers by anionic polymerization Anionic polymerization is the rst living polymerization method introduced by Szwarc about half a century ago and has been utilized as an elegant tool for the synthesis of tailor made polymers with high compositional unity [709,710]. The characteristics of anionic polymerization make its suitable for the synthesis of welldened polymer chains containing reactive terminus at one (monotelechelic) or both ends (telechelic) through postmodication or initiation with functional initiators [711713]. In this polymerization, the propagating species are organometallic species such as carbanions or oxanions and react through nucleophilic reactions in aprotic media as shown below (Scheme 42). Anionic polymerization requires many rigorous experimental conditions including inert atmosphere, absolute purication of most of the reagents used, precise control of temperature, anhydrous solvent, glass-ware manipulation, etc. Once succeeded, utilization of one of two different strategies of anionic polymerization allows the generation of functional termini. These strategies are (i) initiation with (protected) functional initiators and (ii) termination with a suitable electrophile and result in various model functional polymers that have been signicantly used in many applications [714,715]. Functional polymers synthesized by living anionic polymerization are transformed to different topologies such as linear, hyperbranched, star, core-shell polymers or further functional polymers as desired through additional polymerization techniques or effective reactions such as click reactions. 3.1. Functionalization by using functional initiators The rst strategy for the synthesis of functional (or telechelic) polymers is the utilization of functional initia-
498
Scheme 39. Synthesis of amino telechelic and macromonomer by CMRP and postmodication reactions.
Scheme 40. Synthesis of telechelic polymers by combination of CMRP with radical coupling or addition reactions.
Scheme 41. Postfunctionalization of organotellurium terminated polymers.
tors in the polymerization. Certain functional groups such as hydroxy, amino, carboxyl, aldehyde or thiol cannot tolerate the harsh conditions of anionic polymerization, in which highly reactive anionic species such as lithium and other alkali-metals are required for initiation. Therefore, special precautions should be taken prior to polymerization to prevent loss of functional group at the end of polymerization [716,717]. Protected initiators were rst employed in the initiation of anionic polymerization by Schulz et al. in order to overcome this problem [718]. The usual organolithium reagents were substituted with hydroxyl containing initiators protected with acetals of tetra-hydropyranyl and -ethoxyethyl ethers, and acetal groups were converted to hydroxyl groups after the anionic polymerization of 1,3-butadiene. Alternatively, siloxane compounds have been commonly used as protecting agent for hydroxyl, amino or thiol groups in anionic polymerization. For instance, an , -hydroxy poly(styrene-b-1,3-butadiene) was
synthesized, using a silyl-protected initiator, 3-tertbutyldimethylsiloxy-1-propyllithium, and sequential monomer addition of styrene and 1,3-butadiene. Termination of the polymerization with ethylene oxide yielded hydroxyl functionality at the -end. The deprotection of the siloxane moieties at the other end with tetrabutylammonium uoride gave , -hydroxy telechelic polymer which was then employed in synthesis of poly(ethylene oxide-b-styrene-b-1,3-butadiene-b-ethylene oxide) tetrablock copolymer as amphiphilic terpolymers forming vesicles or wormlike micelles in water (Scheme 43) [719]. Using similar protectiondeprotection method with siloxane derivatives, heterofunctional , -polymers of styrene or methacrylates were also prepared [720]. The syntheses were based on the utilization of a protected primary amino initiator, 2,2,5,5-tetramethyl1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane, and postpolymerization modication of active chain ends by
Scheme 42. General mechanism of living anionic polymerization.
499
Scheme 43. Synthesis of , -hydroxy poly(styrene-b-1,3-butadiene) by living anionic polymerization.
Scheme 44. Synthesis of heterotelechelic polymers by living anionic polymerization.
deactivation with electrophiles, such as ethylene sulde, ethylene oxide, anhydride, propane sulfone, 2bromoisobutyrylbromide, or chlorosilane, as precursors of thiol, hydroxy, carboxylic acid, sulfonic acid, bromo, or silane end groups, respectively (Scheme 44). Many other telechelic polymers including monofunctional or , -linear heterofunctional, star [721], branched, etc. prepared by using protected initiators are collected in Table 9. In addition to vinyl polymerization, ring opening polymerizations of cyclic monomers such as -caprolactone [715,749], lactide [750], ethylene oxide [724,751754], glycidyl methyl ether [755] and propylene oxide [756] have also been used to synthesize telechelic polymers by using functional initiator approach. The work reported by Kataoka and co-workers [754] shows the versatility of the method in preparation of -/ , -telechelic polymers. An acetal-protected hydroxyl compound, 2(tetrahydro-2H-pyran-2-yloxy)ethanol, was employed as an initiator in anionic ring opening polymerization of ethylene oxide to form -tetrahydropyranyloxy- -hydroxyl poly(ethylene oxide). Conversion of -OH group to either the azido or the alkyne group and subsequent deprotection of -tetrahydropyranyloxy groups yielded ultimately HO-PEO-N3 or HO-PEO-alkyne (Scheme 45). Moreover, hydroxyl groups can be readily converted to thiol or amino groups. Utilization of highly reactive catalysts (i.e., potassium naphthalene) in anionic ring opening polymerization of ethylene oxide dictates use of protected functional initiators whereas; polymerizations of cyclic esters requiring organometallic catalysts usually do not need any protection. As listed in Table 10, either protected or unprotected initiators yield -functional polymers employed in several applications including synthesis of block copolymers, preparation of self-assembled polymers, surface modication, immobilization of proteins and cells, etc.
In a recent work, an initiator bearing three different functional groups was used in preparation of ABC 3-miktoarm star terpolymers through synthesis of PCL containing two functional groups at the -end. The synthesis of the trifunctional initiator involved formation of radical adduct of 4-vinylbenzyl chloride and benzoyl radical; coupling of the resultant radical with TEMPO; subsequent hydrolysis of the ester and etherication with one of the hydroxyl groups of ethylene oxide by blocking the other hydroxyl group with 3,4-dihydro-2H-pyran; and nally esterication with a typical ATRP initiator (Scheme 46). Defeux and co-workers proposed an elegant way, namely activated-monomer anionic polymerization to produce polymers of epichlorohydrin, ethoxyethyl glycidyl ether, propylene oxide and ethylene oxide with various functionalities such as azide and halide (Scheme 47) [756,766,787,788]. 3.2. Functionalization by termination with suitable electrophile Another method for the synthesis of telechelic polymers (i.e., -functional macromolecules) by anionic polymerization is via termination of the living chain-end with a suitable electrophile containing functional groups including hydoxyl, amino, halide, mercapto, sulfonate, etc. Moreover, these functional groups can be converted to various other groups by postmodications. Therefore, -functional polymers can be prepared by two different approaches of termination of anionic polymerization; direct functionalization by an electrophile and derivatization of primary functional group by postmodication processes. 3.2.1. Direct functionalization The reaction of living chain end with an electrophile such as cyclic ethers, alkyl halides, 1,1-diphenylethylene
500
Table 9 Protected initiators for the synthesis of telechelic polymers by anionic polymerization. Functionality Initiator Polymers
OH
O O
Si O
CH2 Li+
CH2 Li+
PBd [718]
OH
PSt-b-PBd [719]
OH
Si
CH2 Li+
PBd [722]
OH
O O
CH 2 Li+
PSt [723,724]
OH
O Si
n-Bu C Li+
PMMA [725]
OH
Si
O
n
CH2 Li+
n: 3, 6
PMMA [726]
C Li+
OH PMMA [726]
Si O
O
CHO
O
O O
O
CH2 Li+
O CH2 Li+
CH2 Li+
PSt [727,728]
COOH
PSt [729]
COOH
PSt [730]
Si
NH2
N Si
CH 2 Li+
PBd [731], PIP [731]
Si
NH2
N Si
C Li+
PSt [720], PMMA [720], PtBMA [720]
Si
NH2
N Si
C Li+ n: 1, 2
PSt [732], PIP [732]
Si
NH2
N Si
K+NH2N Li+ X
H C Li+ s-Bu
PDMS [733,734]
NH2
PSt [735]
allyl
PDEAEMA [736]
X:H,phenyl,allyl
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 9 (Continued) Functionality Tertiary or quaternary amine Initiator Polymers
501
CH2 Li+
PSt [737741], PMeSt [737741], PBd [737741], PIP [737741]
G
Galactose or glucose
C Li+ G
PMMA [742], PtBMA [742], PtBA [742], PEO [742], PFEMA [742], PSt [743]
Naphthalene
C Li+ X X:-methyl,phenyl
Si O CH2 Li+
PMMA [744,745]
OH and Br
Star PSt [746]
O
OH and Br
Si
Li+ C s-Bu
O Si
Star PSt [746,747], dendrimer PMMA [746,747]
ureidopyrimidinone
NH O O N N N H H
OH
PCL [748]
(DPE) derivatives, carbonyl compounds and alkyl halides can simply produce -functional polymers. In addition, when chlorosilanes are utilized as termination agent precursors of star or branched polymers can be directly obtained [789]. 3.2.1.1. Termination with cyclic ethers. Typical example of this type of functionalization involves termination by the addition of ethylene oxide, and subsequent protonation of hydroxylated end group quantitatively yielding -hydroxyl or , -dihydroxy functional PSt depending on the type of initiator used (Scheme 48) [790793]. The probable initiation of polymerization of ethylene oxide is prevented by immediate quenching since the rate of the ethylene oxide polymerization is low enough [794]. In addition to polystyrene, polyisopyrene [795], polybuta-
diene [796,797], and poly(1,3-cyclohexadiene) [798] have been functionalized by this method. On the other hand, substituted ethylene oxide has also been used as a tool to functionalize polymers [799,800]. Quirk et al. showed styrene oxide containing any substituents on the benzene ring can be used to obtain -functional PSt [799]; whereas precursors of diene-functionalized macromonomers can be obtained in high yields by the reaction of polymeric organolithiums with 3,4-epoxy-1-butene in a hydrocarbon [800]. This approach has been also employed in effective synthesis of , -difunctional polymers [718]. Similar to ethylene oxide, oxetane, a 4-membered cyclic ether, can be also utilized as a hydroxylation agent by for terminating poly(styryl)lithium living chain [801].
Scheme 45. Synthesis of heterotelechelic PEOs by living anionic polymerization.
502
Table 10 Functional polymers synthesized by anionic ring opening polymerization. Functionality Initiator Polymers
KO
COOH
S K O
PEO [757]
O
CHO
O K+
PEO [752]
O
CHO or sugar
O K+ O
O K+
9
PEO [724,758], PEO-b-PDLLA [724,758]
SH halide
PEO [759] PCL [760]
Br 3C O K +
O
halide
Br
Cl
OH
OH
PCL [14,761,762]
halide halide, N3 halide, N3
PCL [763] PPO [755,756,764], PGME [755,756,764], PEO [755,756,764]
N(Oct)4Br- / (i-Bu)3Al
HO OH Br Br
OH N3
PCL [765]
azide
PEO [766], PPO [766], PEEGE [766], PECH [766]
N
tertiary amine
O Cs+
PEO [767], PEEGE [767]
tertiary amine
O K+
PEO [768,769]
nitroxide
N O K+ OH
PEO [770]
nitroxide
N O
PCL [72]
nitroxide
N O OH
PCL [771]
nitroxide
HO
NH O
P(O)(OEt)2
PCL [356]
N O
halide and nitroxide
Br
allyl allyl
O O
O K+
O O Cs+
PCL [772]
OH
PEO [773775], PEO-b-PMM [776] PEO [767], PEEGE [767]
O
acrylate
OH
PDLLA [750]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 10 (Continued) Functionality norbornenyl Initiator Polymers
503
CH2 Li+
O K+
PEO [753]
thiophene
S
O K+
O O O O K+ O K
+
PEO [777,778]
styrene
PEO [779784]
vinyl ether vinyl ether
PEO [779,785] PEO [779,785]
N H 2N
uracil
N
PCL [786]
OH
Scheme 46. Synthesis of the trifunctional initiator for ABC 3-miktoarm star terpolymers.
Scheme 47. Synthesis of telechelic polymers by anionic polymerization via activated-monomer mechanism.
Scheme 48. Synthesis of various telechelics by anionic polymerization using substituted cyclic ethers as terminating agents.
504
3.2.1.2. Termination with alkyl/acyl halides. Other type of suitable nucleophiles for the termination of anionic polymerization is alkyl or acyl halides that contain two different functionalities. While the halide functionality is utilized for coupling with living chain, the second functional group is the aimed special group. This approach is based on covalent CC bond formation by the reaction of an alkyl/acyl halide with a living anionic chain giving rise to a functional polymer and an inorganic by-product, in most cases LiBr. In a typical example, shown in Scheme 49, DPE-ended anionic PSt is terminated with 2,5-dimethoxybenzyl bromide, a termination agent with two protected hydroxyl groups, and consequent deprotection yielded corresponding hydroxyl functionalities [802]. Likewise, the synthesis of polymers bearing terminal uorescent groups was reported by Jenkins and co-workers using alkyl/acyl halides including 1-chloronaphthalene, 1-bromonaphthalene, acid chloride of 1-naphthylacetic acid and 1-naphthoyl chloride as termination agent [803]. Moreover, diene [804] or epoxy [805] endfunctionalized PIP and PSt was synthesized by addition of 6-bromo-3-methylene-1-hexene or 2-bromoethyloxirane, respectively, to the living propagating chains. This way anhydride end-functionalized PSt was also synthesized by terminating anionic polymerization of styrene with 6-bromo-3-methylene-1-hexene and consequent DielsAlder reaction of the terminal ene with maleic anhydride [806]. Other end-functionalized polymers by termination with alkyl/acyl halides are summarized in Table 11. Functionalized polymers by anionic polymerization can be utilized in another controlled polymerization such as ATRP [807]. Matyjaszewski showed that anionic polymerization of St was terminated with styrene oxide and bromoisobutyryl bromide yielding an ATRP macrointiator with bromo end group (Scheme 50). By sequential monomer addition block copolymers of macroinitiator such as PSt-b-PIP-Br can be also obtained. 3.2.1.3. Addition of DPE derivatives. This approach is based on the addition reactions of DPE derivatives containing functional group(s) on aromatic ring(s) and following protonation (Scheme 51) [823832]. Quirk and coworkers reported the preparation of 4-hydroxyphenyl [824] and 4-aminophenyl-terminated [825] PSt by termination of living poly(styryl) lithium with 1-[4(tert-butyldimethylsiloxy) phenyl]-1-phenylethylene and 1-[4-[N,N-bis(trimethylsilyl)amino] pheny1]-1phenylethylene, respectively, and subsequent hydrolysis with dilute hydrochloric acid. Similarly, -oxazolyl PSt was synthesized in quantitative yields by using 4,5-dihydro4,4-dimethyl-2-[4-(l-phenylethenyl) phenyl]oxazole as a DPE derivative [826]. Depending on the structure of the DPE derivative, hyperbranched or star polymers have been synthesized by this approach [746,833837]. 3.2.1.4. Termination with carbonyl compounds. Termination of an anionic polymerization with CO2 called carbonation is the most commonly used method to obtain carboxyl end-functionalized polymers [793,808,838843]. However, this method brings some problems related to contamination of resultant polymer with considerable
