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Progress in Polymer Science 36 (2011) 455–567

Contents lists available at ScienceDirect

Progress in Polymer Science

journa l homepage: www.e lsev ier .com/ locate /ppolysc i

elechelic polymers by living and controlled/living polymerizationethods

ehmet Atilla Tasdelen, Muhammet U. Kahveci, Yusuf Yagci ∗

stanbul Technical University, Faculty of Science and Letters, Chemistry Department, Maslak, TR-34469 Istanbul, Turkey

r t i c l e i n f o

rticle history:vailable online 20 October 2010

eywords:elechelic polymers

a b s t r a c t

Telechelic polymers, defined as macromolecules that contain two reactive end groups,are used as cross-linkers, chain extenders, and important building blocks for variousmacromolecular structures, including block and graft copolymers, star, hyperbranched ordendritic polymers. This review article describes the general techniques for the prepa-ration of telechelic polymers by living and controlled/living polymerization methods;

nd-functionalized polymersiving polymerizationontrolled/living polymerizationlick chemistry

namely atom transfer radical polymerization, nitroxide mediated radical polymerization,reversible addition-fragmentation chain transfer polymerization, iniferters, iodine transferpolymerization, cobalt mediated radical polymerization, organotellurium-, organostibine-,organobismuthine-mediated living radical polymerization, living anionic polymerization,living cationic polymerization, and ring opening metathesis polymerization. The efficientclick reactions for the synthesis of telechelic polymers are also presented.

© 2010 Elsevier Ltd. All rights reserved.

∗ Corresponding author. Tel.: +90 212 285 3241; fax: +90 212 285 6389.E-mail address: [email protected] (Y. Yagci).Abbreviations: PAA, poly(acrylic acid); PAAL, poly(N-acryloylalanine); PAEPC, poly(2-acryloyloxyethyl phosphorylcholine); PAEL, poly(2-

cryloyloxyethyl lactoside); PAGA, poly(acryloyl glucosamine); PAM, polyacrylamide; PAMA, poly(2-aminoethyl methacrylate hydrochloride); PAMBA,oly(sodium 3-acrylamido-3-methylbutanoate); PAMPS, poly(2-acrylamido-2-methylpropanesulfonate); PAMMA, poly(9-anthracenylmethyl methacry-

ate); PAN, polyacrylonitrile; PAzPMA, poly(3-azidopropyl methacrylate); PBA, poly(butyl acrylate); PtBA, poly(tert-butyl acrylate); PtBAM, poly(tert-butylcrylamide); PBd, poy(1,3-butadiene); PBMA, poly(butyl methacrylate); PtBMA, poly(tert-butyl methacrylate); PBONBI, poly(N-butyloxanorbornenimide);tBSt, poly(tert-butyl styrene); PnBuOx, poly(2-n-butyl-2-oxazolines); PbzMA, poly(benzyl methacrylate); PChA, poly(cholesteryl acry-ate); PChMA, poly(cholesteryl methacrylate); PCO, poly(cyclooctene); PCOD, poly(1,5-cyclooctadiene); PCOT, poly(1,3,5,7-cyclooctatetraene);DADMAC, poly(diallyldimethylammonium chloride); PDDMA, poly(2,2-dimethyl-1,3-dioxolane)methyl acrylate; PDDMAA, poly((2,2-dimethyl-1,3-ioxolane)methyl acrylamide); PDEAEMA, poly(2-(diethylamino)ethyl methacrylate); PDEAM, poly(N,N-diethylacrylamide); PDEGMA, poly(diethylenelycol monomethyl ether methacrylate); PDEVBA, poly(N,N-diethyl vinylbenzylamine); PDLLA, poly(d,l-lactide); PDMA, poly(N,N-dimethylcrylamide); 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,oly(divinylbenzene); PEA, poly(ethyl acrylate); PECH, polyepichlorohydrin; PEEA, poly(1-ethoxyethyl acrylate); PEEGE, poly(1-ethoxyethyl glycidylther); PEHA, poly(2-ethylhexyl acrylate); PEMA, poly(ethyl methacrylate); PEMAM, poly(N-ethyl-N-methyl acrylamide); PEO, poly(ethylene oxide); PEtOx,oly(2-ethyl-2-oxazoline); PFABu, poly(butyl 2-fluoroacrylate); PFMA, poly(pentafluorophenyl methacrylate); PGalEMA, poly(2-(b-d-galactosyloxy)ethylethacrylate); PGAMA, poly(d-gluconamidoethyl methacrylate); PGME, poly(glycidyl methyl ether); PGlMA, poly(glycerol monomethacrylate);

HFDA, poly(heptadecafluorodecyl acrylate); PHEA, poly(2-hydroxyethyl acrylate); PHEMA, poly(2-hydroxyethyl methacrylate); PHMA, poly(hostasolethacrylate); PHMS, poly(4-(hydroxymethyl) styrene); PHPA, poly(2-hydroxypropyl acrylate); PHPMA, poly(2-hydroxypropyl methacrylate);

079-6700/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.oi:10.1016/j.progpolymsci.2010.10.002

dx.doi.org/10.1016/j.progpolymsci.2010.10.002

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http://www.elsevier.com/locate/ppolysci

mailto:[email protected]

dx.doi.org/10.1016/j.progpolymsci.2010.10.002

456 M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455–567

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4572. Telechelic polymers by controlled/living radical polymerization (C/LRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457

2.1. Iniferters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4582.2. Atom transfer radical polymerization (ATRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 459

2.2.1. Functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4592.2.2. Protected initiator . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4602.2.3. Atom transfer radical addition and coupling (ATRA/C) reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4672.2.4. Postmodification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4712.2.5. Macromonomer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471

2.3. Nitroxide mediated radical polymerization (NMRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4712.3.1. Functional nitroxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4712.3.2. Postmodification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 473

2.4. Reversible addition-fragmentation chain transfer polymerization (RAFT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4842.4.1. Functional chain transfer agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4842.4.2. Postmodification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 494

2.5. Other controlled radical polymerization techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4962.5.1. Iodine transfer polymerization (ITP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4962.5.2. Cobalt mediated radical polymerization (CMRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4962.5.3. Organometallic radical polymerization (OMRP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497

3. Telechelic polymers by anionic polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973.1. Functionalization by using functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4973.2. Functionalization by termination with suitable electrophile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499

3.2.1. Direct functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4993.2.2. Derivatization of functional groups by postmodification processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 508

4. Telechelic polymers by cationic polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5114.1. Telechelic polymers by cationic polymerization of vinylic monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 511

4.1.1. Functionalization by using functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5134.1.2. Functionalization by using termination with suitable nucleophile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5144.1.3. Functionalization by post-modification processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5174.1.4. New cationic polymerization techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520

4.2. Telechelic polymers by cationic polymerization of cyclic monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5224.2.1. Functionalization by using functional initiators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5224.2.2. Functionalization by using termination agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 522

5. Telechelic polymers by metathesis polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5255.1. ADMET polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5275.2. Ring-opening metathesis polymerization (ROMP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527

6. Telechelic polymers by the combination of “click” chemistry and C/LRP methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5317. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 538

PHPMAM, poly(N-(2-hydroxypropyl) methacrylamide); PIB, polyisobutylene; PIBVE, poly(isobutylvinyl ether); PIP, polyisoprene; PKSPMA, poly(potassium3-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-isopropylidene-d-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-(2-methoxyethoxy)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 deriva-tive 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(N-succinimide-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-propylacrylamide); PPATS, poly((3-acryloxypropyl)-trimethoxysilane); PPBA, poly(1-pyrenebutyl acrylate); PPDSM, poly((2-(2-pyridyldisulfide)ethyl methacry-late)); 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-protectedpropargyl methacrylate); PNBDHMA, poly(7-nitrobenz-2-oxa-1,3-diazole hexyl methacrylate); PMMA, poly(methyl methacrylate); PMeSt, poly(alpha-methyl styrene); PPO, poly(propylene oxide); PSMA, poly(solketal methacrylate); PSt, polystyrene; PSTA, poly(stearyl acrylate); PSSS, poly(sodium 4-styrenesulfonate); 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-vinylpyridine); PVPGVG, poly(valine-proline-glycine-valine-glycine methacrylate).

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M.A. Tasdelen et al. / Progress i

. Introduction

A major concern of polymer and material sciences designing functional materials with physical featuresuned to match the needs of expanding technology. Inarticular, end-functional polymers have an importantconomic position because of their possible applicationss components in the synthesis of block copolymers,hermoplastic elastomers, polymer networks, surfac-ants, macromonomers, etc. [1]. According to the IUPAC,elechelic polymers are defined as polymeric moleculesith reactive end groups that have the capacity to enter

nto further polymerization or other reactions. Reactivend-groups in telechelic polymers come from the initia-or or the terminating or chain-transfer agents in chainolymerizations, but not from monomer(s) as in poly-ondensations and polyadditions [2]. Functionalizationf polymer chain ends can also take place in post-olymerization reactions.

Pioneering work on the synthesis of telechelic polymersnd their conversion to the final products with specificroperties by reacting with functional groups may be datedo 1947 [3]. However, the concept was not fully recognizedntil 1960 [4]. Significant contributions to the develop-ent of this class of polymeric materials continue in the

urrent literature [4–6]. In the last decade there has beenrapid growth in the development and understanding ofew controlled/living radical polymerizations (C/LRP) [7].recise control of functionality, molecular weight, and uni-ormity (molecular weight distribution) can now be madeot only by living ionic polymerization routes but alsoy newly developed controlled/living radical polymeriza-ion techniques. Another striking development has beenchieved in metathesis polymerization and click chemistry.n addition, many new catalysts have been developed andpplied to prepare advanced materials [8–11]. The range ofonomers and functional groups used in the preparation

f telechelic polymers has been expanded in recent yearss a result of such developments. This article describes theeneral techniques for the preparation of telechelics withpecial emphasis on living and controlled/living polymer-zation methods.

A polymer can be considered to be telechelic if it con-ains end groups that react selectively to give a bond withnother molecule. Depending on the functionality, whichust be distinguished from the functionality of the end

roup itself, telechelics can be classified as mono- or semi-di-, tri-, and multifunctional telechelics (polytelechelics)5]. The functionality is defined as:

= Number of functional groupsNumber of polymer chains

In the polymer science community, the term “telechelic”ommonly refers to a linear polymer having the sameunctionality at both chain-ends. When the polymer chainontains two different functional groups at the ends, it is
alled “heterotelechelic”. As the concept of telechelics isow expanding from classical linear bifunctional polymersoward many other types varying the number and positionsf functional groups (semi-, eso-, etc.) and more impor-antly the topology of polymer chains (star-, dendritic-,
er Science 36 (2011) 455–567 457

kyklo-, multicyclic, etc.), new classifications and notationsare needed.

Telechelic polymers can be used as cross-linkers,chain extenders, and pre-cursors for block and graftcopolymers [12–14]. Moreover, star and hyper-branchedor dendritic (or hyper-branched) are obtained by cou-pling reactions of monofunctional and multifunctionaltelechelics with appropriate reagents. Various macro-molecular architectures obtained by the reactions oftelechelics are represented in Fig. 1. The functionality of theend group is important. When such groups are bifunctional(e.g., vinyl groups) they can participate in polymeriza-tion reactions, yielding graft copolymers or networks; suchtelechelic polymers are called macromolecular monomers,macromonomers, or macromers.

Industrial interest in telechelics was stimulated by thedevelopment of thermoplastic elastomers, which consistof ABA block and multiblock copolymers. Liquid telechelicpolymers are the basis for reaction injection molding. Liq-uid telechelics that can be used for network formationoffer processing advantages and may result in materi-als with improved properties [6]. For example, alcoholand carboxylic acid functional telechelic polymers canbe used to make their respective polyesters via poly-condensation. Hydroxyl telechelic functional polymersare also reacted with difunctional isocyanates to formpolyurethanes. When telechelic polymers are designedfor use in synthesizing networks, they are stoichiometri-cally reacted with multifunctional cross-linkers containinga complimentary antagonist group. This leads to a well-defined polymer network, which can be very important forcommercial applications.

2. Telechelic polymers by controlled/living radicalpolymerization (C/LRP)

Accurate control of polymerization process is an impor-tant aspect for the preparation of well-defined telechelicsand end-functionalized macromolecules [15]. Such controlof chain ends was traditionally accomplished using livingionic polymerization techniques. But it is well known thatthe ionic processes suffer from rigorous synthetic require-ments and in some cases they are sensitive to the functionalgroups to be incorporated. On the other hand, free radicalpolymerization is flexible and less sensitive to the poly-merization conditions and functional groups. However,conventional free radical processes yield polymers withoutcontrol of molecular weight and chain end. Competing cou-pling and disproportionation steps and the inefficiency ofthe initiation step lead to functionalities less than or greaterthan those theoretically expected. Recent developmentsin controlled/living radical polymerization provided thepossibility to synthesize well-defined telechelic polymerswith controlled functionality [16]. As described below,all the controlled/living radical polymerization meth-ods, namely atom transfer radical polymerization (ATRP)
[17,18], nitroxide mediated radical polymerization (NMRP)also called as stable free radical mediated polymeriza-tion (SFRP) [19], reversible addition-fragmentation chaintransfer polymerization (RAFT) [20], iniferters [21], iodinetransfer polymerization (ITP) [22], cobalt mediated rad-


btained
Fig. 1. Various architectures o
ical polymerization (CMRP) [23], and organotellurium-,organostibine-, organobismuthine-mediated polymeriza-tion (OMRP) [24] have been used for the preparation oftelechelic polymers.

There are two strategies for synthesizing telechelicpolymers using the widely used C/LRP methods includingATRP, RAFT, or NMRP processes [25,26]. Functionality canbe incorporated onto the initiating segment of ATRP, RAFT,or NMRP initiators which afford �-functional telechelicpolymer. Equally, functionality can be affixed to the ter-minating portion of initiators which provides �-functionaltelechelic polymer (Scheme 1). Polymers can be function-alized at one end (semi-telechelic), both ends (telechelic),or possess differing functionality at the ends (hetero-telechelic). As an alternative, functionalization of polymerchain ends can be achieved by post-polymerization reac-tions.

2.1. Iniferters

Iniferter is a useful and convenient method for the syn-thesis of vinyl polymers under mild reaction conditions,although the polymerization is quasiliving radical poly-
merization [21]. Photochemically or thermally activatedpolymerization can proceed in the presence of radicallypolymerizable vinyl monomers under appropriate reactionconditions through radical pair generation, monomer addi-tion, and rapid recombination [27]. The peculiar behavior
by the reactions of telechelics.

of thiuram disulfides in free radical polymerization wasfirst identified by Ferington and Tobolsky [28,29]. Thesemolecules can act simultaneously as an initiator, chaintransfer agent, and terminator in a polymerization reactionand generally referred as iniferters by anomy to their role[30,31].

So far, many iniferters have been reported and utilizedfor the synthesis of telechelic polymers. Telechelic prepa-ration is based on the concept of locating the requiredfunction on the alkyl group of the thiuram disulfide andusing it in the photo or thermal polymerization. Since endgroups are introduced via initiation and transfer and com-mon bimolecular termination between two growing chainsare negligible, perfect bifunctional telechelics are availablealong this route. Several functional disulfides and substi-tuted tetraphenylethylenes were also used as inifertersin free radical polymerization. The functionalities of thetelechelics prepared by iniferter method were reported tobe close to 2, within experimental error. The formation ofthe nonfunctional polymers was claimed to be negligiblebecause of the triple function of the iniferter. For example,carboxylic acid and amino functionalities were introducedto polystyrene using the corresponding disulfides [32].
Diamino functional poly (t-butyl acrylate) was also pre-pared [33]. In this case, polymers were readily hydrolyzedto polyacrylic acid possessing amino terminal groups,which is a useful material for the application of poly-electrolytes. The photochemically and thermally induced

M.A. Tasdelen et al. / Progress in Polymer Science 36 (2011) 455–567 459

lechelic

iif(i

2

a[mmmbmcmcSati

eA

Scheme 1. General synthesis strategies for te

niferter properties of the tetraalkylthiuram disulfides dur-ng free radical polymerization were also exploited to endunctionalize poly(methyl methacrylate) and polystyreneScheme 2) [30,34]. Table 1 summarizes the functionalniferters used for obtaining telechelic polymers.

.2. Atom transfer radical polymerization (ATRP)

Among the C/LRP strategies, ATRP, coined by Wangnd Matyjaszewski [45] and Sawamoto and co-workers46] in 1995, has turned out to be the most promising

ethod allowing good control on the molecular weight andicrostructure of the polymers in a targeted manner. In thisethod, control is achieved by the equilibrium maintained

etween an active (Pn•) and a dormant chain (Pn − X). The

echanism involves reversible homolytic cleavage of aarbon–halogen bond by a redox reaction between an dor-ant species and a metal/ligand complex, such as copper (I)

omplexes with 2,2-bipyridine, as illustrated in Scheme 3.everal monomers are added at each activation step. Inwell-adjusted slow activation and a fast deactivation,

ransfer and termination reactions have mostly been elim-nated.

As illustrated in Scheme 4, several strategies can bemployed for the synthesis of telechelic polymers usingTRP.

(I) The most convenient strategy is based on the useof initiators carrying reactive functional groups (e.g.,alcohol, ester, epoxide) that do not require any pro-tection.

(II) Conversely, initiators containing specific functional
groups such as thiol or carboxylic acid can be usedonly after an initial protection step, because of theirparticipation in the polymerization process.
(III) Atom transfer radical addition or coupling (ATRA/C)reaction relies on the same mechanism as ATRP,

Scheme 2. Synthesis of telechelic po

polymers by ATRP, NMRP and RAFT methods.

but instead of polyadditions, only a single moleculeis added. Functionalization by ATRA/C reaction wasdemonstrated with a co-monomer which does nothomopolymerize in radical polymerization or a chaintransfer agents or a stable radical or a combination oflow molecular weight or polymeric radicals.

(IV) Finally, an alternative route to reach telechelic poly-mers is to transform the terminal halide groups tothe desired functionality by postmodification reac-tions such as nucleophilic substitutions.

2.2.1. Functional initiatorsTelechelic polymers are easily accessible with ATRP

using functional initiators. To date, well-defined styreneand acrylate type telechelic polymers have been success-fully prepared with functional groups such as amine, ester,nitro, hydroxyl, aldehyde, phenyl and acid via the corre-sponding functional initiator (Table 2). It should be pointedout that besides the desired functionality, the initiatorsneed to be equipped with a radical stabilizing group on the�-carbon atom such as aryl, carbonyl, nitrile, and multiplehalogens to ensue successful ATRP. Notably, direct bond-ing of halogen to aryl or carbonyl group does not facilitateradical generation. For example, ATRP of methyl methacry-late with copper/ligand complex in the presence of hydroxyfunctional alkyl bromide initiator leads to �-hydroxy func-tional PMMA with controlled architecture without the useof protecting group chemistry (Scheme 5) [47].

Like ATRP, reverse atom transfer radical polymeriza-tion, RATRP, has been shown to produce similarly telechelicpolymers suitable for continued polymerization. RATRPinvolves initiation by conventional azo or peroxy ini-tiators in the presence of appropriate transition-metal
complexes in a higher oxidation state [48]. Monotelechelicpolystyrenes with cyano, carboxylic acid, and hydroxylterminal groups can be prepared via RATRP using corre-sponding azo initiators in conjunction with metal/ligandcomplexes (Scheme 6) [49].
lymers by iniferter method.

n Polym
460 M.A. Tasdelen et al. / Progress i
2.2.2. Protected initiatorProtection of the functional groups of initiators suscep-

tible to ATRP process has proven to be a general methodenabling the preparation of functional polymers with well-

Table 1Functional iniferters.

Functionality Iniferter

–OH HO NC

S

S

2

–OH CO2

Si

–COOH NC

S

S

HOOC

–COOH

HOOC COOH

COOH

–NH2 CNS

S

2

N

O

O

–OH and –COOH HO NC

S

S

COO

–OH and –COOH HO NC

S

S

OOH

–NH2 and –COOHHOOC N

CS

S

NH2

–chloride CNC2

Cl

Cl

–phosphorylamide N NC

S

S

2OP

O

O

–furanylCO

R

2

Si

O

-phenyl,R:-mesty-tolyl,

er Science 36 (2011) 455–567

defined architecture. The functional group in the ATRPinitiators can be an aldehyde, an amine, a hydroxyl, aphenyl, a nitro, or an acid. Unfortunately, to obtain analiphatic acid and an amine or an anhydride functions, it

Polymers

PMMA [35]

PMMA [36]

PMMA [37]

PSt [38]

PIP [39]

H

PSt [40], PDMA [40]

PSt [40], PDMA [40]

PSt [40], PDMA [40]

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

PSt [43], PMMA [43]

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


Table 2Functional initiators for ATRP.

