摘要
1、合成,表征了四个含烯丙基的茂锆配合物(C_3H_5C_5H_4)RCpZrCl_2(R=allyl,1;H,2;~tBu,3;~tBu_2,4)。X-射线单晶衍射解析了其中配合物1和3的分子结构。这类含烯丙基的茂锆配合物作催化剂催化烯烃聚合时,催化剂分子中的乙烯基团会共聚到增长的聚烯烃链上。因而,这种催化体系不需要任何载体,却具有为自身提供载体的能力。所以也被称作自固载烯烃聚合催化剂。这类自固载化烯烃聚合催化剂在MAO的作用下,显示出了较高的乙烯聚合活性。我们将配合物3与苯乙烯共聚制备了的高分子化的烯烃聚合催化剂5和壳核结构的高分子化烯烃聚合催化剂6,并进行了表征。高分子化的茂金属催化剂5的聚合实验表明这类催化剂保持了较高的活性,并能有效地避免粘釜的现象。壳核结构的高分子化催化剂6产生的聚乙烯有很好的形态和堆密度,基本达到了工业化的要求,具有很好的工业化前景。
2、进行了茂锆配合物1的介孔分子筛SBA-15的负载化。这种SBA-15的负载化的茂金属催化剂不仅保持了茂金属均相催化剂的高活性,而且利用载体的孔道效应合成了纤维状聚乙烯产品。
3、合成,表征了两个双β-二酮半夹心锆配合物CpZr(acac)_2Cl(7)、Cp~*Zr(acac)_2Cl(8)和两个三β-二酮半夹心锆配合物CpZr(acac)_3(9)、CpZr(tfac)_3(10)(acac=acetylacetonato,tfac=trisfluoroacetylacetonato)。X-射线单晶衍射表明双(β-二酮)半夹心锆配合物7采用一种不对称的顺式结构。三(β-二酮)半夹心锆配合物9和10的空间构型是五角双锥结构。乙烯聚合实验表明,这类锆配合物是优良的乙烯聚合催化剂。在5atm,70℃下,乙烯均聚高达7100kgPE/molZr.h,得到高分子量的聚乙烯(M_v=89×10~4)。另外,锆配合物7和8还能够催化乙烯和1-己烯的共聚。
4、合成了三齿席夫碱[O,N,O]类双苯酚半夹心钛配合物(11,12),锆的配合物(13,14)和含硫三齿席夫碱[S,N,O]类双苯酚半夹心钛(15)、锆的配合物(16)。X-射线单晶衍射显示配合物11、12、13和15的配体中的N原子都与中心金属原子有配位作用。乙烯聚合实验表明,钛配合物11的乙烯聚合活性较低。而锆配合物13的乙烯聚合活性较高,在常压,70℃时,活性达1.53×10~5gPE/molZr.h,且活性随温度的升高而增大。含硫钛配合物15乙烯聚合活性高于钛配合物11。实验表明,钛配合物11还能催化乙烯和1-己烯共聚。
1. Metallocene catalysts, (C_3H_5C_5H_4)RCpZrCl_2 (R= allyl, 1; H, 2; ~tBu; 3; ~tBu_2, 4), containing an allyl group, have been synthesized and characterized. In the presence of excess methylaluminoxane (MAO), the allyl group of the metallocene catalysts can be co-polymerized in the polymer chain as co-monomer in the polymerization process and so they were also called as self-immobilized catalysts for ethylene polymerization. The molecular structures of catalyst 1 and 3 have been determined by single-crystal X-ray diffraction. The polymerized metallocene catalyst 5 is prepared by the copolymerization of allyl metallocene complex with styrene in the presence of radical initiator. The result of ethylene polymerization showed that the polymerized metallocene catalyst kept high activity of 2300kgPE/molM.h for ethylene polymerization and was a potential supported catalyst for olefin polymerization.
2. This thesis discussed the synthesis and characterization of SBA-15 supported metallocene catalyst. The function of SBA-15 in controlling the morphology and improving the properties of polymers was studied through ethylene polymerization. The two-dimensional ordered channel structure of SBA-15 could control the relative position of polyethylene chains. As a result, the polyethylene fibers were obtained.
3. The half-sandwich Zr complexes of CpZr(acac)_2Cl(7), Cp*Zr(acac)_2Cl(8), CpZr(acac)_3(9) and CpZr(tfac)_3(10) ( acac=acetylacetonato, tfac= trisfluoroacetylacetonato) have been synthesized and characterized. The molecular structures of 7, 9 and 10 have been determined by X-ray diffraction methods. The geometrys around Zr atom in the tis(β-diketonato) Zr complexes 9 and 10 is pentagonal bipyramid. When activated by excess MAO, these catalysts were well active for ethylene polymerization, offering polyethylenes with high molecular weights. Catalyst 9 showed very high activity for ethylene polymerization of up to 7100kgPE/molZr.h at 5 atm and the resulted polymer has a high molecular weight (M_v = 89×10~4). Catalysts 7 and 8 were also active for ethylene/1-hexene copolymerization.
4. The Ti and Zr half-sandwich catalysts 11-16 with [O(S),N,O] tridentate Schiff base ligand have been synthesized. The molecular structures of catalysts 11,12, 13 and 15 have been determined by X-ray diffraction methods. The nitrogen atoms in 11,12,13 and 15 are coordinated to the metal centers. In the presence of excess MAO, the Zr catalyst 13 exhibited more active than the Ti complex for ethylene polymerization with a activity of 1.53×10~5gPE/molZr.h at 70℃, 1atm. [S,N,O] tridentate Schiff base Ti complex 15 is more active than its analogue 11. Catalyst 11 was also active for ethylene/1-hexene copolymerization.
引文
[1] Gibson V. C., Spitzmesser S. K., "Advances in Non-metallocene Olefin Polymerization Catalysis", Chem. Rev., 2003, 103, 283-315.
[2] Ziegler K.; Holzkamp E.; Breil H., "Das müheimer normaldruck polyathylen verfahren",Angew. Chem. 1955, 67, 541~547.
[3] Natta G., "Einige dokumentationsfragen auf dem gebiet der organischen chemie", Angew. Chem. 1955, 67, 430~432.
[4] 钱伯章,“世界乙烯工业及其进展”,石化技术与应用,2003,21(1),37~45.
[5] 钱伯章,“中国化工和石化业近期发展现状与进展”,石油化工技术经济,2003,19(2),4~11.
[6] Sinn H., Kaminsky W., Vollmer H. J., Woldt R., "Living Polymers on Polymerization with Extremely Productive Ziegler Catalysts", Angew. Chem., Int. Ed. Engl., 1980, 19, 390-392.
[7] Kaminsky W.; Kulper K.; Brintzinger H. H.; et al.." Polymerization of Propene and Butene with a Chiral Zirconocene and Methylalumoxane as Cocatalyst", Angew Chem. Int. Ed. Engl. 1985, 24, 507-508.
[8] Coates G. W., Waymouth R. M., "Oscillation Stereocontrol: A Strategy for the Synthesis of Thermoplastic Elastomeric Polypropylene", Science, 1995, 267(5195), 217—219.
[9] (a) Natta G.; Pino P.; Mazzanti G.; Giannini U., "Bis(cyclopentadienyl) titanium dichlorides alkylaluminium complexes as catalysts for the polymerization of ethylene", J. Am. Chem. Soc. 1957, 79, 5072-5073;
(b) Breslow D. S.; Newburg N. R. "Bis(cyclopentadienyl) titanium dichlorides alkylalunium complexes as soluble catalysts for the polymerization of ethylene", J. Am. Chem. Soc. 1959, 81, 81-86.
[10] Reichert L. H.; Meyer K. R. "Zur Kinetic der niederdruck polymerization von Athylen mit ioslichen Ziegler-Katalysatoren", Makromol. Chem. 1973, 169, 163~176.
