氧化异丁烯与CO_(2)共聚物的合成及其结构与性能  

Synthesis,Structure and Properties of Isobutylene Oxide-CO_(2) Copolymer

作　　者：曹晓瀚 吕俊奇 赵佳 张成建 孙悦[1] 虞卿磊 侯家祥 张兴宏[1,2] Xiao-han Cao;Jun-qi Lv;Jia Zhao;Cheng-jian Zhang;Yue Sun;Qing-lei Yu;Jia-xiang Hou;Xing-hong Zhang(State Key Laboratory of Motor Vehicle Biofuel Technology,International Research Center for X Polymers,Department of Polymer Science and Engineering,Zhejiang University,Hangzhou 310027;China Center of Chemistry for Frontier Technologies,Zhejiang University,Hangzhou 310027;Shandong Shida Shenghua Chemical Group Co.Ltd.,Dongying 257000)

机构地区：[1]浙江大学,车用生物燃料技术国家重点实验室,高分子新物质创制国际研究中心,高分子科学与工程学系,杭州310027 [2]浙江大学化学前瞻技术研究中心,杭州310027 [3]山东石大胜华化工集团股份有限公司,东营257000

出　　处：《高分子学报》2022年第9期1104-1111,共8页Acta Polymerica Sinica

摘　　要：氧化异丁烯(IBO)是石化行业重要C4产品异丁烯的衍生物.将IBO与二氧化碳(CO_(2))共聚制备脂肪族聚碳酸酯,是一条高附加值利用异丁烯和CO_(2)的可行途径,但迄今仅有零星的研究报道.本文采用非均相的锌-钴双金属氰化络合物(Zn-Co DMCC)在40℃的反应温度下催化IBO与CO_(2)共聚,催化效率高达1.6 kg共聚物/g催化剂,所得产物聚碳酸亚丁酯(PIBC)具有全交替序列结构,区域规整度高达95%,数均分子量达18.6 kDa.特别的,PIBC为结晶性高分子,熔点高达93.7℃,初始热分解温度仅为145℃.PIBC的拉伸强度达4.4 MPa,断裂伸长率达350%,因此PIBC有望应用于牺牲型粘接剂.另外,Zn-Co DMCC也能催化CO_(2)、IBO与马来酸酐共聚,得到了具有全交替结构的三元共聚物.研究结果为异丁烯的应用开拓了一条可持续发展的新路径.Isobutene oxide(IBO)is a derivative of isobutene that is an important C4 product in petrochemical industry.The preparation of aliphatic polycarbonates by the copolymerization of IBO with carbon dioxide(CO_(2))is a feasible way to utilize isobutene and CO_(2)with high added value,but only few studies have been reported so far.In this paper,heterogeneous Zn-Co bimetal cyanidation complex(Zn-Co DMCC)was used to catalyze the copolymerization of IBO with CO_(2)at 40℃,and the catalytic efficiency was up to 1.6 kg copolymer/g DMCC.The product of poly(butyl carbonate)(PIBC)had a fully alternating structure and a regional regularity of 95%.The number-average molecular weight was up to 18.6 k Da,and the lowest content of cyclic by-product was 7 mol%.PIBC is a crystalline polymer with a melting point of 93.7℃,but the crystallization rate of PIBC is slow.The initial thermal decomposition temperature of PIBC is only 145℃.The tensile strength of PIBC is 4.4 MPa and the elongation at break is 350%.Therefore,PIBC may be used in sacrificial adhesives.DMCC also catalyzed the copolymerization of CO_(2),IBO and maleic anhydride(MA)to obtain a fully alternating terpolymer.The results provide a new sustainable development path for the application of isobutene.

关 键 词：二氧化碳 聚碳酸酯 氧化异丁烯 马来酸酐 结晶高分子 

分 类 号：TQ317[化学工程—高聚物工业] TQ426[环境科学与工程—环境工程] X701