CN106977633B - A kind of vanadium-based catalyst systems for olefinic polymerization - Google Patents

A kind of vanadium-based catalyst systems for olefinic polymerization Download PDF

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CN106977633B
CN106977633B CN201610030967.3A CN201610030967A CN106977633B CN 106977633 B CN106977633 B CN 106977633B CN 201610030967 A CN201610030967 A CN 201610030967A CN 106977633 B CN106977633 B CN 106977633B
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chloro
tri
aluminium
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methyl
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CN106977633A (en
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吴一弦
张志乾
张树
何兰霞
张腾
王云杰
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Changzhou Hanwei polymer Co.,Ltd.
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Beijing Spark Technology Co Ltd
Beijing University of Chemical Technology
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    • 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
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • 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

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Abstract

Containing vfanadium compound major catalyst, organo-aluminum compound co-catalyst and contain carbon-halogen chemical bond compound regulator the present invention relates to a kind of vanadium-based catalyst systems for olefinic polymerization, in catalyst system.The vanadium-based catalyst systems being copolymerized for alkene homopolymerization and ethylene and other alkene or alkadienes, the vanadium-based catalyst systems have high catalytic activity, catalyst amount can be reduced, and random sequence distribution content improves in prepared copolymer, comonomer insertion rate significantly improves.

Description

A kind of vanadium-based catalyst systems for olefinic polymerization
Technical field
The present invention relates to a kind of vanadium-based catalyst systems for olefinic polymerization, and in particular to for ethylene and other alkene Or/or alkadienes copolymerization vanadium-based catalyst systems.The vanadium-based catalyst systems have high catalytic activity, can reduce catalysis Agent dosage, and random sequence distribution content improves in prepared copolymer, comonomer insertion rate improves, comonomer utilization rate It improves.
Background technique
Polyolefin is most important product in synthetic resin, such as polyethylene, polypropylene, polybutene and its copolymer.Second The copolymer of alkene and at least one alpha-olefin and/or alkadienes is contained from crystal type resin to unformed elastomer, is had only Special performance, makes it have various uses.For example, ethylene and a certain amount of butylene, hexene or octene copolymer, can prepare linear low Density polyethylene or thermoplastic elastomer product；Ethylene and propylene are copolymerized, and can prepare rubber product.
In ethylene and alpha-olefin copolymer, usual alpha-olefin copolymer low efficiency.If improving in ethylene and alpha olefin copolymer Alpha-olefin content needs the extraordinary catalyst using restriction geometry, or needs to be added a large amount of 'alpha '-olefin monomers, causes Increased production cost, and alpha-olefin utilization rate reduces, and recycling load increases.In particular, being prepared using Ziegler-Natta catalyst Ethylene and alpha olefin copolymer in, the content of random sequence distribution is on the low side, influences production process and product quality.With ethylene with For propylene copolymer EP rubbers, EP rubbers is one of seven big general purpose synthetic rubber kinds, including ethylene and third in the world (such as ice drops to bipolymer and ethylene, the propylene and Third monomer of alkene in dicyclopentadiene, 1,4- hexadiene, 5- ethylidene -2- Piece alkene or 5- vinyl -2- norbornene) terpolymer.EP rubbers has excellent elastic, resistance to ozone, heat-resisting, resistance to Time and ageing-resistant performance etc., can be widely used for automobile component, building water-proof material, electric wire and cable jacket, heat-resistant rubber hose, glue Band, automotive sealant and other products etc..Currently, EP rubbers industrialized producing technology mainly has polymerisation in solution and suspends poly- It closes, wherein solution polymerization process is that the leading technology of EP rubbers is produced in the world today (referring to Xu Yibing, synthetic rubber work Industry, 2011,34 (4): 324-327).In EP rubbers polymer composition, the content of ethylene and propylene can be wider at one Proportional region in variation, it is considered that, when ethylene contents are within the scope of 20~80mol%, polymer have General Purpose Rubber Elasticity (referring to Tang Bin, " EP rubbers application technology ", Chemical Industry Press, 2005).The performance of EP rubbers not only takes Certainly in the composition of copolymer, molecular weight and molecular weight distribution, and it is distributed dependent on the sequence of copolymer, comonomer structure list The random sequence distribution content of member increases, the elasticity of copolymer is better, can be used as excellent elastic material and uses (referring to H.F Mark,Ethylene propylene elastomers,《Encyclopedia of Polymer Science and Technology ", John Wiley&Sons, Inc.2007,178-195).If EP rubbers strand methylene number reaches When to 8 or more, longer regular methylene segment can lead to crystallization, generates microgel, influences EP rubbers and normally produce, and drop The elasticity and physical mechanical property of low EP rubbers are (referring to D.R.Burfiled, Macromolecules, 1987,20:3020- 3023).Therefore, improve EP rubbers in structural unit random sequence distribution content, to improve EP rubbers elasticity and Physical mechanical property is of great significance.
