CN115894745B - Catalyst composition, olefin polymerization process and use - Google Patents
Catalyst composition, olefin polymerization process and use Download PDFInfo
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- CN115894745B CN115894745B CN202111158858.7A CN202111158858A CN115894745B CN 115894745 B CN115894745 B CN 115894745B CN 202111158858 A CN202111158858 A CN 202111158858A CN 115894745 B CN115894745 B CN 115894745B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to the field of olefin polymerization, and discloses a catalyst composition, an olefin polymerization method using the catalyst composition and application of the catalyst composition in olefin polymerization. The catalyst composition of the present invention comprises: a) a metallocene compound, b) a cocatalyst component, c) a phenol. By using the catalyst composition, the molecular weight of the polymer can be increased, so that the product quality is improved, and the product brand is expanded.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a catalyst composition, an olefin polymerization method using the catalyst composition and application of the catalyst composition in olefin polymerization.
Background
Metallocene catalysts for olefin polymerization have been the focus of research in metal organic chemistry, catalytic chemistry, polymer chemistry and materials for decades. Because of the use of such catalysts, olefin polymers having very uniform molecular weight distribution and chemical composition distribution can be obtained, and the molecular structure and molecular weight of the polymer can be controlled highly by adjusting the catalyst structure. The metallocene has strong copolymerization capability, and is characterized in two aspects: on the one hand, under the same polymerization conditions, the metallocene-derived copolymer contains comonomer in a higher amount than other catalysts, which is the high efficiency of copolymerization; on the other hand, some monomers which cannot be polymerized by other catalysts can also be used as comonomers of metallocene catalyst systems, which is a broad spectrum of their copolymerization. Because of the high efficiency and broad spectrum of the metallocene catalyst, the metallocene catalyst can catalyze and obtain a plurality of novel copolymers, and compared with copolymers obtained by other catalysts, the copolymers have novel compositions and structures, so that the novel properties can be realized, and the application of polyolefin materials in the novel field can be realized.
Metallocene catalysts require the presence of a cocatalyst to be able to be activated in order to carry out efficient polymerization. The most effective and most widely used cocatalysts at present are methylaluminoxane and organoboron compound and organoaluminum compound compositions. In olefin polymerization by coordination polymerization, an organoaluminum compound is a highly effective chain transfer agent. This means that during the polymerization of olefins, there is a transfer of the polymerization active chain to the aluminum atom, thereby reducing the molecular weight of the polymer.
Disclosure of Invention
The invention aims to overcome the problem of the prior art that the molecular weight of a polymer is reduced, and provides a catalyst composition, an olefin polymerization method using the catalyst composition and application of the catalyst composition in olefin polymerization. By using the catalyst composition, the molecular weight of the polymer can be increased, so that the product quality is improved, and the product brand is expanded.
The reason why the molecular weight of the polymer can be increased by using the catalyst composition of the present invention is not clearly understood, but it is presumed that: in the invention, phenol is added into metallocene-methylaluminoxane catalytic system for olefin polymerization, and free alkyl aluminum or organic boron compound in phenol and methylaluminoxane or solution thereof reacts with organic aluminum compound in organic aluminum compound combination to form phenoxy-containing aluminoxane or alkyl aluminum, and the phenol has steric hindrance larger than methyl on the methylaluminoxane or free alkyl aluminum, so that mass transfer resistance is caused for chain transfer reaction, thereby inhibiting chain transfer reaction.
Thus, in a first aspect the present invention provides a catalyst composition, wherein the catalyst composition comprises the following composition:
a) Metallocene compounds of the structure of formula (I) and/or (II),
in the formula (I) and the formula (II),
Cp 1 and Cp 2 A cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a indenyl group or an unsubstituted indenyl group, a fluorenyl group or an unsubstituted fluorenyl group, each independently being a hydrocarbyl group of 1 to 20 carbon atoms, a hydrocarbyl group of 1 to 20 carbon atoms;
m is titanium, zirconium or hafnium;
X 1 and X 2 Each independently is a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbon group,
in the formula (II), Q is a bond Cp 1 And Cp 2 Is a group or groups of atoms of (a),
b) A co-catalyst component comprising a co-catalyst,
c) Phenols having a structure represented by the formula (III),
in the formula (III), R 1 、R 2 、R 3 、R 4 And R is 5 Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and is represented by R 1 、R 2 、R 3 、R 4 And R is 5 When each is independently a hydrocarbon group having 1 to 30 carbon atoms, any two of them may be closed to form a ring.
Preferably, in formula (I) and formula (II), cp 1 And Cp 2 A cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a indenyl group or an unsubstituted indenyl group, a fluorenyl group or an unsubstituted fluorenyl group, each independently being a hydrocarbyl group of 1 to 16 carbon atoms, a hydrocarbyl group of 1 to 16 carbon atoms; m is titanium or zirconium; x is X 1 And X 2 Each independently a halogen atom.
