乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物合成及其胶束化研究  

Synthesis of Ethyl Cellulose Grafted Poly(N-isopropylacrylamide) Copolymer and Its Micellization

作　　者：康宏亮[1] 刘瑞刚[1] 黄勇[1,2] 

机构地区：[1]中国科学院化学研究所高分子物理与化学国家重点实验室北京分子科学中心,北京100190 [2]中国科学院理化技术研究所工程塑料国家工程研究中心,北京100190

出　　处：《化学学报》2013年第1期114-120,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20974114;21174156);中国科学院知识创新工程(No.KJCX2-YW-H19)资助~~

摘　　要：通过单电子转移"活性"/可控自由基聚合的方法制备了具有双亲性及温度响应性的乙基纤维素接枝聚N-异丙基丙烯酰胺共聚物(EC-g-PNIPAm).通过凝胶渗透色谱、核磁氢谱和红外光谱等对合成的接枝共聚物进行了表征.我们发现此反应在混合溶剂四氢呋喃/甲醇的混合溶剂中是活性可控的.EC-g-PNIPAm接枝共聚物能够在选择性溶剂水中发生自组装现象,形成稳定的以乙基纤维素为核、聚N-异丙基丙烯酰胺为壳的球形胶束.并且随着温度的升高,支链聚N-异丙基丙烯酰胺发生塌缩使得球形胶束发生收缩.Thermo-responsive graft copolymers, ethyl cellulose grafting poly（N-isopropylacrylamide） （EC-g-PNIPAm）, were synthesized by single-electron transfer living radical polymerization （SET-LRP） in THF/methanol mixed solvent. Ethyl cellulose macro-initiators （EC-Br） for SET-LRP were synthesized by the esterification between the hydroxyl groups on EC backbones and 2-bromoisobutyryl bromides. The degree of substitution of the EC-Br macro-initiator was tailored by varying the feeding mole ratio of 2-bromoisobutyryl bromide to the hydroxyl group on ethyl cellulose. Three EC-Br macro-initiators with different Br substitutions were used as the macro-initiators and it was found that the converting degree of the initiator sites was efficient and the graft density of graft copolymer was controllable. The SET-LRP of NIPAm was efficient that the monomer conversion was above 60% within 25 h. The linear plot of ln（[M]0/[M]t） versus the conversion indicated that the reaction was living and controllable. The graft copolymers were characterized by means of gel permeation chromatography （GPC）, IH NMR and FTIR spectroscopy. GPC peak of the graft copolymer became narrower and shifted to the low elution time with the increase of reactive time. The molecular weight of the side-chain linearly increased with the reaction time. EC-g-PNIPAm copolymers were typical amphiphilic graft copolymers, having the hydrophobic EC backbone and the hydro- philic PNIPAm side chains. They could be self-assembled and form stable micelles in a selective solvent, water. The micelles were in spherical shape with typical diameter around 100 nm. Rod-like and flower shaped particles were also observed, which was probably due to the fusion of the spherical shaped micelles. The structure of the spherical shaped micelles was that the EC backbone collapsed to form the core of the micelles and the hydrophilic PNIPAm chains stayed in the outside of the micelles to stabilize the micelles. Due to the thermoresponsive branch chains of PNIPAm, the mic

关 键 词：乙基纤维素 聚N-异丙基丙烯酰胺 单电子转移“活性” 可控自由基聚合 接枝聚合反应 温敏性 

分 类 号：O631.3[理学—高分子化学]