烯烃聚合用茂金属催化剂及其载体

摘要/Abstract

摘要： 由于在α-烯烃、二烯烃以及苯乙烯聚合中的单中心催化性能，茂金属催化剂备受学术界和企业界的关注。为了进一步提高催化剂的活性、利用效率以及防止粘釜现象的发生和有效控制催化产物的微形貌，茂金属催化剂通常要负载在载体上进行使用。对茂金属催化剂的基本结构及发展历程进行了介绍，综述了茂金属催化剂载体的种类，包括MgCl₂、分子筛或多孔材料、层状材料、聚合物、碳纳米管和石墨、硅胶载体，总结了其自负载的特点和性能，指出开发高活性催化剂及其高效负载化工艺仍是今后该领域的重要工作。

关键词: 茂金属催化剂, 单中心催化, 聚烯烃, 载体

Abstract: Metallocene catalysts have attracted attention from both academic and business communities due to the single center catalytic performance in the polymerization of α-olefins, dienes and styrene. In order to further improve the activity and utilization efficiency of catalysts, prevent the occurrence of kettle sticking phenomenon and effectively control the microstructure of catalytic products, metallocene catalysts are usually loaded on the carrier for use. The basic structure and development history of metallocene catalysts were introduced, and the kinds of supports for metallocene catalysts were summarized, including MgCl₂, molecular sieves or porous materials, layered materials, polymers, carbon nanotubes and graphite, and silica gel, and self-loading characteristics and properties were summarized. It was pointed out that it was still an important work to search for highly active catalysts and their efficient loading processes in this field in the future.

Key words: metallocene catalyst, single center catalysis, polyolefins, carrier

冯思涵周晨光王东军王伟众郝海军贾建光徐庆红. 烯烃聚合用茂金属催化剂及其载体[J]. 石油炼制与化工, 2024, 55(9): 177-186.

