SYNTHESIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND THEIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES  

作　　者：Huai-chao Wang Ming-zu Zhang 倪沛红 Jin-lin He Ying Hao Yi-xian Wu 

机构地区：[1]College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Soochow University [2]State Key Lab of Chemical Resource Engineering, Beijing University of Chemical Technology

出　　处：《Chinese Journal of Polymer Science》2013年第2期218-231,共14页高分子科学（英文版）

基　　金：financially supported by the National Natural Science Foundation of China (Nos. 20974074 and 21074078);Natural Science Foundation of Jiangsu Province for Rolling Support Project (BK2011045);a project funded by the PriorityAcademic Program Development of Jiangsu Higher Education Institutions, State Key Lab of Chemical Resource Engineering(Beijing University of Chemical Technology);the Innovation Project of Graduate Students of Jiangsu Province, China(CXZZ11_0091)

摘　　要：Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid） （PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.

关 键 词：Oxyanion-initiated polymerization POLYISOBUTYLENE Stimuli responsivity Amphiphilic copolymer Self- assembly. 

分 类 号：O631.3[理学—高分子化学]