1:1 Alternating and 1:2 Sequence-Controlled Radical Copolymerization of 1,3-Pentadiene isomers with Maleic Anhydride/N-phenylalkyl maleimide
1:1 Alternating and 1:2 Sequence-Controlled Radical Copolymerization of 1,3-Pentadiene isomers with Maleic Anhydride/N-phenylalkyl maleimide
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1,3-戊二烯异构体与马来酸酐/N-苯基烷基马来酰亚胺的1:1交替和1:2顺序控制自由基共聚
DOI：
10.1039/c9py01642b
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发表时间：
2020
影响因子：
4.6
通讯作者：
Haoyun Deng
中科院分区：
文献类型：
--
作者：
Kun Liu;Min Sun;Fengli Xie;Cainan Hu;Zan Yang;An Li;JinKui Xia;Xu Qiu;Xu Wang;Haoyun Deng
研究了顺丁烯二酸酐/N-苯基烷基马来酰亚胺（MAH/NPMI）与1，3-戊二烯（PD）异构体的Diels-Alder环加成反应与顺丁烯二酸酐/N-苯基烷基马来酰亚胺（MAH/NPMI）序列控制自由基共聚反应之间的竞争。共聚行为显着依赖于异构体构象以及进料比，导致形成AB-交替和AAB-周期（2：1序列控制）共聚物，Mn值高达105 g mol−1在温和条件下。 基于“成键引发理论”，通过关键的四亚甲基中间体，讨论了顺序控制的自由基共聚反应机理，与动力学分析和NMR测定的微观结构分析结果相一致。研究表明，该反应机理为s-transPD与MAH反应生成π-烯丙基-2-己烯-1，6-双自由基，引发MAH-CP交替共聚。
The competition between the Diels–Alder cycloaddition and the sequence-controlled radical copolymerization of maleic anhydride/N-phenylalkyl maleimide (MAH/NPMI) with 1,3-pentadiene (PD) isomers was investigated. The copolymerization behavior significantly depended on the isomer conformation as well as the feeding ratio, leading to the formation of AB-alternating and AAB-periodic (2 : 1 sequence-controlled) copolymers with Mn values up to 105 g mol−1 under mild conditions. The sequence-controlled radical copolymerization mechanism was discussed based on the “bond-forming initiation theory” via the key tetramethylene-intermediate, which is in agreement with the results of the kinetics analysis and the microstructure analysis determined by NMR. The suggested mechanism involved the formation of a π-allyl-2-hexene 1,6-diradical formed by the reaction of s-trans PD with MAH, which initiates the MAH-CP alternating copolymerization.