Functionality Initiator Polymers

–OHCl

ClCl

HO PMMA [50]

–OHSOCl 2Cl

Cl

OH

PSt [51], PMMA [51,52]

–OH SO2ClHO PSt [51], PMMA [51]

–OHN

HOCl

PSt [53,54], PMMA [55]

–OH O

OHO

BrPSt [47,56–60], PMMA [47,56,58–62], PFOMA [63], PtBMA [64], PBA[65,66], PtBA [66], PMMA-b-PBA [67], POEGMA [68], PNaMA [69]

–OHBr

OOHO PSt [70]

–OH BrHOPMMA [71], PBA [71]

–OH BrBr

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

–OHPh

ClOHOO

PMMA [74]

–OHHO

OBrO

PSt [75]

–OHO

OBr

OO

NH

HO 4 PSt [76]

–OH Br

OO

OO

N

HO

HOPDMAEMA [77]

–OHCl

OHOO

PMMA [62]

–OHN N

ClHOPSt [78]

–OHN N

OHO

OBr

PMMA [78]

–OH NH

OBr

N

OHPTyMA [79]

–OH N NHN

CNNHNC

O

OOHHO PSt [49]

–COOH HOOC Cl PSt [80], PAM [81]

–COOHHOOC

Br PSt [80], PMMA [71,82], PBA [71]


Table 2 (Continued)


–COOH HOOCCl

PSt [38,75,80,83–85], PMMA [84,85]

–COOH SO2ClHOOC PSt [51], PMMA [51], PBMA [51]

–COOHHOOC O O Br

O PSt [80]

–COOHO

OBr

OHOOC PSt [76]

–COOHBr

HOOC PSt [80,86]

–COOH NN

OHO

NC OOH

CNPMMA [48], PSt [49]

–CHO OHC O

O Br PSt [75]

–CHOBr

OOOHC PSt [75,87], PMMA [87]

–CHOOHC

OCl PSt [88]

–OH and –CHOOHC

HOCl PSt [88]

–NH2 Br

OOH2N PSt [87], PMMA [87]

–NH2

Br

PhH2N Ph PSt [89]

–NH2 OOO

XY

Y2

O

Br

:(NOX,Y 2, (NHH), 2, H)(H,NH 2 (H,NO), 2)

PMMA [90]

–N(CH3)2 SO2Cl

NPMMA [51]

–N(CH3)2 N Br

OPtBA [91], PMMA [62]

–N(CH3)2 BrO

ON POEGMA [92,93], PMMA [62]

–N(CH3)2Br

ONH

NPGlMA [94]

–N(CH3)2

Br

PhN Ph PSt [95]

–N(CH3)2

N O

O Br PSt [75,96]


Table 2 (Continued)


–N(CH3)2 O BrO

NO

PHEMA [97], PHEMA-co-PGlMA [97], PHEMA-co-PHPMA [97]

–N(CH3)2Cl

ONO

PMMA [62]

–NO2SO2ClO2N PSt [98], PMMA [99]

–NO2 Br

OOO2N PSt [87], PMMA [87], PBA [100]

–N3 BrO

OON3 PDMAEMA [101–103]

–N3Br

OON3 n

2,3,4,6n: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],

–N3 NO

ClN3

N3PNIPAM [106]

–N3 NH

OClN3 PNIPAM [109,110]

–N3

OO

ONH

3ON3

O

Br

PSt [76]

–CNNC

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

–CN NC Br PSt [111], PMMA [111], PAN [112]

–CNNN

CN NCPSt [49]

–amide Br

ONH

R -CHR: 2(C6H5 or)-CH(CH3)COOCH3

PBMA [113], PbzMA [113], PSt [113], PDMAEMA [113], POEGMA [113]

–amideCl

NH

OPMMA [62]

–phthalic anhydride O

O

O

BrPSt [86]

–phthalimide ON

O

O

OBr PMMA [114]

–acetalO

O BrOO

PtBA [115]

–succinimide O BrN

O

O OPMMA [114], POEGMA [116], PMAIpGlc [117], PMAIpGpc [117],POEGMA-co-PHMA [118],


Table 2 (Continued)


–triazine

O

OBr

HNN

NN

Cl

H3CO PMMA [114]

–coumarineO

CH3

O OO

BrPSt [119], PMMA [120]

–coumarineO OO

O

Br

PMMA [120]

–alkyne O Br

OPSt [121–124], PMMA [57,124–126], PtBA [57,127], PbzMA[128], PDMAEMA [103]

–alkyneO

OBr

OO

NHPSt [76]

–alkyneBr

OOO

OPSt [129]

–alkyne O BrO

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

–benzoyl O

OBr

OPSt [134,135]

–benzoylO

O

Br

O

PMMA [136], PSt [137]

–benzophenone

O

O

OBr PSt [138], PMMA [138]

–naphthaleneSO2Cl

PMMA [51]

–fluorene

Br

PSt [139]

–carbazole NBr

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

–anthracene O Br

O

PMMA [141,142], PSt [143–146]

–pyrene

BrPSt [147–150], PBA [151], POEGMA [151], PNIPAM [152],PAM [153], PDMAPAA [153], PHEMA [154]

–fullerene

N

O BrO PSt [155]


Table 2 (Continued)


–trimethylsilyl NN

OO

NC

CNSi

11 PSt [156]

–imidazoliumBr

OO

NN +PF6

- PMMA [157]

–adamantyl OO

Br PDMAEMA [131]

–pyridineBr

OOS

SNPHEMA [158], PMAGA [159]

–bipyridine NN

XX

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

PSt [160], PMMA [161]

–amino acid

OBrN

HO

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

–nucleoside and –oligosaccharides XO

O

Br-nucleosideorX:

-oligosaccharidePSt [163,164], PMMA [163,164], POEGMA [164], PMAIpGlc[164], PDMAEMA [164]

–naphthyridine NN NH

NH

OOO

OBr3 PBA [128]

–ureido pyrimidinone NH

N NH

OO

BrNHO

O PbzMA [128], PBA [128]

–oligopeptideO

HN Br

NH

Ph

OPh

O

On

31,0,n:

PtBMA [165], PDEAEMA [165]

–biotinNH

NH

O

HHNH

S

OO

3

O

XR

2

-CH-ClR:-Br,X: 3 -H,

PMAGA [166], PtBA [167], PNIPAM [168–170], PtBA-b-PMA[167]

–azobenzene NC

S

S

O

OazobenzenePMMA [171]

–azobenzene OO

Brazobenzene PSt [172], PMMA [172–174]

–azobenzene SO2Clazobenzene PMMA [51]

–porphyrinO Br

O

porphyrinPSt [175]

–diphenyloxazolePh

Ph

N

O BrPMMA [132]


Table 2 (Continued)


–estroneBr

OO

O

HH

HPSt [176], PMMA [176]

–naphthopyran O BrO

OO

O

O

PBA [177]

–spirooxazineO

O

ClN

ON

PSt [178]

–benzothiazoleS

NHO

Br

PSt [179]

–halideBr

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

–halideSO2ClX

-Cl-F,X:PSt [98,180], PMMA [99,180]

–flouro F3CCl

ClCl

PSt [181]

–flouro BrO

OF

FF

n7,8=n

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

–flouro OF

FF

7O

O

Br6 PMEA [185], POEGMA [185], PMMA [183–185],

–flouro

C8F17H6H3CO

BrC8F17H6H3CO

PSt [186], PMMA [186]

–flouro

C8F17H6H3CO

OO

Br

X

C8F17H6H3CO

orHX: OCH3H6C8F17

PSt [186], PMMA [186]

Scheme 3. General mechanism for ATRP.


e synthe

icmigaggdt

uiifg

Scheme 4. General strategies for th

s necessary to protect such groups in order to circumventomplexation with the copper catalyst during the poly-erization. Ketal, acetal and phthalate functional ATRP

nitiator can be used in the polymerization as protectingroups for the following functional groups: diol, aldehyde,nd phthalic anhydride, respectively [187]. A trimethysilylroup and isobutyrate in initiator are efficient protectingroup of alkyne and maleimide functionalities with simpleeprotection steps. Table 3 gives some examples of pro-ected initiators used in ATRP.

Previously, Zhang and Matyjaszewski have reported the
se of protected and unprotected �-halocarboxylic acids as
nitiators for the ATRP of styrene [188]. The unprotectednitiator efficiency was quite low and was not effectiveor the ATRP of styrene. Protection of the carboxylic acidroup by a trimethylsilyl, tert-butyldimethylsilyl, or tert-

Scheme 5. Synthesis of hydroxy-telechelic PM

Scheme 6. Synthesis of hydroxy-telechelic PS

sis of telechelic polymers by ATRP.

butyl group led to high initiator efficiencies for the ATRPof styrene. Subsequent hydrolysis of the protecting groupscan provide well-defined PSt with terminal carboxylic acidgroups (Scheme 7). The advantages of these techniquesinclude quantitative functionality and the ability to pro-duce 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 reac-tion mechanism is mechanistically similar to ATRP withthe exception that the reaction conditions are modifiedin such a way that only one addition step occurs. Thismechanism can be subdivided into four sections accord-
MA by ATRP using functional initiator.

t by RATRP using functional initiator.


Table 3Protected initators for ATRP.

Functionality Initiators Polymers

–OH

OO Br

O

OPSt [189]

–OH OO

O

O

Br PBA [190]

–COOH O BrO

PSt [60,80,191], PMMA [60]

–COOH Br

OO

O

O

OO PMMA PSt [192], PNBDHMA [193], PMMA-co-PAMMA

[193]

–COOH O

CH3 BrOOC

CH3OOC

PSt [194,195]

–COOHO

O

BrPSt [195]

–COOH

OO

BrPSt [195]

–COOHO

O BrPSt [195]

–COOH

OO

BrPBA [196]

–CHOO

O BrOOO

POEGMA [197]

–NH2 Br

ONH

HN

Boc PSt [191], PMMA [198,199]

–NH2OO

HN

BocO

OO

4 Br PNIPAM [200], PHEMA [200], POEGMA [200]

–NH2OO

HN

BocO

OO

Cl4 PNIPAM [200], PHEMA [200], POEGMA [200]

–NH2 Br

OON

H

BocPBA [100], PSt [201], POEGMA [202]

–NH2N

O

O

O BrO

n

1,2=n

PSt [203]

–NH2N

O

O

O BrO

2PtBA [204]


Table 3 (Continued)


–NH2 OO

N

O

OO

BrPSt [205]

–NH2 BrN

O

OPSt [203]

–NH2

ONOH

OO

Br5

PMPC-b-PDMAEMA [206], PMPC-b-PDPAEMA [206]

–NH2

ONOH

O

O OH

OBr PHEMA [207]

–NH2O

NOH

OHN

O

Cl PSt [207]

–NH2

OO N

HNH

OO

3 OBr

OPSt [76]

–alkyne O Br

O

TMSPSt [80,189,208,209], PMMA [208,210,211], PHEMA [212],PtBA [189,210], PSt-co-PMI [213], PiBA [214]

–alkyne O Br

O

TIPSPSt [80,215], PMA [80,215], PtBA [80,215], PS-b-PtBA[80,215], PMA-b-PSt-b-PtBA [80,215]

–maleimide O BrO

N

O

O

OPMMA [143–146,216–218], PSt [219], POEGMA [202],PHMA [220], PtBA [144,145,218],PSMA-co-PPgMA-co-PTMS-co-PgMA [221], PMnsTzMA[221], PRhBMA [221],

–maleimide O BrO

N

O

OPSt [219]

–maleimide OO

BrN

O

O

OPSt [205]

–SH Br

OO

S

NO2O2NPMMA [222]

–SH O BrO

SSN nn: 1, 2

PMMA [223], PNHSMA [223], PNIPAM [224]

–SH O BrO

SSO

Br PSt [225], PEEA [226]

–SH O BrO

SSO

Br PMMA [227], PtBMA [227], PBMA [227]


Table 3 (Continued)


–sugar

O

OO

O

O

OO

Br

POEGMA [228], PbzMA [228]

OO

OO

–sugarO O

OBr

ing to the molecules used for end-group functionalization(Scheme 8):

a) Functional monomers, that is, monomers includingdesired functionality such as allyl alcohol, ethene, C60fullerene, and maleic anhydride, which is unable toundergo homopolymerization under the polymeriza-tion conditions. They are mainly added one unit withoutfurther propagation.

b) Functional addition-fragmentation transfer agents(AFTs). AFTs lose a radical fragment after addition to thepolymer radical, producing an irreversibly terminatedpolymer chain and a small radical. This radical could
be terminated by the deactivating copper (II) speciespresent in the reactive system during a classical ATRAexperiment to give a stable product.
c) Functional stable radicals, such as nitroxides, that canbe added to the polymerization medium to terminate

Scheme 7. Synthesis of hydroxyl telechelic polymers by ATRP u

Scheme 8. End-group modification of polystyrenes by ATRA/C with a functional mradical (c), or by ATRC process (d).

POEGMA [228], PbzMA [228]

all produced polymer radicals as well as introducedefined end groups. For styrenes and acrylates, the pro-cess mainly takes places through combination. When amethacrylate is used, trapping via disproportionation iscompetitive with coupling with nitroxides. The combi-nation is the main process at low temperatures. On theother hand, disproportionation via hydrogen abstrac-tion from an �-hydrogen atom of the polymeric radicalleads to introduce vinyl end groups at high tempera-tures. Also, tetraphenylethane derivatives can be usedas a stable radical to trap polymeric radicals.

d) Termination by combination of radicals (atom transferradical coupling (ATRC)). When the polymers termi-
nated by combination, telechelic polymers can beprepared with increasing radical concentration that inthe absence of monomer to increase the probability oftermination events. Thus, utilizing a functional ATRPinitiator to produce the polymer and coupling of the
sing protected and unprotected �-halocarboxylic acids.

onomer (a), or a functional chain transfer agent (b), or a functional stable

n Polym

foaps

2

tTbpofa

mf(wTtc

tfiathhdh

toe


halogen chain ends is an alternate pathway to telechelicpolymer. If the main termination reaction consists ofdisproportionation, this scheme cannot be followed,and small amount of second monomer such as styreneshould be added to promote the combination mecha-nism by reacting with two polymer radicals. The methodwas firstly applied by Fukuda and co-workers [229]The technical term ‘atom transfer radical coupling’ wasestablished by Yagci who was the first to recognize thesynthetic potential of ATRC for the preparation of �,�-telechelic polystyrene containing variety of functionalgroups at both ends, including alcohols, carboxylic acidsand aldehydes [75]. Other groups also reported thesuccessful syntheses of telechelics with various func-tional groups by ATRC including phenol [75], aniline[75], aldehyde [75,230], hydroxyl [49,231,232], car-boxylic acid [49,75,233], ester [234–236], phthalimide[205], dimethylfulvene-protected maleimide [219], N-Boc [201], and trimethylsilyl [233,237] groups [238].Moreover, Matyjaszewski et al. performed the success-ful ATRC of hydroxy-terminated poly(methyl acrylate)sby introducing small amounts of styrene to provide effi-cient coupling [231].

Combination of ATRP and ATRA/C strategy could be use-ul in designing the reactive groups at one or both endsf the polymer chains by polymerizing styrenes, acrylatesnd methacrylates from a functional initiator and then cou-ling. Telechelic polymers prepared by these reactions areummarized in Table 4.

.2.4. PostmodificationObviously, polymer chain prepared by ATRP always con-

ains terminal halogen due to the fast deactivation process.herefore, �-mono- and �-, �-telechelics can be preparedy transformation of the halide end group by means of post-olymerization reactions such as nucleophilic substitutionr electrophilic addition of catalyzed by Lewis acids. Dif-erent compounds including sodium azide, n-butylamine,nd n-butylphosphine have been tested.

A representative example is the successive transfor-ation of a halogen into an azide and then to an amine

unctionality to afford �, �-amino functional polystyreneScheme 9). Quantitative conversion of the end groupsas observed in each transformation reaction [259–261].

he resulting polymer was further reacted with tereph-haloyl chloride in a polycondensation process to yieldhain extended polystyrenes with internal amide linkages.

The halide displacement reaction is particularly impor-ant in the preparation of �,�-hydroxy telechelics, whichnd application in the preparation of segmented polyesternd polyurethanes [190,241,262,263]. In such applicationshe first hydroxyl group can be incorporated by usingydroxy-functional initiator derivatives [56]. The secondydroxyl group functionalization can then be achieved byirect displacement of halogen group with an amino alco-
ol or utilizing allyl alcohol (Scheme 10).
Recently, Hilborn and co-workers reported a versa-ile method for the transformation of terminal halidef polystyrene into thiol [264]. Well-defined bromond-functional polystyrene was prepared by ATRP and con-

er Science 36 (2011) 455–567 471

verted into thiol end-groups by reaction with thioureafollowed by treatment with NaOH (Scheme 11). Table 5reviews some of the postmodification reactions.

2.2.5. MacromonomerAmong the controlled radical polymerization tech-

niques, perhaps ATRP has received remarkable attentionwith regard to macromonomer synthesis (Scheme 12).ATRP has been utilized for the synthesis of a number ofmacromonomers containing pyrrole, thiophene, lactone,vinyl ester, epoxy, vinyl ether, allyl, and norbornene, poly-merizable end groups by means of which each of thesegroups exhibits a low susceptibility to polymerizationunder ATRP conditions (Table 6).

Incorporation of unsaturated end groups to polymersby ATRP is limited to certain groups. In order to producepolymers with a more reactive unsaturated end groupssuch as methacrylates, a combined ATRP and catalytic chaintransfer (CCT) process was proposed [335]. In this method-ology, the CCT agent was added to the ATRP of MMA nearto the end of polymerization, leading to the formation of�-unsaturated PMMA macromonomer with low polydis-persity and controlled molecular weight (Scheme 13).

Here, the CCT agent acts as a chain transfer terminatorbut does not initiate new chain in the classical manner.Similarly, Haddleton and co-workers used methyl(2-bromomethyl) acrylate in transition-metal-mediated con-trolled radical polymerization to replace the �-halogen endgroup via addition-fragmentation to yield a methacrylate-based macromonomer [250].

More recently, a convenient, one-pot synthesis oftelechelic polymers with unsaturated end groupswas developed [251]. Addition of excess ethyl(2-bromomethyl)acrylate to ATRP of acrylate monomersafter 80–90% conversion resulted in the formation ofmono-and bifunctional polymers (Scheme 14). The aver-age degree of end functionality was almost quantitative(f = 1 for a monofunctional and f = 2 for a bifunctionalinitiator).

2.3. Nitroxide mediated radical polymerization (NMRP)

Another C/LRP method developed in recent years isNMRP, also called SFRP by some authors [19,336]. This typepolymerization can be realized through reversible deacti-vation of propagating chain end by relatively stable rad-ical nitroxides such as 2,2,6,6-tetramethylpiperidinyloxy(TEMPO) (Scheme 15).

2.3.1. Functional nitroxidesIt is possible to prepare telechelic polymers by NMRP

procedure since it tolerates a wide variety of functionalgroups [19]. The presence of the terminal nitroxide speciesin the final products has introduced several strategies forsynthesizing telechelic polymers. The simplest methodis incorporation of desired functionality onto initiator or
nitroxide molecules. For the synthesis of �,�-telechelicpolymers may be reached either through a unimolecularor bimolecular process. The unimolecular procedure forthe synthesis of telechelic polymers relies on the use ofactive species carrying both the desired functional groups


Table 4Summary of telechelic polymers obtained by ATRA/C reactions.

Functionality Polymers

a HO PMMA [56,74,190,239–242], PMA [56,74,190,239–242], PBA[56,74,190,239–242], PEO-b-PEA [56,74,190,239–242]

a HO PMMA [243]

aO

PMA [239]

a PMMA [234]

a ONH

O

PMMA [74]

a PMMA [234]

a

OO PMMA [234]

a PMMA [244–246], PSt [244–246]

a OO O PMMA [234], PSt [247]

bOSi

X-Cl,-F,X:

-OSi(CH3)3PMMA [234,240,248,249], PBA [234,240,248,249]

bO

SiO

Si PMMA [249]

bO

BrOPMMA [250], PSt [251], PBA [251], PMA [251]

b PSt [252]

c N OX -COOH,-OH,X:-NH2 -OCH, 2C≡≡≡≡CH

PSt [240,253–255], PMMA [234], PBA [240,253,254],

c SSS

SPMMA [256], PDMAEMA [256]

c CC

Ph

OSi(CH3)3Ph

(H3C)3SiO

Ph

PhPSt [257]

dX Br

ATRCX X

-OH,-N(CH-COOH,-CHO,X: 3)2, -CH2COOH,-Si(CH 3)3PSt [75,233,237]

d

ATRCBr

OO

XO

OX O

OX

X: -(CH2)3Si(CH3)3, -CH3, -(CH2)2OH,-(CH2)3NHBoc

PSt [201,231–233,258], PMA [235], PMMA [231,232], PBA[235], PtBA [235], PFABu [236]

dATRC

BrN

O

O

N

O

O

N

O

OPSt [205]

dATRCBrN

O

O

N

O

O

N

O

OPSt [219]


Table 4 (Continued)


d

ATRCX XX Br

X: -CN, -COOH, -OH PSt [49]

d ATRCBr

OO Br+

OO PMMA [234]

d

ATRC+ CHOO

O

Br CHOO

O

BrPSt [230]

tion of h

abii(

e(frtds

Scheme 9. Successive postfunctionaliza

nd a nitroxide unit. The alternative bimolecular process isased on a combination of functional nitroxide and radical

nitiators. Functional groups can be placed at the initiat-ng chain end, F1, or the nitroxide mediated chain end, F2

Scheme 16).Telechelics with a variety of functional groups can

ssentially be prepared by using functional nitroxidesTable 7). For example, nitroxides carrying many use-
ul reactive groups such as –OH, –COOH groups wereeadily used for the creation of controlled molecular archi-ectures by NMRP. A recent study has shown that highegree of functionalization, i.e., greater than 95%, is pos-ible even at molecular weights up to 50,000–75,000 by
Scheme 10. Synthesis of �-�-hydroxy telechelics by combinatio

Scheme 11. Synthesis of thiol end-functionalized polys

Scheme 12. Synthesis of �-caprolactone func

alogen end-functionalized polystyrene.

NMRP method [337]. This elegant method provides highlevel of functionalization without using postpolymeriza-tion strategies.Functional groups such as primary aminesor alkynes, which react with radicals during the poly-merization, may interfere with NMRP process and requirechemical protection prior to polymerization (Scheme 17)[21].

2.3.2. PostmodificationA wide variety of functional groups including polynu-

clear aromatic groups such as pyrene can also beintroduced by taking advantage of monoadditioin of maleicanhydrides and maleimide derivatives to N-alkoxyamine

n of functional initiator and postmodification strategies.

tyrene by ATRP and postmodification reaction.

tionalized macromonomer by ATRP.


Table 5Summary of telechelic polymers obtained by postmodification reactions.

