Ring‐opening polymerization of cyclobutane adducts of tetracyanoethylene and vinyl ethers with quaternary ammonium halides
Ring‐opening polymerization of cyclobutane adducts of tetracyanoethylene and vinyl ethers with quaternary ammonium halides
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四氰乙烯和乙烯基醚环丁烷加合物与季铵卤化物的开环聚合
DOI：
10.1002/macp.1996.021970717
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发表时间：
1996
期刊：
影响因子：
--
通讯作者：
Kimitada Hida
中科院分区：
文献类型：
--
作者：
T. Yokozawa;Takanori Mori;Kimitada Hida
介绍了四氰乙烯（TCNE）和乙烯醚（VE）的环丁烷加合物与季铵盐的开环聚合反应。用10 mol-%的四丁基碘化铵（TBAI）在N，N-二甲基乙酰胺（DMAc）中室温聚合TCNE的环丁烷加合物5a与乙基乙烯醚（EVE），得到了产率高、产率高的TCNE与EVE共聚物，且不受TBAI污染。在最优条件下，TCNE的环丁烷加合物与多种VEs如丁基乙烯醚、异丁基乙烯醚、2,3-二氢呋喃和3,4-二氢- 2h -吡喃进行了聚合，得到了类似的聚合物。基于聚合物分子量在初始阶段迅速增加，而在消耗完所有单体后仍缓慢增加的事实，我们提出TBAI的碘离子引发环丁烷加合物的阴离子链聚合，产生碘取代的大阴离子6，并以阶梯反应的方式进行分子间的亲核取代。在氯离子存在下，环丁烷与氯甲基醚的模型反应进一步证实了6的分子间反应。
Ring-opening polymerizations of cyclobutane adducts of tetracyanoethylene (TCNE) and vinyl ethers (VE) with quaternary ammonium halides are described. The polymerization of the cyclobutane adduct 5a of TCNE and ethyl vinyl ether (EVE) was carried out with 10 mol-% of tetrabutylammonium iodide (TBAI) in N,N-dimethylacetamide (DMAc) at ambient temperature to afford the alternating copolymer of TCNE and EVE with high molecular weight in good yield without contamination by TBAI. Under the optimum conditions, the cyclobutane adducts of TCNE and a variety of VEs such as butyl vinyl ether, isobutyl vinyl ether, 2,3-dihydrofuran, and 3,4-dihydro-2H-pyran were polymerized to yield similar polymers. On the basis of the fact that the polymer molecular weight increased rapidly at the initial stage and slowly even after the consumption of all monomers, we propose that the iodide ion of TBAI initiates the anionic chain polymerization of the cyclobutane adduct to afford an iodide-substituted macroanion 6, which is subjected to intermolecular nucleophilic substitution with each other in a step reaction manner. This intermolecular reaction of 6 was further confirmed by a model reaction of cyclobutane with chloromethyl methyl ether in the presence of chloride ion.