CN109134716B - Vanadium catalyst and method for preparing olefin polymer - Google Patents

Vanadium catalyst and method for preparing olefin polymer Download PDF

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CN109134716B
CN109134716B CN201710499569.0A CN201710499569A CN109134716B CN 109134716 B CN109134716 B CN 109134716B CN 201710499569 A CN201710499569 A CN 201710499569A CN 109134716 B CN109134716 B CN 109134716B
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CN109134716A (en
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吴一弦
张树
郝小飞
周百青
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Beijing Yinfa Technology Co ltd
Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B

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Abstract

The invention belongs to the field of olefin polymerization, and relates to a vanadium catalyst and a method for preparing an olefin polymer by using the vanadium catalyst. The vanadium-based catalyst comprises: the component A is as follows: a main catalyst which is a vanadium-containing compound; and (B) component: a cocatalyst which is an organoaluminum compound; and (C) component: a complex additive, and optionally component D: an activator. The catalyst system can greatly improve the copolymerization catalytic activity, and the polymerization reaction activity of the invention is improved by about one time; the conversion rate and the insertion rate of alpha-olefin and diene are improved, the recovery amount of non-participated comonomer is reduced, and the monomer utilization rate is improved; in addition, the content of random sequence distribution in the copolymer can be increased in the copolymerization reaction, the molecular weight of the copolymer is increased, and the product quality is improved.

Description

Vanadium catalyst and method for preparing olefin polymer
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a vanadium catalyst and a method for preparing an olefin polymer by using the vanadium catalyst.
Background
The olefin-based polymer comprises general high molecular materials with large consumption, such as polyethylene, polypropylene, polybutylene and the like, and also comprises a copolymer of ethylene and alpha-olefin, wherein the polymers comprise crystalline resin and amorphous elastomer, and have unique properties and wide application.
The preparation of polyolefins by coordination polymerization of olefins is a common process. The copolymerization of different olefins is more complex than the homopolymerization of olefins, and the properties of the resulting copolymers are influenced not only by molecular weight and molecular weight distribution, but also by copolymerization composition and sequence distribution. Catalysts are key factors affecting the structure of olefin copolymers, and current catalysts capable of catalyzing coordination polymerization of olefins include ziegler-natta catalysts, metallocene catalysts, and non-metallocene transition metal catalysts. Ziegler-natta catalysts were developed in the fifties of the last century, driving the rapid development of coordination polymerization of olefins. The vanadium Ziegler-Natta catalyst has unique performance in catalyzing the copolymerization of ethylene and alpha-olefin, is widely applied to catalyzing the copolymerization of ethylene and propylene to prepare ethylene-propylene rubber, is the earliest catalyst used in industry, has low cost and small consumption of cocatalyst, can prepare ethylene/propylene random copolymer, has mature production process and is the catalyst mainly used for producing ethylene-propylene rubber in industry at present. The vanadium based ziegler-natta catalyst has relatively low catalytic activity compared to the metallocene catalyst, and the polymerization product needs to be washed in order to remove excessive catalyst residues in the polymerization product. If the catalytic activity of the vanadium-based catalytic system is further improved, the washing times can be reduced, even washing is not needed, and the industrial wastewater discharge is reduced. The catalytic activity of the vanadium catalyst can be improved by introducing organic groups into the main catalyst to replace chlorine in the vanadium oxychloride, for example, phosphate ligands (see CN101092466) or acetylacetone ligands (see CN1165141) are introduced into the catalyst to stabilize active centers, so that the catalytic activity is improved; or adding an activating agent, such as ethyl trichloroacetate, butyl 2,3,4, 4-tetrachloro-3-crotonate, ethyl dichlorophenylacetate, n-butyl perchlorocorotonate, dichloromethane, chloroform, trichlorofluoromethane, 1,3,3, 3-tetrachloropropylbenzene, perchloropropene, hexachlorobutadiene, etc. (see: CN 1099395, CN 85108910, CN 104418964A, CN 10337408), to reactivate the deactivated active sites to increase the catalytic activity.
The properties of Ethylene-propylene rubber depend not only on the composition, molecular weight and molecular weight distribution of the copolymer, but also on the sequence distribution of the copolymer, and the higher the random sequence distribution content of the comonomer structural units, the better the elasticity of the copolymer, and can be used as an excellent elastic material (see: H.F Mark, Ethylene propylene elastomers, Encyclopedia of Polymer Science and Technology, John Wiley & Sons, Inc.2007, 178-195). If the number of methylene groups in the molecular chain of the ethylene-propylene rubber reaches more than 8, the longer regular methylene chain segment can cause crystallization, generate microgel, influence the normal production of the ethylene-propylene rubber, and reduce the elasticity and the physical and mechanical properties of the ethylene-propylene rubber (see: D.R. Burfilled, Macromolecules,1987,20: 3020-3023). Therefore, the improvement of the content of the random sequence distribution of the structural units in the ethylene propylene rubber has important significance for improving the elasticity and the physical and mechanical properties of the ethylene propylene rubber. However, in the prior art, there is no report on the simultaneous improvement of catalytic activity, comonomer insertion rate and random sequence content by adding an additive to a vanadium-based catalyst.
Therefore, if the catalytic activity, the comonomer insertion rate and the random sequence content in the copolymer can be simultaneously improved, the product performance can be further improved, the cost can be reduced, and the method has extremely important significance for the industrial production of the ethylene propylene rubber.
Disclosure of Invention
The invention aims to provide a vanadium catalyst and a method for preparing olefin polymers by using the vanadium catalyst, and the vanadium catalyst has high catalytic activity, high comonomer insertion rate and high random sequence content of the obtained copolymer when the catalyst system is used for olefin polymerization.
In order to achieve the above object, the present invention provides a vanadium-based catalyst comprising:
the component A is as follows: a main catalyst which is a vanadium-containing compound;
and (B) component: a cocatalyst which is an organoaluminum compound;
and (C) component: a complex additive, and
optional component D: an activator;
wherein,
the composite additive is at least two of an additive C1, an additive C2 and an additive C3, or at least three of an additive C1, an additive C2, an additive C3 and an additive C4; additive C1 is C1～C10Alkyl alcohol or halogenated alkyl alcohol of (2), additive C2 being C6～C20The additive C3 is an alpha-diimine compound shown in the formula I,
Figure BDA0001333350460000031
wherein R is1～R12Each independently selected from hydrogen and C1～C6Alkyl of (C)3～C6Cycloalkyl or phenyl of, R1～R2Preferably selected from hydrogen, methyl, ethyl or phenyl; r3～R12Preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl or tert-butyl;
additive C4 is R1CX3、R2R3CX2And R4R5R6At least one compound represented by CX, wherein X is halogen, preferably chlorine or bromine; r1～R6Each independently selected from C1～C20Alkyl or haloalkyl of, C3～C20Cycloalkyl or halocycloalkyl of, C6～C20Aryl or halogenated aryl of (a);
the component D is an activating agent which is commonly used in the field and can oxidize low-valence vanadium into high-valence vanadium, and preferably C containing 2-5 chlorine atoms2～C20Ester of (a), C containing 2 to 5 chlorine atoms2～C20Olefin of (C) or C containing 2 to 5 chlorine atoms6～C20Preferably C containing 2 to 5 chlorine atoms2～C20Esters of (a);
the dosage of the component B is related to the impurity content in the system, the dosage of the main catalyst, the dosage of the monomer, the molecular weight of the polymerization product, the molecular weight distribution and other factors. Generally, the polymerization activity can be improved by increasing the amount of the cocatalyst in the polymerization system within a certain range, and the cocatalyst is too small, so that the number of generated active centers is small, the catalytic activity is low, and the monomer polymerization conversion rate is low. However, when the amount of the cocatalyst is too large, the main catalyst is excessively reduced to affect the monomer conversion, and chain transfer is caused to decrease the molecular weight of the polymer. In addition, too much cocatalyst can also lead to increased catalyst costs. The molar ratio of the component B calculated by Al element to the component A calculated by V element is 7-80: 1, preferably 10 to 70: 1, more preferably 15 to 60: 1;
the molar ratio of the component C to the component A calculated by the element V is 0.1-6.0: 1, preferably 0.2 to 5.0: 1; more preferably 0.3 to 4.5: 1;
the molar ratio of the component D to the component A calculated by the element V is 0-10: 1, preferably 0 to 8: 1, more preferably 0 to 7: 1; most preferably 0-6: 1.