[11] 黄葆同,陈伟等著《茂金属催化剂及其烯烃聚合物》,化学工业出版社,北京,2000,第一版.
[12] 黄葆同,沈之荃等著,《烯烃、双烯烃配为聚合进展》,科学出版社,北京,1998,第一版.
[13] (a) Erker J. K. G.; Frohlich R. "Internal Fluorocarbon Coordination as a Tool for the Protection of Active Catalytic Sites: Experimental Characterization of the Zr…F-C Interaction in the Group 4 Metallocene(butadiene)/B(C6F5)3 Betaine Ziegler Catalyst Systems", J. Am. Chem. Soc. 1996, 119, 11165~11173;
(b) Duchatean R.; Lancaster S. J.; Pett M. T. "Synthesis of Cyclopentadienyl-, Indenyl-, and Fluorenylbis(pentafluorophenyl)boranes as Ligands in Titanium and Zirconium Half-Sandwich Complexes. The Crystal Structures of C_(13)H_9B(C_6F_5)_2·t-BuNH_2, C_(13)H_8SiMe_3B(C_6F_5)_2, and {η~5-C_5H_4B(C_6F_5)_2}TiCl_3" Organometallics 1997, 16, 4995-5005;
(c) Yang X.; Stem C. L.; Marks T. J. "Cation-like homogeneous olefin polymerization catalysts based upon zirconocene alkyls and tris(pentafluorophenyl)borane", J. Am. Chem. Soc. 1991, 113, 3623-3625;
(d) Yang X.; Stem C. L.; Marks T. J. "Cationic Zirconocene Olefin Polymerization Catalysts Based on the Organo-Lewis Acid Tris(pentafluorophenyl)borane. A Synthetic,Structural, Solution Dynamic, and Polymerization Catalytic Study", J. Am. Chem. Soc. 1994,116,10015-10031.
[14] (a) Manzer, L. E. "Paramagnetic organometallic and dialkylamide complexes of trivalent titanium, vanadium, and chromium stabilized by diketonate ligands", J. Am. Chem. Soc. 1977, 99, 276-277;
(b) Biradar, N. S.; Patil, B. R. "Titanium(IV) complexes with 2,2'-dihydroxychalcones", Rev. Roum. Chim. 1978, 23(9-10), 1425.
[15] Flores, J. C; Chien, J. C. W.; Rausch, M. D. "{[2-(Dimethylamino)ethyl] cyclopentadienyl}trichlorotitanium: A New type of Olefin Polymerization Catalyst", Organometallics 1994, 13, 4140-4142.
[16] Skoog, S. J.; Mateo, C.; Lavoie, G. G.; Hollander, F. J.; Bergman,R. G. "Synthesis of Novel Group 4 Complexes Bearing the Tropidinyl Ligand: Investigations of Dynamic Behavior, Reactivity, and Catalytic Olefin Polymerization", Organometallics 2000,19,1406-1421.
[17] Chien, J. C. W.; Yu, Z. T.; Marques, M. M.; Flores, J. C; Rausch, M. D. "Polymerizations of olefins and diolefins catalyzed by monocyclopentadienyltitanium complexes containing a (dimethylamino)ethyl substituent and comparison with ansa-zirconocene systems", J. Polynt. Sci. Polym. Chem. 1998, 36, 319-328.
[18] Blais, M. S.; Chien, J. C. W.; Rausch, M. D. "Pendent Aminoalkyl-Substituted Monocyclopentadienyltitanium Compounds and Their Polymerization Behavior", Organometallics 1998, 17, 3775-3783.
[19] Deckers, P. J. W.; Hessen, B.; Teuben, J. H. "Switching a catalyst system from ethene polymerization to ethene trimerization with a hemilabile ancillary ligand", Angew. Chem., Int.Ed. 2001, 40, 2516-2519.
[20] Canich, J. A. M. (Exxon Chemical Patents, Inc., USA). U.S.Patent US5055438, 1991.
[21] Canich, J. A. M.; Turner, H. W.; Hlatky, G. G. (Exxon ChemicalPatents Inc., USA). U.S. Patent US5621126,1997; Chem. Abstr.1997,126, 343988.
[22] Santos, J. M.; Ribeiro, M. R.; Portela, M. F.; Cramail, H.;Deffieux, A.; Antinolo, A.; Otero, A.; Prashar, S. "[(η~5-C_5Me_4)SiMe_2(NtertBu)]TiCl_2 as Pre-Catalyst for the Copolymerisation of Ethylene with 5,7-Dimethylocta-l,6-diene and with 3,7-Dimethylocta-1,6-diene" Macromol. Chem. Phys. 2002, 203, 139-145
[23] Marques, M. M.; Correia, S. G.; Ascenso, J. R.; Ribeiro, A. F. G.;Gomes, P. T.; Dias, A. R.; Foster, P.; Rausch, M. D.; Chien, J. C.W. J. "Polymerization with TMA-protected polar vinyl comonomers. I. Catalyzed by group 4 metal complexes with η~5-type ligands." Polym. Sci. Polym. Chem. 1999, 37, 2457-2469.
[24] Alt, H. G.; Reb, A. "Amido functionalized ansa fluorenylidene half-sandwich complexes of zirconium as catalyst precursors for homogeneous ethylene polymerization", J. Mol. Catal. A: Chem. 2001,175, 43-50.
[25] Hasan, T.; Ioku, A.; Nishii, K.; Shiono, T.; Ikeda, T. "Syndiospecific Living Polymerization of Propene with [t-BuNSiMe_2Flu]TiMe_2 Using MAO as Cocatalyst", Macromolecules 2001, 34, 3142-3145.
[26] Feng, S. G.; Klosin, J.; Kruper, W. J.; McAdon, M. H.; Neithamer,D. R.; Nickias, P. N.; Patton, J. T.; Wilson, D. R.; Abboud, K. A.;Stern, C. L. "Synthesis and Characterization of Cyclohexadienyl-Based Constrained Geometry Complexes", Organometallics 1999,18,1159-1167. [27] Britovsek, G. J. P.; Gibson, V. C.; Wass, D. F. "The search for new-generation olefin polymerization catalysts: Life beyond metallocenes", Angew. Chem. Int. Ed. 1999, 38,428-447.
[28] Brown, S. J.; Gao, X. L.; Harrison, D. G.; Koch, L.; Spence, R.E. V.; Yap, G. P. A. "Bridged Phospholyl-Amido Titanium Catalysts for Ethylene Polymerization", Organometallics 1998,17, 5445-5447.
[29] Kotov, V. V.; Avtomonov, E. V.; Sundermeyer, J.; Harms, K.;Lemenovskii, D. A."Alkyl(amino)- and alkyl(chloro)phosphanyl-substituted cyclopentadienyl complexes of titanium and zirconium", Eur. J. Inorg. Chem. 2002, 678-691.
[30] Van Leusen, D.; Beetstra, D. J.; Hessen, B.; Teuben, J. H. "Ethylene-Bridged Tetramethylcyclopentadienylamide Titanium Complexes: Ligand Synthesis and Olefin Polymerization Properties", Organometallics 2000,19, 4084-4089.
[31] Kunz, K.; Erker, G.; Doring, S.; Frohlich, R.; Kehr, G. "Generation of Homogeneous (sp3-Cl)-Bridged Cp/Amido and Cp/Phosphido Group 4 Metal Ziegler-Natta Catalyst Systems", J. Am.Chem. Soc. 2001,123, 6181-6182.
[32] Okuda, J.; Eberle, T.; Spaniol, T. P.; Piquet-Faure, V."Complexes of titanium and zirconium containing a tridentate linked amido-cyclopentadienyl ligand with a soft donor group: synthesis, structure, and ethylene polymerization catalysis", J. Organomet. Chem. 1999, 591,127-137.
