Abstract: Functionally-terminated polymer, defined as macromolecules that contain two reactive terminal groups, are used as cross-linkers, chain extenders and important building blocks for various macromolecular structures, including block and graft copolymers, star, hyperbranched or dendritic polymers. This review describes the general techniques for preparing functionally-terminated polymer via controlled/living radical polymerization, including initiator-transfer agent-terminator (inifenter) method, atom transfer radical polymerization, nitroxide mediated radical polymerization, reversible addition-fragmentation chain transfer polymerization. We also provide a prospect upon this field.
1 Tasdelen M A, Kahveci M U, Yagci Y. Telechelic polymers by li-ving and controlled/living polymerization methods[J]. Prog Poly Sci,2011,36(4):455.
2 Bayer O. Das di-isocyanat-polyadditionsverfahren(polyurethane) [J]. Angew Chem, 1947,59(9):257.
3 Liu S Y, Pan Q M, Xie J W, et al. Intermacromolecular complexes due to specific interactions. 12. Graft-like hydrogen bonding complexes based on pyridyl-containing polymers and end-functionalized poly-styrene oligomers [J]. Polymer,2000,24(2):6919.
4 Horrion, J, Jerome R, Teyssie Ph. Halato-telechelic polymers. 12. Block copolymerization of polystyrene and polybutadiene via ionic interactions[J]. Polym Sci C Polym Lett,1986,38:69.
5 Otsu T. Iniferter concept and living radical polymerization[J]. J Polym Sci A Polym Chem,2000,38(12):2121.
6 Ferington T E, Tobolsky A V. Organic disulfides as initiators of polymerization: Tetramethylthiuram disulfide[J]. J Am Chem Soc,1955,77(17):4510.
7 Ferington T, Tobolsky A V. Organic disulfides as initiators of polymerization. Part Ⅱ[J]. J Am Chem Soc,1958,80(13):3215.
8 Kwak J, Lacroix-Desmazes P, Robin J, et al. Synthesis of mono functional carboxylic acid poly(methyl methacrylate) in aqueous medium using sur-iniferter. Application to the synthesis of graft copolymers polyethylene-g-poly(methylmethacrylate) and the compatibilization of LDPE/PVDF blends[J]. Polymer,2003,44(18):5119.
9 Clouet G, Juhl H J. Free-radical synthesis of alpha-omega-primary amino functionalized polyisoprene through the functional thermal iniferter [bis(N-(2-phthalimidoethyl)piperazine)]thiuramdisulfide[J]. Macromol Chem Phys,1994,195(1):243.
10 Lu J M, Xia X W, Guo X, et al. Synthesis, characterization, and property of end-functionalized telechelic PSt via ATRP[J]. J Appl Polym Sci,2008,108(5):3430.
11 Arimori S, Ohashi S, Matsuda T. Novel iniferter-based synthetic approach to hetero-telechelic precursors and multiblock copolymers composed of vinyl polymer blocks and condensation linkages[J]. React Funct Polym,2007,67(11):1346.
12 Nair C P R, Clouet G, Chaumont P. Functionalization of PMMA by a functional iniferter— Kinetics of polymerization of MMA using N,N′-diethyl-N,N′-bis(2-hydroxyethyl)thiuram disulfide[J]. J Polym Sci A Polym Chem,1989,27(6):1795.
13 Wang J S, Matyjaszewski K. Controlled/“living” radical polymerization. Halogen atom transfer radical polymerization promoted by a Cu (Ⅰ)/Cu (Ⅱ) redox process[J]. Macromolecules,1995,28(23):7901.
14 Taskina O S, Binnur Temel A, Tasdelen M A, et al. Synthesis of block copolymers by selective H-abstraction and radical coupling reactions using benzophenone/benzhydrol photoinitiating system[J]. Eur Poly J,2015,62:304.
15 Urbani C N, Bell C A, Whittaker M R, et al. Self-Assembly of amphiphilic polymeric dendrimers synthesized with selective degradable linkages[J]. Macromolecules,2008,41(1):1057.
16 Agut W, Taton D, Lecommandoux S. A versatile synthetic approach to polypeptide based rod-coil block copolymers by click che-mistry[J]. Macromolecules,2007,40(16):5653.
17 Okcu S S, Durmaz Y Y, Yagci Y. Synthesis and characterization of telechelic block co-polymers by combination of atom transfer radical polymerization and click chemistry processes[J]. Des Monomers Polym,2010,13(5):459.