Catalyst is the principal element for influencing structural unit sequence distribution in ethylene copolymer activity and copolymer, and is adjusted The important means of molecular weight of copolymer and composition.The production of EP rubbers generallys use ziegler-nata at present and metallocene is The solution polymerization process of catalyst, wherein using ziegler-nata catalytic component based on vanadium, (such as: major catalyst is helped and is urged for vanadium oxytrichloride Agent is ethylaluminum sesquichloride) production capacity account for about the 70% of aggregated capacity.Pentavalent vanadium in major catalyst is acted in co-catalyst Under be reduced into trivalent vanadium, trivalent vanadium be typically considered catalytic polymerization activated centre (referring to H.Hagen, J.Boersma,G.van Koten,Chem.Soc.Rev.,2002,31:357–364.).Although the neat lattice of current industrial application Le-Natta catalytic component based on vanadium comparative maturity, but that there is also catalyst activities is lower, catalyst amount is larger and needs The problem of massive laundering is washed.In order to further increase catalytic component based on vanadium activity, in the prior art by the way that following kind of work is added Agent: (1) halogen-containing organic acid ester compound, such as ethyl trichloroacetate, 2,3,4,4- tetra- chloro- 3-butenoic acid butyl esters, two Chlorophenylacetic acid ethyl ester or perchloro- crotonic acid N-butyl (referring to: CN 1099395A, CN 101092466A and CN 116514A)；(2) halogen-containing hydrocarbon compound, such as chloromethanes, methylene chloride, chloroform, trichlorofluoromethane, 1,3,3,3- tetrachloros Propylbenzene, perchloro- propylene, hexachlorobutadiene are (referring to CN 1099395A, CN 85108910A, CN 104418964A and CN 103374088A)；(3) halogen-containing silane, as alkyltrichlorosilanes (referring to: CN 102718908A).In above-mentioned polymerization process In, the activator generates chlorine radical, and the bivalent vanadium of inactivation is oxidized to active trivalent vanadium, improves catalytic activity (referring to: H.Hagen, J.Boersma, G.van Koten, Chem.Soc.Rev., 2002,31:357-364.). CN103923235A discloses a kind of vanadium series catalyst being mixed to get by major catalyst and co-catalyst, wherein major catalyst by The compound or complex of vanadium and electron donor form, electron donor be mononuclear aromatics class compound, acrylic ester compound, The ether or alcohol compound (literary Chinese style I-III) of methyl acrylic ester compound or the specific structure being halogen-free, co-catalysis Agent includes organo-aluminum compound and accelerative activator, and pentavalent vanadium plays main catalytic action, electron in the vanadium series catalyst Body plays stabilizing active center, promotes reactivity, the random copolymerization ability of enhancing ethylene and propylene and reduce ethylene-propylene-diene monomer The generation of glue gel in the course of the polymerization process, but under same polymerizing condition, propylene content is only in ethylene-propylene copolymer obtained It is slightly higher.
Therefore, on the basis of the ziegler-nata catalytic component based on vanadium largely used at present, it is further improved activated centre property Matter adapts to olefin polymerization while improving its catalytic activity, and reaches and improve alpha-olefin and/or alkadienes participation altogether The content of poly- probability and copolymer molecule chain random sequence distribution, further improves properties of product, in field of scientific study and It is all extremely important in industrial application.
Summary of the invention
The object of the present invention is to provide a kind of Ziegler-Natta type vanadium-based catalyst systems for olefinic polymerization, have High catalytic activity, and improved in ethylene and alpha-olefin, ethylene and alkadienes or the copolymerization of ethylene and alpha-olefin and/or alkadienes The content of random sequence distribution in the copolymerization efficiency of alpha-olefin or alkadienes, alpha-olefin or alkadienes utilization rate and copolymer.
Vanadium catalyst system provided by the invention contains major catalyst, co-catalyst and regulator.Wherein,
Major catalyst is vanadium oxytrichloride (VOCl3) or general formula be VOClnL3-nVfanadium compound, V is+5 valence vanadium in formula, and n is 0,1 or 2, preferably 2；L is phenol anion, preferably phenol anion or the alkyl or aryl substituent group containing 1~20 carbon atom Phenol anion, the position of substituent group can be ortho position, any position of meta or para position, the number of substituent group be 1~5 it is whole Number；More preferable phenol anion, 4- methylphenol anion, 2- methylphenol anion, 2,6- xylenol anion, 2, 6- di-tert-butyl-4-methy phenol anion or 2,4,6- tri-butyl-phenol anion.Above-mentioned vanadium may be selected in major catalyst Close one of object or a variety of mixtures.
Co-catalyst is organo-aluminum compound, selected from alkyl aluminum, alkyl aluminium halide, alkylaluminoxane or their mixing Object.The general formula of the alkyl aluminum or alkyl aluminium halide is RmAlX3-m, wherein R contains 1~10 carbon to be same or different The alkyl or cycloalkyl of atom or their isomers, X are halogen, preferably Cl or Br, m 1,1.5,2 or 3, preferably 1 or 1.5. The preferred trimethyl aluminium of the alkyl aluminum, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, triisobutyl One or more of aluminium, three n-pentyl aluminium, tri-n-hexyl aluminum, thricyclohexyl aluminium；The alkyl aluminium halide preferably is selected from a chlorine Dimethyl aluminium, aluminium diethyl monochloride, a chlorine di-n-butyl aluminium, a chloro-di-isobutyl aluminum, dichloromethyl aluminium, ethyl aluminum dichloride, two Chloro-n-butyl aluminium, dichloro aluminium isobutyl, sesquialter methyl chloride aluminium, sesquialter ethylmercury chloride aluminium, sesquialter n-butylmagnesium chloride aluminium, sesquialter are different One of butyl aluminium chloride is a variety of；The alkylaluminoxane preferably is selected from methylaluminoxane, ethylaluminoxane, aluminium isobutyl One or more of oxygen alkane, the alkyl in the commercialized alkylaluminoxane usually also containing a certain amount of (such as~20%) Aluminium.
Impurity content in co-catalyst dosage and system, major catalyst dosage, monomer dosage, polymerizate molecular weight and The factors such as molecular weight distribution are related.In general, improving co-catalyst dosage in polymerization system in a certain range, polymerization can be improved Activity, co-catalyst is very few, and the number for generating activated centre is few, and catalytic activity is low, and monomer polymerization conversion ratio is low.But co-catalyst Amount is excessive, and major catalyst on the one hand can be made by over reduction, influence monomer conversion, on the other hand cause chain-transferring agent serious, Polymer molecular weight decline.In addition, co-catalysis dosage is excessive, the raising of catalyst cost is also resulted in.
The molar ratio (abbreviation Al/V ratio) of co-catalyst and major catalyst be 8~150, preferably 10~120, more preferable 12~ 110。
Regulator is to contain carbon-halogen chemical bond compound, general formula R1CX3、R2R3CX2、R4R5R6CX or R7OH, Wherein X is halogen；R1~R6Group is selected from alkyl, the naphthenic base, aromatic radical that carbon atom number is 1~20, R2With R3Group or R4、R5 With R6Group may be the same or different；R7Group be selected from halogen replace carbon atom number be 1~20 alkyl, naphthenic base, Aromatic radical.Regulator can interact with catalytic component, adjust catalytic active center and characteristic electron, catalysis can be improved Activity increases random sequence distribution content in the probability and raising copolymer of 'alpha '-olefin monomers participation copolymerization.