[33] Kleinschmidt, R.; Griebenow, Y.; Fink, G. "Stereospecific propylene polymerization using half-sandwich metallocene/MAO systems: a mechanistic insight", J. Mol. Catal. A: Chem. 2000, 157, 83-90.
[34] Zhang, Y.; Mu, Y.; Lue, C.; Li, G.; Xu, J.; Zhang, Y.; Zhu, D.; Feng, S. "Constrained Geometry Tetra methylcyclopentadienyl-phenoxytitanium Dichlorides: Template Synthesis, Structures, and Catalytic Properties for Ethylene Polymerization." Organometallics 2004, 23(3), 540-546.
[35] Irwin, Levi J.; Reibenspies, Joseph H.; Miller, Stephen A. "A Sterically Expanded "Constrained Geometry Catalyst" for Highly Active Olefin Polymerization and Copolymerization: An Unyielding Comonomer Effect." Journal of the American Chemical Society 2004, 126(51), 16716-16717
[36] Ashe, A. J.; Al-Ahmad, S.; Fang, X. G. "Boratabenzenes: from chemical curiosities to promising catalysts", J. Organomet. Chem. 1999, 581, 92-97.
[37] Ashe A. J., Al-Ahmad S., Kampf J. W.,"Bridged Boratabenzene Zirconium Complexes: Analogues of the ansa-Zirconocene Polymerization Catalysts", Organometallics, 1998, 17, 3883-3888
[38] Skoog, S. J.; Mateo, C; Lavoie, G. G.; Hollander, F. J.; Bergman,R. G. "Synthesis of Novel Group 4 Complexes Bearing the Tropidinyl Ligand: Investigations of Dynamic Behavior, Reactivity, and Catalytic Olefin Polymerization", Organometallics 2000,19,1406-1421.
[39] Murtuza, S.; Casagrande, O. L.; Jordan, R. F. "Ethylene Polymerization Behavior of Tris(pyrazolyl)borate Titanium(IV) Complexes", Organometallics 2002, 21, 1882-1890.
[40] Stephan, D. W.; Stewart, J. C; Guerin, F.; Spence, R.; Xu, W.; Harrison, D. G. "Phosphinimdes as a Steric Equivalent to Cyclopentadienyl: An Approach to Ethylene Polymerization Catalyst Design" Organometallics 1999, 18, 1116-1118.
[41] Yue, N. L. S.; Stephan, D. W. "Phosphinimide-Phosphinimide Ligands: New Bulky Ligands for Ethylene Polymerization Catalysts" Organometallics 2001, 20, 2303-2308.
[42] Yue, N.; Hollink, E.; Guerin, F.; Stephan, D. W. "Zirconium Phosphinimide Complexes: Synthesis, Structure, and Deactivation Pathways in Ethylene Polymerization Catalysis", Organometallics 2001, 20, 4424-4433.
[43] Kretschmer, W. P.; Dijkhuis, C.; Meetsma, A.; Hessen, B.;Teuben, J. H. "A highly efficient titanium-based olefin polymerisation catalyst with a monoanionic iminoimidazolidide p-donor ancillary ligand", Chem. Commun. 2002, 608-609.
[44] Sone M. and Yano A., Organic "Transition Metal Compound having Pi-Bonding Heterocyclic Ligand and Method of Polymerizing Olefins" U. S. Patent, 5434116. 1995
[45] Dias A. R., Galvao A. M., Galvao A. C. et al, Synthesis, Characterisation, Crystsal Structure, Reactivity and Bonding in Titanium Complexes Containing 2,3,4,5-tetramethylpyrrolyl, J. Chem. Soc. Dalton. Trans. 1997, 6,1055-1061
[46] Jordan R. F.and Crowther D. J., "Cyclopentadienyl dicarollide complexes of Titanium, Zirconium, and Hafnium" U. S. Patent, 5214173, 1993.
[47] Said, M.; Thornton-Pett, M.; Bochmann, M. "Titanium and zirconium complexes with sterically hindered aryl-substituted iminophosoranato ligands" J. Chem. Soc.,Dalton Trans. 2001, 2844-2849.
[48] Ray, B.; Neyroud, T. G.; Kapon, M.; Eichen, Y.; Eisen, M. S. "Synthesis, Characterization, and Catalytic Activities for the Polymeriztion of oldfin Promoted by Zirconium(III) and Titanium(III) Allyl Complexes." Organometallics 2001,20, 3044-3055.
[49] Scollard, J. D.; McConville, D. H. "Living Polymerization of α-Olefins by Chelating Diamide Complexes of Titanium" J. Am. Chem. Soc. 1996, 118, 10008-10009
[50] Scollard, J. D.; McConville, D. H.; Vittal, J. J.; Payne, N. C. "Chelating diamide complexes of titanium: new catalyst precursors for the highly active and living polymerization of alpha-olefins", J.Mol. Catal. A: Chem. 1998,128,201-214.
[51] Hagimoto, H.; Shiono, T.; Ikeda, T. "Living Polymerization of Propene with a Chelating Diamide Complex of Titanium Using Dried Methylaluminoxane", Macromol. Rapid Commun. 2002,23, 73-76.
[52] Lorber, C; Donnadieu, B.; Choukroun, R. "Synthesis and structure of Group 4 and 5 Metal Complexes with an Ancillary Sterically Demanding Diamido Ligand" Organometallics 2000,19,1963-1966.
[53] Horton, A. D.; von Hebel, K. L.; de With, J. " New highly active and selective Et oligomerization catalysts based on cationic diamide zirconium complexes" Macromol. Symp. 2001,173,123-136.
[54] Shafir, A.; Arnold, J. "Stabilization of a Cationic Ti Center by a Ferrocene Moiety: A Remarkably Short Ti-Fe Interaction in the Diamide {[(η~ 5-C_5H_4NSiMe_3)_2Fe]TiCl}_2~(2+)",J. Am. Chem. Soc. 2001, 123, 9212-9213.
[55] (a)Aizenberg, M.; Turculet, L.; Davis, W. M.; Schattenmann, F.;Schrock, R. R. Organometallics 1998,17, 4795-4812.
(b)Mehrkhodavandi, P.; Schrock, R. R. J. Am. Chem. Soc. 2001,123,10746-10747.
[56] Kim, W. K.; Fevola, M. J.; Liable-Sands, L. M.; Rheingold, A.L.; Theopold, K. H. "[(Ph)_2nacnac]MCl_2(THF)_2 (M = Ti, V, Cr): A New Class of Homogeneous Olefin Polymerization Catalysts Featuring β-Diiminate Ligands", Organometallics 1998, 17, 4541-4543.
[57] Vollmerhaus, R.; Rahim, M.; Tomaszewski, R.; Xin, S. X.; Taylor,N. J.; Collins, S. "Ethylene Polymerization Using β-Diketimine Complexes of Zirconium", Organometallics 2000, 19, 2161-2169.
[58] Matsugi, T.; Matsui, S.; Kojoh, S.-i.; Takagi, Y.; Inoue, Y.;Nakano, T.; Fujita, T.; Kashiwa, N. "New Titanium Complexes Bearing Two Indolide-Imine Chelate Ligands for the Polymerization of Ethylene", Macromolecules 2002, 35,4880-4887.
[59] Yoshida, Y.; Matsui, S.; Takagi, Y.; Mitani, M.; Nakano, T.;Tanaka, H.; Kashiwa, N.; Fujita, T. "New Titanium Complexes Having Two Pyrrolide-Imine Chelate Ligands: Syntheses, Structures, and Ethylene Polymerization Behavior", Organometallics 2001, 20, 4793-4799.
[60] Yoshida, Y.; Saito, J.; Mitani, M.; Takagi, Y.; Matsui, S.; Ishii,S.; T., N.; Kashiwa, N.; Fujita, T. "Living ethylene/norbornene copolymerisation catalyzed by titanium complexes having two pyrrolide-imine chelate ligands", Chem. Commun. 2002,1298-1299.