Preferably, in formula (II), Q is-CH 2 CH 2 -，Cp 1 And Cp is Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom.
Preferably, in formula (II), Q is-SiR 6 R 7 -，Cp 1 And Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom, R 6 And R is 7 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Preferably, in formula (II), Q is-SiR 8 R 9 -，Cp 1 And Cp 2 Are all 2-methyl-4-phenyl-indenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 8 And R is 9 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
Preferably, in formula (II), Q is-CR 10 R 11 -，Cp 1 Is cyclopentadienyl, cp 2 Is fluorenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 10 And R is 11 Is methyl or phenyl.
Preferably, in formula (II), Q is-CR 12 R 13 -，Cp 1 Is cyclopentadienyl, cp 2 Is 2, 7-di-tert-butyl-fluorenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 12 And R is 13 Is methyl orPhenyl.
Preferably, the metallocene compound is selected from the group consisting of dicyclopentadiene zirconium dichloride, di (n-butylcyclopentadienyl) zirconium dichloride, di (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (4, 4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4' -methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4 '-methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium, (4, 4' -methyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4-methyl-4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3, 3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (3, 3 '-trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3, 3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4 '-chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride or (4, 4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, one or more of rac-vinyl-bis-indenyl zirconium dichloride, rac-dimethylsilyl-bis (2-methyl-indenyl) zirconium dichloride and rac-dimethylsilyl-bis (2-methyl-4-phenylindenyl) zirconium dichloride; more preferably, the metallocene compound is one or more of dicyclopentadiene zirconium dichloride, di (n-butylcyclopentadienyl) zirconium dichloride, di (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, rac-vinylbisindenyl zirconium dichloride, rac-dimethylsilylbisindenyl zirconium dichloride and rac-dimethylsilylbis (2-methyl-4-indenyl) zirconium dichloride.
Preferably, the promoter component comprises one or more of an alkyl aluminoxane, an organoboron compound, and an organoaluminum compound; more preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.
Preferably, the alkylaluminoxane is a compound selected from structures represented by formula (IV) and/or formula (V),
in the formula (IV) and the formula (V), R is selected from alkyl groups with 1-15 carbon atoms, and n represents an integer of 4-30; more preferably, R is selected from alkyl groups having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.
Preferably, the alkylaluminoxane is methylaluminoxane.
Preferably, the organoboron compound is one or more of triphenylmethyl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and tris (pentafluorophenyl) boron.
Preferably, the organoaluminum compound is of the formula AlX 1 X 2 X 3 Compounds of the structure shown, X 1 、X 2 And X 3 Respectively halogen atom, alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, aryloxy with 6-12 carbon atoms, X 1 、X 2 And X 3 May be the same or different, and at least one is an alkyl group having 1 to 8 carbon atoms.
Preferably, the organoaluminum compound is triisobutylaluminum.
Preferably, in formula (III), R 1 、R 2 、R 3 、R 4 And R is 5 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 10 carbon atoms; more preferably, in formula (III), R 1 、R 2 、R 3 、R 4 And R is 5 Independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 8 carbon atoms.
Preferably, the phenol is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 4-di-tert-butylphenol, 4-chloro-2-benzylphenol, 4-chloro-2-isopropyl-5-methylphenol and 2, 4-dichloro-1-naphthol.
Preferably, the cocatalyst is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated as aluminum is 1: (50-20000), preferably 1: (200-10000), more preferably 1: (500-3000).
Preferably, the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound being 1: (1-5), preferably 1: (1-2) the molar ratio of the metallocene compound to the organoaluminum compound is 1: (10-1000), preferably 1: (10-200).
Preferably, the molar ratio of the metallocene compound to the phenol is 1: (1-1000), preferably 1: (10-500).
According to a second aspect of the present invention there is provided a process for the polymerisation of olefins comprising contacting an olefin with a catalyst composition according to the first aspect of the present invention to effect polymerisation.
Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1X 10 -9 Molar/liter-1×10 -3 Moles/liter, preferably 1X 10 -8 Molar/liter-1×10 -4 Moles/liter.
Preferably, the polymerization temperature is 0-200 ℃ and the polymerization time is 1-300 minutes; more preferably, the polymerization temperature is 50-160℃and the polymerization time is 5-60 minutes.
Preferably, the olefin partial pressure is from 0.1 to 10MPa, preferably from 0.1 to 4.0MPa.
Preferably, the olefin is ethylene, or ethylene and 1-olefin.
Preferably, the 1-olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene.
According to a third aspect of the present invention there is provided the use of the catalyst composition according to the first aspect of the present invention in the polymerisation of olefins.