The regulator can be selected from one of following compound or their mixture: n-propyl chloride, 2 cbloropropane isopropyl chloride, 1-chlorobutane, Sec-Butyl Chloride, 1- chloro-2-methyl propane, 2- chloro-2-methyl propane, 1-chloropentane, 2- chloropentane, the chloro- 2- first of 1- The chloro- 3- methyl-butan of base-butane, 1-, the chloro- 2,2- dimethylpropane of 1-, 2- chloro-2-methyl-butane, 1- chlorohexane, 2- chlorine oneself Alkane, 1- chloro-2-methyl-pentane, the chloro- 3- methyl-pentane of 1-, the chloro- 4- methyl-pentane of 1-, 2- chloro-2-methyl-pentane, 3- are chloro- The chloro- 2- ethyl-butane of 3- methyl-pentane, 1-, the chloro- 2,2- dimethylbutane of 1-, 1- chloroheptane, 2- chloroheptane, the chloro- 2- first of 1- Base-hexane, 2- chloro-2-methyl-hexane, the chloro- 3- methyl-hexane of 3-, the chloro- 2,2- dimethyl pentane of 1-, 1- chloro-octane, 2- chlorine are pungent Alkane, 1- chloro-2-methyl-heptane, 2- chloro-2-methyl-heptane, the chloro- 3- methyl-heptan of 3-, the chloro- 4- methyl-heptan of 4-, 1- are chloro- The chloro- 3- methyl-octane of 2,2- dimethylhexane, 1- chlorononane, 2- chlorononane, 1- chloro-2-methyl-octane, 1-, the chloro- 4- first of 1- The chloro- 2,2- dimethyl heptane of base-octane, 1-, 1- chlorodecane, 2- chlorodecane, the chloro- 2,2- diphenyl propane of 1-, cumyl chlorine, α-chlorine Toluene, 2- chloroethyl benzene, the chloro- 1,1- diphenylethane of 2-, the chloro- 1,1,1- triphenylethane of 2-, 1,1- dichloroethanes, 1,1- bis- Chloropropane, 2,2- dichloropropane, 1,1- dichloroetane, 2,2- dichloroetane, the chloro- 2- methylpropane of 1,1- bis-, 1,1- dichloro penta Alkane, 2,2- dichloropentane, the chloro- 2,2- dimethylpropane of 1,1- bis-, the chloro- 2- methybutane of 1,1- bis-, 1,1- dichloro hexane, 2,2- Dichloro hexane, the chloro- 2,2- dimethylbutane of 1,1- bis-, the chloro- 2,3- dimethylbutane of 1,1- bis-, the chloro- 2- methylpentane of 1,1- bis-, The chloro- 3- methylpentane of 1,1- bis-, the chloro- 4- methylpentane of 1,1- bis-, bis- chloroheptane of 1,1-, bis- chloroheptane of 2,2-, the chloro- 2- of 1,1- bis- Methyl hexane, the chloro- 3- methyl hexane of 1,1- bis-, the chloro- 4- methyl hexane of 1,1- bis-, the chloro- 5- methyl hexane of 1,1- bis-, 1,1- bis- Chloro- 2,2- methylpentane, bis- chloro-octane of 1,1-, bis- chloro-octane of 2,2-, the chloro- 2- methyl heptane of 1,1- bis-, the chloro- 3- methyl of 1,1- bis- Heptane, the chloro- 4- methyl heptane of 1,1- bis-, the chloro- 5- methyl heptane of 1,1- bis-, the chloro- 6- methyl heptane of 1,1- bis-, 1,1- bis- chloro- 2, 2- dimethylhexane, bis- chlorononane of 1,1-, bis- chlorononane of 2,2-, the chloro- 2- methyloctane of 1,1- bis-, bis- chlorodecane of 1,1-, 2,2- Two chlorodecanes, alpha, alpha dichlorotoluene, 2,2- styrenedichloridea, the chloro- 1,1- diphenylethane of 2,2- bis-, the chloro- 1,1,1- of 2,2- bis- Triphenylethane, 1,1,1- trichloroethanes, 1,1,1- trichloropropane, tri- chlorobutane of 1,1,1-, the chloro- 2- methyl-prop of 1,1,1- tri- Alkane, tri- chloropentane of 1,1,1-, the chloro- 2,2- dimethylpropane of 1,1,1- tri-, the chloro- 2- methybutane of 1,1,1- tri-, 1,1,1- tri- are chloro- 3- methybutane, 1,1,1- genklene, the chloro- 2,2- dimethylbutane of 1,1,1- tri-, the chloro- 3,3- dimethyl butyrate of 1,1,1- tri- Alkane, the chloro- 2- methylpentane of 1,1,1- tri-, tri- chloroheptane of 1,1,1-, the chloro- 2- methyl hexane of 1,1,1- tri-, the chloro- 3- first of 1,1,1- tri- Base hexane, the chloro- 4- methyl hexane of 1,1,1- tri-, the chloro- 5- methyl hexane of 1,1,1- tri-, tri- chloro-octane of 1,1,1-, 1,1,1- trichlorine Nonane, the chloro- 2- methyloctane of 1,1,1- tri-, the chloro- 3- methyloctane of 1,1,1- tri-, 1,1,1- trichlorodecane, the chloro- 2- of 1,1,1- tri- Methylnonane, α, α, α-trichloromethylcyclohex alkane, α, α, α-benzotrichloride, 2,2,2- trichloroethyl benzene, the chloro- 1,1- of 2,2,2- tri- Diphenylethane, the chloro- 1,1,1- triphenylethane of 2,2,2- tri-, the chloro- 1- ethyl alcohol of 2-, the chloro- 2- propyl alcohol of 1-, 1- chloro-2-methyl -2- Propyl alcohol, trimethylene chlorohydrin, 2- trimethylewne chlorohydrin 3-, 2- chloro-2-methyl -1- propyl alcohol, the chloro- 2- butanol of 1-, 1- chloro-2-methyl -2- fourth The chloro- n-butyl alcohol of alcohol, 2-, 2- chloro-2-methyl-n-butyl alcohol, the chloro- n-butyl alcohol of 3-, the chloro- 3- methyl-1-butanol of 3-, the chloro- 2- amylalcohol of 1-, 1- chloro-2-methyl -2- amylalcohol, the chloro- 1- amylalcohol of 3-, the chloro- 3- methyl-1-pentene alcohol of 3-, the chloro- 1- amylalcohol of 2-, the chloro- 2- hexanol of 1-, 1- The chloro- 1- hexanol of chloro-2-methyl -2- hexanol, 3-, the chloro- 1- hexanol of 2-, the chloro- 2- enanthol of 1-, 1- chloro-2-methyl -2- enanthol, 3- are