单一位点第Ⅳ族聚烯烃催化剂研究进展
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摘要
聚烯烃主要通过第Ⅳ族金属催化剂进行配位聚合制备,单一位点催化剂一直为研发热点。该类催化剂通常被分为茂金属催化剂和后茂金属催化剂,并逐渐由单金属催化剂发展成双金属催化剂。介绍了茂金属催化剂和后茂金属催化剂的分类、结构特征以及配体结构对烯烃聚合性能和聚烯烃结构的影响。其中,茂金属催化剂的结构对称性对烯烃聚合影响较大,而后茂金属催化剂的配体取代基对烯烃聚合影响较大。建议加强后茂金属催化剂的设计合成,并尽快应用到聚烯烃新材料产业化中。
Polyolefins are mainly produced by groupⅣ metal catalysts.A single site catalyst has been a hot area for years.As for single site group Ⅳ metal catalysts,they are generally considered to have two types:metallocene catalysts and post-metallocene catalysts,evolving from scaffolds with single active center to those with double active centers.This review covered the main characteristics of the two types of catalysts such as classification,structures,influences of ligands substitutes to polymerization processes and the polymer properties.For metallocene catalysts,their symmetry is a key factor in the olefin polymerization,while the substituted groups of post-metallocene ligands impact a lot on the properties of polymer.We should take more attention on the synthesis of post-metallocene catalysts and their application in new materials such as polyolefin elastomers.
Polyolefins are mainly produced by groupⅣ metal catalysts.A single site catalyst has been a hot area for years.As for single site group Ⅳ metal catalysts,they are generally considered to have two types:metallocene catalysts and post-metallocene catalysts,evolving from scaffolds with single active center to those with double active centers.This review covered the main characteristics of the two types of catalysts such as classification,structures,influences of ligands substitutes to polymerization processes and the polymer properties.For metallocene catalysts,their symmetry is a key factor in the olefin polymerization,while the substituted groups of post-metallocene ligands impact a lot on the properties of polymer.We should take more attention on the synthesis of post-metallocene catalysts and their application in new materials such as polyolefin elastomers.
引文
[1]Severn J R,Chadwick J C.Immobilisation of homogeneous olefin polymerization catalysts.Factors influencing activity and stability[J].Dalton Trans,2013,42:8979-8987.
[2]刘伟娇,黄启谷,义建军,等.烯烃配位聚合催化剂的研究进展[J].高分子通报,2010,6:1-33.
[3]唐岩,李延亮,王群涛,等.茂金属催化剂及茂金属聚乙烯现状[J].合成树脂及塑料,2014,31(2):76-80.
[4]Natta G,Pino P,Mazzanti G,et al.A crystallizable organometallic complex containing titanium and aluminum[J].J.Am.Chem.Soc.,1957,79(11):2975-2976.
[5]Sinn H,Kaminsky D W,Vollmer,H.“Living Polymers”on polymerization with extremely productive Ziegler catalysts[J].Angew.Chem.,Int.Ed.Engl.,1980,19(5):390-392.
[6]Ewen J A.Mechanisms of stereochemical control in propylene polymerizations with soluble Group 4B metallocene/methylalumoxane catalysts[J].J.Am.Chem.Soc.,1984,106(21):6355-6364.
[7]Razavi A,Atwood J L.Isospecific propylene polymerization with unbridged Group 4metallocenes[J].J.Am.Chem.Soc.,1993,115(16):7529-7530.
[8]Ewen J A,Haspeslach L,Atwood J L,et al.Crystal structures and stereospecific propylene polymerizations with chiral hafnium metallocene catalysts[J].J.Am.Chem.Soc.,1987,109(21):6544-6545.
[9]Mise T,Miya S,Yamazaki H.Excellent stereoregular isotactic polymerizations of propylene with C2-symmetric silylene-bridged metallocene catalysts[J].Chem.Lett.,1989,18(10):1853-1856.
[10]Ewen J A,Jones R L,Razavi A,et al.Syndiospecific propylene polymerizations with Group IVB metallocenes[J].J.Am.Chem.Soc.,1988,110(18):6255-6256.
[12]Coates G W,Waymouth R M.Oscillating stereocontrol:a strategy for the synthesis of thermoplastic elastomeric polypropylene[J].Science,1995,267(5195):217-219.
[13]Coates G W.Precise control of polyolefin stereochemistry using single-site metal catalysts[J].Chem.Rev.,2000,100(4):1223-1252.
