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

含磷/氮给电子体铁系催化剂催化1,3-双烯烃定向聚合

徐世亮,赵英男,余尧,那丽华,房梁,刘恒,张春雨,张学全   

  1. 青岛科技大学
  • 收稿日期:2024-12-16 修回日期:2025-03-06 出版日期:2025-03-18 发布日期:2025-03-18
  • 通讯作者: 张春雨 E-mail:cyzhang@qust.edu.cn
  • 基金资助:
    国家重点研发计划（批准号：2022YFB3704700）资助

Stereospecific polymerization of 1,3-dienes catalyzed by iron-based catalysts with P/N electron donors

XU Shiliang, ZHAO Yingnan, YU Yao, NA Lihua, FANG Liang, LIU Heng, ZHANG Chunyu, ZHANG Xuequan   

  1. Qingdao University of Science and Technology
  • Received:2024-12-16 Revised:2025-03-06 Online:2025-03-18 Published:2025-03-18
  • Contact: Chunyu Zhang E-mail:cyzhang@qust.edu.cn
  • Supported by:
    Supported by the National Key R&D Program of China(No.2022YFB3704700)

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摘要： 本工作考察了不同含磷/氮化合物对Fe(acac)3/AlR3体系催化1,3-丁二烯和异戊二烯聚合的影响。结果显示，采用异氰亚氨基三苯基膦（IITP）作为给电子体的铁系催化剂在己烷溶剂中高活性地合成了间同1,2-聚丁二烯和3,4-聚异戊二烯，活性最高可达1.52×106 g·PBd/mol·Fe和1.47×106 g·PIp/mol·Fe. 所得聚丁二烯具有较低的熔点（Tm：64.0-115.0 ℃），1,2-链节含量最高可达80.2%. 而聚异戊二烯则呈现中等的3,4-链节含量（48.8-52.4%），Tg在-18.5到-15.8 ℃之间. GPC曲线呈单峰分布，证明催化剂为单活性中心. 此外，通过异戊二烯的动力学实验和种子聚合实验，证明了该催化体系具备准活性聚合特征.

关键词: 配位聚合, 共轭双烯烃, 铁催化剂, 给电子体

Abstract: This work investigated the effects of different phosphorus-nitrogen compounds on the polymerization of 1,3-butadiene and isoprene catalyzed by Fe(acac)3/AlR3. The results showed that the use of isocyanoimino-triphenylphosphorane (IITP) as an electron donor can synthesize syndiotactic 1,2-polybutadiene and 3,4-polyisoprene with high activity in hexane, and the highest catalytic activity can achieve 1.52×106 g·PBd /mol·Fe and 1.47×106 g·PIp /mol·Fe. The obtained polybutadiene displays a low melting point (Tm: 64.0-115 ℃), and the1,2-unit content can reach up to 80.2%. The 3,4-incorporation content of polyisoprene is between 48.8-52.4%, and the Tg is kept from -18.5 to -15.8 ℃. The unimodal distribution GPC curve indicates that the catalytic system has a single active center. Moreover, the quasi living polymerization characteristics of the catalytic system are verified through kinetics and seeding polymerization experiments of isoprene.

Key words: Coordination polymerization, Conjugated diene, Fe-based catalyst, Electron donor

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