异戊二烯对苯乙烯-间戊二烯共聚合的影响  

Influence of Isoprene on Anionic Copolymerization of 1,3-Pentadiene and Styrene

作　　者：熊巧巧 古卓玮 谢锋历 杨帅 彭承俊 刘文强 陈豪 陈仕兵 张迪青 龚林林 肖哲 袁煜艳 佘振银 夏金魁 许俊东 李安 刘坤 Qiaoqiao Xiong;Zhuowei Gu;Fengli Xie;Shuai Yang;Chengjun Peng;Wenqiang LiuHao Chen;Shibing Chen;Qiding Zhang;Linlin Gong;Zhe Xiao;Yuyang Yuan;Zhenyin SheJinkui Xia;Jundong Xu;An Li;Kun Liu(College of Chemistry and Chemical Engineering,Hunan Institute of Science and Technology,Yueyang 414000,China;China Petroleum and Chemical Corporation Baling Branch,Yueyang 414000,China)

机构地区：[1]湖南理工学院化学化工学院,湖南岳阳414000 [2]中石化巴陵石油化工有限公司,湖南岳阳414000

出　　处：《高分子材料科学与工程》2023年第3期16-25,共10页Polymer Materials Science & Engineering

基　　金：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基金资助项目(2019JJ50213);湖南省自然科学基金面上项目(C5衍生δ-戊内酯高效绿色制备及其活性可控阴离子开环聚合研究);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)。

摘　　要：二烯烃-苯乙烯类单体序列结构极大程度上影响相关橡胶类产品(丁苯橡胶、多元集成橡胶)或树脂产品(丁苯树脂)的综合性能。活性阴离子聚合在共聚单体序列类型调控方面具有极大的优势,如严格嵌段序列、渐变嵌段序列、无规序列及交替序列等。新型间戊二烯(PD)单体可以通过阴离子共聚合实现其与苯乙烯类单体特殊交替序列共聚物的合成,异戊二烯(IP)阴离子聚合可以实现高顺式1,4-结构聚合物的定向合成。文中以PD、苯乙烯(ST)和IP为共聚单体,在环己烷中(含0.015%四氢呋喃)通过正丁基锂(n-BuLi)引发聚合合成了多元共聚物,重点考察了共聚动力学和共聚物的微观结构。实验结果表明:(1)聚合动力学显示均聚合速率ST>IP>>PD,ST/IP和PD/IP二元共聚显示经典“双S”转化率曲线,ST/PD二元共聚速率与IP均聚速率相当(;2)核磁氢谱和竞聚率数据显示ST/PD二元共聚符合经典交替共聚行为,结合红外数据表明,二元共聚产物1,4-结构含量高于90%,反1,4-结构含量高于85%;(3)三元共聚转化率与瞬时共聚单体组成关系表明,异戊二烯以高顺1,4-结构插入苯乙烯-间戊二烯序列中,三元共聚产物中无明显苯乙烯微嵌段序列和聚间戊二烯序列,无规化程度高(;4)三元共聚均具有明显的活性可控聚合特征,相对分子质量与理论值高度吻合,分子量分布(D)均小于1.10;(5)差示扫描量热分析结果显示,三元序列共聚物是只有唯一Tg的无定形聚合物,共聚单体倾向无规序列排布(;6)基于ST/PD特殊的二元交替共聚,推测了ST/IP/PD可能的三元聚合机理。The sequence structure of diene-styrene copolymer greatly affects the comprehensive properties of related rubber products(like styrene-butadiene rubber and similarly integrated rubber)or resin products(like styrene-butadiene resin).Living anionic polymerization has great advantages in controlling the comonomer sequence types,such as ideal block sequence,tapered block sequence,random sequence and alternating sequence.A novel conjugated diene,1,3-pentadiene(PD),can undergo anionic copolymerization with styrene to afford the special alternating sequence,whereas the high sequence 1,4-structure can be obtained by anionic polymerization of isoprene(IP).In this paper,the copolymerization of PD,styrene(ST)and IP was carried out in cyclohexane(containing 150×10-6 tetrahydrofuran)initiated by n-butyllithium(n-BuLi).The copolymerization kinetics and microstructure of the resultant copolymer were investigated in details.The results show that(1)the homo-polymerization kinetics shows that the polymerization rate is listed in this order ST>IP>>PD,and ST/IP and PD/IP binary copolymerization show the classical"double S"curve(conversion vs.time).Moreover,the ST/PD binary copolymerization rate is similar to the IP homopolymerization rate;(2)NMR and reactivity ratio data show that ST/PD binary copolymerization conforms to classical alternating copolymerization behavior.Infrared data show that the 1,4-structure content of binary copolymer is higher than 90%,and the trans-1,4-structure is higher than 85%;(3)the relationship between the conversion rate of terpolymerization and composition of instantaneous terpolymer shows that isoprene is inserted into the ST-PD sequence with a high cis-1,4-structure,and there is no obvious ST or PD microblock sequence in the terpolymer,and thus the sequence of ST/IP/PD is almost random;(4)the ternary copolymerization show obvious living and controllable polymerization,and the molecular weight is highly consistent with the theoretical value,and the molecular weight distribution is all less than 1.10;(

关 键 词：间戊二烯 苯乙烯 异戊二烯 交替共聚 无规共聚 序列分布 

分 类 号：O631.5[理学—高分子化学]