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Epoxidation modification of strictly alternating copolymer via living and controlled anionic alternating copolymerization of 1,3-pentadiene and styrene derivatives

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Abstract

Styrene/1,3-diene copolymers are widely used in rubber tires, adhesives, waterproof materials, automotive parts and others. However, their oil resistance, compatibility with polar materials, and poor adhesion limit their applications. Polarization modification strategy can further expand the application field of such materials. In this paper, a series of strictly alternating copolymers were synthesized in cyclohexane via living and controlled anionic alternating copolymerization of styrene derivatives (including styrene (ST), p-methylstyrene (MST), p-tert-butylstyrene (TBS), and 1,1-diphenylethylene (DPE)) with 1,3-pentadiene (PD) using n-BuLi initiator. The above-mentioned alternating copolymers were epoxidized in cycloamyl methyl ether (CPME, green solvent) using m-Chloroperoxybenzoic acid (m-CPBA) as the oxygen source. The 1H NMR and FTIR results showed that the degree of epoxidation (DE) of the alternating copolymers was controllable and the cross-linking gels can be avoided (determined by solubility experiment), and the DE of nearly 100% could be achieved by optimizing processes. As for these PD-based alternating copolymers, the type of substituents on rigid benzene rings has a certain impact on the epoxidation rate as well as the DE. DSC results showed that not only the high steric hindrance groups in polymer side chains but also the epoxidation strategy can greatly improve the heat resistance of the product.

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Acknowledgements

We are gratful to YueYang BaLing Petrochemical Chem. Co. Ltd. and ShangHai Petrochemical Chem. Co. Ltd. and for PD isomers and other polymer-grade reagents as gifts. The authors thank JinKui Xia, HongWen Liang, Zhenyin She, Yijiao Chen and JianSong Fu for helpful discussion. We are grateful for the support of the Challenge Cup Project and Internet Plus Innovation Project of Hunan Institute of Technology. We gratefully acknowledge the Changsha Municipal Natural Science Foundation (kq2208219), the financial support of Educational Commission of Hunan Province of China (No. 20B263, 20B268), Natural Science Foundation of Hunan Province of China (No.2019JJ50213, No.2022JJ30279) and National Natural Science Foundation of China (No. 21901070).

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Authors and Affiliations

  1. Province Key Laboratory for Fine Petrochemical Catalysis and Separation, College of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang, 414006, P. R. China

    Qiaoqiao Xiong, Shuai Yang, Chengjun Peng, Fengli Xie, Zhuowei Gu, Yawen Fu, Haoyun Tan, QiQi Dai, Lijun Li & Kun Liu

  2. College of Materials Science and Engineering, Changsha University of Science &Technology, Changsha, 410082, P. R. China

    Wenjun Yi

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  1. Qiaoqiao Xiong
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Xiong, Q., Yang, S., Peng, C. et al. Epoxidation modification of strictly alternating copolymer via living and controlled anionic alternating copolymerization of 1,3-pentadiene and styrene derivatives. J Polym Res 30, 326 (2023). https://doi.org/10.1007/s10965-023-03708-4

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