According to the present invention, by using a catalyst composition comprising phenol, the molecular weight of the resulting polymer is significantly higher than that of a polymer obtained without using a catalyst composition comprising phenol, the regulatory range of polyolefin products can be widened, and the quality and variety of polyolefin products can be improved.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a catalyst composition comprising the following composition:
a) Metallocene compounds of the structure of formula (I) and/or (II),
in the formula (I) and the formula (II),
Cp 1 and Cp 2 Respectively are provided withIndependently a hydrocarbyl mono-or polysubstituted cyclopentadienyl or unsubstituted cyclopentadienyl of 1 to 20 carbon atoms, a hydrocarbyl mono-or polysubstituted indenyl or unsubstituted indenyl of 1 to 20 carbon atoms, a hydrocarbyl mono-or polysubstituted fluorenyl or unsubstituted fluorenyl of 1 to 20 carbon atoms;
m is titanium, zirconium or hafnium;
X 1 and X 2 Each independently is a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbon group,
in the formula (II), Q is a bond Cp 1 And Cp 2 Is a group or groups of atoms of (a),
b) A co-catalyst component comprising a co-catalyst,
c) Phenols having a structure represented by the formula (III),
in the formula (III), R 1 、R 2 、R 3 、R 4 And R is 5 Each independently is a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and is represented by R 1 、R 2 、R 3 、R 4 And R is 5 When each is independently a hydrocarbon group having 1 to 30 carbon atoms, any two of them may be closed to form a ring.
The catalyst component according to the invention, preferably of the formulae (I) and (II), cp 1 And Cp 2 A cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a indenyl group or an unsubstituted indenyl group, a fluorenyl group or an unsubstituted fluorenyl group, each independently being a hydrocarbyl group of 1 to 16 carbon atoms, a hydrocarbyl group of 1 to 16 carbon atoms; m is titanium or zirconium; x is X 1 And X 2 Each independently a halogen atom.
The above-mentioned hydrocarbon group is more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms.
The alkyl group having 1 to 10 carbon atoms is a linear alkyl group, a branched alkyl group or a cycloalkyl group having 1 to 10 carbon atoms, and examples thereof include a linear alkyl group, a branched alkyl group or a cycloalkyl group having 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, and examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl and the like.
Examples of the aryl group having 6 to 12 carbon atoms include: phenyl, benzyl, phenethyl, diphenylmethylene, diphenylethylene, and the like.
In the compounds of the present invention represented by the formula (I) and the formula (II), X 1 And X 2 Each independently is a halogen atom, an alkoxy group, an aryloxy group, or a hydrocarbon group.
Examples of the halogen atom include: fluorine, chlorine, bromine or iodine is preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, particularly preferably chlorine.
The alkoxy group may be, for example, an alkoxy group having 1 to 8 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and still more preferably an alkoxy group having 1 to 3 carbon atoms.
Examples of the alkoxy group having 1 to 8 carbon atoms include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, sec-butoxy, isobutoxy, pentoxy, hexoxy, heptoxy, octoxy and the like.
The aryloxy group may be, for example, an aryloxy group having 6 to 12 carbon atoms, and specific examples thereof include: phenoxy, methylphenoxy, ethylphenoxy, naphthyloxy, and the like.
The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group), more preferably a hydrocarbon group having 1 to 12 carbon atoms (preferably an alkyl group), and still more preferably a hydrocarbon group having 1 to 6 carbon atoms (preferably an alkyl group). Specific examples include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, phenyl, benzyl, phenethyl and the like.
In a preferred embodiment of the invention, in formula (II), Q is- (CH) 2 ) n - (n is an integer of 2 to 20), cp 1 And Cp is Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom.
In another preferred embodiment of the invention, Q is-CH 2 CH 2 -，Cp 1 And Cp is Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom.
In another preferred embodiment of the present invention, in formula (II), Q is-SiR 6 R 7 -，Cp 1 And Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom, R 6 And R is 7 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
In another preferred embodiment of the present invention, in formula (II), Q is-SiR 8 R 9 -，Cp 1 And Cp 2 Are all 2-methyl-4-phenyl-indenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 8 And R is 9 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
In another preferred embodiment of the present invention, in formula (II), Q is-CR 10 R 11 -，Cp 1 Is cyclopentadienyl, cp 2 Is fluorenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 10 And R is 11 Is methyl or phenyl.
In another preferred embodiment of the present invention, in formula (II), Q is-CR 12 R 13 -，Cp 1 Is cyclopentadienyl, cp 2 Is 2, 7-di-tert-butyl-fluorenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 12 And R is 13 Is methyl or phenyl.
The hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Specific examples of the metallocene compound include: dicyclopentadiene zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4' -methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4' -methyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4-methyl-4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3, 3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (3, 3 '-trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3, 3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4 '-chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride or (4, 4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, one or more of rac-vinyl diindenyl zirconium dichloride, rac-dimethylsilyl bis (2-methyl-indenyl) zirconium dichloride and rac-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride. Of these, one or more of dicyclopentadiene zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-t-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, rac-vinylbisindenyl zirconium dichloride, rac-dimethylsilylbisindenyl zirconium dichloride, and rac-dimethylsilylbis (2-methyl-4-indenyl) zirconium dichloride are more preferable.