[14]Stevens J C,Timmers F J,Wilson D R,et al.Constrained geometry addition polymerization catalysts,processes for their preparation,precursors therefor,methods of use,and novel polymers formed therewith[P].Eur.Pat.Appl.,EU416 815A2,1991-13-13.
[15]Lapointe R E,Stevens J C,Nickias P N,et al.Preparation of homogeneous olefin polymerization catalysts by ligand abstraction with Lewis acids[P].Eur.Pat.Appl.,EU520 732 A1,1992-12-30.
[16]Soga K,Uozumi T,Nakamura S,et al.Structures of polyethylene and copolymers of ethylene with 1-octene and oligoethylene produced with the Cp2ZrCl2and[(C5Me4)SiMe2N(tertBu)]TiCl2catalysts[J].Macromol.Chem.Phys.,1996,197(12):4237-4251.
[17]Sernetz F G,Muelhaupt R.Influence of polymerization conditions on the copolymerization of styrene with ethylene using Me2Si(Me4Cp)(N-tert-butyl)TiCl2/methylaluminoxane Ziegler-Natta catalysts[J].Macromol.Chem.Phys.,1996,197(3),1071-1083.
[18]Li H B,Marks T J.Nuclearity and cooperativity effects in binuclear catalysts and cocatalysts for olefin polymerization[J].Proc.Natl.Acad.Sci.,2006,103(42):15295-15302.
[19]Scollard J D,McConville D,Payne N C,et al,.Polymerization ofα-olefins by chelating diamide complexes of titanium[J].Macromolecules,1996,29(15):5241-5243.
[20]Flores M A,Manzon M R,Baumann R,et al.Zirconium complexes that contain a diamido O-donor ligand with a restricted geometry[J].Organometallics,1999,18(16):3220-3227.
[21]Jin X,Novak B M.Synthesis ofβ-iminoaminate zirconium complexes and their application in ethylene polymerization[J].Macromolecules,2000,33(17):6205-6207.
[22]Vollmerhaus R,Rahim M,Tomaszewsk R,et al.Ethylene polymerization usingβ-diketimine complexes of zirconium[J].Organometallics,2000,19(11):2161-2169.
[23]Matsugi T,Matsui S,Kojoh S,et al.New titanium complexes bearing two indolide-imine chelate ligands for the polymerization of ethylene[J].Macromolecules,2002,35(13):4880-4887.
[24]Yoshida Y,Matsui S,Takagi Y,et al.Post-metallocenes:new bis(pyrrolyl-2-aldiminato)titanium complexes for ethylene polymerization[J].Chem.Lett.,2000,29(11):1270-1271.
[25]Dawson D M,Walker D A,Pett M T,et al.Synthesis and reactivity of sterically hindered iminopyrrolato complexes of zirconium,iron,cobalt and nickel[J].J.Chem.Soc.,Dalton Trans.,2000,4:459-466.
[26]Murray R E.Heteroaryl bridged metallocene catalyst for the production of olefin polymers,catalyst precursors,and their preparation[P].PCT Int.Appl.,WO9901460,1999-01-14.
[27]Boussie T R,Diamond G M,Goh C,et al.Substituted pyridyl amine ligands,complexes,catalysts and processes for polymerizing olefins[P].PCT Int.Appl.WO0238628,2002-05-16.
[28]Duncan A P,Mullins S M,Arnold J,et al.Synthesis,structural investigation,and reactivity of neutral and cationic bis(guanidinato)zirconium(IV)complexes[J].Organometallics,2001,20(18):1808-1819.
[29]Kuhl O,Koch T,Somoza F B,et al.Formation of elastomeric polypropylene promoted by the dynamic complexes[TiCl2{N(PPh2)2}2]and[Zr(NPhPPh2)4][J].J.Organomet.Chem.,2000,604(1):116-125.
[30]GibsonV C,Spitzmesser S K.Advances in non-metallocene olefin polymerization catalysis[J].Chem.Rev.,2003,103(1),283-315.
[31]Makio H,Fujita T.Development and application of FI catalysts for olefin polymerization:unique catalysis and distinctive polymer formation[J].Acc.Chem.Res.,2009,42(10):1532-1544.
[32]Matsugi T,Fujita T.High-performance olefin polymerization catalysts discovered on the basis of a new catalyst design concept[J].Chem.Soc.Rev.,2008,37(6):1264-1277.
