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.
出处
《高分子学报》
SCIE
CAS
CSCD
北大核心
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
关键词
双金属氰化络合物
二硫化碳
氧化环己烯
共聚
Double metal cyanide complex, Carbon disulfide, Cyclohexene oxide, Copolymerization