Synthesis of alternating copolymer of tetracyanoethylene and ethyl vinyl ether by ring‐opening polymerization
Synthesis of alternating copolymer of tetracyanoethylene and ethyl vinyl ether by ring‐opening polymerization
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开环聚合合成四氰乙烯与乙基乙烯基醚交替共聚物
DOI：
10.1002/marc.1993.030140405
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发表时间：
1993
期刊：
影响因子：
--
通讯作者：
S. Futamura
中科院分区：
文献类型：
--
作者：
T. Yokozawa;Yuichiro Miyamoto;S. Futamura
给体烯烃与受体烯烃的自发热反应形成各种各样的有机小分子和聚合物。在Hall，Jr.提出的“成键引发理论”中，共振稳定取代基导致双自由基四亚甲基，其可引发给体和受体烯烃的共聚，而强给体和强受体取代基导致两性离子四亚甲基，其可产生环丁烷加合物或引发给体烯烃的阳离子均聚和/或受体烯烃的阴离子均聚。这意味着强给体烯烃和强受体烯烃的共聚物不能通过两性离子中间体获得。例如，等摩尔的四氰基乙烯（TCNE）与乙基乙烯基醚（EVE）的自发反应通过两性离子四亚甲基中间体z）的中间作用仅提供环丁烷加合物。然而，我们想到，由强给体和受体烯烃衍生的环丁烷加合物的开环聚合将允许获得强给体和强受体烯烃的共聚物。由于这些环丁烷衍生自两性离子四亚甲基，它们将能够进行阴离子和阳离子开环聚合（方案1）。
The spontaneous, thermal reaction of donor olefins with acceptor olefins form a remarkable variety of both small organic molecules and polymers. In the “bondforming initiation theory” proposed by Hall, Jr.’) resonance-stabilizing substituents lead to diradical tetramethylenes which can initiate the copolymerization of donor and acceptor olefins, whereas strong donor and strong acceptor substituents lead to zwitterionic tetramethylenes which can produce a cyclobutane adduct or initiate the cationic homopolymerization of the donor olefin and/or the anionic homopolymerization of the acceptor olefin. This means that the copolymers of strong donor olefins and strong acceptor olefins cannot be obtained through zwitterionic intermediates. For example, the spontaneous reaction of equimolar tetracyanoethylene (TCNE) with ethyl vinyl ether (EVE) affords only a cyclobutane adduct through the intermediacy of zwitterionic tetramethylene intermediates z). However, it occurred to us that the ring-opening polymerization of the cyclobutane adducts derived from strong donor and acceptor olefins would permit access to the copolymers of strong donor and strong acceptor olefins. Since these cyclobutanes are derived from zwitterionic tetramethylenes, they would be able to undergo both anionic and cationic ring-opening polymerizations (Scheme 1).