钴配合物在烯烃聚合中的应用

doi:10.6023/cjoc202204036

摘要/Abstract

聚烯烃材料年产量巨大, 用途广泛, 与人类生产生活密切相关. 聚烯烃研究领域的核心在于催化剂, 催化剂的性能往往决定了聚烯烃的性质. 因此, 高性能的催化剂设计与合成成为研究的一大热点. 随着科技工作者的不懈努力, 大量的催化剂相继问世. 其中钴配合物是一类十分重要的烯烃聚合催化剂, 它能够用于催化多种单体聚合. 这些钴配合物结构丰富, 配位原子种类多样(例如N、O、P、S等), 且合成简便. 因此, 通过对催化剂结构进行精确调控, 可以实现提高其催化活性、调整聚合物的微观结构、改善聚合物的宏观性能等目的. 综述了钴配合物在乙烯、共轭二烯、降冰片烯、丙烯酸酯等常见单体均聚中的应用, 并从结构的角度将钴配合物进行了分类. 此外, 还详细讨论了催化剂结构、助催化剂、反应温度等因素对催化剂活性、聚合物分子量以及聚合物微观结构等性质的影响, 期望为钴配合物的设计与合成提供参考.

关键词: 钴配合物, 乙烯, 共轭二烯, 降冰片烯, 丙烯酸酯

Polyolefin materials have huge annual output and wide applications, which are closely related to human production and life closely. The core of polyolefin research lies in the catalyst, the performance of which often determines the properties of polyolefins. Therefore, the design and synthesis of high-performance catalyst have become a hot research topic, and a large number of catalysts have come out. Cobalt complexes are very important kind of olefin polymerization catalysts, which can be used to catalyze a variety of monomer polymerization. These cobalt complexes are structure diversity and have a variety of coordination atoms (such as, N, O, P, S etc.), and the synthesis is relatively simple. Therefore, the structure of the catalyst can be precisely regulated to improve the catalytic activity, adjust the microstructure of the polymer, and improve the macroscopical properties of the polymer. In this paper, the applications of cobalt complexes in homopolymerization of ethylene, conjugated dienes, norbornene, acrylates and other common monomers are reviewed, and the cobalt complexes are classified from the perspective of structure. What’s more, the effects of catalyst structure, temperature, cocatalyst on catalyst activity, polymer molecular weight and polymer microstructure are discussed in detail. It is expected to provide a reference for the design and synthesis of cobalt complexes in the future.

Key words: cobalt complexes, ethylene, conjugated dienes, norbornene, acrylates

引用此文

付联荣, 王艳冰, 姜辉, 郝新奇, 宋毛平. 钴配合物在烯烃聚合中的应用[J]. 有机化学, 2022, 42(11): 3530-3548.

Lianrong Fu, Yan-Bing Wang, Hui Jiang, Xin-Qi Hao, Mao-Ping Song. Applications of Cobalt Complexes in Olefin Polymerization[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3530-3548.

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图/表 32

图1. 乙烯齐聚/聚合方程式

Figure 1. Oligomerization/polymerization of ethylene

图2. 共轭二烯的聚合

Figure 2. Polymerization of conjugated dienes

图3. 降冰片烯的聚合

Figure 3. Polymerization of norbornene

图4. 丙烯酸酯类单体的聚合

Figure 4. Polymerization of acrylates

图5. 乙烯聚合的可能机理

Figure 5. Possible mechanism of ethylene polymerization

图6. 单茂钴配合物

Figure 6. Half-cobaltcene complexes

图7. 含α-双亚胺配体的钴配合物

Figure 7. Cobalt complexes bearing α-diimine ligands

图8. 基于吡啶亚胺配体的[N,N]双齿钴配合物

Figure 8. [N,N] Bidentate cobalt complexes based on iminopyridine ligands

图9. 基于喹啉衍生物的[N,N]双齿钴配合物

Figure 9. [N,N] bidentate cobalt complexes based on quinoline derivatives

图10. 含其它类型配体的双齿钴配合物

Figure 10. Bidentate cobalt complexes bearing other types of ligands

图11. 吡啶双亚胺钴配合物的合成

Figure 11. Synthesis of cobalt complexes bearing 2,6-bis- (imino)pyridine ligands

图12. 基于2,6-双亚胺吡啶及其衍生物的[N,N,N]三齿钴配合物

Figure 12. [N,N,N] tridentate cobalt complexes based on 2,6- bis(imino)pyridine and their derivatives

图13. 含有吸电子基的吡啶双亚胺钴配合物

Figure 13. Bis(imino)pyridine cobalt complexes bearing electron-withdrawing group

图14. 基于1,10-菲罗啉衍生物的[N,N,N]三齿钴配合物

Figure 14. [N,N,N] cobalt complexes based on 1,10-phenan- throline derivatives

图15. 基于喹啉衍生物的[N,N,N]三齿钴配合物

Figure 15. [N,N,N] cobalt complexes based on quinoline derivatives

图16. 含有并环结构的[N,N,N]三齿钴配合物

Figure 16. [N,N,N] tridentate cobalt complexes bearing cyclo-fused structure

图17. 含其它类型配体的三齿钴配合物

Figure 17. Tridentate cobalt complexes bearing other types of ligands

图18. 共轭二烯聚合的可能机理

Figure 18. Possible mechanism of conjugated diene polymerization

图19. 含膦配体的钴配合物

Figure 19. Cobalt complexes bearing phosphine ligands

图20. 含[N,N]双齿配体的钴配合物

Figure 20. Cobalt complexes bearing [N,N] bidentate ligands

图21. 含[N,N,N]三齿配体的钴配合物

Figure 21. Cobalt complexes bearing [N,N,N] tridentate ligands

图22. 基于PN3型配体及其衍生物的三齿钴配合物

Figure 22. Tridentate cobalt complexes based on PN3-type ligands and their derivatives

图23. 基于水杨醛亚胺及其衍生物的钴配合物

Figure 23. Cobalt complexes based on imino-salicylaldehyde and its derivatives

图24. 含[P,N,P]三齿配体的钴配合物

Figure 24. Cobalt complexes bearing [P,N,P] tridentate ligands

图25. 含其它类型配体的三齿钴配合物

Figure 25. Tridentate cobalt complexes bearing other types of ligands

图 26. 降冰片烯聚合的可能机理

Figure 26. Possible mechanism of norbornene polymerization

图27. 用于催化降冰片烯聚合的钴配合物

Figure 27. Cobalt complexes used for polymerization of norbornene

图28. 丙烯酸酯类单体聚合的可能机理

Figure 28. Possible mechanism of acrylates polymerization

图29. 立体异构现象示意图

Figure 29. The phenomenon of stereoisomerism

图30. 基于水杨醛亚胺配体及其衍生物的钴配合物

Figure 30. Cobalt complexes based on imino-salicylaldehyde ligands and their derivatives

图31. 基于吡啶亚胺配体及其衍生物的钴配合物

Figure 31. Cobalt complexes based on imino-pyridine ligands and their derivatives

图32. 含其它类型配体的钴配合物

Figure 32. Cobalt complexes bearing other types of ligands

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