Ring‐opening polymerization of cyclobutane adducts of tetracyanoethylene and vinyl ethers with tertiary amines
Ring‐opening polymerization of cyclobutane adducts of tetracyanoethylene and vinyl ethers with tertiary amines
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四氰乙烯和乙烯基醚环丁烷加合物与叔胺的开环聚合
DOI：
10.1002/pola.1995.080330802
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发表时间：
1995
期刊：
影响因子：
--
通讯作者：
H. Fukata
中科院分区：
文献类型：
--
作者：
T. Yokozawa;H. Fukata
本文叙述了四氰基乙烯（TCNE）与乙烯基醚（VE）或对甲氧基苯乙烯的环丁烷加合物与叔胺的开环聚合。在室温下，用10mol%的三乙胺在乙腈中进行TCNE与乙基乙烯基醚（EVE）的环丁烷加成物1a的聚合，在各种条件下以良好的产率得到了高分子量的TCNE与EVE交替共聚物。在最佳条件下，TCNE与正丁基乙烯基醚、异丁基乙烯基醚、2，3-二氢呋喃和3，4-二氢-2H-吡喃等多种乙烯基醚的环丁烷加成物进行了聚合，得到了类似的聚合物。尽管TCNE和对甲氧基苯乙烯的环丁烷加合物4在这些条件下不发生溶胀，但在60°C下在乙腈中用1，8-二氮杂双环[5.4.0]十一碳-7-烯（DBU）处理4得到聚合物。根据聚合物分子量在初始阶段增长迅速，在单体消耗后增长缓慢的事实，我们提出叔胺引发环丁烷加合物的链阴离子聚合，得到大分子两性离子铵3，它以分步聚合的方式进行分子间亲核取代。John Wiley & Sons，Inc.
Ring-opening polymerizations of cyclobutane adducts of tetracyanoethylene (TCNE) and vinyl ethers (VE) or p-methoxystyrene with tertiary amines are described. The polymerization of the cyclobutane adduct 1a of TCNE and ethyl vinyl ether (EVE) was carried out with 10 mol % of triethylamine in acetonitrile at ambient temperature to afford the alternating copolymer of TCNE and EVE with high molecular weight in good yield under various conditions. Under the optimum condition, the cyclobutane adducts of TCNE and a variety of VEs such as n-butyl vinyl ether, isobutyl vinyl ether, 2,3-dihydrofuran, and 3,4-dihydro-2H-pyran were polymerized to yield similar polymers. Although the cyclobutane adduct 4 of TCNE and p-methoxystyrene did not polymerize under these conditions, the treatment of 4 with 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in acetonitrile at 60°C gave the polymer. 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 of monomers, we propose that the tertiary amine initiates the chain anionic polymerization of the cyclobutane adduct to afford an ammonium macrozwitterion 3, which is subjected to the intermolecular nucleophilic substitution with each other in a step polymerization manner. © 1995 John Wiley & Sons, Inc.