amounts of the analogous ketone and tertiary alcohol (Scheme 52) [840,841]. Fortunately, this problem can be overcome by manipulating solvent system. For instance, formation of tertiary alcohols was not observed when carbonations of poly(styryl)lithium, poly(isoprenyl)lithium, and poly(styrene-bisopreny1)lithium were performed in benzene. The process led to the formation of carboxylic acids (60% yields) and the corresponding ketone dimers (40% yields) [844]. Whereas, when the carbonation was carried out in THF/benzene (25/75, v/v) mixture, only carboxyl end-functional polymers (100% yields) were obtained [844]. In recent reports, HOOC-PIP-b-PSt-b-PIP-COOH and NaOOC-PIP-b-PSt-b-PIP-COONa triblock copolymers were synthesized by addition of CO2 at the end of the sequential polymerization of styrene and isopyrene initiated by potassium naphthalenide and their phase transition properties were investigated [839,845]. Hall and co-workers reported an alternative method involving the reaction of living polyanions with excess succinic anhydride to prepare carboxyl end-functionalized polymers. In the case of PtBA, the conversion reaches up to 95% (Scheme 53) [846]. In addition to CO2 , formaldehyde [847,848] and aromatic aldehydes [849] can be also used as carbonyl termination agent yielding hydroxyl end groups. These compounds produce hydroxyl and aromatic end functionalized polymers depending on structure of the aldehyde. It should be pointed out aldehydes and ketones lead to complications, particularly if keto-enol tautomerism is possible. 3.2.1.5. Termination with nitrogen compounds. Termination of anionic polymerization with the blocked amino groups give rises to the formation of primary [813,850] or secondary [851,852] amines end groups after acid hydrolysis (Scheme 54). Moreover, termination of anionic polymerization with pivalonitrile and subsequent reduction yields primary amine end-functionalized polymers (Scheme 55) [853]. In addition, secondary amine groups are generated by reaction with N-benzylidenemethyl amine (Scheme 56) [851]. As stated previously alkyl halides are other alternative terminating agents for anionic polymerization producing functional groups at terminus of polymers. This method can be also employed in generation of tertiary amine terminated polymers when termination reactions are made with -chloro- -amino-alkanes (Scheme 57) [854]. 3.2.1.6. Termination by addition to C C bond. Termination of anionic polymerization with ene compounds with functionality yield corresponding end-capped polymers. According to a method reported by Kim and co-workers ditert-butyl ester, dicarboxylic acid or maleic anhydride terminated block copolymers were synthesized by endcapping of PSt-b-PBMA anion with di-tert-butyl maleate (Scheme 58) [855]. Anionic polymerization also allows preparation of C60 fullerene end-capped polymers [856859]. Indeed, this
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 11 Functional polymers obtained by anionic polymerization and following termination with alkyl/acyl halides. Functionality Termination agent Polymers
505
OCH 3 Br
OH PSt [802]
OCH3
OH
PBd [808]
OH
Br
O Si
PSt [809]
OH COOH
Br
O Si
PVP [810] PBd [808]
O C O
Br OCH3 C OCH3 OCH3 OCH3 CH OCH3
SiMe3 N SiMe3
COOH
PSt [811,812]
CHO
Cl
PBd [808]
NH2
Br
PSt [813,814]
Si
NH2
X
n
O
N Si
O O O
O
X: Cl, Br, I n: 1, 2, 3
PSt [732,815,816], PIP [732,815,816]
anhydride
Cl
PSt [817]
anhydride
Br
O O
PSt [806]
halide
X
O
X
n
n: 3, 5 or 10 X: Cl, Br or I
PSt [818], PIP [818]
anthracene
Cl
PMMA [803]
pyrene
Br
PMMA [803]
O
naphthalene
Cl
PMMA [803]
butadiene
Br
PSt [804,811,819]
506 Table 11 (Continued) Functionality epoxy
Termination agent
Polymers PSt [804,811]
O Br
styrene
X
X: Cl, Br, I
PSt [820,821]
diphenyl ethylene
Br
PIP [815]
O O
monosaccharide
OO
PSt [822]
Cl O
interesting termination agent, C60 -fullerene, provides a core for star polymers generated by anionic polymerization [856,860]. For example, termination of sequential anionic polymerization of IP and St with C60 results in 6-armed star polymers with C60 core [C60 (PSt-b-PIP)] [860]. Dienefunctionalized macromonomers is another product of this technique when the poly(styryl)lithium is reacted with hexa-1,3,5-triene [861]. 3.2.1.7. Termination with silyl compounds. Another termination agent for anionic polymerization is chlorosilanes to produce a variety of end-functionalized polymers (Scheme 59) [850,862871]. Very recently, such termination was employed in the synthesis of silica hybrid nanoparticles [872], hydride functional PDMS [873], and poly(ferrocenylsilane)-b-poly d,l-lactide block copolymers [871].
Termination of anionic polymerization with chlorosilanes also provides a convenient way to produce macromonemers. Styrenic macromonomers have been synthesized by end capping of anionic PtBA by aromatic aldehydes and chlorosilanes containing styrene moiety [849]. DeSimone and co-workers reported successful synthesis of amino or hydroxy end-functionalized PSt, PDMS, PSt-b-PIP. These authors used a wide variety of chlorosilanes with certain functionalities as termination agent containing protected functionalities, and free functionalities are obtained quantitatively by simple deprotection process [870]. The polymers with functional groups listed in Table 12 can be synthesized by their method. 3.2.1.8. Termination with sulfur compounds. Living PSt reacts quantitatively with thiirane to form terminal mercapto groups [793,874,875]. The synthesis of functional PIP
Scheme 49. Synthesis of diol end-functionalized polystyrene by anionic polymerization using substituted alkyl/acyl halides as terminating agents.
Scheme 50. Synthesis of ATRP macroinitiator by anionic polymerization.
507
Scheme 51. Synthesis of various telechelics by addition of substituted DPE derivatives into anionic polymerization.
Scheme 52. Termination of anionic polymerization by carbonyl compounds.
Scheme 53. Functionalization of living polyanions by succinic anhydride.
Scheme 54. Functionalization of polyanions by nitrogen compounds.
508
Scheme 55. Synthesis of amino telechelics by combination of anionic polymerization and reduction reaction.
Scheme 56. Functionalization of polyanions by N-benzylidenemethyl amine.
Scheme 57. Synthesis of tert-amine end-functionalizated polymers by termination of anionic polymerization with alkyl halides.
Scheme 58. Functionalization of polyanions by di-tert-butyl maleate.
Scheme 59. End-capping reactions of polyanions with chloro silanes.
containing SH end groups was also performed by termination with thiirane (Scheme 60). Moreover, reaction of living polymers with sulfur trioxide gives sulfonate salts. The reactivity of such salts as well as side reactions is reduced by complexation with a tertiary amine (Scheme 61a) [876]. Termination of living polymers with sultones produces sulfonates [793,877,878] in THF at 78 C with quantitative yield (Scheme 61b) [737].
3.2.2. Derivatization of functional groups by postmodication processes Alternative to direct functionalization by termination of a living anionic polymer with an electrophile, -functional group of polymers can be modied after termination with a suitable reagent. In recent decades, there have been huge numbers of reports on this two-step functionalization process employed in synthesis of various polymers including PEO, PSt, PBd, PIP and so on. The postmodication reac-
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 12 Chlorosilane derivatives used as terminating agents for polymer functionalization. Protecting groups Functional groups CH2 OH
509
CH2 O Si
CH2 S Si
CH2 SH
O Si
OH
SiMe3
C
SiMe3
NH2
CH2 N
O CH2 N
SiMe3 SiMe3
CH2 NH2
O CH2 OH
CH2 CH2
N N
CH2 NH2
O CH2 OH
functional polymers, and is based on coupling of polymeric organolithium with chlorosilane generating silyl hydride functionalized polymers. Subsequent hydrosilylation of allyl derivatives (functionalized alkenes) with the silylhydride-functionalized polymers in the presence of Karstedts catalyst yields -functional polymers [864866,869,883]. 3.2.2.3. Derivatization by esterifaction or amidation. Esterication or amidation reactions are other postmodication methods for the preparation of telechelic polymers obtained by living anionic polymerization and subsequent termination with a proper compound. These versatile reactions have been utilized in syntheses of polymers with various functionalities. Gruber and co-workers synthesized several telechelic polymers using such typical organic reactions [808]. In the rst method they used, the telechelic dicarboxylic acid obtained by termination of anionic living polymerization of 1,3-butadiene with CO2 . Its hydrogenated polybutadiene was reacted with SOCl2 and subsequently with ammonia to give the diamide end-functionalized polymer. In the following step, the diamide polymer was converted to the amino-telechelic polyolen by dehydration with SOCl2 followed by reduction with LiAlH4 (Scheme 66).
tions include substitution, hydrosilylation, esterication, amidation and cycloaddition reactions. 3.2.2.1. Derivatization by substitution. These functionalization methods have been widely used in synthesis of azide end-functionalized polymers for further modications via click reactions. For instance, tosyl or mesyl end-functionalized polymers (such as PEO-OTs, TsO-PEOOTs, TsO-PEO-b-PPO-b-PEO-OTs) can be easily converted to corresponding azide end-functionalized polymers in the presence of sodium azide (Scheme 62) [267,850,879882]. In an alternative method, azido-monotelechelic polymers are obtained by coupling of polymeric organolithium with chloro alkyl functional chlorosilane and subsequent azidation reactions (Scheme 63) [863]. Reduction of the azide group by lithium aluminum hydride yields another monotelechelic polymer, PSt-NH2 . Moreover, methoxy or tert-butyldimethylsilyloxy groups at a polymer end can be transformed to chloro group by treatment with BCl3 or Me3 SiCl-LiBr, respectively (Scheme 64) [809,831]. 3.2.2.2. Derivatization by hydrosilylation. This novel two-step functionalization technique, depicted in Scheme 65, allows preparation of various chain-end
Scheme 60. Synthesis of thiol telechelics by termination of anionic polymerization with thiiranes.
510
Scheme 61. Functionalization of polyanions by sulfur trioxides (a) or sultones (b).
Scheme 62. Synthesis of azide end-functionalized polymers by substitution reaction.
Scheme 63. Synthesis of azido- and amino- monotelechelic polymers by substitution and reduction reactions.
Scheme 64. Functionalization of methoxy or tert-butyldimethylsilyloxy terminated polymer by BCl3 or Me3 SiClLiBr.
Scheme 65. Functionalization of polyanions by chlorosilane coupling and subsequent hydrosilylation reactions.
Scheme 66. Synthesis of amino-telechelic polyolen by termination of anionic polymerization with CO2 and amidation reaction.
511
In the second method also reported by Gruber, dicarboxylic acid end-functionalized oligomers were converted to the acid chlorides and subsequently reacted with 2,2,6,6tetramethyl-4-aminopiperidine and 2,2,6,6-tetramethyl4-hydroxypiperidine yielding ester and amide linkage, respectively [808]. Moreover, hydroxyl end-functionalized polymers obtained by termination of anionic polymerization of 1,3-butadiene with ethylene oxide were converted further telechelic polymers using acid chlorides [808]. In a very recent report, HOOC-PIP-b-PSt-b-PIP-COOH triblock copolymer synthesized by anionic polymerization was converted to corresponding acid chloride telechelics and used in synthesis of multiblock polymers by amidation with N,N -dimethyl-1,6-hexanediamine or hexamethylenediamine [839]. The formation of polymeric micelles made of this triblock chains were studied in a solvent selectively poor for the middle PSt block (Scheme 67). In an alternative method, hydroxyl groups of dihydoxytelechelic PEO-b-PPO-b-PEO were converted acetylene by esterication with phosgene and following amidation with propargyl amine. Subsequent click reaction with the same triblock copolymer with azido-functionality resulted in the corresponding multi block polymer (Scheme 68) [879]. Similarly, hydroxyl groups of PEO can be simply derivatized to alkyne [217,884,885], carboxylic acid [209], anthracene [144] or maleimide [143,146,216,886888] functionality by esterication, as presented in Scheme 69. In another work, Hadjichristidis and co-workers synthesized supramolecular polymers by introducing 2ureido-4-pyrimidone as a structural unit at the end of PSt-b-PIP. The molecule was linked to polymer through reaction of its isocyanate group with the hydroxyl group of an anionically prepared polymer (Scheme 70) [889]. Matsushita and co-workers developed a novel and efcient synthesis of polymers terminated with nucleotides via the reaction of thymidine phosphoramidite with hydroxyl end-capped PSt obtained by anionic polymerization (Scheme 71) [890]. In recent years, polymers containing nucleodites at their terminus have been widely used as building blocks of supramolecular self-assembled systems due to their hydrogen bonding abilities. For instance, thymine or adenine end functionalized polymers were utilized in diblock formation via hydrogen bonding [891]. Synthesis of Ru(bpy)3 -functionalized PSt was achieved through amidation of Ru(bpy)3 -COOH with aminefunctionalized PSt [870]. This typical example of derivatization clearly demonstrates that the method can virtually be used in the preparation of any functional polymer. 3.2.2.4. Derivatization by cycloaddition reactions. DielsAlder reaction has been also employed for the transformation of functional groups of polymers prepared by anionic polymerization. According to the reported method, dienefunctionalized PSt or PBd can readily be converted to the corresponding anhydride forms through Diels-Alder cycloaddition reactions (Scheme 72) [861,892]. Another cycloaddition reaction was used for endcapping PEO with C60 fullerene. Azide containing polymers can react selectively with C60 through a monoaddition reaction. This way 3-arm C60 end-capped PEO was synthesized