according to the invention, component A is preferably VOCl3、VOCl2OR1And VOCl (OR)2)(OR3) At least one of (1), R1、R2And R3Are the same or different and are each independently selected from C1～C10Alkyl or haloalkyl of, C3～C10Cycloalkyl or halocycloalkyl groups of (a). Preferably, R1、R2And R3Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, cyclopentyl, cyclohexyl, 2-chloro-1-ethyl, 1-chloro-2-propyl, 1-chloro-2-methyl-2-propyl, 3-chloro-1-propyl, 2-chloro-2-methyl-1-propyl, 1-chloro-2-butyl, 1-chloro-2-methyl-2-butyl, 2-chloro-1-butyl, 2-chloro-2-methyl-1-butyl, 3-chloro-3-methyl-1-butyl, 1-chloro-2-pentyl, 1-chloro-2-methyl-2-pentyl, 3-chloro-1-pentyl, 3-chloro-3-methyl-1-pentyl, 2-chloro-1-pentyl, 1-chloro-2-hexyl, 1-chloro-2-methyl-2-hexyl, 3-chloro-1-hexyl, 2-chloro-1-hexyl, 1-chloro-2-heptyl, 1-chloro-2-methyl-2-heptyl, 3-chloro-1-heptyl, 2-chloro-1-heptyl, 1-chloro-2-octyl, 1-chloro-2-methyl-2-octyl, and mixtures thereof, 3-chloro-1-octyl, 2-chloro-1-octyl, 1-chloro-2-nonyl, 1-chloro-2-methyl-2-nonyl, 1-chloro-2-decyl, 1-chloro-2-methyl-2-decyl, 2-chloromethylcyclohexyl, 3-chloromethylcyclohexyl, 2-dichloro-1-ethyl, 1-dichloro-2-propyl, 1-dichloro-2-methyl-2-propyl, 3-dichloro-1-propyl, 2, 2-dichloro-1-propyl, 1-dichloro-2-butyl, 3-dichloro-1-butyl, 2, 2-dichloro-1-butyl, 1-dichloro-2-pentyl, 2, 2-dichloro-1-pentyl, 1-dichloro-2-hexyl, 2, 2-dichloro-1-hexyl, 2-dichloromethylcyclohexyl, 2,2, 2-trichloro-1-ethyl, 3, 3-trichloro-1-propyl, 1,1, 1-trichloro-2-methyl-2-propyl, 1,1, 1-trichloro-2-butyl, 1,1, 1-trichloro-2-methyl-2-butyl, 1,1, 1-trichloro-2-pentyl, 1,1, 1-trichloro-2-methyl-2-pentyl, 1,1, 1-trichloro-2-hexyl, 1,1, 1-trichloro-2-methyl-2-hexyl, 1,1, 1-trichloro-2-heptyl, 1,1, 1-trichloro-2-methyl-2-heptyl, 1,1,1, 1,1, 1-trichloro-2-octyl, 1,1, 1-trichloro-2-methyl-2-octyl, 1,1, 1-trichloro-2-nonyl, 1,1, 1-trichloro-2-decyl; more preferably selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2, 2-dichloro-1-ethyl, 1-dichloro-2-propyl, 1-dichloro-2-methyl-2-propyl, 3-dichloro-1-propyl, 2, 2-dichloro-1-propyl, 1-dichloro-2-butyl, 3-dichloro-1-butyl, 2, 2-dichloro-1-butyl, 1-dichloro-2-pentyl, 2, 2-dichloro-1-pentyl, 1-dichloro-2-hexyl, 2, 2-dichloro-1-hexyl, 2,2, 2-trichloro-1-ethyl, isobutyl, 2, 2-dichloro-1-ethyl, 1-dichloro-2-1-butyl, 3-dichloro-1-pentyl, 3,3, 3-trichloro-1-propyl, 1,1, 1-trichloro-2-methyl-2-propyl, 1,1, 1-trichloro-2-butyl or 1,1, 1-trichloro-2-methyl-2-butyl.
According to the present invention, preferably, component B is at least one of an alkylaluminum, an alkylaluminum halide and an alkylaluminoxane, the alkylaluminum and the alkylaluminum halide having the general formula RmAlX3-mWherein R is C1～C10Alkyl of (C)3～C10Cycloalkyl of, C7～C10Aralkyl of (2), C6～C10Each R may be the same or different, X is halogen, preferably chlorine or bromine, and m is 1, 1.5, 2 or 3. Wherein the alkyl aluminum is preferably selected from at least one of trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-n-pentyl aluminum, tri-n-hexyl aluminum, and tricyclohexyl aluminum; the alkylaluminum halide is preferably selected from the group consisting of dimethylaluminum monochloride, diethylaluminum monochloride, di-n-butylaluminum monochloride,At least one of diisobutylaluminum monochloride, methylaluminum dichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, methylaluminum sesquichloride, ethylaluminum sesquichloride, n-butylaluminum sesquichloride and isobutylaluminum sesquichloride; the alkylaluminoxane is preferably at least one selected from methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. Commercial alkylaluminoxanes also typically contain a certain amount (e.g., -20%) of an alkylaluminum.
According to the invention, the additive C1 is preferably selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, 2-chloro-1-ethanol, 1-chloro-2-propanol, 1-chloro-2-methyl-2-propanol, 3-chloro-1-propanol, 2-chloro-2-methyl-1-propanol, 1-chloro-2-butanol, 1-chloro-2-methyl-2-butanol, 2-chloro-1-butanol, 2-chloro-2-methyl-1-butanol, 3-chloro-3-methyl-1-butanol, 1-chloro-2-pentanol, 2-chloro-1-ethanol, 1-chloro-2-propanol, 1, 1-chloro-2-methyl-2-pentanol, 3-chloro-1-pentanol, 3-chloro-3-methyl-1-pentanol, 2-chloro-1-pentanol, 1-chloro-2-hexanol, 1-chloro-2-methyl-2-hexanol, 3-chloro-1-hexanol, 2-chloro-1-hexanol, 1-chloro-2-heptanol, 1-chloro-2-methyl-2-heptanol, 3-chloro-1-heptanol, 2-chloro-1-heptanol, 1-chloro-2-octanol, 1-chloro-2-methyl-2-octanol, 3-chloro-1-pentanol, 3-chloro-3-methyl-1-pentanol, 3-chloro-, 2-chloro-1-octanol, 1-chloro-2-nonanol, 1-chloro-2-methyl-2-nonanol, 1-chloro-2-decanol, 1-chloro-2-methyl-2-decanol, 2-chloromethylcyclohexanol, 3-chloromethylcyclohexanol, 2-dichloro-1-ethanol, 1-dichloro-2-propanol, 1-dichloro-2-methyl-2-propanol, 3-dichloro-1-propanol, 2-dichloro-1-propanol, 1-dichloro-2-butanol, 3-dichloro-1-butanol, 2-dichloro-1-butanol, 2-chloro-2-butanol, 1-chloro-2-nonanol, 2-chloro-2-methyl-2-nonanol, 2-chloro-1-2-methyl-, 1, 1-dichloro-2-pentanol, 2, 2-dichloro-1-pentanol, 1, 1-dichloro-2-hexanol, 2, 2-dichloro-1-hexanol, 2-dichloromethylcyclohexanol, 2,2, 2-trichloro-1-ethanol, 3,3, 3-trichloro-1-propanol, 1,1, 1-trichloro-2-methyl-2-propanol, 1, 1-trichloro-2-butanol, 1,1, 1-trichloro-2-methyl-2-butanol, 1, 1-trichloro-2-pentanol, 1,1, 1-trichloro-2-methyl-2-pentanol, 1, 1-dichloro-2-pentanol, 2, 2-dichloro-1-hexanol, 2-dichloro-1-methyl cyclohexanol, 2-, At least one of 1,1, 1-trichloro-2-hexanol, 1,1, 1-trichloro-2-methyl-2-hexanol, 1,1, 1-trichloro-2-heptanol, 1,1, 1-trichloro-2-methyl-2-heptanol, 1,1, 1-trichloro-2-octanol, 1,1, 1-trichloro-2-methyl-2-octanol, 1,1, 1-trichloro-2-nonanol, and 1,1, 1-trichloro-2-decanol; more preferably selected from the group consisting of methanol, ethanol, propanol, n-butanol, isobutanol, 2, 2-dichloro-1-ethanol, 1, 1-dichloro-2-propanol, 1, 1-dichloro-2-methyl-2-propanol, 3, 3-dichloro-1-propanol, 2, 2-dichloro-1-propanol, 1, 1-dichloro-2-butanol, 3, 3-dichloro-1-butanol, 2, 2-dichloro-1-butanol, 1, 1-dichloro-2-pentanol, 2, 2-dichloro-1-pentanol, 2,2, 2-trichloro-1-ethanol, 3,3, 3-trichloro-1-propanol, 1,1, 1-trichloro-2-propanol, 1, 1-dichloro-2-propanol, 1, 2-dichloro-1-propanol, 1,1, 1-trichloro-2-methyl-2-propanol, 1,1, 1-trichloro-2-butanol, 1,1, 1-trichloro-2-methyl-2-butanol, 1,1, 1-trichloro-2-pentanol, 1,1, 1-trichloro-2-methyl-2-pentanol, 1,1, 1-trichloro-2-hexanol, 1,1, 1-trichloro-2-methyl-2-hexanol, 1,1, 1-trichloro-2-heptanol, 1,1, 1-trichloro-2-methyl-2-heptanol, 1,1, 1-trichloro-2-octanol, 1,1, 1-trichloro-2-methyl-2-octanol, 1,1, 1-trichloro-2-nonanol and 1,1, 1-trichloro-2-decanol.
