Study of Cationic Copolymerization of Isobutylene and <italic style="font-style: italic">p</italic>-(Chloromethyl)styrene

Ke Yang; Qiang Liu; Shuai Wen; Shu-xin Xu; Chen-qi Shi

doi:10.11777/j.issn1000-3304.2019.19179

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Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene

更新时间：2021-01-26

- Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene
- Acta Polymerica Sinica Vol. 51, Issue 4, Pages: 355-365(2020)
- 作者机构：
  
  橡塑材料与工程教育部重点实验室青岛科技大学　青岛 266042
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2019.19179
  CLC：
- Published：2020-4，
  
  Published Online：11 December 2019，
  
  Received：30 September 2019，
  
  Revised：30 October 2019，
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Ke Yang, Qiang Liu, Shuai Wen, Shu-xin Xu, Chen-qi Shi. Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene. [J]. Acta Polymerica Sinica 51(4):355-365(2020)
DOI：

Ke Yang, Qiang Liu, Shuai Wen, Shu-xin Xu, Chen-qi Shi. Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene. [J]. Acta Polymerica Sinica 51(4):355-365(2020) DOI： 10.11777/j.issn1000-3304.2019.19179.

摘要

以四氯化钛(TiCl

)、二氯乙基铝(AlEtCl

)、倍半铝(AlEt

1.5

)、三氯化铝(AlCl

)等路易斯酸为共引发剂，水或枯基醇(CumOH)为引发剂，在−80 °C下的正己烷/二氯甲烷(

= 6/4)的混合溶剂内，研究了异丁烯(IB)与对氯甲基苯乙烯(

-CMS)的正离子共聚合. 利用示差凝胶渗透色谱仪(GPC-RI)以及核磁氢谱(

H-NMR)对共聚物的表观分子量及分子量分布、共聚组成等进行分析，采用Kelen-Tüdős与Yezreielv-Brokhina-Roskin法计算了单体竞聚率，初步探讨了

-CMS与IB正离子共聚合的反应机理. 结果表明，AlEtCl

、AlEt

1.5

、AlCl

均可催化大分子间的烷基化反应，产生凝胶；TiCl

作为共引发剂，可以得到无凝胶单峰分布共聚物；邻位氯甲基苯乙烯(

-CMS)不能参与共聚，

-CMS的共聚活性较低，IB与

-CMS的单体竞聚率为

= 4.67，

CMS

= 0.70；随反应时间延长，共聚物中

-CMS的含量及共聚物分子量均逐渐增加；

-CMS单体自身几乎不参与引发，共聚到大分子链后，苄基氯缓慢参与引发，形成支化. 提高共聚合温度至− 60和− 40 °C，聚合速率降低，

-CMS的引发活性未发生明显变化.

Abstract

Cationic copolymerization of isobutylene (IB) and chloromethylstyrene was investigated with

-hexane (Hex)/dichloromethane (CH

) (

= 6/4) as solvent

TiCl

AlEt

1.5

AlEt

AlCl

as co-initiators and water or cumyl alcohol as initiators. The molecular weight

molecular weight distribution (MWD) and structure composition of the resulting copolymers were analyzed by gel permeation chromatography (GPC) and

H-NMR spectroscopy. The reactivity ratios were determined by Kelen-Tüdős and Yezreielv-Brokhina-Roskin formula

and the copolymerization mechanism was proposed. It was found that co-initiators with strong Lewis acidity

such as AlEtCl

AlEt

1.5

and AlCl

can catalyze intermolecular alkylations to form gels while no gel formed with the relatively weaker TiCl

. The chloromethylstyrene with para-substituent

-(chloromethyl)styrene (

-CMS) was found to have a low reactivity during the copolymerization with IB (

= 4.67

-CMS

= 0.70) while the ortho-isomer exhibited no activity. The chemical structure of resulting copolymers indicated that

-(chloromethyl)styrene cannot initiate the polymerization of IB which may be due to its low initiation rate compared to the highly active cumyl group at

-CMS/IB molar ratio of 4.11. However

the benzyl chloride group in the formed copolymer chain can slowly initiate polymerization of IB and

-(chloromethyl)styrene

forming branched structures. The content of

-(chloromethyl)styrene increased with increasing molecular weight and monomer conversion. Systematic research on the branched structure

rheological properties and other physical properties of the resulting copolymers is in progress.

关键词

异丁烯对氯甲基苯乙烯竞聚率正离子共聚合支化

Keywords

Isobutylenep-(Chloromethyl)styreneReactivity ratioCationic copolymerizationBranching

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School of Applied Chemistry and Engineering, University of Science and Technology of China

Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

School of Materials Science and Engineering, Key Laboratory of Polymer Composites & Functional Materials of Ministry of Education, Sun Yat-sen University

Daqing Chemical Engineering Research Center, Petrochemical Research Institute, China National Petroleum Corporation

Faculty of Materials Science and Chemical Engineering, Ningbo University

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Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene

DOI：10.11777/j.issn1000-3304.2019.19179

摘要

Abstract

关键词

Keywords

references