by Gnanou and co-workers [893]. More recently, Click reaction, the Huisgen 1,3-dipolar cycloaddition of azides and alkynes, was employed for the synthesis of cyclodextrin end-functionalized PEO (Scheme 73) [885]. 4. Telechelic polymers by cationic polymerization Cationic polymerization is known as chain polymerization in which propagating chains, namely active species are positively charged carbon centered ions or onium ions in vinyl polymerization or ring opening polymerization, respectively (Scheme 74). Various types of the initiation processes involving addition of Brnsted acids, Lewis acids, Lewis acids in conjunction with a proton or carbocation source, photochemical reactions, and treatment with high electric eld have been described. The initiation process is followed by propagation in which a nucleophilic attack of the monomer onto the active growing centers paired with non-nucleophilic counterions occurs. Nucleophilicty of counterion of the cationic growing species is crucial to achieve the living character of the polymerization. Therefore, counterions differ with respect to type of the monomer including vinyl ethers; styrenic monomers; substituted alkenes; and cyclic monomers, and mode of the polymerization (conventional or living cationic polymerization). As stated previously, C/LRP methods are great tools for the synthesis of well-dened polymeric materials and also excellent way to introduce functional moieties at one or both termini of polymer chains. Like the other polymerization methods, living mode of cationic polymerization also provides to introduce functional groups at polymer chain termini. The method involves the use of a functional initiator or a termination agent. Moreover, transformation of the primary end-capping groups to any other functional groups is an alternative method to obtain functional polymers. In this section, living cationic polymerization of both vinyl and cyclic monomers, used as a method for the synthesis of telechelic polymers, will be dealt. For the clarication, living polymerization of vinyl and cyclic monomers will be treated separately since the mechanisms are quite different from each other. 4.1. Telechelic polymers by cationic polymerization of vinylic monomers The living cationic polymerizations have been studied over a period of 30 years [894899]. One of the rst reports related to living cationic polymerization of vinyl monomers described the sequential block copolymerization of ethylvinyl ether and isobutylvinyl ether with N-vinyl carbazole through pseudo-living systems in late 1970s [900]. After this time, several different methodologies of living polymerizations of vinyl monomers have been developed [894,896898,901906] and employed in telechelic polymers [907909]. For instance, synthesis of dicarboxylic acid end-functionalized poly(vinyl ether)s was reported by using an adduct generated by addition of hydrogen iodide to vinyl ether containing malonic ester functionality as an initiator and sodiomalonic ester as an end-capping agent (Scheme 75) [909]. In recent years,
512
Scheme 67. Synthesis of acid chloride telechelic by anionic polymerization and its polycondesation reaction with a diamine.
Scheme 68. Synthesis of clickable PEOs and their multiblock copolymerization via click reaction.
Scheme 69. Synthesis of various telechelic PEOs by esterication reaction.
Scheme 70. Synthesis bio-related telechelics by anionic polymerization and amidation reaction.
Scheme 71. Synthesis bio-related telechelics by anionic polymerization and phosphoramidite reaction.
Scheme 72. Synthesis of telechelics by DielsAlder coupling.
513
Scheme 73. Synthesis of cyclodextrin end-functionalized PEO by combination of anionic and click reactions.
Scheme 74. General mechanism of cationic vinyl and ring opening polymerizations.
Scheme 75. Synthesis of telechelic polymers by living cationic polymerization of vinylic monomers.
telechelic polymers of isobutylene have been widely studied and used in many applications especially in biomedical eld [910]. The example presented in Scheme 75 shows both functional initiators and end-capping agents can be employed in polymer functionalization. These two different approaches will be evaluated separately in detail. 4.1.1. Functionalization by using functional initiators Using functional initiators in cationic polymerization is an elegant tool to synthesize -end-functionalized polymers with well-dened properties. Several different functional groups including carboxylic acid [909], hydroxyl [911], halogen, etc. can be introduced to -end of polymers. As presented in Scheme 75, a malonic ester derivative was utilized as functional initiator in living cationic
polymerization to generate carboxyl -end-functionalized poly(vinyl ether)s [909]. In the recent decade, the use of functional initiator strategy involving initiation with -methylstyrene epoxide/TiCl4 was also employed in synthesis of , hetero telechelic [911,912] or hyperbranched [913,914] PIBs. Polymerization of isobutylene yielded -hydroxyl telechelic PIB when the polymerization was initiated with the -methylstyrene epoxide/TiCl4 system. Additionally, quenching of the polymerization with methanol leaded to formation of chloro terminal group of the polymer (Scheme 76). In an interesting work, PIB-b-PSt based macroinitiator for ATRP was prepared by utilization of a functional initiator containing ester-protected hydroxyl group in sequential polymerization of IB and St. After the polymer-
514
Scheme 76. Synthesis of , -hetero telechelic polyisobutylene by cationic polymerization.
Scheme 77. Synthesis of dibromo functional ATRP macroinitiator by cationic polymerization.
ization, the dibromo functional group was attached to the -end of the polymer by trans-esterication. Subsequent ATRP of tert-butyl acrylate initiated by the macroinitiator yielded corresponding miktoarm star polymers (Scheme 77) [915]. In another work, 4-arm star telechelic polymer of isobutylvinyl ether was synthesized by HCl/ZnCl2 coinitiating system (Scheme 78) [916]. After polymerization, the living polymer was terminated with tetra-functional silyl enol ethers giving 4-arm star polymer. Depending on the initiator, styrene; methacrylate or ketone endfunctionalized polymers were obtained. Various -end functionalized polymers including hydroxyl [911,912,917], carboxylic acid [909], halide [915], allyl [918], acetate [916], methacrylate [916], styrene [916], and cyclopentene [919] can be synthesized by utilization of functional initiators in living cationic polymerization. 4.1.2. Functionalization by using termination with suitable nucleophile Living cationic polymerization of vinyl monomers, in which halide-based catalyst system is utilized, directly yields halogen-terminated telechelic polymers. These telechelic polymers can be used directly or transformed to other telechelic polymers. Typically, the polymerization of vinyl ether polymerization initiated with HII2 yields -iodine end-functionalized polymers with narrow molecular weight distribution (Scheme 79) [920922]. Similarly the reaction of bifunctional initiators with HII2 gives , -diiodine telechelics, and used directly in chain extension or functionalized with amine [923]. Moreover, living cationic polymerization of tetrahydroindene initiated with chloro-functional initiator and SnCl4 yields , -dichloro telechelic polymers [924]. Termination of living chain of a polymer with an end-capping agent with functional group(s) is an alternative way to synthesize endfunctionalized polymers. -Functional polymers are the products of this strategy in contrast to previous strategy,
using functional initiators. By this way, polymers with wide variety of end-functionalities have been prepared using various end-capping agents such as olens, silanes and aromatic compounds. 4.1.2.1. Olens. End-capping of a growing cationic chain with a compound containing C C double bond such as butadiene yields end-functionalized polymers. In a typical example for this approach, termination of living polymerization of isobutylene initiated by Me3 Al2 Br3 with Bd leads to formation bromoallyl end-functional polymers (Scheme 80) [925]. Similarly, chloroallyl analogous of this polymer was also prepared by quenching of Ti2 Cl8 catalyzed polymerization of isobutylene with butadiene [837]. Such telechelic polymers were used as a coupling agent with living anionic polymers such as poly(vinyl ferrocene) [926] and PMMA [927]; or a macroinitiator for ATRP of St and MMA [928] for block copolymer synthesis (Scheme 81). An alternative quenching agent containing C C double bond, namely 1,4-bis(1-phenylethenyl)benzene, was utilized to obtain - or , -DPE-functionalized PIB (PIB-DPE or DPE-PIB-DPE) [929932]. The reaction of living PIB with 1,4-bis(1-phenylethenyl)benzene and subsequent methylation of the resulting diphenyl carbenium ion with a large excess of Zn(CH3 )2 yielded the telechelic PIB. Furthermore, living PIB chains were quantitatively quenched with DPE yielding polymers with 1,1-diphenyl1-methoxy or 2,2-diphenylvinyl termini, or both. These functional groups were quantitatively metalated with Li, or K/Na leading to the formation of anionic species that initiated anionic polymerization of tBMA; as a result, PIBb-PtBMA was obtained quantitatively (Scheme 82) [933]. 4.1.2.2. Silanes. Quenching of living cationic polymerization of vinyl monomers with silanes is another elegant method to introduce functionalities at -termini of polymers (Scheme 83). A pioneering work by Kennedy and
515
Scheme 78. Synthesis of 4-arm star telechelic PIBVE by cationic polymerization.
Scheme 79. Synthesis of halogen end-functionalized polyvinyl ethers by cationic polymerization using iodide as terminating agent.
Scheme 80. Synthesis of bromoallyl end-functionalized PIB by cationic polymerization using butadiene as terminating agent.
Scheme 81. Reactions of bromoallyl end-functionalized PIB.
co-workers reported the preparation of terminally functionalized polymers by using allyltrimethylsilane as a quenching agent [934939]. The methodology involves the living cationic polymerization of IB by mono-, di-, or tri-functional initiating systems in conjunction with TiCl4 co-initiator and subsequent electrophilic derivatization of the living PIB cation with allyltrimethylsilane.
As presented in Scheme 84, this telecelic polymer was used as a precursor in macrocyclization through the Rucatalyzed metathesis reaction [936], or the synthesis of amphiphilic networks [940]. Moreover, carboxylate functional PIB was prepared by the termination of the polymerization with suitable silane compound [941]. For this purpose, quasiliving
516
Scheme 82. Transformation of living PIB chains to polyanion using DPE and LiCl.
Scheme 83. Synthesis of allyl terminated polymers by termination of living cationic polymerization with allyl silanes.
Scheme 84. Synthesis of macrocyclic PIB by the metathesis reaction of , -bisallyl-PIB.
cationic polymerization was rstly quenched with DPE to obtain stable carbocation and then with 1-methoxy1-trimethylsiloxypropene yielding methyl ester of the carboxylic acid. Subsequent hydrolysis of the ester resulted in carboxylate end-functionalized PIB which is the macroinitiator of polymerization of pivalonitrile (Scheme 85) [941]. Styrenic [942] or olenic [943] macromonomers were prepared by using similar approach where 2phenylallyltrimethylsilane or isobutenyltrimethylsilane was utilized as termination agent, respectively. Analogously, aromatic ketone -end functionalized poly(isobutyl vinyl ether) were synthesized by using silyl enol ethers as a quenching agents (Scheme 86) [916,944947].
or amino terminated functionalized PIB was very recently reported by quenching of quasi-living polymerization of IB with -haloalkoxybenzene (Scheme 87) [948]. The halogen end-functionalized polymers were also converted to azido- or amino-functionalized polymers by typical organic reactions. Likewise, electrophilic aromatic substitution of Nmethylpyrrole containing functional group with cationic PIB yielded terminally functionalized polymers [950952]. In a typical work, Storey et al. reported synthesis of PIB with primary alcohol at the -terminal by quenching of the quasiliving cationic polymerization with protected alcohol containing pyrrole and consequent deprotection [951].
4.1.2.3. Aromatic compounds. Substituted aromatic compounds can undergo reaction with living cationic chains yielding end-functionalized polymers [948,949]. Alkoxybenzene and arylamino derivatives are novel termination agents for the preparation of telechelic polymers via electrophilic aromatic substitution reaction. Synthesis of halide
4.1.2.4. End-capping with other nucleophilic compounds. Mono- and di-suldes are other quenchers of cationic polymerization leading to the formation of telechelic polymers. The end-capping of TiCl4 -catalyzed quasi-living polymerization of isobutylene with such compounds under different conditions were investigated by Storey and co-workers [953]. Termination of the living PIBs with the suldes and subsequent addition of more reactive
517
Scheme 85. Synthesis of carboxylate end-functionalized PIB by silane coupling.
Scheme 86. Functionalization of living PIBVE chains with silyl enol ether.
Scheme 87. Synthesis of halide and amino end-functionalized PIB via electrophilic aromatic substitution reaction.