18 Duxbury C J, Wang W X, Heise A, et al. Can block copolymers be synthesized by a single-step chemoenzymatic route in supercritical carbon dioxide? [J]. J Am Chem Soc,2005,127(8):2384.
19 Yurteri S, Cianga I, Yagci Y. Synthesis and characterization of α, ω-telechelic polymers by atom transfer radical polymerization and coupling processes[J]. Macromol Chem Phys,2003,204(14):1771.
20 Blazquez J A, Areizaga J, Iruin J J, et al. Synthesis of aromatic amine end-functional poly(methylmethacrylate) by atom-transfer ra-dical polymerisation[J]. React Funct Polym,2006,66(10):1073.
21 Lammens M, Fournier D, Fijten M W M, et al. Star-shaped polyacrylates: Highly functionalized architectures via CuAAc click conjugation[J]. Macromol Rapid Commun,2009,30(23):2049.
22 Li C H, Hu J M, Yin J, et al. Click coupling fullerene onto thermoresponsive water-soluble diblock copolymer and homopolymer chains at defined positions[J]. Macromolecules,2009,42(14):5007.
23 Storms-Miller W K, Pugh C. Prop-2-yn-1-yl 2-Bromo-2-methylpro- panoate: Identification and suppression of side reactions of a commonly used terminal alkyne-functional ATRP initiator[J]. Macromolecules,2015,48(12),3803.
24 Tasdelen M A, Kahveci M U, Yagci Y. Telechelic polymers by li-ving and controlled/living polymerization methods[J].2011,36(4):456.
25 Coessens V, Matyjaszewski K. End group transformation of polymers prepared by ATRP substitution to azides[J]. J Macromol Sci A Pure Appl Chem,1999,36(5-6):667.
26 Ouchi M, Terashima T, Sawamoto M. Transition metal-catalyzed living radical polymerization: Toward perfection in catalysis and precision polymer synthesis[J]. Chem Rev,2009,109(11):4963.
27 Opsteen J A, van Hest J C M. Modular synthesis of abc type block copolymers by “click” chemistry[J]. J Polym Sci A Polym Chem,2007,45(14):2913.
28 Coessens V, Matyjaszewski K. Synthesis of polymers with amino end groups by atom transfer radical polymerization[J]. J Macromol Sci A Pure Appl Chem,1999,36(5-6):811.
29 Garamszegi L, Donzel C, Carrot G, et al. Synthesis of thiol end-functional polystyrene via atom transfer radical polymerization [J]. React Funct Polym,2003,55(2):179.
30 Kyeremateng S O, Amado E, Blume A, et al. Synthesis of ABC and CABAC triphilic block copolymers by ATRP combined with ‘click’ chemistry[J]. Macromol Rapid Commun,2008,29:1140.
31 Kyeremateng S O, Henze T, Busse K, et al. Effect of hydrophilic block—A length tuning on the aggregation behavior of alphaomega-perfluoroalkyl end-capped ABA triblock copolymers in water[J]. Macromolecules,2010,43(5):2502.
32 Uygun M, Tasdelen M A, Yagci Y. Influence of type of initiation on thiol-ene “click” chemistry[J]. Macromol Chem Phys,2010,211(1):103.
33 Yoshikawa C, Goto A, Fukuda T. Reactions of polystyrene radicals in a monomer-free atom transfer radical polymerization system[J]. E-Polymers,2002,013:1.
34 Sarbu T, Lin K Y, Spanswick J, et al. Synthesis of hydroxy- telec-helic poly(methyl acrylate) and polystyrene by atom transfer radical coupling[J]. Macromolecules,2004,37(26):9694.
35 Qin Y, Cui C Z, Jakle F. Silylated initiators for the efficient preparation of borane-end-functionalized polymers via ATRP[J]. Macromolecules,2007,40(5):1413.
36 Toquer G, Monge S, Antonova K, et al. Synthesis via ATRP and anchoring properties of ammonium-terminated monofunctional or telechelic polystyrenes[J]. Macromol Chem Phys,2007,208(1):94.
37 Kopping J T, Tolstyka Z P, Maynard H D. Telechelic aminooxy polystyrene synthesized by ATRP and ATR coupling[J]. Macromo-lecules,2007,40(24):8593.
38 Tolstyka Z P, Kopping J T, Maynard H A. Straightforward synthesis of cysteine-reactive telechelic polystyrene[J]. Macromolecules,2008,41(3):599.
