微尺度铜管催化三臂星形聚合物的制备  

Micro-scale Cu Catalyzed Preparation of Three-arm Star Polymers

作　　者：黄卫军 计文希[1] 张龙贵[1] 宋建会[1] 贾雪飞[1] Wei-jun Huang;Wen-xi Ji;Long-gui Zhang;Jian-hui Song;Xue-fei Jia(SINOPEC Beijing Research Institute of Chemical Industry,Beijing 100013)

机构地区：[1]中国石化北京化工研究院,北京100013

出　　处：《高分子学报》2023年第9期1312-1319,共8页Acta Polymerica Sinica

基　　金：中国石油化工股份有限公司科技部项目(项目号420008-1)资助.

摘　　要：利用微尺度Cu(0)催化可逆失活自由基聚合的方法设计并合成了具有三臂星形结构的聚甲基丙烯酸酯类嵌段共聚物,并通过核磁共振、凝胶渗透色谱、流变等方法对聚合物的结构和性能进行了研究.首先,设计并搭建了微尺度铜管催化的聚合反应平台,以1,1,1-三(2-溴异丁酰氧甲基)乙烷为引发剂,高效合成了聚甲基丙烯酸甲酯(PMMA)和聚甲基丙烯酸十二烷基酯(PLMA)均聚物,研究表明微尺度铜管催化的可逆失活自由基聚合反应速率快,聚合过程可控,制备的聚合物分子量调节范围宽,分子量分布窄.通过铜管微反应单元的串联,制备了PMMA-b-PLMA共聚物.实验结果表明微尺度下铜管催化制备的聚甲基丙烯酸酯类嵌段共聚物具有结构可控,分子量可调节,分子量分布窄,分子链为三臂星形结构等特点.以制备的PMMA-b-PLMA和PMMA-b-聚甲基丙烯酸十六烷基酯(PMMA-b-PHMA)为润滑油添加剂,实现了对烷烃类润滑油缠结性能的响应性调节,提高了润滑油在不同温度下的黏度保持率.本研究为高效合成和应用三臂星形结构的聚甲基丙烯酸酯类聚合物提供了新的方法.Polymethacrylate block copolymers with three-arm star structure were designed and synthesized by micro-scale Cu(0)-catalyzed reversible deactivation radical polymerization.The structure and properties of the copolymers were studied by nuclear magnetic resonance,gel permeation chromatograph and rheological.Firstly,micro-scale Cu catalyzed polymerization platform was designed for the synthesis of poly(methyl methacrylate)and poly(laurylmethacrylate)intiated by 1,1,1-tris(2-bromoisobutyryloxymethyl)ethane(3f-BiB).Fast polymerization,controlled reaction process,wide range of molecular weight and narrow distribution were achieved under the micro-scale Cu catalyzed reversible deactivation radical polymerization platform.Poly(methyl methacrylate)-blockpoly(dodecyl methacrylate)copolymer was efficiently obtained in the assembled tandem microreactor system.The result demonstrated that controlled structure,adjustable molecular weight,narrow distribution and three-arm star structure were achieved by employing the micro-scale Cu catalyzed copolymerization.Additionally,responsive adjustment of the entanglement performance to the alkane solvents,improved viscosity retention rate of lubricating oil at different temperatures were achieved when the three-arm star polymethacrylate block copolymer was used as lubricating oil additives.

关 键 词：微尺度 铜催化 可逆失活自由基聚合 三臂星形聚合物 

分 类 号：TQ317[化学工程—高聚物工业]