Additive C2 is preferably selected from the group consisting of phenol, p-methylphenol, 2-methylphenol, 3-methylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 2-tert-butylphenol, 2-sec-butylphenol, 2, 3-dimethylphenol, 2, 4-dimethylphenol, 2, 5-dimethylphenol, 2, 6-dimethylphenol, 2,3, 4-trimethylphenol, 2,3, 5-trimethylphenol, 2,3, 6-trimethylphenol, 2,4, 6-trimethylphenol, 2, 3-diethylphenol, 2, 4-diethylphenol, 2, 5-diethylphenol, 2, 6-diethylphenol, 2,3, 4-triethylphenol, At least one of 2,3, 5-triethylphenol, 2,3, 6-triethylphenol, 2,4, 6-triethylphenol, 2, 3-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 5-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2,3, 4-tri-tert-butylphenol, 2,3, 5-tri-tert-butylphenol, 2,3, 6-tri-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, 4-tert-amylphenol, and hydroquinone; more preferably selected from the group consisting of p-methylphenol, 2-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 2-tert-butylphenol, 2-sec-butylphenol, 2, 4-dimethylphenol, 2, 6-dimethylphenol, 2,3, 4-trimethylphenol, 2,3, 5-trimethylphenol, 2,3, 6-trimethylphenol, 2, 4-diethylphenol, 2, 6-diethylphenol, 2,4, 6-triethylphenol, 2, 3-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 5-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2,3, 4-tri-tert-butylphenol, 2,3, at least one of 5-tri-tert-butylphenol, 2,3, 6-tri-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol and 4-tert-amylphenol.
The additive C4 is preferably selected from the group consisting of 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane, 1-chloropentane, 2-chloropentane, 1-chloro-2-methyl-butane, 1-chloro-3-methyl-butane, 1-chloro-2, 2-dimethylpropane, 2-chloro-2-methyl-butane, 1-chlorohexane, 2-chlorohexane, 1-chloro-2-methyl-pentane, 1-chloro-3-methyl-pentane, 1-chloro-4-methyl-pentane, 2-chloro-2-methyl-pentane, 1-chloro-methyl-butane, 2-, 3-chloro-3-methyl-pentane, 1-chloro-2-ethyl-butane, 1-chloro-2, 2-dimethylbutane, 1-chloroheptane, 2-chloroheptane, 1-chloro-2-methyl-hexane, 2-chloro-2-methyl-hexane, 3-chloro-3-methyl-hexane, 1-chloro-2, 2-dimethylpentane, 1-chlorooctane, 2-chlorooctane, 1-chloro-2-methyl-heptane, 2-chloro-2-methyl-heptane, 3-chloro-3-methyl-heptane, 4-chloro-4-methyl-heptane, 1-chloro-2, 2-dimethylhexane, 1-chlorononane, 2-chlorononane, 1-chloro-2-methyl-octane, 1-chloro-3-methyl-octane, 1-chloro-4-methyl-octane, 1-chloro-2, 2-dimethylheptane, 1-chlorodecane, 2-chlorodecane, 1-chloro-2, 2-diphenylpropane, cumyl chloride, alpha-chlorotoluene, 2-chloroethylbenzene, 2-chloro-1, 1-diphenylethane, 2-chloro-1, 1, 1-triphenylethane, 1, 1-dichloroethane, 1, 1-dichloropropane, 2-dichloropropane, 1, 1-dichlorobutane, 2-dichlorobutane, 1, 2-dichlorobutane, 1, 1-dichloro-2-methylpropane, 1-dichloropentane, 2-dichloropentane, 1-dichloro-2, 2-dimethylpropane, 1-dichloro-2-methylbutane, 1-dichlorohexane, 2-dichlorohexane, 1-dichloro-2, 2-dimethylbutane, 1-dichloro-2, 3-dimethylbutane, 1-dichloro-2-methylpentane, 1-dichloro-3-methylpentane, 1-dichloro-4-methylpentane, 1-dichloroheptane, 2-dichloroheptane, 1-dichloro-2-methylhexane, 1, 1-dichloro-3-methylhexane, 1-dichloro-4-methylhexane, 1-dichloro-5-methylhexane, 1-dichloro-2, 2-methylpentane, 1-dichlorooctane, 2-dichlorooctane, 1-dichloro-2-methylheptane, 1-dichloro-3-methylheptane, 1-dichloro-4-methylheptane, 1-dichloro-5-methylheptane, 1-dichloro-6-methylheptane, 1-dichloro-2, 2-dimethylhexane, 1-dichlorononane, 2-dichlorononane, 1-dichloro-2-methyloctane, 1-dichloro-2-methylheptane, 1-dichloro-4, 1, 1-dichlorodecane, 2-dichlorodecane, α -dichlorotoluene, 2-dichloroethylbenzene, 2-dichloro-1, 1-diphenylethane, 2-dichloro-1, 1, 1-triphenylethane, 1,1, 1-trichloroethane, 1,1, 1-trichloropropane, 1,1, 1-trichlorobutane, 1,1, 1-trichloro-2-methylpropane, 1,1, 1-trichloropentane, 1,1, 1-trichloro-2, 2-dimethylpropane, 1,1, 1-trichloro-2-methylbutane, 1,1, 1-trichloro-3-methylbutane, 1,1, 1-trichlorohexane, 1,1, 1-trichloro-2, 2-dimethylbutane, 1,1, 1-trichloro-3, 3-dimethylbutane, 1,1, 1-trichloro-2-methylpentane, 1,1, 1-trichloroheptane, 1,1, 1-trichloro-2-methylhexane, 1, 1-trichloro-3-methylhexane, 1,1, 1-trichloro-4-methylhexane, 1,1, 1-trichloro-5-methylhexane, 1,1, 1-trichlorooctane, 1,1, 1-trichlorononane, 1,1, 1-trichloro-2-methyloctane, 1,1, 1-trichloro-3-methyloctane, 1,1, 1-trichlorodecane, 1,1, 1-trichloro-2-methylnonane, 1,1, 1-trichloro, At least one of α, α, α -trichloromethylcyclohexane, α, α, α -trichlorotoluene, 2,2, 2-trichloroethylbenzene, 2,2, 2-trichloro-1, 1-diphenylethane and 2,2, 2-trichloro-1, 1, 1-triphenylethane; more preferably selected from the group consisting of 2-chloropropane, 2-chlorobutane, 2-chloro-2-methylpropane, 2-chloropentane, 2-chloro-2-methylbutane, cumylchloride, 2-chloroethylbenzene, 1, 1-dichloroethane, 1, 1-dichloropropane, 2-dichloropropane, 1, 1-dichlorobutane, 2-dichlorobutane, 1, 1-dichloro-2-methylpropane, 1, 1-dichloro-2, 2-dimethylpropane, 1, 1-dichloro-2-methylbutane, 1,1, 1-trichloroethane, 1,1, 1-trichloropropane, 1,1, 1-trichlorobutane, 1,1, 1-trichloro-2-methylpropane, 1,1, 1-trichloropentane, 1,1, 1-trichloro-2, 2-dimethylpropane, 1,1, 1-trichloro-2-methylbutane or and 1,1, 1-trichloro-3-methylbutane.
