端糖基化聚(N-异丙基丙烯酰胺)的合成及其温敏性表征  

Synthesis and thermo-responsive property of end-functionalized poly(N-isopropylacrylamide) with two saccharide groups

作　　者：高正国[1] 崔媛[1] 陶祥东[1] 韩双丽[2] 段潜[1] 

机构地区：[1]长春理工大学材料科学与工程学院,吉林长春130022 [2]中国科学院长春光学精密机械与物理研究所,吉林长春130033

出　　处：《功能材料》2012年第2期190-195,共6页Journal of Functional Materials

基　　金：吉林省自然科学基金资助项目(20070556)

摘　　要：制备了两种糖基引发剂(AcCDBr和AcG-lABr),以CuBr/三-(N,N-二甲基氨基乙基)胺(Me6TREN)为催化体系,应用原子转移自由基聚合方法,在60℃下引发N-异丙基丙烯酰胺聚合,脱去乙酰基保护后得到末端分别带有β-环糊精和2-氨基葡萄糖基团的线形聚(N-异丙基丙烯酰胺)(CD-PAM和GlA-PAM)。对产物的结构进行了表征,凝胶渗透色谱(GPC)测得聚合物分子量分布较窄(PDI=1.12～1.20)。采用紫外-可见吸收光谱仪(UV-Vis)和示差扫描量热仪(DSC)对聚合物水溶液的相转变行为进行了测试,结果表明末端引入糖类结构使得PNIPAM的最低临界溶解温度(LCST)升高,并随着分子量的增大而降低,而且相同聚合度的GlA-PAM的LCST比CD-PAM的高3.7℃左右。Two kinds of derived carbohydrates（AcCDBr and AcGlABr） were synthesized as the initiators for atom transfer radical polymerization（ATRP） of N-isopropylacrylamide.The polymerizations of end-functionalized poly（N-isopropylacrylamide） with different saccharide groups（CD-PAM and GlA-PAM for short） were carried out using CuBr/tris（2-dimethylaminoethyl）amine（Me6TREN） as the catalyst system with the feed ratio of n[monomer]0∶n[initiator]0∶n0∶n[Me6TREN]0 = 50∶1∶1∶1 in DMF/water at 60℃.The structures of the initiators and the polymers were characterized by means of FT-IR and NMR.Low polydispersity indices（PDI = 1.12-1.20） were obtained by gel permeation chromatography（GPC）.Ultraviolet-visible spectroscopy（UV-vis） and differential scanning calorimetry（DSC） were employed to measure the lower critical solution temperature（LCST） of the end-functionalized PNIPAMs.The results showed the LCSTs of end-functionalized PNIPAM were increased due to the hydrophilicity of the saccharide groups,and the LCST of GlA-PAM was about 3.7℃ higher than that of CD-PAM.Furthermore,the end-functionalized PNIPAM showed an inverse molecular weight dependence of their cloud points.

关 键 词：聚(N-异丙基丙烯酰胺) 原子转移自由基聚合 最低临界溶解温度 Β-环糊精 氨基葡萄糖 

分 类 号：O633.22[理学—高分子化学] O629.1[理学—化学]