[61] Murray, R. E. (Union Carbide Chemicals & Plastics TechnologyCorp., USA). PCT Int. Appl. WO9901481,1999; Chem. Abstr. 1999,130,125531.
[62] Boussie, T. R.; Diamond, G. M.; Goh, C.; Hall, K. A.; Lapointe,A. M.; Leclerc, M. K.; Lund, G; Murphy, V. (Symyx Technologies,Inc, USA). PCT Int. Appl.WO0238628, 2002; Chem. Abstr. 2002,136, 386578.
[63] Goh, C; Diamond, G. M.; Murphy, V.; Leclerc, M. K.; Hall, K.;Lapointe, A. M.; Boussie, T. R.; Lund, C; Uno, T. (SymyxTechnologies, Inc., USA). PCT Int. Appl. WO0174910, 2001;Chem. Abstr. 2001, 135, 289200.
[64] Averbuj, C; Tish, E.; Eisen, M. S. "Stereoregular Polymerization of α-Olefins Catalyzed by Chiral Group 4 Benzamidinate Complexes of C_1 and C_3 Symmetry" J. Am. Chem. Soc. 1998,120, 8640-8646.
[65] Jayaratne, K. C; Sita, L. R. "Stereospecific Living Ziegler-Natta Polymerization of 1-Hexene" J. Am. Chem. Soc. 2000,122, 958-959.
[66] Duncan, A. P.; Mullins, S. M.; Arnold, J.; Bergman, R. G. "Synthesis, Structural Investigation, and Reactivity of Neutral and Cationic Bis(guanidinato)zirconium(IV) Complexes" Organometallics 2001, 20, 1808-1819.
[67] Kuhl, O.; Koch, T.; Somoza, F. B.; Junk, P. C; Hey-Hawkins,E.; Plat, D.; Eisen, M. S. "Formation of elastomeric polypropylene promoted by the dynamic complexes [TiCl_2{N(PPh_2)_2}_2] and [Zr(NPhPPh_2)_4]", J. Organomet. Chem. 2000, 604,116-125.
[68] Volkis, V.; Schmulinson, M.; Shaviv, E.; Lisovskii, A.; Plat, D.;Kuehl, O.; Koch, T.; Hey-Hawkins, E.; Eisen, M. S. PMSEPreprints,223rd ACS National Meeting, Orlando, FL, April7-11, 2002; American Chemical Soceity: Washington, DC, 2002;Vol. 86, pp 301-303.
[69]Cozzi, P. G.; Gallo, E.; Floriani, C.; Chiesivilla, A.; Rizzoli, C. "(Hydroxyphenyl)oxazoline: a Novel and Remarkably Facile Entry into the Area of Chiral Cationic Alkylzirconium Complexes Which Serve as Polymerization Catalysts", Organometallics 1995,14, 4994-4996.
[70] Kojoh, S.; Matsugi, T.; Saito, J.; Mitani, M.; Fujita, T.; Kashiwa,N. Chem. Lett. 2001,822-823.
[71] Ishii, S.; Mitani, M.; Saito, J.; Matsuura, S.; Kojoh, S.; Kashiwa,N.; Fujita, T. "Zirconium complexes having phenoxy/cycloalkylimine chelate ligands for the polymerization of ethylene for vinyl-terminated low molecular weight polyethylenes", Chem. Lett. 2002, 740-741.
[72] Matsui S., Fujita T., "FI Catalysts: Super Active New Ethylene Polymerization Catalysts" Catal Today 2001, 66, 63-73.
[73] Matsui, S.; Mitani, M.; Saito, J.; Tohi, Y.; Makio, H.; Matsukawa,N.; Takagi, Y.; Tsuru, K.; Nitabaru, M.; Nakano, T.; Tanaka,H.; Kashiwa, R; Fujita, T. "A Family of Zirconium Complexes Having Two Phenoxy-lmine Chelate Ligands for Olefin Polymerization", J Am. Chem. Soc. 2001, 123, 6847-6856.
[74] Matsukawa, R; Matsui, S.; Mitani, M.; Saito, J.; Tsuru, K.; Kashiwa, R; Fujita, T. "Ethylene polymerization activity under practical conditions displayed by zirconium complexes having two phenoxy-imine chelate ligands" J. Mol. Catal. A: Chem. 2001, 169, 99-104.
[75] Matsui S., Fujita T., "FI Catalysts: Super Active New Ethylene Polymerization Catalysts" Catal. Today 2001, 66, 63-73.
[76] Inoue, Y.; Nakano, T.; Tanaka, H.; Kashiwa, N.; Fujita, T. "Ethylene polymerization behavior of new titanium complexes having two phenoxy-pyridine chelate ligands" Chem.Lett. 2001,1060-1061.
[77] Suzuki, Y.; Kashiwa, N.; Fujita, T. "Synthesis and ethylene polymerization behavior of a new titanium complex having two imine-phenoxy chelate ligands", Chem. Lett. 2002, 358-359.
[78] Tian, J.; Hustad, P. D.; Coates, G. W. "A new catalyst for highly syndiospecific living olefin polymerization: Homopolymers and block copolymers from ethylene and propylene", J. Am. Chem. Soc. 2001,123, 5134-5135.
[79] Wang C, Sun X., Guo Y., Gao Y., Liu B., Ma Z., Xia, W. Shi L., Tang Y. Novel Titanium Catalysts Bearing an [O, N, S] Tridentate Ligand for Ethylene Homo- and Copolymerization Macromolecular Rapid Communications 2005, 26, 1609-1614
[80] W. Hu, X. Sun, C. Wang, Y. Gao, Y. Tang, Li. Shi, W. Xia, J. Sun, H. Dai, X. Li, X. Yao, X. Wang. Synthesis and Characterization of Novel Tridentate [NOP] Titanium Complexes and Their Application to Copolymerization and Polymerization of Ethylene Organometallics 2004, 23,1684-1688
[81] Tshuva, E. Y.; Goldberg, I.; Kol, M.; Weitman, H.; Goldschmidt,Z. "Novel zirconium complexes of amine bis(phenolate) ligands. Remarkable reactivity in polymerization of hex-1-ene due to an extra donor arm", Chem. Commun. 2000, 379-380.
[82] Tshuva, E. Y.; Groysman, S.; Goldberg, I.; Kol, M.; Goldschmidt,Z. "[ONXO]-Type Amine Bis(phenolate) Zirconium and Hafnium Complexes as Extremely Active 1-Hexene Polymerization Catalysts", Organometallics 2002, 21, 662-670.
[83] Tshuva, E. Y.; Goldberg, I.; Kol, M.; Goldschmidt, Z. "Zirconium Complexes of Amine-Bis(phenolate) Ligands as Catalysts for 1-Hexene Polymerization: Peripheral Structural Parameters Strongly Affect Reactivity", Organometallics 2001, 20, 3017-3028.
[84] Tshuva, E. Y.; Goldberg, I.; Kol, M. "Isospecific Living Polymerization of 1-Hexene by a Readily Available Nonmetallocene C2-Symmetrical Zirconium Catalyst", J. Am. Chem. Soc. 2000,122, 10706-10707.
[85] W. Wang, M. Fujiki, K. Nomura Ethylene Polymerization Catalyzed by Titanium(IV) Complexes of a Triaryloxoamine Ligand [TiX{(OArCH_2)_3N}] Macromol Rapid Commun. 2004, 25, 504-507
[86] Rhodes, B.; Chien, J. C. W.; Wood, J. S.; Chandrasekaran, A.;Rausch, M. D. "Synthesis of titanium(IV) complexes containing 2,6-dimethylaniline substituted amino alcohols and their utilization in ethylene polymerizations", J. Organomet. Chem. 2001, 625, 95-100.
