Cationic copolymerization of isobutylene and bio-renewable β-myrcene towards sustainable elastomers: synthesis and mechanism

IF 2.8 4区化学 Q3 POLYMER SCIENCE Journal of Polymer Research Pub Date : 2025-02-25 DOI:10.1007/s10965-025-04306-2

Yanqing Feng, Penghui Guo, Wei Ding, Yushun Jin, Ruofan Liu, Yibo Wu

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Abstract

The use of renewable bio-based monomers to prepare polyisobutylene-based polymers can not only reduce the dependence on petroleum resources but also promote the green transformation of the cationic polymerization industry. Herein, 2-chloro-2,4,4-trimethylpentane (TMPCl) was synthesized as the main initiator and then cooperated with co-initiator TiCl₄ to construct a cationic initiation system, which was successfully used in preparing poly(isobutylene-co-β-myrcene). The effects of co-initiator concentration, monomer concentration and monomer feed ratio on the copolymerization of isobutylene (IB) and β-myrcene were investigated. The results showed that the molecular weight (M_n) first increased and then decreased with elevating the concentration of TiCl₄. When the monomer concentration was 15 wt% and the monomer feed ratio (mole ratio between IB and β-myrcene) was 98:2, an IB-co-β-myrcene random copolymer with a molecular weight of 7.3 × 10³ g/mol and a lower T_g (-67.97 ℃) was obtained. According to the ¹H NMR analysis of the polymer structure and terminal groups, it was suggested that IB and β-myrcene mainly formed the copolymer with 1,4 structural unit under this initiation system, thus the cationic polymerization mechanism of IB and β-myrcene was further proposed. This work can provide basic data and theoretical guidance for the manufacture of greener polyisobutylene-based polymers in the future.

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异丁烯与生物可再生β-月子烯阳离子共聚制备可持续弹性体：合成及机理

利用可再生生物基单体制备聚异丁烯基聚合物，不仅可以减少对石油资源的依赖，而且可以促进阳离子聚合工业的绿色转型。本文以2-氯-2,4,4-三甲基戊烷（TMPCl）为主引发剂，与助引发剂TiCl4协同构建阳离子引发体系，成功制备了聚异丁烯-co-β-月桂烯。研究了共引发剂浓度、单体浓度和单体投料比对异丁烯（IB）与β-月子烯共聚反应的影响。结果表明，随着TiCl4浓度的升高，其分子量（Mn）先升高后降低。当单体质量浓度为15 wt%，单体投料比（IB与β-月桂烯的摩尔比）为98:2时，可制得分子量为7.3 × 103 g/mol、Tg（-67.97℃）较低的IB-co-β-月桂烯无规共聚物。通过对聚合物结构和端基的1H NMR分析可知，在该引发体系下，IB与β-月子烯主要形成了结构单元为1,4的共聚物，从而进一步提出了IB与β-月子烯的阳离子聚合机理。该工作可为今后生产更环保的聚异丁烯基聚合物提供基础数据和理论指导。

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公司名称

产品信息

阿拉丁

2,4,4-Trimethyl-1-pentene

来源期刊

Journal of Polymer Research 化学-高分子科学

CiteScore

4.70

自引率

7.10%

发文量

472

审稿时长

3.6 months

期刊介绍： Journal of Polymer Research provides a forum for the prompt publication of articles concerning the fundamental and applied research of polymers. Its great feature lies in the diversity of content which it encompasses, drawing together results from all aspects of polymer science and technology. As polymer research is rapidly growing around the globe, the aim of this journal is to establish itself as a significant information tool not only for the international polymer researchers in academia but also for those working in industry. The scope of the journal covers a wide range of the highly interdisciplinary field of polymer science and technology, including: polymer synthesis; polymer reactions; polymerization kinetics; polymer physics; morphology; structure-property relationships; polymer analysis and characterization; physical and mechanical properties; electrical and optical properties; polymer processing and rheology; application of polymers; supramolecular science of polymers; polymer composites.