RAFT polymerization of styrenic-based phosphonium monomers and a new family of well-defined statistical and block polyampholytes

被引:55
作者
Wang, Ran [1 ]
Lowe, Andrew B. [1 ]
机构
[1] Univ So Mississippi, Dept Chem & Biochem, Hattiesburg, MS 39406 USA
关键词
block copolymers; kinetics (polym); polyampholytes; reversible addition-fragmentation chain transfer (RAFT); stimuli-sensitive polymers; water-soluble polymers; FRAGMENTATION CHAIN TRANSFER; FREE-RADICAL POLYMERIZATION; AQUEOUS-SOLUTION PROPERTIES; WATER-SOLUBLE (CO)POLYMERS; CONTROLLED/LIVING POLYMERIZATION; TRIBLOCK COPOLYMERS; DIBLOCK COPOLYMERS; MOLECULAR-WEIGHT; MEDIA; TEMPERATURE;
D O I
10.1002/pola.22009
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
We describe herein the first example of the controlled reversible addition-fragmentation chain transfer (RAFT) radical homo- and copolymerization of phosphonium-based styrenic monomers mediated with a trithiocarbonate-based RAFT chain transfer agent (CTA) directly in aqueous media. In the case of homopolymer syntheses the polymerizations proceed in a controlled fashion yielding materials with predetermined molecular characteristics as evidenced from the narrow molecular mass distributions (MMD) and the excellent agreement between the theoretical and experimentally determined molecular masses (MM). We also demonstrate the controlled nature of the homopolymerization of 4-vinylbenzoic acid with the same CTA in DMSO. We subsequently prepared both statistical and block copolymers from the phosphonium/4-vinyl-benzoic acid monomers to yield the first examples of polyampholytes in which the cationic functional group is a quaternary phosphonium species. We show that the kinetic characteristics of the statistical copolymerizations are different from the homopolymerizations and proceed, generally, at a significantly faster rate although there appears to be a composition dependence on the rate. Given the inherent problems in characterizing such polyampholytic copolymers via aqueous size exclusion chromatography we have qualitatively proved their successful formation via FTIR spectroscopy. Finally, in a preliminary experiment we qualitatively demonstrate the ability of such pH-responsive block copolymers to undergo supramolecular self-assembly. (C) 2007 Wiley Periodicals, Inc.
引用
收藏
页码:2468 / 2483
页数:16
相关论文
共 53 条
[1]   Mechanism and kinetics of dithiobenzoate-mediated RAFT polymerization. I. The current situation [J].
Barner-Kowollik, Christopher ;
Buback, Michael ;
Charleux, Bernadette ;
Coote, Michelle L. ;
Drache, Marco ;
Fukuda, Takeshi ;
Goto, Atsushi ;
Klumperman, Bert ;
Lowe, Andrew B. ;
Mcleary, James B. ;
Moad, Graeme ;
Monteiro, Michael J. ;
Sanderson, Ronald D. ;
Tonge, Matthew P. ;
Vana, Philipp .
JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY, 2006, 44 (20) :5809-5831
[2]   Synthesis of various glycopolymer architectures via RAFT polymerization: From block copolymers to stars [J].
Bernard, J ;
Hao, XJ ;
Davis, TP ;
Barner-Kowollik, C ;
Stenzel, MH .
BIOMACROMOLECULES, 2006, 7 (01) :232-238
[3]   Temperature-controlled properties of DNA complexes with poly(ethylenimine)-graft-poly(N-isopropylacrylamide) [J].
Bisht, HS ;
Manickam, DS ;
You, YZ ;
Oupicky, D .
BIOMACROMOLECULES, 2006, 7 (04) :1169-1178
[4]   Facile synthesis of zwitterionic diblock copolymers without protecting group chemistry [J].
Bories-Azeau, X ;
Armes, SP ;
van den Haak, HJW .
MACROMOLECULES, 2004, 37 (07) :2348-2352
[5]   Living free-radical polymerization by reversible addition-fragmentation chain transfer: The RAFT process [J].
Chiefari, J ;
Chong, YK ;
Ercole, F ;
Krstina, J ;
Jeffery, J ;
Le, TPT ;
Mayadunne, RTA ;
Meijs, GF ;
Moad, CL ;
Moad, G ;
Rizzardo, E ;
Thang, SH .
MACROMOLECULES, 1998, 31 (16) :5559-5562
[6]   Thiocarbonylthio compounds (S=C(Z)S-R) in free radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). Effect of the activating group Z [J].
Chiefari, J ;
Mayadunne, RTA ;
Moad, CL ;
Moad, G ;
Rizzardo, E ;
Postma, A ;
Skidmore, MA ;
Thang, SH .
MACROMOLECULES, 2003, 36 (07) :2273-2283
[7]   Thiocarbonylthio compounds [S=C(Ph)S-R] in free radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization). Role of the free-radical leaving group (R) [J].
Chong, YK ;
Krstina, J ;
Le, TPT ;
Moad, G ;
Postma, A ;
Rizzardo, E ;
Thang, SH .
MACROMOLECULES, 2003, 36 (07) :2256-2272
[8]   Direct synthesis of thermally responsive DMA/NIPAM diblock and DMA/NIPAM/DMA triblock copolymers via aqueous, room temperature RAFT polymerization [J].
Convertine, AJ ;
Lokitz, BS ;
Vasileva, Y ;
Myrick, LJ ;
Scales, CW ;
Lowe, AB ;
McCormick, CL .
MACROMOLECULES, 2006, 39 (05) :1724-1730
[9]   Facile, controlled, room-temperature RAFT polymerization of N-isopropylacrylamide [J].
Convertine, AJ ;
Ayres, N ;
Scales, CW ;
Lowe, AB ;
McCormick, CL .
BIOMACROMOLECULES, 2004, 5 (04) :1177-1180
[10]   Controlled/"living" polymerization of sulfobetaine monomers directly in aqueous media via RAFT [J].
Donovan, MS ;
Sumerlin, BS ;
Lowe, AB ;
McCormick, CL .
MACROMOLECULES, 2002, 35 (23) :8663-8666