[87] Lavanant, L.; Toupet, L.; Lehmann, C. W.; Carpentier, J.-F. Group 4 Metal Complexes of Nitrogen-Bridged Dialkoxide Ligands: Synthesis, Structure, and Polymerization Activity Studies Organometallics 2005,24, 5620-5633
[88] Daniel C. H. Oakes, Brian S. Kimberley, Vernon C. Gibson, David J. Jones, Andrew J. P. White and David J. Williams The surprisingly beneficial effect of soft donors on the performance of early transition metal olefin polymerisation catalysts Chem. Commun., 2004, 2174-2175
[89] Long, R. J.; Gibson, V. G; White, A. J. P.; Williams, D. J.Combining Hard and Soft Donors in Early-Transition-Metal Olefin Polymerization Catalysts Inorg. Chem., 2006,45,511-513
[90] Doherty, S.; Errington, R. J.; Jarvis, A. P.; Collins, S.; Clegg,W.; Elsegood, M. R. J. "Polymerization of Ethylene by the Electrophilic Mixed Cyclopentadienylpyridylalkoxide Complexes [CpM{NC_5H_4(CR_2O)-2}Cl_2] (M =Ti, Zr, R = Ph, Pr~i)", Organometallics 1998,17, 3408-3410.
[91] Nomura, K.; Naga, N.; Miki, M.; Yanagi, K.; Imai, A. "Synthesis of Various Nonbridged Titanium(IV) Cyclopentadienyl-Aryloxy Complexes of the Type CpTi(OAr)X_2 and Their Use in the Catalysis of Alkene Polymerization. Important Roles of Substituents on both Aryloxy and Cyclopentadienyl Groups", Organometallics 1998,17, 2152-2154.
[92] W. Kaminsky, Zirconocene Catalysts for Olefin Polymerization, Catal. Today, 1994, 20, 257-271
[93] G G Hlatky, Heterogeneous Single-Site Catalysts for Olefin Polymerization, Chem. Rev. 2000,100,1347-1376
[94] J. Boor Jr., Ziegler-Natta Catalysts and Polymerization, New York: Academic Press Inc., 1979
[95] J. C. W. Chien, Magnesium Chloride Supported high-Mileage Catalysts for Olefin Polymeization I Chemical Composition and Oxidation States of Titanium, J. Polym. Sci. A, Poly. Chem., 1972, 20, 2019-2032
[96] D. Slotfeldt-Ellingsen, I. M. Dahi, O. Ellested, Heterogenization of Homogeneous Catalysts I EPR Study of (C_5H_5)TiCl_5(C_2H_5)_n(n=1-3) Supported on Silica Gel, J. Mol. Catal., 1980,9, 423-434
[97] (a) K. Soga, In Catalyst Design for Tailor-Made Polyolefins, Tokyo: Eisevier-Kodansha, 1994, 307
(b) K. Soga, Highly Isospecific Immobilized Zirconocene Catalysts Supported on Chemically Modified SiO_2, Makromol. Symp., 1995, 89: 294
(c) K. Soga, M. Kaminada, Copolymerization of Olefin with SiO_(2~-), Al_2O_(3~-) and MgCl_2-supported Catalysts Activated by Trialkylaluminiums, Macromol Chem. Phys., 1994, 195: 1369-1379
(d) K. Soga, M. Kaminada, Polymerization of Propene with a rac-(CH_3)_2Si(2,4-(CH_3)C_5H_3)ZrCl_2/MAO/SiO_2-Al(iC_4H_9) Catalyst system, Macromol. Rapid Commun. 1994,15: 593-596
(e) K. Soga, T. Shiono, H. J. Kim, Activation of SiO_2-supported Zirconocene Catalyst Activated by Ordinary Alkylaluminiums, Macromol. Rapid Commun. 1994, 15: 139-143
(f) J. Jin, T. Uozomi, K. Soga, Ethylene Polymerization Initiated by SiO_2-supported Neodymocene catalysts, Macromol. Rapid Commun. 1995, 16: 317-319
(g) K. Soga, T. Arai, H. Nozawa, T. Uozomi, Recent Development in Heterogeneous Metallocene Catalysts, Makromol. Symp., 1995, 97, 53-57
[98] S. K. Ihm, K. J. Chu, J. H. Yim, In Catalyst Design for Tailor-Made Polyolefins, Tokyo: Eisevier-Kodansha, 1994, 299
[99] K. Soga, T. Shiono, H. J. Kim, Activation of SiO_2 Supported Zirconocene Catalyst by Common Trialkylaluminiums, Macromol. Chem. 1993, 194, 3499-3504
[100] (a) F. Langhauser, D. Fischer, J. ,G. Schweier, E. Barsties, H. H. Brintzinger, S. Schaible, W. Roell, Metallocenes with Heterofunctional Groups Containing Fused Cyclopentadienyl Groups for Polymerization of C2-10, Eur. Pat. Appl. EP. 670,325 20pp
(b) F. Langhauser, D. Fischer, J. ,G. Schweier, E. Barsties, H. H. Brintzinger, S. Schaible, W. Roell, Metallocenes with Heterofunctional Groups Containing Fused Cyclopentadienyl Groups for Use as Polymerization Catalysts, Eur. Pat. Appl. EP. 670,336 15pp
[101] E. I. Iiskola, S. Timonen, T. T. Pakkanen, O. Haerkki, P. Lehnus, J. V. Seppaelae, Cyclopentadienyl Surface as a Support for Zirconium Polyethylene Catalysts, Macromolecules, 1997, 30, 2853-2859
[102] L. Gila, A. Proto, E. Ballato, D. Vigliarolo, G. Lugli, Supported Metallocene Catalyst for Olefin Polymerization, Eur. Pat. Appl. EP. 725,086 14pp
[103] K. Soga, H. J. Kim, T. Shiono, Polymerization of Propene with Highly Isospecific SiO_2-supported Zirconocene Catalysts Activated with Common Alkylaluminiums, Macromol. Chem. Phys., 1994, 195, 3347-3360
[104] K. Soga, T. Arai, T. Uozomi, Polymerization of Propene over a MgCl_2-supported Dichlorosilylenebisindenylzirconium Dichloride catalyst Combined with Methyalumoxane, Polymer, 1997, 38, 4993-4995
[105] T. Asanuma, T. Shiomura, T. Iwatani, K. Takeuchi, S. Uchikawa, Manufacture of Syndiotactic Polypropene, Jpn. Kokai Tokkyl Koho JP 0,366,710[9,166,710]4pp
[106]G. Satyanarayana, S. Sivaram, An unusually Stable Supported Bis(cyclopentadienyl)titaniumdichloride Trialkyaluminum Catalyst for Ethylene Polymerization, Macro-moleculars, 1993, 26, 4712-4714,
[107] S. S. Sarma, G Satyanarayana, S. Sivaram, Polymerization of Ethylene-supported Metallocene-Methylaluminoxane Catalyst System, Polym. Sci., 1994,1, 315-320
[108] S. S. Reddy, S. Sivaram, Homogeneous Metallocene-Methylalumoxane Catalyst Systems for Ethylene Polymerization, Prog. Polym. Sci., 1995, 20: 309-364
[109] S. I. Woo, Y. S. Koo, US 5,968,417 5pp
[110] F. Ciardelli, A. Altomare, G Arribas, et al., In Catalyst Design for Tailor-Made Polyolefins, Tokyo: Eisevier-Kodansha, 1994, 257
[111] S. I. Woo, Y. S. Koo, T. K. Han, Polymerization of Ethylene over Matallocene Confined inside the Supercage of a NaY Zeolite, Macromol. Rapid Commun. 1995,16, 489-495
[112] (a) K. Soga, T. Arai, B. T. Hoang, T. Uozomi, Olefin Polymerization with Metallocene Catalysts Supported on Polysiloxane Derivatives, Macromol. Rapid Commun. 1995, 16: 905-909
(b) T. Arai, H. T. Ban, T. Uozomi, K. Soga, Syntheses of Polysiloxane-Supported Zirconocene Catalysts and Application to Ethene Polymerization, Macromol. Chem. Phys. 1997,198, 229-237