According to the invention, when the composite additive is at least two of the additive C1, the additive C2 and the additive C3, the molar ratio of C1 to C2 is 0.001-500: 1, preferably 0.002 to 300: 1, more preferably 0.003 to 120: 1; the molar ratio of C2 to C3 is 0.1-1750: 1, preferably 0.2 to 600: 1, more preferably 0.5 to 320: 1; the molar ratio of C1 to C3 is 0.005-6: 1, preferably 0.006-5: 1, more preferably 0.008-4: 1.
when the composite additive is at least three of an additive C1, an additive C2, an additive C3 and an additive C4, the proportion of the C4 to any one of the other three components is 0.001-2000: 1, preferably 0.003-800: 1, more preferably 0.005 to 400: 1.
the invention also provides a method for preparing olefin polymer by adopting the vanadium catalyst, and in the polymerization reaction, the adding mode of each component is one of the following modes:
(1) mixing the component A with a monomer and a reaction medium, then mixing with the component C, and then mixing with the component B;
(2) mixing the component C with a monomer and a reaction medium, then mixing with the component A, and then mixing with the component B;
(3) mixing the component A and the component C, then mixing the component A and the component C with a monomer and a reaction medium, and then mixing the component A and the component C with the component B;
(4) mixing the component B with a monomer and a reaction medium, and further mixing with a mixture of the component A and the component C;
(5) component A, B is mixed with component C, and then the mixture of A, B and component C is further mixed with monomer and reaction medium;
(6) component A, C is mixed with component B, and then the mixture of A, B and component C is further mixed with monomer and reaction medium;
(7) components A, B and C are mixed with the monomer and the reaction medium simultaneously;
(8) the catalyst components are mixed with the alpha-olefin monomer in any of the above manners and then mixed with the ethylene monomer.
Optionally, component D is added to the reaction system described above.
The components in the component C can be added after being mixed or can be added respectively.
According to the invention, in the mode of mixing the components, the mixing temperature is-40-50 ℃, preferably-30-40 ℃, and more preferably-20-35 ℃; the mixing time is related to the reaction temperature and also to the amount of the components added, the lower the reaction temperature, the more procatalyst and additive are added and the longer the reaction time, and generally, the mixing time is from 1 minute to 15 hours, preferably from 2 minutes to 14 hours, and more preferably from 3 minutes to 13 hours.
According to the invention, component C is added in the form of a solution using a solvent C3～C10Saturated alkane of (C)3～C10Cycloalkane of C6～C10At least one aromatic hydrocarbon of (2), preferably at least one selected from the group consisting of n-butane, n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclopentane, methylcyclohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, toluene and xylene.
Too high monomer concentration can result in too high system viscosity and affect the production process. The excessively low monomer concentration leads to an increase in the amount of solvent used and an increase in cost. In the present invention, an appropriate monomer concentration is essential, and preferably, the monomer concentration is from 30g/L to 150g/L, preferably from 35g/L to 120g/L, and more preferably from 45g/L to 100 g/L.
According to the invention, the molar ratio of component A to monomer, expressed as the element V (V/M ratio for short), is preferably 1.0X 10-5～5.0×10-4:1, preferably 3.0X 10-5～4.0×10-4:1, more preferably 5.0X 10-5～3.0×10-4：1。
According to the invention, the monomer is preferably an olefin selected from one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, norbornene, cyclopentene, cyclohexene, 1, 3-cyclohexadiene, 1, 4-cyclohexadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 1, 4-hexadiene, 2-methyl-1, 4-hexadiene and 1, 6-octadiene; preferably one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, norbornene, cyclopentene, cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene and 1, 6-octadiene; more preferably at least one of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, norbornene, cyclopentene, cyclohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene and 1, 6-octadiene.
The vanadium catalyst provided by the invention is preferably used for homopolymerization of ethylene or alpha-olefin, copolymerization of ethylene and diene, or ternary copolymerization of ethylene, alpha-olefin and non-conjugated diene.
According to the invention, the polymerization reaction may be a heat-insulating polymerization or a constant-temperature polymerization. The initial temperature of the polymerization reaction is-60 to 55 ℃, preferably-55 to 50 ℃, and more preferably-50 to 45 ℃.
The monomer conversion and the polymer yield increase with the extension of the reaction time, but the reaction rate is faster at the beginning of the polymerization reaction for the vanadium-based catalyst, and as the reaction time is extended, part of the catalyst is deactivated and the reaction rate becomes slower. Therefore, the polymerization reaction time is generally selected from 1 minute to 2 hours, preferably from 2 minutes to 1.5 hours, and more preferably from 2.5 minutes to 1.2 hours.
The polymerization pressure is related to the polymerization temperature, the higher the pressure. In addition, increasing the pressure is favorable for the gas monomer to dissolve in the solution for polymerization, but too high a pressure will place high demands on the pressure resistance of the polymerization reactor. Therefore, the polymerization pressure is generally selected from 0.01MPa to 3MPa, preferably from 0.05MPa to 2MPa, and more preferably from 0.1MPa to 1 MPa.
The polymerization method of the present invention includes bulk polymerization, solution polymerization or slurry polymerization, and may be a batch process or a continuous process. The monomers can be fed in one portion or in batches or continuously.
When solution polymerization is employed, the solvent used may be selected from C3～C10Preferably at least one selected from the group consisting of n-butane, n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclopentane, methylcyclohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, toluene and xylene. The choice of solvent is related to the polymerization process conditions, the polymer molecular weight and the molecular weight distribution. Generally, to prepare high molecular weight polymers, solvents are selected that are not susceptible to chain transfer; to prepare low molecular weight polymers, the fugitive chains may be selectedThe transferred solvent.
By adopting the catalyst system and the polymerization method, the copolymerization reaction activity of monomers such as ethylene, alpha-olefin and the like can be greatly improved, and the conversion rate and the insertion rate of the alpha-olefin and the diene are improved, so that the monomer utilization rate is improved, the recovery load of unreacted monomers is reduced, the energy is saved, and the consumption is reduced; in addition, the content of random sequence distribution in the copolymer can be increased in the copolymerization reaction, the molecular weight of the copolymer is increased, and the product quality is improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following will describe preferred embodiments of the invention in more detail to further illustrate the invention, but should not be construed to limit the scope of the invention.
Ethylene or propylene content of the ethylene-propylene copolymer was determined by Fourier Infrared Spectroscopy (FTIR) according to ASTM-D3900-95.
