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

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

Abstract

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

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

CLC Number:

TQ31

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.

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.

Figures/Tables 12

References 80

1	PATEL Nikunj, VALODKAR Vaibhav, TEMBE Gopal. Recent developments in catalyst systems for selective oligomerization and polymerization of higher α-olefins[J]. Polymer Chemistry, 2023, 14(21): 2542-2571.
2	MAITZ M F. Applications of synthetic polymers in clinical medicine[J]. Biosurface and Biotribology, 2015, 1(3): 161-176.
3	BENDA R, BULLEN J, PLOMER A. Synthetics basics: Polyalphaolefins—Base fluids for high-performance lubricants[J]. Journal of Synthetic Lubrication, 1996, 13(1): 41-57.
4	NICHOLAS Christopher P. Applications of light olefin oligomerization to the production of fuels and chemicals[J]. Applied Catalysis A: General, 2017, 543: 82-97.
5	陈志康, 毛远洪, 曹育才, 等. 茂金属催化剂体系及其丙烯聚合性能调控[J].有机化学，2018, 38(11): 2937-2992.
	CHEN Zhikang, MAO Yuanhong, CAO Yucai, et al. Metallocene catalyst systems and control over the propylene polymerization[J]. Chinese Journal of Organic Chemistry, 2018, 38(11): 2937-2992.
6	何垒垒, 苏朔, 龙军. 聚α-烯烃合成基础油分子结构与性能关系研究进展[J]. 石油学报(石油加工), 2024, 40(1): 266-276.
	HE Leilei, SU Shuo, LONG Jun. Research progress on the relationship between molecular structure and properties of poly-α-olefins synthetic base oil[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2024, 40(1): 266-276.
7	黄葆同, 陈伟. 茂金属催化剂及其烯烃聚合物[M]. 北京: 化学工业出版社, 2000.
	HUANG Baotong, CHEN Wei. Metallocene catalysts and their olefin polymers[M]. Beijing: Chemical Industry Press, 2000.
8	KUMAR Shubham, DHOLAKIYA Bharatkumar Z, JANGIR Ritambhara. Role of organometallic complexes in olefin polymerization: A review report[J]. Journal of Organometallic Chemistry, 2021, 953: 122066.
9	Ilya NIFANT’EV, IVCHENKO Pavel. Fair look at coordination oligomerization of higher α-olefins[J]. Polymers, 2020, 12(5): 1082.
10	LIN Shirley, WAYMOUTH Robert M. 2-Arylindene metallocenes: Conformationally dynamic catalysts to control the structure and properties of polypropylenes[J]. Accounts of Chemical Research, 2002, 35(9): 765-773.
11	RAZAVI Abbas, THEWALT Ulf. Site selective ligand modification and tactic variation in polypropylene chains produced with metallocene catalysts[J]. Coordination Chemistry Reviews, 2006, 250(1/2): 155-169.
12	PRASHAR Sanjiv, Antonio ANTIÑOLO, OTERO Antonio. Insights into group 4 and 5 ansa-bis(cyclopentadienyl) complexes with a single-atom bridge[J]. Coordination Chemistry Reviews, 2006, 250(1/2): 133-154.
13	COBZARU Cecilia, HILD Sabine, BOGER Andreas, et al. “Dual-side” catalysts for high and ultrahigh molecular weight homopolypropylene elastomers and plastomers[J]. Coordination Chemistry Reviews, 2006, 250(1/2): 189-211.
14	JALALI Aazam, Mehdi NEKOOMANEHS-HAGHIGHI, DEHGHANI Sevda, et al. Effect of metal type on the metallocene-catalyzed oligomerization of 1-hexene and 1-octene to produce polyα-olefin-based synthetic lubricants[J]. Applied Organometallic Chemistry, 2020, 34(2): e5338.
15	NIFANT’EV Ilya E, IVCHENKO Pavel V. Synthesis of heteroarene-fused cyclopentadienes and related compounds suitable for metallocene preparation[J]. Advanced Synthesis & Catalysis, 2020, 362(18): 3727-3767.