nucleophiles such as alcohol or amine caused destruction of the suldePIB adducts. Both the elimination and substitution products including exo-olen, thioether or bromide-terminated PIBs were obtained (Scheme 88). 4.1.3. Functionalization by post-modication processes End-functionalized polymers obtained by cationic polymerization can be transformed further to functional polymers by typical organic reactions including nucleophilic substitution, addition, elimination and esterication reactions (Scheme 89) [954,955]. 4.1.3.1. Addition reactions. Allyl end-functionalized PIB was readily converted to corresponding hydroxyl functional polymer by regioselective hydroboration of the double bond with 9-borabicyclo[3.3.l]nonane followed by oxidation reaction (Scheme 90) [934,936]. Recently, synthesis of PEOPIB amphiphilic co-network was reported through coupling reaction of hydroxyltelechelic three-arm star PIB synthesized by this way with HOPEOOH in the presence of diisocyanate [956].
Reverse addition reactions, addition of a polymeric ion to functional group, were also employed to obtain telechelic polymers. Synthesis of carboxylic acid end-functionalized PIBs was achieved by dehydrochlorinationmetalation with n-BuLi/t-BuOK and carbonation of telechelic PIB anions with CO2 and H+ [957]. Moreover, epoxidation on the double bond with mchloroperbenzoic acid leads to epoxy end-functional PIB, which then can be cured easily [934]. Table 13 lists all other telechelic polymers obtained by the transformation of allyl terminated PIBs. 4.1.3.2. Nucleophilic substitution reactions. Nucleophilic substitution reactions have been widely employed in the transformation of telechelic polymers from one to another (Table 14). Similar to esterication reactions, etherication also provides a route to generate end-functionalized polymers. Reactions of dibromo telechelic PIB with epoxy or vinyl ether based hydroxyl compounds in the presence of strong base and tetrabutylammonium bromide were
518
Scheme 88. Functionalization of living PIB cations by mono- and di-suldes.
Scheme 89. Various post-modication reactions of halide-terminated PIBs.
Scheme 90. Transformation of allyl functionality of PIB to hydroxyl functionality by hydroboration. Table 13 Terminally functionalized polymers obtained by addition reactions. Functionality OH OH OH COOH COOH COOH CHO CN Cl Br epoxy epoxy Addition reagents 9-BBN/NaOH/H2 O2 9-BBN/NaOH/H2 O2 LiAlH4 Dimethyldioxirane 1. Ozone; 2. Oxidation 4-(4-Urazolyl)benzoic acid ZnBr2 Acetonitrile CH2 O/HCl HBr m-Chloroperbenzoic acid Dimethyldioxirane Precursor polymers PIB-allyl [934,936] Linear PDVB [958] PIB-aldehyde [959] PIB-aldehyde [960] PIB-allyl or -diphenylvinyl [961,962] PIB-olen [963] PIB-epoxide [959] PIB-OH [964] PIB-OH [965] PIB-allyl [966969] PIB-allyl [934] PIB-olen [959]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 14 Terminally functionalized polymers by nucleophilic substitution reactions. Functionality OH COOH COOH NH2 N3 phthalimide alkyne (meth)acrylates allyl, epoxy nucleobase nucleobase Precursor Polymers PIB-Br [939,948,954,966,970] PIB-Br [939,948,954,970] PIB-aldehyde [960] PIB-Br [939,948,954,966970] PIB-Br [939,948,954,970,971] PIB-Br [939,948,954,966,970] PIB-Br [939,948,954,970] PIB-Br [955,966] PIB-OH [955] PIB-Br [939,948,954,965,970] PIB-OH [972]
519
shown to yield corresponding PIB-based macromonomers (Scheme 91) [955]. Nucleophilic substitution reactions have been also commonly used in the synthesis of nucleobase endfunctionalized polymers using silylated nucleobases. Direct nucleophilic substitution reactions of such nucleobases with halo-terminated PIB have failed due to partial solubility of PIB in dipolar aprotic solvents. Therefore Saf and co-workers developed an alternative way involving a synthetic strategy with activated chloromethyl ethers which are more favorable to nucleophilic subtitution reactions with nucleophiles such as thymine, uracil, and cytosine [965]. Ether formation reactions were also used for the preparation of glucose-terminated PIBs. The method involves glycosylation of the dihydroxy-terminated PIB with sugar molecules containing thioglycosidic bond, which was activated by iodonium ions. Removal of the protecting benzyl moieties attached to hydroxyl groups of the sugar molecule was performed by a Pd-catalyzed hydrogenation reaction in the presence of a small amount of acetic acid (Scheme 92) [973]. Anionic species were also used for the transformation of end groups. For example, 1,1-diphenylalkyl anion obtained from the reaction of 1,1-bis(3-tert-butyldimethylsilyloxy
methylphenyl) ethylene with s-BuLi was coupled with chloroallyl-PIB to prepare -dibromo functional PIB for the synthesis of branched polymers [837]. Furthermore, azido-telechelic PIBs were obtained by nucleophilic substitution reaction of trimethylsilylazide with bromine functionalized PIBs and utilized in click reaction with telechelic alkyne-PEO to generate silica shell stabilized polymersomes [971]. Reaction between sodium salts of (meth)acrylates and bromo-telechelic polymers also leads to corresponding macromonomers [955,966]. 4.1.3.3. Elimination reactions. Elimination reactions conducted in the presence of a base is another strategy to produce telechelic polymers, especially olen-terminated polymers [974,975]. PIBs containing exo-olen terminal groups were prepared by quenching of TiCl4 -catalyzed living cationic polymerization of isobutylene with a hindered base such as potassium tert-butoxide, 2,5-dimethylpyrrole, 1,2,2,6,6-pentamethylpiperidine, or 2-tert-butylpyridine (Scheme 93) [959,975]. 4.1.3.4. Esterication reactions. More recently, further derivatization of hydroxyl end groups of telecehelic polymers was performed via esterication with hex-5-
Scheme 91. Synthesis of epoxy and vinyl ether macromonomers by etherication of dibromo terminated PIB.
520
Scheme 92. Synthesis of glucose-terminated PIBs by etherication of dihydroxy-terminated PIB.
Scheme 93. Synthesis of by olen-terminated PIB by quenching of TiCl4 -catalyzed living cationic polymerization with a hindered base.
Scheme 94. Synthesis of alkyne telechelic PIB and its macrocyclization with azido-telechelic PIB via click reaction.
ynoic acid (Scheme 94)[936] or methacryloyl chloride [935,976980] to synthesize alkyne-telechelic PIB or bismethacrylate functional PIB, respectively. These functional polymers were used as precursors for specic applications (i.e. precursor of cyclic polymers.) in the subsequent stage. On the other hand, MAPIBMA telechelic polymers have been extensively used in the formation of amphiphilic polymer networks particularly for biological applications [981]. Other terminally functionalized polymers by esterication reactions and their applications are summarized in Table 15. In addition to esterication reactions, urea, carbamate or urethane formation reactions were extensively applied in the preparation of telechelic polymers through transformation approach. Hydroxyl groups of PIB can be also converted quantitatively to carbamates by phenyl isocyanate [990]. Alternatively, amino groups of telechelic PIBs are used in polyurethaneureas formation by the reaction of diisocyanates with amine moieties [967969].
4.1.4. New cationic polymerization techniques Very recently, a novel Pd-based catalyst system for living cationic polymerization was developed and its mechanistic details were investigated. The reactions of ( -diimine)PdMe+ derivatives with various vinyl ethers such as butyl, ethyl, silyl, etc. generated polymers by two different pathways. The polymeric product of one of these pathways was an olen -terminally functionalized poly(vinyl ether) (Scheme 95) [918]. This new initiation mechanism is a potential method to synthesize polymers with other functional end groups. Pd catalyzed living cationic polymerization method was also applied for the polymerization of strong electron donating cyclic monomers such as 2-alkoxy-1methylenecyclopropanes. The living ring opening polymerization of various methylenecyclopropane derivatives was initiated with -allylpalladium complexes and corresponding polymers with Pd2 Cl2 core were obtained. Following conduction with nucleophiles such as NaOH/MeOH, NaOH/H2 O, AgOAc, NaCMe(COOEt)2 or PPh3 generated end-functionalized polymers (Scheme 96) [991,992].
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 15 Telechelic polymers derivatized by esterication reactions and their applications. Functional groups Polymers Applications
521
O HO O O
O O CN
PIB [936]
Macrocyclic polymers by click chemistry
PIB [935,976980]
Macromonemer in networked materials
Star PIB [982984]
Network formation
CH 2
O O X
PIB [985] Cross-linking
X: NCO, NHCOCl
O O
O O
H N O O O N H NCO
PIB [989,990] Polyurethane formation
S S C12H25 CN S
Br
PIB [986,987]
CTA in RAFT of MMA and NIPAm
Star PIB [988]
Star block copolymer synthesis by ATRP
NCO
PIB [967969] Polyurea formation
Scheme 95. Synthesis of macromonomer by Pd-based living cationic polymerization.
Scheme 96. Synthesis of various telechelic polymers via Pd catalyzed cationic polymerization of 2-alkoxy-1-methylenecycloropane.
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Scheme 97. Synthesis of mono- and di-telechelic polyphosphazenes via living cationic polymerization.
Furthermore, synthesis of mono- and telechelic polyphosphazenes was achieved through the living cationic polymerization of phosphoranimines initiated by PCl5 (Scheme 97) [993997]. Telechelic polymers were prepared by quenching living poly(dichlorophosphazene) chains, with small quantities of the amino phosphoranimines. Depending on the structure of initial phosphoranimines and termination agent mono- and mixed-telechelic polymers were readily obtained. Recently, an alternative polymerization system based on photoinduced living cationic polymerization was developed by Mah [998,999] and Yagci [785,10001002] as a potential method for the preparation of halogenterminated polymers. In this system, the initiating adduct is produced by reaction between photochemically generated cationic species and isobutylvinyl ether. The rest of the polymerization process follows the usual route proposed by Higashimura and Sawamoto (Scheme 98) [906]. 4.2. Telechelic polymers by cationic polymerization of cyclic monomers The synthesis of telechelics by cationic ring opening polymerization has the greatest practical interest due to the commercial value of the resulting compounds, such as polyether, polyols and so on. Although a wide variety of heterocyclic monomers can be polymerized by cationic mechanisms, only tetrahydrofuran (THF), oxazolines, Nsubstituted aziridines, and cyclic suldes are shown to polymerize under controlled or living conditions [1003]. This is because of the occurrence of chain scission reactions (chain transfer and/or termination) in most cases. The functional end groups are introduced by either an initiation or a termination reaction. 4.2.1. Functionalization by using functional initiators Living polymerization of THF can be initiated from either commercially available methyl triate or in situ
formed triates by the reaction of corresponding alcohols with triic anhydride in the presence of a sterically hindered amine as proton trap [1004]. A functional alcohol with triic anhydride can be used as a functional initiator which is capable to introduce functional group on the polymer chain-end. Addition of various kinds of alcohols with triic anhydride into THF polymerization leads to halide, allyl, alkenyl, acrylate, and methacrylate telechelics with a high living character [10051022]. The use of a suitable end-capping agent to terminate the polymerization, would then permit to introduce a second (equal or a different) functional chain end leading to telechelic or heterotelechelic polymers (Scheme 99). Cationic polymerization of oxazolines provides an excellent methodology for the facile introduction of functional end groups [10231025]. Polymerization proceeds via oxazolinium species and functional groups can be incorporated at both initiation and termination steps by using a functional initiator and a nucleophile, respectively. Various functional initiators have been reported for the preparation of end-functionalized polyoxazolines including, unsaturated hydrocarbon [10261028], allyl [1029,1030], alkyne [579,10311033], vinyl [1034,1035], butadiene [1036], styryl [1037,1038], acrylate [1039], methacrylate [1039,1040], naphthalene [1041], -acetal [1042], and -anthracene [1043] (Scheme 100).
4.2.2. Functionalization by using termination agent Another route for the preparation of telechelic polymers is the use of suitable nucleophiles in the cationic polymerization of cyclic monomers (Scheme 101). Semitelechelic polytetrahydrofuran (PTHF) can be obtained after end capping of the living polymers produced with a monofunctional initiator such as methyl triate. Anhydrides of super acids such as triuoromethane sulfonic acid or uorosulfonic acid yield two active ends [1004,1044,1045]. Molecular weight and functionality are controlled only at
Scheme 98. Halogen-terminated PVEs via photoinduced living cationic polymerization.
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Scheme 99. Synthesis of telechelic or heterotelechelic PTHF by cationic ring-opening polymerization.
Scheme 100. Synthesis of telechelic or heterotelechelic POx by cationic ring-opening polymerization.
low initiator concentration because of the low solubility of the initial bisoxonium salt [1044]. For the synthesis of bi- or tri-functional telechelics, initiators with corresponding functionality must be used (Chart 1). Independent activity of all initiator functions of these initiators has been also reported [1046,1047]. Because of the reversibility of the polymerization and the high reactivity of the oxonium functions, bi- and trifunctional PTHFs are not easy to use. These drawbacks are eliminated by the transformation of the oxonium end-groups into more stable but still reactive cyclic ammonium or sulfonium salts. The slight excess addition of an azetidine or thiolane in the THF polymerization gives azetidinium [1048,1049] or thiolanium [1050] end-functionalized PTHFs which can be isolated without any modication, for example by precipitation in water (Scheme 102). By the addition of a convenient nucleophile into the solution of living polymer, telechelic polymers with various functionalities can be easily obtained [1051]. End-capping reagents and the resulting end groups are shown in Table 16. Proton-initiated polymerization of THF in the presence of carboxylic anhydrides as chain transfer agent gives esterterminated end groups [10841086] (Scheme 103).