[113] H. G Alt, Polymerization of Ethylene with Metallocene/Methylaluminoxane Catalysts Supported on Polysiloxane Micro Gels and Silica, J. Organomet. Chem. 1998, 568, 263-269
[114] R. H. Grubbs, C. Gibbons, L.C. Kroll, W. D. Bonds, C. H. Brubaker, Activation of Homogeneous Catalysts by Polymer Attachment, J. Am. Chem. Soc, 1973, 95, 2373-2375
[115] T. Yorisue, S. Jpn Kanejima, Laid-Open Application 07/206914,1995
[116] A. J. Daimaio, Olefin Polymer-Supported Metallocene Catalysts for Olefin Polymerization, US Appl. 439,810 50pp
[117] S. Peter, H. G. Alt, B. Peifer, S. J. Palackal, M. B. Welch, Process to Prepare Polymeric Metallocene, US Patent 5,770,755 10pp
[118] G M. Barrett, Y. R. Miguel, Well-defined Metallocene Catalyst Supported on Polystyrene Beads, Chem. Commun., 1998, 17, 2079-2080
[119] M. J. Farrall, J. M. J. Frechet, Bromination and Lithiation: Two Important Steps in the Functionalization of Polystyrene Resins, J. Org. Chem., 1976, 41, 3877-3882
[120] F. H. Meng, G Q. Yu, B. T. Huang, Polymer-Supported Zirconocene Catalysts for Ethylene Polymerization, J. Polym. Sci. Part A: Polym. Chem., 1999, 37 37-46
[121] Antberg et al., Meallocene (Co)Polymers, Process for their Preparation and their Use as Catalysts, US Patent 5,169,818
[122] (a) Janiak, C., Scharmann, T. G, Lange, K. C. H., "Zirconium 8-diketonate methylaluminoxane systems as single-site catalysts for the preparation of high-molecular-weight polyethylene", Macromol. Rapid Commun., 1994, 15(8) 655-658;
(b) Janiak, C, Lange, K.C.H., Scharmann, T.G., Zirconium-chelate and mons-eta-cyclopentadienyl zirconium-chelate/methylalumoxane systems as soluble Ziegler-Natta olefin polymerization catalysts, Appl. Organometal. Chem., 2000, 14(6), 316-324.
[123] Owiny D.; Parkin S.; Ladipo F. T. "Synthesis, structural determination, and ethylene polymerization chemistry of mono(salicylaldiminato) complexes of titanium(IV)", J. Organomet. Chem. 2003, 678, 134-141
[124] (a)D. Zhang, G X. Jin, N. H. Hu, Self-immobilized Catalysts for Ethylene Polymerization: Neutral, Single-Component Salicylaldiminato Phenyl Nickel(Π) Complexes Bearing Allyl Substitutents, Chem. Commun., 2002: 574-575
(b)D. Zhang, G X. Jin, N. H. Hu, Ethylene Polymerization by Self-Immobilized Neutral Nickel Catalysts Bearing Allyl Groups, Eur. J. Inorg. Chem., 2003: 1570-1576
[125] (a)C. K. Liu, G. X. Jin, Polymer-incorporated iron catalysts for ethylene polymerization a new approach to immobilize iron olefins catalysts on polystyrene chains, New J. Chem., 2002, 26: 1485-1489
(b)D. Zhang, G X. Jin, Micron-granula Polyolefin with self-immobilized Nickel and Iron Diimine Catalysts Bearing One or Two Allyl Groups, J. Poly. Sci. Part A: Poly. Chem., 2004, 42,1018-1024
[1] H. G. Alt, A. Koppl, Effect of the Nature of Metallocene Complexes of Group Ⅳ Metals on their performance in Catalyic Ethylene and Propylene Polymerization, Chem. Rev., 2000, 100:1205-1222
[2] (a)D. Zhang, G. X. Jin, N. H. Hu, Self-immobilized Catalysts for Ethylene Poly- merization: Neutral, Single-Component Salicylaldiminato Phenyl Nickel(Π) Complexes Bearing Allyl Substitutents, Chem. Commun., 2002 574-575;
(b)D. Zhang, G. X. Jin, N. H. Hu, Ethylene Polymerization by Self-Immobilized Neutral Nickel Catalysts Bearing Allyl Groups, Eur. J. Inorg. Chem., 2003: 1570-1576
[3] D. Zhang, G X. Jin, N. H. Hu, Self-Immobilized Titanium and Zirconium Catalysts with Phenoxy-Imine Ligands for Ethylene Polymerization. X-ray Crystal Structure of Bis(N-(3-tert-butylsalicylidene)-4 -allyloxyailinato) Zirconium(IV) Dichloride, Applied Catalysis A: General, 2004, 262,13-18
[4] F. A. R Kaul, G T. Puchta, H. Schneider, F. Bielert, D. Mihalios, W. A. Hermann, Immobilization of Bis(imino)pyridyliron(Π ) Complexes on Silica, Organometallics, 2002, 21: 74-82
[5] D. Zhang, G X. Jin, Micron-granula Polyolefin with self-immobilized Nickel and Iron Diimine Catalysts Bearing One or Two Allyl Groups, J. Poly. Sci. Part A: Poly. Chem., 2004, 42,1018-1024 [6] H. B. Zhu, G X. Jin, N. H. Hu, Polymer immobilized silane bridged metallocene catalysts for ethylene polymerization, J. Organomet. Chem., 2002, 655:167-171
[7] Kageyama, K.; Tamazawa, J-I; Aida,T. Extrusion polymerization: catalyzed synthesis of crystalline linear polyethylene nanofibers within a mesoporous silica, Science, 1999,285,2113
[8] Kageyama,K.; Ogino,S-i.; Aida,T. "Mesoporous zeolite as a new class of catalyst for controlled polymerization of Lactones", Macromolecules,1998,31,4069-4073
[9] Tajima,K.;Ogawa,G; Aida,T. Novel molecularly hybridized polyethylene silica composite material: Polymerization of ethylene with supported tianocenes by mesoporous silicates, Journal of polymer Science: Part A: Polymer Science 2000, 38,4821-4825
[10] Zhao D., Feng J., Hou Q., Melosh N., Fredrickson G H., Chmelka B. F., Stuky G D. "Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores", Science, 1998, 279, 548-565.
[11] Jun S., Too S. H., Ryoo R., Kruk M., Jaroniec M., Liu Z., Obsuna T., Terasaki.O. "Synthesis of New, Nanoporous Carbon with Hexagonally Ordered Mesostructure", J. Am. Chem. Soc, 2000,122,10712-10713.
[12] Qian Y. L., Qian X. M., Huang J. L., Sun J. Q. "Synthesis of mixed-ring zirconocene complexes containing alkenyl group and ethylene polymerization catalyzed with them", Chinese Journal of Chemistry, 2003, 21, 347-351.
[13] G Y. Zhou, Doctor Paper (1999)
[14] Chen S. S., Wei R. B., Chin. Sci. Bull. 15,1983, 921-924
[1] Sinn, H., Kaminsky, W., Vollmer, H. J., Woldt, R., "Living polymers on polymerization with extremely productive Ziegler catalysts", Angew. Chem. Int. Ed. Eng., 1980,19(3): 390-392.
[2] (a) Brintzinger, H. H., Fischer, D., Mullhaupt, R., Rieger, B., Waymouth, R. M., Stereospecific olefin polymerization with chiral metallocene catalysts, Angew. Chem., Int. Ed. Engl., 1995 34(11):1143-1170;
(b) Bochmann, M., Cationic Group 4 metallocene complexes and their role in polymerisation catalysis: The chemistry of well defined Ziegler catalysts, J. Chem. Soc, Dalton Trans., 1996, 3: 255-270.
