High-Efficiency Preparation of Macrocyclic Diblock Copolymers via Selective Click Reaction in Micellar Media

被引:148
作者
Ge, Zhishen [1 ]
Zhou, Yueming [1 ]
Xu, Jian [1 ]
Liu, Hewen [1 ]
Chen, Daoyong [2 ]
Liu, Shiyong [1 ]
机构
[1] Univ Sci & Technol China, Hefei Natl Lab Phys Sci Microscale, CAS Key Lab Soft Matter Chem, Dept Polymer Sci & Engn, Hefei 230026, Anhui, Peoples R China
[2] Fudan Univ, Dept Macromol Sci, Shanghai 200433, Peoples R China
关键词
AQUEOUS-SOLUTION PROPERTIES; BLOCK-COPOLYMER; CYCLIC POLYSTYRENES; RADICAL POLYMERIZATION; ENERGY-TRANSFER; POLYMERS; CYCLIZATION; ROUTE; MICELLIZATION; FLUORESCENCE;
D O I
10.1021/ja808772z
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We report a novel strategy for the high-efficiency preparation of macrocyclic diblock copolymers at relatively high concentrations via the combination of supramolecular self-assembly and "selective" click reactions, relying on the fine control of spatial accessibility between terminal reactive groups. The linear precursor, alpha-alkynyl-omega-azido heterodifunctional poly(2-(2-methoxyethoxy)ethyl methacrylate)-b-poly(oligo(ethylene glycol) methyl ether methacrylate), linear-PMEO(2)MA-b-POEGMA-N-3, self-assembles into micelles with PMEO(2)MA cores and POEGMA coronas at elevated temperatures. The spatial separation between reactive alkynyl and azide groups precludes click reactions within micelle entities. On the other hand, due to the unimer-micelle exchange equilibrium and the fact that unimer concentration is typically tow (critical micellization concentration, CMC), click reactions occur exclusively for unimers. This eventually led to complete intramolecular cyclization of all linear precursors.
引用
收藏
页码:1628 / +
页数:4
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