Functionality Reactions Polymers

–OH Et3NOHBr

NH2(CH2)nOH

(n: 2, 4)PSt [56,261], PMA [56,261]

–OH OHBrSH(CH2)nOH

PBA [240]

–OHNH2(CH2)5OH

25 oCHO OHHO Br PMMA-b-PBA [67]

–COOHHOOC Br

tBuONa

COOHHOOC COOH

i)

ii) PSt [38]

–COOH HO Bri) Et3N, DMF

HOOC Br

OO O

ii) %10 aq HCl

POEGMA [68]

–COOH HO BrEt3N

OCl

4-methoxyphenol

HOOC Br PBA [65]

–COOC2H5 HOOC BrKOH

OC2H5

OC2H5O

OOC2H5

OC2H5O

O

HOOCPSt [38]

–CHOBr

Br

BrOHC

B(OH)2

Pd(PPh3)4,Na2CO3 aq./THF

Br

OHC

OHC

2

PSt [265,266]

–N3

NaN3

DMFN3Br PSt

[70,121,122,130,137,146,189,215,259,267–275],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]

–N3

Me3SiN3

TBAFN3Br PSt [208,282–284], PBA [260], PMMA [260],

PiBA [133]

–N3

NaN3

DMSON3 N3Br Br PSt [68,121,189,274,285], PtBA [126,286],

PSMA-b-PPO-b-PSMA [287,288]

–N3N3 N3Br Br

Me3SiN3

TBAFPSt [208]

–NH2Br

N-K+

O

ONH2N

O

O

KOH

tBuOH,reflux

DMF,reflux

PSt [203], PtBA [289]

–NH2

i. Ph3P

ii.H2O

Me3SiN3

TBAFN3Br

NaN3

DMFN3Br

NH2 PBA [260], PMMA [260]

–NH2NH2

LiAlH4

Et2O

NaN3

DMFN3Br PSt [283]


Table 5 (Continued)

Functionality Reactions Polymers

NH2NH4HCO2, Pd/C

DMF

NaN3

DMFN3Br PSt [290]

–NH2

Br

Br

BrH2N

B(OH)21/2 H2SO4,

Pd(PPh3)4,NaHCO3 aq./THF

Br

H2N

H2N

2PSt [265,291–293]

–NH2 Br Brii) TFA (20%, v/v)/ CHCl3, r.t

i) N-Boc-1, TEA/THF, r.t.4-diaminobutane H2N NH2 PAEL [294]

–SH BrH2N

SNH2

DMF

NaOHSH

PSt [38,264,295]

–SH SBr SHS BrBu3P / H2O

Oxidation2 PMMA [227], PbzMA [227], PtBMA [227]

–cyclopentadiene

NiCp2/NaI/PBu3

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

–cyclopentadieneNaCp

THF, r.t.Br PSt [297,298]

–acrylate or –methacrylate BrR

OOH

OO

R+ DBUH

DBU,EtOAc

PBA [299,300]

–allyl Br

SnBu3

BenzenePMA [301,302]

–BBr2

BBr3Si Br BrB PSt [237]

–phosphonium

Ph3PBrR PhR 3 BrP

R : -H, -CH3, -(C6H5), -C4H9, PMA [303], PSt [303]

–OH and –OH, –NH2, –piperidineO

ONu

O

HO

Nucleophile

NaOH,alcohol,piperidine,butylNu:N,N-dimethyl-1,3-propanediamine

PSt [304]

–benzodioxinoneBr

K2CO3 60, oCacetone,

O

OO

O

PhPh

HO OO

O

PhPh PSt [305]

–dithiocarbamate BrBrr.t.DMF,48h,

NO

SS

NO

SS

NO

S- Na+

S PSt [306]


Table 6Macromonomers prepared by ATRP.


–oxazoline

Br

O

OO

NPSt [86]

–thiophene NH

ClO

Cl

ClO

OS PMMA [307,308]

–pyrrole N O Br

OPSt [308,309], PMMA [309], PtBA [309], PDMAEMA [309],POEGMA [309], PBA [309], PMEEMA [309]

–caprolactone O Br

OOO

PMMA [310]

–caprolactone OO

BrPSt [304]

–butyrolactone O

OBr PSt [60], PMMA [60]

–vinyl acetate OBr

OPSt [60,311], PMMA [60,311]

–vinyl acetate O N O Br

OO

BrPNaVBz [312], POEGMA [92,93]

–epoxy O BrO

OPSt [60,91], PMMA [60,91]

–epoxy OBr

O

O PSt [313]

–vinyloxyCl

Cl

ONH

ClO PMMA [314], PDAEMA [314]

–vinyloxyO

O BrO PSt [314,315], PMMA [314,315], PDAEMA [314,315]

–oxazoline Br

O

N PSt [316]

–oxazolineO

N Br PSt [316]

–oxazoline OO

BrO

NPSt [316]

–allylO

O BrPSt [273,315], PMMA [273,315], PDMAEMA [317]

–allyl Br PSt [284,318], PMMA [318]

–allylO

O Br9PSt [273], PMMA [273]


Table 6 (Continued)


–norborneneO

O BrO PSt [319], PMMA [319], PtBA [319], PtBMA [319], PMA[319]

–norbornene NH

OBr

PMMA [320]

–acetylene O Br

OPSt [321–323], PMMA [321–323]

–halideBr

Br

BrPSt [265,266,292,293,324–327]

–halide

Br

BrBr

Br PSt [265,292,293,327–331]

–halideBBO

O

O

O

BrPSt [332]

OO

Br

eitr

–halide BBO O

Br

nd group followed by elimination of mediating nitrox-de radical (Scheme 18) [401]. The thermal stability of theelechelics was increased as the alkoxyamine group wasemoved.

Scheme 13. Synthesis of �-methacrylate end-functio

Scheme 14. Synthesis of �-,�-methacrylate end-functi

Scheme 15. General schem

PSt [333,334]

Another postmodification methodology of chain endfunctionalization relies on the stability of N-alkoxyamineradicals. In this methodology, the precursor polymer pre-pared with any N-alkoxyamine initiator can be exchanged

nalized polymers by ATRP and CCT processes.

onalized polymers by ATRP and CCT processes.

e for NMRP process.


Table 7Some functional unimolecular and bimolecular nitroxides for NMRP.

Functionality Nitroxide structure Polymers

–OH ONHO PSt [338–342], PBA [342]

–OH ON

HO

HO

PSt [343], PBA [343]

–OH

Ph

N O

OHHO

HO

PSt [344,345], PBA [344], PIP [344], PDMA [344]

–OH NO

OO

O

O

HO PSt [346]

–OH N OHO PSt [347], PBA [348]

–OHONHO

PSt [347,349], PBA [348]

–OHONHO

PSt [349]

–OH NO

HO

PSt [350,351], PSt-co-PMMA [352,353], PSt-co-PBA[352,353]

–OH NO

HO

OH PSt [338,352]

–OH NOHO

PSt [354]

–OH NO

NH

P(O)(OEt)2O

HOPSt [355], PBA [356]

–OHNO

OHO

PSt [357], PtBA [357]

–OH N O

HO

PSt [342,345,358], PBA [342,358]

–OH N O(EtO)2(O)P

HO

PSt [345]


Table 7 (Continued)


–OHNOHO

PSt [359], PNIPAM [359], PDMA [359]

–OHON

HOPSt [360]

–OH NONNH

HO +2

OPSt-co-PVK [361]

–COOH NOHOOC

PSt [362,363]

–COOHHOOC

ON PSt [364]

–COOHNO

HOOCCOOH PSSS [365]

–COOHONO

OHOOC

PSt [360], PtBA [360]

–COOHNOHOOC

P(O)(OEt)2PSt [366–369], 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 [376–378], 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]

–COOH NONHOCN

+2

OPSt-co-PAN [383]

–COOH and –OHNOHO

COOH PSt [365]

–protected –COOH and–OH

O OOO O

N N PSt [354]

–protected OH ON

OSi

OSi

PSt [343,384], PBA [343]

–protected OH ON

OSi

PSt [342,358], PBA [342,358]


Table 7 (Continued)


–protected NH2NOBocHN

PSt [357], PtBA [357]

–protected NH2

NO

NH

O

Boc

PSt [357], PtBA [357]

–protected NH2NOO

NBoc

PSt [385]

–protected NH2NO

BocHN

OPSt [359]

–protected NH2

NO

OBocHN

PhPh

OHPSt [359]

–protected NH2

NOO

BocHN

PSt [351]

–halideNOCl

PSt [357,359,386–388], PtBA [357], PNIPAM [389], PBA[389]

–halide NO

Cl

PSt [390]

–halide NOBr

PSt [362,363]

–N3NON3

PSt [357], PtBA [357], PBA [389], PNIPAM [389]

–protected alkyneNO

Si PSt [357]

–quaternized ammonium ONN PSSS [391]

–quaternized ammonium N ON

PSSS [391]

–sulfonate N O+Na -O3S

PSSS [391]


Table 7 (Continued)


–trifluoromethylN O

F3C PSt [342], PBA [342]

–pyrene

3N O

OO

PSt [337], PtBA [337]

–pyreneNO

O4

PSt [337], PtBA [337]

–pyrene 3O

O

O NPSt-co-PMMA [352,353], PSt-co-PBA [352,353]

–pyrene NONOCN

+2

OPSt [392]

–fluorene NO PSt [393]

–naphthalene N OO

O

PSt [346]

–dansyl NONH

SO

ON(CH3)2

PSt [337], PtBA [337]

–perylene diimideNO

perylene diimide

PSt [394,395], PBA [394,395], PIP [394,395], PB [394,395]

–terpyridineterpyridine

NO

OPSt [396,397]

–terpyridine and –ureidopyrimidinone R1:terpyridine,

R2:ureidopyrimidinone

NOR1O

OHN

O

R26 PSt [398]

–barbituric acid

NO

RR:1,2-dihydroxyalkyl

orbarbituricacid

PBA [389], PNIPAM [389]

–uracil NONH

HNO

OPSt [399], PBA [399]


Table 7 (Continued)


–uracil NOP(O)(OEt)2

NH

HNO

O PSt [399], PBA [399]

–succinimideNO

P(O)(OEt)2

OON

O

OPSt [376], PBA [376]

–oxazoline NON +2

O

N

by addition of a large excess of functional nitroxides underheating. At this temperature the equilibrium between non-functional nitroxide and the polymer chain is establishedand the exchange of nonfunctional nitroxide with the func-tional nitroxide can lead to the desired end functionalizedpolymer. Turro et al. have elegantly taken advantage of thisnitroxide mediated free radical procedures to develop astrategy for the facile preparation photoactive telechelicpolymers (Scheme 19) [346]. This strategy presents anumber of advantages, reactive functional groups can beintroduced under mild conditions and from the sameprecursor polymer a variety of functional group can beincorporated [402].

Schubert et al. used the terpyridine-nitroxide initia-tor to synthesize semitelechelic terpyridine polystyrene.With the chain end functionalization methodology of themaleimide unit, they were able to synthesize telechelicterpyridine polystyrene. They utilized a terpyridine-functionalized maleimide that replaced the nitroxidechain end of semitelechelic polystyrene (Scheme 20).The telechelic polymers would be significant value toprepare ABA metallo-supramolecular triblock copolymers[396,397].

Hemery and co-workers described synthesis of heterot-elechelic polystyrene containing �-hydroxy-�-carboxylicacid end groups and their intramolecular cyclization(Scheme 21) [403]. The nitroxide mediated radical poly-merization of styrene was carried out using 4,4-azobis(4-

Scheme 16. General strategies for the synthe

PSt [400]

cyanovaleric acid) as the initiator with 4-hydroxy-TEMPOas the mediator to prepare heterotelechelic polystyrene[383]. The intramolecular cyclization was performed byesterification reaction. Although the cyclization efficiencywas greatly reduced in the case of high molecular weightpolymers due to the formation of various polycondensateby-products, the yield of cyclization was close to 95% forthe low molecular weight polymers.

Another method involves the combination of NMRPand reduction processes. In the first step, the polymeriza-tion of styrene in the presence of a hydroxyl-functionalalkoxyamine yielded �-hydroxy functional polystyrenewith an alkoxyamine group in the � position [404,405]. Bythe same strategy, �-hydroxy, �-carboxylic acid telechelicpolymer can also be prepared [366]. In the second post-polymerization step, the reduction of the alkoxyaminegroup into an alcohol using an acetic acid/zinc mixture,allows in principle the preparation of well-defined �,�-telechelic polystyrene (Scheme 22).

In a similar way, Hawker and Hedrick syn-thesized �-amino,�-aminoxyl polystyrene usingtert-butyloxycarbonyl protected azo initiator. The tert-butyloxycarbonyl protected group was replaced by an
amino group with trifluoroacetic acid (Scheme 23) [351].
Recently, telechelic nucleobase functional polymershave gathered attention due to the thermally reversiblehydrogen bonding associations that play a part in the inter-esting rheological and mechanical properties they impart

sizing telechelic polymers by NMRP.


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.


Scheme 23. Synthesis of �-amino telechelic polymers by NMRP using protected initiator.

of urac
Scheme 24. Hydrogen bonding network
when combined with polymers. Long and co-workersdeveloped uracil functional alkoxyamines to afford mul-tiple hydrogen bonding at the polymer chain ends of thepolymer chains (Scheme 24) [399]. Such functionalizationleads to increase in Tg and melt viscosity of polymers.

2.4. Reversible addition-fragmentation chain transferpolymerization (RAFT)

Reversible addition-fragmentation chain transfer(RAFT) polymerization is one of the most recent entrantsand one of the most efficient methods in C/LRP techniques[20,406–409]. A major advantage of the RAFT process overother controlled radical polymerization techniques is itstolerance of protic and other functionalities that can beincorporated into the chain transfer agent [407,410–412].In this technique, after the initiation, the RAFT agentsreversibly deactivate the polymer chains as the rate con-stant of chain transfer is faster than the rate constant ofpropagation (Scheme 25).

2.4.1. Functional chain transfer agentIn the RAFT polymerization, the functional group

present on the chain transfer agent (CTA) is retained atthe end of the polymerization. This enables the incorpo-ration a wide range of functional end-groups such as –OH,–COOH, –NR2, –CONR2, –SCO3Na, etc. �-Functional groupscan be introduced via the R group while the Z group of the

il functionalized PSt prepared by NMRP.

CTA contribute to the incorporation of �-functional groups(Scheme 26). A number of RAFT agents that could be usedfor the synthesis of novel �- and/or �-telechelic polymersare available (see Table 8).

For example, Scheme 27 shows how Lai et al. [413] andLui et al. [414] used appropriate trithiocarbonate transferagents and conventional free radical initiator (2,2′azobis(isobutyronitrile)) to prepare polymers capped with func-tional groups (carboxylic, hydroxyl, etc.).

1,3-Dipolar cycloaddition reaction between an azideand an alkyne has received a great deal of attention dueto its high specificity and nearly quantitative yields inthe presence of many functional groups [415]. Therefore,the use of simple RAFT process to directly generate poly-mers that bear either azide or alkyne units has gainedconsiderable importance (Scheme 28) [416]. Various func-tional RAFT agents that have been successfully utilizedin this context are listed in Table 8. Recently, a uniquefunctionalization strategy that relies on hetero-Diels-Alderreactions of dienes with terminal thiocarbonylthio groupson RAFT polymers was introduced by Barner-Kowollik andco-workers [297,298,417–420]. RAFT agents with electron-withdrawing Z groups such as, diethoxyphosphoryl, benzyl
pyridinyl and sulfonyl dithioformates result in polymerscapable of highly efficient hetero-Diels-Alder cycloadditionreactions [421–427].
At the present time, primary and secondary amine end-functionalized polymers are not directly accessible through


Table 8Functional RAFT agents for the synthesis of telechelic polymers.

Functionality RAFT agent Polymers

–OH SC

S

S

OO

OO

OHHO PNIPAM [429], PMA [414], PSt [414]

–OHN

S

S

OO

NS

S

OO

OHHOPMMA-co-PEA-co-PAA [430], PEA-co-PSt [430], PBA-co-PAA-co-PSt[430]

–OH CS

SNC

HO PMMA [20,431,432], PSt [419]

–OH CS

SHN

OHO PMMA [432]

–OH SC

S

S

HO PSt [433,434]

–OHC

S

SCNH

NO

HO

HO

PSt [435]

–OH SC

S

SCN

OOO

HO PHPMAM [436]

–COOHS

CS

S

HOOC COOH 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 [442,444–447], PGAMA [448], PLAMA [448], PSt-co-PAzPMA[449], POEGMA-co-PDDMAA [450], POEGMA-co-PDDMA [450]

–COOHS

CS

S

HOOC COOHPtBA [451], PDEHEA [451], PMA [452], PBA [452], PDA [452]

–COOHS

CS

S

HOOC C12H25 PSt [413,453–455], PMMA [433,456], PEA [413], PHEA [413], PtBAm[413,457], PAA [413,454],PHFDA [458], PBA [413,431,439], PNIPAAM[457,459–465], 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]

–COOHS

CS

S

HOOCPAAL [477,478], PDMA [477,479]

–COOH CH3S

CS

S

HOOCPSt [480], PBA [481]

C4H9S

CS

SNC

HOOCPMMA [280]

–COOH C4H9S

CS

S

HOOCPAA [453,482–484], PBA [453], PAA-b-PBA [482–484], PAA-b-PSt[482–484]


Table 8 (Continued)


–COOH C12H25S

CS

S

HOOCPAA [485], PBA [486], PSt [453]

–COOH C12H25S

CS

S

HOOCPMMA [280]

–COOH C12H25S

CS

SNC

HOOCPMMA [280,409], PNVPh [487], PMAA-co-PChMA [488]

–COOHS

CS

SNC

HOOCPNIPAM [489], PDMAEMA [489,490], PDMAEMA-b-PPAA-co-PBMA[489,490]

–COOH NC

S

SNC

HOOC PVAGP [491]

–COOH SC

S

S

HOOC PSt [433,492–495], 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]

–COOHS

CS

S

HOOC COOH PSt [438], PBA [439]

–COOHS

CS

S

HOOC COOHPSt [438], PBA [439], PAm [505,506]

–COOHS

CS

S

HOOC COOHPSt [438], PBA [439]

–COOHS

CS

S

COOHHOOC PSt [438,445]

–COOHO

CS

S

HOOC O S4

S

COOHPVAc [507]

–COOH OC

S

SHOOC

CH3

OPVAc [508]

–COOHO

CS

S

HOOCPVAc [507,509], PNVP [509]

–COOH CS

S

HOOCPNAM [510]

–COOH CS

S

HOOCPNAM [510], PAA [453]

–COOHHOOC

SS

PMMA [511,512], PSt [513,514], PMAA [515], PMAA-b-PSt [515]


Table 8 (Continued)


–COOH SHOOCS

PSt [514,516], PMMA [516,517], PBA [515], PMAA [518], PNIPAM [518],PAm [517,519]

PDEAM [517], PDMAM [517]

–COOH HOOC SS

PAA [520]

–COOH SHOOCS

PSt [514]

–COOH CS

SNC

HOOCPSt [521–523], PDMAEMA [20,524], PDPAEMA [525], PMAMGlc[526–530], PGalEMA [530], POEGMA [531–534], 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 [493,545–547], PNIPAM [493,548,549], PMA [548], PMAA[550,551], PEILPMA [550], PMILEMA [550], PEILEMA [550], PBMA[552], PAMA [553–555],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]

–COOH SC

S

S

HOOC OO

PO

OO

PSt [568], PNIPAM [568], POEGA [568]

–COOHS

CS

S

OHOOC PEGO PINAM [569], POEGA [569]

–COOHO

CS

SHOOC

HOOCPAA [453]

PBA-co-PAA [570]

–COOHO

CS

S

HOOCPDADMAC [503]

–COOH NC

S

S

HOOC PNVCL [571]

–CHO SC

S

S

C12H25OO3

OO

OHC

PSt [572], PMMA [572], PIP [572]

–NH2 SC

S

S

C12H25OO

O6H2N

PSt [572]

–N3 SC

S

S

C12H25OO

N33

PSt [416], PDMA [416], PNIPAM [573], PBA [574], PNIPAM [574],POEGA [574]

–N3C

S

SNC

OO

N33

PSt [416,575,576], PNIPAM [577], PDMA [416,577]


Table 8 (Continued)


–N3 SC

S

S

O3O

ON3 S

O

SN

PNIPAM [578,579], PSt [578], POEGA [578], PMMA [578], PHPMAM[578], PDMA [579]

–N3 OC

S

S

OO

N33

PSt [575], PVAc [575,580]

–N3 SC

S

S

OO

ON3 PNIPAM [581]

–N3C

S

SNC

OO

N3PSt [582]

–N3 OC

S

S

ON3

PVAc [583]

–N3 SC

S

S

OO

N3PDMA [584], PNIPAM [584]

–N3 SC

O

S

N3 [585] PVAc

–N3 SC

S

S

OO

N3PNIPAM [586]

–alkyne CS

SNC

OO

TMSPSt [575], PMAMMns [587]

–alkyne SC

S

S

C12H25OO

PAM [123], PMMA [124], PSt [124]

–alkyne CS

S

OO

PTHPA [357], PTHPA-b-PSt [357]

–alkyne CS

S

OO

PSt [588], PSt-b-PMAH [588]

–alkyne CS

SCN

O

OPOEGA [589], POEGA-b-PAPTS-co-PPBA [589]

–alkyne SSS

OO PSt [590]


Table 8 (Continued)


–alkyne CS

S

OO

S OO

PVNP [591,592]

–pentafluoro phenylC

S

SNC

OOF

FF

FF

POEGMA [593–596], PLMA [593,596], PMMA [593,597], PDEGMA[593,598,599], PNIPMA [593]

–pentafluoro phenylC

S

S

CNF

FF

FF

PMMA [600]

–pentafluoro phenylO

CS

SFF

F

FF

PSt [601], PODA [602], PtBA-co-PVAc [603], PODA-co-PAN [602],PODA-b-PNVP [602]

–pyridylS

SN PSt [298], PiBA [298,419]

–pyridyl SC

S

S

OSO

SN

PBA [604,605], POEGA [604,605]

–pyridylS

CS

PEG

S

OSO

SN PNIPAM [569,606], PHEA [606], POEGA [569]

–pyridyl SC

S

S

OSS

N

OPOEGA [607]

–pyridyl SC

S

OSS

N

2O

POEGA [608,609], POEGA-b-PSt-b-POEGA [609]

–pyridyl CS

S

NPSt [417,421,422]