参考文献

[1] Montagna A A, Burkhart R M, Dekmezian A H. The evolution of single-site catalysis [J]. Chemtech, 1997, 27(12): 26–31.
[2] Kealy T J, Pauson P L. A new type of organo-iron compound [J]. Nature, 1951, 168: 1039–1040.
[3] Breslow D S, Newburg N R. Bis-(Cyclopentadienyl)-Titanium Dichloride- lkylaluminum Complexls as Catalysts for the Polymerization of Ethylene [J]. Journal of the American Chemical Society, 1957, 79(18): 5072–5073.
[4] Reichert K H, Meyer K R. Zur kinetik der niederdruckpolymerisation von ?thylen mit l?slichen Ziegler-katalysatoren [J]. Makromolecular Chemistry, 1973, 169: 163–176.
[5] Andersen A, Cordes H G, Herwig H, et.al. Halogen-Free Soluble Ziegler Catalysts for the Polymerization of Ethylene. Control of Molecular Weight by Choice of Temperature [J]. Angewandte Chemie. International Ed. in English, 1976, 15: 630–632.
[6] Wild F R W P, Wasiucionek M, Huttner G, et.al. ansa-Metallocene derivatives: VII. Synthesis and crystal structure of a chiral ansa-zirconocene derivative with ethylene-bridged tetrahydroindenyl ligands [J]. Journal of Organometallic Chemistry, 1985, 288: 63–67.
[7] Kaminsky W, Külper K, Brintzinger H H, et.al. Polymerisation von propen und buten mit einem chiralen zirconocen und methylaluminoxan als cokatalysator [J]. Angewandte Chemie. International Ed. in English, 1985, 97: 507–508.
[8] Hamielec A E, Soares J B P. Polymerization reaction engineering-Metallocene catalysts [J]. Progress in Polymer Science. 1996, 21(4): 651–706.
[9] Johnson J C. Metallocene Technology, Noys Data Corporation: Park Bridge, New Jersey. 1973.
[10] Long N J Metallocenes. Blackwell Science Ltd. 1998.
[11] Reddy S S, Sivaram S. Homogeneous metallocene-methylaluminoxane catalyst systems for ethylene polymerization [J]. Progress in Polymer Science, 1995, 20(2): 309–367.
[12] Alt H G, Jung M, Kehr G. C1-verbrückte Fluorenyliden-Indenylidenkomplexe des Typs (C13H8-CR2-C9H6-nR′n)ZrCl2 (n=0, 1; R=Me, Ph, Butenyl; R′=Alkyl, Alkenyl) als Metallocenkatalysatorvorstufen für die Ethylenpolymerisation [J]. Journal of Organometallic Chemistry, 1998, 562: 153–181.
[13] Alt H G, K?ppl A. Effect of the Nature of Metallocene Complexes of Group IV Metals on Their Performance in Catalytic Ethylene and Propylene Polymerization [J]. Chemical Reviews, 2000, 100(4): 1205–1221.
[14] Alt H G. The heterogenization of homogeneous metallocene catalysts for olefin polymerization [J]. Journal of the chemical society-dalton transactions, 1999, 11: 1703–1709.
[15] Kaminsky W, Steiger R. Polymerization of olefins with homogeneous zirconocene/alumoxane catalysts [J]. Polyhedron, 1988, 7(22?23): 2375–2381.
[16] Olabisi O, Atiqullah M, Kaminsky W, et.al. Group 4 metallocenes: supported and unsupported [J]. Macromolecular Chemistry and Physics C. 1997, 37(3): 519–554.
[17] Flory P J. Principles of polymer chemistry, Cornell university: Ithaca, New York, 1953.
[18] Soares J B P, Hamielec A E. Deconvolution of chain-length distributions of linear polymers made by multiple-site-type catalysts [J]. Polymer, 1995, 36(11): 2257–2263.
[19] 韩云光, 郭桂悦, 满艳茹, 等. 茂金属催化剂载体化研究进展 [J]. 江苏化工. 2005, 33(3):18–21.
[20] Manabu K, Kazuo S. Polymerization of propene with the catalyst systems composed of Al2O3- or MgCl2-supported Et[IndH4]2ZrCl2 and AlR3 (R=CH3, C2H5) [J]. Makromolecular Chemical Rapid Communication. 1991, 12, 367–372.
[21] Kazuo S, Toshiya U, Masayoshi S, et al. Structure of polypropene and poly(ethylene-co-propene) produced with an alumina-supported CpTiCl3/common alkylaluminium catalyst system [J]. Macromolecular Chemistry and Physics. 1994, 195: 1503–1515.
[22] Kazuo S, Ryutaro K, Toshiya U. Syndiotactic polymerization of styrene with Al2O3-supported Cp(*)TiCl3 (Cp: Cyclopentadienyl, Cp(*): 1,2,3,4,5-pentamethylcyclopentadienyl) catalyst activated by trialkylaluminiums [J]. Makromolecular Chemical Rapid Communication, 1993, 14: 511–514.
[23] Maria de F V M, Moacir de A. Alumina as support for metallocene catalyst in ethylene polymerization [J]. Journal of Polymer Science Part A Polymer Chemistry, 2004, 42: 9–21.
[24] Motta A, Fragalà I L, Marks T J. Links between single-site heterogeneous and homogeneous catalysis [J]. Journal of the American Chemical Society, 2008, 130: 16533-16546.
[25] Bailly J C, Chabrand C J. Catalyst and prepolymer used for the preparation of polyolefins [J]. EP0435514 [P], 1991.
[26] Bailly J C, Bres P, Chabrand C, et.al. Catalyst and prepolymer used for the preparation of polyolefins. US5106804 [P], 1992.
[27] Sensarma S, Sivaram S. Magnesium chloride supported bis(cyclopentadienyl)titanium(IV) dichloride-MAO catalyst for ethylene polymerization [J]. Macromol Chemistry and Physics, 1997, 198: 495–503.
[28] Sensarma S, Sivaram S. A magnesium chloride supported bis(cyclopentadienyl)- zirconium(IV) dichloride catalyst for the polymerization of ethylene [J]. Macromolecular Chemistry and Physics, 1999, 200: 323–329.
[29] Soga K, Arai T, Uozumi T. Polymerization of propene over a MgCl2-supported dichlorosilylenebisindenylzirconium dichloride catalyst combined with methylalumoxane [J]. Polymer, 1997, 38(19): 4993–4995.
[30] Kang K K, Oh J K, Jeong Y T, et al. Highly active MgCl2-supported CpMCl3 (M=Ti, Zr) catalysts for ethylene polymerization [J]. Macromolecular Rapid Communication, 1999, 20(6): 308–311.
[31] Xu J T, Zhao J, Fan Z Q, et al. ESR study on MgCl2-supported half-titanocene catalyst for
syndiospecific polymerization of styrene [J]. European Polymer Journal. 1999, 35(1): 127–132.
