高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

胺端基官能化反式丁戊共聚橡胶的制备及其配位链转移机理研究

罗淑芳1，赵远进1，王硕1，周润川2，杨霞2，贺爱华1   

  1. 1. 青岛科技大学高分子科学与工程学院，橡塑材料与工程教育部重点实验室，山东省高性能聚烯烃材料与循环利用重点实验室(筹) 2. 青岛科技大学化工学院，计算机与化工研究所

  • 收稿日期:2025-03-07 修回日期:2025-04-27 网络首发:2025-05-19 发布日期:2025-05-19
  • 通讯作者: 贺爱华 E-mail:ahhe@qust.edu.cn
  • 基金资助:
    国家重点研发计划项目(批准号: 2022YFB3704700(2022YFB3704702))、山东省重大科技创新工程项目(批准号: 2021CXGC010901)和泰山学者工程资助

Preparation of Amine-capped Functionalized Trans-1,4-poly (butadiene-co-isoprene) Rubber and Coordination Chain Transfer Mechanism

LUO Shufang1, ZHAO Yuanjin1, WANG Shuo1, ZHOU Runchaun2, YANG Xia2, HE Aihua1   

  1. 1. Shandong Key Laboratory of High Performance Polyolefin Materials and Recycling, Key Laboratory of Rubber-plastics(Ministry of Education), School of Polymer Science and Engineering, Qingdao University of Science and Technology 2. Research Center for Computer and Chemical Engineering，College of Chemical Engineering，Qingdao University of Science and Technology

  • Received:2025-03-07 Revised:2025-04-27 Online First:2025-05-19 Published:2025-05-19
  • Supported by:
    Supported by the National Key Research and Development Program of China(No.2022YFB3704700(2022YFB3704702)), the Major Scientific and Technological Innovation Project of Shandong Province, China(No.2021CXGC010901) and the Taishan Scholar Program, China.

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摘要： 端基官能化橡胶在改善填料分散性、增加橡胶与填料之间相互作用力，进而影响橡胶复合材料性能方面发挥重要作用. 本文采用非均相TiCl4/MgCl2型Ziegler-Natta催化剂以二环己胺(DCHA)为链转移剂，通过配位链转移聚合一步合成了组成和结构可控的胺端基官能化的高反式-1,4-丁二烯-异戊二烯共聚橡胶(F-TBIR). 研究了DCHA用量、助催化剂三乙基铝(AlEt3)用量对催化效率、胺端基官能化效率(CE)和F-TBIR链微观结构的影响，发现DCHA不改变催化剂的定向能力，DCHA用量增加，催化效率及聚合物的分子量降低，CE显著提高；AlEt3用量增加，催化效率先增加后降低，CE与聚合物分子量均逐渐降低. 计算得到了本文实验条件下DCHA的链转移常数为0.0537，AlEt3的链转移常数为0.016. 结合密度泛函理论(DFT)模拟，本文讨论了DCHA和AlEt3在非均相Ziegler-Natta催化剂催化二烯烃配位聚合中的链转移机理，为制备端基官能化的合成橡胶提供了一种简便可行的策略.

关键词: 配位链转移, 端基官能化橡胶, 反式-1,4-丁二烯-异戊二烯共聚橡胶, Ziegler-Natta催化剂

Abstract: The chain-end functionalized rubbers play important roles in improving the filler dispersion, increasing the interaction force between rubbers and filler particles, both of which affect the properties of the final products. In this paper, amine-capped trans-1,4-poly (butadiene-co-isoprene) copolymers (F-TBIR) with controllable composition and micro-structure were synthesized through in one-step coordination chain transfer polymerization by using heterogeneous TiCl4/MgCl2 type Ziegler-Natta catalyst with dichyclohexylamine (DCHA) as chain transfer agent. The effects of the amount of DCHA and co-catalyst triethylaluminum (AlEt3) on the the catalytic efficiency, amine-capped efficiency (CE) and chain micro-structure of the F-TBIR were investigated. The results indicated that DCHA did not change the stereo-regularity of the catalytic species. With the increase in DCHA dosage, the catalytic efficiency and molecular weight of the copolymers decreased, while CE increased significantly. With the increase in the amount of AlEt3, the catalytic efficiency initially increased then subsequently decreased, and the molecular weight of polymer and CE gradually decreased. Under the specified experimental conditions, the chain transfer constants of DCHA and AlEt3 were 0.0537 and 0.016, respectively. Combined with Density Functional Theory (DFT) simulation, the chain transfer mechanism of DCHA and AlEt3 in the diene coordination polymerization catalyzed by heterogeneous Ziegler-Natta catalyst was discussed. This work was expected to provide a straightforward and feasible strategy for developing chain-end functionalized synthetic rubber.

Key words: Coordination chain transfer; Chain-end functionalization, Trans-1,4-(butadiene-co-isoprene) copolymer rubber; Ziegler-Natta catalyst

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