FI催化剂在制备乙烯基共聚物中的应用
|
摘要
综述了带有芳氧基亚胺配体的ⅣB族金属络合物(FI催化剂)催化的乙烯类共聚合。Ti-FI催化剂可用于乙烯与α-烯烃、乙烯与环烯烃的共聚合。相比传统的茂金属催化剂,FI催化剂可以制备共聚单体含量更高的共聚物。FI催化剂对极性基团具有良好的耐受性,将其用于乙烯与极性单体的共聚合,可取得理想的效果。与亚胺N原子相连的芳香环上的邻位H原子被F原子所取代的Ti-FI催化剂催化乙烯类聚合时,表现出活性聚合的特征。因此可通过控制单体加入顺序制备嵌段共聚物。用两种不同的FI催化剂,且以二乙基锌为链穿梭剂,可制备多嵌段共聚物。优化配体结构可制备高效的乙烯类共聚合催化剂。这些将有利于实现聚烯烃的功能化和高性能化。
This article reviewed the application of group Ⅳ metal complexes bearing phenoxy-imine ligand(FI catalyst) to ethylene copolymerization.The Ti-FI catalysts could be applied to the copolymerization of ethylene and α-olefin,ethylene and cycloolefin.Compared with traditional metallocene catalysts,the Ti-FI catalysts can produce copolymers with much more content of comonomers.FI catalysts can be used to the copolymerization of ethylene and polar comonomer with satisfactory results because of their good tolerance of polar function group.With ortho-F atom on N-aromatic ring,the Ti-FI catalyst can show a performance of living polymerization.Therefore,block copolymers can be obtained by controlling sequences of adding monomers.The multi-block copolymers were obtained by employing FI catalyst with metallocene at the same time in the presence of diethyl zinc as a chain shuttling reagent.High efficient catalysts for ethylene copolymerization can be synthesized through optimizing the structure of ligands.These can make great contribution to the functionalization and high performance of polyolefins.
This article reviewed the application of group Ⅳ metal complexes bearing phenoxy-imine ligand(FI catalyst) to ethylene copolymerization.The Ti-FI catalysts could be applied to the copolymerization of ethylene and α-olefin,ethylene and cycloolefin.Compared with traditional metallocene catalysts,the Ti-FI catalysts can produce copolymers with much more content of comonomers.FI catalysts can be used to the copolymerization of ethylene and polar comonomer with satisfactory results because of their good tolerance of polar function group.With ortho-F atom on N-aromatic ring,the Ti-FI catalyst can show a performance of living polymerization.Therefore,block copolymers can be obtained by controlling sequences of adding monomers.The multi-block copolymers were obtained by employing FI catalyst with metallocene at the same time in the presence of diethyl zinc as a chain shuttling reagent.High efficient catalysts for ethylene copolymerization can be synthesized through optimizing the structure of ligands.These can make great contribution to the functionalization and high performance of polyolefins.
引文
[1]Terao H,Iwashita A,Matsukawa N,et al.Ethylene and eth-ylene/α-olefin(co)polymerization behavior of bis(phenoxy-imine)Ti catalysts:significant substituent effects on activity and comonomer incorporation[J].ACS Catalysis,2011,1(4):254-265.
[2]Makio H,Ochiai T,Tanaka H,et al.FI catalysts:a molecular zeolite for olefin polymerization[J].Advanced Synthesis&Catalysis,2010,352(10):1635-1640.
[3]Terao H,Iwashita A,Ishii S,et al.Ethylene/norbornene copolymerization behavior of bis(phenoxy-imine)Ti complexes combined with MAO[J].Macromolecules,2009,42(13):4359-4361.
[4]Terao H,Ishii S,Mitani M,et al.Ethylene/polar monomer co-polymerization behavior of bis(phenoxy-imine)Ti complexes:formation of polar monomer copolymers[J].J Am Chem Soc,2008,130(52):17636-17637.
[5]Mitani M,Yoshida Y,Mohri J,et al.Processes and catalysts for preparation of olefin polymers with narrow molecular weight distribution:WO,2001055231[P].2001-01-26.
[6]Saito J,Mitani M,Mohri J,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.
[7]Mason A F,Coates G W.New phenoxyketimine titanium c omplexes:combining isotacticity and living behavior in propylene polymerization[J].J Am Chem Soc,2004,126(50):16326-16327.