39 Bon S A F, Steward A G, Haddleton D M. Modification of the ω-bromo end group of poly(methacrylate)s prepared by copper(Ⅰ)-mediated living radical polymerization[J]. J Polym Sci A Polym Chem,2000,38(15):2678.
40 Durmaz Y Y, Cianga I, Yagci Y. Studies on the preparation of telechelic polymers by atom transfer radical polymerization and cross coupling processes[J]. E-Polymers,2006,050:1.
41 Vinas J, Chagneux N, Gigmes D, et al. SG1-based alkoxyamine bearing a N-succinimidyl ester: A versatile tool for advanced polymer synthesis[J]. Polymer,2008,49(17):3639.
42 Chagneux N, Trimaille T, Rollet M, et al. Synthesis of poly(n-butyl acrylate)-b-poly(ε-caprolactone) through combination of SG1 nitroxide-mediated polymerization and Sn(Oct)2-catalyzed ring-ope-ning polymerization: Study of sequential and one-step approaches from a dual initiator[J]. Macromolecules,2009,42(24):9435.
43 Hill N L, Braslau R. Synthesis of arylethyl-functionalized nalko-xyamine initiators and use in nitroxide-mediated radical polymerization[J]. J Polym Sci A Polym Chem,2007,45(11):2341.
44 Ruehl J, Morimoto C, Stevens D J, et al. Carboxylic acid-and hydroxy-functionalized alkoxyamine initiators for nitroxide mediated radical polymerization[J]. React Funct Polym,2008,68(11):1563.
45 Nicolay R, Marx L, Hemery P, et al. Synthesis and evaluation of a functional, water-and organo-soluble nitroxide for “living” free radical polymerization [J]. Macromolecules,2007,40(17):6067.
46 Lessard B, Tervo C, De Wahl S, et al. Poly(tert-butyl methacrylate/styrene) macroinitiators as precursors for organo- and water-soluble functional copolymers using nitroxide-mediated controlled radical polymerization[J]. Macromolecules,2010,43(2):868.
47 Becer C R, Babiuch K, Pilz D, et al. Clicking pentafluorostyrene copolymers: Synthesis, nanoprecipitation, and glycosylation[J]. Macromolecules,2009,42(7):2387.
48 Rodlert M, Harth E, Rees I, et al. End-group fidelity in nitroxide-mediated living free-radical polymerizations[J]. J Polym Sci A Polym Chem,2000,38(1):4749.
49 Turro N J, Lem G, Zavarine I S. A living free radical exchange reaction for the preparation of photoactive end-labeled monodisperse polymers[J]. Macromolecules,2000,33(26):9782.
50 Lepoittevin B, Perrot X, Masure M, et al. New route to synthesis of cyclic polystyrenes using controlled free radical polymerization[J]. Macromolecules,2001,34(3):425.
51 Chessa G, Scrivanti A, Matteoli U, et al. Synthesis of three-and six-arms polystyrene via living/controlled free radical polymerisation[J]. Polymer,2001,42(23):9347.
52 Guillaneuf Y, Dufils P E, Autissier L, et al. Radical chain end chemical transformation of SG1-based polystyrenes[J]. Macromolecules,2010,43(1):91.
53 Keddie D J. A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization[J]. Chem Soc Rev,2014,43(2),496.
54 Hill M R, Carmean R N, Sumerlin B S. Expanding the scope of RAFT polymerization: Recent advances and new horizons[J]. Macromolecules,2015,48(16),5459.
55 Golas P L, Matyjaszewski K. Marrying click chemistry with polymerization: Expanding the scope of polymeric materials[J]. Chem Soc Rev,2010,39(4):1338.
56 Moad G, Chong Y K, Postma A, et al. Advances in raft polymerization: The synthesis of polymers with defined end-groups[J]. Polymer,2005,46(19):8458.
57 Willcock H, O′Reilly R K. End group removal and modification of RAFT polymers[J]. Polym Chem,2010,1(2):149.
58 Boyer C, Otazaghine B, Boutevin B, et al. Synthesis of maleimide- terminated n-butyl acrylate oligomers by atom transfer radical polymerization: Study of their copolymerization with vinyl ethers[J]. J Polym Sci A Polym Chem,2005,43(18):4303.
59 Thomas D B, Convertine A J, Hester R D, et al. Hydrolytic susceptibility of dithioester chain transfer agents and implications in aqueous RAFT polymerizations[J]. Macromolecules,2004,37(5):1735.
60 Boyer C, Bulmus V, Davis T P. Efficient usage of thiocarbonates for both the production and the biofunctionalization of polymers[J]. Macromol Rapid Commun,2009,30(7):493.
