Progress of CO2/epoxide copolymerization catalyst

doi:10.16085/j.issn.1000-6613.2022-1190

Abstract

Abstract:

Synthesis of poly(ether carbonate) polyol from CO₂ and epoxides is an effective way of CO₂ chemical utilization. Efficient catalysts can promote the reactions of CO₂ and epoxides to produce high-performance polymer products. This paper summarized the main progress of the catalysts for ring-opening copolymerization of CO₂ and epoxides in the latest three years. Catalysts of metal carboxylates, double metal cyanides, metal Salen complexes, metalloporphyrin and other novel organic catalysts are classified and reviewed from two aspects of heterogeneous and homogeneous catalysts. Inexpensive heterogeneous catalysts are still preferred for industrial applications, but how to control the distribution of active sites in the catalyst preparation process, thereby controlling the quality of polymer products, is the focus of future research. Metal Salen complexes are the hot research areas at present. The diversity of their organic ligand structures endows a variety of metal combinations. It is expected to develop more efficient and inexpensive catalysts in the near future.

Key words: catalyst, carbon dioxide, epoxide, polymerization, polymers, polyol

摘要：

“双碳”背景下，利用CO₂与环氧化合物为原料制备聚醚碳酸酯多元醇是CO₂化工利用的有效途径。高效的催化剂能够促进CO₂与环氧化物反应，制备更高性能的聚合物产品。本文详细介绍了近3年CO₂与环氧化合物开环共聚催化剂研究的主要进展。文中从非均相催化剂和均相催化剂两个方面，分别对金属羧酸盐、双金属氰化物、金属Salen、金属卟啉以及新型有机催化剂进行归类和综述。低廉的非均相催化剂仍是工业化实验的首选，但如何通过催化剂制备工艺控制活性位点分布，从而控制聚合物产品质量，是未来需要研究的重点。金属Salen催化剂是目前最热门的研究方向，其有机配体结构的多样性赋予多种金属组合配位的可能，期待开发更高效低廉的催化剂。

关键词: 催化剂, 二氧化碳, 聚合, 聚合物, 环氧化合物, 多元醇

CLC Number:

O633

HE Zhiyong, GUO Tianfo, WANG Jinli, LYU Feng. Progress of CO₂/epoxide copolymerization catalyst[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1847-1859.

何志勇, 郭天佛, 王金利, 吕锋. 二氧化碳/环氧化合物开环共聚催化剂进展[J]. 化工进展, 2023, 42(4): 1847-1859.

Figures/Tables 26

References 38

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序号	催化剂	温度/℃	时间/h	压力/MPa	TON/g∙g^-1	F_CO2/%	Mn浓度/kg∙mol^-1	PDI	参考文献	备注
1	ZnGA	60	40	2	72.4	94.9	156.4	3.5	[18]	—
2	ZnGA酸蚀刻	60	40	2	98.2	93.0	135	2.1	[18]	—
3	ZnGA化学修饰	60	40	2	100.1	94.9	208	1.8	[19]	—
4	ZnGA+不同转移剂	60	4	3	385	91.5	36	3.6	[20]	CTA:乙二醇苯醚
5	Co-Ni-DMC	92	3	4.3	233	30	48.3	6.8	[21]	CTA:PPG-425
6	DMC-ZnGA	80	20	3	2543	40.5	2.27	1.21	[22]	CTA:PPG-400
7	DMC-MAA配位	105	3	3	—	41.5	2.9	2.1	[23]	CTA:PPG
8	Co-Co-DMC多孔	90	24	2	181	20.0	68.6	4.1	[24]	—
9	Co-Fe-DMC多孔	90	24	2	111	33.5	50	5.9	[24]	—
10	Fe-Co-DMC多孔	90	24	2	142	16.3	85.4	6.3	[24]	—
11	DMC-RC-PBA	100	24	5	—	74.1	4.788	2.74	[25]	单体CHO

序号	催化剂	温度/℃	时间/h	压力/MPa	TON/g∙g^-1	F_CO2/%	Mn浓度/kg∙mol^-1	PDI	参考文献	备注
1	ZnGA	60	40	2	72.4	94.9	156.4	3.5	[18]	—
2	ZnGA酸蚀刻	60	40	2	98.2	93.0	135	2.1	[18]	—
3	ZnGA化学修饰	60	40	2	100.1	94.9	208	1.8	[19]	—
4	ZnGA+不同转移剂	60	4	3	385	91.5	36	3.6	[20]	CTA:乙二醇苯醚
5	Co-Ni-DMC	92	3	4.3	233	30	48.3	6.8	[21]	CTA:PPG-425
6	DMC-ZnGA	80	20	3	2543	40.5	2.27	1.21	[22]	CTA:PPG-400
7	DMC-MAA配位	105	3	3	—	41.5	2.9	2.1	[23]	CTA:PPG
8	Co-Co-DMC多孔	90	24	2	181	20.0	68.6	4.1	[24]	—
9	Co-Fe-DMC多孔	90	24	2	111	33.5	50	5.9	[24]	—
10	Fe-Co-DMC多孔	90	24	2	142	16.3	85.4	6.3	[24]	—
11	DMC-RC-PBA	100	24	5	—	74.1	4.788	2.74	[25]	单体CHO