The catalyst composition according to the present invention, the cocatalyst component may be various cocatalyst components generally used in the art. Preferably, the promoter component comprises one or more of an alkyl aluminoxane, an organoboron compound, and an organoaluminum compound; more preferably, the cocatalyst component is an alkylaluminoxane or a combination of an organoboron compound and an organoaluminum compound.
The alkylaluminoxane is preferably a compound having a structure represented by formula (IV) and/or formula (V),
in the formula (IV) and the formula (V), R is selected from alkyl groups with 1-15 carbon atoms, and n represents an integer of 4-30; more preferably, R is selected from alkyl groups having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.
Specific examples of the alkyl group include, for example: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and the like.
Examples of n include: 4. 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc.
Specific examples of the alkylaluminoxane include, for example: methylaluminoxane, ethylaluminoxane, propylaluminoxane, etc., among which methylaluminoxane is preferred.
The organoboron compound according to the catalyst composition of the present invention may be various organoboron compounds used in the art as cocatalysts, and examples thereof include: one or more of triphenylmethyl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and tris (pentafluorophenyl) boron.
The organoaluminum compound according to the catalyst composition of the present invention may be various organoaluminum compounds used in the art as cocatalysts. Preferably, the organoaluminum compound is of the formula AlX 1 X 2 X 3 Compounds of the structure shown, X 1 、X 2 And X 3 Respectively halogen atom, alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, aryloxy with 6-12 carbon atoms, X 1 、X 2 And X 3 May be the same or different, and at least one is an alkyl group having 1 to 8 carbon atoms.
Examples of the alkyl group having 1 to 8 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl, heptyl, octyl and the like.
Examples of the alkoxy group having 1 to 8 carbon atoms include various alkoxy groups having "alkyl group having 1 to 8 carbon atoms" specifically exemplified above,
examples of the halogen atom include: fluorine, chlorine, bromine or iodine is preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, particularly preferably chlorine.
In the present invention, specific examples of the organoaluminum compound include, for example: one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tri-n-pentylaluminum, triisopentylaluminum, trihexylaluminum, ethyldimethylaluminum, methyldiethylaluminum and tripentylaluminum. Among them, triisobutylaluminum is preferably used.
The catalyst composition according to the invention preferably has the formula (III) R 1 、R 2 、R 3 、R 4 And R is 5 Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 10 carbon atoms; more preferably, in formula (III), R 1 、R 2 、R 3 、R 4 And R is 5 Independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms or an aralkyl group having 7 to 8 carbon atoms.
Examples of the alkyl group having 1 to 6 carbon atoms include: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, isobutyl, pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-methylbutyl, 2-methylbutyl, isopentyl, hexyl.
Examples of the aralkyl group having 7 to 10 carbon atoms include: benzyl, phenethyl, and the like. Among them, benzyl is preferred.
Examples of the halogen atom include: fluorine, chlorine, bromine or iodine is preferably fluorine, chlorine or bromine, more preferably chlorine or bromine, particularly preferably chlorine.
In the present invention, specific examples of the phenol include: one or more of 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 4-di-tert-butylphenol, 4-chloro-2-benzylphenol, 4-chloro-2-isopropyl-5-methylphenol and 2, 4-dichloro-1-naphthol.
According to the catalyst composition of the present invention, when the cocatalyst is an alkylaluminoxane, and the molar ratio of the metallocene compound to the alkylaluminoxane calculated as aluminum is 1: (50-20000), more preferably 1: (200-10000), more preferably 1: (500-3000).
When the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of the metallocene compound to the organoboron compound is 1: (1-5), preferably 1: (1-2) the molar ratio of the metallocene compound to the organoaluminum compound is 1: (10-1000), preferably 1: (10-200).
The catalyst composition according to the invention preferably has a molar ratio of the metallocene compound to the phenol of 1: (1-1000), more preferably 1: (10-500), further preferably 1: (20-200), further preferably 1: (50-150), still more preferably 1: (100-150).
According to a second aspect of the present invention there is provided a process for the polymerisation of olefins comprising contacting an olefin with a catalyst composition according to the first aspect of the present invention to effect polymerisation.
According to the process of the present invention, the metallocene compound in the polymerization reaction system may be used in an amount usual in the art for the synthesis of polyolefins. Preferably, the concentration of the metallocene compound in the polymerization reaction system is 1X 10 -9 Molar/liter-1×10 -3 More preferably 1X 10 mol/liter -8 Molar/liter-1×10 -4 Moles/liter.