The pyridinium salt end-functionalized PTHFs can be used as polymeric initiators for photoinduced reactions (Scheme 104). Upon photolysis the pyridinium moiety decomposes and polymeric radicals are formed. Depending on the additives present in the system, hydroxy telechelics [1063] or block copolymers [1061] are thus formed. Interesting variation of end-capping reaction with Nphenylpyrrolidine can be used to prepare mono-, bi-, and tri-functional star-shaped, telechelic PTHF having N-phenylpyrrolidinium salt groups as illustrated in the example of tri-functional living PTHF. Heat treatment of the polymers carrying carboxylate anions results in a quantitative ring-opening reaction. Another class of telechelic PTHFs has been also prepared, in which functional groups were located not only at the chain ends but also at the interior desired position. In this case, the tert-butyldimethylsilyl-protecting group was removed during the precipitation to yield , -kentro-telechelic polymers (Scheme 105) [1017]. Moreover, eso-telechelic PTHF having pyrrolidinium salt groups at the prescribed inner positions were also prepared [1087]. Cyclic polymers, having one or two functional groups, are termed as kyklo-telechelics with analogy to the Greek word kyklos (which means cyclic). Such telechelics can be
Scheme 101. Synthesis of monotelechelic and telechelic PTHFs by cationic ring-opening polymerization.
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Chart 1. Examples of bi- and trifunctional initiators with BF4 , PF6 or SbF6 as counterions.
Scheme 102. Transformation of oxonium ions by azetidine or thiolane derivatives. Table 16 End-capping reagents and end groups of PTHF. Reagents Ammonia Potassium cyanate Hydrogen sulde Succinic acid Lithium or sodium-4-(methoxycarbonyl) phenolate Sodium diethyl malonate 4,4-Dimethyl-2-oxazolin-2-yl methyl lithium ((1-Methoxy-2-methyl prop-1-en-1-yl)oxy)silane Ethyl amine 2-Propene amine Lithium bromide Sodium phenolate N,N -diethyl dithiocarbamic acid sodium salt 4-Hydroxy butyl bromoisobutyrate Sodium salt of benzoin N-oxide derivatives Pyrrolyl potassium Sodium thiophene Allyl alcohol Propargyl alcohol Sodium methacrylate or methacrylic anhydride or methacrylic acid Sodium acrylate or acrylic anhydride or acrylic acid Sodium p-vinylbenzyloxide 3-Acrylaminopropanoic acid Functionality NH2 [1004,1051] NCO [1004,1051] SH [1004,1051] COOH [1051] COOH [1052,1053] COOH [1053] COOH [1054] COOH [1055] NHC2 H5 [1051,1056] NHCH2 CH CH2 [1051,1056] Br [1004,1051] phenolate [1004,1051,1057] dithiocarbamate [1058] bromoisobutyrate [1012,1013,1059] benzoin [1060] alkoxy pyridinium [1015,10611064] pyrrole [10651070] thiophene [1071,1072] allyl [1073,1074] propargyl [1010] methacrylate [10751079] acrylate [1050,1078,1080] styrene [1050,10811083] acrylamide [1080]
prepared again by the electrostatic self-assembly and covalent xation process as depicted in Scheme 106. By suitably selecting R and R groups, various mono- and bifunctional telechelics having hydroxyl and allyl groups were prepared [1088].
The termination of living polyoxazolines chain occurred via ring-opening of the oxazolinium cation by a nucleophile such as water, alcohol, or amine (ammonia, piperidine, etc.) [1089]. The nucleophile can attack at the 2- and 5-position of oxazoline ring. For a quantitative end functionalization,
Scheme 103. Functionalization of polyoxonium ion with carboxylic anhydrides.
Scheme 104. Reactions of pyridinium salt end-functionalized PTHFs.
525
Scheme 105. Synthesis of , -kentro-telechelic polymers by cationic polymerization.
Scheme 106. Synthesis of kyklo-telechelics by the electrostatic self-assembly and covalent xation process.
secondary cyclic amines can be used as terminating agents because they terminate selectively in 5-position, as demonstrated by Nuyken et al. [1090]. Polyoxazoline telechelics consisting of various functionalities have also been prepared by living cationic polymerization, as presented in Table 17. Reaction of methyltosylate with bisoxazolines gives rise to the formation of bis(oxazolinium tosylate) [1097]. Living polymerization of monofunctional oxazolines having propagating species at both ends can be initiated by the addition of the monomer. Termination of the living ends with suitable nucleophiles yields difunctional telechelics (Scheme 107). The usual cationic polymerization of oxiranes cannot be used to synthesize telechelic polymers owing to a high tendency of backbiting resulting in cyclic oligomers [11231125]. However, to eliminate such side reactions a process involving the addition of a hydroxyl end group to an activated (protonated) monomer has been proposed [11231125]. The polymer chain contains the less reactive (nucleophilic) hydroxyl end group. The driving force for this reaction comes from the protonated monomer, and no cyclic oligomers are formed. Similar results have been obtained from the polymerization of methyloxirane and chloromethyloxirane in the presence of ethylene glycol [11261129]. A series of telechelics and macromonomers were also prepared by CROP of propylene oxide and epichlorohydrin via activated monomer mechanism (Scheme 108) [11301135]. The activated monomer polymerization of valerolactone proceeds also living fashion and enables to prepare heterotelechelic(anthracene, acrylate, bromo,
and norbornene in -position and hydroxy in -position) polyesters [1136]. The three-membered cyclic amines and the fourmembered cyclic amines can be polymerized only by cationic mechanism [1137]. Monofunctional initiators, such as methyl triate [1138], produce monofunctional telechelics from t-butylaziridine. Addition of the monomer to a bifunctional living PTHF solution gives bifunctional poly(t-butylaziridine). This is a method of making ABA block copolymers. The aziridinium end groups react with various nucleophiles including, water, pyridine, benzylamine, lithium bromide, sodium phenolate, potassium hydroxide, lithium phenylacetate, 2-aminoethanol, benzyl amine, sodium 2-aminoethylate, maleic anhydride, dimethyl phosphonate, sodium ally1 alcoholate, allylamine, sodium acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and methacrylic acid to form the corresponding telechelics and macromonomers (Scheme 109) [11391144]. Reactions with pyrommellitic acid or with polyamines such as diethylene triamine give cross-linked products [1145]. End capping with aminopropyltriethoxysilane groups yields telechelics that form networks after hydrolysis [1145]. 5. Telechelic polymers by metathesis polymerization The olen metathesis as a synthetic tool can be applied to prepare telechelic polymers with precisely controlled structures, adjustable molecular weights and narrow polydispersities, and high degrees of end-functionalization. Mechanistically related metathesis reactions include ring opening metathesis (ROM), ring-closing metathesis (RCM),
526
Table 17 Telechelic polyoxazolines by living cationic ring opening polymerization. Functionality OH Diol Acetal SH Polymers PMeOx [1039,10911093], PEtOx [1039,1091,1092,1094], PPrOx [1039], PiPrOx [1042,1095], PnBuOx [1091] PMeOx [1096], PEtOx [1096] PiPrOx [1042] Poly(2-alkyl-2-oxazoline)[1097]
R N H N
Quarternary ammonium Silane COOH PMeOx [1098], PEtOx [1098], PiPrOx [1099,1100] PPhOx [1101], poly(2-alkyl-2-oxazoline)[11] PMeOx [1102,1103], PEtOx [1094,1102,1103], PPhOx [1103] PMeOx [1029,1030,11041107], PEtOx [1106,11081110] Poly(2-alkyl-2-oxazoline)[1097,1111,1112]
O N O N O O O O O O C NH O
N3 PPhOx [1120] PMeOx [1121] PMeOx [1040,1116,1117], PEtOx [1118], PnBuOx [1117], poly(2-alkyl-2-oxazoline)[1119] Poly(2-alkyl-2-oxazoline)[1037,1038,1097,1119] PMeOx [1115,1116], PEtOx [1115] PMeOx [1114] PEtOx [1111] PMeOx [1113]
CH2 n
Poly(2-alkyl-2-oxazoline)[1122]
Scheme 107. Functionalization of POx with suitable nucleophiles.
Scheme 108. Mechanism of activated monomer polymerization.
Scheme 109. Synthesis of poly(t-butylaziridine) macromonomers via cationic polymerization.
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a functional group protected -olen. Telechelic polymers containing silacyclobutane, epoxy and dimethylsilane end groups have been also synthesized by ADMET polymerization [11681170]. 5.2. Ring-opening metathesis polymerization (ROMP) Three synthetic routes have been reported for incorporating functional groups to the polymer chain-ends during different stages of the ROMP. Route A involves the use of functional initiators which makes it possible to prepare either homo- or hetero-telechelic polymers. Alternatively, the telechelic polymer can be prepared by coupling of a reactive linear polymer with an appropriate functional terminating agent (route B). The third strategy is the addition of functional chain-transfer agents (CTAs) not only permits the regulation of the polymer molecular weight but also transfers functionality to the ends of the polymer chains (route C). Synthesis of telechelic polymers by ROMP methods using titanium, tungsten, molybdenum, and ruthenium containing metathesis catalysts have been summarized recently in an excellent review [1171]. Telechelic polymers obtained by three modes of ROMP are summarized in Table 18. Few reports discussed the preparation of telechelic polymers using the functional initiator strategy due to the fact that limited synthetic procedures for functionalized metal catalysts are available. Three pathways can be applied for the functionalization ruthenium carbenes via cross-metathesis [1203] or by direct synthesis of the carbene from a precursor complex [1177] and diazoalkane [1178,1204]. Telechelic polymers with various functionalities such as acetate, hydroxyl, halide, etc. (Table 18, Route A) can be obtained in a controlled way by the use of corresponding ruthenium initiators in the polymerization (Scheme 112). Another means for the synthesis of telechelic polymers is through the use of a functional terminating agent that can terminate the ROMP as well as transferring the desired functional group to the terminal ends of the polymer chains. By the addition of carbonyls such as ketones or aldehydes can be used to terminate the polymerization by means of titanium, molybdenum and tungsten metathesis catalysts and install functional end-groups. This Wittig-type capping reaction proceeds smoothly and quantitatively and has been used for the preparation of a series of telechelic polymers [11791186,12051208]. As ruthenium carbenes only react with olens in a metathesis reaction, the terminating agent must have a desired functionality and an olenic group to form an inactive metathesis complex [1171]. Substituted vinyl ethers have been shown to react with ruthenium catalysts to form a Fischer carbene which does not undergo further metathesis with alkenes (Scheme 113) [1178,1209]. By this way, several functional groups have been introduced end of various polymers (Table 18, Route B2). On the other hand, carbonyl functional CTAs have been also employed to obtained end-functionalized polymers after ROMP catalyzed W or Co based catalysts (Table 18, Route B1). The hydroxyl monotelechelic polymers can also be prepared by ROMP of norbornene using vinylic suldes as a terminating agent
Scheme 110. Metathesis pathways.
ring-opening metathesis polymerization (ROMP), crossmetathesis (CM), and acyclic diene metathesis (ADMET) polymerization (Scheme 110) [9,11,11461150]. ROMP is a popular chain polymerization that is thermodynamically driven by the release of ring strain in cyclic olen monomers to form high polymer. ADMET is a condensation polymerization that normally employs a diene, usually a terminal diene, in conjunction with a metathesis catalyst to produce high molecular unsaturated polymer [1151]. The reaction is driven by the removal of a small molecule, usually ethylene from the system, which can be accomplished with a nitrogen purge. Most commonly used catalysts in metathesis polymerization are listed in Chart 2. Both ROMP and ADMET polymerization are capable of the preparation of telechelic polymers. In addition to providing highly functional-group-tolerant catalysts, allowing the polymerizations to be performed under extremely mild and user-friendly conditions, such features make ROMP and ADMET attractive synthetic tools for preparing telechelic polymers. 5.1. ADMET polymerization ADMET polymerization and depolymerization methods can be used in the synthesis of telechelic oligomers. The depolymerization of 1,4-polybutadiene is accomplished in the presence of a difunctional monoene by using a metathesis catalyst presented in Scheme 111. Diester, disilyl ether, borane and diimide telechelic 1,4-polybutadiene oligomers have been prepared via ADMET depolymerization [11521158]. The depolymerization was performed under a mild vacuum to remove the ethylene by-product. This approach was also applied to the synthesis of telechelic cis-1,4polyisoprenes, furan-based polymers, polyisobutylenes and poly(ethylene-co-isobutylene)s through the metathetical degradation of polyisobutylene-co-butadiene copolymers [11591163]. Amine and alcohol functions are not well tolerated with the current catalysts and can be incorporated to polymers by using protecting group strategy such as acetoxy [11641166] or phtalimide [1167] groups. Telechelics with both of these types of end groups were synthesized using direct ADMET polymerization of dienes in the presence of
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Table 18 End-functionalized polymers obtained by ROMP. Functionality Routea Polymers
O N O O
,
Br
O ,
Fe
Route A
PNBs [1172,1173], PCO [1172], PDCPD [1172]
,
Route A PCOD [1174]
O N H O H N O N N N H H N
Route A
PBONBI [1175] PNBOE [1176]
(Hamilton receptor)
N N R
Route A PNBs [1177]
(fluorescent dye)
C X
X: H, OMe, NMe2, NO2, F, Cl, Me X: H, CF3, OMe, NMe2, CN, NO2,
Route A
PNB [1178]
Route B1
PNB [1179]
CHO, CO2Me, NH2, Cl

