锌-钴双金属氰化络合物催化二硫化碳与氧化环己烯共聚研究  

COPOLYMERIZATION OF CARBON DISULFIDE AND CYCLOHEXENE OXIDE WITH A DOUBLE-METAL CYANIDE COMPLEX CATALYST

作　　者：张兴宏[1] 黄亦军[2] 刘斐[1] 孙学科[1] 范志强[1] 戚国荣[1] 

机构地区：[1]浙江大学高分子科学与工程学系高分子合成与功能构造教育部重点实验室,杭州310027 [2]杭州师范大学钱江学院,杭州310036

出　　处：《高分子学报》2009年第6期546-552,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20704034);中国博士后科学基金(基金号20060400339)资助项目

摘　　要：报道了锌-钴双金属氰化络合物(double metal cyanide complex,DMCC)催化CS2与氧化环己烯(CHO)直接共聚生成脂环族聚硫代碳酸酯的反应.傅立叶红外光谱(FTIR)及拉曼(Raman)光谱结果表明该共聚物端基为-OH和-SH结构;核磁共振(1H和13C-NMR)结果表明共聚物主链含碳酸酯-O(CO)O-链节和4种硫代碳酸酯-O(CO)S-、-S(CO)S-、-O(CS)S-和-S(CS)S-链节结构;气相色谱-质谱(GC-MS)联用结果表明产物中含有环硫环己烷及3种环状硫代碳酸酯.聚合物链结构和产物种类表明CS2/CHO共聚反应存在氧-硫原子交换反应过程.A novel alicyclic polythiocarbonate with a complex structure sequence has been synthesized by a convenient one-pot polymerization of carbon disulfide （CS2） and cyclohexene oxide （CHO） with Zn-Co^Ⅲ doublemetal cyanide complex （DMCC） as the catalyst. The catalytic activity of the Zn-Co^Ⅲ DMCC could reach to 445 g polymer/g catalyst when the reaction temperature was 100℃ and molar ratio of CHO/CS2 was 2. Further increasing or decreasing the temperature resulted in a decrease in the catalytic activity. The weight-average molecular weight （Mw ） of the obtained eopolymer was in the range of 1.1 × 10^3 -1.3× 10^3 with a molecular weight distribution （MWD） of 1.57 - 1.71 .The copolymer has terminated --OH and-SH groups from the results of FTIR spectrum and Raman spectrum. Furthermore, one carbonate unit -O （O）CO-, and four thiocarbonate units -S（O）-CO-,- S（O） CS-,-S（S） CO-, and -S（S） CS- in the copolymer were found from l H and 13 C-NMR spectra, and the monothiocarbonate unit （-S（O）CO-） was the main unit in the eopolymer,whieh was consistent with the results from FFIR spectrum. Cyclohexene sulfide, which was a direct evidence for O-S atom-exchange reaction, was detected by GC-MS technique from the products. Only hexahydro-benzo[ 1,3] oxathiol-2-one, hexahydro-benzo [ 1,3 ] dithiol-2-one, and hexahydro-benzo [ 1,3 ] dithiole-2-thione （ theoretically six five-membered cyclic products） were detected due to the monomer structural factors and tbermodynamical factors. The eopolymer chain structure and variety of cyclic products indicates that an O-S atom-exchange reaction existed in the copolymerization. Further efforts and experiments are on going in order to further explore the mechanism of the atom-exchange copolymerization and with a view to synthesizing a sulfur-containing polymer with high molecular weights, controllable stereochemical structures, as well as high catalytic activity.

关 键 词：双金属氰化络合物 二硫化碳 氧化环己烯 共聚 

分 类 号：O631.3[理学—高分子化学]