多重响应性杂臂星型聚合物的RAFT聚合合成及性能研究  

Synthesis of Multi-responsive Mikto-arm Star Polymers by RAFT Polymerization

作　　者：吴鹏[1] 申迎华[1] 耿文博[1] 贾兰[2] 刘旭光[1,3] 郭兴梅[1] 杜海燕[1] 戴胜[4] 

机构地区：[1]太原理工大学化学化工学院,太原030024 [2]太原理工大学材料科学与工程学院,太原030024 [3]太原理工大学新材料界面科学与工程教育部重点实验室,太原030024 [4]澳大利亚阿德莱德大学化工学院,澳大利亚阿德莱德SA5005

出　　处：《高分子学报》2015年第9期1114-1120,共7页Acta Polymerica Sinica

基　　金：山西省国际科技合作计划项目(项目号2014081007-2);山西省回国留学人员科研项目(项目号2014-027);国家自然科学基金青年科学基金(基金号51303124)资助项目

摘　　要：耦合先臂法("arm first")和可逆加成-断裂链转移(RAFT)自由基聚合制备以温度响应性聚(聚乙二醇甲醚丙烯酸酯-co-2-(2-乙氧基乙氧基)乙基丙烯酸酯)(POD)和p H响应性聚丙烯酸二甲氨基乙酯(PDMAEA)为臂,含二硫键的N,N'-双丙烯酰胱胺(BAC)为核的杂臂星型聚合物(MAS).采用傅里叶红外光谱(FTIR)、核磁共振氢谱(1H-NMR)和凝胶渗透色谱(GPC)对聚合物的结构、相对分子质量及分子量分布进行了表征.结果表明,该法能有效控制星型聚合物的合成(分子量分布指数PDI<1.3).采用紫外可见吸收光谱法(UV-Vis)、动态光散射(DLS)考察了MAS在水中的相变行为.结果表明,随着臂PDMAEA含量的增加,星型聚合物的LCST增大.当臂POD与PDMAEA的摩尔投料比为5∶5时,聚合物浓度为1 mg/m L时其在纯水中的LCST为38.2℃.A series of water-soluble multi-responsive miktoarm star polymers（ MAS）,in which poly（ oligo（ ethylene oxide） acrylate-co-di（ ethylene oxide） ethyl ether acrylate） P（ OEGA-co-DEGA） and poly（ 2-dimethylaminoethyl acrylate）（ PDMAEA） served as the thermoresponsive and p H-responsive building blocks,have been successively prepared via reversible addition-fragmentation chain transfer（ RAFT） polymerization using the ＂arm-rst ＂ approach. Firstly,P（ OEGA-co-DEGA） and PDMAEA were prepared via RAFT technique to give well-dened linear trithiocarbonate terminated macro-RAFT agents. Then the two preformed linear macro-RAFT agents were cross-linked by a disulde crosslinker N,N＇-double acryloyl cystamine（ BAC）to give the desired multi-responsive（ temperature,p H and redox） star polymers. The structure and composition of the resultant polymers were characterized by the FTIR and1H-NMR,the molecule weight and molecular weight distribution of the polymers were obtained by GPC. Besides,DLS and UV-Vis were used to investigate the lower critical solution temperature（ LCST） of the polymers in aqueous solutions. The results show that this method can obtain narrow polydispersity star polymers（ PDI〈 1. 3） and the polymers exhibit reversible thermal-induced volume phase transition and p H responsibility. The LCST of the star polymers in aqueous solutions could be tuned by changing the feed ratio of the arms or the p H values. For example,the LCST of the star polymer as determined to be 38. 2 ℃ when the molar feed ratio of P（ OEGA-co-DEGA） and PDMAEA was5∶ 5 and the polymer concentration was 1 mg / m L.

关 键 词：杂臂星型聚合物 RAFT 多重响应性 核交联 

分 类 号：O631.5[理学—高分子化学]