Synthesis, kinetic study and characterization of C5-dienes/styrene copolymers via living anionic polymerization in cyclopentyl methyl ether solvent
Yawen Fu, Shuai Yang, Qiaoqiao Xiong, Zhuowei Gu, Qiqi Dai, Haoyun Tan, Le Zhou, Menghan Geng, Fengli Xie, Wen-jun Yi, Lijun Li, Kun Liu
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Abstract
1,3-Dienes/styrene sequence-controlled copolymers are widely used as thermoplastic elastomers, transparent impact resin and synthetic rubber and other materials. In this work, the binary anionic copolymerization of styrene (S ) and C5-dienes including 1,3-pentadiene (P , E /Z = 65/35) and isoprene (I ) were studied in cyclopentyl methyl ether (CPME) ‘green’ solvent using n -BuLi as initiator, and the effects of copolymerization monomer ratio and polar additive (PA) on the copolymerization kinetics and monomer sequence distributions were investigated. The kinetic analysis results showed that all copolymerization systems were the first-order reaction and the C5-dienes/S could be quantitatively consumed. The addition of S or I was conducive to the efficient conversion of P . Although the addition of PAs had little effect on the polymerization rate, it had a great influence on the microstructure and sequence distribution of the copolymer. 1 H NMR tracking analysis showed that, for S/P copolymerization with different feeding ratios 1/3 < f P < 2/3, the instant composition F P in the copolymer remained relatively constant at 15% < F P < 35% when the monomer conversion rate was below 60%, and thus the inevitable formation of P microblocks in subsequent polymerization sequences was observed. Additionally, similar sequence distributions were obtained in the case of I/P copolymerization systems. By contrast, S /I copolymerization conformed to the typical random copolymerization pattern, and the copolymerization activity of S was slightly higher than that of the I in CPME. The use of strong PAs such as 2,2-di(2-tetrahydrofuran)propane directly resulted in a change of monomer sequence from a random pattern to a gradual block pattern. Moreover, the 3,4-isoprene branch units were much more sensitive to solvent and PA than 1,2-pentadiene units for C5-dienes; also Fourier transform infrared and DSC analysis verified the microstructure and sequence analysis results mentioned above. In addition, the results of gel permeation chromatography showed that the copolymerization process in CPME had excellent controllable characteristics. © 2023 Society of Industrial Chemistry.
环戊基甲基醚阴离子活性聚合c5 -二烯/苯乙烯共聚物的合成、动力学研究及表征
1,3-二烯/苯乙烯序控共聚物广泛应用于热塑性弹性体、透明冲击树脂和合成橡胶等材料。本文以n-BuLi为引发剂,在环戊基甲基醚(CPME)“绿色”溶剂中,研究了1,3-戊二烯(P, E/Z = 65/35)和异戊二烯(I)与苯乙烯(S)二元阴离子共聚反应,考察了共聚单体比例和极性添加剂对共聚动力学和单体序列分布的影响。动力学分析结果表明,所有共聚体系均为一级反应,c5 -二烯/S可以定量消耗。极性助剂(PA)的加入对聚合速率影响不大,但对共聚物的微观结构和序列分布有较大影响。1H NMR跟踪分析表明,对于不同投料比1/3 < fP < 2/3的S/P共聚,当单体转化率低于60%时,共聚物中的瞬时组成fP保持在15% < fP < 35%的相对恒定,因此在随后的聚合序列中不可避免地形成P微嵌段。此外,在I/P共聚体系中也得到了类似的序列分布。相比之下,S/I的共聚符合典型的随机共聚模式,并且S的共聚活性略高于CPME中的I。2,2-二(2-四氢呋喃)丙烷(DTHFP)等强PAs的使用直接导致单体序列由随机模式转变为逐渐的嵌段模式。此外,3,4- ip支基对溶剂和PA的敏感性远高于1,2- pd支基对c5 -二烯的敏感性,FTIR和DSC分析也验证了上述结构和序列分析结果。GPC实验结果表明,CPME共聚过程具有良好的可控性。
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