茂金属催化线性α-烯烃聚合获取高分子量产物研究进展

doi:10.16085/j.issn.1000-6613.2024-0411

化工进展 ›› 2025, Vol. 44 ›› Issue (3): 1309-1322.DOI: 10.16085/j.issn.1000-6613.2024-0411

茂金属催化线性α-烯烃聚合获取高分子量产物研究进展

刘俊杰¹^,²^,³(), 吴建民¹^,²^,³(), 孙启文¹^,²^,³(), 王建成¹^,², 孙燕¹^,²^,³

^1.太原理工大学化学工程与技术学院，山西太原 030024
^2.怀柔实验室山西研究院，山西太原 030000
^3.上海兖矿能源科技研发有限公司煤液化气化及高效低碳利用全国重点实验室，上海 201203

收稿日期:2024-03-12 修回日期:2024-05-17 出版日期:2025-03-25 发布日期:2025-04-16
通讯作者: 吴建民,孙启文
作者简介:刘俊杰（1997—），男，博士研究生，研究方向为费托合成产物高值化加工。E-mail：18834809943@163.com。

Research of metallocene catalysts for linear α-olefins polymerization to obtain high molecular weight products

LIU Junjie¹^,²^,³(), WU Jianmin¹^,²^,³(), SUN Qiwen¹^,²^,³(), WANG Jiancheng¹^,², SUN Yan¹^,²^,³

^1.College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Shanxi Research Institute of Huairou Laboratory, Taiyuan 030000, Shanxi, China
^3.State Key Laboratory of Coal Liquification, Gasification and Utilization with High Efficiency and Low Carbon Technology, Shanghai Yankuang Energy;R&D Co. , Ltd. , Shanghai 201203, China

Received:2024-03-12 Revised:2024-05-17 Online:2025-03-25 Published:2025-04-16
Contact: WU Jianmin, SUN Qiwen

摘要/Abstract

摘要：

相比传统Ziggler-Natta催化剂和Lewis酸催化剂，茂金属催化剂具备活性高、产物分子量高、分布单一和环境友好等特点。但催化剂的复杂制备过程和无水无氧的反应环境等苛刻要求严重限制其发展。基于此，本文概述了以往研究中催化聚合不同种类线性α-烯烃（LAO）的茂金属催化剂及其反应条件和性能表现，从催化剂的空间结构、催化剂的电子结构、助催化剂的影响等方面详细分析了造成不同性能表现的主要原因，如空间位阻、β-H占比和整体分子刚性等，并分别提出适合于催化聚合不同种类LAO的茂金属催化剂类型和最佳操作条件。对以有机硼化物为助催化剂的催化聚合LAO的体系构建，后续LAO的催化聚合机理和影响因素研究，以铪为金属活性中心的茂金属催化剂的合成设计进行了展望。旨在为LAO催化聚合获取高分子量产物的茂金属催化剂的开发设计提供理论指导。

关键词: 茂金属催化剂, 线性α-烯烃, 催化聚合, 聚合物, 高分子量产品

Abstract:

Compared to Ziggler-Natta and Lewis acid catalysts, many characteristics, including better activity, higher molecular weight, single product distribution and greater environmental friendliness, have been found in metallocene catalysis for linear α-olefins (LAO) polymerization. However, its development is limited due to the complex preparation process and strict requirements for the content of water and oxygen in catalytic systems. Based on this, the types, reaction conditions and performance of metallocene catalysts used in previous studies on different LAO monomers were summarized firstly. Subsequently, the main reasons for different performance of catalysts were anal yzed in spatial structure, electronic structure and the cocatalyst influence such as spatial hindrance, β-H proportion and rigidity. Meanwhile, the suitable metallocene catalyst and optimal operating condition for the polymerization of different LAO were proposed. Finally, the construction of catalytic system using organoboron compound as cocatalyst, the subsequent study of the mechanism and influence factors, and the design synthesis of metallocene catalysts with hafnium as metal active center for LAO polymerization were discussed. This review intended to provide theoretical guidance for the development and design of metallocene catalyst for LAO polymerization obtaining high molecular weight products.

Key words: metallocene catalysts, linear α-olefins, catalytic polymerization, polymers, high molecular weight products

中图分类号:

TQ31

刘俊杰, 吴建民, 孙启文, 王建成, 孙燕. 茂金属催化线性α-烯烃聚合获取高分子量产物研究进展[J]. 化工进展, 2025, 44(3): 1309-1322.

LIU Junjie, WU Jianmin, SUN Qiwen, WANG Jiancheng, SUN Yan. Research of metallocene catalysts for linear α-olefins polymerization to obtain high molecular weight products[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1309-1322.