C
Fe
Route B1
PNBFer [1180,1181], PNBPhT [1180,1181],
Route B1
PNB [1182]
OH
OSiMe3
,
Route B1 PNBs [11831185]
OSiMe3 C OSiMe3 O C C Br O
Route B1
PNBs [1185]
Route B1
PNB [1181,1186]
M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567 Table 18 (Continued) Functionality Routea Polymers
529
OH O
Route B2 Polymers of sugar based NB derivatives [1187], PNBs [1188]
N H
CO2H
(fluorescein)
O N N O O N H O H N O N N N H H N O
Route B2 PNBs [1190], PCOs [1190]
HN S
NH
Route B2 PBONBI [1189]
(biotin)
O
(Hamilton receptor)
O CH2 N H CH2 O CH2 N N O N N H O N SPh CH2 O Pd Cl SPh O O O O Cl CH2 CH2 F O F O O Br N3 F O O F F
Route B2 PNBs [1195] Route B2 PNBs [1193] Route B2 PNBs [1191] Route B2 PNBs [1176,1191]
O
Route B2 PNBs [1175]
NH O
Route B2
PNBs [1175,1176,1190], PCOs [1190]
CH2
Br
CH2
O O Cl ,
Route B2 PNB [1192]
,
Cl
CH2
Route B2
PNBs [1194]
Routea
Polymers
OH O N H O
Route C Route C PCOD [11971199] PCOT [318]
Route B2
PNBs [1196]
CO2H
OH (OAc) OH (OAc or silane)
O O OH O NH2
NH2 (CN)
O O Ot-Bu
Route C PCOD [1200]
N H
Ot-Bu
Route C PCOD [1201,1202]
a Route A refers functionalization using functional initiators (Scheme 112). Route B1 refers functionalization by termination using carbonyl end-capping agents. Route B2 refers functionalization by chain transfer reactions using vinyl ether derivatives as CTA (Scheme 113). Route C refers functionalization by chain transfer agent containing protected functionality (Scheme 114).
[1210]. In addition, the termination with vinyl lactones such as vinylene carbonate and 3H-furanone utilize the introduction of aldehydes [1211,1212] and carboxylic acids [12111213], which does not require extensive work-up
or deprotection reactions, offers access to reactive terminal functional groups. Allyl acetate [1214] and substituted acrylates [1215] are readily available can be used as endgroup functionalization agents in ROMP. The addition of
Chart 2. Well-dened metathesis catalysts (Mes = 2,4,6-trimethylphenyl, Cy = cyclohexyl).
Scheme 111. Depolymerization of PBd producing telechelic polymers via ADMET mechanism.
Scheme 112. Synthesis of monotelechelic polynorbornenes by ROMP using functionalized ruthenium catalyst.
531
symmetrically substituted olens in the ROMP method leads to monofunctional telechelics [12161218] which are further used as a macroinitiator [1193,1217,1219] or building blocks for copper catalyzed azidealkyne cycloaddition (CuAAC) click reactions [1220,1221]. The use of functionalized acyclic alkenes as chain transfer agents not only permits the regulation of the polymer molecular weight but also opens a simple and efcient route to the synthesis of telechelic polymers during ROMP. Because of their higher reactivity, cis-alkenes are preferably employed for this purpose. This method was rst used for the synthesis of telechelic polymers using molybdenium and tungsten catalyst [12221226]. The Grubbs group reported the synthesis of commercially interesting hydroxy telechelic polybutadienes by ruthenium-catalyzed ROMP of 1,5-cyclooctadiene in the presence of cis-1,4-bis(acetoxy)-2-butene followed by a post-polymerization deprotection step (Scheme 114) [11971199]. By the same strategy, a broad variety of difunctional allylic olens have been used for the synthesis of hydroxyl- [318,12271231], amino- [12001202], carboxyl- [1200] and halide- [318,1202,12321235] functional telechelic polymers (Table 18, Route C). Biorelated telechelic polymers of cyclooctene derivatives end-functionalized with hydrogen-bonding or metalcoordination sites could be prepared through the combination of ROMP with a corresponding functional chain transfer agent (CTA) [1190,1236]. ROMP in the presence of unprotected alcohols led to decreased yields and signicant amounts of aldehyde end groups due to isomerization [318,1197,1198,1237]. However, ROMP with the addition of 1,4-bis(acetoxy)-2-butene or even the related unprotected diols was performed successfully with the highly active Grubbs catalyst II [318,1197]. In the latter case, THF was added to minimize isomerization to aldehydes. Halide and trithiocarbonate functional telechelic polybutadienes were employed for the synthesis of ABA triblock copolymers by subsequent grafting from the ROMP polymers with methyl (meth)acrylates or styrene via ATRP or RAFT process [1232,1233,1238]. The preparation of poly(butadiene)s with cross-linkable end groups, such as epoxides or methacrylates, was reported by Grubbs and co-workers [1239]. Related syntheses of acetoxy end-terminated polymers with Grubbs-type catalysts were performed not only for cyclooctadiene but also for norbornene and 7-oxanorbornene derivatives [1240]. End-functionalized polynorbornenes capped with one or two acetoxy or alcohol groups were prepared with the Grubbs catalyst
I and mixed NHC/phosphine catalysts [1214]. Acetoxy and hydroxyl end-capped polymers were prepared by Gibson and Okada from bis(tert-butylester)-substituted norbornene by means of the Grubbs catalyst I. Subsequent hydrogenation of the hydroxy functionalized polymer gave the corresponding polynorbornene [1227]. Another interesting approach for chain-end functionalization concerns the treatment of a living ROM polymer Grubbs catalyst I with molecular oxygen. This process led to monoaldehyde-end-capped polymers in high yields [1241]. With W- or Mo-based catalysts, the analogous synthetic protocol would partially lead to a coupling reaction, thereby yielding polymers with doubled molecular weight [1241,1242]. The synthesis of a homologous series of unsaturated oligomeric esters by cross-metathesis of cyclopentene and MMA was also reported [1243]. Nomura and co-workers reported that norbornenebased macromonomers can be efciently prepared by the ROMP using well-dened molybdenum catalysts and subsequent end-group reactions [1244,1245]. Interestingly, these macromonomers were copolymerized with norbornene derivatives via ROMP to yield various macromolecular architectures [1192]. ROMP approach was also applied by several groups to prepare polymers having functional groups reactive toward ATRP [1186,1192,1232]. Another more recent chain end-functionalization strategy is the sacricial approach to generating a block copolymer with one block comprised of the desired monomer and the other block comprised of a readily degradable monomer (Scheme 115). Hydroxyl- [1237,12461249], and thiol- [1250] functionalized ROMP polymers were successfully synthesized employing cyclic acetal monomers, which can be degraded by hydrogenation leaving the desired hydroxyl and thiol group behind. The cleavage of multiblock copolymer containing weak ester linkage would also provide an alternative method toward the formation carboxyl-telechelic polymers [1251]. This strategy is quite simple and effective, but it is limited to only a few functional groups. Heterotelechelic ROMP polymers were also synthesized by the combination of sacricial synthesis with the vinyl lactone termination technique [1211]. 6. Telechelic polymers by the combination of click chemistry and C/LRP methods Recently, Sharpless et al. proposed the click chemistry as a new tool in organic synthesis that includes a handful of almost perfect chemical reactions. The key features of these reactions are represented by quantita-
Scheme 113. Synthesis of telechelic polymers by termination of ruthenium carbene-initiated ROMP reaction with an enolether.
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Scheme 114. Mechanism for the synthesis of hydroxyl telechelic PBds using a protected chain transfer agent.
Scheme 115. Synthesis of telechelic polymers by sacricial monomer addition route.
tive yields, toleration to many functional groups, superior regioselectivity, producing inoffensive by-products, simple product isolations and mild reaction conditions. These reactions have been classied in four categories: (i) cycloaddition reactions (most commonly Huisgen 1,3-dipolar cycloaddition (copper catalyzed azide/alkyne cycloaddition), but also the DielsAlder reaction), (ii) nucleophilic ring-opening reactions of strained heterocyclic electrophiles (epoxides, aziridines and aziridinium ions), (iii) non-aldol carbonyl chemistry (ureas, oximes and hydrazones) and (iv) additions to carboncarbon multiple bonds (especially oxidative addition, such as epoxidation, dihydroxylation and aziridination but also Michael additions) [12521254]. Among them, CuAAC click reaction is generally regarded as quintessential example of click chemistry. Because of its high selectivity, quantitative yields, short reaction time, mild reaction conditions and high delity in the presence of most functional groups, the CuAAC click chemistry has been presented as a versatile tool for the post-functionalization of synthetic polymers. Click reactions have been subsequently expanded in macromolecular engineering [1255,1256] and as a versatile method for the synthesis of functional monomers and polymers [12571260], bioconjugated polymers [104,279,1261,1262], and postfunctionalization of polymer [1257,1258]. The use of click reactions would lead to fruitful approaches when combined with living and controlled/living polymerization techniques, such as ATRP, NMRP, RAFT, and living ionic polymerization [1263]. In many of these cases, this marriage has been used for the quantitative preparation of telechelic polymers with otherwise difcultly accessible functional groups at the chain ends. Combining the chain-end functionality control of ATRP and the efciency of click chemistry is an important pathway for the synthesis of functional polymers, because halide end groups of polymers prepared by ATRP can be easily transformed into azides and subsequent click coupling with alkyne-modied species. This strategy can be used for the preparation of telechelics from a wide variety of polymers and functional groups [279]. An interesting review by Matyjaszewski highlights combination of these two powerful techniques for the preparation of novel polymeric architectures, functional
materials, and bioconjugates by choosing the appropriate reaction conditions [1264]. Well-dened azidoterminated polystyrene was synthesized by ATRP followed by a nucleophilic substitution with sodium azide in N,N-dimethylformamide. Click coupling reaction can subsequently be used to introduce alcohol, amine, carboxylic acid and vinylic functionalities by reaction with several commercially available low molecular weight alkynes such as propargyl alcohol, propargyl amine, propiolic acid, 2methyl-1-buten-3-yne, 1,2-diphenyl-2-(2-propynyloxy)1-ethanone, ethynylpyrene, diphenylurea derivatives and alkyne-functionalized POSS respectively (Scheme 116) [109,110,137,274,278,279,1261,1265]. Other groups also reported the use of ATRP-click methodology to combine azido terminated polymers with various biomolecules [104,279,282,1261]. Alternatively, functional initiators [102,104,121,208] (i.e., azide or alkyne functional molecules) can be used in ATRP for preparing well-dened clickable polymers. These polymers were then clicked with alkyne-modied compounds to yield telechelic polymers. Haddleton and coworkers [104] reported the synthesis of telechelic polymers by one-pot tandem ATRP and CuAAC methods without any chemical transformation or protection of initiating sites. In fact, both ATRP and CuAAC reactions could share the same copper catalyst and nitrogen-based ligands. The synthetic strategy consisted of the use of azido functional initiator for copper catalyzed ATRP of methyl methacrylate and allowing the polymerization to proceed up to 95% conversion before the addition of the functional terminal alkynes such as propargyl alcohol, diaza and coumarin dyes (Scheme 117). Several groups [107,272,1266] reported the combination of ATRP and click chemistry to prepare well dened -(meth)acryloyl macromonomers in an efcient manner. In the rst strategy, poly(n-butyl acrylate), poly(tert-butyl acrylate), polystyrene, and PSt-b-PBA were prepared by ATRP and subsequently transformed to azido end groups. In the second strategy, an azido functionalized initiator was used for the preparation of well-dened -azido polymethacrylates via ATRP in protic media. The click reaction of the resulting polymers with propargyl acrylate or propargyl methacrylate resulted in well-dened macromonomers with high degrees of functionalization.
533
Scheme 116. Synthesis of telechelic polymer by combining ATRP and CuAAC click reaction.
Scheme 117. Synthesis of telechelic polymers by one-pot tandem ATRP and CuAAC methods.
Matyjaszewski and coworkers [232,1267] reported the synthesis of , -dihydroxy telechelic polystyrene by the combination of ATRP from a difunctional initiator (dimethyl 2,6-dibromoheptanedioate), nucleophilic substitution of bromine chain ends by reaction with NaN3 , and subsequent click reactions with propargyl alcohol (Scheme 118). This click reaction was used as a model reaction for the quantication of the different telechelic species present at various reaction times and determination of apparent rate constants of consecutive click reactions. The concentrations of modied polymers (nonhydroxyl-, monohydroxyl- and dihydroxyl-polystyrene) were monitored by gradient polymer elution chromatographysize exclusion chromatography as a function of time. At the beginning of the reaction with propargyl alcohol, all of the polymers were nonhydroxyl-polystyrene. With increased reaction time, the population of nonhydroxyl-polystyrene decreased and the population of dihydroxyl-polystyrene increased. The fraction of monohydroxyl-polystyrene reached its maximum at ca. 1.5 h and then decreased with reaction time. These results indicated the second click reaction on a polymer chain was three times slower than the rst reaction. Recently, Opsteen and Van Hest [215] described the synthesis of -hydroxyl- -carboxylic acid heterotelechelic polystyrene using the combination of ATRP and CuAAC reactions. Polystyrene containing both azide and triisopropylsilyl protected acetylene end groups was prepared in good control by ATRP. Subsequently, the end groups were independently applied in two successive click reactions, that is: rst the azide termini were functionalized with propargyl alcohol and, after deprotection, the acety-