According to GB/T21464-2008, the ethylene, propylene or ENB content in the ethylene-propylene-ENB copolymer is measured by adopting FTIR.
The catalyst activity is in g polymer (mol) per mol procatalyst-1of V)。
To polymers13C NMR measurement, calculating EPE, PEP, EEP and PPE sequence contents in the copolymer, and defining the sum of the four sequence contents as random sequence content.
The viscosity average molecular weight of the polymer was measured according to literature reported methods using trichlorobenzene as solvent at 135 ℃, see Macromolecules,1984, 17: 2767-2775.
The 1-octene content of the copolymers of ethylene and 1-octene is determined by DSC according to the methods reported in the literature, see Macromolecules,1987,20:3020 to 3023.
In the following examples, the molar ratios of component A to other components are based on the element V in component A, the molar ratios of component B to other components are based on the element Al in component B, and the molar number of component C is the sum of the molar numbers of the additives in component C.
Example 1
Propylene and ethylene monomers were mixed in a molar ratio (ethylene: propylene ═ 1: 3) with hexane to form a monomer solution (50 g/L). At 7.5 ℃ in VOCl2(OC(CH3)2CCl3) (component A) adding 2, 6-di-tert-butyl-4-methylphenol (additive C2) into a hexane solution, reacting for 10 hours, then adding chlorobutanol (additive C1), and reacting for 10 hours to obtain a catalyst solution, wherein the molar ratio of the component C to the component A is 1.01: 1, the molar ratio of C1 to C2 is 0.01: 1.
under the protection of nitrogen and at the temperature of 20-25 ℃, adding a component B (aluminum sesquiethyl chloride) and a catalyst solution containing a component A and a component C into a monomer solution in sequence to ensure that the molar ratio of the component A to the monomer is 7.5 multiplied by 10-5:1, the molar ratio of the component B to the component A is 50: 1. after the polymerization reaction is carried out for 10 minutes, adding 5 percent by mass of hydrochloric acid ethanol solution to terminate the reaction, and drying the obtained polymer at 40 ℃ in vacuum to constant weight to obtain the ethylene-propylene copolymer. The catalytic activity was 152kg of polymer (mol)-1of V), the conversion of ethylene was 89%, the conversion of propylene was 18%, the content of propylene in the copolymer was 47% by weight, the content of random sequence distribution was 68%, and the viscosity-average molecular weight of the copolymer was 22 ten thousand.
The catalyst activity was increased by 32kg of polymer (mol.) under the same polymerization conditions, compared with comparative example 1-1of V) (increase of 27%), ethylene conversion increased by 7% (increase of 9%) and propylene conversion increased by 7% (increase of 64%); the propylene content in the copolymer is increased by 8 wt% (the improvement range is 21%), the random sequence distribution content is increased by 12% (the improvement range is 21%), and the molecular weight is increased by 3 ten thousand (the improvement range is 16%).
Example 2
The polymerization process was as described in example 1, except that the molar ratio of component C to component a was 0.41: 1, the molar ratio of C1 to C2 is 0.005: 1. in the polymerization process, the component A is added into the monomer solution, then the component C is added, and finally the component B is added. The catalytic activity was 128kg of polymer (mol)-1of V), the conversion of ethylene was 83%, the conversion of propylene was 13%, and the propylene content in the copolymer was 42 wt%, the content of random sequences was 64%, and the viscosity-average molecular weight of the copolymer was 28 ten thousand.
The catalyst activity was increased by 8kg of polymer (mol.) under the same polymerization conditions, compared with comparative example 1-1of V) (increase of 7%), 1% increase in ethylene conversion (increase of 1.2%), 2% increase in propylene conversion (increase of 18%); the propylene content in the copolymer is increased by 3 wt% (the improvement range is 8%), the random sequence content is increased by 8% (the improvement range is 14%), and the molecular weight is increased by 9 ten thousand (the improvement range is 47%).
Example 3
The polymerization process was as described in example 1, except that the molar ratio of component C to component a was 2.01: 1, the molar ratio of C1 to C2 is 0.005: 1, mixing the component A and the component C, adding the mixture into a monomer solution, and then adding the component B. The catalytic activity was 132kg of polymer (mol)-1of V), the conversion of ethylene was 88%, the conversion of propylene was 13%, the content of propylene in the copolymer was 40% by weight, the content of random sequence was 67%, and the viscosity-average molecular weight of the copolymer was 31 ten thousand.
The catalyst activity was increased by 12kg of polymer (mol.) under the same polymerization conditions, compared with comparative example 1-1of V) (10% improvement), 6% improvement in ethylene conversion (7% improvement), 2% improvement in propylene conversion (18% improvement), 1% improvement in propylene content (2.6% improvement), 11% improvement in random sequence content in the copolymer (20% improvement), and 12% improvement in molecular weight (63% improvement).
Example 4
The polymerization was as in example 1 except that component A was VOCl3The molar ratio of the component C to the component A is 4: 1, the molar ratio of C1 to C2 is 3:1, the molar ratio of the component B to the component A is 20: 1. the component C is mixed and then added into the monomer solution, then the component C is added, and finally the component B is added. The catalytic activity was 150kg of polymer (mol)-1of V), the conversion of ethylene was 100%, the conversion of propylene was 15%, the content of propylene in the copolymer was 39% by weight, the content of random sequence distribution was 61%, and the viscosity-average molecular weight of the copolymer was 28 ten thousand.
The catalyst activity was increased by 70kg of polymer (mol.) under the same polymerization conditions, compared with comparative example 2-1of V) (88% improvement), 51% improvement in ethylene conversion (104% improvement), 6% improvement in propylene conversion (67% improvement), 5% increase in random sequence content in the copolymer (8.9% improvement), and 15 ten thousand improvement in molecular weight (115% improvement).
Example 5
At-10 ℃ in VOCl2(OCH2CCl3) Adding a mixture of 2, 6-di-tert-butyl-4-methylphenol (additive C2) and trichloroethanol (additive C1) into the solution of the component A, reacting for 5 minutes, and adding the component B, wherein the molar ratio of the component C to the component A is 1.01: 1, the molar ratio of C1 to C2 is 100: 1, the molar ratio of the component B to the component A is 30: 1. adding the solution into an ethylene and propylene monomer solution containing 5-ethylidene-2-norbornene (ENB), wherein the ratio of ethylene: propylene: ENB ═ 1: 3: 0.07, the molar ratio of the component A to the monomer is 2.2X 10-4:1, the polymerization temperature is 0 ℃. The catalytic activity was 67kg of polymer (mol)-1of V), the ethylene conversion was 100%, the propylene conversion was 24%, the ENB conversion was 85%, the propylene content in the copolymer was 51% by weight, the ENB content was 6.7% by weight, the random sequence distribution content was 69%, and the copolymer viscosity-average molecular weight was 31 ten thousand.
The addition of component C increased the catalytic activity by 10kg of polymer (mol) under the same polymerization conditions compared with comparative example 3-1of V) (18% improvement), ethylene conversion is unchanged, propylene conversion is improved by 4% (20% improvement), ENB conversion is improved by 13% (18% improvement), propylene content in the copolymer is improved by 11 wt% (28% improvement), ENB content is improved by 1 wt% (18% improvement), random sequence content is improved by 3% (4.5% improvement), and molecular weight is improved by 9 ten thousand (41% improvement).
Example 6
The polymerization was carried out as described in example 1, except that the polymerization temperature was in the range of 40 to 45 ℃ and the catalytic activity was 80kg of polymer (mol.)-1of V), ethylene conversion of 63% and propylene conversion of 6%, in the copolymerThe propylene content was 30% by weight, the random sequence content was 53% and the copolymer had a viscosity average molecular weight of 26 ten thousand.
Compared with comparative example 4, the catalytic activity was increased by 28kg of polymer (mol.) under the same polymerization conditions- 1of V) (increase of 54%), ethylene conversion increased by 22% (increase of 54%), propylene conversion increased by 2% (increase of 50%), propylene content in the copolymer increased by 1 wt% (increase of 3%), random sequence content increased by 4% (increase of 8%), molecular weight increased by 1 ten thousand (increase of 4%).
