ISSN 1000-3304CN 11-1857/O6

Citation: Ke Yang, Qiang Liu, Shuai Wen, Shu-xin Xu and 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

  • Corresponding author: Qiang Liu, liuqiang@qust.edu.cn

  • Received Date: 2019-09-30
    Accepted Date: 2019-10-30
    Available Online: 2020-04-01

Figures(14) / Tables(5)

  • Cationic copolymerization of isobutylene (IB) and chloromethylstyrene was investigated with n-hexane (Hex)/dichloromethane (CH2Cl2) (V/V = 6/4) as solvent, TiCl4, AlEt1.5Cl1.5, 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, AlEt1.5Cl1.5 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 (rIB = 4.67, rp-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.
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