图/表 12

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图1编号	催化剂种类	活性/kg·(mmol Zr)^-1·h^-1	M_v	M_w	M_w/M_n	参考文献
(a)	C₂H₄(Ind)₂ZrCl₂	—	—	35102^①	1.876	[24]
(b)	Me₂Si(Ind)₂ZrCl₂	33.20	16000^②	—	—	[25]
(c)	rac-Me₂Si(2-Me-Ind)₂ZrCl₂	49.00	202100	272200^③	2.2	[25]
(c)	rac-Me₂Si(2-Me-Ind)₂ZrCl₂	37.961	—	14262^④	1.46	[30]
(d)	rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂	7.9	111000	152500^⑤	2.5	[25]
(e)	rac-Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	46.901	—	12258^④	1.76	[30]
(f)	Me₂Si(1-Ind)(S₂-3)ZrCl₂	—	132400	173400^⑥	2.1	[32]
(g)	Me₂Si(2-Me-Ind)(S₂-3)ZrCl₂	—	134400	176000^⑦	2.2	[32]
(h)	Me₂Si(2-Me-4-Ph-Ind)(S₂-3)ZrCl₂	—	204000	236000^⑥	2.0	[32]
(i)	Me₂Si(2-Me-4-p-^tBuPh-Ind)(S₂-3)ZrCl₂	—	243000	315000^⑥	2.0	[32]
(j)	Me₂Si(2-Me-苯并[e]Ind)(S₂-3)ZrCl₂	—	321000	414000^⑥	2.0	[32]
(k)	Me₂Si(2,5,5,7,7-五甲基-Ind)(S₂-3)ZrCl₂	—	216000	280000^⑥	2.1	[32]
(l)	Me₂Si(2,4,7-Me₃-Ind)(S₂-3)ZrCl₂	—	229000	297000^⑥	2.1	[32]
(m)	Me₂Si(4,7-Me₂-Ind)(S₂-3)ZrCl₂	—	189000	228000^⑥	2.0	[32]
(n)	Me₂Si(2,4,6-Me₃-Ind)(S₂-3)ZrCl₂	40.0	365200^⑧	—	—	[25]

图1编号	催化剂种类	活性/kg·(mmol Zr)^-1·h^-1	M_v	M_w	M_w/M_n	参考文献
(a)	C₂H₄(Ind)₂ZrCl₂	—	—	35102^①	1.876	[24]
(b)	Me₂Si(Ind)₂ZrCl₂	33.20	16000^②	—	—	[25]
(c)	rac-Me₂Si(2-Me-Ind)₂ZrCl₂	49.00	202100	272200^③	2.2	[25]
(c)	rac-Me₂Si(2-Me-Ind)₂ZrCl₂	37.961	—	14262^④	1.46	[30]
(d)	rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂	7.9	111000	152500^⑤	2.5	[25]
(e)	rac-Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	46.901	—	12258^④	1.76	[30]
(f)	Me₂Si(1-Ind)(S₂-3)ZrCl₂	—	132400	173400^⑥	2.1	[32]
(g)	Me₂Si(2-Me-Ind)(S₂-3)ZrCl₂	—	134400	176000^⑦	2.2	[32]
(h)	Me₂Si(2-Me-4-Ph-Ind)(S₂-3)ZrCl₂	—	204000	236000^⑥	2.0	[32]
(i)	Me₂Si(2-Me-4-p-^tBuPh-Ind)(S₂-3)ZrCl₂	—	243000	315000^⑥	2.0	[32]
(j)	Me₂Si(2-Me-苯并[e]Ind)(S₂-3)ZrCl₂	—	321000	414000^⑥	2.0	[32]
(k)	Me₂Si(2,5,5,7,7-五甲基-Ind)(S₂-3)ZrCl₂	—	216000	280000^⑥	2.1	[32]
(l)	Me₂Si(2,4,7-Me₃-Ind)(S₂-3)ZrCl₂	—	229000	297000^⑥	2.1	[32]
(m)	Me₂Si(4,7-Me₂-Ind)(S₂-3)ZrCl₂	—	189000	228000^⑥	2.0	[32]
(n)	Me₂Si(2,4,6-Me₃-Ind)(S₂-3)ZrCl₂	40.0	365200^⑧	—	—	[25]

