Page 95 - 《精细化工》2023年第5期

第 40 卷第 5 期 精 细 化 工 Vol.40, No.5
20 23 年 5 月 FINE CHEMICALS May 2023

功能材料
Grubbs 三代催化剂的合成及其

催化双环戊二烯可控成型

1*
杨维成 1,2,3,4 ，刘 建 2,3,4 ，马海燕
（1. 华东理工大学 化学与分子工程学院，上海 200237；2. 上海化工研究院有限公司，上海 200062；
3. 上海市聚烯烃催化技术重点实验室，上海 200062；4. 聚烯烃催化技术与高性能材料国家重点实验室，
上海 200062）

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摘要：用 Grubbs 二代催化剂（G2）与吡啶类配体反应制备了一系列 Grubbs 三代催化剂（G3），采用 HNMR
对其进行了结构表征。利用制备的 G3 催化双环戊二烯（DCPD）本体聚合，在添加三苯基膦阻聚剂实现 DCPD
聚合过程可控的基础上，采用模具浇注法制备了聚双环戊二烯（p-DCPD）板材，探讨了阻聚剂、不同催化剂及
催化剂用量对 p-DCPD 板材性能的影响，采用 FTIR、TGA 和 DSC 对制备的 p-DCPD 板材进行了表征，通过同
步热分析仪、差示扫描量热仪、微机控制电子万能实验机、悬臂梁冲击试验机对 p-DCPD 板材的力学性能进行
了测试。结果表明，三苯基膦对 G3 的调控效果优于 G2，合成的 G3 在催化 DCPD 本体聚合时，表现出较高的
催化活性，且其催化制备的 p-DCPD 板材的力学性能明显优于 G2 催化制备的样品。尤其是，由苯亚甲基-[1,3-
双(三甲基苯基)-2-咪唑啉亚基]-二氯-二(3-甲基吡啶)合钌（G3-5）制得的 p-DCPD 板材表现出优异的热稳定性，
具有紧致的交联结构。
关键词：Grubbs 三代催化剂；聚双环戊二烯；阻聚剂；可控成型；功能材料
中图分类号：TQ426；TQ 322.4+1 文献标识码：A 文章编号：1003-5214 (2023) 05-1015-07

Synthesis of Grubbs 3rd generation catalysts and their controllable

polymerization of bulk dicyclopentadiene

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YANG Weicheng 1,2,3,4 , LIU Jian 2,3,4 , MA Haiyan
（1. School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237,
China; 2. Shanghai Research Institute of Chemical Industry Co., Ltd., Shanghai 200062, China; 3. Shanghai Key
Laboratory of Catalysis Technology for Polyolefins, Shanghai 200062, China; 4. State Key Laboratory of Polyolefins and
Catalysis Materials, Shanghai 200062, China）

Abstract: Several creative Grubbs catalysts 3rd generation (G3) were synthesized from reaction of Grubbs
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catalyst 2nd generation (G2) with different pyridine ligands, characterized and confirmed by HNMR. The
G3 samples obtained then were evaluated for their catalytic performance in the bulk polymerization of
dicyclopentadiene (DCPD) via mold casting method, of which the polymerization process was controlled
by polymerization inhibitor triphenylphosphine. The effects of polymerization inhibitor, catalyst type and
catalyst dosage on the properties of p-DCPD sheet materials were investigated. The p-DCPD sheet
materials were characterized by FTIR, TGA and DSC, and their mechanical properties were tested by
synchronous thermal analyzer, differential scanning calorimeter, microcomputer controlled electronic
universal testing machine and cantilever impact testing machine. The results indicated triphenylphosphine
was more effective in the regulation of G3 than in that of G2. G3 exhibited excellent catalytic performance
for DCPD bulk polymerization with the mechanical properties of p-DCPD sheet material significantly
improved. In particular, the prepared p-DCPD sheet material catalyzed by benzomethylene-[1,3-

收稿日期：2022-08-16; 定用日期：2022-10-17; DOI: 10.13550/j.jxhg.20220759
基金项目：上海自然科学基金（20ZR1424400）；上海市浦江人才（21PJ1421000）
作者简介：杨维成（1982—），男，高级工程师，E-mail：ywcjc@163.com。联系人：马海燕（1973—），女，教授，E-mail：
haiyanma@ecust.edu.cn。