Highly Controlled Organotellurium-Mediated Living Radical Polymerization (TERP) in Ionic Liquids (ILs). The New Role of ILs in Radical Reactions

被引：10

作者：

Feng, Shuo ^{[1
]}

Xu, Weijian ^{[1
]}

Nakanishi, Koji ^{[2
]}

Yamago, Shigeru ^{[2
,3
]}

机构：

[1] Hunan Univ, Coll Chem & Chem Engn, Changsha 410082, Hunan, Peoples R China

[2] Kyoto Univ, Inst Chem Res, Uji, Kyoto 6110011, Japan

[3] Japan Sci & Technol Agcy, CREST, Tokyo, Japan

来源：

ACS MACRO LETTERS | 2012年 / 1卷 / 01期

基金：

美国国家科学基金会; 日本科学技术振兴机构;

关键词：

METHYL-METHACRYLATE; BLOCK-COPOLYMERS; TRANSFER AGENTS; ACRYLATES; STYRENE; ACTIVATION; POLYMERS; ATRP; POLYSTYRENES; GENERATION;

D O I：

10.1021/mz200133d

中图分类号：

O63 [高分子化学（高聚物）];

学科分类号：

070305 ; 080501 ; 081704 ;

摘要：

Ionic liquids (ILs) served perfectly as solvents for the organotellurium-mediated living radical polymerization (TERP) of methyl methacrylate (MMA), methyl acrylate (MA), and styrene. The reaction rate of polymerizing MMA and MA was significantly increased as previously reported, and the controllability of the polydispersity index (PDI) was also improved by a great margin. The TERP of MMA can now give poly(methyl methacrylates) (PMMAs) with PDIs less than 1.1 and nearly full conversion in a half hour without the presence of (TeMe)(2). The kinetic study revealed that the improved control could be ascribed to a faster degenerative chain transfer (DT) reaction which plays a key role in the control of PDI for TERP. Besides the polar effect of ILs, the existence of Lewis acid-base interaction between ILs and the Te atom was proven by UV-vis spectroscopy and Te-125 NMR results. Such positive interaction lowered the activation energy of the DT process.

引用

页码：146 / 149

页数：4

共 65 条

[1] Termination kinetics of free-radical polymerization in ionic liquids [J].

Barth, Johannes ;

Buback, Michael ;

Schmidt-Naake, Gudrun ;

Woecht, Inga .

POLYMER, 2009, 50 (24) :5708-5712

[2] Ionic liquids as reaction media for polymerization processes: atom transfer radical polymerization (ATRP) of acrylates in ionic liquids [J].

Biedron, T ;

Kubisa, P .

POLYMER INTERNATIONAL, 2003, 52 (10) :1584-1588

[3]

Biedron T, 2001, MACROMOL RAPID COMM, V22, P1237, DOI 10.1002/1521-3927(20011001)22:15<1237::AID-MARC1237>3.0.CO

[4]

2-E

[5] Nitroxide-Mediated Controlled/Living Radical Copolymerization of Methyl Methacrylate with a Low Amount of Styrene in Ionic Liquid [J].

Brusseau, Segolene ;

Boyron, Olivier ;

Schikaneder, Christopher ;

Santini, Catherine C. ;

Charleux, Bernadette .

MACROMOLECULES, 2011, 44 (02) :215-220

[6]

Byers J., 2001, RADICALS ORGANIC SYN, V1, P73

[7] Copper(I) mediated living radical polymerisation in an ionic liquid [J].

Carmichael, AJ ;

Haddleton, DM ;

Bon, SAF ;

Seddon, KR .

CHEMICAL COMMUNICATIONS, 2000, (14) :1237-1238

[8] Spotlight on ionic liquids [J].

Castner, Edward W., Jr. ;

Wishart, James F. .

JOURNAL OF CHEMICAL PHYSICS, 2010, 132 (12)

[9] Organostibine-Mediated Controlled/Living Radical Polymerization of Methyl Methacrylate and Styrene in Ionic Liquids [J].

Cui, Guoyou ;

Li, Jun ;

Liu, Zhengping ;

Dou, Junyan .

MACROMOLECULAR CHEMISTRY AND PHYSICS, 2010, 211 (11) :1222-1228

[10]

Curran D. P., 1991, RADICAL ADDITION REA, V4

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