[8]Edson J B,Wang Z,Kramer E J,et al.Fluorinated bis(phenoxyketimine)titanium complexes for the living,isoselective polymerization of propylene:multiblock isotactic polypropylene copolymers via sequential monomer addition[J].J Am Chem Soc,2008,130(14):4968-4977.
[9]Weiser M-S,Muelhaupt R.Formation of polyolefin-block-polystyrene block copolymers on phenoxyimine catalysts[J].Macromol Rapid Commun,2006,27(13):1009-1014.
[10]Furuyama R,Mitani M,Mohri J,et al.Ethylene/higherα-olefin copolymerization behavior of fluorinated bis(phenoxy-imine)titanium complexes with methylalumoxane:synthesis of new polyethylene-based block copolymers[J].Macromolecules,2005,38(5):1546-1552.
[11]Arriola D J,Carnahan E M,Hustad P D,et al.Catalytic production of olefin block copolymers via chain shuttling polymerization[J].Science,2006,312(5774):714-719.
[12]Arriola D J,Carnahan E M,Hustad P D,et al.Ethylene-based olefin block copolymers by chain shuttling[J].Polym Prepr,2006,47(2):513-514.
[13]Hustad P D,Kuhlman R L,Carnahan E M,et al.An exploration of the effects of reversibility in chain transfer to metal in olefin polymerization[J].Macromolecules,2008,41(12):4081-4089.
[14]Wang H P,Khariwala D U,Cheung W,et al.Characterization of some new olefinic block copolymers[J].Macromolecules,2007,40(8):2852-2862.
[15]Shigekazu Matsui,Terunori Fujita.FI Catalysts:super active new ethylene polymerization catalysts[J].Catalysis Today,2001,66(1):63-73.
[2]Makio H,Ochiai T,Tanaka H,et al.FI catalysts:a molecular zeolite for olefin polymerization[J].Advanced Synthesis&Catalysis,2010,352(10):1635-1640.
[3]Terao H,Iwashita A,Ishii S,et al.Ethylene/norbornene copolymerization behavior of bis(phenoxy-imine)Ti complexes combined with MAO[J].Macromolecules,2009,42(13):4359-4361.
[4]Terao H,Ishii S,Mitani M,et al.Ethylene/polar monomer co-polymerization behavior of bis(phenoxy-imine)Ti complexes:formation of polar monomer copolymers[J].J Am Chem Soc,2008,130(52):17636-17637.
[5]Mitani M,Yoshida Y,Mohri J,et al.Processes and catalysts for preparation of olefin polymers with narrow molecular weight distribution:WO,2001055231[P].2001-01-26.
[6]Saito J,Mitani M,Mohri J,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.
[7]Mason A F,Coates G W.New phenoxyketimine titanium c omplexes:combining isotacticity and living behavior in propylene polymerization[J].J Am Chem Soc,2004,126(50):16326-16327.
[8]Edson J B,Wang Z,Kramer E J,et al.Fluorinated bis(phenoxyketimine)titanium complexes for the living,isoselective polymerization of propylene:multiblock isotactic polypropylene copolymers via sequential monomer addition[J].J Am Chem Soc,2008,130(14):4968-4977.
[9]Weiser M-S,Muelhaupt R.Formation of polyolefin-block-polystyrene block copolymers on phenoxyimine catalysts[J].Macromol Rapid Commun,2006,27(13):1009-1014.
[10]Furuyama R,Mitani M,Mohri J,et al.Ethylene/higherα-olefin copolymerization behavior of fluorinated bis(phenoxy-imine)titanium complexes with methylalumoxane:synthesis of new polyethylene-based block copolymers[J].Macromolecules,2005,38(5):1546-1552.
[11]Arriola D J,Carnahan E M,Hustad P D,et al.Catalytic production of olefin block copolymers via chain shuttling polymerization[J].Science,2006,312(5774):714-719.
[12]Arriola D J,Carnahan E M,Hustad P D,et al.Ethylene-based olefin block copolymers by chain shuttling[J].Polym Prepr,2006,47(2):513-514.
[13]Hustad P D,Kuhlman R L,Carnahan E M,et al.An exploration of the effects of reversibility in chain transfer to metal in olefin polymerization[J].Macromolecules,2008,41(12):4081-4089.
[14]Wang H P,Khariwala D U,Cheung W,et al.Characterization of some new olefinic block copolymers[J].Macromolecules,2007,40(8):2852-2862.
[15]Shigekazu Matsui,Terunori Fujita.FI Catalysts:super active new ethylene polymerization catalysts[J].Catalysis Today,2001,66(1):63-73.