Citation: 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, ;2020, 51(4): 355-365. doi: 10.11777/j.issn1000-3304.2019.19179 shu

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

Key Laboratory of Rubber-Plastics of Ministry of Education, Qingdao University of Science & Technology, Qingdao 266042

Corresponding author: Qiang Liu, liuqiang@qust.edu.cn
Received Date: 30 September 2019
Revised Date: 30 October 2019
Available Online: 11 December 2019

Figures(13)

Cationic copolymerization of isobutylene (IB) and chloromethylstyrene was investigated with n-hexane (Hex)/dichloromethane (CH₂Cl₂) (V/V = 6/4) as solvent, TiCl₄, AlEt_1.5Cl_1.5, AlEt₂Cl, AlCl₃ 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 ¹H-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 AlEtCl₂, AlEt_1.5Cl_1.5 and AlCl₃ can catalyze intermolecular alkylations to form gels while no gel formed with the relatively weaker TiCl₄. The chloromethylstyrene with para-substituent, i.e., p-(chloromethyl)styrene (p-CMS) was found to have a low reactivity during the copolymerization with IB (r_IB = 4.67, r_p_-CMS = 0.70) while the ortho-isomer exhibited no activity. The chemical structure of resulting copolymers indicated that p-(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 p-CMS/IB molar ratio of 4.11. However, the benzyl chloride group in the formed copolymer chain can slowly initiate polymerization of IB and p-(chloromethyl)styrene, forming branched structures. The content of p-(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.
- Isobutylene,
- p-(Chloromethyl)styrene,
- Reactivity ratio,
- Cationic copolymerization,
- Branching
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