β-环糊精基刺激响应星形聚合物的制备及响应行为  

Synthesis of β-CD-Based Stimuli-Responsive Star-Shaped Polymers and Its Response Behavior

作　　者：王玲[1] 吕嫚 王俊[1] 丁伟[1] 杨二龙[2] Ling Wang;Man Lü;Jun Wang;Wei Ding;Erlong Yang(Provincial Key Laboratory of Oil&Gas Chemical Technology,Chemistry and Chemical Engineering College of Northeast Petroleum University,Daqing 163318,China;Key Laboratory of Enhanced Oil and Gas Recovery of Ministry of Education of China,Northeast Petroleum University,Daqing 163318,China)

机构地区：[1]东北石油大学化学化工学院石油与天然气重点实验室,黑龙江大庆163318 [2]东北石油大学提高油气采收率教育部重点实验室,黑龙江大庆163318

出　　处：《高分子材料科学与工程》2022年第8期35-41,共7页Polymer Materials Science & Engineering

基　　金：国家自然科学基金重点基金(51834005);黑龙江省应用技术研究与开发计划项目(GA20A201);海南省科技专项资助(ZDYF2022SHFZ107),深远海低渗透油藏智能纳米体系驱油方法应用研究;中央支持地方高效改革发展资金人才培养项目,大庆油田致密油藏纳米体系驱油方法研究;吉林大学无机合成与制备化学国家重点实验室开放项目基金;东北石油大学提高采收率教育部重点实验室开放项目基金;东北石油大学化学工程与技术优势特色学科青年学术骨干支持计划。

摘　　要：采用单电子转移活性自由基聚合法(SET-LRP)合成星形嵌段聚合物。以改性环糊精(Br-β-CD)为引发剂,以溴化亚铜/三-(2-二甲氨基乙基)胺(CuBr/Me_(6)TREN)原位歧化得到的初生零价铜(Cu^(0))及二价铜与配体的络合物(Cu^(Ⅱ)Br_(2)/Me_(6)TREN)为催化体系,在室温成功实现了N-异丙基丙烯酰胺(NIPAM)与甲基丙烯酸二甲氨基乙酯(DMAEMA)的水相活性自由基聚合。通过扩链反应(DP=50100)研究了该聚合反应的活性特征。结果表明,单体转化率在30 min内可达100%且聚合产物分子量分布(PDI)小于1.55。为了证明这一方法可制备多嵌段刺激响应性的凝胶材料,通过连续加料链延伸的方法,分别加入温敏单体NIPAM和温度及pH双重刺激响应单体DMAEMA,合成了嵌段聚合物PNIPAM_(100)-b-PDMAEMA_(100)。产物只需要在最后一步提纯即可,链延伸后的PDI均小于1.55。用核磁共振和红外光谱对聚合物结构进行了表征。所得的刺激响应聚合物在选择性溶剂中可进行自组装,并用浊度法、透射电镜研究了星形共聚物的响应行为,发现可组装成立体楔形结构及球形结构,且星形聚合物具有良好的抗疲劳性。The synthesis of a novel star-block copolymer by single-electron-transfer living radical polymerization(SET-LRP)was reported.The polymerization of NIPAM and DMAEMA was carried out at room temperature in aqueous solution,using Brβ-CD as iniator,full in situ disproportionation of CuBr/Me_(6)TREN to Cu(0)powder and CuⅡBr_(2)/Me_(6)TREN as catalyst system.Conditions for iterative block formation were optimized for a N isopropylacrylamide star-shaped polymer,which was prepared with DP=50~100 with full conversion in 30 min with polydispersity index(PDI)<1.55.To demonstrate this approach for true block stimuli-responsive copolymer materials,a well-defined block polymer PNIPAM_(100)-b-PDMAEMA_(100) was prepared in high purity,with purification only required at the final step.The PDI after each chain extension is below 1.55.The polymer was characterized by FT-IR spectroscopy and ^(1)H-NMR spectrometry.The responsive behaviors of the block-star copolymer were studied by turbidity measurements and transmission electron microscopy.The star-block copolymer shows a strong thermal response and forms three-dimensional wedge assemblies and spherical micelles.And the star-shaped polymer has good fatigue resistance.

关 键 词：单电子转移活性自由基聚合 星形嵌段聚合物 Β-环糊精 刺激响应性凝胶 

分 类 号：TQ316.322[化学工程—高聚物工业]