聚(1,4-环己二烯碳酸酯)立体低聚物的合成及微结构分析  

Synthesis and Microstructure Analysis of Stereoregular Poly(1,4-cyclohexadiene carbonate)Oligomers

作　　者：王霞弟 孙星宇 罗婧[1] 朱晴 周辉[1] 吕小兵[1] Xia-di Wang;Xing-yu Sun;Jing Luo;Qing Zhu;Hui Zhou;Xiao-bing Lu(State Key Laboratory of Fine Chemicals,Dalian University of Technology,Dalian 116024)

机构地区：[1]精细化工国家重点实验室,大连理工大学,大连116024

出　　处：《高分子学报》2021年第10期1316-1322,共7页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号91856108,21690073)资助项目。

摘　　要：聚合物微结构控制是配位催化聚合领域最重要的目标之一.而合成各种立构规整性低聚物及其核磁碳谱研究是聚合物微结构定性和定量分析的关键.本文以手性环己-4-烯-1,2-二醇为原料,采用N,N'-羰基二咪唑和三光气作为羰化试剂,设计合成了CO_(2)/1,2-环氧-4-环己烯交替共聚物(聚(1,4-环己二烯碳酸酯),PCEC)全同立构和间同立构的二聚体、四聚体、六聚体、八聚体和十二聚体模型化合物.通过分析全同立构和间同立构模型化合物的核磁碳谱,完成了PCEC微结构的碳谱信息归属.发现聚合物全同立构序列的羰基、次甲基和亚甲基区域的出峰位置分别在δ=154.04、73.83和29.91;间同立构序列的羰基、次甲基和亚甲基区域的出峰位置分别在δ=153.72、72.97和28.98.The alternating copolymerization of carbon dioxide(CO_(2))and epoxides to prepare degradable polycarbonates is an important green polymerization process,since CO_(2) is an abundant,cheap and nontoxic renewable C1 resource.Because of their good environmental friendliness and degradability,these materials are expected to be widely used in disposable packaging,degradable agricultural films,foaming agents and adhesives.For the copolymerization of substituted epoxides with CO2,the stereochemistry inherent to the epoxide monomer provides the possibility to synthesize stereoregular polycarbonates by establishing chiral centers in the main chain of the resultant copolymers with control of the absolute configuration.Indeed,there is a great correlation between the stereochemistry of polymer main chain and its physical properties.The precise control of polymer microstructure is one of the most important goals in the field of coordination catalysis polymerization.The synthesis of the corresponding model oligomers and analysis of their 13C-NMR spectra play a critical role in qualitative and quantitative analysis of polymer microstructure.In the present contribution,(R,R)/(S,S)-cyclohex 4-ene-1,2-diols were used as starting materials to synthesize various isotactic and syndiotactic model compounds(oligomers with 2,4,6,8 and 12 degree of polymerization)of poly(1,4-cyclohexadiene carbonate)(PCEC),using N,N'-carbonyldiimidazole and triphosgene as carbonylation reagents.By comparing the signals in the 13C-NMR spectra of various steroregular oligomers,it can be concluded that the signals atδ=154.04,73.83 and 29.91 are assigned to carbonyl,methine and methylene of isotactic PCEC,respectively,while the signals atδ=153.72,72.97 and 28.98 are attributed to carbonyl,methine and methylene of syndiotactic polycarbonate,respectively.

关 键 词：二氧化碳 聚碳酸酯 全同结构 间同结构 核磁碳谱 

分 类 号：TQ317[化学工程—高聚物工业]