61 Scales C W, Convertine A J, McCormick C L. Fluorescent labeling of RAFT-generated poly (N-isopropylacrylamide) via a facile ma-leimide-thiol coupling reaction[J]. Biomacromolecules,2006,7(5):1389.
62 Roth P J, Wiss K T, Zentel R, et al. Synthesis of reactive telechelic polymers based on pentafluorophenyl esters[J]. Macromolecules,2008,41(22):8513.
63 Schilli C, Lanzendorfer M G, Muller A H E. Benzyl and cumyl dithiocarbamates as chain transfer agents in the RAFT polymerization of N-isopropylacrylamide. In situ FT-NIR and MALDI-TOF MS investigation[J]. Macromolecules,2002,35(18):6819.
64 Llauro M F, Loiseau J, Boisson F, et al. Unexpected end-groups of poly(acrylic acid) prepared by RAFT polymerization[J]. J Polym Sci A Polym Chem,2004,42(21):5439.
65 Hruby M, Korostyatynets V, Benes M J, et al. Bifunctional ion exchange resin with thiol and quaternary ammonium groups for the sorption of arsenate[J]. Collect Czech Chem Commun,2003,68(11):2159.
66 Zhou T C, Jørgensen L, Mattebjerg A M, et al. Molecularly imprinted polymer beads for nicotine recognition prepared by RAFT preci-pitation polymerization: A step forward towards multi-functio-nalities[J]. RSC Adv,2014,4(57):30292.
67 Alfurhood J A, Sun H, Bachler P R. Hyperbranched poly(N-(2-hydroxypropyl)methacrylamide) via RAFT self-condensing vinyl polymerization[J]. Polym Chem,2016,7(11):2099.
68 Xu J T, Tao L, Boyer C, et al. Combining thio-bromo “click” che-mistry and RAFT polymerization: A powerful tool for preparing functionalized multiblock and hyperbranched polymers[J]. Macromolecules,2010,43(1):20.
69 Hiruta Y, Nagumo Y, Miki A. Effects of terminal group and chain length on temperature-responsive chromatography utilizing poly(N-isopropylacrylamide) synthesized via RAFT polymerization[J]. RSC Adv,2015,5(89):73217.
70 Tao L, Kaddis C S, Maynard H D, et al. Synthetic approach to homodimeric protein-polymer conjugates[J]. Chem Commun,2009,16:2148.
71 Postma A, Davis T P, Evans R A, et al. Synthesis of well-defined polystyrene with primary amine end groups through the use of phthalimido-functional RAFT agents[J]. Macromolecules,2006,39(16):5293.
72 Spruell J M, Levy B A, Dichtel W R, et al. Facile postpolymerization end-modification of RAFT polymers[J]. J Polym Sci A Polym Chem,2009,47(2):346.
73 Qiu X P, Tanaka F, Winnik F M. Temperature-induced phase transition of well-defined cyclic poly (N-isopropylacrylamide)s in aqueous solution[J]. Macromolecules,2007,40(20):7069.
74 Dietrich M, Glassner M, Barner-Kowollik C, et al. Facile conver- sion of RAFT polymers into hydroxyl functional polymers: A detailed investigation of variable monomer and RAFT agent combinations[J]. Polym Chem,2010,1(5):634.
75 Braunecker W A, Matyjaszewski K. Controlled/living radical poly- merization: Features, developments, and perspectives[J]. Prog Polym Sci,2007,32(1):93.
76 Boutevin B, David G, Boyer C. Telechelic oligomers and macromo- nomers by radical techniques[J]. Adv Polym Sci,2006,206:31.
77 Debuigne A, Caille J R, Jerome R. Highly efficient cobalt-mediated radical polymerization of vinyl acetate[J]. Angew Chem Int Ed,2005,44(7):1101.
78 Wayland B B, Poszmik G, Mukerjee S L, et al. Living radical polymerization of acrylates by organocobalt porphyrin complexes[J]. J Am Chem Soc,1994,116(17):7943.
79 Goto A, Tsujii Y, Fukuda T. Reversible chain transfer catalyzed polymerization (RTCP): A new class of living radical polymerization[J]. Polymer,2008,49(24):5177.
80 Yamago S, Yamada T, Togai M, et al. Synthesis of structurally well-defined telechelic polymers by organostibine-mediated living radical polymerization: In situ generation of functionalized chain-transfer agents and selective ω-end-group transformations[J]. Chem Eur J,2009,15(4):1018.
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