Grubbs三代催化剂的合成及其催化双环戊二烯可控成型  

Synthesis of Grubbs 3r d catalysts and their controllable polymerization of bulk dicyclopentadiene

作　　者：杨维成 刘建 马海燕[1] YANG Weicheng;LIU Jian;MA Haiyan(East China University of Science and Technology,Shanghai 200237,China;Shanghai Research Institute of Chemical Industry Co.,Ltd.,Shanghai 200062,China;Shanghai Key Laboratory of Catalysis Technology for Polyolefins,Shanghai 200062,China;State Key Laboratory of Polyolefins and Catalysis Materials,Shanghai 200062,China)

机构地区：[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

出　　处：《精细化工》2023年第5期1015-1021,共7页Fine Chemicals

基　　金：上海自然科学基金(20ZR1424400);上海市浦江人才(21PJ1421000)。

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^(1)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。Several creative Grubbs 3rd catalysts(G3)were synthesized from reaction of Grubbs 2nd catalyst(G2)with different pyridine ligands,characterized and confirmed by 1HNMR.The G3 catalysts 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 content on the properties of p-DCPD were investigated with the p-DCPD characterized by FTIR,TGA and DSC,and tested by synchronous thermal analyzer,differential scanning calorimeter,microcomputer controlled electronic universal testing machine and cantilever impact testing machine for mechanical property analyses.The results indicated triphenylphosphine was more effective in the regulation of G3 than of G2.G3 exhibited excellent catalytic performance for DCPD polymerization with the mechanical properties of p-DCPD significantly improved.In particular,the prepared p-DCPD catalyzed by benzomethylene-[1,3-bis(trimethylphenyl)-2-imidazoline subunit]-dichloro-bis(3-methylpyridine)ruthenium(G3-5)displayed better thermal stability and compact cross-linking structure.

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 

分 类 号：TQ426[化学工程] TQ322.41