chloro- The chloro- 1-heptanol of 1-heptanol, 2-, the chloro- sec-n-octyl alcohol of 1-, 1- chloro-2-methyl-sec-n-octyl alcohol, the chloro- 1- octanol of 3-, the chloro- 1- octanol of 2-, 1- Chloro- 2- nonyl alcohol, 1- chloro-2-methyl -2- nonyl alcohol, the chloro- 2- decyl alcohol of 1-, 1- chloro-2-methyl -2- decyl alcohol, 2- chloromethylcyclohex alcohol, 3- Chloromethylcyclohex alcohol, the chloro- 1- ethyl alcohol of 2,2- bis-, the chloro- 2- propyl alcohol of 1,1- bis-, bis- chloro-2-methyl-2-propanol of 1,1-, 3,3- bis- are chloro- 1- propyl alcohol, bis- trimethylewne chlorohydrin 3- of 2,2-, the chloro- 2- butanol of 1,1- bis-, the chloro- n-butyl alcohol of 3,3- bis-, the chloro- n-butyl alcohol of 2,2- bis-, 1,1- bis- Chloro- 2- amylalcohol, the chloro- 1- amylalcohol of 2,2- bis-, the chloro- 2- hexanol of 1,1- bis-, the chloro- 1- hexanol of 2,2- bis-, 2- dichloromethyl cyclohexanol, 2, The chloro- 1- ethyl alcohol of 2,2- tri-, tri- trimethylewne chlorohydrin 3- of 3,3,3-, 1,1,1- trichloro-2-propanol, tri- chloro-2-methyl-2-propanol of 1,1,1-, The chloro- 2- butanol of 1,1,1- tri-, tri- chloro-2-methyl -2- butanol of 1,1,1-, the chloro- 2- amylalcohol of 1,1,1- tri-, the chloro- 2- first of 1,1,1- tri- Base -2- amylalcohol, the chloro- 2- hexanol of 1,1,1- tri-, tri- chloro-2-methyl -2- hexanol of 1,1,1-, the chloro- 2- enanthol of 1,1,1- tri-, 1,1,1- Three chloro-2-methyl -2- enanthol, the chloro- sec-n-octyl alcohol of 1,1,1- tri-, tri- chloro-2-methyls of 1,1,1--sec-n-octyl alcohol, the chloro- 2- nonyl of 1,1,1- tri- Alcohol, the chloro- 2- decyl alcohol of 1,1,1- tri-, 2- chlorobenzyl alcohol, the chloro- 1- o-tolyl ethyl alcohol of 2,2,2- tri-, 2- trichloromethyl -4- bromobenzyl alcohol.
The regulator preferably is selected from one of following compound or their mixture: 2 cbloropropane isopropyl chloride, Sec-Butyl Chloride, 2- Chloro- 2 methylpropane, 2- chloropentane, 2- chloro-2-methyl-butane, 2- chlorohexane, 2- chloro-2-methyl-pentane, the chloro- 3- methyl-of 3- Pentane, cumyl chlorine, alpha-chlorotoluene, 2- chloroethyl benzene, 1,1- dichloroethanes, 1,1- dichloropropane, 2,2- dichloropropane, 1,1- bis- Chlorobutane, 2,2- dichloroetane, the chloro- 2- methylpropane of 1,1- bis-, the chloro- 2,2- dimethylpropane of 1,1- bis-, the chloro- 2- first of 1,1- bis- Base butane, 1,1,1- trichloroethanes, 1,1,1- trichloropropane, tri- chlorobutane of 1,1,1-, the chloro- 2- methylpropane of 1,1,1- tri-, 1, Tri- chloropentane of 1,1-, the chloro- 2,2- dimethylpropane of 1,1,1- tri-, the chloro- 2- methybutane of 1,1,1- tri-, the chloro- 3- first of 1,1,1- tri- Base butane, 1,1,1- genklene, the chloro- 2,2- dimethylbutane of 1,1,1- tri-, the chloro- 3,3- dimethylbutane of 1,1,1- tri-, 1, The chloro- 2- methylpentane of 1,1- tri-, α, the chloro- 1- ethyl alcohol of α, α-trichloromethylcyclohex alkane, 2-, the chloro- 2- propyl alcohol of 1-, 1- chloro-2-methyl- 2- propyl alcohol, trimethylene chlorohydrin, 2- trimethylewne chlorohydrin 3-, 2- chloro-2-methyl -1- propyl alcohol, the chloro- 2- butanol of 1-, 1- chloro-2-methyl -2- The chloro- n-butyl alcohol of butanol, 2-, 2- chloro-2-methyl-n-butyl alcohol, the chloro- 2- amylalcohol of 1-, 1- chloro-2-methyl -2- amylalcohol, the chloro- 1- penta of 2- The chloro- 2- hexanol of alcohol, 1-, 1- chloro-2-methyl -2- hexanol, the chloro- 1- hexanol of 2-, the chloro- 2- enanthol of 1-, 1- chloro-2-methyl -2- enanthol, The chloro- 1-heptanol of 2-, the chloro- sec-n-octyl alcohol of 1-, 1- chloro-2-methyl-sec-n-octyl alcohol, the chloro- 1- octanol of 2-, 2- chloromethylcyclohex alcohol, 2,2- bis- Chloro- 1- ethyl alcohol, the chloro- 2- propyl alcohol of 1,1- bis-, bis- chloro-2-methyl-2-propanol of 1,1-, bis- trimethylewne chlorohydrin 3- of 2,2-, the chloro- 2- of 1,1- bis- Butanol, the chloro- n-butyl alcohol of 2,2- bis-, the chloro- 2- amylalcohol of 1,1- bis-, the chloro- 1- amylalcohol of 2,2- bis-, the chloro- 2- hexanol of 1,1- bis-, 2,2- bis- Chloro- 1- hexanol, 2- dichloromethyl cyclohexanol, the chloro- 1- ethyl alcohol of 2,2,2- tri-, tri- trimethylewne chlorohydrin 3- of 3,3,3-, the chloro- 2- of 1,1,1- tri- Propyl alcohol, tri- chloro-2-methyl-2-propanol of 1,1,1-, the chloro- 2- butanol of 1,1,1- tri-, tri- chloro-2-methyl -2- butanol of 1,1,1-, 1,1, The chloro- 2- amylalcohol of 1- tri-, tri- chloro-2-methyl -2- amylalcohol of 1,1,1-, the chloro- 2- hexanol of 1,1,1- tri-, tri- chloro-2-methyl -2- of 1,1,1- Hexanol, the chloro- 2- enanthol of 1,1,1- tri-, tri- chloro-2-methyl -2- enanthol of 1,1,1-, the chloro- sec-n-octyl alcohol of 1,1,1- tri-, 1,1,1- tri- are chloro- 2- methyl-sec-n-octyl alcohol, 2- chlorobenzyl alcohol, the chloro- 1- o-tolyl ethyl alcohol of 2,2,2- tri-, 2- trichloromethyl -4- bromobenzyl alcohol.