According to the process of the present invention, the polymerization is preferably carried out in an inert organic solvent. The inert organic solvent may be one or a mixture of several of linear aliphatic hydrocarbon, branched aliphatic hydrocarbon, substituted or unsubstituted cyclic aliphatic hydrocarbon and substituted or unsubstituted aromatic hydrocarbon. Specific examples of the inert organic solvent include: hexane, heptane, cyclohexane, cyclooctane, toluene, xylene. In addition, the amount of organic solvent can be determined by the reactivity, ensuring good dissolution of the resulting polymer in the system, at least without affecting the dispersion.
The polymerization conditions according to the process of the present invention may be those commonly used in the art for the synthesis of polyolefins. Preferably, the polymerization temperature is 0-200 ℃ and the polymerization time is 1-300 minutes; more preferably, the polymerization temperature is 50-160℃and the polymerization time is 5-60 minutes.
According to the process of the invention, the olefin preferably has a partial pressure of from 0.1 to 10MPa, preferably from 0.1 to 4.0MPa.
Preferably, the olefin is ethylene or ethylene and 1-olefin according to the process of the present invention.
Preferably, the 1-olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene and 4-methyl-1-pentene according to the process of the present invention.
In a preferred embodiment of the present invention, when the cocatalyst component is an alkylaluminoxane, the preparation method thereof comprises: the well-dried polymerization apparatus was evacuated, flushed with nitrogen, and repeated several times. Adding solid cycloolefin, vacuumizing, charging ethylene, sequentially adding reaction solvent, phenol and alkyl aluminoxane, heating to polymerization reaction temperature, adding metallocene compound for polymerization reaction, continuously introducing ethylene in the polymerization process, supplementing ethylene consumed by polymerization, closing ethylene after the polymerization reaction is completed, adding acidified ethanol into the reaction solution, stirring, and filtering to obtain the polymer.
In another preferred embodiment of the present invention, when the cocatalyst component is a combination of an organoboron compound and an organoaluminum compound, the preparation method thereof comprises: the well-dried polymerization apparatus was evacuated, flushed with nitrogen, and repeated several times. Adding solid cycloolefin, vacuumizing, charging ethylene, sequentially adding reaction solvent, phenol and organic aluminum compound, heating to polymerization reaction temperature, sequentially adding metallocene compound and organic boron compound, performing polymerization reaction, continuously charging ethylene during polymerization, supplementing ethylene consumed by polymerization, closing ethylene after polymerization reaction is completed, adding acidified ethanol into reaction solution, stirring, and filtering to obtain the polymer.
According to a third aspect of the present invention there is provided the use of the catalyst composition according to the first aspect of the present invention in the polymerisation of olefins.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
The raw materials used in the following examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.
Polymer test method:
weight average molecular weight and molecular weight distribution test
The molecular weight and molecular weight distribution of the samples were determined by GPC type PL-GPC 220 from UK Polymer Laboratories, the chromatographic column being 3 columns of PLgel 10 μm MIXED-B in series. The solvent and the mobile phase are 1,2, 4-trichlorobenzene (containing 0.025 wt% of antioxidant 2, 6-dibutyl p-cresol), the column temperature is 150 ℃, the flow rate is 1.0ml/min, the sample concentration is 1mg/ml, an IR5 infrared concentration detector is equipped, and the narrow-distribution polystyrene standard sample is adopted for universal calibration.
The phenols used in the comparative examples and examples are as follows:
phenol 1:2, 6-Di-tert-butyl-4-methylphenol
Phenol 2:2, 6-Di-tert-butylphenol
Phenol 3:2, 4-Di-tert-butylphenol
Phenol 4: 4-chloro-2-benzylphenol
Phenol 5: 4-chloro-2-isopropyl-5-methylphenol
Phenol 6:2, 4-dichloro-1-naphthol
Phenol 7:2,4, 6-tri-tert-butylphenol
Comparative example 1
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuum was applied, 1atm of ethylene was charged, 26 ml of toluene, 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) was added, the temperature was raised to 70 ℃, 1 ml of catalyst solution (containing 5. Mu. Mol of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the time was started, and during the reaction, the ethylene pressure in the polymerization flask was lowered due to the consumption of ethylene, and ethylene was replenished so as to maintain the pressure at 1atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The polymerization data and characterization results are shown in Table 1.
Comparative example 2
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuum was applied, 1atm ethylene was charged, 25 ml of toluene, 1 ml of 1-octene, 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) was added, the temperature was raised to 70 ℃, 1 ml of catalyst solution (containing 5. Mu. Moles of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the time was started, and during the reaction, the ethylene pressure in the polymerization flask was lowered due to the consumption of ethylene, ethylene was replenished, and the pressure was kept at 1atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The polymerization data and characterization results are shown in Table 2.