Example 7
The polymerization process was as described in example 1, except that the component C was added in addition to the compound of formula II (additive C3) and 1,1, 1-trichloroethane (component C4) in such a way that the molar ratio of C1 to C3 was 0.01: 1, the molar ratio of C2 to C3 is 1: 1, the molar ratio of C4 to C2 is 0.01: 1. the catalytic activity was 128kg of polymer (mol)-1of V), ethylene conversion of 92%, propylene conversion of 11%; the propylene content of the copolymer was 40% by weight, the random sequence distribution content was 66%, and the viscosity-average molecular weight of the copolymer was 28 ten thousand.
The catalyst activity was increased by 47kg of polymer (mol.) under the same polymerization conditions, compared with that of comparative example 5-1of V) (58% improvement), 37% improvement in ethylene conversion (67% improvement), 4% improvement in propylene conversion (57% improvement), 2% improvement in propylene content in the copolymer (5.3% improvement), 13% improvement in random sequence content (24.5% improvement), 14 ten thousand improvement in molecular weight (100% improvement).
Figure BDA0001333350460000161
Example 8
The polymerization was carried out as described in example 7, except that 1,1, 1-trichloroethane (component C4) was added in such a way that the molar ratio of C1 to C3 was 3:1, molar ratio of C2 to C3 300: 1, the molar ratio of C4 to C1 is 300: 1. the catalytic activity was 162kg of polymer (mol)-1of V), ethylene conversionThe ratio was 99%, the propylene conversion was 15%, the propylene content in the copolymer was 45% by weight, and the random sequence distribution content was 66%. The viscosity average molecular weight of the copolymer was 28 ten thousand.
The catalyst activity was increased by 42kg of polymer (mol.) under the same polymerization conditions, compared with comparative example 1-1of V) (increase of 35%), ethylene conversion increased by 17% (increase of 21%), propylene conversion increased by 4% (increase of 36%); the propylene content in the copolymer is increased by 6 wt% (the improvement range is 15%), the random sequence content is increased by 10% (the improvement range is 18%), and the molecular weight is increased by 9 ten thousand (the improvement range is 47%).
Example 9
1-octene was dissolved in hexane to form a solution having a concentration of 0.3mol/L, and ethylene was introduced while maintaining the pressure at 0.4MPa by adding a catalyst in accordance with the method of example 1. Polymerization and post-treatment were carried out in the same manner as in example 1 to obtain an ethylene-octene copolymer. The catalytic activity was 225kg of polymer (mol)-1of V), the octene conversion was 6%, the octene content in the copolymer was 9.8% by weight, and the intrinsic viscosity of the copolymer at 135 ℃ in trichlorobenzene was 2.6dL g-1。
The catalyst activity was increased by 24kg of polymer (mol.) under the same polymerization conditions, compared with that of comparative example 6-1of V) (increase of 12%), octene conversion of 4% (increase of 200%), octene content of 6.8 wt% in copolymer (increase of 227%), intrinsic viscosity of copolymer increased by 0.4dL g-1(the improvement was 18%).
Comparative example 1
The polymerization process was as described in example 1, except that component C was not added. The catalytic activity was 120kg of polymer (mol)-1of V), the ethylene conversion was 82%, the propylene conversion was 11%, the propylene content in the copolymer was 39% by weight, the random sequence content was 56%, and the viscosity-average molecular weight of the copolymer was 19 ten thousand.
Comparative example 2
The polymerization was as described in example 4, except that component C was not added. The catalytic activity was 80kg of polymer (mol)-1of V), ethylene conversion of 49%,the conversion of propylene was 9%, the propylene content in the copolymer was 39% by weight, the random sequence content was 56%, and the viscosity-average molecular weight of the copolymer was 13 ten thousand.
Comparative example 3
The polymerization was as described in example 5, except that component C was not added. The catalytic activity was 57kg of polymer (mol)-1of V), the ethylene conversion was 100%, the propylene conversion was 20%, the ENB conversion was 72%, the propylene content in the copolymer was 40% by weight, the ENB content was 5.7% by weight, the random sequence content was 66%, and the copolymer viscosity average molecular weight was 22 ten thousand.
Comparative example 4
The polymerization was as described in example 6, except that component C was not added. The catalytic activity was 52kg of polymer (mol)-1of V), the ethylene conversion was 41%, the propylene conversion was 4%, the propylene content in the copolymer was 29% by weight, the random sequence distribution content was 49%, and the viscosity-average molecular weight of the copolymer was 25 ten thousand.
Comparative example 5
The polymerization was as described in example 7, except that component C was not added. The catalytic activity was 81kg of polymer (mol)-1of V), the ethylene conversion was 55%, the propylene conversion was 7%, the propylene content in the copolymer was 38% by weight, the random sequence distribution content was 53%, and the viscosity-average molecular weight of the copolymer was 14 ten thousand.
Comparative example 6
The polymerization was as described in example 9, except that component C was not added. The catalytic activity was 201kg of polymer (mol)-1ofV), octene conversion 2%, octene content in copolymer 3 wt%, intrinsic viscosity of copolymer at 135 deg.C in trichlorobenzene 2.2dL g-1。
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (35)

1. A vanadium-based catalyst, comprising:
the component A is as follows: a main catalyst which is a vanadium-containing compound;
and (B) component: a cocatalyst which is an organoaluminum compound;
and (C) component: a complex additive, and
optional component D: an activator;
wherein,
the composite additive is at least two of an additive C1, an additive C2 and an additive C3, or at least three of an additive C1, an additive C2, an additive C3 and an additive C4; additive C1 is C1～C10Alkyl alcohol or halogenated alkyl alcohol of (2), additive C2 being C6～C20The additive C3 is an alpha-diimine compound shown in the formula I,
Figure FDA0002678544910000011
wherein R is1～R12Each independently selected from hydrogen and C1～C6Alkyl of (C)3～C6Cycloalkyl or phenyl of (a);
additive C4 is R1CX3、R2R3CX2And R4R5R6At least one compound represented by CX, wherein X is halogen; r1～R6Each independently selected from C1～C20Alkyl or haloalkyl of, C3～C20Cycloalkyl or halocycloalkyl of, C6～C20Aryl or halogenated aryl of (a);
the component D is C containing 2-5 chlorine atoms2～C20Ester of (a), C containing 2 to 5 chlorine atoms2～C20Olefin of (C) or C containing 2 to 5 chlorine atoms6～C20The aromatic compound of (1);
the molar ratio of the component B calculated by Al element to the component A calculated by V element is 7-80: 1;
the molar ratio of the component C to the component A calculated by the element V is 0.1-6.0: 1;
the molar ratio of the component D to the component A calculated by the element V is 0-10: 1.
2. the vanadium-based catalyst according to claim 1, wherein R is1～R2Selected from hydrogen, methyl, ethyl or phenyl.
3. The vanadium-based catalyst according to claim 1, wherein R is3～R12Selected from hydrogen, methyl, ethyl, propyl, isopropyl or tert-butyl.
4. The vanadium-based catalyst according to claim 1, wherein in the additive C4, X is chlorine or bromine.
5. The vanadium-based catalyst according to claim 1, wherein the component D is C containing 2 to 5 chlorine atoms2～C20An ester of (a).
6. The vanadium-based catalyst according to claim 1, wherein the molar ratio of the component B in terms of Al element to the component A in terms of V element is 10 to 70: 1.
7. the vanadium-based catalyst according to claim 6, wherein the molar ratio of the component B in terms of Al element to the component A in terms of V element is 15 to 60: 1.
8. the vanadium-based catalyst according to claim 1, wherein the molar ratio of component C to component a, calculated as the element V, is from 0.2 to 5.0: 1.
9. the vanadium-based catalyst according to claim 8, wherein the molar ratio of component C to component A, calculated as element V, is 0.3 to 4.5: 1.