16	VITTORIA Antonio, GORYUNOV Georgy P, IZMER Vyatcheslav V, et al. Hafnium vs. zirconium, the perpetual battle for supremacy in catalytic olefin polymerization: A simple matter of electrophilicity?[J]. Polymers, 2021, 13(16): 2621.
17	SPALECK Walter, KUEBER Frank, WINTER Andreas, et al. The influence of aromatic substituents on the polymerization behavior of bridged zirconocene catalysts[J]. Organometallics, 1994, 13(3): 954-963.
18	RESCONI Luigi, PIEMONTESI Fabrizio, CAMURATI Isabella, et al. Highly regiospecific zirconocene catalysts for the isospecific polymerization of propene[J]. Journal of the American Chemical Society, 1998, 120(10): 2308-2321.
19	RAZAVI Abbas, THEWALT Ulf. Preparation and crystal structures of the complexes (η ⁵-C₅H₃TMS-CMe₂-η ⁵-C₁₃H₈)MCl₂ and [3,6-di ^t ButC₁₃H₆-SiMe₂-N ^t Bu]MCl₂ (M=Hf, Zr or Ti): Mechanistic aspects of the catalytic formation of a isotactic-syndiotactic stereoblock-type polypropylene[J]. Journal of Organometallic Chemistry, 2001, 621(1/2): 267-276.
20	SEYFERTH Dietmar. Comprehensive organometallic chemistry. The synthesis, reactions, and structures of organometallic compounds[J]. Organometallics, 1984, 3(7): 1135-1136.
21	RESCONI L, CAVALLO L, FAIT A, et al. Selectivity in propene polymerization with metallocene catalysts[J]. Chemical Reviews, 2000, 100(4): 1253-1346.
22	COATES G W. Precise control of polyolefin stereochemistry using single-site metal catalysts[J]. Chemical Reviews, 2000, 100(4): 1223-1252.
23	KEIM Wilhelm, HOFFMANN Bernd, LODEWICK Rainer, et al. Linear Oligomerization of olefins via nickel chelate complexes and mechanistic considerations based on semi-empirical calculations[J]. Journal of Molecular Catalysis, 1979, 6(2): 79-97.
24	Urszula DOMAŃSKA, KOZŁOWSKA Marta Karolina. Phase relationships and thermodynamic interactions of isotactic poly(1-butene) and organic solvent systems[J]. Chemistry—A European Journal, 2005, 11(2): 776-785.
25	RESCONI Luigi, CAMURATI Isabella, MALIZIA Federica. Metallocene catalysts for 1-butene polymerization[J]. Macromolecular Chemistry and Physics, 2006, 207(24): 2257-2279.
26	SPALECK Walter, ANTBERG Martin, Jürgen ROHRMANN, et al. High molecular weight polypropylene through specifically designezirconocene catalysts[J]. Angewandte Chemie International Edition in English, 1992, 31(10): 1347-1350.
27	J A Martinho SIMOES, BEAUCHAMP J L. Transition metal-hydrogen and metal-carbon bond strengths: The keys to catalysis[J]. Chemical Reviews, 1990, 90(4): 629-688.
28	KULYABIN Pavel S, GORYUNOV Georgy P, SHARIKOV Mikhail I, et al. Ansa-zirconocene catalysts for isotactic-selective propene polymerization at high temperature: A long story finds a happy ending[J]. Journal of the American Chemical Society, 2021, 143(20): 7641-7647.
29	ZHAO Yanan, XU Xianming, WANG Yulong, et al. Ancillary ligand effects on α-olefin polymerization catalyzed by zirconium metallocene: A computational study[J]. RSC Advances, 2022, 12(33): 21111-21121.
30	DE TUESTA J L Diez, CASAS E, MORENO J, et al. Synthesis and characterization of low molecular weight poly(1-butene) macromolecules prepared using metallocene catalysts[J]. Applied Catalysis A: General, 2013, 460: 70-77.
31	Al-haj ALI M, BETLEM B, ROFFEL B, et al. Hydrogen response in liquid propylene polymerization: Towards a generalized model[J]. AIChE Journal, 2006, 52(5): 1866-1876.