[32] Ferreira M L, Damiani D E, Juan A. Semiempirical study of metallocenes adsorption on α-MgCl2 [J]. Computational Materials Science, 1998, 9(3-4): 357–366.
[33] Marco M, Angelina A, Francesco C, et al. Zeolite supported polymerization catalysts: Copolymerization of ethylene and α-olefins with metallocenes supported on HY zeolite [J]. Journal of Molecular Catalysis A Chemical, 1998, 129: 241–248.
[34] Seong I W, Young S K, Taek K H. Polymerization of ethylene over metallocenes confined inside the supercage of a NaY zeolite [J]. Macromolecular Rapid Communication, 1995, 16: 489–494.
[35] Young S K, Taek K H, Je W P, et al. Propene polymerization catalyzed over MCM-41 and VPI-5-supported Et(ind)2ZrCl2 catalysts [J]. Macromolecular Rapid Communication, 1996, 17: 749–758.
[36] Young S K, Seong I W. Shape and diffusion of the monomer-controlled copolymerization of ethylene and α-olefins over Cp2ZrCl2 confined in the nanospace of the supercage of NaY [J]. Journal of Polymer Science: Part A: Polymer Chemistry, 2003, 41: 2171–2179.
[37] Kumkaew P, Wanke S E, Praserthdam P, et al. Gas-phase ethylene polymerization using zirconocene supported on mesoporous molecular sieves [J]. Journal of Applied Polymer Science, 2003, 87: 1161–1177.
[38] Lee K S, Oh C G, Yim J H, et al. Characteristics of zirconocene catalysts supported on Al-MCM-41 for ethylene polymerization [J]. Journal of Molecular Catalysis A: Chemistry, 2000, 159: 301–308.
[39] Kageyama K, Tamazawa J I, Aida T. Catalyzed synthesis of crystalline linear polyethylene nanofibers within a mesoporous silica [J]. Science, 1999, 285: 2113–2115.
[40] Kageyama K, Ng S M, Ichikawa H, et.al. Macromolecular synthesis using mesoporous zeolites [J]. Macromolecular Symposia. 2000, 157: 137–142.
[41] Ikenaga K, Chen S Z, Ohshima M, et al. Ethylene polymerization over zirconocenes supported on alumina- and titania-based acidic oxides [J]. Catalysis Communication. 2007, 8: 36–38.
[42] Grieken R V, Carrero A, Suarez I, et al. Ethylene polymerization over supported MAO/(nBuCp)2ZrCl2 catalysts: influence of support properties [J]. European Polymer Journal, 2007, 43:1267–1277.
[43] Heinemann J, Reichert P, Thomann R, et al. Polyolefin nanocomposites formed by melt compounding and transition metal catalyzed ethene homo- and copolymerization in the presence of layered silicates [J]. Macromolecular Rapid Communication, 1999, 20: 423–430.
[44] Weiss K, Wirth-Pfeifer C, Hofmann M, et al. Polymerisation of ethylene or propylene with heterogeneous metallocene catalysts on clay minerals [J]. Journal of Molecular Catalysis A-Chemical. 2002, 182-183: 143–149.
[45] Liu C B, Tang T, Huang B T. Zirconocene catalyst well spaced inside modified montmorillonite for ethylene polymerization: role of pretreatment and modification of montmorillonite in tailoring polymer properties [J]. Journal Catalysis, 2004, 221: 162–169.
[46] Yang F, Zhang X Q, Zhao H C, et.al. Influence of montmorillonite on syndiotactic polymerization behavior of styrene [J]. Journal of Applied Polymer Sciences, 2007, 104: 2755–2759.
[47] Buffet J C, Byles C F H, Felton R, et.al. Metallocene supported core@LDH catalysts for slurry phase ethylene polymerisation [J]. Chemical Communication, 2016, 52: 4076–4079.
[48] Beck S, Brough A R, Bochmann M. á-Zirconium phosphonates as new supports for metallocene catalysts [J]. Journal of Molecular Catalysis A: Chemistry, 2004, 220: 275–284.
[49] Markus S, Fabian K, Yi T, et al. Novel Graphene UHMWPE Nanocomposites Prepared by Polymerization Filling Using Single-Site Catalysts Supported on Functionalized Graphene Nanosheet Dispersions [J]. Macromolecules, 2012, 45(17): 6878–6887.
[50] Herrmann H F, Bachmann B, Hierholzer B, et.al. Catalyst for the polymerization of olefins, process for its preparation and its use. US5942586 [P], 1999.
[51] Nishida H, Uozumi T, Arai T, et al. Polystyrene-supported metallocene catalysts for olefin polymerizations [J]. Macromolecular Rapid Communication, 1995, 16(11): 821–830.
[52] Park S, Yoon S W, Lee K B, et.al. Carbon Nanotubes as a Ligand in Cp2ZrCl2-Based Ethylene Polymerization [J]. Macromolecular Rapid Communication, 2006, 27: 47–50.
[53] Choi Y Y, Shin S Y A, Soare J B P. Preparation of polyethylene/montmorillonite nanocomposites through in situ polymerization using a montmorillonite-supported nickel diimine catalyst [J]. Macromolecular Chemistry and Physics. 2010, 211: 1026–1034.
[54] Kaminsky W, Renner F. High melting polypropenes by silica-supported zirconocene catalysts [J]. Macromolecular Rapid Communication, 1993, 14(4): 239–243.
[55] Chien J C W, He D W. Olefin copolymerization with metallocene catalysts. III. Supported metallocene/methylaluminoxane catalyst for olefin copolymerization [J]. Journal of Polymer Sciences A Polym Chem. 1991, 29(11): 1603–1607.
[56] Soga K, Kim H J, Shiono T. Polymerization of propene with highly isospecific. SiO2-supported zirconocene catalysts activated with common alkylaluminiums [J]. Macromolecular Chemistry and Physics. 1994, 195(10): 3347–3360.
[57] Lotfia E M, Shi Y S, Yuan Y, Zhou A N, Abubaker A, Xu Q H. Preparation, characterization, and catalytic activity of zirconocenebridged on surface of silica gel [J]. Applied Surface Sciences, 2015, 353: 376–381.
[58] Licht A I, Alt H G. Umsetzungen von ù-alkenylsubstituierten Zirconocendichloridkomplexen mit n-Alkyllithiumverbindungen in gegenwart von Alkenen bzw. alkinen [J]. Journal of Organometallic Chemistry. 2003, 687: 142–152.