–phosphonylO P

SS

O

OPSt [298,417,418,421], PiBA [297]

–thiazolidine-2-thione CS

SNC

NO

S

SPHPMAM [564,610]

–thiazolidine-2-thione SC

S

S

ONC

OO 2

ON

4S

SPHPMAM [436]

–tetrathiafulvalene SC

S

S

OO

S

S

S

S PSt [611], PBA [611], PNIPAM [611]


Table 8 (Continued)


–tertiary amine CS

SX

NO

X:-phenylX: -CH3, -H

PSt [612], PMA [612], PDMA [612], PDMA [613,614]

–tertiary amine CS

S

N PMA [584], PSt [584]

–protected amine SC

S

SHN

OO

OO

NH

Boc2

PNIPAM [615]

–succinimideC

S

SCN

ON

O

O

O

PNSVB [616]

–phthalimido SC

S

S

N

O

O

PSt [428], PBA [617], PNIPAM [617], PAA-co-PChPA [618], PAA-co-PPgA[618]

–phthalimido SC

S

S

N

O

O2

PSt [409,428], PBA [617], PNIPAM [617]

–phthalimido N

O

O

SC

S

S

N

O

O

PSt [428], PBA [617], PNIPAM [617]

–phthalimido OC

S

S

N

O

O

PNVP [617,619], PVAc [617]

–phthalimidoC12H25S

CS

S

N

O

O

PSt [433], PtBA [433]

–maleimide SC

S

S

N

O

O OO

OPOEGA [620,621]

–naphthalene SC

S

S

PSt [622,623]

–anthraceneC

S

S

PSt [624], PMA [624]

–anthracene CS

SNC

OO

PAcN [625]


Table 8 (Continued)


–anthracene SC

S

S

PSt [622]

–pyreneC

S

S

PSt [626]

–coumarin

CS

S

NOO

CN

PAcN [627]

–benzodioxoleC

S

S

O

O O

O PSt [628]

–terpyridine

CS

S

N

N

N PSt [629], PNIPAM [629]

–terpyridine

S

N

N

N

S

2

PSt [630], PBA [630]

–allylS

CS

SPSt [631], PtBA [631], PtBA-b-PSt [631], PSt-b-PtBA [631]

–allyl CS

SNC

OO

8PSt [632], PMMA [632], PMA [632]

–norbornene CS

SNC

OO

PSt [632], PMMA [632], PMA [632]

–cinnamate CS

SNC

OO

OO

PSt [632], PMMA [632], PMA [632]

–epoxy C12H25S

CS

S

OO

O PSt [633], PBA [633], PLA [633], PEHA [633], PBMA [633]

–oxetane C12H25S

CS

S

OO

OPSt [633], PBA [633], PLA [633], PEHA [633], PBMA [633]


Table 8 (Continued)


–pincer ligand C12H25S

CS

S

OO

S

S PMA [634], PMA-b-PtBA [634]

–disulfide SC

S

S

C12H25OO

SSO

PEGO

PSt [635]

–boronic acid SC

S

S

C12H25OO

(HO)2B PSt [636], PDMA [636], PNIPAM [636]

–trimethoxysilylS

CS

S

O(H3CO)3SiO

PSt [637], PMMA [637], PMA [637], PBA [637], PtBA [637], PDMA [637],PNIPAM [637], PNAM [637]

–thymineO

CS

S

OO

N9

HN OO

PVAc [638]

–cysteineNO OH

O

SNHNH2

HOOO

SS

O

X

-COOCH-H,X: 3

PMA [639], PBA [639], NIPAM [639], PSt [639], PDMA [639], PMMA[639]

–glutathione

OHOS

SSO N

H X-COOCH-H,X: 3 PMA [639], PBA [639], NIPAM [639], PSt [639], PDMA [639], PMMA

[639]

–carbohydrate

OO

OO

O

CS

S

O

HN PNAM [640,641]

–carbohydrate

S NH

O NH

HN NH

O

OS

22

O

C

S PNAM [640,641], PNAM-co-PGalAm [642]

–carbohydrate

HN O S

OS

C

S

XO

S

NHHN

O -CX: 2H5, -C12H25

PNIPAM [643,644], PHPMAM [643]

–carbohydrate

S R1R2 O

HN NH

O

OS

2

OS

C

SR1 RO,orNH= 2 SSorO=

PNIPAM [645]

–carbohydrate OC

S

S

oligosaccharide NN

NPNVP [646]

–peptideS

CS

S

C12H25peptide

PNIPAM [647]


Table 8 (Continued)


–peptidepeptide N

HS

O

C

SPBA [648,649]

–peptidepeptide S

O

CNC

SO

HN

PBA [648]

–protein SC

S

S

OSO

SBSA POEGA [605]

–protein

BSA

C12H25SC

S

S

O

ON 2

O

OS 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.


Scheme 28. Synthesis of azido-functionalized telechelic polymers by using functional RAFT agents.

teleche
Scheme 29. Synthesis of amino functionalized
RAFT polymerization due to the rapid reaction of trithiocar-bonate group with the unprotected primary and secondaryamine groups to form a thiol and a dithiocarbamate deriva-tive [409]. It is, therefore, necessary to protect amine endgroups during RAFT polymerization. Typical protection ofthe amine groups involves the use of phthalimido [428] ortert-butyloxycarbonate (t-Boc) [100] groups. This approachrequires the removal of the thiocarbonylthio groups beforethe deprotection step (Scheme 29). Afterward, the phthal-imido and t-Boc groups can be efficiently converted toamine groups by deprotection in the presence of hydrazineand of trifluoroacetic acid, respectively.

2.4.2. PostmodificationOne of the typical features of the RAFT poly-

merization is the incorporation of the dithiocarbonylmoiety from the CTA at the end of all the poly-mer chains. Such an end group facilitates to introducethe desired functionality in the polymer chain end bypost-polymerization. Common postmodification reactionsused for end group transformation of the dithiocar-bonate group including hydrolysis [651–656], aminol-ysis [20,409,431,459,480,651,657–669], metal assisted[20,212,409,619,670–672] and radical-induced reductions[409,593], are summarized in Scheme 30.

Hydrolysis, under certain temperature and pH condi-tions, is a powerful method to convert the dithiocarbonategroups into thiols. Treatment of dithiocarbonyl group ofpolymers with a strong base such as sodium hydroxideyielded thiol functional telechelic polymers [652,655,673].However, this method has some side reactions, such as for-mation of disulfide bridges, elimination to form vinyl endgroups and cyclizations [673]. On the other hand, the acidichydrolysis of polymers containing a dithiocarbonate groupcan be catalyzed at 90 ◦C using 35% hydrochloric acid. Thefinal hydrolyzed polymer contained thiol end groups corre-sponding to a quantitative reduction of the dithiocarbonyl
groups [656].
An alternative approach for modification of the dithio-carbonate groups into thiols is aminolysis. Both primaryand secondary amines, acting as nucleophiles, can trans-form the dithiocarbonyl function into a thiol, and this

lic polymers by using protected RAFT agents.

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 ofRAFT synthesized polymers can be achieved by using suit-able transition metal complex such as sodium borohydrideor lithium aluminum hydride [671,672].

In a recent communication, Perrier et al. reporteda simple technique to cleave the dithiocarbonyl endfunctionality of polymer by mixing the polymericchains with an excess of thermal radical genera-tors such as (4,4′-azobis(cyanovaleric acid) [676] andbis(2-(2,4-dinitrophenylthio)-ethyl) 4,4′-(diazene-1,2-diyl)bis(4-cyanopentanoate) [677]). During the process ofaddition-fragmentation, the formation of the polymericchain radical can be recombined irreversibly with one ofthe free radicals present in excess in solution, thus forminga dead polymeric chain. This method not only providesthe elimination of the dithiocarbonate end group, but alsopioneers a new functionality at the end of the polymerchain as shown in Scheme 32 [51]. This strategy wasfurther expanded. Maynard et al. installed the maleimidofunctionality by a radical cross-coupling reaction betweenthe trithiocarbonate chain-end and a protected-maleimideazo-initiator [644,645,678].

Amine end-functionalized polymers cannot be synthe-sized directly using RAFT due to the reactivity of thetrithiocarbonyl compounds with primary and secondaryamines. In such cases, polymers are indirectly prepared byusing RAFT agents with protected amine functionality, suchas phthalimido groups in RAFT agents. Upon removal of thetrithiocarbonayl end groups, the phthalimido protectinggroup can be efficiently removed through hydrazinolysisto reveal primary amine telechelic polymers (Scheme 33)[428,617].

Recently, Dichtel and co-workers [521] and Winnik andco-workers [581] investigated the one-pot transformationsthat achieve the removal of the dithioester moiety and the
introduction of a functional group to a polymer chain endsimultaneously (Scheme 34). In this process, the thiol groupformed after the reduction of dithioester moiety either byhydrolysis or aminolysis is trapped through a Michael addi-tion reaction with an acceptor such as an acrylate. This


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.

nate te

mt

[ft

Scheme 32. End group transformation of dithiocarbo

ethod affords telechelic polymers with a variety of func-
ionalities in high conversions.
In a recent paper, Theato and Maynard groups596,679,680] showed that combination of aminolysis andunctional methane thiosulfonate addition can be usedo attach not only methyl disulfides but also functional

Scheme 33. Indirect synthesis of amino teleche

Scheme 34. One-pot transformation of the polymer end groups v

rminated RAFT polymer by radical-induced reaction.

groups onto various polymers. The polymers originating
from different common chain transfer agents include poly-methacrylates, poly(ethylene glycol) methyl ether acrylate,poly(N-isopropyl acrylamide) and polystyrene were suc-cessfully used (Scheme 35). The thiol released at thepolymer end group prefers to react with the methyl-MTS.
lic polystyrene by RAFT polymerization.

ia hydrolysis or aminolysis/Michael additions reactions.


Scheme 35. End group transformation of dithiocarbonate terminated RAFT polymers by combination of aminolysis and functional methane thiosulfonateaddition.

minated
Scheme 36. End group transformation of dithiocarbonate ter
Barner-Kowollik and co-workers demonstrated thatone-pot transformation reactions of trithiocarbonatefunctional (meth)acrylate polymers into hydroxyl func-tional polymers proceeds with a very high efficiency[681–683]. In the reported procedure, dilute solutionof the RAFT polymer and a radical initiator in THF isstirred at elevated temperatures (60 ◦C) in the presenceof atmospheric oxygen to yield hydroperoxide functionalpolymer. Subsequent reduction by triphenylphosphineleads 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 iodinetransfer polymerization [22,684,685] (ITP), cobalt medi-ated radical polymerization (CMRP) [686–689] andorganotellurium- [690,691], organostibine- [692,693],and organobismuthine-mediated [694], polymerization(OMRP) offers alternative routes to prepare well-definedpolymer with predetermined molecular weights, low poly-dispersities, 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 successfulin telechelic synthesis. They are still under construc-tion to optimize polymerization conditions with variousmonomers [16].
Scheme 37. Postfunctionalization o

RAFT polymers into a hydroperoxyl or hydroxyl end-groups.

2.5.1. Iodine transfer polymerization (ITP)One of the new methods for preparing polymers with

controlled molecular weights is the iodine transfer poly-merization. Like RAFT, ITP is a degenerative transferpolymerization using alkyl iodides as the degenerativetransfer agent. In the process, the iodine atom is exchangedbetween a polymeric radical and a dormant chain with-out formation of an intermediate radical. Polymerizationsof styrene and certain fluoro-monomers in the presenceof alkyl iodides are the first reported examples [684,695].More recently, several post-functionalization studies haveshown that ITP can also be used in the preparation ofwell-defined telechelic polymers. These are (i) direct func-tionalization, (ii) functionalization by substitution afterethylenation and (iii) radical coupling (Scheme 37) [696].Telechelic fluoropolymers having diol, diacid, diisocyanate,diamine, diene functionalities are very promising startingmaterials for the production of commercial polymers viacondensation polymerizations or polyaddition polymer-izations [697].

2.5.2. Cobalt mediated radical polymerization (CMRP)Although, cobalt mediated radical polymerization is

the first example of C/LRP [686–688], the method had
not been established well, because it is limited to onlyacrylates. Recently, Jerome and co-workers reported theCMRP of a non-acrylic monomers, cobalt(II) acetylaceto-nate (Co(acac)2) complex provides the high efficiency incontrolled radical polymerization of vinyl acetate [689]. In
f iodine terminal polymers.


echelic

tib

hlb

iuchaspolwm

aeeimcp

2

oopamtedsdattwcd(tp

taw

Scheme 38. Synthesis of tel

his method, (Co(acac)2) reacts reversibly with the grow-ng chains, which are accordingly involved in equilibriumetween active and dormant species (Scheme 38).

Functional organocobaloxime photoinitiators [698]ave been reported for the synthesis of telechelic polyacry-

ates containing various functional groups, such as phenyl,romide, hydroxyl, carboxyl and nitrile groups [699,700].

The fundamental characteristic of the CMRP processs all the polymer chains having terminal cobalt complexsed as controlling agent. The modification of alkyl-obalt complexes is well known, and a few methodologiesave been applied to remove and modify this group inton alternative functional group. For example, photoly-is of cobalt dimethylglyoximes pyridine end-functionaloly(ethyl acrylate) (PEA-Co(DMG)2(Py)) in the presencef bis(p-aminophenyl) disulfide and methyl methacry-ate yielded corresponding amino-functional PEA and

ell-defined PEA macromonomers via radical additionechanism (Scheme 39) [700,701].Growing PVAc chains can be quenched either by

ddition of functional non-polymerizable monomers (1,2-poxy-5-hexene and 3-butene-1-ol, fullerene C60) or byxchange of the Co(acac)2 moiety with a functional nitrox-des (with epoxy, �-bromo ketone and �-bromo ester

oieties) [702–704]. This one-pot technique is an effi-ient strategy to prepare well-defined, cobalt free telechelicoly(vinyl acetate)s (Scheme 40).

.5.3. Organometallic radical polymerization (OMRP)The most recent examples of CLRP involve the use of

rganotellurium [690,691], organostibine [692,693], andrganobismuthine [694] compounds. The polymerizationroceeds via a combination of degenerative chain transfernd thermal dissociation mechanisms [24,705]. The com-on feature of these methods is their high versatility for

he polymerization of different monomers and good tol-rance to functional groups. Despite these features it isifficult to obtain �-functional polymers due to the fact thatynthesis of the chain transfer agents requires specific con-itions and heteroatom groups of the chain transfer agentsre sensitive to oxygen. Therefore, an alternative route forhe synthesis of functional chain transfer agents involvinghe reaction of azo-initiators with chain-transfer agentsas described. As the reactions take place under neutral

onditions, a variety of functional groups can be intro-uced from the corresponding functional azo-initiatorsScheme 41). Using in situ generated functional chain-ransfer agents leads to the synthesis of �-homotelechelic
olymers [706].
Transformations of the organometallic end-groups ofhe polymers via radical and ionic reactions endow with

variety of telechelic polymers with defined structureith various functional groups. Thus, trapping of the grow-

polymers by CMRP process.

ing polymeric radical with ethyl 2-(tributylstannyl)methylacrylate afforded the well-defined macromonomer withquantitative yield [706,707]. Furthermore, the end-groupof polymer could be transformed by ionic reactions throughtransmetalation reactions followed by esterification withpyrene butanol or treatment with aqueous HCl to give�-pyrene and carboxylic acid telechelic polymers, respec-tively [708].

Organstibine-end functionalized polymers were alsotransformed into a number of different functional groupsby radical-coupling, radical-addition, and oxidation reac-tions. For example, the reaction of functional diazo initiatorwith tetramethyldistibine terminated polystyrene gave�,�-diol functionalized telechelic polystyrene as the majorproduct, but disproportionation product �-hydroxyl PStalso formed as a side product [706].

3. Telechelic polymers by anionic polymerization

Anionic polymerization is the first living polymeriza-tion method introduced by Szwarc about half a centuryago and has been utilized as an elegant tool for thesynthesis of tailor made polymers with high compo-sitional unity [709,710]. The characteristics of anionicpolymerization make its suitable for the synthesis of well-defined polymer chains containing reactive terminus atone (monotelechelic) or both ends (telechelic) throughpostmodification or initiation with functional initiators[711–713]. In this polymerization, the propagating speciesare organometallic species such as carbanions or oxanionsand react through nucleophilic reactions in aprotic mediaas shown below (Scheme 42).

Anionic polymerization requires many rigorous exper-imental conditions including inert atmosphere, absolutepurification of most of the reagents used, precise controlof temperature, anhydrous solvent, glass-ware manipula-tion, etc. Once succeeded, utilization of one of two differentstrategies of anionic polymerization allows the generationof functional termini. These strategies are (i) initiation with(protected) functional initiators and (ii) termination with asuitable electrophile and result in various model functionalpolymers that have been significantly used in many appli-cations [714,715]. Functional polymers synthesized byliving anionic polymerization are transformed to differenttopologies such as linear, hyperbranched, star, core-shellpolymers or further functional polymers as desired throughadditional polymerization techniques or effective reactionssuch as click reactions.

3.1. Functionalization by using functional initiators

The first strategy for the synthesis of functional (ortelechelic) polymers is the utilization of functional initia-


Scheme 39. Synthesis of amino telechelic and macromonomer by CMRP and postmodification reactions.

Scheme 40. Synthesis of telechelic polymers by combination of CMRP with radical coupling or addition reactions.

of organ
Scheme 41. Postfunctionalization
tors in the polymerization. Certain functional groups suchas hydroxy, amino, carboxyl, aldehyde or thiol cannot tol-erate the harsh conditions of anionic polymerization, inwhich highly reactive anionic species such as lithium andother alkali-metals are required for initiation. Therefore,special precautions should be taken prior to polymeriza-tion to prevent loss of functional group at the end ofpolymerization [716,717]. Protected initiators were firstemployed in the initiation of anionic polymerization bySchulz et al. in order to overcome this problem [718].The usual organolithium reagents were substituted withhydroxyl containing initiators protected with acetals oftetra-hydropyranyl and -ethoxyethyl ethers, and acetalgroups were converted to hydroxyl groups after the anionic
polymerization of 1,3-butadiene.
Alternatively, siloxane compounds have been com-monly used as protecting agent for hydroxyl, amino orthiol groups in anionic polymerization. For instance,an �,�-hydroxy poly(styrene-b-1,3-butadiene) was

Scheme 42. General mechanism of li

otellurium terminated polymers.

synthesized, using a silyl-protected initiator, 3-tert-butyldimethylsiloxy-1-propyllithium, and sequentialmonomer addition of styrene and 1,3-butadiene. Termi-nation of the polymerization with ethylene oxide yieldedhydroxyl functionality at the �-end. The deprotection ofthe siloxane moieties at the other end with tetrabutylam-monium fluoride gave �,�-hydroxy telechelic polymerwhich was then employed in synthesis of poly(ethyleneoxide-b-styrene-b-1,3-butadiene-b-ethylene oxide) tetra-block copolymer as amphiphilic terpolymers formingvesicles or wormlike micelles in water (Scheme 43)[719].

Using similar protection–deprotection method withsiloxane derivatives, heterofunctional �,�-polymers of
styrene or methacrylates were also prepared [720].The syntheses were based on the utilization of aprotected primary amino initiator, 2,2,5,5-tetramethyl-1-(3-lithiopropyl)-1-aza-2,5-disilacyclopentane, and post-polymerization modification of active chain ends by
ving anionic polymerization.


Scheme 43. Synthesis of �,�-hydroxy poly(styrene-b-1,3-butadiene) by living anionic polymerization.

lic poly

dfibts

teT

m[ghubip(alpttHhg

netotiept

Scheme 44. Synthesis of heteroteleche

eactivation with electrophiles, such as ethylene sul-de, ethylene oxide, anhydride, propane sulfone, 2-romoisobutyrylbromide, or chlorosilane, as precursors ofhiol, hydroxy, carboxylic acid, sulfonic acid, bromo, orilane end groups, respectively (Scheme 44).

Many other telechelic polymers including monofunc-ional or �,�-linear heterofunctional, star [721], branched,tc. prepared by using protected initiators are collected inable 9.

In addition to vinyl polymerization, ring opening poly-erizations of cyclic monomers such as �-caprolactone

715,749], lactide [750], ethylene oxide [724,751–754],lycidyl methyl ether [755] and propylene oxide [756]ave also been used to synthesize telechelic polymers bysing functional initiator approach. The work reportedy Kataoka and co-workers [754] shows the versatil-

ty of the method in preparation of �-/�,�-telechelicolymers. An acetal-protected hydroxyl compound, 2-tetrahydro-2H-pyran-2-yloxy)ethanol, was employed asn initiator in anionic ring opening polymerization of ethy-ene oxide to form �-tetrahydropyranyloxy-�-hydroxyloly(ethylene oxide). Conversion of �-OH group to eitherhe azido or the alkyne group and subsequent deprotec-ion of �-tetrahydropyranyloxy groups yielded ultimatelyO-PEO-N3 or HO-PEO-alkyne (Scheme 45). Moreover, �-ydroxyl groups can be readily converted to thiol or aminoroups.

Utilization of highly reactive catalysts (i.e., potassiumaphthalene) in anionic ring opening polymerization ofthylene oxide dictates use of protected functional initia-ors whereas; polymerizations of cyclic esters requiringrganometallic catalysts usually do not need any protec-
ion. As listed in Table 10, either protected or unprotectednitiators yield �-functional polymers employed in sev-ral applications including synthesis of block copolymers,reparation of self-assembled polymers, surface modifica-ion, immobilization of proteins and cells, etc.
mers by living anionic polymerization.

In a recent work, an initiator bearing three differ-ent functional groups was used in preparation of ABC3-miktoarm star terpolymers through synthesis of PCL con-taining two functional groups at the �-end. The synthesisof the trifunctional initiator involved formation of radi-cal adduct of 4-vinylbenzyl chloride and benzoyl radical;coupling of the resultant radical with TEMPO; subsequenthydrolysis of the ester and etherification with one of thehydroxyl groups of ethylene oxide by blocking the otherhydroxyl group with 3,4-dihydro-2H-pyran; and finallyesterification with a typical ATRP initiator (Scheme 46).