Comparative example 3
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuum was applied, 1atm ethylene was charged, 26 ml of toluene, 1 ml of 1-octene, 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) was added, the temperature was raised to 70 ℃, 1 ml of catalyst solution (containing 5. Mu. Moles of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, 1 ml of triphenylmethyl tetrakis (pentafluorophenyl) borate toluene solution (containing 6. Mu. Moles of triphenylmethyl tetrakis (pentafluorophenyl) borate) was added, and the timing was started, and during the reaction, the ethylene pressure in the polymerization flask was lowered due to the consumption of ethylene, and ethylene was replenished so that the pressure was kept at 1atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The polymerization data and characterization results are shown in Table 3.
Comparative examples 4 to 12
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuumizing, filling ethylene with 1atm, adding toluene, adding comonomer, heating to a set temperature, adding cocatalyst and catalyst solution, adding 30 ml of all reagents and solvent, starting timing, and reducing the ethylene pressure in a polymerization bottle due to ethylene consumption in the reaction process, and supplementing ethylene to keep the pressure at 1atm. After the set time, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The raw materials, the amounts, the polymerization data and the characterization results are shown in Table 5.
When the cocatalyst and the catalyst were added in each example, the methylaluminoxane was added in the same order as in comparative examples 1 and 2, and the organoaluminum-organoboron was added in the same order as in comparative example 3.
Examples 1 to 8
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuum was applied, 1atm of ethylene was charged, 25 ml of toluene, 1 ml of phenol solution (the amount of phenol used in each example is shown in Table 1), 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane) was added, the temperature was raised to 70 ℃, 1 ml of catalyst solution (containing 5. Mu. Mol of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the time was started, and during the reaction, the ethylene pressure in the polymerization flask was lowered due to the consumption of ethylene, and ethylene was replenished so that the pressure was kept at 1atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The molar ratio of phenol to catalyst (calculated as metallocene), polymerization data and characterization results are shown in Table 1.
Examples 9 to 15
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuum was applied, 1atm of ethylene was charged, 24 ml of toluene, 1 ml of phenol solution (the amount of phenol used in each example is shown in Table 2), 1 ml of 1-octene, 3 ml of methylaluminoxane toluene solution (containing 5.0 mmol of methylaluminoxane), the temperature was raised to 70℃and 1 ml of catalyst solution (containing 5. Mu. Moles of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, and the time was started, and during the reaction, the ethylene pressure in the polymerization flask was lowered due to the consumption of ethylene, and ethylene was replenished so as to maintain the pressure at 1atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The molar ratio of phenol to catalyst (calculated as metallocene), polymerization data and characterization results are shown in Table 2.
Examples 16 to 21
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuum was applied, 1atm ethylene was charged, 25 ml of toluene, 1 ml of phenol solution (the amount of phenol used in each example is shown in Table 3), 1 ml of 1-octene, 1 ml of triisobutylaluminum toluene solution (containing 1.0 mmol of triisobutylaluminum) were added, the temperature was raised to 70 ℃, 1 ml of catalyst solution (containing 5. Mu. Moles of diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride) was added, 1 ml of triphenylmethyl tetrakis (pentafluorophenyl) borate toluene solution (containing 6. Mu. Moles of triphenylmethyl tetrakis (pentafluorophenyl) borate) was added, and the time was started, and during the reaction, the ethylene pressure in the polymerization flask was lowered due to the consumption of ethylene, and the ethylene was replenished so that the pressure was kept at 1atm. After 20 minutes, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The molar ratio of phenol to catalyst (calculated as metallocene), polymerization data and characterization results are shown in Table 3.
Examples 22 to 37
The fully dried polymerization bottle is vacuumized, flushed by nitrogen and repeated three times. Vacuumizing, filling ethylene with 1atm, adding toluene, adding phenol solution, adding comonomer, heating to a set temperature, adding cocatalyst and catalyst solution, keeping the volume of the solvent of all reagents at 30 ml, starting timing, and during the reaction, reducing the ethylene pressure in a polymerization bottle due to ethylene consumption, supplementing ethylene and keeping the pressure at 1atm. After the set time, the ethylene was closed, the reaction solution was poured into a beaker, acidified ethanol was added, stirred for more than 6 hours, and filtered to obtain a polymer. The raw materials, the amounts, the polymerization data and the characterization results are shown in Table 4.
When the cocatalyst and the catalyst were added in each example, the methylaluminoxane was added in the same order as in comparative examples 1 and 2, and the organoaluminum-organoboron was added in the same order as in comparative example 3.
The polymerization characterization data are shown in tables 1-4 below (polymerization activity units: kg-polymer/mol-catalyst/hr in tables 1-4).