The regulator is more preferably from one of following compound or their mixture: 2 cbloropropane isopropyl chloride, Sec-Butyl Chloride, Chloro- 2 methylpropane of 2-, 2- chloropentane, 2- chloro-2-methyl-butane, cumyl chlorine, 2- chloroethyl benzene, 1,1- dichloroethanes, 1,1- Dichloropropane, 2,2- dichloropropane, 1,1- dichloroetane, 2,2- dichloroetane, the chloro- 2- methylpropane of 1,1- bis-, 1,1- bis- are chloro- 2,2- dimethylpropane, the chloro- 2- methybutane of 1,1- bis-, 1,1,1- trichloroethanes, 1,1,1- trichloropropane, tri- neoprene of 1,1,1- Alkane, the chloro- 2- methylpropane of 1,1,1- tri-, tri- chloropentane of 1,1,1-, the chloro- 2,2- dimethylpropane of 1,1,1- tri-, 1,1,1- tri- are chloro- 2- methybutane, the chloro- 3- methybutane of 1,1,1- tri-, the chloro- 1- ethyl alcohol of 2-, the chloro- 2- propyl alcohol of 1-, 1- chloro-2-methyl-2-propanol, Trimethylene chlorohydrin, 2- trimethylewne chlorohydrin 3-, 2- chloro-2-methyl -1- propyl alcohol, the chloro- 2- butanol of 1-, 1- chloro-2-methyl -2- butanol, 2- Chloro- n-butyl alcohol, 2- chloro-2-methyl-n-butyl alcohol, 2- chloromethylcyclohex alcohol, the chloro- 1- ethyl alcohol of 2,2- bis-, the chloro- 2- propyl alcohol of 1,1- bis-, Bis- chloro-2-methyl-2-propanol of 1,1-, bis- trimethylewne chlorohydrin 3- of 2,2-, the chloro- 2- butanol of 1,1- bis-, the chloro- n-butyl alcohol of 2,2- bis-, 2- dichloro Methyl cyclohexanol, the chloro- 1- ethyl alcohol of 2,2,2- tri-, tri- trimethylewne chlorohydrin 3- of 3,3,3-, 1,1,1- trichloro-2-propanol, 1,1,1- tri- are chloro- 2- methyl-2-propanol, the chloro- 2- butanol of 1,1,1- tri-, tri- chloro-2-methyl -2- butanol of 1,1,1-, 2- chlorobenzyl alcohol, 2,2,2- tri- are chloro- 1- o-tolyl ethyl alcohol, 2- trichloromethyl -4- bromobenzyl alcohol.
In general, increasing regulator dosage in polymerization system, it can play and improve polymerization activity, improve alpha-olefin or two Olefin-copolymerization efficiency reduces polymer gel content and improves the effect of copolymer random distribution content.If regulator dosage is too It is few, it is not enough to have an effect with catalyst, then effect of the invention is not achieved；If regulating dosage is excessive, increase catalyst at This.Therefore, it is necessary for suitable regulator being added in the present invention.
The molar ratio of regulator and major catalyst is 0.4~35, preferably 0.5~28 in catalyst system of the present invention, more Preferably 0.8~22.
The regulator, which can be, is separately added into polymerization system with catalyst components, or with main catalyst component or help Polymerization system is added after mixing respectively in catalyst.Condensate is added after mixing according to regulator with major catalyst or co-catalyst The mode of system, then low temperature is more advantageous, but temperature is too low, and energy consumption is high.Mixing temperature be chosen as -40 DEG C~29 DEG C, preferably -20 DEG C ~25 DEG C, more preferably -5 DEG C~20 DEG C；Incorporation time is chosen as 2 seconds~19 minutes, and preferably 5 seconds~17 minutes, more preferably 10 seconds~15 minutes.Incorporation time is short, is conducive to improve production efficiency.
