1-(4-二甲基硅氢苯基)-1-苯乙烯/异戊二烯的活性阴离子交替共聚合调控研究

董承威; 冷雪菲; 韩丽; 李超; 杨琳燦; 沈禾雨; 马红卫; 李杨

doi:10.11777/j.issn1000-3304.2020.20204

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1-(4-二甲基硅氢苯基)-1-苯乙烯/异戊二烯的活性阴离子交替共聚合调控研究

研究论文 | 更新时间：2021-03-05

- 1-(4-二甲基硅氢苯基)-1-苯乙烯/异戊二烯的活性阴离子交替共聚合调控研究
  增强出版
- Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene
- 高分子学报 2021年52卷第3期页码：287-296
- 作者机构：
  
  大连理工大学化工学院　大连 116024
- 作者简介：
  
  E-mail: mahw@dlut.edu.cn Hong-wei Ma, E-mail: mahw@dlut.edu.cn
  E-mail: liyang@dlut.edu.cn Yang Li, E-mail: liyang@dlut.edu.cn
- 基金信息：
  
  国家重点研发计划(项目号 2017YFB0307101)资助()
- DOI：10.11777/j.issn1000-3304.2020.20204
  中图分类号：
- 纸质出版日期：2021-3-3，
  
  网络出版日期：2020-10-16，
  
  收稿日期：2020-8-31，
  
  修回日期：2020-9-21，
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董承威, 冷雪菲, 韩丽, 李超, 杨琳燦, 沈禾雨, 马红卫, 李杨. 1-(4-二甲基硅氢苯基)-1-苯乙烯/异戊二烯的活性阴离子交替共聚合调控研究[J]. 高分子学报, 2021,52(3):287-296.

Cheng-wei Dong, Xue-fei Leng, Li Han, Chao Li, Lin-can Yang, He-yu Shen, Hong-wei Ma, Yang Li. Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene[J]. Acta Polymerica Sinica, 2021,52(3):287-296.
董承威, 冷雪菲, 韩丽, 李超, 杨琳燦, 沈禾雨, 马红卫, 李杨. 1-(4-二甲基硅氢苯基)-1-苯乙烯/异戊二烯的活性阴离子交替共聚合调控研究[J]. 高分子学报, 2021,52(3):287-296. DOI： 10.11777/j.issn1000-3304.2020.20204.

Cheng-wei Dong, Xue-fei Leng, Li Han, Chao Li, Lin-can Yang, He-yu Shen, Hong-wei Ma, Yang Li. Study on the Regulation of Living Anionic Alternating Copolymerization of 1-(4-Dimethylsiloxphenyl)-1-styrene and Isoprene[J]. Acta Polymerica Sinica, 2021,52(3):287-296. DOI： 10.11777/j.issn1000-3304.2020.20204.

摘要

采用活性阴离子聚合方法研究了硅氢基功能化的1

1-二苯基乙烯(DPE)衍生物1-(4-二甲基硅氢苯基)-1-苯乙烯(DPE-SiH)与异戊二烯(Ip)在苯中的共聚反应，采用多种方法对序列分布、竞聚率和表观速率常数等进行测定. 结果表明无调节剂下共聚物链中异戊二烯的插入量远多于DPE-SiH，DPE-SiH主要分布在聚合物链末端，得到了一种梯度共聚物，竞聚率

=9.28，2种单体的表观速率常数分别为

=0.00134 min

−1

，

=0.01421 min

−1

，Ip在无调节剂条件下的共聚中表现出高活性. 同时研究了添加调节剂(

N′N'N'N

-四甲基乙二胺(TMEDA)和叔丁醇钾(

-BuOK))后的共聚物链中的序列分布，加入调节剂TMEDA和

-BuOK后得到了交替共聚物，实现了DPE-SiH和Ip单元在共聚物链中的序列调控，且对链中Ip单元的微观结构含量进行了调控，对形成交替共聚物的原因做了探讨，并通过Gaussian模拟探究了活性中心对Ip微观结构具有选择性的机理以及调节剂对活性中心的作用机理.

Abstract

The alternating regulation of living anionic copolymerization of 1-(4-dimethylsiloxphenyl)-1-styrene (DPE-SiH) and isoprene (Ip) was studied. By combining

in situ

H-NMR with MALDI-TOF MS technologies

the sequence distribution and apparent rate constant of monomers in the copolymer

as well as the reactivity ratio of Ip were determined. The results showed that the amount of DPE-SiH unit entering in the copolymer was less than that of Ip

and the site of DPE-SiH unit was mainly gathered at the end of copolymer when without the addition of regulators. Meanwhile

the gradient copolymer was obtained with the reactivity ratio

=9.28. The apparent rate constants of DPE-SiH and Ip unit were

=0.00134 min

−1

and

=0.01421 min

−1

respectively. In addition

the sequence distribution characteristics of the two monomers in the copolymer chain after the addition of the regulators [

N'N'N'N

-tetramethylethylenediamine (TMEDA) and potassium

tert

-butoxide (

-BuOK)] were investigated. The copolymer with the alternating sequence feature was obtained when the regulator TMEDA and

-BuOK were added

achieving the sequence control of DPE-SiH and Ip unit in the copolymer chain. Meanwhile

the alternating entry of two monomers in the copolymer chain and the improvement of

trans

-1

4 Ip contents of copolymer were attributed to the “space-limited” living species resulted by the addition of regulators according to the results of Gaussian simulation.

关键词

活性阴离子聚合交替序列调控1-(4-二甲基硅氢苯基)-1-苯乙烯异戊二烯

Keywords

Living anionic polymerizationAlternating sequence control1-(4-Dimethylsiloxphenyl)-1-styreneIsoprene

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