[33]Mitani M,Saito J,Ishii S I,et al.FI catalysts:New olefin polymerization catalysts for the creation of value-added polymers[J].Chem.Rec.,2004,4(3),137-158.
[34]Mitani M,Mohri J,Yoshida Y,et al.Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands[J].J.Am.Chem.Soc.,2002,124(13):3327-3336.
[35]Saito J,Mitani M,Mohri J I,et al.Living polymerization of ethylene with a titanium complex containing two phenoxy-imine chelate ligands[J].Angew.Chem.Int.Ed.,2001,40(15):2918-2920.
[36]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].J.Am.Chem.Soc.,2001,123(21):5134-5135.
[37]Domski G J,Rose J M,Coates G W.Living alkene polymerization:New methods for the precision synthesis of polyolefins[J].Prog.Polym.Sci.,2007,32(1):30-92.
[38]Yao E D,Wang J C,Chen Z T,et al,.Homo and heteroligated salicylaldiminato titanium complexes with different substituents ortho to the phenoxy oxygens for ethylene and ethylene/1-hexene(Co)polymerization[J].Macromolecules,2014,47(23):8164-8170.
[39]Han S L,Yao E D,Qin W,et al.Binuclear heteroligated titanium catalyst based on phenoxyimine ligands:Synthesis,characterization,and ethylene(Co)polymerization[J].Macromolecules,2012,45(10):4054-4059.
[40]Tshuva E Y,Versano M,Goldberg I,et al.Titanium complexes of chelating dianionic amine bis(phenolate)ligands:an extra donor makes a big difference[J].Chem.Commun.,1999,2(8):371-373.
[41]Rhodes B,Chien J C W,Wood J S,et al.Synthesis of titanium(Ⅳ)complexes containing 2,6-dimethylaniline substituted amino alcohols and their utilization in ethylene polymerizations[J].J.Organomet.Chem.,2001,625[1]:95-100.
[42]Sobota P,Przybylak K,Utko J,et al.Syntheses,structure,and reactivity of chiral titanium compounds:procatalysts for olefin polymerization[J].Chem.Eur.J.,2001,7(5):951-958.
[43]Beckerle K,Manivannan R,Lian B,et al.Stereospecific styrene enchainment at a titanium site within a helical ligand framework:evidence for the formation of homochiral polystyrene[J].Angew.Chem.Int.Ed.,2007,46(25):4790-4793.
[44]Nakayama Y,Miyamoto K,Ueyama N,et al.Synthesis,structure and catalytic activity of a seven-coordinate titanium(IV)tris(pyridine-2-thiolate)complex[J].Chem.Lett.,1999,28(5):391-392.
[45]Gibson V C,Long N J,Martin J,et al.Titanium and zirconium complexes bearing(S,S’)-ferrocenyldithiolate ligands[J].J.Organomet.Chem.,1999,590(1):115-117.
[46]Wang C,Ma Z,Sun X L,et al.Synthesis and characterization of titanium(Ⅳ)complexes bearing monoanionic[O-NX](X=O,S,Se)tridentate ligands and their behaviors in ethylene homo and copolymerization with 1-hexene[J].Organometallics,2006,25(13):3259-3266.
[47]Liu S F,Sun W H,Zeng Y N,et al.Syntheses,characterization,and ethylene(Co-)polymerization screening of amidate half-titanocene dichlorides[J].Organometallics,2010,29(11):2459-2464.
[2]刘伟娇,黄启谷,义建军,等.烯烃配位聚合催化剂的研究进展[J].高分子通报,2010,6:1-33.
[3]唐岩,李延亮,王群涛,等.茂金属催化剂及茂金属聚乙烯现状[J].合成树脂及塑料,2014,31(2):76-80.
[4]Natta G,Pino P,Mazzanti G,et al.A crystallizable organometallic complex containing titanium and aluminum[J].J.Am.Chem.Soc.,1957,79(11):2975-2976.
[5]Sinn H,Kaminsky D W,Vollmer,H.“Living Polymers”on polymerization with extremely productive Ziegler catalysts[J].Angew.Chem.,Int.Ed.Engl.,1980,19(5):390-392.
[6]Ewen J A.Mechanisms of stereochemical control in propylene polymerizations with soluble Group 4B metallocene/methylalumoxane catalysts[J].J.Am.Chem.Soc.,1984,106(21):6355-6364.
[7]Razavi A,Atwood J L.Isospecific propylene polymerization with unbridged Group 4metallocenes[J].J.Am.Chem.Soc.,1993,115(16):7529-7530.