Catalytic component based on vanadium provided by the invention can be used for ethylene and alpha-olefin and/or alkadienes is copolymerized, and polymerize implementation method Including bulk polymerization, polymerisation in solution or slurry polymerization, batch process can be, be also possible to continuous process.Monomer can be primary It feeds intake or continuous dosing.Major catalyst and monomer mole ratio (abbreviation V/M ratio) are 9.5 × 10-5~8.5 × 10-2, preferably 8.5 ×10-5~9.5 × 10-2, more preferable 7.5 × 10-5~1.1 × 10-3。
The alkene is selected from ethylene, propylene, 1- butylene, isobutene, 1- amylene, 1- hexene, 1- heptene, 1- octene, the 1- last of the ten Heavenly stems Alkene, 1- hendecene, 1- laurylene, 1- tridecylene, 1-tetradecylene, ten pentaene of 1-, 1- hexadecylene, norbornene, cyclopentene, hexamethylene Alkene, cyclopentadiene, 1,3- cyclohexadiene, 1,4- cyclohexadiene, 5- ethylidene -2- norbornene, 5- vinyl -2- norborneol Alkene, dicyclopentadiene, 1,4- hexadiene, 2- methyl-1,4- hexadiene and 1,6- octadiene；Optimal ethylene, propylene, 1- butylene, Isobutene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- decene, 1- hendecene, 1- laurylene, 1- tridecylene, norborneol Alkene, cyclopentene, cyclohexene, cyclopentadiene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, dicyclopentadiene With 1,6- octadiene；More preferable ethylene, propylene, 1- butylene, isobutene, 1- amylene, 1- hexene, 1- heptene, 1- octene, the 1- last of the ten Heavenly stems Alkene, norbornene, cyclopentene, cyclohexene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, dicyclopentadiene With 1,6- octadiene.
The molar ratio of ethylene and alpha-olefin and/or alkadienes is according to ethylene contents or copolymerization in target product in copolyreaction Depending on composition.The range of the molar ratio of alpha-olefin and vinyl monomer is 1~5, preferably 1.5~4.5 in copolyreaction of the present invention, More preferable 1.8~4.2；In copolyreaction the range of the molar ratio of alkadienes and ethylene be 0.01~0.20, preferably 0.02~ 0.15, more preferable 0.03~0.12.
Polymerisation in solution solvent for use is selected from the saturated alkane that carbon atom number is 3~9 or cycloalkane and aromatic hydrocarbon；It is preferred that fourth One of alkane, pentane, hexane, heptane, octane, hexamethylene, toluene, dimethylbenzene or a variety of compositions.The selection of solvent with Polymerization process condition, polymer molecular weight and molecular weight distribution are related.In general, may be selected to prepare heavy polymer It is not susceptible to the solvent of chain tra nsfer；In order to prepare low-molecular weight polymer, the solvent that chain tra nsfer easily occurs may be selected.Monomer concentration Excessively high, it is excessive to will lead to system viscosity, influences production process.Monomer concentration is too low, and solvent usage is caused to increase, and increases cost. In the present invention, suitable monomer concentration is necessary, and the range of monomer concentration [M] is 30g/L~150g/L, preferably 35g/L ~120g/L, more preferably 45g/L~100g/L.The initial temperature of polymerization reaction be -60~60 DEG C, preferably -55~50 DEG C, More preferably -50~40 DEG C.
Polymerization reaction can carry out adiabatic polymerisation or constant temperature polymerization.
Polymerization reaction time is 3 minutes~48 hours, preferably 5 minutes~36 hours, more preferably 8 minutes~24 hours.
Polymerization pressure is 0.01Mpa~3Mpa, preferably 0.05Mpa~2Mpa, more preferably 0.1Mpa~1Mpa.
After the polymerization reaction, polymer solution is added in the ethanol solution that hydrochloric acid mass concentration is 5%, warp Polymerizate is obtained after filtering, ethanol washing, drying to constant weight, measures polymerisation conversion.It is red that Fourier is carried out to polymerizate External spectrum, Nuclear Magnetic Resonance, differential scanning calorimetry instrument test obtain in copolymer copolymerization composition (referring to ASTM-D3900-95 And David R.Burfield, Macromolecules, 1987,20:3020-3023) and sequence distribution content (random sequence point The content of cloth is expressed as the sum of the content of EPE, PEP, EEP and PPE sequence distribution, referring to: H.N.Cheng, Macromolecules,1984,17:1950-1955).Catalyst activity generates polymer meter with every mole of major catalyst (kg·(mol-1V))。
The polymerizate can be olefin homo, be also possible to ethylene and alpha-olefin and/or diene copolymer.? Alpha-olefin content is 5mol%~70mol% (7wt%~78wt%), preferably 10mol%~63mol% in copolymer (14wt%~72wt%), more preferable 13mol%~58mol% (18wt%~67wt%)；Diene content is 0.1mol% ~10mol% (0.4wt%~23wt%), preferably 0.3mol%~8mol% (1wt%~20wt%), more preferable 0.5mol% ~6mol% (1.5wt%~16wt%).Ethylene and alpha-olefin and/or diene can be improved using catalyst system of the invention The catalytic activity of hydrocarbon copolymerization has the function that alpha-olefin dosage in reduction monomer, reduces amplitude up to 23%, utilization efficiency mentions It is high；Catalyst amount is reduced, especially reduction co-catalyst dosage reduces production cost up to 54%；In ethylene and alpha-olefin And/or the conversion ratio and insertion rate of alpha-olefin and/or alkadienes can be improved in alkadienes copolymerization, reduce and has neither part nor lot in comonomer Yield, improve monomer utilization ratio, it is energy-saving, reduce loss；In addition, nothing in copolymer also can be improved in copolyreaction The content for advising sequence distribution improves product quality and properties of product, widens products application up to 10%.
Specific embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described below with reference to embodiment, still These descriptions are only further explanation the features and advantages of the present invention, rather than limiting to the claimed invention.
Embodiment 1
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=2.0) it is mixed with hexane, formation monomer solution ([M]= 57g/L).At -45 DEG C, it is added and contains VOCl3、EtAl1.5Cl1.5And the catalyst of 2- chloro-2-methyl propane (abbreviation TB), wherein V/M molar ratio is 5.1 × 10-4, Al/V molar ratio is that 20, TB/V molar ratio is 5.After ten minutes, quality point is added in polymerization reaction Number terminates reaction for 5% ethanol solution hydrochloride, and resulting polymers are dried under vacuum to constant weight at 40 DEG C, obtain ethylene-propylene Copolymer.Catalytic activity is 21kg (mol-1V), propylene content is 53mol% (63wt%) in copolymer, random sequence distribution Content is 67%.