序号	催化剂	温度/℃	时间/h	压力/MPa	TON/g∙g^-1	F_CO2/%	Mn浓度/kg∙mol^-1	PDI	参考文献	备注
1	salen-Co(Ⅲ)-三核	60	4	3	305	98	24.7	1.1	[29]	—
2	[(babhq)CrN₃(solv)]	100	4	2.5	743	—	16.5	1.57	[30]	单体CHO
3	Salen-Co(Ⅲ)-季铵盐	30	24	2	63.8	36.2	56.2	1.61	[16]	—
4	SalenCoCl/n-Bu₄NBr	50	6	3	11.3	—	—	—	[31]	—
5	氨基双(酚盐)合铬(Ⅲ)配合物	60	24	4	450	—	11.5	1.31	[32]	单体CHO
6	Salcy-CoCl配合物	40	6	3	31.3	96	12.7	1.27	[33]	—
7	Co₃/Ln配合物催化剂	130	8	2	1050	99	66	1.04	[34]	单体CHO
8	Co(Ⅲ)/M(Ⅰ)杂双核	50	5	2	96	99	2.3	1.08	[35]	—
9	Co(Ⅲ)/Na(Ⅰ)杂双核	100	8	0.1	54.5	96	2.5	1.16	[36]	单体CHO
10	Al卟啉-不同取代基	70	3	3	102	99.9	45.8	1.19	[37]	—
11	Al卟啉-低聚物催化剂	100	1	4	78.3	62	42.6	1.3	[38]	—
12	Al卟啉-刷状低聚物催化剂	50	20	—	168	15.6	3.5	1.11	[39]	CO₂含量4.05g
13	有机催化-TEB+季铵盐	50	—	1	2.19	—	1.4	1.3	[40]	—
14	有机催化-两性离子	60	4	2	31	93	14.6	1.13	[41]	—
15	吡嗪胺配位催化剂	100	3	1.5	323.8	—	—	—	[42]	—
16	NHC配位铪催化剂	60	18	0.1	474	99	21	1.3	[43]	单体CHO
17	离子功能化金属配合物催化剂	80	12	1	21.7	—	—	—	[44]	—

序号	催化剂	温度/℃	时间/h	压力/MPa	TON/g∙g^-1	F_CO2/%	Mn浓度/kg∙mol^-1	PDI	参考文献	备注
1	salen-Co(Ⅲ)-三核	60	4	3	305	98	24.7	1.1	[29]	—
2	[(babhq)CrN₃(solv)]	100	4	2.5	743	—	16.5	1.57	[30]	单体CHO
3	Salen-Co(Ⅲ)-季铵盐	30	24	2	63.8	36.2	56.2	1.61	[16]	—
4	SalenCoCl/n-Bu₄NBr	50	6	3	11.3	—	—	—	[31]	—
5	氨基双(酚盐)合铬(Ⅲ)配合物	60	24	4	450	—	11.5	1.31	[32]	单体CHO
6	Salcy-CoCl配合物	40	6	3	31.3	96	12.7	1.27	[33]	—
7	Co₃/Ln配合物催化剂	130	8	2	1050	99	66	1.04	[34]	单体CHO
8	Co(Ⅲ)/M(Ⅰ)杂双核	50	5	2	96	99	2.3	1.08	[35]	—
9	Co(Ⅲ)/Na(Ⅰ)杂双核	100	8	0.1	54.5	96	2.5	1.16	[36]	单体CHO
10	Al卟啉-不同取代基	70	3	3	102	99.9	45.8	1.19	[37]	—
11	Al卟啉-低聚物催化剂	100	1	4	78.3	62	42.6	1.3	[38]	—
12	Al卟啉-刷状低聚物催化剂	50	20	—	168	15.6	3.5	1.11	[39]	CO₂含量4.05g
13	有机催化-TEB+季铵盐	50	—	1	2.19	—	1.4	1.3	[40]	—
14	有机催化-两性离子	60	4	2	31	93	14.6	1.13	[41]	—
15	吡嗪胺配位催化剂	100	3	1.5	323.8	—	—	—	[42]	—
16	NHC配位铪催化剂	60	18	0.1	474	99	21	1.3	[43]	单体CHO
17	离子功能化金属配合物催化剂	80	12	1	21.7	—	—	—	[44]	—

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Progress of CO₂/epoxide copolymerization catalyst

二氧化碳/环氧化合物开环共聚催化剂进展

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