High-Order Multiblock Copolymers via Iterative Cu(0)-Mediated Radical Polymerizations (SET-LRP): Toward Biological Precision

被引:294
作者
Soeriyadi, Alexander H. [1 ]
Boyer, Cyrille [1 ]
Nystroem, Fredrik [1 ]
Zetterlund, Per B. [1 ]
Whittaker, Michael R. [1 ]
机构
[1] Univ New S Wales, Ctr Adv Macromol Design, Sch Chem Engn, Sydney, NSW 2052, Australia
基金
澳大利亚研究理事会;
关键词
PHASE PEPTIDE-SYNTHESIS; BROMO CLICK CHEMISTRY; METHYL ACRYLATE; ELECTRON-TRANSFER; MACROMOLECULES; STRATEGY; SEQUENCE;
D O I
10.1021/ja205080u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report a new approach for the facile synthesis of high-order multiblock copolymers comprising very short blocks. The approach entails sequential addition of different monomers via an iterative single electron transfer-living radical polymerization technique, allowing nearly perfect control of the copolymer microstructure. It is possible to synthesize high-order multiblock copolymers with unprecedented control, i.e., A-B-C-D-E-etc., without any need for purification between iterative 24 h block formation steps. To illustrate this concept, we report the synthesis of model P(MA-b-MA ... ) homopolymer and P(MA-b-nBuA-b-EA-b-2EHA-b-EA-b-nBuA) copolymer in extremely high yield. Finally, the halide end-group can be modified via "click chemistry", including thiol-bromide click chemistry, sodium methanethiosulfonate nucleophilic substitution, and atom transfer radical nitroxide coupling reaction, to yield functional, structurally complex macromolecules.
引用
收藏
页码:11128 / 11131
页数:4
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