Deffieux and co-workers proposed an elegant way,namely activated-monomer anionic polymerization to pro-duce polymers of epichlorohydrin, ethoxyethyl glycidylether, propylene oxide and ethylene oxide with vari-ous functionalities such as azide and halide (Scheme 47)[756,766,787,788].

3.2. Functionalization by termination with suitableelectrophile

Another method for the synthesis of telechelic polymers(i.e., �-functional macromolecules) by anionic polymer-ization is via termination of the living chain-end with asuitable electrophile containing functional groups includ-ing hydoxyl, amino, halide, mercapto, sulfonate, etc.Moreover, these functional groups can be converted tovarious other groups by postmodifications. Therefore,�-functional polymers can be prepared by two differ-ent approaches of termination of anionic polymerization;direct functionalization by an electrophile and derivati-zation of primary functional group by postmodification
processes.
3.2.1. Direct functionalizationThe reaction of living chain end with an electrophile

such as cyclic ethers, alkyl halides, 1,1-diphenylethylene


Table 9Protected initiators for the synthesis of telechelic polymers by anionic polymerization.


–OH CH2 Li+OO PBd [718]

–OH SiO CH2 Li+ PSt-b-PBd [719]

–OH SiO CH2 Li+

PBd [722]

–OH CH2 Li+OO PSt [723,724]

–OH SiO

C Li+n-Bu

PMMA [725]

–OH SiO

CH2 Li+n n: 3, 6 PMMA [726]

–OHC

OSi

Li+

PMMA [726]

–CHO CH2 Li+OO

PSt [727,728]

–COOHCH2 Li+

O

OO

PSt [729]

–COOHCH2 Li+O

O PSt [730]

–NH2N

Si

SiCH2 Li+ PBd [731], PIP [731]

–NH2N

Si

SiC Li+ PSt [720], PMMA [720], PtBMA [720]

–NH2 NSi

SiC Li+ n: 1, 2

n PSt [732], PIP [732]

–NH2N

Si

SiC Li+

s-Bu

H

PDMS [733,734]

–NH2K+NH2

-PSt [735]

–allyl NX

Li+X:H,phenyl,allyl

PDEAEMA [736]


Table 9 (Continued)


Tertiary or quaternary amine CH2 Li+N PSt [737–741], PMeSt [737–741], PBd [737–741], PIP [737–741]

Galactose or glucose C Li+

G

G

PMMA [742], PtBMA [742], PtBA [742], PEO [742], PFEMA [742], PSt [743]

Naphthalene C

XLi+

X:-methyl,phenyl

PMMA [744,745]

–OH and –Br SiO CH2 Li+

Star PSt [746]

–OH and –Br C

s-Bu

Li+ OSi

OSi

Star PSt [746,747], dendrimer PMMA [746,747]

PC

(cwco

3ott�opitI

This approach has been also employed in effective

–ureidopyrimidinone NH

ONH

NNH

OHO

DPE) derivatives, carbonyl compounds and alkyl halidesan simply produce �-functional polymers. In addition,hen chlorosilanes are utilized as termination agent pre-

ursors of star or branched polymers can be directlybtained [789].

.2.1.1. Termination with cyclic ethers. Typical examplef this type of functionalization involves termination byhe addition of ethylene oxide, and subsequent protona-ion of hydroxylated end group quantitatively yielding-hydroxyl or �,�-dihydroxy functional PSt depending
n the type of initiator used (Scheme 48) [790–793]. Therobable initiation of polymerization of ethylene oxide
s prevented by immediate quenching since the rate ofhe ethylene oxide polymerization is low enough [794].n addition to polystyrene, polyisopyrene [795], polybuta-

Scheme 45. Synthesis of heterotelechelic PE

L [748]

diene [796,797], and poly(1,3-cyclohexadiene) [798] havebeen functionalized by this method.

On the other hand, substituted ethylene oxide hasalso been used as a tool to functionalize polymers[799,800]. Quirk et al. showed styrene oxide contain-ing any substituents on the benzene ring can be usedto obtain �-functional PSt [799]; whereas precursors ofdiene-functionalized macromonomers can be obtainedin high yields by the reaction of polymeric organo-lithiums with 3,4-epoxy-1-butene in a hydrocarbon[800].

synthesis of �,�-difunctional polymers [718]. Similar toethylene oxide, oxetane, a 4-membered cyclic ether, canbe also utilized as a hydroxylation agent by for terminatingpoly(styryl)lithium living chain [801].

Os by living anionic polymerization.


Table 10Functional polymers synthesized by anionic ring opening polymerization.


–COOHK+KO S

O PEO [757]

–CHO K+OO

OPEO [752]

–CHO or sugarK+O

OO

PEO [724,758], PEO-b-PDLLA [724,758]

–SHK+O

9 PEO [759]

–halide Br3C O K+PCL [760]

–halideO

O OHBr PCL [14,761,762]

–halideOH

Cl PCL [763]

–halide, –N3N(Oct)4 (i-Bu)/Br- 3Al PPO [755,756,764], PGME [755,756,764], PEO [755,756,764]

–halide, –N3 BrBr

OHHOPCL [765]

–azide N3

OHPEO [766], PPO [766], PEEGE [766], PECH [766]

–tertiary amine

Cs+N O

PEO [767], PEEGE [767]

–tertiary amineK+

N OPEO [768,769]

–nitroxide K+ON PEO [770]

–nitroxide O

OH

N PCL [72]

–nitroxide ON

OHPCL [771]

–nitroxideO

N P(O)(OEt)2O

NHHO

PCL [356]

–halide and –nitroxide OOH

ON

O

OBr

PCL [772]

–allyl K+O PEO [773–775], PEO-b-PMM [776]

–allyl Cs+O O PEO [767], PEEGE [767]

–acrylateO

O OH PDLLA [750]


Table 10 (Continued)


–norbornenyl CH2 Li+ PEO [753]

–thiopheneK+O

SPEO [777,778]

–styrene K+O PEO [779–784]

–vinyl ether K+OO PEO [779,785]

–vinyl ether K+O OO PEO [779,785]

–uracilOHNN

NN

H2NPCL [786]

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.

n Polym
3.2.1.2. Termination with alkyl/acyl halides. Other type ofsuitable nucleophiles for the termination of anionic poly-merization is alkyl or acyl halides that contain two differentfunctionalities. While the halide functionality is utilized forcoupling with living chain, the second functional group isthe aimed special group. This approach is based on cova-lent C–C bond formation by the reaction of an alkyl/acylhalide with a living anionic chain giving rise to a func-tional polymer and an inorganic by-product, in most casesLiBr. In a typical example, shown in Scheme 49, DPE-endedanionic PSt is terminated with 2,5-dimethoxybenzyl bro-mide, a termination agent with two protected hydroxylgroups, and consequent deprotection yielded correspond-ing hydroxyl functionalities [802]. Likewise, the synthesisof polymers bearing terminal fluorescent groups wasreported by Jenkins and co-workers using alkyl/acyl halidesincluding 1-chloronaphthalene, 1-bromonaphthalene, acidchloride of 1-naphthylacetic acid and 1-naphthoyl chlorideas termination agent [803].

Moreover, diene [804] or epoxy [805] end-functionalized PIP and PSt was synthesized by addition of6-bromo-3-methylene-1-hexene or 2-bromoethyloxirane,respectively, to the living propagating chains. This wayanhydride end-functionalized PSt was also synthesizedby terminating anionic polymerization of styrene with6-bromo-3-methylene-1-hexene and consequent Diels-Alder reaction of the terminal ene with maleic anhydride[806]. Other end-functionalized polymers by terminationwith alkyl/acyl halides are summarized in Table 11.

Functionalized polymers by anionic polymerization canbe utilized in another controlled polymerization such asATRP [807]. Matyjaszewski showed that anionic poly-merization of St was terminated with styrene oxide andbromoisobutyryl bromide yielding an ATRP macrointia-tor with bromo end group (Scheme 50). By sequentialmonomer addition block copolymers of macroinitiatorsuch as PSt-b-PIP-Br can be also obtained.

3.2.1.3. Addition of DPE derivatives. This approach is basedon the addition reactions of DPE derivatives containingfunctional group(s) on aromatic ring(s) and followingprotonation (Scheme 51) [823–832]. Quirk and co-workers reported the preparation of 4-hydroxyphenyl[824] and 4-aminophenyl-terminated [825] PSt bytermination of living poly(styryl) lithium with 1-[4-(tert-butyldimethylsiloxy) phenyl]-1-phenylethyleneand 1-[4-[N,N-bis(trimethylsilyl)amino] pheny1]-1-phenylethylene, respectively, and subsequent hydrolysiswith dilute hydrochloric acid. Similarly, �-oxazolyl PSt wassynthesized in quantitative yields by using 4,5-dihydro-4,4-dimethyl-2-[4-(l-phenylethenyl) phenyl]oxazole as aDPE derivative [826]. Depending on the structure of theDPE derivative, hyperbranched or star polymers have beensynthesized by this approach [746,833–837].

3.2.1.4. Termination with carbonyl compounds. Termina-
tion of an anionic polymerization with CO2 calledcarbonation is the most commonly used method to obtaincarboxyl end-functionalized polymers [793,808,838–843].However, this method brings some problems related tocontamination of resultant polymer with considerable
er Science 36 (2011) 455–567

amounts of the analogous ketone and tertiary alcohol(Scheme 52) [840,841].

Fortunately, this problem can be overcome by manip-ulating solvent system. For instance, formation oftertiary alcohols was not observed when carbona-tions of poly(styryl)lithium, poly(isoprenyl)lithium, andpoly(styrene-bisopreny1)lithium were performed in ben-zene. The process led to the formation of carboxylic acids(60% yields) and the corresponding ketone dimers (40%yields) [844]. Whereas, when the carbonation was carriedout in THF/benzene (25/75, v/v) mixture, only carboxylend-functional polymers (100% yields) were obtained[844].

In recent reports, HOOC-PIP-b-PSt-b-PIP-COOH andNaOOC-PIP-b-PSt-b-PIP-COONa triblock copolymers weresynthesized by addition of CO2 at the end of the sequentialpolymerization of styrene and isopyrene initiated by potas-sium naphthalenide and their phase transition propertieswere investigated [839,845].

Hall and co-workers reported an alternative methodinvolving the reaction of living polyanions with excesssuccinic anhydride to prepare carboxyl end-functionalizedpolymers. In the case of PtBA, the conversion reaches up to95% (Scheme 53) [846].

In addition to CO2, formaldehyde [847,848] and aro-matic aldehydes [849] can be also used as carbonyltermination agent yielding hydroxyl end groups. Thesecompounds produce hydroxyl and aromatic end function-alized polymers depending on structure of the aldehyde.It should be pointed out aldehydes and ketones lead tocomplications, particularly if keto-enol tautomerism ispossible.

3.2.1.5. Termination with nitrogen compounds. Termina-tion of anionic polymerization with the blocked aminogroups give rises to the formation of primary [813,850] orsecondary [851,852] amines end groups after acid hydrol-ysis (Scheme 54).

Moreover, termination of anionic polymerization withpivalonitrile and subsequent reduction yields primaryamine end-functionalized polymers (Scheme 55) [853].

In addition, secondary amine groups are generated byreaction with N-benzylidenemethyl amine (Scheme 56)[851].

As stated previously alkyl halides are other alternativeterminating agents for anionic polymerization producingfunctional groups at terminus of polymers. This methodcan be also employed in generation of tertiary amine ter-minated polymers when termination reactions are madewith �-chloro-�-amino-alkanes (Scheme 57) [854].

3.2.1.6. Termination by addition to C C bond. Termina-tion of anionic polymerization with ene compounds withfunctionality yield corresponding end-capped polymers.According to a method reported by Kim and co-workersditert-butyl ester, dicarboxylic acid or maleic anhydride
terminated block copolymers were synthesized by end-capping of PSt-b-PBMA anion with di-tert-butyl maleate(Scheme 58) [855].
Anionic polymerization also allows preparation of C60-fullerene end-capped polymers [856–859]. Indeed, this


Table 11Functional polymers obtained by anionic polymerization and following termination with alkyl/acyl halides.

Functionality Termination agent Polymers

–OHBr

OCH3

OCH3

PSt [802]

–OH O PBd [808]

–OHBr

O Si PSt [809]

–OH BrO Si PVP [810]

–COOH C OO PBd [808]

–COOH COCH3

OCH3

OCH3Br

PSt [811,812]

–CHO CHOCH3

OCH3Cl PBd [808]

–NH2 Br NSiMe3

SiMe3

PSt [813,814]

–NH2 NSi

SiX

n 32,1,n:IBr,Cl,X: PSt [732,815,816], PIP [732,815,816]

–anhydride O

O

O

OCl

PSt [817]

–anhydride O

O

O

Br PSt [806]

–halideX X

n

10or53,n:IorBrCl,X: PSt [818], PIP [818]

–anthraceneCl

O

PMMA [803]

–pyreneBr

PMMA [803]

–naphthalene ClO

PMMA [803]

–butadiene Br PSt [804,811,819]



Functionality Termination agent Polymers

–epoxy BrO

PSt [804,811]

–styrene XX: Cl, Br, I

PSt [820,821]

–diphenyl ethylene Br PIP [815]

OOOO

O
–monosaccharide Cl
O

interesting termination agent, C60-fullerene, provides acore for star polymers generated by anionic polymerization[856,860]. For example, termination of sequential anionicpolymerization of IP and St with C60 results in 6-armedstar polymers with C60 core [C60(PSt-b-PIP)] [860]. Diene-functionalized macromonomers is another product of thistechnique when the poly(styryl)lithium is reacted withhexa-1,3,5-triene [861].

3.2.1.7. Termination with silyl compounds. Another termi-nation agent for anionic polymerization is chlorosilanesto produce a variety of end-functionalized polymers
(Scheme 59) [850,862–871].
Very recently, such termination was employed in thesynthesis of silica hybrid nanoparticles [872], hydridefunctional PDMS [873], and poly(ferrocenylsilane)-b-polyd,l-lactide block copolymers [871].

Scheme 49. Synthesis of diol end-functionalized polystyrene by anionic polymer

Scheme 50. Synthesis of ATRP macroinit

PSt [822]

Termination of anionic polymerization with chlorosi-lanes also provides a convenient way to producemacromonemers. Styrenic macromonomers have beensynthesized by end capping of anionic PtBA by aromaticaldehydes and chlorosilanes containing styrene moiety[849]. DeSimone and co-workers reported successful syn-thesis of amino or hydroxy end-functionalized PSt, PDMS,PSt-b-PIP. These authors used a wide variety of chlorosi-lanes with certain functionalities as termination agentcontaining protected functionalities, and free functional-ities are obtained quantitatively by simple deprotectionprocess [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 PStreacts quantitatively with thiirane to form terminal mer-capto groups [793,874,875]. The synthesis of functional PIP

ization using substituted alkyl/acyl halides as terminating agents.

iator by anionic polymerization.


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.


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.

ions of p
Scheme 59. End-capping react
containing SH end groups was also performed by termina-tion with thiirane (Scheme 60).

Moreover, reaction of living polymers with sulfur triox-ide gives sulfonate salts. The reactivity of such salts as well
as side reactions is reduced by complexation with a tertiaryamine (Scheme 61a) [876].
Termination of living polymers with sultones producessulfonates [793,877,878] in THF at −78 ◦C with quantitativeyield (Scheme 61b) [737].

olyanions with chloro silanes.

3.2.2. Derivatization of functional groups bypostmodification processes

Alternative to direct functionalization by termination ofa living anionic polymer with an electrophile, �-functional
group of polymers can be modified after termination witha suitable reagent. In recent decades, there have been hugenumbers of reports on this two-step functionalization pro-cess employed in synthesis of various polymers includingPEO, PSt, PBd, PIP and so on. The postmodification reac-


Table 12Chlorosilane derivatives used as terminating agents for polymer functionalization.

Protecting groups Functional groups

CH2 O Si –CH2 –OH

CH2 S Si –CH2 –SH

O SiC OHC

NCSiMe3

SiMe3

NH2C

CH2 NSiMe3

SiMe3–CH2 –NH2

CH2N

OCH2

O

OH

NCH2 CH2 NH2

O

ta

3tateOtp

mwaam

gg(

3tS

NCH2 CH2OH

ions include substitution, hydrosilylation, esterification,midation and cycloaddition reactions.

.2.2.1. Derivatization by substitution. These functionaliza-ion methods have been widely used in synthesis ofzide end-functionalized polymers for further modifica-ions via click reactions. For instance, tosyl or mesylnd-functionalized polymers (such as PEO-OTs, TsO-PEO-Ts, TsO-PEO-b-PPO-b-PEO-OTs) can be easily converted

o corresponding azide end-functionalized polymers in theresence of sodium azide (Scheme 62) [267,850,879–882].

In an alternative method, azido-monotelechelic poly-ers are obtained by coupling of polymeric organolithiumith chloro alkyl functional chlorosilane and subsequent

zidation reactions (Scheme 63) [863]. Reduction of thezide group by lithium aluminum hydride yields anotheronotelechelic polymer, PSt-NH2.Moreover, methoxy or tert-butyldimethylsilyloxy

roups at a polymer end can be transformed to chlororoup by treatment with BCl3 or Me3SiCl-LiBr, respectively
Scheme 64) [809,831].
.2.2.2. Derivatization by hydrosilylation. This novelwo-step functionalization technique, depicted incheme 65, allows preparation of various chain-end

Scheme 60. Synthesis of thiol telechelics by terminat

functional polymers, and is based on coupling of poly-meric organolithium with chlorosilane generating silylhydride functionalized polymers. Subsequent hydrosily-lation of allyl derivatives (functionalized alkenes) withthe silylhydride-functionalized polymers in the pres-ence of Karstedt’s catalyst yields �-functional polymers[864–866,869,883].

3.2.2.3. Derivatization by esterifaction or amidation. Esteri-fication or amidation reactions are other postmodificationmethods for the preparation of telechelic polymersobtained by living anionic polymerization and subsequenttermination with a proper compound. These versatile reac-tions have been utilized in syntheses of polymers withvarious functionalities.

Gruber and co-workers synthesized several telechelicpolymers using such typical organic reactions [808]. In thefirst method they used, the telechelic dicarboxylic acidobtained by termination of anionic living polymerizationof 1,3-butadiene with CO2. Its hydrogenated polybutadiene
was reacted with SOCl2 and subsequently with ammonia togive the diamide end-functionalized polymer. In the fol-lowing step, the diamide polymer was converted to theamino-telechelic polyolefin by dehydration with SOCl2 fol-lowed by reduction with LiAlH4 (Scheme 66).
ion of anionic polymerization with thiiranes.


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 Me3SiCl–LiBr.

Scheme 65. Functionalization of polyanions by chlorosilane coupling and subsequent hydrosilylation reactions.

Scheme 66. Synthesis of amino-telechelic polyolefin by termination of anionic polymerization with CO2 and amidation reaction.

n Polym

btt4rptf

titbhmv

teptc

daf

suPro

cvhicusiw[

tfzb

3Atpftc

cct


In the second method also reported by Gruber, dicar-oxylic acid end-functionalized oligomers were convertedo the acid chlorides and subsequently reacted with 2,2,6,6-etramethyl-4-aminopiperidine and 2,2,6,6-tetramethyl--hydroxypiperidine yielding ester and amide linkage,espectively [808]. Moreover, hydroxyl end-functionalizedolymers obtained by termination of anionic polymeriza-ion of 1,3-butadiene with ethylene oxide were convertedurther telechelic polymers using acid chlorides [808].

In a very recent report, HOOC-PIP-b-PSt-b-PIP-COOHriblock copolymer synthesized by anionic polymer-zation was converted to corresponding acid chlorideelechelics and used in synthesis of multiblock polymersy amidation with N,N′-dimethyl-1,6-hexanediamine orexamethylenediamine [839]. The formation of polymericicelles made of this triblock chains were studied in a sol-

ent selectively poor for the middle PSt block (Scheme 67).In an alternative method, hydroxyl groups of dihydoxy-

elechelic PEO-b-PPO-b-PEO were converted acetylene bysterification with phosgene and following amidation withropargyl amine. Subsequent click reaction with the sameriblock copolymer with azido-functionality resulted in theorresponding multi block polymer (Scheme 68) [879].

Similarly, hydroxyl groups of PEO can be simplyerivatized to alkyne [217,884,885], carboxylic acid [209],nthracene [144] or maleimide [143,146,216,886–888]unctionality by esterification, as presented in Scheme 69.

In another work, Hadjichristidis and co-workersynthesized supramolecular polymers by introducing 2-reido-4-pyrimidone as a structural unit at the end ofSt-b-PIP. The molecule was linked to polymer througheaction of its isocyanate group with the hydroxyl groupf an anionically prepared polymer (Scheme 70) [889].

Matsushita and co-workers developed a novel and effi-ient synthesis of polymers terminated with nucleotidesia the reaction of thymidine phosphoramidite withydroxyl end-capped PSt obtained by anionic polymer-

zation (Scheme 71) [890]. In recent years, polymersontaining nucleodites at their terminus have been widelysed as building blocks of supramolecular self-assembledystems due to their hydrogen bonding abilities. Fornstance, thymine or adenine end functionalized polymers

ere utilized in diblock formation via hydrogen bonding891].

Synthesis of Ru(bpy)3-functionalized PSt was achievedhrough amidation of Ru(bpy)3-COOH with amine-unctionalized PSt [870]. This typical example of derivati-ation clearly demonstrates that the method can virtuallye used in the preparation of any functional polymer.

.2.2.4. Derivatization by cycloaddition reactions. Diels-lder reaction has been also employed for the transforma-

ion of functional groups of polymers prepared by anionicolymerization. According to the reported method, diene-unctionalized PSt or PBd can readily be converted tohe corresponding anhydride forms through Diels-Alder
ycloaddition reactions (Scheme 72) [861,892].
Another cycloaddition reaction was used for end-apping PEO with C60 fullerene. Azide containing polymersan react selectively with C60 through a monoaddition reac-ion. This way 3-arm C60 end-capped PEO was synthesized

er Science 36 (2011) 455–567 511

by Gnanou and co-workers [893]. More recently, “Click”reaction, the Huisgen 1,3-dipolar cycloaddition of azidesand alkynes, was employed for the synthesis of cyclodex-trin end-functionalized PEO (Scheme 73) [885].