10. the vanadium-based catalyst according to claim 1, wherein the molar ratio of component D to component A, calculated as element V, is 0 to 8: 1.
11. the vanadium-based catalyst according to claim 10, wherein the molar ratio of component D to component a, calculated as the element V, is from 0 to 7: 1.
12. the vanadium-based catalyst according to claim 11, wherein the molar ratio of component D to component a, calculated as the element V, is from 0 to 6: 1.
13. the vanadium-based catalyst according to claim 1, wherein component A is VOCl3、VOCl2OR1And VOCl (OR)2)(OR3) At least one of (1), R1、R2And R3Each independently selected from C1～C10Alkyl or haloalkyl of, C3～C10Cycloalkyl or halocycloalkyl groups of (a).
14. The vanadium-based catalyst according to claim 1, wherein the component B is at least one of an alkylaluminum, an alkylaluminum halide and an alkylaluminoxane, the alkylaluminum and the alkylaluminum halide having the general formula RmAlX3-mWherein R is C1～C10Alkyl of (C)3～C10Cycloalkyl of, C7～C10Aralkyl of (2), C6～C10X is halogen and m is 1, 1.5, 2 or 3.
15. The vanadium-based catalyst according to claim 14, wherein the general formula RmAlX3-mWherein X is chlorine or bromine.
16. The vanadium-based catalyst according to claim 14, wherein the aluminum alkyl is selected from at least one of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum, and tricyclohexylaluminum; the alkyl aluminum halide is selected from at least one of dimethyl aluminum monochloride, diethyl aluminum monochloride, di-n-butyl aluminum monochloride, diisobutyl aluminum monochloride, methyl aluminum dichloroide, ethyl aluminum dichloroide, n-butyl aluminum dichloroide, isobutyl aluminum dichloroide, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, n-butyl aluminum sesquichloride and isobutyl aluminum sesquichloride; the alkylaluminoxane is at least one selected from methylaluminoxane, ethylaluminoxane and isobutylaluminoxane.
17. The vanadium-based catalyst according to claim 1, wherein,
additive C1 is selected from methanol, ethanol, propanol, butanol, pentanol, 2-chloro-1-ethanol, 1-chloro-2-propanol, 1-chloro-2-methyl-2-propanol, 3-chloro-1-propanol, 2-chloro-2-methyl-1-propanol, 1-chloro-2-butanol, 1-chloro-2-methyl-2-butanol, 2-chloro-1-butanol, 2-chloro-2-methyl-1-butanol, 3-chloro-3-methyl-1-butanol, 1-chloro-2-pentanol, 2-chloro-1-ethanol, 1-chloro-2-propanol, 1-chloro-2-methyl-1-propanol, 1-chloro-2-butanol, 1-, 1-chloro-2-methyl-2-pentanol, 3-chloro-1-pentanol, 3-chloro-3-methyl-1-pentanol, 2-chloro-1-pentanol, 1-chloro-2-hexanol, 1-chloro-2-methyl-2-hexanol, 3-chloro-1-hexanol, 2-chloro-1-hexanol, 1-chloro-2-heptanol, 1-chloro-2-methyl-2-heptanol, 3-chloro-1-heptanol, 2-chloro-1-heptanol, 1-chloro-2-octanol, 1-chloro-2-methyl-2-octanol, 3-chloro-1-pentanol, 3-chloro-3-methyl-1-pentanol, 3-chloro-, 2-chloro-1-octanol, 1-chloro-2-nonanol, 1-chloro-2-methyl-2-nonanol, 1-chloro-2-decanol, 1-chloro-2-methyl-2-decanol, 2-chloromethylcyclohexanol, 3-chloromethylcyclohexanol, 2-dichloro-1-ethanol, 1-dichloro-2-propanol, 1-dichloro-2-methyl-2-propanol, 3-dichloro-1-propanol, 2-dichloro-1-propanol, 1-dichloro-2-butanol, 3-dichloro-1-butanol, 2-dichloro-1-butanol, 2-chloro-2-butanol, 1-chloro-2-nonanol, 2-chloro-2-methyl-2-nonanol, 2-chloro-1-2-methyl-, 1, 1-dichloro-2-pentanol, 2, 2-dichloro-1-pentanol, 1, 1-dichloro-2-hexanol, 2, 2-dichloro-1-hexanol, 2-dichloromethylcyclohexanol, 2,2, 2-trichloro-1-ethanol, 3,3, 3-trichloro-1-propanol, 1,1, 1-trichloro-2-methyl-2-propanol, 1, 1-trichloro-2-butanol, 1,1, 1-trichloro-2-methyl-2-butanol, 1, 1-trichloro-2-pentanol, 1,1, 1-trichloro-2-methyl-2-pentanol, 1, 1-dichloro-2-pentanol, 2, 2-dichloro-1-hexanol, 2-dichloro-1-methyl cyclohexanol, 2-, At least one of 1,1, 1-trichloro-2-hexanol, 1,1, 1-trichloro-2-methyl-2-hexanol, 1,1, 1-trichloro-2-heptanol, 1,1, 1-trichloro-2-methyl-2-heptanol, 1,1, 1-trichloro-2-octanol, 1,1, 1-trichloro-2-methyl-2-octanol, 1,1, 1-trichloro-2-nonanol, and 1,1, 1-trichloro-2-decanol;
additive C2 is selected from the group consisting of phenol, p-methylphenol, 2-methylphenol, 3-methylphenol, 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-isopropylphenol, 2-tert-butylphenol, 2-sec-butylphenol, 2, 3-dimethylphenol, 2, 4-dimethylphenol, 2, 5-dimethylphenol, 2, 6-dimethylphenol, 2,3, 4-trimethylphenol, 2,3, 5-trimethylphenol, 2,3, 6-trimethylphenol, 2,4, 6-trimethylphenol, 2, 3-diethylphenol, 2, 4-diethylphenol, 2, 5-diethylphenol, 2, 6-diethylphenol, 2,3, 4-triethylphenol, 2,3, 5-triethylphenol, 2,3, 6-triethylphenol, 2,4, 6-triethylphenol, 2, 3-di-tert-butylphenol, 2, 4-di-tert-butylphenol, 2, 5-di-tert-butylphenol, 2, 6-di-tert-butylphenol, 2,3, 4-tri-tert-butylphenol, 2,3, 5-tri-tert-butylphenol, 2,3, 6-tri-tert-butylphenol, 2,4, 6-tri-tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, 4-tert-amylphenol, and hydroquinone.