图2编号	催化剂类型	活性/kg·(mmol Zr)^-1·h^-1	M_w	M_w/M_n	参考文献
(a)	Cp₂ZrCl₂	—	—	—	[35]
(b)	Cp₂HfCl₂	—	8700^①	1.85	[35]
(c)	[(CH₃)₅C₅]₂ZrCl₂	—	8200^①	2.22	[35]
(d)	C₂H₄(Ind)₂ZrCl₂	—	20800^①	4.08	[35]
(d)	C₂H₄(Ind)₂ZrCl₂	2.025	43300^②	1.9	[36]
(e)	Me₂Si(Ind)₂ZrCl₂	—	17600^①	3.52	[35]
(e)	Me₂Si(Ind)₂ZrCl₂	1.345	37100^②	1.7	[36]
(f)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	—	149000^①	2.08	[35]
(g)	rac-Me₂Si(2-Me-Ind)₂ZrCl₂	0.251	280300^②	1.8	[36]
(h)	rac-Me₂Si(4-Ph-Ind)₂ZrCl₂	1.770	33600^②	1.7	[36]
(i)	rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂	1.124	67200^③	2.0	[36]
(j)	Me₂C(Cp)(Flu)ZrCl₂	1.766	37100^④	2.2	[36]
(k)	Me₂C(3-Me-Cp)(Flu)ZrCl₂	0.386	98900^④	1.9	[36]
(l)	Me₂C(3-^tBu-Cp)(Flu)ZrCl₂	0.247	46300^④	2.3	[36]
(m)	Me₂C(3-^tBu-Cp)(2,7-^tBu₂-Flu)ZrCl₂	0.537	137500^④	2.1	[36]
(n)	Ph₂C(3-^tBu-Cp)(Flu)ZrCl₂	0.083	57900^④	2.2	[36]
(o)	Ph₂C(3-^tBu-Cp)(2,7-^tBu₂-Flu)ZrCl₂	0.781	200400^④	2.0	[36]

图2编号	催化剂类型	活性/kg·(mmol Zr)^-1·h^-1	M_w	M_w/M_n	参考文献
(a)	Cp₂ZrCl₂	—	—	—	[35]
(b)	Cp₂HfCl₂	—	8700^①	1.85	[35]
(c)	[(CH₃)₅C₅]₂ZrCl₂	—	8200^①	2.22	[35]
(d)	C₂H₄(Ind)₂ZrCl₂	—	20800^①	4.08	[35]
(d)	C₂H₄(Ind)₂ZrCl₂	2.025	43300^②	1.9	[36]
(e)	Me₂Si(Ind)₂ZrCl₂	—	17600^①	3.52	[35]
(e)	Me₂Si(Ind)₂ZrCl₂	1.345	37100^②	1.7	[36]
(f)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	—	149000^①	2.08	[35]
(g)	rac-Me₂Si(2-Me-Ind)₂ZrCl₂	0.251	280300^②	1.8	[36]
(h)	rac-Me₂Si(4-Ph-Ind)₂ZrCl₂	1.770	33600^②	1.7	[36]
(i)	rac-Me₂Si(2-Me-4-Ph-Ind)₂ZrCl₂	1.124	67200^③	2.0	[36]
(j)	Me₂C(Cp)(Flu)ZrCl₂	1.766	37100^④	2.2	[36]
(k)	Me₂C(3-Me-Cp)(Flu)ZrCl₂	0.386	98900^④	1.9	[36]
(l)	Me₂C(3-^tBu-Cp)(Flu)ZrCl₂	0.247	46300^④	2.3	[36]
(m)	Me₂C(3-^tBu-Cp)(2,7-^tBu₂-Flu)ZrCl₂	0.537	137500^④	2.1	[36]
(n)	Ph₂C(3-^tBu-Cp)(Flu)ZrCl₂	0.083	57900^④	2.2	[36]
(o)	Ph₂C(3-^tBu-Cp)(2,7-^tBu₂-Flu)ZrCl₂	0.781	200400^④	2.0	[36]

图3编号	名称	活性/kg·(mmol Zr)^-1·h^-1	M_w	M_w/M_n	参考文献
(a)	Cp₂HfCl₂	—	6900^①	1.90	[37]
(b)	C₂H₄(Ind)₂ZrCl₂	—	23500^②	1.98	[37]
(c)	Me₂C(Cp)(Flu)ZrCl₂	1.766	42500^①	2.21	[37]
(d)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	—	153000^③	2.04	[35]
(e)	(^tBu-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.09	131856^④	1.64	[39]
(f)	(1,3-Me₂-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.184	161505^④	1.85	[39]
(g)	(1,3-^tBu₂-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.026	34992^④	1.62	[39]
(h)	(Me₅-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.728	1124280^⑤	1.62	[39]
(i)	CpTiMe₃	23.3	70000, 10000^⑥	1.5~3.0	[40]
(j)	(Me₅-Cp)TiCl₂[NMe₂]	0.0292	20482^⑦	1.33	[41]
(k)	(Me₅-Cp)TiCl₂[N(Et)(Me)]	0.0181	18768^⑦	1.38	[41]
(l)	(Me₅-Cp)TiCl₂[N(Cy)(Me)]	0.017	20083^⑦	1.33	[41]
(m)	(1,3-Me₂C₅H₃)TiCl₂[N(Cy)(Me)]	0.0386	28600^⑦	1.73	[41]
(n)	(1,3-Me₂C₅H₃)TiCl₂[N(Cy)₂]	0.0386	19000^⑦	1.73	[41]