[8]Ewen J A,Haspeslach L,Atwood J L,et al.Crystal structures and stereospecific propylene polymerizations with chiral hafnium metallocene catalysts[J].J.Am.Chem.Soc.,1987,109(21):6544-6545.
[9]Mise T,Miya S,Yamazaki H.Excellent stereoregular isotactic polymerizations of propylene with C2-symmetric silylene-bridged metallocene catalysts[J].Chem.Lett.,1989,18(10):1853-1856.
[10]Ewen J A,Jones R L,Razavi A,et al.Syndiospecific propylene polymerizations with Group IVB metallocenes[J].J.Am.Chem.Soc.,1988,110(18):6255-6256.
[12]Coates G W,Waymouth R M.Oscillating stereocontrol:a strategy for the synthesis of thermoplastic elastomeric polypropylene[J].Science,1995,267(5195):217-219.
[13]Coates G W.Precise control of polyolefin stereochemistry using single-site metal catalysts[J].Chem.Rev.,2000,100(4):1223-1252.
[14]Stevens J C,Timmers F J,Wilson D R,et al.Constrained geometry addition polymerization catalysts,processes for their preparation,precursors therefor,methods of use,and novel polymers formed therewith[P].Eur.Pat.Appl.,EU416 815A2,1991-13-13.
[15]Lapointe R E,Stevens J C,Nickias P N,et al.Preparation of homogeneous olefin polymerization catalysts by ligand abstraction with Lewis acids[P].Eur.Pat.Appl.,EU520 732 A1,1992-12-30.
[16]Soga K,Uozumi T,Nakamura S,et al.Structures of polyethylene and copolymers of ethylene with 1-octene and oligoethylene produced with the Cp2ZrCl2and[(C5Me4)SiMe2N(tertBu)]TiCl2catalysts[J].Macromol.Chem.Phys.,1996,197(12):4237-4251.
[17]Sernetz F G,Muelhaupt R.Influence of polymerization conditions on the copolymerization of styrene with ethylene using Me2Si(Me4Cp)(N-tert-butyl)TiCl2/methylaluminoxane Ziegler-Natta catalysts[J].Macromol.Chem.Phys.,1996,197(3),1071-1083.
[18]Li H B,Marks T J.Nuclearity and cooperativity effects in binuclear catalysts and cocatalysts for olefin polymerization[J].Proc.Natl.Acad.Sci.,2006,103(42):15295-15302.
[19]Scollard J D,McConville D,Payne N C,et al,.Polymerization ofα-olefins by chelating diamide complexes of titanium[J].Macromolecules,1996,29(15):5241-5243.
[20]Flores M A,Manzon M R,Baumann R,et al.Zirconium complexes that contain a diamido O-donor ligand with a restricted geometry[J].Organometallics,1999,18(16):3220-3227.
[21]Jin X,Novak B M.Synthesis ofβ-iminoaminate zirconium complexes and their application in ethylene polymerization[J].Macromolecules,2000,33(17):6205-6207.
[22]Vollmerhaus R,Rahim M,Tomaszewsk R,et al.Ethylene polymerization usingβ-diketimine complexes of zirconium[J].Organometallics,2000,19(11):2161-2169.
[23]Matsugi T,Matsui S,Kojoh S,et al.New titanium complexes bearing two indolide-imine chelate ligands for the polymerization of ethylene[J].Macromolecules,2002,35(13):4880-4887.
[24]Yoshida Y,Matsui S,Takagi Y,et al.Post-metallocenes:new bis(pyrrolyl-2-aldiminato)titanium complexes for ethylene polymerization[J].Chem.Lett.,2000,29(11):1270-1271.
[25]Dawson D M,Walker D A,Pett M T,et al.Synthesis and reactivity of sterically hindered iminopyrrolato complexes of zirconium,iron,cobalt and nickel[J].J.Chem.Soc.,Dalton Trans.,2000,4:459-466.
[26]Murray R E.Heteroaryl bridged metallocene catalyst for the production of olefin polymers,catalyst precursors,and their preparation[P].PCT Int.Appl.,WO9901460,1999-01-14.
[27]Boussie T R,Diamond G M,Goh C,et al.Substituted pyridyl amine ligands,complexes,catalysts and processes for polymerizing olefins[P].PCT Int.Appl.WO0238628,2002-05-16.