[3] (a) Britovsek, G. J. P., Gibson, V. C, Wass, D. F., The search for new-generation olefin polymerization catalysts: Life beyond metallocenes, Angew. Chem., Int. Ed., 1999, 38(4): 428-447;
(b) Ittel, S. D., Johnson, L. K., Brookhart, M., Late-metal catalysts for ethylene homo- and copolymerization, Chem. Rev., 2000, 100(4): 1169-1203;
(c) Gibson, V. C, Spitzmesser, S. K., Advances in non-metallocene olefin polymerization catalysis, Chem. Rev. 2003, 103(1): 283-315.
[4] (a) Linden, A., Schaverien, C. J., Meijboom, N., Ganter, C, Orpen, A. G., Polymerization of a-olefins and butadiene and catalytic cyclotrimerization of 1-alkynes by a new class of group IV catalysts: Control of molecular weight and polymer microstructure via ligand tuning in sterically hindered chelating phenoxide titanium and zirconium species, J. Am. Chem. Soc, 1995, 117(11), 3008-3021;
(b) Sernetz, F. G., Mulhaupt, R., Fokken, S., Okuda, J., Copolymerization of ethene with styrene using methylaluminoxane-activated bis(phenolate) complexes, Macromol., 1997, 30(6), 1562-1569;
(c) Fokken, S., Spaniol, T. P., Okuda, J., Sernetz, F. G., Mulhaupt, R., Nine-membered titanacyclic complexes based on an ethylene-bridged bis(phenolato) ligand: Synthesis, structure, and olefin polymerization activity, Organometallics, 1997, 16(20), 4240-4242.
(d) Nakayama, Y., Watanabe, K., Ueyama, N., Nakamura, A., Harada, A., Okuda, J., Titanium complexes having chelating diaryloxo ligands bridged by tellurium and their catalytic behavior in the polymerization of ethylene, Organometallics, 2000, 19(13), 2498-2503.
[5] (a) Bei, X., Swenson, D. C, Jordan, R. F., Synthesis, structures, bonding, and ethylene reactivity of group 4 metal alkyl complexes incorporating 8-quinolinolato ligands, Organometallics, 1997, 16(15), 3282-3302;
(b) Tsukahara, T., Swenson, D. C, Jordan, R. F., Neutral and cationic zirconium benzyl complexes containing bidentate pyridine alkoxide ligands. Synthesis and olefin polymerization chemistry of (pyCR_2O)_2Zr(CH_2Ph)_2 and (pyCR_2O)_2Zr(CH_2Ph)~+ complexes, Organometallics, 1997, 16(15), 3303-3313;
(c) Kim, I., Nishihara, Y., Jordan, R. F. R., Rogers, D., Rheingold, A. L., Yap, G. P. A., Synthesis, structures, dynamics, and olefin polymerization behavior of group 4 metal (pyCAr_2O)_2M(NR_2)_2 complexes containing bidentate pyridine alkoxide ancillary ligands, Organometallics, 1997,16, 3314-3323;
(d) Kim. Y., Han, Y., Do, Y., New half-sandwich metallocene catalysts for polyethylene and polystyrene, J. Organomet. Chem., 2001, 634(1): 19-24;
(e) Gauvin, R. M., Osborn, J. A., Kress, J., Zirconium-benzyl complexes of a tridentate C-2-symmetric dialkoxo ligand. Diastereoselectivity of olefin single-insertion reactions, Organometallics, 2000,19(16): 2944-46.
[6] (a) Nomura, K., Naga, N., Miki, M., Yanagi, K., Imai, A., Synthesis of various nonbridged titanium(IV) cyclopentadienyl-aryloxy complexes of the type CpTi(OAr)X_2 and their use in the catalysis of alkene polymerization. Important roles of substituents on both aryloxy and cyclopentadienyl groups, Organometallics, 1998, 17(11): 2152-2154.
(b) Nomura, K., Naga, N., Miki, M., Yanagi, K., Olefin polymerization by (cyclopentadienyl)(aryloxy)titanium(IV) complexes-cocatalyst systems, Macromolecules, 1998, 31(22): 7588-7597;
(c) Nomura, K., Komatsu, T., Imanishi, Y., Syndiospecific styrene polymerization and efficient ethylene/styrene copolymerization catalyzed by (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO
system, Macromolecules, 2000, 33(22), 8122-8124;
(d) Nomura, K., Okumura, H., Komatsu, T., Naga, N., Ethylene/styrene copolymerization by various (cyclopentadienyl)(aryloxy)titanium(IV) complexes-MAO catalyst systems, Macromolecules, 2002, 35(14): 5388-5395;
(e) Nomura, K., Tsubota, M., Fujiki, M., Efficient ethylene/norbornene copolymerization by (aryloxo)(indenyl)-titanium(IV) complexes-MAO catalyst system, Macromolecules, 2003, 36(11): 3797-3799;
(f) Wang, W., Fujiki, M., Nomura, K., Copolymerization of ethylene with cyclohexene (CHE) catalyzed by nonbridged half-titanocenes containing aryloxo ligand: Notable effect of both cyclopentadienyl and anionic donor ligand for efficient CHE incorporation, J, Am. Chem. Soc. 2005,127(13): 4582-4583.
[7] Gibson, V. C, Structural and bonding patterns in tetrahedral and pseudo-tetrahedral transition-metal complexes containing Pi-donor ligands, J. Chem. Soc. Dalton Trans., 1994, 11: 1607-1618.
[8] (a) Ziegler, K., Breil, H., Martin, H., Holzkamp, E., US Patent 3257332, 1954, Chem. Abstr., 1966, 65, 7308;
(b) Meyer, G., Siggel, E., Roesener, W., (Glanzstoff AG). German Patent 1236790, 1967, Chem. Abstr., 1967, 67, 11947,
(c) Zuech, F. A., (Phillips Petroleum Co.) US Patent 3393245,1968, Chem. Abstr., 1968, 69, 51519.
[9] Shmulinson, M., Galan-Fereres, M., Lisovskii, A., Nelkenbaum, E., Semiat, R., Eisen, M. S., Formation of elastomeric polypropylene promoted by racemic acetylacetonate group 4 complexes, Organometallics, 2000, 19(7): 1208-1210.
[10] (a) Ueki, S., Furubashi, H., Murata, M., Toki, S., US Patent (Tonen Corporation) 5223465, 1993, Chem. Abstr., 1990, 116, 7090;
(b)Longo, P., Proto, A., Oliva, L., Zirconium catalysts for the syndiotactic polymerization of styrene, Macromol. Rapid Commun., 1994,15(2): 151-154.
[11] (a) Janiak, C, Scharmann, T. G., Lange, K. C. H., Zirconium β-diketonate methylaluminoxane systems as single-site catalysts for the preparation of high-molecular-weight polyethylene, Macromol. Rapid Commun., 1994, 15(8): 655-658;
(b) Janiak, C, Lange, K.C.H., Scharmann, T.G., Zirconium-chelate and mons-eta-cyclopentadienyl zirconium-chelate/methylalumoxane systems as soluble Ziegler-Natta olefin polymerization catalysts, Appl. Organometal. Chem., 2000,14(6): 316-324.
[12] Bau, D., Carta, G., Crociani, L., Paolucci, G., Raggiotto, F., Rossetto, G., Zanella, P., Non-cyclopentadienyl zirconium complexes as catalysts for 1-hexene polymerization, Inorg. Chim. Acta, 2005, 358(1), 36-40.