Compared with comparative example 1, in obtaining copolymer in situation similar in propylene content, the dosage of propylene is reduced in monomer 23%, propylene utilization efficiency improves；Catalytic activity improves 50%, and major catalyst dosage (being indicated with V/M molar ratio) reduces 24%；Co-catalyst dosage (being indicated with Al/M molar ratio) reduces 49%；Random sequence distribution content increases in copolymer 4%.
Embodiment 2
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=2.1) it is mixed with hexane, formation monomer solution ([M]= 59g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2AlCl and 1, the catalyst of 1,1- trichloroethanes (abbreviation TC), In, V/M molar ratio is 2.5 × 10-4, Al/V molar ratio is that 15, TC/V molar ratio is 20.Polymerization reaction 10 minutes, terminate and after Processing mode obtains ethylene-propylene copolymer product with embodiment 1, and catalytic activity is 52kg (mol-1V), propylene in copolymer Content is 34mol% (46wt%), and random sequence distribution content is 55%.
Compared with comparative example 2, in obtaining copolymer in situation similar in propylene content, propylene content is reduced in monomer 16%, propylene utilization efficiency improves, and catalytic activity improves 27%；Co-catalyst dosage (being indicated with Al/M ratio) reduces 46%；Random sequence distribution content increases 6% in copolymer.
Embodiment 3
5- ethylidene -2- norbornene (ENB), propylene, vinyl monomer are pressed into certain mol proportion (ENB/C3/C2=0.1/ 4.2/1) it mixes, is formed monomer solution ([M]=50g/L) with hexane.At -45 DEG C, it is added and contains VOCl2(Me2C6H3O)、 EtAlCl2/Et2The catalyst of AlCl and TC, wherein V/M molar ratio is 6.1 × 10-4, Al/V molar ratio is 30, TC/V moles Than being 2.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene-ENB copolymerization product, be catalyzed Activity is 20kg (mol-1V), conversion of ethylene 97%, propylene conversion 20%, propylene content is in copolymer 45mol% (55wt%), ENB content are 4.4mol% (14wt%), and random sequence distribution content is 72%.
Compared with comparative example 3, under same polymeric condition, ethylene, propylene and ENB utilization efficiency are improved, catalysis Activity improves 33%；Propylene copolymerization insertion rate (content) improves 3mol%, and ENB copolymerization insertion rate (content) improves 1.0wt%, random sequence distribution content increases 4% in copolymer.
Embodiment 4
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=3.0) it is mixed with hexane, formation monomer solution ([M]= 52g/L).At -45 DEG C, it is added and contains VOCl3With mixture and EtAlCl of the 1,1,1- anesin TCB at 16 DEG C2/ Et2The catalyst of AlCl, wherein V/M molar ratio is 5.9 × 10-4, Al/V molar ratio is that 20, TCB/V molar ratio is 3.Polymerization is anti- It answers 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene copolymer product, catalytic activity 22kg (mol-1V), propylene content is 53mol% (63wt%) in copolymer, and random sequence distribution content is 59%.
Compared with comparative example 4, in obtaining copolymer in situation similar in propylene content, propylene dosage is reduced in monomer 9%, propylene utilization efficiency improves, and catalytic activity improves 83%；Major catalyst dosage (being indicated with V/M molar ratio) reduces 36%, co-catalyst dosage (being indicated with Al/M ratio) reduces 36%；Random sequence distribution content improves in copolymer 4%.
Embodiment 5
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=3.0) it is mixed with hexane, formation monomer solution ([M]= 49g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl and ethapon (abbreviation TCE), wherein V/M Molar ratio is 6.2 × 10-4, Al/V molar ratio is that 20, CB/V molar ratio is 1.Polymerization reaction 10 minutes, terminate and post processing mode With embodiment 1, ethylene-propylene copolymer product is obtained, catalytic activity is 16kg (mol-1V), propylene content is in copolymer 45mol% (55wt%), random sequence distribution content are 69%.
Compared with comparative example 5, in obtaining copolymer in situation similar in propylene content, propylene utilization efficiency is improved, and is urged Change activity and improves 14%；Co-catalyst dosage (being indicated with Al/M ratio) reduces 30%；Random sequence distribution in copolymer Content increases 4%.
Embodiment 6
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=3.2) it is mixed with hexane, formation monomer solution ([M]= 62g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl and TC, wherein V/M molar ratio be 4.8 × 10-4, Al/V molar ratio is that 20, TC/V molar ratio is 2.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain To ethylene-propylene copolymer product, catalytic activity is 26kg (mol-1V), conversion of ethylene 100%, propylene conversion are 18%, propylene content is 35mol% (45wt%) in copolymer, and random sequence distribution content is 55%.
Compared with comparative example 6, under the conditions of same polymeric, propylene utilization efficiency is improved, and catalytic activity improves 8%；Third Alkene copolymerization insertion rate (content) improves 3mol%, and random sequence distribution content increases 10% in copolymer.
Embodiment 7
5- ethylidene -2- norbornene (ENB), propylene, vinyl monomer are pressed into certain mol proportion (ENB/C3/C2=0.03/ 3.2/1) it mixes, is formed monomer solution ([M]=50g/L) with hexane.At -45 DEG C, it is added and contains VOCl3、EtAl1.5Cl1.5And TC Catalyst, wherein V/M molar ratio be 7.3 × 10-5, Al/V molar ratio is that 100, TC/V molar ratio is 2.Polymerization reaction 10 is divided Clock, terminates and post processing mode is with embodiment 1, obtains ethylene-propylene-ENB copolymerization product, catalytic activity is 138kg (mol- 1V), conversion of ethylene 78%, propylene conversion 14%, propylene content is 44mol% (54wt%) in copolymer, and ENB contains Amount is 1.2mol% (4wt%), and random sequence distribution content is 70%.
Compared with comparative example 7, under same polymeric condition, ethylene, propylene and ENB utilization efficiency are improved, and catalysis is lived Property improves 23%；Propylene copolymerization insertion rate (content) improves 5mol%, and ENB copolymerization insertion rate (content) improves 1.2wt%, random sequence distribution content increases 8% in copolymer.
