苯乙烯-间戊二烯-对甲基苯乙烯阴离子共聚合
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湖南理工学院 化学化工学院,湖南 岳阳 414000

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国家自然科学基金青年基金资助项目(21901070);湖南省自然科学基金青年项目(2019JJ50213);湖南省教育厅重点项目(20B263);中石化巴陵石油化工有限公司博士后项目;湖南省创新群体项目(2020JJ1004)


Anionic Copolymerization of Styrene, 1,3-Pentadiene and p-Methyl-Styrene
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    摘要:

    间戊二烯单体与苯乙烯可以通过阴离子共聚合实现特殊交替序列结构共聚物,此类材料在高抗冲击性树脂和增韧材料方面有特殊用途。本文以间戊二烯(PD)、苯乙烯(ST)和对甲基苯乙烯(MST)为共聚单体、正丁基锂(n-BuLi)为引发剂,在环己烷中通过“一步法”合成系列二元/三元共聚物,重点考察共聚动力学和共聚物微观结构。实验结果表明:聚合单体活性ST>MST>>PD,均共聚动力学显示聚合符合经典一级反应特征,共聚单体可以定量转化; 1H-NMR在线分析表明,PD/ST和PD/MST共聚单体等摩尔消耗,结合竞聚率数据推测PD倾向与苯乙烯类单体形成二元交替结构,且分析表明PD主要是1,4-加成方式嵌入主链;三元共聚合过程具有活性可控聚合特征,相对分子质量与转化率成良好的线性关系,分子量分布低于1.10;三元共聚物中间戊二烯组成(FPD = 0.5)似乎与转化率无关,但ST和MST共聚单体含量均与转化率成线性关系;基于PD特殊的二元交替共聚,推测了可能共聚合机理。

    Abstract:

    1,3-Pentadiene can undergo anionic copolymerization with styrene derivatives to give special alternating sequence-controlled copolymers, which have significantly applications in the area of impact resistance of resins and toughening agents. In this article, a series of copolymers were obtained via anionic copolymerization using styrene (ST), 1,3-pentadiene (PD) and p-methyl-Styrene (MST) as monomers and n-BuLi as initiator. The copolymerization kinetics analysis as well as the microstructure of copolymers was investigated in detail and some results show that :(1) the hopolymerization activities order is ST>MST>>PD and all polymerization kinetics analysis all show the evolution of -ln(1-x) versus t is strictly linear, and the copolymer yield easily reaches up to 100%; (2) the real-time NMR analysis show the composition of PD in poly(PD-alt-ST) or poly(PD-alt-MST) is constant (FPD=50%), and the NMR spectra results together with the reactivity ratio data all prove the alternating sequence microstructure. Moreover, the PD monomer has priority to undergo 1,4-addition reaction to give the predominant 1,4-units; (3) the alternating copolymerization and terpolymerization proceed in a living and controlled manner, and the molecular weight is well agreement with the theoretical value, also the molecular weight distribution is lower than 1.10; (4) in the case of n(MST)/n(ST)/n(PD)=1/1/2 system, the composition of PD in terpolymer is constant (FPD = 0.5) and the evolution of styrene composition (FST or FMST) versus x is strictly linear; (5) based on the dual-alternating copolymerization strategy of PD, the possible alternating polymerization mechanism was proposed.

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  • 收稿日期:2022-04-26
  • 最后修改日期:2022-10-03
  • 录用日期:2022-10-04
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