4. Telechelic polymers by cationic polymerization

Cationic polymerization is known as chain polymeriza-tion in which propagating chains, namely active speciesare positively charged carbon centered ions or onium ionsin vinyl polymerization or ring opening polymerization,respectively (Scheme 74). Various types of the initiationprocesses involving addition of Brønsted acids, Lewis acids,Lewis acids in conjunction with a proton or carboca-tion source, photochemical reactions, and treatment withhigh electric field have been described. The initiation pro-cess is followed by propagation in which a nucleophilicattack of the monomer onto the active growing centerspaired with non-nucleophilic counterions occurs. Nucle-ophilicty of counterion of the cationic growing species iscrucial to achieve the living character of the polymeriza-tion. Therefore, counterions differ with respect to type ofthe monomer including vinyl ethers; styrenic monomers;substituted alkenes; and cyclic monomers, and mode of thepolymerization (conventional or living cationic polymer-ization).

As stated previously, C/LRP methods are great tools forthe synthesis of well-defined polymeric materials and alsoexcellent way to introduce functional moieties at one orboth termini of polymer chains. Like the other polymeriza-tion methods, living mode of cationic polymerization alsoprovides to introduce functional groups at polymer chaintermini. The method involves the use of a functional initia-tor or a termination agent. Moreover, transformation of theprimary end-capping groups to any other functional groupsis an alternative method to obtain functional polymers.

In this section, living cationic polymerization of bothvinyl and cyclic monomers, used as a method for thesynthesis of telechelic polymers, will be dealt. For theclarification, living polymerization of vinyl and cyclicmonomers will be treated separately since the mechanismsare quite different from each other.

4.1. Telechelic polymers by cationic polymerization ofvinylic monomers

The living cationic polymerizations have been stud-ied over a period of 30 years [894–899]. One of thefirst reports related to living cationic polymerization ofvinyl monomers described the sequential block copoly-merization of ethylvinyl ether and isobutylvinyl ether withN-vinyl carbazole through pseudo-living systems in late1970s [900]. After this time, several different methodolo-gies of living polymerizations of vinyl monomers havebeen developed [894,896–898,901–906] and employedin telechelic polymers [907–909]. For instance, synthesis
of dicarboxylic acid end-functionalized poly(vinyl ether)swas reported by using an adduct generated by addition ofhydrogen iodide to vinyl ether containing malonic esterfunctionality as an initiator and sodiomalonic ester as anend-capping agent (Scheme 75) [909]. In recent years,


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 esterification 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 Diels–Alder coupling.


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.

y living

tifi

fee

4

ipf[

t

Scheme 75. Synthesis of telechelic polymers b

elechelic polymers of isobutylene have been widely stud-ed and used in many applications especially in biomedicaleld [910].

The example presented in Scheme 75 shows bothunctional initiators and end-capping agents can bemployed in polymer functionalization. These two differ-nt approaches will be evaluated separately in detail.

.1.1. Functionalization by using functional initiatorsUsing functional initiators in cationic polymerization

s an elegant tool to synthesize �-end-functionalized
olymers with well-defined properties. Several differentunctional groups including carboxylic acid [909], hydroxyl911], halogen, etc. can be introduced to �-end of polymers.
As presented in Scheme 75, a malonic ester deriva-ive was utilized as functional initiator in living cationic

cationic polymerization of vinylic monomers.

polymerization to generate carboxyl �-end-functionalizedpoly(vinyl ether)s [909].

In the recent decade, the use of functional initia-tor strategy involving initiation with �-methylstyreneepoxide/TiCl4 was also employed in synthesis of �,�-hetero telechelic [911,912] or hyperbranched [913,914]PIBs. Polymerization of isobutylene yielded �-hydroxyltelechelic PIB when the polymerization was initiated withthe �-methylstyrene epoxide/TiCl4 system. Additionally,quenching of the polymerization with methanol leadedto formation of chloro terminal group of the polymer
(Scheme 76).
In an interesting work, PIB-b-PSt based macroinitia-tor for ATRP was prepared by utilization of a functionalinitiator containing ester-protected hydroxyl group insequential polymerization of IB and St. After the polymer-


Scheme 76. Synthesis of �,�-hetero telechelic polyisobutylene by cationic polymerization.

al ATRP
Scheme 77. Synthesis of dibromo function
ization, the dibromo functional group was attached to the�-end of the polymer by trans-esterification. SubsequentATRP of tert-butyl acrylate initiated by the macroini-tiator yielded corresponding miktoarm star polymers(Scheme 77) [915].

In another work, 4-arm star telechelic polymer ofisobutylvinyl ether was synthesized by HCl/ZnCl2 co-initiating system (Scheme 78) [916]. After polymerization,the living polymer was terminated with tetra-functionalsilyl enol ethers giving 4-arm star polymer. Dependingon the initiator, styrene; methacrylate or ketone end-functionalized polymers were obtained.

Various �-end functionalized polymers includinghydroxyl [911,912,917], carboxylic acid [909], halide [915],allyl [918], acetate [916], methacrylate [916], styrene [916],and cyclopentene [919] can be synthesized by utilization offunctional initiators in living cationic polymerization.

4.1.2. Functionalization by using termination withsuitable nucleophile

Living cationic polymerization of vinyl monomers, inwhich halide-based catalyst system is utilized, directlyyields halogen-terminated telechelic polymers. Thesetelechelic polymers can be used directly or transformedto other telechelic polymers. Typically, the polymerizationof vinyl ether polymerization initiated with HI–I2 yields�-iodine end-functionalized polymers with narrow molec-ular weight distribution (Scheme 79) [920–922].

Similarly the reaction of bifunctional initiators withHI–I2 gives �,�-diiodine telechelics, and used directly inchain extension or functionalized with amine [923]. More-over, living cationic polymerization of tetrahydroindeneinitiated with chloro-functional initiator and SnCl4 yields
�,�-dichloro telechelic polymers [924]. Termination of liv-ing chain of a polymer with an end-capping agent withfunctional group(s) is an alternative way to synthesize end-functionalized polymers. �-Functional polymers are theproducts of this strategy in contrast to previous strategy,
macroinitiator by cationic polymerization.

using functional initiators. By this way, polymers with widevariety of end-functionalities have been prepared usingvarious end-capping agents such as olefins, silanes and aro-matic compounds.

4.1.2.1. Olefins. End-capping of a growing cationic chainwith a compound containing C C double bond such asbutadiene yields end-functionalized polymers. In a typicalexample for this approach, termination of living poly-merization of isobutylene initiated by Me3Al2Br3 withBd leads to formation bromoallyl end-functional poly-mers (Scheme 80) [925]. Similarly, chloroallyl analogousof this polymer was also prepared by quenching of Ti2Cl8-catalyzed polymerization of isobutylene with butadiene[837].

Such telechelic polymers were used as a coupling agentwith living anionic polymers such as poly(vinyl ferrocene)[926] and PMMA [927]; or a macroinitiator for ATRP of Stand MMA [928] for block copolymer synthesis (Scheme 81).

An alternative quenching agent containing C C doublebond, namely 1,4-bis(1-phenylethenyl)benzene, was uti-lized to obtain �- or �,�-DPE-functionalized PIB (PIB-DPEor DPE-PIB-DPE) [929–932]. The reaction of living PIB with1,4-bis(1-phenylethenyl)benzene and subsequent methy-lation of the resulting diphenyl carbenium ion with a largeexcess of Zn(CH3)2 yielded the telechelic PIB.

Furthermore, living PIB chains were quantitativelyquenched with DPE yielding polymers with 1,1-diphenyl-1-methoxy or 2,2-diphenylvinyl termini, or both. Thesefunctional groups were quantitatively metalated with Li,or K/Na leading to the formation of anionic species thatinitiated anionic polymerization of tBMA; as a result, PIB-b-PtBMA was obtained quantitatively (Scheme 82) [933].

4.1.2.2. Silanes. Quenching of living cationic polymeriza-tion of vinyl monomers with silanes is another elegantmethod to introduce functionalities at �-termini of poly-mers (Scheme 83). A pioneering work by Kennedy and


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.

romoall

ctqttct

Scheme 81. Reactions of b

o-workers reported the preparation of terminally func-ionalized polymers by using allyltrimethylsilane as a
uenching agent [934–939]. The methodology involveshe living cationic polymerization of IB by mono-, di-, orri-functional initiating systems in conjunction with TiCl4o-initiator and subsequent electrophilic derivatization ofhe living PIB cation with allyltrimethylsilane.
yl end-functionalized PIB.

As presented in Scheme 84, this telecelic polymer wasused as a precursor in macrocyclization through the Ru-
catalyzed metathesis reaction [936], or the synthesis ofamphiphilic networks [940].
Moreover, carboxylate functional PIB was preparedby the termination of the polymerization with suitablesilane compound [941]. For this purpose, quasiliving


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.

B by the
Scheme 84. Synthesis of macrocyclic PI
cationic polymerization was firstly quenched with DPEto obtain stable carbocation and then with 1-methoxy-1-trimethylsiloxypropene yielding methyl ester of thecarboxylic acid. Subsequent hydrolysis of the esterresulted in carboxylate end-functionalized PIB whichis the macroinitiator of polymerization of pivalonitrile(Scheme 85) [941].

Styrenic [942] or olefinic [943] macromonomerswere prepared by using similar approach where 2-phenylallyltrimethylsilane or isobutenyltrimethylsilanewas utilized as termination agent, respectively.

Analogously, aromatic ketone �-end functionalizedpoly(isobutyl vinyl ether) were synthesized by usingsilyl enol ethers as a quenching agents (Scheme 86)[916,944–947].

4.1.2.3. Aromatic compounds. Substituted aromatic com-
pounds can undergo reaction with living cationic chainsyielding end-functionalized polymers [948,949]. Alkoxy-benzene and arylamino derivatives are novel terminationagents for the preparation of telechelic polymers via elec-trophilic aromatic substitution reaction. Synthesis of halide
metathesis reaction of �,�-bisallyl-PIB.

or amino terminated functionalized PIB was very recentlyreported by quenching of quasi-living polymerization of IBwith �-haloalkoxybenzene (Scheme 87) [948]. The halo-gen end-functionalized polymers were also converted toazido- or amino-functionalized polymers by typical organicreactions.

Likewise, electrophilic aromatic substitution of N-methylpyrrole containing functional group with cationicPIB yielded terminally functionalized polymers [950–952].In a typical work, Storey et al. reported synthesis of PIBwith primary alcohol at the �-terminal by quenching of thequasiliving cationic polymerization with protected alcoholcontaining pyrrole and consequent deprotection [951].

4.1.2.4. End-capping with other nucleophilic compounds.Mono- and di-sulfides are other quenchers of cationicpolymerization leading to the formation of telechelic
polymers. The end-capping of TiCl4-catalyzed quasi-livingpolymerization of isobutylene with such compounds underdifferent conditions were investigated by Storey andco-workers [953]. Termination of the living PIBs withthe sulfides and subsequent addition of more reactive


Scheme 85. Synthesis of carboxylate end-functionalized PIB by silane coupling.

Scheme 86. Functionalization of living PIBVE chains with silyl enol ether.

ionalize

ntsb

4

ptni

4wtdo

wtH

Scheme 87. Synthesis of halide and amino end-funct

ucleophiles such as alcohol or amine caused destruc-ion of the sulfide–PIB adducts. Both the elimination andubstitution products including exo-olefin, thioether orromide-terminated PIBs were obtained (Scheme 88).

.1.3. Functionalization by post-modification processesEnd-functionalized polymers obtained by cationic

olymerization can be transformed further to func-ional polymers by typical organic reactions includingucleophilic substitution, addition, elimination and ester-

fication reactions (Scheme 89) [954,955].

.1.3.1. Addition reactions. Allyl end-functionalized PIBas readily converted to corresponding hydroxyl func-

ional polymer by regioselective hydroboration of theouble bond with 9-borabicyclo[3.3.l]nonane followed by
xidation reaction (Scheme 90) [934,936].
Recently, synthesis of PEO–PIB amphiphilic co-networkas reported through coupling reaction of hydroxyl-

elechelic three-arm star PIB synthesized by this way withO–PEO–OH in the presence of diisocyanate [956].

d PIB via electrophilic aromatic substitution reaction.

Reverse addition reactions, addition of a poly-meric ion to functional group, were also employedto obtain telechelic polymers. Synthesis of car-boxylic acid end-functionalized PIBs was achieved bydehydrochlorination–metalation with n-BuLi/t-BuOK andcarbonation of telechelic PIB anions with CO2 and H+ [957].

Moreover, epoxidation on the double bond with m-chloroperbenzoic acid leads to epoxy end-functional PIB,which then can be cured easily [934]. Table 13 lists all othertelechelic polymers obtained by the transformation of allylterminated PIBs.

4.1.3.2. Nucleophilic substitution reactions. Nucleophilicsubstitution reactions have been widely employed in thetransformation of telechelic polymers from one to another(Table 14).

Similar to esterification reactions, etherification alsoprovides a route to generate end-functionalized poly-mers. Reactions of dibromo telechelic PIB with epoxy orvinyl ether based hydroxyl compounds in the presenceof strong base and tetrabutylammonium bromide were


Scheme 88. Functionalization of living PIB cations by mono- and di-sulfides.

Scheme 89. Various post-modification reactions of halide-terminated PIBs.

Scheme 90. Transformation of allyl functionality of PIB to hydroxyl functionality by hydroboration.

Table 13Terminally functionalized polymers obtained by addition reactions.

Functionality Addition reagents Precursor polymers

–OH 9-BBN/NaOH/H2O2 PIB-allyl [934,936]–OH 9-BBN/NaOH/H2O2 Linear PDVB [958]–OH LiAlH4 PIB-aldehyde [959]–COOH Dimethyldioxirane PIB-aldehyde [960]–COOH 1. Ozone; 2. Oxidation PIB-allyl or -diphenylvinyl [961,962]–COOH 4-(4-Urazolyl)benzoic acid PIB-olefin [963]–CHO ZnBr2 PIB-epoxide [959]–CN Acetonitrile PIB-OH [964]–Cl CH2O/HCl PIB-OH [965]–Br HBr PIB-allyl [966–969]–epoxy m-Chloroperbenzoic acid PIB-allyl [934]–epoxy Dimethyldioxirane PIB-olefin [959]


Table 14Terminally functionalized polymers by nucleophilic substitution reactions.

Functionality Precursor Polymers

–OH PIB-Br [939,948,954,966,970]–COOH PIB-Br [939,948,954,970]–COOH PIB-aldehyde [960]–NH2 PIB-Br [939,948,954,966–970]–N3 PIB-Br [939,948,954,970,971]–phthalimide PIB-Br [939,948,954,966,970]–alkyne PIB-Br [939,948,954,970]

s(

cfnwbctaw[

rgmvmwi[

ef

–(meth)acrylates–allyl, –epoxy–nucleobase–nucleobase

hown to yield corresponding PIB-based macromonomersScheme 91) [955].

Nucleophilic substitution reactions have been alsoommonly used in the synthesis of nucleobase end-unctionalized polymers using silylated nucleobases. Directucleophilic substitution reactions of such nucleobasesith halo-terminated PIB have failed due to partial solu-

ility of PIB in dipolar aprotic solvents. Therefore Saf ando-workers developed an alternative way involving a syn-hetic strategy with activated chloromethyl ethers whichre more favorable to nucleophilic subtitution reactionsith nucleophiles such as thymine, uracil, and cytosine

965].Ether formation reactions were also used for the prepa-

ation of glucose-terminated PIBs. The method involveslycosylation of the dihydroxy-terminated PIB with sugarolecules containing thioglycosidic bond, which was acti-

ated by iodonium ions. Removal of the protecting benzyloieties attached to hydroxyl groups of the sugar moleculeas performed by a Pd-catalyzed hydrogenation reaction

n the presence of a small amount of acetic acid (Scheme 92)973].

Anionic species were also used for the transformation ofnd groups. For example, 1,1-diphenylalkyl anion obtainedrom the reaction of 1,1-bis(3-tert-butyldimethylsilyloxy

Scheme 91. Synthesis of epoxy and vinyl ether macromono

PIB-Br [955,966]PIB-OH [955]PIB-Br [939,948,954,965,970]PIB-OH [972]

methylphenyl) ethylene with s-BuLi was coupled withchloroallyl-PIB to prepare �-dibromo functional PIB for thesynthesis of branched polymers [837].

Furthermore, azido-telechelic PIBs were obtained bynucleophilic substitution reaction of trimethylsilylazidewith bromine functionalized PIBs and utilized in click reac-tion with telechelic alkyne-PEO to generate silica shellstabilized polymersomes [971].

Reaction between sodium salts of (meth)acrylates andbromo-telechelic polymers also leads to correspondingmacromonomers [955,966].

4.1.3.3. Elimination reactions. Elimination reactions con-ducted in the presence of a base is another strategy toproduce telechelic polymers, especially olefin-terminatedpolymers [974,975]. PIBs containing exo-olefin terminalgroups were prepared by quenching of TiCl4-catalyzed liv-ing cationic polymerization of isobutylene with a hinderedbase 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. Esterification reactions. More recently, furtherderivatization of hydroxyl end groups of telecehelicpolymers was performed via esterification with hex-5-

mers by etherification of dibromo terminated PIB.


Scheme 92. Synthesis of glucose-terminated PIBs by etherification of dihydroxy-terminated PIB.

Scheme 93. Synthesis of by olefin-terminated PIB by quenching of TiCl4-catalyzed living cationic polymerization with a hindered base.

macroc
Scheme 94. Synthesis of alkyne telechelic PIB and its
ynoic acid (Scheme 94)[936] or methacryloyl chloride[935,976–980] to synthesize alkyne-telechelic PIB or bis-methacrylate functional PIB, respectively. These functionalpolymers were used as precursors for specific applications(i.e. precursor of cyclic polymers.) in the subsequent stage.On the other hand, MA–PIB–MA telechelic polymers havebeen extensively used in the formation of amphiphilicpolymer networks particularly for biological applications[981].

Other terminally functionalized polymers by esterifica-tion reactions and their applications are summarized inTable 15.

In addition to esterification reactions, urea, carba-mate or urethane formation reactions were extensivelyapplied in the preparation of telechelic polymers throughtransformation approach. Hydroxyl groups of PIB can
be also converted quantitatively to carbamates byphenyl isocyanate [990]. Alternatively, amino groups oftelechelic PIBs are used in polyurethaneureas formationby the reaction of diisocyanates with amine moieties[967–969].
yclization with azido-telechelic PIB via click reaction.

4.1.4. New cationic polymerization techniquesVery recently, a novel Pd-based catalyst system for

living cationic polymerization was developed and itsmechanistic details were investigated. The reactions of(�-diimine)PdMe+ derivatives with various vinyl etherssuch as butyl, ethyl, silyl, etc. generated polymers bytwo different pathways. The polymeric product of one ofthese pathways was an olefin �-terminally functionalizedpoly(vinyl ether) (Scheme 95) [918]. This new initiationmechanism is a potential method to synthesize polymerswith other functional end groups.

Pd catalyzed living cationic polymerization methodwas also applied for the polymerization of strongelectron donating cyclic monomers such as 2-alkoxy-1-methylenecyclopropanes. The living ring opening poly-merization of various methylenecyclopropane derivatives
was initiated with �-allylpalladium complexes and corre-sponding polymers with Pd2Cl2 core were obtained. Fol-lowing conduction with nucleophiles such as NaOH/MeOH,NaOH/H2O, AgOAc, NaCMe(COOEt)2 or PPh3 generatedend-functionalized polymers (Scheme 96) [991,992].


Table 15Telechelic polymers derivatized by esterification reactions and their applications.

Functional groups Polymers Applications

HOO

PIB [936] Macrocyclic polymers by click chemistry

OO

PIB [935,976–980] Macromonemer in networked materials

CN

OO

Star PIB [982–984] Network formation

CH2 O X

O

NHCOClNCO,X: PIB [985] Cross-linking

O

OS

CN

S

SC12H25

PIB [986,987] CTA in RAFT of MMA and NIPAm

OO

BrStar PIB [988] Star block copolymer synthesis by ATRP

HN

O

RNCO

PIB [967–969] Polyurea formation

O NH

O

NCOPIB [989,990] Polyurethane 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.


ic polyp
Scheme 97. Synthesis of mono- and di-telechel
Furthermore, synthesis of mono- and telechelicpolyphosphazenes was achieved through the livingcationic polymerization of phosphoranimines initiated byPCl5 (Scheme 97) [993–997]. Telechelic polymers wereprepared by quenching living poly(dichlorophosphazene)chains, with small quantities of the amino phos-phoranimines. Depending on the structure of initialphosphoranimines and termination agent mono- andmixed-telechelic polymers were readily obtained.

Recently, an alternative polymerization system basedon photoinduced living cationic polymerization was devel-oped by Mah [998,999] and Yagci [785,1000–1002] asa potential method for the preparation of halogen-terminated polymers. In this system, the initiating adductis produced by reaction between photochemically gener-ated cationic species and isobutylvinyl ether. The rest of thepolymerization process follows the usual route proposedby Higashimura and Sawamoto (Scheme 98) [906].

