镍催化可控/活性自由基聚合反应研究进展

doi:10.11949/0438-1157.20231407

摘要/Abstract

摘要：

可控/活性自由基聚合是近年来发展的温和、聚合反应进程可控、分子结构可设计性强的自由基聚合反应技术，其核心在于活性自由基中间体与催化剂/链转移剂的可逆活化/失活过程，常用于极性单体聚合制备结构多样的有机高分子材料。镍催化剂具有多变的中心金属价态及多样的聚合反应机理，在可控/活性自由基聚合领域存在独特的优势。对近年来原子转移自由基聚合（ATRP）和有机金属控制的活性自由基聚合（OMRP）中的镍催化剂结构、聚合反应机理、反应行为和产物结构特征进行了综述，并对镍催化的可控/活性自由基聚合未来发展方向和应用前景进行了展望。

关键词: 镍, 催化剂, 自由基, 聚合, 可控/活性自由基聚合

Abstract:

Controlled/living radical polymerization reactions are developed to take the advantages of mild reaction conditions, well controlled reaction processes and accessible modification of polymer structures to build a variety of organic polymer materials with polar monomers as the starting materials in recent years, of which the fundamental mechanism is the reversible activation/deactivation between radical intermediates and transition-metal catalysts/chain transfer reagents. Because of the different oxidation states and the variable polymerization mechanisms, nickel catalysts have unique advantages in controlled/living radical polymerization. This article reviews the structure of catalysts, polymerization mechanisms and the structure of products of nickel catalyzed atom-transfer radical polymerization (ATRP) and organometallic mediated radical polymerization (OMRP). The future development direction and application prospects of controlled/living radical polymerization are prospected.

Key words: nickel, catalyst, radical, polymerization, controlled/living radical polymerization

中图分类号:

TQ 316.3

程骁恺, 历伟, 王靖岱, 阳永荣. 镍催化可控/活性自由基聚合反应研究进展[J]. 化工学报, 2024, 75(4): 1105-1117.

Xiaokai CHENG, Wei LI, Jingdai WANG, Yongrong YANG. Advances in nickel catalyzed controlled/living radical polymerization reactions[J]. CIESC Journal, 2024, 75(4): 1105-1117.

图/表 17

图1 自由基聚合与过渡金属催化的活性自由基聚合

Fig.1 Free radical polymerization and transition-metal catalyzed living radical polymerization

图2 镍催化体系特性

Fig.2 Characteristics of nickel catalysis

图3 原子转移自由基聚合机理

Fig.3 Mechanism of atom-transfer radical polymerization

图4 含氮配体配位的镍催化剂及其催化ATRP机理

Fig.4 Nitrogen coordinated nickel catalyst and its catalytic mechanism in ATRP

图5 基于三苯基膦类配体的镍催化剂

Fig.5 Nickel catalysts based on PPh3-derivative ligands

图6 Ni(PPh3)2Br2催化PMMA-b-PBuA-b-PMMA三嵌段共聚物合成

Fig.6 Ni(PPh3)2Br2 catalyzed synthesis of PMMA-b-PBuA-b-PMMA block polymer

图7 NiCl2/PPh3催化体系

Fig.7 NiCl2/PPh3 catalytic system

图8 氢原子转移引发的ATRP

Fig.8 Hydrogen-atom transfer induced ATRP

图9 炔烃配位镍催化剂

Fig.9 Alkyne coordinated nickel catalyst

图10 PS-TPP/镍催化制备的PMMA

Fig.10 PMMA products synthesized by PS-TPP/nickel catalyst

图11 负载的镍催化剂

Fig.11 Heterogeneous nickel catalysts

图12 OMRP反应机理

Fig.12 Reaction mechanism of OMRP

图13 (TMP)Rh催化的首个OMRP反应

Fig.13 First OMRP reaction catalyzed by (TMP)Rh catalyst

图14 镍催化配位聚合/自由基聚合可切换反应体系

Fig.14 Nickel catalyzed switchable coordination polymerization/radical polymerization reaction

图15 水杨醛亚胺-镍催化的OMRP反应

Fig.15 Salicylaldimine-nickel catalyzed OMRP reaction

图16 激发态的活化模式

Fig.16 Activation mode through photo excited state

图17 Salen-镍催化的OMRP反应

Fig.17 Salen-nickel catalyzed OMRP reaction

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