[28]Duncan A P,Mullins S M,Arnold J,et al.Synthesis,structural investigation,and reactivity of neutral and cationic bis(guanidinato)zirconium(IV)complexes[J].Organometallics,2001,20(18):1808-1819.
[29]Kuhl O,Koch T,Somoza F B,et al.Formation of elastomeric polypropylene promoted by the dynamic complexes[TiCl2{N(PPh2)2}2]and[Zr(NPhPPh2)4][J].J.Organomet.Chem.,2000,604(1):116-125.
[30]GibsonV C,Spitzmesser S K.Advances in non-metallocene olefin polymerization catalysis[J].Chem.Rev.,2003,103(1),283-315.
[31]Makio H,Fujita T.Development and application of FI catalysts for olefin polymerization:unique catalysis and distinctive polymer formation[J].Acc.Chem.Res.,2009,42(10):1532-1544.
[32]Matsugi T,Fujita T.High-performance olefin polymerization catalysts discovered on the basis of a new catalyst design concept[J].Chem.Soc.Rev.,2008,37(6):1264-1277.
[33]Mitani M,Saito J,Ishii S I,et al.FI catalysts:New olefin polymerization catalysts for the creation of value-added polymers[J].Chem.Rec.,2004,4(3),137-158.
[34]Mitani M,Mohri J,Yoshida Y,et al.Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands[J].J.Am.Chem.Soc.,2002,124(13):3327-3336.
[35]Saito J,Mitani M,Mohri J I,et al.Living polymerization of ethylene with a titanium complex containing two phenoxy-imine chelate ligands[J].Angew.Chem.Int.Ed.,2001,40(15):2918-2920.
[36]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].J.Am.Chem.Soc.,2001,123(21):5134-5135.
[37]Domski G J,Rose J M,Coates G W.Living alkene polymerization:New methods for the precision synthesis of polyolefins[J].Prog.Polym.Sci.,2007,32(1):30-92.
[38]Yao E D,Wang J C,Chen Z T,et al,.Homo and heteroligated salicylaldiminato titanium complexes with different substituents ortho to the phenoxy oxygens for ethylene and ethylene/1-hexene(Co)polymerization[J].Macromolecules,2014,47(23):8164-8170.
[39]Han S L,Yao E D,Qin W,et al.Binuclear heteroligated titanium catalyst based on phenoxyimine ligands:Synthesis,characterization,and ethylene(Co)polymerization[J].Macromolecules,2012,45(10):4054-4059.
[40]Tshuva E Y,Versano M,Goldberg I,et al.Titanium complexes of chelating dianionic amine bis(phenolate)ligands:an extra donor makes a big difference[J].Chem.Commun.,1999,2(8):371-373.
[41]Rhodes B,Chien J C W,Wood J S,et al.Synthesis of titanium(Ⅳ)complexes containing 2,6-dimethylaniline substituted amino alcohols and their utilization in ethylene polymerizations[J].J.Organomet.Chem.,2001,625[1]:95-100.
[42]Sobota P,Przybylak K,Utko J,et al.Syntheses,structure,and reactivity of chiral titanium compounds:procatalysts for olefin polymerization[J].Chem.Eur.J.,2001,7(5):951-958.
[43]Beckerle K,Manivannan R,Lian B,et al.Stereospecific styrene enchainment at a titanium site within a helical ligand framework:evidence for the formation of homochiral polystyrene[J].Angew.Chem.Int.Ed.,2007,46(25):4790-4793.
[44]Nakayama Y,Miyamoto K,Ueyama N,et al.Synthesis,structure and catalytic activity of a seven-coordinate titanium(IV)tris(pyridine-2-thiolate)complex[J].Chem.Lett.,1999,28(5):391-392.
[45]Gibson V C,Long N J,Martin J,et al.Titanium and zirconium complexes bearing(S,S’)-ferrocenyldithiolate ligands[J].J.Organomet.Chem.,1999,590(1):115-117.
[46]Wang C,Ma Z,Sun X L,et al.Synthesis and characterization of titanium(Ⅳ)complexes bearing monoanionic[O-NX](X=O,S,Se)tridentate ligands and their behaviors in ethylene homo and copolymerization with 1-hexene[J].Organometallics,2006,25(13):3259-3266.
[47]Liu S F,Sun W H,Zeng Y N,et al.Syntheses,characterization,and ethylene(Co-)polymerization screening of amidate half-titanocene dichlorides[J].Organometallics,2010,29(11):2459-2464.