32	DE ROSA Claudio, AURIEMMA Finizia, RESCONI Luigi. Metalloorganic polymerization catalysis as a tool to probe crystallization properties of polymers: The case of isotactic poly(1-butene)[J]. Angewandte Chemie International Edition, 2009, 48(52): 9871-9874.
33	HANIFPOUR Ahad, Naeimeh BAHRI-LALEH, MOHEBBI Ali, et al. Oligomerization of higher α‑olefins to poly(α‑olefins)[J]. Iranian Polymer Journal, 2022, 31(1): 107-126.
34	SPALECK Walter, AULBACH Michael, BACHMANN Bernd, et al. Stereospecific metallocene catalysts: Scope and limits of rational catalyst design[J]. Macromolecular Symposia, 1995, 89(1): 237-247.
35	Robert BRÜLL, KGOSANE Desmond, NEVELING Arno, et al. Synthesis and properties of poly-1-olefins[J]. Macromolecular Symposia, 2001, 165(1): 11-18.
36	DESCOUR Camille, DUCHATEAU Rob, MOSIA Mamoeletsi R, et al. Catalyst behaviour for 1-pentene and 4-methyl-1-pentene polymerisation for C₂-, C_s- and C₁-symmetric zirconocenes[J]. Polymer Chemistry, 2011, 2(10): 2261-2272.
37	GRUMEL Valérie, Robert BRÜLL, PASCH Harald, et al. Homopolymerization of higher 1-olefins with metallocene/MAO catalysts[J]. Macromolecular Materials and Engineering, 2001, 286(8): 480-487.
38	HANIFPOUR Ahad, Naeimeh BAHRI-LALEH, Mehdi NEKOOMANESH-HAGHIGHI, et al. Poly1-hexene: New impact modifier in HIPS technology[J]. Journal of Applied Polymer Science, 2016, 133(35): 43882.
39	NOMURA Kotohiro, KOMATSU Takashi, IMANISHI Yukio. Polymerization of 1-hexene, 1-octene catalyzed by Cp’TiCl₂(O-2,6-ⁱPr₂C₆H₃)-MAO system. Unexpected increase of the catalytic activity for ethylene/1-hexene copolymerization by (1,3-^tBu₂C₅H₃)TiCl₂(O-2,6-ⁱPr₂C₆H₃)-MAO catalyst system[J]. Journal of Molecular Catalysis A: Chemical, 2000, 152(1/2): 249-252.
40	MURRAY Michael C, BAIRD Michael C. Polymerization of 1-hexene catalyzed by Cp^*TiMe₃-B(C₆F₅)₃; a mechanistic and structural study[J]. Canadian Journal of Chemistry, 2001, 79(5/6): 1012-1018.
41	NOMURA Kotohiro, FUJII Kensaku. Effect of cyclopentadienyl and amide fragment in olefin polymerization by nonbrid ged (amide)(cyclopentadienyl)titanium(Ⅳ) complexes of the type Cp’TiCl₂[N(R¹)R²]-Methylaluminoxane (MAO) catalyst systems[J]. Macromolecules, 2003, 36(8): 2633-2641.
42	DONG Su, MI Puke, XU Sheng, et al. Preparation and characterization of single-component poly-α-olefin oil base stocks[J]. Energy & Fuels, 2019, 33(10): 9796-9804.
43	NIFANT’EV Ilya E, VINOGRADOV Alexey A, VINOGRADOV Alexander A, et al. Zirconocene-catalyzed dimerization of 1-hexene: Two-stage activation and structure-catalytic performance relationship[J]. Catalysis Communications, 2016, 79: 6-10.
44	CANO Jesus, KUNZ Klaus. How to synthesize a constrained geometry catalyst (CGC)—A survey[J]. Journal of Organometallic Chemistry, 2007, 692(21): 4411-4423.
45	ATIQULLAH Muhammad, ABDELAAL Ahmed F, ADAMU Sagir, et al. Catalytic making of ethylene-1-hexene elastomers: Thermodynamic guide to process development[J]. AIChE Journal, 2024, 70(2): e18258.
46	COLLINS RICE Clement G, BUFFET Jean-Charles, TURNER Zoë R, et al. Efficient synthesis of thermoplastic elastomeric amorphous ultra-high molecular weight atactic polypropylene (UHMWaPP)[J]. Polymer Chemistry, 2022,13(39): 5597-5603.
47	Christian EHM, MINGIONE Alessio, VITTORIA Antonio, et al. High-throughput experimentation in olefin polymerization catalysis: facing the challenges of miniaturization[J]. Industrial & Engineering Chemistry Research, 2020, 59(31): 13940-13947.