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
The catalysts, aluminum alkyls, organoboron and comonomer used in table 4 are shown below:
catalyst
C1: diphenylmethyl (cyclopentadienyl) (fluorenyl) zirconium dichloride
C2: racemic ethylene bisindenyl zirconium dichloride
And C3: bis (indenyl) zirconium dichloride
And C4: racemic dimethylsilyl-bis (2-methyl-4-phenyl-indenyl) zirconium dichloride
C5: racemic dimethylsilyl-bisindenyl zirconium dichloride
C6: diphenylmethyl (cyclopentadienyl) (2, 7-di-tert-butyl-fluorenyl) zirconium dichloride
C7: bis (1-methyl-3-n-butyl-cyclopentadienyl) zirconium dichloride
Aluminum alkyl
A1: triisobutylaluminum
A2: tri-n-octyl aluminum
Organoboron
B1: triphenylmethyl tetrakis (pentafluorophenyl) borate
B2: n, N-dimethylanilinium tetrakis (pentafluorophenyl) borate
B3: tris (pentafluorophenyl) boron
Co-monomers
M1: 1-hexene
M2: 4-methyl-1-pentene
M3: 1-octene
As is evident from comparison of comparative example 1 with examples 1 to 8, by using the catalyst composition comprising phenol of the present invention, the molecular weight of the obtained polymer is significantly higher than that of the polymer obtained without using the catalyst composition comprising phenol, and thus the regulatory range of polyolefin products can be widened and the quality and variety of polyolefin products can be improved.
As is also evident from a comparison of comparative example 2 with examples 9-15, in the synthesis of olefin copolymers, the molecular weight of the polymer obtained by using the catalyst composition of the present invention comprising phenol is significantly higher than that of the polymer obtained by using the catalyst composition without phenol.
As is also evident from a comparison of comparative example 3 with examples 16-21, in the synthesis of olefin copolymers, the molecular weight of the polymer obtained by using the catalyst composition of the present invention comprising phenol is significantly higher than that of the polymer obtained by using the catalyst composition without phenol.
As is also evident from the comparison of comparative examples 4 to 12 with examples 22 to 37, by using a catalyst composition comprising phenol, the molecular weight of the resulting polymer is significantly higher than that of a polymer obtained by using a catalyst composition without phenol, and thus the regulatory range of polyolefin products can be widened and the quality and variety of polyolefin products can be improved.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (28)
1. A catalyst composition, characterized in that the catalyst composition comprises the following composition:
a) Metallocene compounds of the structure of formula (I) and/or (II),
In the formula (I) and the formula (II),
Cp 1 and Cp 2 A cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a indenyl group or an unsubstituted indenyl group, a fluorenyl group or an unsubstituted fluorenyl group, each independently being a hydrocarbyl group of 1 to 20 carbon atoms, a hydrocarbyl group of 1 to 20 carbon atoms;
m is titanium, zirconium or hafnium;
X 1 and X 2 Each independently is a halogen atom, an alkoxy group, an aryloxy group or a hydrocarbon group,
in the formula (II), Q is a bond Cp 1 And Cp 2 Is a group or groups of atoms of (a),
b) A co-catalyst component comprising a co-catalyst,
c) A phenol which is used as a base for the phenol,
the phenol is one or more of 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 4-di-tert-butylphenol, 4-chloro-2-benzyl phenol, 4-chloro-2-isopropyl-5-methylphenol and 2, 4-dichloro-1-naphthol,
the cocatalyst component is a combination of an alkylaluminoxane or an organoboron compound and an organoaluminum compound.
2. The catalyst composition according to claim 1, wherein,
in the formula (I) and the formula (II),
Cp 1 and Cp 2 A cyclopentadienyl group or an unsubstituted cyclopentadienyl group, a indenyl group or an unsubstituted indenyl group, a fluorenyl group or an unsubstituted fluorenyl group, each independently being a hydrocarbyl group of 1 to 16 carbon atoms, a hydrocarbyl group of 1 to 16 carbon atoms;
M is titanium or zirconium;
X 1 and X 2 Each independently a halogen atom.
3. The catalyst composition according to claim 1 or 2, wherein in formula (II), Q is-CH 2 CH 2 -，Cp 1 And Cp is Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom;
alternatively, in formula (II), Q is-SiR 6 R 7 -，Cp 1 And Cp 2 Are indenyl groups, M is zirconium, X 1 And X 2 Is a chlorine atom, R 6 And R is 7 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
alternatively, in formula (II), Q is-SiR 8 R 9 -，Cp 1 And Cp 2 Are all 2-methyl-4-phenyl-indenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 8 And R is 9 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms;
alternatively, in formula (II), Q is-CR 10 R 11 -，Cp 1 Is cyclopentadienyl, cp 2 Is fluorenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 10 And R is 11 Methyl or phenyl;
alternatively, in formula (II), Q is-CR 12 R 13 -，Cp 1 Is cyclopentadienyl, cp 2 Is 2, 7-di-tert-butyl-fluorenyl, M is zirconium, X 1 And X 2 Is a chlorine atom, R 12 And R is 13 Is methyl or phenyl.