4.2. Telechelic polymers by cationic polymerization ofcyclic monomers

The synthesis of telechelics by cationic ring openingpolymerization has the greatest practical interest due tothe commercial value of the resulting compounds, suchas polyether, polyols and so on. Although a wide varietyof heterocyclic monomers can be polymerized by cationicmechanisms, only tetrahydrofuran (THF), oxazolines, N-substituted aziridines, and cyclic sulfides are shown topolymerize 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 func-tional end groups are introduced by either an initiation or
a termination reaction.
4.2.1. Functionalization by using functional initiatorsLiving polymerization of THF can be initiated from

either commercially available methyl triflate or in situ

Scheme 98. Halogen-terminated PVEs via photo

hosphazenes via living cationic polymerization.

formed triflates by the reaction of corresponding alcoholswith triflic anhydride in the presence of a sterically hin-dered amine as proton trap [1004]. A functional alcoholwith triflic anhydride can be used as a functional initia-tor which is capable to introduce functional group on thepolymer chain-end. Addition of various kinds of alcoholswith triflic anhydride into THF polymerization leads tohalide, allyl, alkenyl, acrylate, and methacrylate telechelicswith a high living character [1005–1022]. The use of asuitable end-capping agent to terminate the polymeriza-tion, would then permit to introduce a second (equal ora different) functional chain end leading to telechelic orheterotelechelic polymers (Scheme 99).

Cationic polymerization of oxazolines provides anexcellent methodology for the facile introduction of func-tional end groups [1023–1025]. Polymerization proceedsvia oxazolinium species and functional groups can beincorporated at both initiation and termination steps byusing a functional initiator and a nucleophile, respec-tively.

Various functional initiators have been reported forthe preparation of end-functionalized polyoxazolinesincluding, unsaturated hydrocarbon [1026–1028], allyl[1029,1030], alkyne [579,1031–1033], 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 agentAnother route for the preparation of telechelic poly-

mers is the use of suitable nucleophiles in the cationicpolymerization of cyclic monomers (Scheme 101). Semit-elechelic polytetrahydrofuran (PTHF) can be obtained after
end capping of the living polymers produced with a mono-functional initiator such as methyl triflate. Anhydrides ofsuper acids such as trifluoromethane sulfonic acid or flu-orosulfonic acid yield two active ends [1004,1044,1045].Molecular weight and functionality are controlled only at
induced living cationic polymerization.


Scheme 99. Synthesis of telechelic or heterotelechelic PTHF by cationic ring-opening polymerization.

elechelic

lt

i(t

tfaeaotea(

sfrT

ot

Scheme 100. Synthesis of telechelic or heterot

ow initiator concentration because of the low solubility ofhe initial bisoxonium salt [1044].

For the synthesis of bi- or tri-functional telechelics,nitiators with corresponding functionality must be usedChart 1). Independent activity of all initiator functions ofhese initiators has been also reported [1046,1047].

Because of the reversibility of the polymerization andhe high reactivity of the oxonium functions, bi- and tri-unctional PTHFs are not easy to use. These drawbacksre eliminated by the transformation of the oxoniumnd-groups into more stable but still reactive cyclicmmonium or sulfonium salts. The slight excess additionf an azetidine or thiolane in the THF polymeriza-ion gives azetidinium [1048,1049] or thiolanium [1050]nd-functionalized PTHFs which can be isolated withoutny modification, for example by precipitation in waterScheme 102).

By the addition of a convenient nucleophile into theolution of living polymer, telechelic polymers with variousunctionalities can be easily obtained [1051]. End-capping
eagents and the resulting end groups are shown inable 16.
Proton-initiated polymerization of THF in the presencef carboxylic anhydrides as chain transfer agent gives ester-erminated end groups [1084–1086] (Scheme 103).

Scheme 101. Synthesis of monotelechelic and telechelic

POx by cationic ring-opening polymerization.

The pyridinium salt end-functionalized PTHFs can beused as polymeric initiators for photoinduced reactions(Scheme 104). Upon photolysis the pyridinium moietydecomposes and polymeric radicals are formed. Dependingon the additives present in the system, hydroxy telechelics[1063] or block copolymers [1061] are thus formed.

Interesting variation of end-capping reaction with N-phenylpyrrolidine can be used to prepare mono-, bi-,and tri-functional star-shaped, telechelic PTHF havingN-phenylpyrrolidinium salt groups as illustrated in theexample of tri-functional living PTHF. Heat treatment of thepolymers carrying carboxylate anions results in a quanti-tative ring-opening reaction.

Another class of telechelic PTHFs has been also pre-pared, in which functional groups were located not onlyat the chain ends but also at the interior desired posi-tion. In this case, the tert-butyldimethylsilyl-protectinggroup 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 Greekword kyklos (which means cyclic). Such telechelics can be

PTHFs by cationic ring-opening polymerization.


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 16End-capping reagents and end groups of PTHF.

Reagents Functionality

Ammonia –NH2 [1004,1051]Potassium cyanate –NCO [1004,1051]Hydrogen sulfide –SH [1004,1051]Succinic acid –COOH [1051]Lithium or sodium-4-(methoxycarbonyl) phenolate –COOH [1052,1053]Sodium diethyl malonate –COOH [1053]4,4-Dimethyl-2-oxazolin-2-yl methyl lithium –COOH [1054]((1-Methoxy-2-methyl prop-1-en-1-yl)oxy)silane –COOH [1055]Ethyl amine –NHC2H5 [1051,1056]2-Propene amine –NHCH2CH CH2 [1051,1056]Lithium bromide –Br [1004,1051]Sodium phenolate –phenolate [1004,1051,1057]N,N′-diethyl dithiocarbamic acid sodium salt –dithiocarbamate [1058]4-Hydroxy butyl bromoisobutyrate –bromoisobutyrate [1012,1013,1059]Sodium salt of benzoin –benzoin [1060]N-oxide derivatives –alkoxy pyridinium [1015,1061–1064]Pyrrolyl potassium –pyrrole [1065–1070]Sodium thiophene –thiophene [1071,1072]Allyl alcohol –allyl [1073,1074]Propargyl alcohol –propargyl [1010]
Sodium methacrylate or methacrylic anhydride or methacrylic acidSodium acrylate or acrylic anhydride or acrylic acidSodium p-vinylbenzyloxide3-Acrylaminopropanoic acid
prepared again by the electrostatic self-assembly and cova-lent fixation process as depicted in Scheme 106. By suitablyselecting R and R′ groups, various mono- and bifunctionaltelechelics having hydroxyl and allyl groups were prepared[1088].

Scheme 103. Functionalization of polyoxon

Scheme 104. Reactions of pyridinium

–methacrylate [1075–1079]–acrylate [1050,1078,1080]–styrene [1050,1081–1083]–acrylamide [1080]

The termination of living polyoxazolines chain occurredvia ring-opening of the oxazolinium cation by a nucleophilesuch as water, alcohol, or amine (ammonia, piperidine, etc.)[1089]. The nucleophile can attack at the 2- and 5-positionof oxazoline ring. For a quantitative end functionalization,

ium ion with carboxylic anhydrides.

salt end-functionalized PTHFs.


Scheme 105. Synthesis of �,�-kentro-telechelic polymers by cationic polymerization.

electro

sbscpT

tipaw(

bh[at[

otahlemon

vt

Scheme 106. Synthesis of kyklo-telechelics by the

econdary cyclic amines can be used as terminating agentsecause they terminate selectively in 5-position, as demon-trated by Nuyken et al. [1090]. Polyoxazoline telechelicsonsisting of various functionalities have also been pre-ared by living cationic polymerization, as presented inable 17.

Reaction of methyltosylate with bisoxazolines gives riseo the formation of bis(oxazolinium tosylate) [1097]. Liv-ng polymerization of monofunctional oxazolines havingropagating species at both ends can be initiated by theddition of the monomer. Termination of the living endsith suitable nucleophiles yields difunctional telechelics

Scheme 107).The usual cationic polymerization of oxiranes cannot

e used to synthesize telechelic polymers owing to aigh tendency of backbiting resulting in cyclic oligomers1123–1125]. However, to eliminate such side reactionsprocess involving the addition of a hydroxyl end group

o an activated (protonated) monomer has been proposed1123–1125].

The polymer chain contains the less reactive (nucle-philic) hydroxyl end group. The driving force forhis reaction comes from the protonated monomer,nd no cyclic oligomers are formed. Similar resultsave been obtained from the polymerization of methy-

oxirane and chloromethyloxirane in the presence ofthylene glycol [1126–1129]. A series of telechelics andacromonomers were also prepared by CROP of propylene

xide and epichlorohydrin via activated monomer mecha-ism (Scheme 108) [1130–1135].

The activated monomer polymerization of ı-alerolactone proceeds also living fashion and enableso prepare heterotelechelic(anthracene, acrylate, bromo,

static self-assembly and covalent fixation process.

and norbornene in �-position and hydroxy in �-position)polyesters [1136].

The three-membered cyclic amines and the four-membered cyclic amines can be polymerized only bycationic mechanism [1137]. Monofunctional initiators,such as methyl triflate [1138], produce monofunctionaltelechelics from t-butylaziridine. Addition of the monomerto a bifunctional living PTHF solution gives bifunctionalpoly(t-butylaziridine). This is a method of making ABAblock copolymers. The aziridinium end groups react withvarious nucleophiles including, water, pyridine, benzy-lamine, lithium bromide, sodium phenolate, potassiumhydroxide, lithium phenylacetate, 2-aminoethanol, ben-zyl amine, sodium 2-aminoethylate, maleic anhydride,dimethyl phosphonate, sodium ally1 alcoholate, ally-lamine, sodium acrylate, 2-hydroxyethyl methacrylate,2-hydroxypropyl methacrylate, and methacrylic acid toform the corresponding telechelics and macromonomers(Scheme 109) [1139–1144]. Reactions with pyrommel-litic acid or with polyamines such as diethylene triaminegive cross-linked products [1145]. End capping with �-aminopropyltriethoxysilane groups yields telechelics thatform networks after hydrolysis [1145].

5. Telechelic polymers by metathesispolymerization

The olefin metathesis as a synthetic tool can be applied
to prepare telechelic polymers with precisely controlledstructures, adjustable molecular weights and narrow poly-dispersities, and high degrees of end-functionalization.Mechanistically related metathesis reactions include ringopening metathesis (ROM), ring-closing metathesis (RCM),


Table 17Telechelic polyoxazolines by living cationic ring opening polymerization.


–OH PMeOx [1039,1091–1093], PEtOx [1039,1091,1092,1094], PPrOx [1039], PiPrOx [1042,1095], PnBuOx [1091]Diol PMeOx [1096], PEtOx [1096]Acetal PiPrOx [1042]–SH Poly(2-alkyl-2-oxazoline)[1097]

NR

H PMeOx [1098], PEtOx [1098], PiPrOx [1099,1100]

NPPhOx [1101], poly(2-alkyl-2-oxazoline)[11]

Quarternary ammonium PMeOx [1102,1103], PEtOx [1094,1102,1103], PPhOx [1103]Silane PMeOx [1029,1030,1104–1107], PEtOx [1106,1108–1110]–COOH Poly(2-alkyl-2-oxazoline)[1097,1111,1112]

N

O

O PEtOx [1111]

NPMeOx [1113]

O

O

PMeOx [1114]

O

O

PMeOx [1115,1116], PEtOx [1115]

O

O

PMeOx [1040,1116,1117], PEtOx [1118], PnBuOx [1117], poly(2-alkyl-2-oxazoline)[1119]

CPoly(2-alkyl-2-oxazoline)[1037,1038,1097,1119]

O

NH

PPhOx [1120]–N3 PMeOx [1121]

CH2n 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.

M.A. Tasdelen et al. / Progress in Polym

rmp

moduc[mac2tvtmRt

5

cTpuD1Amrapatc

tm[bd

Scheme 110. Metathesis pathways.

ing-opening metathesis polymerization (ROMP), cross-etathesis (CM), and acyclic diene metathesis (ADMET)

olymerization (Scheme 110) [9,11,1146–1150].ROMP is a popular chain polymerization that is ther-

odynamically driven by the release of ring strain in cycliclefin monomers to form high polymer. ADMET is a con-ensation polymerization that normally employs a diene,sually a terminal diene, in conjunction with a metathesisatalyst to produce high molecular unsaturated polymer1151]. The reaction is driven by the removal of a small

olecule, usually ethylene from the system, which can beccomplished with a nitrogen purge. Most commonly usedatalysts in metathesis polymerization are listed in Chart. Both ROMP and ADMET polymerization are capable ofhe preparation of telechelic polymers. In addition to pro-iding highly functional-group-tolerant catalysts, allowinghe polymerizations to be performed under extremely

ild and user-friendly conditions, such features makeOMP and ADMET attractive synthetic tools for preparingelechelic polymers.

.1. ADMET polymerization

ADMET polymerization and depolymerization methodsan be used in the synthesis of telechelic oligomers.he depolymerization of 1,4-polybutadiene is accom-lished in the presence of a difunctional monoene bysing a metathesis catalyst presented in Scheme 111.iester, disilyl ether, borane and diimide telechelic,4-polybutadiene oligomers have been prepared viaDMET depolymerization [1152–1158]. The depoly-erization was performed under a mild vacuum to

emove the ethylene by-product. This approach waslso applied to the synthesis of telechelic cis-1,4-olyisoprenes, furan-based polymers, polyisobutylenesnd poly(ethylene-co-isobutylene)s through the meta-hetical degradation of polyisobutylene-co-butadieneopolymers [1159–1163].

Amine and alcohol functions are not well tolerated with
he current catalysts and can be incorporated to poly-
ers by using protecting group strategy such as acetoxy1164–1166] or phtalimide [1167] groups. Telechelics withoth of these types of end groups were synthesized usingirect ADMET polymerization of dienes in the presence of

er Science 36 (2011) 455–567 527

a functional group protected �-olefin. Telechelic polymerscontaining silacyclobutane, epoxy and dimethylsilane endgroups have been also synthesized by ADMET polymeriza-tion [1168–1170].

5.2. Ring-opening metathesis polymerization (ROMP)

Three synthetic routes have been reported for incorpo-rating functional groups to the polymer chain-ends duringdifferent stages of the ROMP. Route A involves the use offunctional initiators which makes it possible to prepareeither homo- or hetero-telechelic polymers. Alternatively,the telechelic polymer can be prepared by coupling of areactive linear polymer with an appropriate functional ter-minating agent (route B). The third strategy is the additionof functional chain-transfer agents (CTAs) not only permitsthe regulation of the polymer molecular weight but alsotransfers functionality to the ends of the polymer chains(route C). Synthesis of telechelic polymers by ROMP meth-ods using titanium, tungsten, molybdenum, and rutheniumcontaining metathesis catalysts have been summarizedrecently in an excellent review [1171]. Telechelic poly-mers obtained by three modes of ROMP are summarizedin Table 18.

Few reports discussed the preparation of telechelicpolymers using the functional initiator strategy due tothe fact that limited synthetic procedures for functional-ized metal catalysts are available. Three pathways can beapplied for the functionalization ruthenium carbenes viacross-metathesis [1203] or by direct synthesis of the car-bene from a precursor complex [1177] and diazoalkane[1178,1204]. Telechelic polymers with various function-alities such as acetate, hydroxyl, halide, etc. (Table 18,Route A) can be obtained in a controlled way by the use ofcorresponding ruthenium initiators in the polymerization(Scheme 112).

Another means for the synthesis of telechelic poly-mers is through the use of a functional terminating agentthat can terminate the ROMP as well as transferring thedesired functional group to the terminal ends of the poly-mer chains. By the addition of carbonyls such as ketonesor aldehydes can be used to terminate the polymeriza-tion by means of titanium, molybdenum and tungstenmetathesis catalysts and install functional end-groups. This“Wittig-type” capping reaction proceeds smoothly andquantitatively and has been used for the preparation of aseries of telechelic polymers [1179–1186,1205–1208]. Asruthenium carbenes only react with olefins in a metathe-sis reaction, the terminating agent must have a desiredfunctionality and an olefinic group to form an inactivemetathesis complex [1171]. Substituted vinyl ethers havebeen shown to react with ruthenium catalysts to form a Fis-cher carbene which does not undergo further metathesiswith alkenes (Scheme 113) [1178,1209]. By this way, sev-eral functional groups have been introduced end of variouspolymers (Table 18, Route B2). On the other hand, car-
bonyl functional CTAs have been also employed to obtainedend-functionalized polymers after ROMP catalyzed W orCo based catalysts (Table 18, Route B1). The hydroxylmonotelechelic polymers can also be prepared by ROMPof norbornene using vinylic sulfides as a terminating agent


Table 18End-functionalized polymers obtained by ROMP.

Functionality Routea Polymers

N

O

,

O

O , O , S

,

FeRoute A PNBs [1172,1173], PCO [1172], PDCPD [1172]

O

OBr Route A PCOD [1174]

ONH N N

H

O

O

HN N

HN

O

O

(Hamilton receptor)

Route A PBONBI [1175] PNBOE [1176]

N

NR

C

(fluorescent dye)

Route A PNBs [1177]

C X X: H, OMe, NMe2, NO2, F, Cl, Me Route A PNB [1178]

C X X: H, CF3, OMe, NMe2, CN, NO2,

CHO, CO2Me, NH2, Cl Route B1 PNB [1179]

C

,

Fe

, C F

, NC Route B1 PNBFer [1180,1181], PNBPhT [1180,1181],

Route B1 PNB [1182]

C OH ,

C OSiMe3,

C

OSiMe3

OSiMe3

Route B1 PNBs [1183–1185]

C O

ORoute B1 PNBs [1185]

CBr Route B1 PNB [1181,1186]




NH CO2H

O

OH

O

(fluorescein)

Route B2 Polymers of sugar based NB derivatives [1187], PNBs [1188]

S

NHHN

O

N

O

N

(biotin)

Route B2 PBONBI [1189]

ONH N N

H

O

O

HN N

HN

O

O

(Hamilton receptor)

Route B2 PNBs [1190], PCOs [1190]

CH2 NH

O

N N

O

Route B2 PNBs [1175]

CH2 N

NH

NH

O

OORoute B2 PNBs [1175,1176,1190], PCOs [1190]

CH2 O

NRoute B2 PNBs [1176,1191]

CH2 O

SPh

Pd

SPh

Cl Route B2 PNBs [1191]

CH2 O

OBr

,

CH2O

O

Cl ,

CH2 O

OCl

Cl

Route B2 PNB [1192]

CH2 O

OBr Route B2 PNBs [1193]

CH2 N3 Route B2 PNBs [1194]

O O

O FF

F

FF





NH CO2H

O

OH

O


– OH (–OAc) Route C PCOD [1197–1199]

– OH (–OAc or silane) Route C PCOT [318]

O Ot-Bu

O

O OH

O

NH2 NH

O

Ot-Bu

Route C PCOD [1200]

– NH2 (–CN) Route C PCOD [1201,1202]

12). Rouvinyl e

a Route A refers functionalization using functional initiators (Scheme 1agents. Route B2 refers functionalization by chain transfer reactions usingchain transfer agent containing protected functionality (Scheme 114).

[1210]. In addition, the termination with vinyl lactonessuch as vinylene carbonate and 3H-furanone utilize theintroduction of aldehydes [1211,1212] and carboxylic acids[1211–1213], which does not require extensive work-up

Chart 2. Well-defined metathesis catalysts (Mes

Scheme 111. Depolymerization of PBd producing t

Scheme 112. Synthesis of monotelechelic polynorbornenes

te B1 refers functionalization by termination using carbonyl end-cappingther derivatives as CTA (Scheme 113). Route C refers functionalization by

or deprotection reactions, offers access to reactive termi-nal functional groups. Allyl acetate [1214] and substitutedacrylates [1215] are readily available can be used as end-group functionalization agents in ROMP. The addition of

= 2,4,6-trimethylphenyl, Cy = cyclohexyl).

elechelic polymers via ADMET mechanism.

by ROMP using functionalized ruthenium catalyst.

n Polym

slfi(

tpeiawuTcrpa[dtctrecbt

dgeos[iafq([wm[mo7pa


ymmetrically substituted olefins in the ROMP methodeads to monofunctional telechelics [1216–1218] which areurther used as a macroinitiator [1193,1217,1219] or build-ng blocks for copper catalyzed azide–alkyne cycloadditionCuAAC) click reactions [1220,1221].

The use of functionalized acyclic alkenes as chainransfer agents not only permits the regulation of theolymer molecular weight but also opens a simple andfficient route to the synthesis of telechelic polymers dur-ng ROMP. Because of their higher reactivity, cis-alkenesre preferably employed for this purpose. This methodas first used for the synthesis of telechelic polymerssing molybdenium and tungsten catalyst [1222–1226].he Grubbs group reported the synthesis of commer-ially interesting hydroxy telechelic polybutadienes byuthenium-catalyzed ROMP of 1,5-cyclooctadiene in theresence of cis-1,4-bis(acetoxy)-2-butene followed bypost-polymerization deprotection step (Scheme 114)

1197–1199]. By the same strategy, a broad variety ofifunctional allylic olefins have been used for the syn-hesis of hydroxyl- [318,1227–1231], amino- [1200–1202],arboxyl- [1200] and halide- [318,1202,1232–1235] func-ional telechelic polymers (Table 18, Route C). Bio-elated telechelic polymers of cyclooctene derivativesnd-functionalized with hydrogen-bonding or metal-oordination sites could be prepared through the com-ination of ROMP with a corresponding functional chainransfer agent (CTA) [1190,1236].

ROMP in the presence of unprotected alcohols led toecreased yields and significant amounts of aldehyde endroups due to isomerization [318,1197,1198,1237]. How-ver, ROMP with the addition of 1,4-bis(acetoxy)-2-butener even the related unprotected diols was performeduccessfully with the highly active Grubbs catalyst II318,1197]. In the latter case, THF was added to minimizesomerization to aldehydes. Halide and trithiocarbon-te functional telechelic polybutadienes were employedor the synthesis of ABA triblock copolymers by subse-uent grafting from the ROMP polymers with methylmeth)acrylates or styrene via ATRP or RAFT process1232,1233,1238]. The preparation of poly(butadiene)sith cross-linkable end groups, such as epoxides orethacrylates, was reported by Grubbs and co-workers

1239]. Related syntheses of acetoxy end-terminated poly-
ers with Grubbs-type catalysts were performed not
nly for cyclooctadiene but also for norbornene and-oxanorbornene derivatives [1240]. End-functionalizedolynorbornenes capped with one or two acetoxy orlcohol groups were prepared with the Grubbs catalyst

Scheme 113. Synthesis of telechelic polymers by termination of rut

er Science 36 (2011) 455–567 531

I and mixed NHC/phosphine catalysts [1214]. Acetoxyand hydroxyl end-capped polymers were prepared byGibson and Okada from bis(tert-butylester)-substitutednorbornene by means of the Grubbs catalyst I. Subsequenthydrogenation of the hydroxy functionalized polymer gavethe corresponding polynorbornene [1227].

