Spontaneous Alternating Copolymerization of 1-Silyloxy-1,3-dienes and Unsaturated Cyclic Anhydrides
Spontaneous Alternating Copolymerization of 1-Silyloxy-1,3-dienes and Unsaturated Cyclic Anhydrides
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1-甲硅烷氧基-1,3-二烯与不饱和环酐的自发交替共聚
DOI：
10.1295/polymj.33.429
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发表时间：
2001
期刊：
影响因子：
2.8
通讯作者：
T. Hirabayashi
中科院分区：
文献类型：
--
作者：
A. Takasu;Shinsuke Inoue;Y. Inai;T. Hirabayashi
摘要发现1-硅氧基-1,3-二烯即1-丁二烯基氧基三甲基硅烷（BdTMS）或1-丁二烯基氧基叔丁基二甲基硅烷（BdTBDMS）与含马来酸酐（MAn）、柠檬酸酸酐（CAn）和衣康酸酐（IAn）的不饱和环酸酐在苯中形成电荷转移配合物（CTC）。利用紫外光谱法，利用Benesi-Hildebrand方程计算了配合物的平衡常数K为0.4 ~ 1.0。在饲料中添加25 ~ 75 mol%的BdTMS时，建立了硅氧基二烯与不饱和环酸酐的自发共聚反应。所得聚合物的摩尔组成均为50/50，与进料摩尔比无关。有趣的是，1,4-和3,4-加成结构的摩尔比似乎受CTC的K的影响。对聚（BdTMS-alt-MAn）进行脱硅和连续内酯化。交替共聚物中相邻羟基与环酸酐的分子内反应使内酯化转化率超过Flory极限（86.5%），接近100%。
Abstract1-Silyloxy-1,3-dienes, i. e., 1-butadienyloxytrimethylsilane (BdTMS) or 1-butadienyloxytert-butyldimethylsilane (BdTBDMS) and unsaturated cyclic anhydrides, containing maleic anhydride (MAn), citraconic anhydride (CAn), and itaconic anhydride (IAn) were found to form charge transfer complexes (CTC) in benzene. Equilibrium constants, K, of the complexes were calculated by the Benesi-Hildebrand equation using UV spectroscopy to be 0.4-1.0. Spontaneous copolymerizations of silyloxydienes with unsaturated cyclic anhydrides were established from 25 to 75 mol% of BdTMS in the feed. All polymers obtained had molar composition of 50/50 irrespective of feed molar ratios. Interestingly, molar ratio of 1,4- and 3,4-addtion structure seems to be influenced by K of CTC. Desilylation and successive lactonization of poly(BdTMS-alt-MAn) were conducted. Conversions of lactonization were beyond Flory’s limit (86.5%) being nearly 100% due to intramolecular reactions of neighboring hydroxyl groups and cyclic anhydride in alternating copolymers.