茂金属催化线性α-烯烃聚合获取高分子量产物研究进展

Research of metallocene catalysts for linear α-olefins polymerization to obtain high molecular weight products

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图4编号	催化剂类型	活性/kg·(mmol Zr)^-1·h^-1	M_w	M_w/M_n	参考文献
(a)	Me₂Si(Ind)ZrCl₂	—	51000^①	1.52	[52]
(b)	Et(Ind)₂HfCl₂	—	65000^②	1.82	[52]
(c)	MeC₂H₃(Cp)(Flu)ZrCl₂	2.790	10000^③	2.0	[53]
(d)	C₂H₄(4H-Ind)ZrCl₂	4.008	30000^④	2.3	[53]
(e)	(^tBu-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.125	152625^⑤	1.85	[39]
(f)	(1,3-Me₂-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.220	123832^⑤	1.84	[39]
(g)	(1,3-^tBu₂-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.038	26075^⑤	1.49	[39]
(h)	(Me₅-Cp)TiCl₂(o-2,6-ⁱPr₂C₆H₃)	0.970	91080^⑥	1.84	[39]
(i)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	—	155000^⑦	2.15	[35]
(j)	Me₂C(Cp)(Flu)ZrCl₂	—	45000^⑧	2.02	[37]
(k)	C₂H₄(Ind)₂ZrCl₂	0.7	92000^⑨	1.67	[25]

图5编号	催化剂类型	活性/kg·(mmol Zr)^-1·h^-1	M_w	M_w/M_n	参考文献
(a)	C₂H₄(Ind)₂HfCl₂	—	67000^①	1.6	[52]
(b)	Me₂Si(Ind)₂ZrCl₂	—	45000^②	1.78	[52]
		14.0	21640^③	1.82	[72]
		—	34791^④	1.85	[73]
(c)	(Me₅-Cp)TiCl₂(o-2,6-iPr₂C₆H₃)	1.036	688050^⑤	1.65	[39]
(d)	Cp₂HfCl₂	—	10100^⑥	1.90	[37]
(e)	C₂H₄(Ind)₂ZrCl₂	—	7600^⑥	2.36	[37]
(e)	C₂H₄(Ind)₂ZrCl₂	0.8	91000^⑦	1.78	[54]
(f)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	—	182000^⑧	2.56	[35]
(g)	Me₂C(Cp)(Flu)ZrCl₂	—	42600^⑥	2.89	[37]
(h)	Ph₂C(Cp)(Flu)ZrCl₂	—	71000^⑨	1.86	[74]
(h)	Ph₂C(Cp)(Flu)ZrCl₂	—	48500^⑩	1.74	[75]

图6编号	名称	聚合单体	活性/kg·(mmol Zr)^-1·h^-1	M_w	M_w/M_n	参考文献
(a)	Me₂Si(Ind)₂ZrCI₂	1-十二烯	—	50000^①	1.62	[52]
		1-十四烯	—	50000^①	1.69	[52]
		1-十六烯	—	70000^①	1.89	[52]
		1-十八烯	—	68000^①	1.85	[52]
		1-二十烯	—	47000^①	1.86	[52]
(b)	C₂H₄(Ind)₂HfCl₂	1-十二烯	—	99000^②	2.07	[52]
		1-十四烯	—	116000^②	1.53	[52]
		1-十六烯	—	103000^②	2.52	[52]
		1-十八烯	—	70000^②	1.94	[52]
		1-二十烯	—	101000^②	1.94	[52]
(c)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	1-十四烯	—	173000^③	2.40	[35]
(c)	Me₂Si(2-Me-4,5-苯并噻吩基)₂ZrCl₂	1-十八烯	—	126000^③	2.84	[35]
(d)	Me₂C(Cp)(Flu)ZrCl₂	1-十八烯	—	44000^④	2.07	[37]
(e)	Cp₂HfCl₂		—	11000^④	1.75	[37]
(f)	Ph₂C(Cp)(Flu)ZrCl₂		0.472	22700^⑤	1.8	[78]
(g)	C₂H₄(2-Me-Ind)₂ZrCl₂		0.400	22100^⑤	1.7	[78]
(h)	C₂H₄(Ind)₂ZrCl₂	1-十二烯	0.9	90000^⑥	1.74	[54]
		1-十四烯	1.0	88000^⑥	1.66	[54]
		1-十六烯	1.1	87000^⑥	1.74	[54]
		1-十八烯	1.0	72000^⑥	1.88	[54]
		1-十八烯	0.112	37700^⑤	2.2	[78]
		1-二十烯	0.8	61000^⑥	1.84	[54]

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