18. The vanadium-based catalyst according to claim 1, wherein,
additive C4 is selected from the group consisting of 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, 2-chloro-2-methylpropane, 1-chloropentane, 2-chloropentane, 1-chloro-2-methyl-butane, 1-chloro-3-methyl-butane, 1-chloro-2, 2-dimethylpropane, 2-chloro-2-methyl-butane, 1-chlorohexane, 2-chlorohexane, 1-chloro-2-methyl-pentane, 1-chloro-3-methyl-pentane, 1-chloro-4-methyl-pentane, 2-chloro-2-methyl-pentane, 1-chloro-methyl-butane, 2-chloro, 3-chloro-3-methyl-pentane, 1-chloro-2-ethyl-butane, 1-chloro-2, 2-dimethylbutane, 1-chloroheptane, 2-chloroheptane, 1-chloro-2-methyl-hexane, 2-chloro-2-methyl-hexane, 3-chloro-3-methyl-hexane, 1-chloro-2, 2-dimethylpentane, 1-chlorooctane, 2-chlorooctane, 1-chloro-2-methyl-heptane, 2-chloro-2-methyl-heptane, 3-chloro-3-methyl-heptane, 4-chloro-4-methyl-heptane, 1-chloro-2, 2-dimethylhexane, 1-chlorononane, 2-chlorononane, 1-chloro-2-methyl-octane, 1-chloro-3-methyl-octane, 1-chloro-4-methyl-octane, 1-chloro-2, 2-dimethylheptane, 1-chlorodecane, 2-chlorodecane, 1-chloro-2, 2-diphenylpropane, cumyl chloride, alpha-chlorotoluene, 2-chloroethylbenzene, 2-chloro-1, 1-diphenylethane, 2-chloro-1, 1, 1-triphenylethane, 1, 1-dichloroethane, 1, 1-dichloropropane, 2-dichloropropane, 1, 1-dichlorobutane, 2-dichlorobutane, 1, 2-dichlorobutane, 1, 1-dichloro-2-methylpropane, 1-dichloropentane, 2-dichloropentane, 1-dichloro-2, 2-dimethylpropane, 1-dichloro-2-methylbutane, 1-dichlorohexane, 2-dichlorohexane, 1-dichloro-2, 2-dimethylbutane, 1-dichloro-2, 3-dimethylbutane, 1-dichloro-2-methylpentane, 1-dichloro-3-methylpentane, 1-dichloro-4-methylpentane, 1-dichloroheptane, 2-dichloroheptane, 1-dichloro-2-methylhexane, 1, 1-dichloro-3-methylhexane, 1-dichloro-4-methylhexane, 1-dichloro-5-methylhexane, 1-dichloro-2, 2-methylpentane, 1-dichlorooctane, 2-dichlorooctane, 1-dichloro-2-methylheptane, 1-dichloro-3-methylheptane, 1-dichloro-4-methylheptane, 1-dichloro-5-methylheptane, 1-dichloro-6-methylheptane, 1-dichloro-2, 2-dimethylhexane, 1-dichlorononane, 2-dichlorononane, 1-dichloro-2-methyloctane, 1-dichloro-2-methylheptane, 1-dichloro-4, 1, 1-dichlorodecane, 2-dichlorodecane, α -dichlorotoluene, 2-dichloroethylbenzene, 2-dichloro-1, 1-diphenylethane, 2-dichloro-1, 1, 1-triphenylethane, 1,1, 1-trichloroethane, 1,1, 1-trichloropropane, 1,1, 1-trichlorobutane, 1,1, 1-trichloro-2-methylpropane, 1,1, 1-trichloropentane, 1,1, 1-trichloro-2, 2-dimethylpropane, 1,1, 1-trichloro-2-methylbutane, 1,1, 1-trichloro-3-methylbutane, 1,1, 1-trichlorohexane, 1,1, 1-trichloro-2, 2-dimethylbutane, 1,1, 1-trichloro-3, 3-dimethylbutane, 1,1, 1-trichloro-2-methylpentane, 1,1, 1-trichloroheptane, 1,1, 1-trichloro-2-methylhexane, 1, 1-trichloro-3-methylhexane, 1,1, 1-trichloro-4-methylhexane, 1,1, 1-trichloro-5-methylhexane, 1,1, 1-trichlorooctane, 1,1, 1-trichlorononane, 1,1, 1-trichloro-2-methyloctane, 1,1, 1-trichloro-3-methyloctane, 1,1, 1-trichlorodecane, 1,1, 1-trichloro-2-methylnonane, 1,1, 1-trichloro, At least one of α, α, α -trichloromethylcyclohexane, α, α, α -trichlorotoluene, 2,2, 2-trichloroethylbenzene, 2,2, 2-trichloro-1, 1-diphenylethane and 2,2, 2-trichloro-1, 1, 1-triphenylethane.
19. The vanadium-based catalyst according to claim 1, wherein,
when the composite additive is at least two of an additive C1, an additive C2 and an additive C3, the molar ratio of C1 to C2 is 0.001-500: 1; the molar ratio of C2 to C3 is 0.1-1750: 1; the molar ratio of C1 to C3 is 0.005-6: 1;
when the composite additive is at least three of an additive C1, an additive C2, an additive C3 and an additive C4, the proportion of the C4 to any one of the other three components is 0.001-2000: 1.
20. the vanadium-based catalyst according to claim 19, wherein when the composite additive is at least two of additive C1, additive C2 and additive C3, the molar ratio of C1 to C2 is 0.002 to 300: 1; the molar ratio of C2 to C3 is 0.2-600: 1; the molar ratio of C1 to C3 is 0.006-5: 1.
21. the vanadium-based catalyst according to claim 20, wherein when the composite additive is at least two of additive C1, additive C2 and additive C3, the molar ratio of C1 to C2 is 0.003-120: 1; the molar ratio of C2 to C3 is 0.5-320: 1; the molar ratio of C1 to C3 is 0.008-4: 1.
22. the vanadium-based catalyst according to claim 19, wherein when the composite additive is at least three of an additive C1, an additive C2, an additive C3 and an additive C4, the proportions of C4 and any of the other three components are each 0.003 to 800: 1.
23. the vanadium-based catalyst according to claim 22, wherein when the composite additive is at least three of an additive C1, an additive C2, an additive C3 and an additive C4, the proportions of C4 and any of the other three components are each 0.005 to 400: 1.
24. a process for the preparation of an olefin polymer using a vanadium-based catalyst according to any one of claims 1 to 23, wherein the components are added during the polymerisation in one of the following ways:
(1) mixing the component A with a monomer and a reaction medium, then mixing with the component C, and then mixing with the component B;
(2) mixing the component C with a monomer and a reaction medium, then mixing with the component A, and then mixing with the component B;
(3) mixing the component A and the component C, then mixing the component A and the component C with a monomer and a reaction medium, and then mixing the component A and the component C with the component B;
(4) mixing the component B with a monomer and a reaction medium, and further mixing with a mixture of the component A and the component C;
(5) component A, B is mixed with component C, and then the mixture of A, B and component C is further mixed with monomer and reaction medium;
(6) component A, C is mixed with component B, and then the mixture of A, B and component C is further mixed with monomer and reaction medium;
(7) components A, B and C are mixed with the monomer and the reaction medium simultaneously;
(8) the catalyst components are mixed with the alpha-olefin monomer in any of the above manners and then mixed with the ethylene monomer.
Optionally, component D is added to the reaction system described above.
25. The method of claim 24 wherein component C is added as a solution and the solvent used is C3～C10Saturated alkane of (C)3～C10Cycloalkane of C6～C10At least one of the aromatic hydrocarbons of (1).
26. The method of claim 25, wherein the solvent is selected from at least one of n-butane, n-pentane, cyclopentane, n-hexane, cyclohexane, methylcyclopentane, methylcyclohexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, toluene, and xylene.
27. The method of claim 24, wherein the concentration of monomer is 30-150 g/L; the molar ratio of the component A to the monomer is 1.0 multiplied by 10 in terms of the element V-5～5.0×10-4：1。
28. The method of claim 27, wherein the monomer concentration is 35g/L to 120 g/L.
29. The method of claim 28, wherein the concentration of the monomer is 45g/L to 100 g/L.
30. The process of claim 27 wherein the molar ratio of component a to monomer, expressed as V, is 3.0 x 10-5～4.0×10-4：1。
31. The process of claim 30 wherein the molar ratio of component A to monomer, expressed as elemental V, is 5.0 x 10-5～3.0×10-4：1。
32. The process of claim 24 wherein the monomer is ethylene and/or an alpha-olefin, ethylene and a diene, or ethylene with an alpha-olefin and a non-conjugated diene.
33. The process of claim 24, wherein the polymerization reaction has an onset temperature of-60 to 55 ℃; the pressure of the polymerization reaction is 0.01MPa to 3 MPa; the time of the polymerization reaction is 1 minute to 2 hours.
34. The process of claim 33, wherein the polymerization reaction has an onset temperature of-55 to 50 ℃; the pressure of the polymerization reaction is 0.05 MPa-2 MPa; the time of the polymerization reaction is 2 minutes to 1.5 hours.
35. The process of claim 34, wherein the polymerization reaction has an onset temperature of-50 to 45 ℃; the pressure of the polymerization reaction is 0.1MPa to 1 MPa; the time of the polymerization reaction is 2.5 minutes to 1.2 hours.
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