[13] (a) Doherty, S., Errington, R. J., Jarvis, A. P., Collins, S., Clegg, W., Elsegood, M. R. J., Polymerization of ethylene by the electrophilic mixed cyclopentadienylpyridylalkoxide complexes [CpM{NC_5H_4(CR_2O)_2}Cl_2] (M = Ti, Zr, R = Ph, Pr~i), Organometallics, 1998, 17(16), 3408-3410;
(b) Bott, R.K.J., Hughes, D. L., Schormann, M., Bochmann, M., Lancaster, S. J., Monocyclopentadienyl phenoxy-imine and phenoxy-amine complexes of titanium and zirconium and their application as catalysts for 1-alkene polymerisation, J. Organomet. Chem., 2003, 665(1-2): 135-149.
[14] Pinnavaia, T. J., Lott, A. , Dynamic stereochemical properties of some halobis(β-diketonato) cyclopentadienylzirconium and hafnium complexes, Inorg. Chem., 1971,10(7): 1388-1392.
[15] Pinnavaia, T. J.; Howe, J. J. Kinetics and mechanism of stereochemical rearrangement processes for tris(8-diketonato)cyclopentadienylzirconium complexes, J. Am. Chem. Soc, 1970, 92(25): 7342-7348.
[16] Howe, J. J., Pinnavaia, T. J., Synthesis of tris(β-diketonato) complexes cyclopentadienylzirconium, Syn. React. Inorg. Metal-Org. Chem., 1974, 4(4):325-334.
[17] Stezowski. J. J., Eick H. A., Crystal structure of cyclopentadienyl bis(acetylacetonato) chlorozirconium(IV), J. Am. Chem. Soc, 1969, 91(11): 2890-2894.
[18] Elder, M., Crystal structure of tris(hexafluoroacetylacetonato) cyclopentadienylzirconium, Inorg. Chem., 1969, 8(10): 2103-2109.
[19] Antinolo, A., Carrillo-Hermosilla, F., Corrochano, A., Fernandez-Baeza, J., Lara-Sanchez, A., Ribeiro, M. R., Lanfranchi, M., Otero, A., Pellinghelli, M. A., Portela, M. F., Santos, J. V., Synthesis of zirconium(IV) monocyclopentadienyl-aryloxy complexes and their use in catalytic ethylene polymerization. X-ray structure of Cp*Zr{2,6-OC_6H_3(CH_3)_2}_3, Organometallics, 2000,19(15): 2837-2843.
[1] 游效曾,孟庆金,韩万书主编,《配位化学进展》,北京:高等教育出版社,2001,17.
[2] 孙命,段月琴,王瑾玲等,高等学校化学学报,2001,22(7),1160.
[3] Dutta R. L.; Das B. R. "Schiff base complexes of lanthanides", J. Scient. Ind. Res. 1988, 47, 547-564.
[4] Gopinathan, S.; Gopinathan, C Gupta, J. "Chelated oxotitanium(IV) compounds", Indian J. Chem. 1970, 8, 650.
[5] Sharma, R. K.; Singh, R. V; Tandon, J. P. "Mixed Schiff base complexes of titanium(IV) and zirconium(IV)", Indian J. Chem. 1979,18A, 360.
[6] Pandit, S. K.; Gopinathan, S.; Gopinathan, C. J. Chem. Soc. Dalton Trans. 1982, 1004.
[7] Tjaden, E.B.; Swenson, D. C; Jordan, R. F. "Synthesis, Structures, and Reactivity of (R6-acen)ZrR'_2 and (R6-acen)Zr(R')~+ Complexes (R = H, F; R' = CH_2CMe_3, CH_2Ph)", Organometallics 1995,14, 371.
[8] Corazza, F.; Solari, E.; Floriani, C; Chiesi-Villa, A.; Guastini, C. "cis-Dichloro-derivatives and Trans-dichloro-derivatives of 6-coordinated and 7-coordinated Zirconium and Hafnium Bonded to Quadridentate Schiff-base Ligands", J. Chem. Soc. Dalton Trans. 1990, 1335.
[9] Cozzi, P. G; Gallo, E.; Florian, C. "(Hydroxyphenyl)oxazoline: a Novel and Remarkably Facile Entry into the Area of Chiral Cationic Alkylzirconium Complexes Which Serve as Polymerization Catalysts", Organometallics, 1995, 14, 4994-4996.
[10] (a) Pasquali, M.; Marchetti, R; Landi, A.; Floriani, C. "Preparations and structures of NN'-ethylenebis(salicylideneiminato)-titanium(III) derivatives", J. Chem. Soc. Dalton Trans. 1978, 545;
(b) Dell-Amico, G; Marchetti, R; Floriani, C. "Peripheral electrophilic properties of dichloro[NN ' -ethylenebis(salicylideneiminato)]titanium(IV) : a route leading to a stable Ti-H-B unit", J. Chem. Soc. Dalton Trans. 1982, 2197.
[11] Mazzanti, M.; Rosset, J. M.; Floriani, C. "N,N'-ethylene bis(acetylacetone- iminato) titanium complexes: synthesis, crystal structures, and properties of titanium(III) and titanium(IV) derivatives", J. Chem. Soc. Dalton. Trans. 1989, 953.
[12] Hlatky G. G. "Heterogeneous Single-Site Catalysts for Olefin Polymerization", Chem Rev 2000, 100(4), 1347-1376.
[13] Britovesk G J. P.; Gibson V. C; et al. "The search for new-generation olefin polymerization catalysts: Life beyond metallocenes", Angew Chem Int Ed Eng, 1999, 38(4), 428-447.
[14] Matsui S.; Fujita T. "FI Catalysts: super active new ethylene polymerization catalysts", Catal. Today 2001, 66 (1), 61-71.
[15] Bochmann M. "Cationic Group 4 metallocene complexes and their role in polymerisation catalysis: The chemistry of well defined Ziegler catalysts", J Chem Soc, Dalton Trans 1996, 24(3), 255-270.
[16] Zhang D.; Jin G-X.;Hu N. H. "Self-immobilized Catalysts for Ethylene Poly-merization: Neutral, Single-Component Salicylaldiminato Phenyl Nickel(Π) Complexes Bearing Allyl Substitutents", Chem Commun 2002, 37(5), 574-575.
[17] Liu C. K.; Jin G X. "Polymer-incorporated iron catalysts for ethylene polymerization a new approach to immobilize iron olefins catalysts on polystyrene chains", New J Chem 2002, 26(10), 1485-1489.
[18] Zhang D.; Jin G X. "Novel, Highly Active Binuclear 2,5-Disubstituted Amino-p-benzoquinone-Nickel(II) Ethylene Polymerization Catalysts", Organometallics 2003, 22(14), 2851-2854.
[19] Jin G X.; Zhang D. "Micron-granula Polyolefin with Self-immobilized Nickel and Iron Diimine Catalysts Bearing One or Two Allyl Groups", J Polym Sci, Polym. Chem 2004, 42(4), 1018-1024.
[20] Owiny D.; Parkin S.; Ladipo F. T. "Synthesis, structural determination, and ethylene polymerization chemistry of mono(salicylaldiminato) complexes of titanium(IV)", J. Organomet. Chem. 2003, 678,134-141
[21] (a) Wang C, Sun X., Guo Y., Gao Y., Liu B., Ma Z., Xia, W. Shi L., Tang Y. Novel Titanium Catalysts Bearing an [O, N, S] Tridentate Ligand for Ethylene Homo- and Copolymerization, Macromolecular Rapid Communications 2005, 26,1609-1614;
(b)Daniel C. H. Oakes, Brian S. Kimberley, Vernon C. Gibson, David J. Jones, Andrew J. P. White and David J. Williams The surprisingly beneficial effect of soft donors on the performance of early transition metal olefin polymerisation catalysts Chem . Commun., 2004, 2174-2175;
(c) Capacchione, C, Proto, A., Ebeling, H., Mulhaupt, R., Moller, K., Spaniol, T. P., Okuda, J., "Ancillary Ligand Effect on Single-Site Styrene Polymerization: Isospecificity of Group 4 Metal Bis(phenolate) Catalysts", J. Am. Chem. Soc, 2003,125, 4964-4965.