48	FALIVENE Laura, CAVALLO Luigi, TALARICO Giovanni. Buried volume analysis for propene polymerization catalysis promoted by group 4 metals: A tool for molecular mass prediction[J]. ACS Catalysis, 2015, 5(11): 6815-6822.
49	BUFFET Jean-Charles, TURNER Zoë R, Dermot O’HARE. Popcorn-shaped polyethylene synthesised using highly active supported permethylindenyl metallocene catalyst systems[J]. Chemical Communications, 2018, 54(78): 10970-10973.
50	HANIFPOUR Ahad, Naeimeh BAHRI-LALEH, Mehdi NEKOOMANESH-HAGHIGHI, et al. Group Ⅳ diamine bis(phenolate) catalysts for 1-decene oligomerization[J]. Molecular Catalysis, 2020, 493: 111047.
51	SOGA Kazuo, YANAGIHARA Hisayoshi. Extremely highly isospecific polymerization of olefins using solvay-type TiCl₃ and Cp₂TiMe₂ as calalyst [J]. Die Makromolekulare Chemie, 1988, 189(12): 2839-2846.
52	HENSCHKE O, KNORR J, ARNOLD M. Poly-α-olefins from polypropene to poly-1-eicosene made with metallocene catalysts[J]. Journal of Macromolecular Science A, 1998, 35(3): 473-481.
53	ASANUMA T, NISHIMORI Y, ITO M, et al. Preparation of syndiotactic polyolefins by using metallocene catalysts[J]. Polymer Bulletin, 1991, 25(5): 567-570.
54	WANG Xiaoyan, YANG Fei, CAO Dafu, et al. Structure and property of comb-like polyolefins derived from highly Stereospecific homo-polymerization of higher α-olefins[J]. Polymer, 2021, 213: 123223.
55	EHM C, CIPULLO R, BUDZELAAR P M, et al. Role(s) of TMA in polymerization[J]. Dalton Transactions, 2016, 45(16): 6847-6855.
56	BRYLIAKOV Konstantin P, SEMIKOLENOVA Nina V, YUDAEV Dmitrii V, et al. ¹H-, ¹³C-NMR and ethylene polymerization studies of zirconocene/MAO catalysts: Effect of the ligand structure on the formation of active intermediates and polymerization kinetics[J]. Journal of Organometallic Chemistry, 2003, 683(1): 92-102.
57	TRITTO Incoronata, DONETTI Raffaella, SACCHI Maria Carmela, et al. Dimethylzirconocene-methylaluminoxane catalyst for olefin polymerization: NMR study of reaction equilibria[J]. Macromolecules, 1997, 30(5): 1247-1252.
58	TREFZ Tyler K, HENDERSON Matthew A, LINNOLAHTI Mikko, et al. Mass spectrometric characterization of methylaluminoxane-activated metallocene complexes[J]. Chemistry, 2015, 21(7): 2980-2991.
59	KUMAWAT Jugal, GUPTA Virendra Kumar. Single to multiple site behavior of metallocenes through C—H activation for olefin polymerization: A mechanistic insight from DFT[J]. ACS Catalysis, 2020, 10(3): 1704-1715.
60	DORNIK Hans Peter, LUFT Gerhard, Alexander RAU, et al. Deactivation kinetics of metallocene-catalyzed ethene polymerization at high temperature and elevated pressure[J]. Macromolecular Materials and Engineering, 2004, 289(5): 475-479.
61	WANG Jiannan, LIU Man, CHEN Yilong, et al. Coal tar derived metallocene catalyst for polymerization of 1-decene into low-viscosity poly-α-olefin lubricating base oil[J]. China Petroleum Processing & Petrochemical Technology, 2022, 24(3): 52-60.
62	KIM Il, Chang-Sik HA. Copolymerizations of ethylene with 1-decene over various ansa-metallocene complexes combined with Al(i-Bu)₃/[CPh₃][B(C₆F₅)₄] cocatalyst[J]. Polymer Bulletin, 2004, 52(2): 133-139.
63	ZHAO Ruida, MI Puke, XU Sheng, et al. Structure and properties of poly-α-olefins containing quaternary carbon centers[J]. ACS Omega, 2020, 5(16): 9142-9150.
64	HONG Han, ZHANG Zhicheng, CHUNG T C M, et al. Synthesis of new 1-decene-based LLDPE resins and comparison with the corresponding 1-octene- and 1-hexene-based LLDPE resins[J]. Journal of Polymer Science A: Polymer Chemistry, 2007, 45(4): 639-649.