lene moieties were utilized for a second functionalization with azidoacetic acid (Scheme 119). In a recent paper, Voit et al. [387] described the synthesis of an acetylene and azido end functional polystyrenes using trimethylsilyl-protected alkyne- and chloro-functionalized initiators via NMRP. Subsequent deprotection of trimethylsilyl end groups of all polystyrene was conducted by tetrabutylammonium uoride used in tetrahydrofuran. For the installation of the azido moiety within polystyrene chain by nucleophilic substitution of halide with sodium azide was performed after the polymerization. By click chemistry, these polymers can be easily and efciently transformed to a set of functionalities such as 3,5-bis(benzyloxy)benzyl, N-Boc-3-aminopropyl and adenine group at polymer chain ends under mild conditions. Braslau and coworkers [386] reported on a versatile method for the preparation of anthracene and pyrene labeled telechelic polystyrenes by the combination of NMRP and CuAAC process. The process involves the removal of N-alkoxyamine through oxidative cleavage with ammonium cerium (IV) nitrate (CAN) in the presence of propargyl alcohol or thermolysis with ethanesulfonyl azide to incorporate terminal alkyne or azide functionality onto polystyrene, individually. To prepare telechelic polymer, alkyne end functional polystyrene was coupled with azide-substituted anthracene via CuAAC reaction quantitatively (Scheme 120). In order to obtain pyrene functional telechelic polystyrene, the terminal azide group had been functionalized with an alkyne attached pyrene dye using CuAAC reactions successfully (Scheme 121). CuAAC click reactions were also used to incorporate such uorescent group to poly(vinyl alcohol) and micro-
Scheme 118. Synthesis of ,
- dihydroxy telechelic polystyrene by combination of ATRP and CuAAC methods.
534
Scheme 119. Synthesis of -hydroxyl- -carboxylic acid heterotelechelic PSt by combination of ATRP and CuAAC methods.
Scheme 120. Synthesis of anthracene-labeled telechelic PSt by combination of NMRP and CuAAC methods.
spheres which were successfully utilized as biosensors [12681270]. Binder et al. [389] reported the introduction of various functional (pyrimidine and phenyl) groups on nitroxide initiators via CuAAC click reactions. Telechelic poly(N-isopropyl acrylamide) and poly(n-butyl acrylates) were synthesized via an NMRP process initiated by functional nitroxides. The strategy opens a pathway toward functional telechelic polymers with narrow molecular weight distribution and well-dened chain-end functionalities. Among C/LRP techniques, RAFT has arguably the most important commercial impact because it works with a wide range of vinyl monomers and under various experimental conditions. The particular combination of RAFT and click chemistry is a promising strategy to synthesize functional telechelics due to versatility of RAFT polymerization and efciency of click chemistry. RAFT agent containing azide or alkyne moiety was prepared and used to mediate the polymerization of various monomers under a variety of reaction conditions. The resulting azidoand alkyne-terminated polymers were used in click reactions with functional alkynes and azides, respectively, to synthesize various well-dened telechelic polymers and macromonomers [416,583,585]. Combining the synthetic techniques of RAFT polymerization and click chemistry demonstrated the ability to prepare a wide range of functional telechelics (Scheme 122).
Azido-terminated polymers prepared by RAFT can also be readily conjugated to biomacromolecules, as several group recently demonstrated. The polymers were efciently coupled with model biomolecules, i.e., folate [577], and bovine serum albumin [573] by CuAAC click reaction (Scheme 123). Recently, Bulmus et al. have shown the utility of the RAFT technique in the direct synthesis of , heterotelechelic polymers ready for selective bioconjugations. First, a new RAFT agent containing an azide and a dithiopyridine group was used to prepare -azide, -dithiopyridine heterotelechelic polymers in one step. Heterotelechelic functionality of the polymers was proven by the successful conjugation of polymer with alkynemodied biotin and thiol-bearing peptide/protein (i.e., glutathione and bovine serum albumin) via CuAAC and thioldisulde exchange chemistries (Scheme 124) [578]. Stucky et al. have demonstrated a facile methodology for the preparation of heterofunctional polymers by the combination of RAFT and subsequent one-pot Michael addition with click processes. Firstly, they used azidofunctional chain transfer agent, to prepare well-dened polymers bearing a trithiocarbonate group at one end and an azido group. In the Michael addition process, trithiocarbonate group were converted to alcohol functionality by treatment with 2-hydroxyethylamine and 2-hydroxyethyl acrylate at room temperature. They were then subjected
Scheme 121. Synthesis of pyrene-labeled telechelic PSt by combination of NMRP and CuAAC methods.
535
Scheme 122. Synthesis of various telechelic polymers by combination of RAFT and CuAAC methods.
Scheme 123. Synthesis of bioactive telechelic polymers by combination of RAFT and CuAAC methods.
to click reaction with 5-hexynoic acid using CuSO4 /sodium ascorbate catalyst system in water to furnish -hydroxy-carboxylic acid end functional heterotelechelic polymers (Scheme 125) [579]. In a recent study, Schubert et al. reported the preparation of a larger variety of telechelic polymers by the combination of click chemistry with living cationic polymerization (Scheme 126) [579]. Acetylene end-functional various poly(2-oxazoline)s including 2-methyl-, 2-ethyl, 2-nonyl- and 2-phenyl-2-oxazoline were synthesized by using 3-butynyl toluene-4-sulfonate and propargyl toluene-4-sulfonate as initiators. In addition, one of these polymers was used to demonstrate its applicability for the construction of well-dened telechelic poly(2ethyl oxazoline) by CuAAC click reactions using different
azide compounds (9-azidomethyl anthracene or benzyl 2azidoethyl ether). Well-dened cyclic polymers can be also successfully synthesized via intramolecular end-to-end click cyclization of linear -alkyne- -azido heterodifunctional precursors under high dilution conditions [122,130,576,581,936,12711273]. Li and co-workers described the synthesis of telechelic PCL by the combination of ring-opening polymerization and CuAAC click reaction (Scheme 127) [132]. Alkyne terminal PCL is easily clicked with azide containing sugars without signicant degradation of the aliphatic polyester. Recently, Su et al. reported the synthesis of well-dened telechelic PMMAs via the combination of living anionic polymerization and CuAAC click reaction (Scheme 128). In
Scheme 124. Synthesis of heterotelechelic polymers by combination of RAFT, thiol-disulde exchange and CuAAC reactions.
Scheme 125. Synthesis of heterotelechelic polymers by combination of RAFT, Michael addition and CuAAC reactions.
536
Scheme 126. Synthesis of telechelic polymers by combination of living cationic polymerization and CuAAC methods.
Scheme 127. Synthesis of telechelic PCl by combination of ring-opening polymerization and CuAAC methods.
Scheme 128. Synthesis of telechelic PMMAs by combination of living anionic polymerization and CuAAC methods.
this strategy, rst, azido functional PMMA was prepared by anionic polymerization and followed by nucleophilic substitution. Then these polymers were clicked with various functional alkyne compounds (propiolic acid, propargyl alcohol, 2-methyl-1-buten-3-yne, trimethyl propargyl silane, and glycidyl propargyl ether) with high conversion (above 99%). In a similar manner, the telechelic poly(ethylene glycol) containing barbituric acid units at the both ends were prepared by the combination of anionic polymerization and CuAAC click reactions [1274]. Carlotti et al. reported the direct synthesis of a broad series of -azido, -hydroxyl heterotelechelic polyethers [poly(ethylene oxide), poly(propylene oxide), protected polyglycidol and poly(epichloro hydrin)] via living anionic polymerization with tetrabutylammonium azide in the presence of triisobutylaluminum as activator [766]. A series of click coupling reactions using various azido polyethers with 1,7-octadiyne should yield a quantitative formation of coupled -,-hydroxyl telechelic polyethers (Scheme 129). Similar to the CuAAC click chemistry, the DielsAlder click reaction was also successfully combined with C/LRP methods for the preparation of telechelic polymers. Sumerlin et al. present a general strategy for end group functionalization of RAFT-generated polymers by Michael addition and DielsAlder click reaction [459]. Thiol terminated poly(N-isopropylacrylamide), prepared by RAFT/aminolysis, was reacted with 1,8bismaleimide derivative to yield maleimido terminated PNIPAM (Scheme 130). The maleimido activated end group allows efcient coupling with functional thiols or dienes by Michael addition or DielsAlder reactions, respectively. The combination of C/LRP methods with thiolene and CuAAC click chemistries provides a convenient function-
alization tool for the construction of telechelic polymers. Recently, several groups investigated and compared the efciency and orthogonality of thermally and photochemically initiated thiolene click coupling reactions [273,295,1275]. In these studies, a library of thiol- (PSt) and ene-end-functional polymers (PSt, PEO or PCL) were prepared by controlled polymerization techniques and they reacted with functional enes (undecenoic acid, 1,4-butanediol vinyl ether) or thiols (thioglycolic acid, 3mercaptopropionic acid, 3-mercaptopropyl trimethoxysilane, Fmoc-protected cysteine, adamantanethiol and thioglycerol) to synthesize well-dened telechelic polymers via thiolene click chemistry using radical initiators. Furthermore, the asymmetric telechelic polymer from -alkene-, -azido-polystyrene prepared by chain end modication of the corresponding ATRP was synthesized by successive thiolene coupling and CuAAC click reactions (Scheme 131). Haddleton et al. have used the combination of cobalt mediated radical polymerization and thiolene click reaction strategy to synthesize a well-dened telechelic polymer [1276]. Clickable alkene-functional polymethacrylates were prepared by CMRP of trimethylsilane-protected propargyl methacrylate using bis(boron diuorodimethylglyoximate) cobalt(II) as catalyst. Click reaction of the resulting polymer with mercaptoethanol presents hydroxyl monotelechelic polymer in a very convenient manner. In a recent study, dithiobenzoate and trithiocarbonate end-groups of polymers formed by RAFT polymerization were modied with a range of functional enes; maleimide, methacrylate, and acrylate functionalities by simultaneous aminolysis and thiolene addition reactions to yield bioactive telechelic polymers and new macromonomers
537
Scheme 129. Synthesis of -, -hydroxyl telechelic polyethers by combination of living anionic polymerization and CuAAC methods.
Scheme 130. Synthesis of telechelic polymer by successive Michael addition and Diels-Alder click reaction.
Scheme 131. Synthesis of heterotelechelic polymers by successive thiol-ene and CuAAC click reactions.
Scheme 132. Preparation of bioactive telechelic polymer and macromononomer by thiol-ene click reactions.
(Scheme 132) [1277]. Synthesis protocols that are clean (>85% conversion to desired product) and scalable were developed to convert a protected thiol group into desired functionality without side-reactions such as disulde interchain coupling and thiolactone formation. The aminolysis of the RAFT functionalities and the thiolene click reaction are done simultaneously in a one-pot reaction. Using the same approach, thiol-terminated polymers were transformed to new macromonomers by the addition of
diacrylate or dimethacrylate monomers with a high efciency. Lowe et al. described sequential thiolene/thiolene and thiolene/thiolyne reactions as a facile route for the functionalization of RAFT synthesized polymers [1278]. The dithiobenzoate end-groups were modied in a one-pot process via aminolysis/thiolene click reactions with either allyl methacrylate or propargyl acrylate yielding ene and yne terminal PNIPAM quantitatively (Scheme 133). These
538
Scheme 133. Synthesis of telechelic polymers by sequential thiol-ene/thiol-ene and thiol-ene/thiol-yne reactions.
Scheme 134. Synthesis of telechelic polymers via thiol-isocyanate click reaction.
groups were then modied with commercially available thiols (6-mercaptohexanol, 3-mercaptopropyl polyhedral oligomeric silsesquioxane) via radical thiolene and radical thiolyne reactions yielding the monotelechelic and telechelic PNIPAMs. Expanding on these facile and versatile click chemistries, Lowe et al. have claimed an alternative route for the preparation of -telechelic polymers via the highly efcient thiolisocyanate click reactions [1279]. Thiol-terminated polymers, obtained from RAFT/aminolysis steps, can be modied with a wide range of commercially available isocyanates (allyl isocyanate, cyclohexylmethyl isocyanate, tetradecyl isocyanate, 2-isocyanatoethyl methacrylate, 2-(2-isocyanatoethyl)-1,4-dimethoxybenzene, 9isocyanato-9H-uorene, isocyanatomethylene dibenzene, 4-(2-isocyanatoethyl)biphenyl, adamantly isocyanate, heptyl isocyanate, cyclododecyl isocyanate, undecyl isocyanate, octadecyl isocyanate, and hexadecyl isocyanate) to yield corresponding thiocarbamate- -functional polymers with quantitative yields (Scheme 134). The introduction of clickable functionalities in the polymer chain ends is an important issue in macromolecular engineering. Depending on the nature of these functionalities various characteristics may exist and they need to be considered in advance. For example, many azides are explosive, photosensitive [1280], and the limited stability of these compounds at high temperatures might cause cycloaddition reactions with electron-decient monomers during polymerization [586,1281]. In addition, alkynes can undergo some side reactions (chain transfer or chain coupling reactions) during radical polymerization [12821284]. In other applications, the sensitivity of anthracenes [12841286] and maleimides [202] toward radicals should be considered. It is known that radicals can react with anthracene both 9 and 10 positions as well as the reactive double bond of the maleimides. Moreover, ionic and radical polymerizations may interfere with thiols and may be limited by undesirable nucleophilicity, incompatibility with competing radical processes, or the tendency to form disuldes [1287]. These side reactions clearly can have dramatic signicance for the functionalization of polymers and should be limited by short polymerization time and low temperatures [586].
7. Conclusions As presented in this review article, a great deal of research activity has been devoted toward the preparation of telechelic polymers due to the endless demands of synthetic polymer chemistry as well as the industry for high-tech applications. The polymerization processes described in this review, each C/LRP method has distinct advantages and disadvantages. Continual development of these C/LRP systems will provide additional solutions for instances when a single method is not sufcient for the preparation of highly designed telechelic polymers. Still, more functionalization techniques are required which simplify the process of appending functionality onto polymer chains. References
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Progress in Polymer Science 36 (2011) 455567