Another interesting approach for chain-end functional-ization concerns the treatment of a living ROM polymerGrubbs catalyst I with molecular oxygen. This processled to monoaldehyde-end-capped polymers in high yields[1241]. With W- or Mo-based catalysts, the analogoussynthetic protocol would partially lead to a coupling reac-tion, thereby yielding polymers with doubled molecularweight [1241,1242]. The synthesis of a homologous seriesof unsaturated oligomeric esters by cross-metathesis ofcyclopentene and MMA was also reported [1243].

Nomura and co-workers reported that norbornene-based macromonomers can be efficiently prepared bythe ROMP using well-defined molybdenum catalysts andsubsequent end-group reactions [1244,1245]. Interest-ingly, these macromonomers were copolymerized withnorbornene derivatives via ROMP to yield various macro-molecular architectures [1192]. ROMP approach was alsoapplied by several groups to prepare polymers having func-tional groups reactive toward ATRP [1186,1192,1232].

Another more recent chain end-functionalization strat-egy is the sacrificial approach to generating a block copoly-mer with one block comprised of the desired monomerand the other block comprised of a readily degradablemonomer (Scheme 115). Hydroxyl- [1237,1246–1249], andthiol- [1250] functionalized ROMP polymers were suc-cessfully synthesized employing cyclic acetal monomers,which can be degraded by hydrogenation leaving thedesired hydroxyl and thiol group behind. The cleavage ofmultiblock copolymer containing weak ester linkage wouldalso provide an alternative method toward the formationcarboxyl-telechelic polymers [1251]. This strategy is quitesimple and effective, but it is limited to only a few func-tional groups. Heterotelechelic ROMP polymers were alsosynthesized by the combination of sacrificial synthesis withthe 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” chem-istry as a new tool in organic synthesis that includesa handful of almost perfect chemical reactions. The keyfeatures of these reactions are represented by quantita-

henium carbene-initiated ROMP reaction with an enolether.


Scheme 114. Mechanism for the synthesis of hydroxyl telechelic PBds using a protected chain transfer agent.

lymers
Scheme 115. Synthesis of telechelic po
tive yields, toleration to many functional groups, superiorregioselectivity, producing inoffensive by-products, sim-ple product isolations and mild reaction conditions.These reactions have been classified in four categories:(i) cycloaddition reactions (most commonly Huisgen1,3-dipolar cycloaddition (copper catalyzed azide/alkynecycloaddition), but also the Diels–Alder reaction), (ii)nucleophilic ring-opening reactions of strained hetero-cyclic electrophiles (epoxides, aziridines and aziridiniumions), (iii) non-aldol carbonyl chemistry (ureas, oximes andhydrazones) and (iv) additions to carbon–carbon multiplebonds (especially oxidative addition, such as epoxida-tion, dihydroxylation and aziridination but also Michaeladditions) [1252–1254]. Among them, CuAAC click reac-tion is generally regarded as quintessential example ofclick chemistry. Because of its high selectivity, quantita-tive yields, short reaction time, mild reaction conditionsand high fidelity in the presence of most functionalgroups, the CuAAC click chemistry has been presentedas a versatile tool for the post-functionalization of syn-thetic polymers. Click reactions have been subsequentlyexpanded in macromolecular engineering [1255,1256] andas a versatile method for the synthesis of functionalmonomers and polymers [1257–1260], bioconjugatedpolymers [104,279,1261,1262], and postfunctionalizationof polymer [1257,1258].

The use of click reactions would lead to fruit-ful approaches when combined with living and con-trolled/living polymerization techniques, such as ATRP,NMRP, RAFT, and living ionic polymerization [1263]. Inmany of these cases, this marriage has been used for thequantitative preparation of telechelic polymers with oth-erwise difficultly accessible functional groups at the chainends.

Combining the chain-end functionality control of ATRPand the efficiency of click chemistry is an important path-way for the synthesis of functional polymers, becausehalide end groups of polymers prepared by ATRP can beeasily transformed into azides and subsequent click cou-pling with alkyne-modified species. This strategy can be
used for the preparation of telechelics from a wide varietyof polymers and functional groups [279].
An interesting review by Matyjaszewski highlightscombination of these two powerful techniques for thepreparation of novel polymeric architectures, functional

by sacrificial monomer addition route.

materials, and bioconjugates by choosing the appro-priate reaction conditions [1264]. Well-defined azido-terminated polystyrene was synthesized by ATRP followedby a nucleophilic substitution with sodium azide inN,N-dimethylformamide. Click coupling reaction can sub-sequently be used to introduce alcohol, amine, carboxylicacid and vinylic functionalities by reaction with severalcommercially available low molecular weight alkynes suchas propargyl alcohol, propargyl amine, propiolic acid, 2-methyl-1-buten-3-yne, 1,2-diphenyl-2-(2-propynyloxy)-1-ethanone, ethynylpyrene, diphenylurea derivatives andalkyne-functionalized POSS respectively (Scheme 116)[109,110,137,274,278,279,1261,1265]. Other groups alsoreported the use of ATRP-click methodology to combineazido 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 usedin ATRP for preparing well-defined “clickable” polymers.These polymers were then clicked with alkyne-modifiedcompounds to yield telechelic polymers.

Haddleton and coworkers [104] reported the synthe-sis of telechelic polymers by one-pot tandem ATRP andCuAAC methods without any chemical transformationor protection of initiating sites. In fact, both ATRP andCuAAC reactions could share the same copper catalyst andnitrogen-based ligands. The synthetic strategy consisted ofthe use of azido functional initiator for copper catalyzedATRP of methyl methacrylate and allowing the polymeriza-tion to proceed up to 95% conversion before the addition ofthe functional terminal alkynes such as propargyl alcohol,diaza and coumarin dyes (Scheme 117).

Several groups [107,272,1266] reported the combina-tion of ATRP and “click” chemistry to prepare well defined�-(meth)acryloyl macromonomers in an efficient manner.In the first strategy, poly(n-butyl acrylate), poly(tert-butylacrylate), polystyrene, and PSt-b-PBA were prepared byATRP and subsequently transformed to azido end groups.In the second strategy, an azido functionalized initia-tor was used for the preparation of well-defined �-azido
polymethacrylates via ATRP in protic media. The clickreaction of the resulting polymers with propargyl acry-late or propargyl methacrylate resulted in well-definedmacromonomers with high degrees of functionaliza-tion.


Scheme 116. Synthesis of telechelic polymer by combining ATRP and CuAAC click reaction.

ers by o

tt(sa(tpaTmtebprdirrtfi

sprpiwtw

Scheme 117. Synthesis of telechelic polym

Matyjaszewski and coworkers [232,1267] reportedhe synthesis of �,�-dihydroxy telechelic polystyrene byhe combination of ATRP from a difunctional initiatordimethyl 2,6-dibromoheptanedioate), nucleophilic sub-titution of bromine chain ends by reaction with NaN3,nd subsequent click reactions with propargyl alcoholScheme 118). This click reaction was used as a model reac-ion for the quantification of the different telechelic speciesresent at various reaction times and determination ofpparent rate constants of consecutive click reactions.he concentrations of modified polymers (nonhydroxyl-,onohydroxyl- and dihydroxyl-polystyrene) were moni-

ored by gradient polymer elution chromatography–sizexclusion chromatography as a function of time. At theeginning of the reaction with propargyl alcohol, all of theolymers were nonhydroxyl-polystyrene. With increasedeaction time, the population of nonhydroxyl-polystyreneecreased and the population of dihydroxyl-polystyrene

ncreased. The fraction of monohydroxyl-polystyreneeached its maximum at ca. 1.5 h and then decreased witheaction time. These results indicated the second click reac-ion on a polymer chain was three times slower than therst reaction.

Recently, Opsteen and Van Hest [215] described theynthesis of �-hydroxyl-�-carboxylic acid heterotelechelicolystyrene using the combination of ATRP and CuAACeactions. Polystyrene containing both azide and triiso-
ropylsilyl protected acetylene end groups was prepared
n good control by ATRP. Subsequently, the end groupsere independently applied in two successive “click” reac-

ions, that is: first the azide termini were functionalizedith propargyl alcohol and, after deprotection, the acety-

Scheme 118. Synthesis of �, �- dihydroxy telechelic polyst

ne-pot tandem ATRP and CuAAC methods.

lene moieties were utilized for a second functionalizationwith azidoacetic acid (Scheme 119).

In a recent paper, Voit et al. [387] described thesynthesis of an acetylene and azido end functionalpolystyrenes using trimethylsilyl-protected alkyne- andchloro-functionalized initiators via NMRP. Subsequentdeprotection of trimethylsilyl end groups of all polystyrenewas conducted by tetrabutylammonium fluoride used intetrahydrofuran. For the installation of the azido moietywithin polystyrene chain by nucleophilic substitution ofhalide with sodium azide was performed after the polymer-ization. By click chemistry, these polymers can be easily andefficiently transformed to a set of functionalities such as3,5-bis(benzyloxy)benzyl, N-Boc-3-aminopropyl and ade-nine group at polymer chain ends under mild conditions.

Braslau and coworkers [386] reported on a versatilemethod for the preparation of anthracene and pyrenelabeled telechelic polystyrenes by the combination ofNMRP and CuAAC process. The process involves theremoval of N-alkoxyamine through oxidative cleavage withammonium cerium (IV) nitrate (CAN) in the presenceof propargyl alcohol or thermolysis with ethanesulfonylazide to incorporate terminal alkyne or azide functionalityonto polystyrene, individually. To prepare telechelic poly-mer, alkyne end functional polystyrene was coupled withazide-substituted anthracene via CuAAC reaction quantita-tively (Scheme 120). In order to obtain pyrene functional
telechelic polystyrene, the terminal azide group had beenfunctionalized with an alkyne attached pyrene dye usingCuAAC reactions successfully (Scheme 121).
CuAAC click reactions were also used to incorporatesuch fluorescent group to poly(vinyl alcohol) and micro-

yrene by combination of ATRP and CuAAC methods.


Scheme 119. Synthesis of �-hydroxyl-�-carboxylic acid heterotelechelic PSt by combination of ATRP and CuAAC methods.

chelic P
Scheme 120. Synthesis of anthracene-labeled tele
spheres which were successfully utilized as biosensors[1268–1270]. Binder et al. [389] reported the introductionof various functional (pyrimidine and phenyl) groups onnitroxide initiators via CuAAC click reactions. Telechelicpoly(N-isopropyl acrylamide) and poly(n-butyl acrylates)were synthesized via an NMRP process initiated by func-tional nitroxides. The strategy opens a pathway towardfunctional telechelic polymers with narrow molecularweight distribution and well-defined chain-end function-alities.

Among C/LRP techniques, RAFT has arguably the mostimportant commercial impact because it works with awide range of vinyl monomers and under various exper-imental conditions. The particular combination of RAFTand click chemistry is a promising strategy to synthesizefunctional telechelics due to versatility of RAFT poly-merization and efficiency of click chemistry. RAFT agentcontaining azide or alkyne moiety was prepared andused to mediate the polymerization of various monomersunder a variety of reaction conditions. The resulting azido-and alkyne-terminated polymers were used in click reac-tions with functional alkynes and azides, respectively, to
synthesize various well-defined telechelic polymers andmacromonomers [416,583,585]. Combining the synthetictechniques of RAFT polymerization and click chemistrydemonstrated the ability to prepare a wide range of func-tional telechelics (Scheme 122).
Scheme 121. Synthesis of pyrene-labeled telechelic PSt

St by combination of NMRP and CuAAC methods.

Azido-terminated polymers prepared by RAFT can alsobe readily conjugated to biomacromolecules, as severalgroup recently demonstrated. The polymers were effi-ciently 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 ofthe RAFT technique in the direct synthesis of �,�-heterotelechelic polymers ready for selective bioconju-gations. First, a new RAFT agent containing an azideand a dithiopyridine group was used to prepare �-azide,�-dithiopyridine heterotelechelic polymers in one step.Heterotelechelic functionality of the polymers was provenby the successful conjugation of polymer with alkyne-modified biotin and thiol-bearing peptide/protein (i.e.,glutathione and bovine serum albumin) via CuAAC andthiol–disulfide exchange chemistries (Scheme 124) [578].

Stucky et al. have demonstrated a facile methodol-ogy for the preparation of heterofunctional polymers bythe combination of RAFT and subsequent one-pot Michaeladdition with click processes. Firstly, they used azido-functional chain transfer agent, to prepare well-defined
polymers bearing a trithiocarbonate group at one end andan azido group. In the Michael addition process, trithiocar-bonate group were converted to alcohol functionality bytreatment with 2-hydroxyethylamine and 2-hydroxyethylacrylate at room temperature. They were then subjected
by combination of NMRP and CuAAC methods.


Scheme 122. Synthesis of various telechelic polymers by combination of RAFT and CuAAC methods.

olymer

taω(

rcmv,bttfe

Scheme 123. Synthesis of bioactive telechelic p

o click reaction with 5-hexynoic acid using CuSO4/sodiumscorbate 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 prepa-

ation of a larger variety of telechelic polymers by theombination of click chemistry with living cationic poly-erization (Scheme 126) [579]. Acetylene end-functional

arious poly(2-oxazoline)s including 2-methyl-, 2-ethyl-2-nonyl- and 2-phenyl-2-oxazoline were synthesized
y using 3-butynyl toluene-4-sulfonate and propargyloluene-4-sulfonate as initiators. In addition, one ofhese polymers was used to demonstrate its applicabilityor the construction of well-defined telechelic poly(2-thyl oxazoline) by CuAAC click reactions using different
Scheme 124. Synthesis of heterotelechelic polymers by combinati

Scheme 125. Synthesis of heterotelechelic polymers by combi

s by combination of RAFT and CuAAC methods.

azide compounds (9-azidomethyl anthracene or benzyl 2-azidoethyl ether).

Well-defined cyclic polymers can be also suc-cessfully synthesized via intramolecular end-to-end“click” cyclization of linear �-alkyne-�-azido heterod-ifunctional precursors under high dilution conditions[122,130,576,581,936,1271–1273].

Li and co-workers described the synthesis of telechelicPCL by the combination of ring-opening polymerizationand CuAAC click reaction (Scheme 127) [132]. Alkyne ter-
minal PCL is easily clicked with azide containing sugarswithout significant degradation of the aliphatic polyester.
Recently, Su et al. reported the synthesis of well-definedtelechelic PMMAs via the combination of living anionicpolymerization and CuAAC click reaction (Scheme 128). In

on of RAFT, thiol-disulfide exchange and CuAAC reactions.

nation of RAFT, Michael addition and CuAAC reactions.


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.

ination
Scheme 128. Synthesis of telechelic PMMAs by comb
this strategy, first, azido functional PMMA was prepared byanionic polymerization and followed by nucleophilic sub-stitution. Then these polymers were clicked with variousfunctional alkyne compounds (propiolic acid, propar-gyl alcohol, 2-methyl-1-buten-3-yne, trimethyl propargylsilane, 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 pre-pared by the combination of anionic polymerization andCuAAC click reactions [1274].

Carlotti et al. reported the direct synthesis of a broadseries of �-azido, �-hydroxyl heterotelechelic polyethers[poly(ethylene oxide), poly(propylene oxide), protectedpolyglycidol and poly(epichloro hydrin)] via living anionicpolymerization with tetrabutylammonium azide in thepresence of triisobutylaluminum as activator [766]. A seriesof click coupling reactions using various azido polyetherswith 1,7-octadiyne should yield a quantitative formation ofcoupled �-,ω-hydroxyl telechelic polyethers (Scheme 129).

Similar to the CuAAC click chemistry, the Diels–Alderclick reaction was also successfully combined withC/LRP methods for the preparation of telechelic poly-mers. Sumerlin et al. present a general strategy forend group functionalization of RAFT-generated poly-mers by Michael addition and Diels–Alder click reac-tion [459]. Thiol terminated poly(N-isopropylacrylamide),prepared by RAFT/aminolysis, was reacted with 1,8-bismaleimide derivative to yield maleimido terminated
PNIPAM (Scheme 130). The maleimido activated end groupallows efficient coupling with functional thiols or dienes byMichael addition or Diels–Alder reactions, respectively.
The combination of C/LRP methods with thiol–ene andCuAAC click chemistries provides a convenient function-

of living anionic polymerization and CuAAC methods.

alization tool for the construction of telechelic polymers.Recently, several groups investigated and compared theefficiency and orthogonality of thermally and photo-chemically initiated thiol–ene click coupling reactions[273,295,1275]. In these studies, a library of thiol- (PSt)and ene-end-functional polymers (PSt, PEO or PCL) wereprepared by controlled polymerization techniques andthey reacted with functional enes (undecenoic acid,1,4-butanediol vinyl ether) or thiols (thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptopropyl trimethoxysi-lane, Fmoc-protected cysteine, adamantanethiol andthioglycerol) to synthesize well-defined telechelic poly-mers via thiol–ene click chemistry using radical initiators.Furthermore, the asymmetric telechelic polymer from�-alkene-, �-azido-polystyrene prepared by chain endmodification of the corresponding ATRP was synthesizedby successive thiol–ene coupling and CuAAC click reactions(Scheme 131).

Haddleton et al. have used the combination of cobaltmediated radical polymerization and thiol–ene click reac-tion strategy to synthesize a well-defined telechelic poly-mer [1276]. Clickable alkene-functional polymethacrylateswere prepared by CMRP of trimethylsilane-protectedpropargyl methacrylate using bis(boron difluorodimethyl-glyoximate) cobalt(II) as catalyst. Click reaction of theresulting polymer with mercaptoethanol presents �-hydroxyl monotelechelic polymer in a very convenientmanner.

In a recent study, dithiobenzoate and trithiocarbonate
end-groups of polymers formed by RAFT polymerizationwere modified with a range of functional enes; maleimide,methacrylate, and acrylate functionalities by simultane-ous aminolysis and thiol–ene addition reactions to yieldbioactive telechelic polymers and new macromonomers


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.

lymer a

((dfiyrUt

Scheme 132. Preparation of bioactive telechelic po

Scheme 132) [1277]. Synthesis protocols that are clean>85% conversion to desired product) and scalable wereeveloped to convert a protected thiol group into desiredunctionality without side-reactions such as disulfide
nterchain coupling and thiolactone formation. The aminol-sis of the RAFT functionalities and the thiol–ene clickeaction are done simultaneously in a one-pot reaction.sing the same approach, thiol-terminated polymers were
ransformed to new macromonomers by the addition of

nd macromononomer by thiol-ene click reactions.

diacrylate or dimethacrylate monomers with a high effi-ciency.

Lowe et al. described sequential thiol–ene/thiol–eneand thiol–ene/thiol–yne reactions as a facile route for the
functionalization of RAFT synthesized polymers [1278].The dithiobenzoate end-groups were modified in a one-potprocess via aminolysis/thiol–ene click reactions with eitherallyl methacrylate or propargyl acrylate yielding ene andyne terminal PNIPAM quantitatively (Scheme 133). These


Scheme 133. Synthesis of telechelic polymers by sequential thiol-ene/thiol-ene and thiol-ene/thiol-yne reactions.

polyme
Scheme 134. Synthesis of telechelic
groups were then modified with commercially availablethiols (6-mercaptohexanol, 3-mercaptopropyl polyhedraloligomeric silsesquioxane) via radical thiol–ene and rad-ical thiol–yne reactions yielding the monotelechelic andtelechelic PNIPAMs.

Expanding on these facile and versatile clickchemistries, Lowe et al. have claimed an alternativeroute for the preparation of �-telechelic polymersvia the highly efficient thiol–isocyanate click reac-tions [1279]. Thiol-terminated polymers, obtainedfrom RAFT/aminolysis steps, can be modified witha wide range of commercially available isocyanates(allyl isocyanate, cyclohexylmethyl isocyanate, tetrade-cyl isocyanate, 2-isocyanatoethyl methacrylate,2-(2-isocyanatoethyl)-1,4-dimethoxybenzene, 9-isocyanato-9H-fluorene, isocyanatomethylene dibenzene,4-(2-isocyanatoethyl)biphenyl, adamantly isocyanate,heptyl isocyanate, cyclododecyl isocyanate, undecyl iso-cyanate, octadecyl isocyanate, and hexadecyl isocyanate)to yield corresponding thiocarbamate-�-functionalpolymers with quantitative yields (Scheme 134).

The introduction of clickable functionalities in the poly-mer chain ends is an important issue in macromolecularengineering. Depending on the nature of these function-alities various characteristics may exist and they need tobe considered in advance. For example, many azides areexplosive, photosensitive [1280], and the limited stabil-ity of these compounds at high temperatures might causecycloaddition reactions with electron-deficient monomersduring polymerization [586,1281]. In addition, alkynescan undergo some side reactions (chain transfer orchain coupling reactions) during radical polymerization[1282–1284]. In other applications, the sensitivity ofanthracenes [1284–1286] and maleimides [202] towardradicals should be considered. It is known that radicals canreact with anthracene both 9 and 10 positions as well as thereactive double bond of the maleimides. Moreover, ionicand radical polymerizations may interfere with thiols andmay be limited by undesirable nucleophilicity, incompat-
ibility with competing radical processes, or the tendencyto form disulfides [1287]. These side reactions clearly canhave dramatic significance for the functionalization ofpolymers and should be limited by short polymerizationtime and low temperatures [586].
rs via thiol-isocyanate click reaction.

7. Conclusions

As presented in this review article, a great deal ofresearch activity has been devoted toward the prepara-tion of telechelic polymers due to the endless demandsof synthetic polymer chemistry as well as the industryfor high-tech applications. The polymerization processesdescribed in this review, each C/LRP method has distinctadvantages and disadvantages. Continual development ofthese C/LRP systems will provide additional solutions forinstances when a single method is not sufficient for thepreparation of highly designed telechelic polymers. Still,more functionalization techniques are required which sim-plify the process of appending functionality onto polymerchains.

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