4. The catalyst composition of claim 1 or 2, wherein the metallocene compound is selected from the group consisting of dicyclopentadiene zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4' -methoxy-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, 4' -tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride (4-methyl-4 '-tert-butyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3, 3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (3, 3 '-trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (3, 3' -trifluoromethyl-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4' -fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride, (4, 4 '-fluoro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, (4, 4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -titanium dichloride, (4, 4 '-chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -zirconium dichloride or (4, 4' -chloro-diphenylmethylene) -cyclopentadienyl- (1-indenyl) -hafnium dichloride, one or more of rac-vinyl diindenyl zirconium dichloride, rac-dimethylsilyl bis (2-methyl-indenyl) zirconium dichloride and rac-dimethylsilyl bis (2-methyl-4-phenylindenyl) zirconium dichloride.
5. The catalyst composition of claim 1 or 2, wherein the metallocene compound is one or more of dicyclopentadiene-based zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, bisindenyl zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-tert-butyl-9-fluorenyl) zirconium dichloride, isopropyl (cyclopentadienyl) (fluorenyl) zirconium dichloride, rac-vinyl bisindenyl zirconium dichloride, rac-dimethylsilylbisindenyl zirconium dichloride, and rac-dimethylsilylbis (2-methyl-4-indenyl) zirconium dichloride.
6. The catalyst composition according to claim 1, wherein the alkylaluminoxane is a compound selected from the structures represented by the formula (IV) and/or the formula (V),
in the formula (IV) and the formula (V), R is selected from alkyl groups having 1 to 15 carbon atoms, and n represents an integer of 4 to 30.
7. The catalyst composition according to claim 6, wherein R is selected from alkyl groups having 1 to 5 carbon atoms, and n represents an integer of 10 to 30.
8. The catalyst composition of claim 7, wherein the alkylaluminoxane is methylaluminoxane.
9. The catalyst composition of claim 1, wherein the organoboron compound is one or more of triphenylmethyl tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and tris (pentafluorophenyl) boron.
10. The catalyst composition of claim 1 wherein the organoaluminum compound is of the formula AlX 1 X 2 X 3 Compounds of the structure shown, X 1 、X 2 And X 3 Respectively halogen atom, alkyl with 1-8 carbon atoms, alkoxy with 1-8 carbon atoms, aryloxy with 6-12 carbon atoms, X 1 、X 2 And X 3 May be the same or different, and at least one is an alkyl group having 1 to 8 carbon atoms.
11. The catalyst composition of claim 10, wherein the organoaluminum compound is triisobutylaluminum.
12. The catalyst composition of claim 1 or 2, wherein the cocatalyst is an alkylaluminoxane and the molar ratio of the metallocene compound to alkylaluminoxane calculated as aluminum is 1: (50-20000).
13. The catalyst composition of claim 12, wherein the molar ratio of metallocene compound to alkylaluminoxane calculated as aluminum is 1: (200-10000).
14. The catalyst composition of claim 13, wherein the molar ratio of metallocene compound to alkylaluminoxane calculated on aluminum is 1: (500-3000).
15. The catalyst composition of claim 1 or 2, wherein the cocatalyst is a combination of an organoboron compound and an organoaluminum compound, the molar ratio of metallocene compound to organoboron compound being 1: (1-5) the molar ratio of the metallocene compound to the organoaluminum compound is 1: (10-1000).
16. The catalyst composition of claim 15, wherein the molar ratio of metallocene compound to organoboron compound is 1: (1-2) the molar ratio of the metallocene compound to the organoaluminum compound is 1: (10-200).
17. The catalyst composition of claim 1 or 2, wherein the molar ratio of the metallocene compound to the phenol is 1: (1-1000).
18. The catalyst composition of claim 17, wherein the molar ratio of the metallocene compound to the phenol is 1: (10-500).
19. A process for the polymerization of olefins comprising contacting an olefin with the catalyst composition of any of claims 1-18 to effect polymerization.
20. The method of claim 19, wherein the polymerization system comprisesThe concentration of the metallocene compound was 1X 10 -9 Molar/liter-1×10 -3 Moles/liter.
21. The method of claim 20, wherein the metallocene compound is present in the polymerization system at a concentration of 1 x 10 -8 Molar/liter-1×10 -4 Moles/liter.
22. The process of claim 19, wherein the polymerization reaction is carried out at a temperature of 0 to 200 ℃ for a time of 1 to 300 minutes.
23. The process of claim 22, wherein the polymerization reaction is carried out at a temperature of 50-160 ℃ for a period of 5-60 minutes.
24. The process of claim 19, wherein the olefin partial pressure is from 0.1 to 10MPa.
25. The method of claim 24, wherein the olefin partial pressure is 0.1-4.0MPa.
26. The process of any of claims 19-25, wherein the olefin is ethylene or ethylene and 1-olefin.
27. The process of claim 26, wherein the 1-olefin is one or more of propylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene.
28. Use of the catalyst composition of any one of claims 1-18 in the polymerization of olefins.
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