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Progress in Polymer Science

Telechelic polymers by living and controlled/living polymerization methods

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

Fig. 1. Various architectures obtained by the reactions of telechelics.

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

Scheme 2. Synthesis of telechelic polymers by iniferter method.

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

Table 1 Functional iniferters. Functionality Iniferter Polymers

PSt [40], PDMA [40]

PSt [40], PDMA [40]

PSt [40], PDMA [40]

PSt [41,42], PMMA [41,42]

PSt [43], PMMA [43]

R: -phenyl, -tolyl, -mestyl

PSt [44], PMMA [44], PBA [44], PSTA [44]

PSt [51], PMMA [51,52]

PSt [51], PMMA [51]

PSt [53,54], PMMA [55]

PMMA [71], PBA [71]

PSt [72], PMMA [50,71,73], PHEMA [71,73], PBA [71,73]

462 Table 2 (Continued) Functionality

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

PSt [51], PMMA [51], PBMA [51]

PMMA [48], PSt [49]

PSt [75,87], PMMA [87]

PSt [87], PMMA [87]

Y X,Y :(NO2, H), (NH2, H)

(H,NH 2), (H,NO 2)

PtBA [91], PMMA [62]

POEGMA [92,93], PMMA [62]

PSt [98], PMMA [99]

PSt [87], PMMA [87], PBA [100]

PSt [60,92,93], PMMA [60,92,93]

PSt [111], PMMA [111], PAN [112]

464 Table 2 (Continued) Functionality

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

PSt [119], PMMA [120]

PSt [130], PNIPAM [131,132], PEEA [133], PMMA-co-PHMA [108],

PMMA [136], PSt [137]

PSt [138], PMMA [138]

PVK [140], PVK-b-PMMA [140]

PMMA [141,142], PSt [143146]

PHEMA [158], PMAGA [159]

PSt [160], PMMA [161]

X : -H, -CH2Cl, -CH2OCOC(CH3)2Cl

PtBA [162], PtBA-b-PSt [162]

nucleoside and oligosaccharides

PbzMA [128], PBA [128]

O X: -Br, -ClR: -CH3, -H HN NH O O H H O R N 3 2 X S H

PMAGA [166], PtBA [167], PNIPAM [168170], PtBA-b-PMA [167]

PSt [172], PMMA [172174]

466 Table 2 (Continued) Functionality

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455567

PSt [176], PMMA [176]

PSt [98,180], PMMA [99,180]

PSt [182], PMMA [183,184], PBMA [182], POEGMA [183,184]

PMEA [185], POEGMA [185], PMMA [183185],

PSt [186], PMMA [186]