65	RISHINA Laura A, LALAYAN Svetlana S, GAGIEVA Svetlana C, et al. Polymers of propylene and higher 1-alkenes produced with post-metallocene complexes containing a saligenin-type ligand[J]. Polymer, 2013, 54(24): 6526-6535.
66	LÓPEZ-BARRÓN Carlos R, TSOU Andy H, HAGADORN John R, et al. Highly entangled α-olefin molecular bottlebrushes: Melt structure, linear rheology, and interchain friction mechanism[J]. Macromolecules, 2018, 51(17): 6958-6966.
67	SHAO Huaiqi, LI Hui, LIN Jichao, et al. Metallocene-catalyzed oligomerizations of 1-butene and α-olefins: Toward synthetic lubricants[J]. European Polymer Journal, 2014, 59: 208-217.
68	KISSIN Yury V, SCHWAB Frederick C. Post-oligomerization of α-olefin oligomers: A route to single-component and multicomponent synthetic lubricating oils[J]. Journal of Applied Polymer Science, 2009, 111(1): 273-280.
69	XU J T, WU F, FAN Z Q, et al. Phase separation in the melt of polypropylene-1-decene copolymers[J]. Journal of Macromolecular Science B, 2002, 41(4/5/6): 1331-1348.
70	HANIFPOUR Ahad, Naeimeh BAHRI-LALEH, Mehdi NEKOOMANESH-HAGHIGHI, et al. 1-Decene oligomerization by new complexes bearing diamine-diphenolates ligands: Effect of ligand structure[J]. Applied Organometallic Chemistry, 2021, 35(6): e6227.
71	RISHINA Laura А, KISSIN Yury V, LALAYAN Svetlana S, et al. Polymerization of alkenes with a post-metallocene catalyst containing a titanium complex with an oxyquinolinyl ligand[J]. Journal of Polymer Science A—Polymer Chemistry, 2017, 55(11): 1844-1854.
72	JIANG Hongbo, YU Kaijian. Catalytic polymerization of 1-decene using a silicon-bridged metallocene system[J]. Petroleum Science and Technology, 2017, 35(14): 1451-1456.
73	江洪波, 俞凯健, 洪显忠, 等. 硅桥联茂金属催化1-癸烯聚合的研究[J]. 石油炼制与化工, 2017, 48(1): 61-66.
	JIANG Hongbo, YU Kaijian, HONG Xianzhong, et al. Polymerization of 1-decene catalyzed by silicon-bridged metallocene[J]. Petroleum Processing and Petrochemicals, 2017, 48(1): 61-66.
74	江洪波, 樊宗明, 雪小峰. 茂金属/有机硼化物催化体系催化1-癸烯聚合[J]. 化学反应工程与工艺, 2015, 31(4): 359-366.
	JIANG Hongbo, FAN Zongming, XUE Xiaofeng. Polymerization of 1-decene catalyzed by metallocene/organic boron catalytic system[J]. Chemical Reaction Engineering and Technology, 2015, 31(4): 359-366.
75	毋少庚. 桥联茂金属催化1-癸烯聚合制备润滑油基础油的研究[D]. 上海: 华东理工大学, 2015.
	WU Shaogeng. Synthesis of base oil of lubricant by polymerizing alpha-olefin catalyzed by bridged metallocene catalytic system[D]. Shanghai: East China University of Science and Technology, 2015.
76	SHI Bingyu, LIU Man, CHEN Jiangang. N-doped metallocene catalysts for synthesis of high quality lubricant base oils from Fishcher-Tropsch synthesized α-olefin[J]. Catalysis Letters, 2024, 154(3): 1050-1060.
77	WANG Wei, HOU Liping, SHENG Jianfang. Syndiotactic polymer of allylcyclopentane by a metallocene catalyst[J]. ChemCatChem, 2016, 8(20): 3218-3223.
78	ADAMU Sagir, ATIQULLAH Muhammad, MALAIBARI Zuhair O, et al. Metallocene-catalyzed ethylene-α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016, 60: 92-105.
79	MAKARYAN I A, SEDOV I V. Market potential of industrial technologies for production of synthetic bases of motor oils[J]. Russian Journal of General Chemistry, 2021, 91(6): 1243-1259.
80	QUIJADA Raúl, GUEVARA Juan Luis, Mehrdad YAZDANI-PEDRAM, et al. Study of the polymerization of 1-octadecene with different rnetallocene catalysts[J]. Polymer Bulletin, 2002, 49(4): 273-280.

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]