Embodiment 8
At 10 DEG C, in ethylene and octene copolymer reaction system, it is added and contains VOCl3、EtAlCl2/Et2AlCl's and TCB urges Agent, wherein V/M molar ratio is 1.3 × 10-3, Al/V molar ratio is that 20, TCB/V molar ratio is 3.Polymerization reaction 30 minutes, eventually Only and post processing mode is with embodiment 1, obtains ethylene-octene copolymer.Catalytic activity is 14kg (mol-1V), in copolymer Octene content is 14mol%.
Compared with comparative example 8, under the conditions of same polymeric, octene monomers utilization rate is improved, and catalytic activity improves 56%； Octene copolymer insertion rate (content) improves 11mol% in copolymer.
Comparative example 1
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=2.6) it is mixed with hexane, formation monomer solution ([M]= 57g/L).At -45 DEG C, it is added and contains VOCl3、EtAl1.5Cl1.5Catalyst, wherein V/M molar ratio be 6.7 × 10-4, Al/V rubs You are than being 30.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene copolymer product, be catalyzed Activity is 14kg (mol-1V), propylene content is 53mol% (63wt%) in copolymer, and random sequence distribution content is 63%.
Comparative example 2
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=2.5) it is mixed with hexane, formation monomer solution ([M]= 63g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl, wherein V/M molar ratio is 2.3 × 10-4, Al/V molar ratio is 30.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene copolymer production Object, catalytic activity are 41kg (mol-1V), propylene content is 35mol% (45wt%), random sequence distribution content in copolymer It is 49%.
Comparative example 3
5- ethylidene -2- norbornene (ENB), propylene, vinyl monomer are pressed into certain mol proportion (ENB/C3/C2=0.1/ 4.2/1) it mixes, is formed monomer solution ([M]=50g/L) with hexane.At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2AlCl Catalyst, wherein V/M molar ratio be 6.1 × 10-4, Al/V molar ratio is 30.It polymerization reaction 10 minutes, terminates and post-processes Mode obtains ethylene-propylene-ENB copolymerization product with embodiment 1, and catalytic activity is 15kg (mol-1V), conversion of ethylene is 86%, propylene conversion 15%, propylene content is 42mol% (52wt%) in copolymer, and ENB content is 4.0mol% (13wt%), random sequence distribution content are 68%.
Comparative example 4
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=3.3) it is mixed with hexane, formation monomer solution ([M]= 64g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl, wherein V/M molar ratio is 9.2 × 10-4, Al/V molar ratio is 20.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene copolymer production Object, catalytic activity are 12kg (mol-1V), propylene content is 52mol% (62wt%), random sequence distribution content in copolymer It is 55%.
Comparative example 5
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=3.0) it is mixed with hexane, formation monomer solution ([M]= 53g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl, wherein V/M molar ratio is 5.9 × 10-4, Al/V molar ratio is 30.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene copolymer production Object, catalytic activity are 14kg (mol-1V), propylene content is 46mol% (56wt%), random sequence distribution content in copolymer It is 65%.
Comparative example 6
Propylene, vinyl monomer are pressed into certain mol proportion (C3/C2=3.2) it is mixed with hexane, formation monomer solution ([M]= 62g/L).At -45 DEG C, it is added and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl, wherein V/M molar ratio is 4.8 × 10-4, Al/V molar ratio is 20.It polymerization reaction 10 minutes, terminates and post processing mode is with embodiment 1, obtain ethylene-propylene copolymer production Object, catalytic activity are 24kg (mol-1V), conversion of ethylene 100%, propylene conversion 16%, propylene contains in copolymer Amount is 32mol% (42wt%), and random sequence distribution content is 45%.
Comparative example 7
5- ethylidene -2- norbornene (ENB), propylene, vinyl monomer are pressed into certain mol proportion (ENB/C3/C2=0.03/ 3.2/1) it mixes, is formed monomer solution ([M]=50g/L) with hexane.At -45 DEG C, it is added and contains VOCl3、EtAl1.5Cl1.5Catalysis Agent, wherein V/M molar ratio is 7.3 × 10-5, Al/V molar ratio is 100.It polymerization reaction 10 minutes, terminates and post processing mode is same Embodiment 1, obtains ethylene-propylene-ENB copolymerization product, and catalytic activity is 112kg (mol-1V), conversion of ethylene 69%, Propylene conversion is 10%, and propylene content is 39mol% (49wt%) in copolymer, and ENB content is 0.8mol% (2.8wt%), random sequence distribution content are 62%.
Comparative example 8
At 10 DEG C, it is added in ethylene and octene copolymer reaction system and contains VOCl3、EtAlCl2/Et2The catalyst of AlCl, Wherein, V/M molar ratio is 1.3 × 10-3, Al/V molar ratio is 20.Polymerization reaction 30 minutes, terminate and post processing mode simultaneously reality Example 1 is applied, ethylene-octene copolymer is obtained.Catalytic activity is 9kg (mol-1V), octene content is 3mol% in copolymer.

Claims (7)

1. a kind of vanadium-based catalyst systems for alpha-olefinic copolymerization, contain major catalyst, co-catalyst and regulator, in which:
Major catalyst is VOCl3Or general formula is VOClnL3-nVfanadium compound or VOCl3It is VOCl with general formulanL3-nVfanadium compound Mixture, V is+5 valence vanadium, n 0,1 or 2 in formula；L is phenol anion；
Co-catalyst is organo-aluminum compound, selected from alkyl aluminum, alkyl aluminium halide, alkylaluminoxane or their mixture；Institute The general formula of the alkyl aluminum or alkyl aluminium halide stated is RmAlX3-m, wherein R contains 1~10 carbon atom to be same or different Alkyl or cycloalkyl or their isomers, X is halogen, m 1,1.5,2 or 3；
Regulator is selected from one of following compound or their mixture: 2- chloro-2-methyl propane, 2- chloro-2-methyl-fourth Alkane, cumyl chlorine, 2,2- dichloropropane, 2,2- dichloroetane, the chloro- 2- methylpropane of 1,1- bis-, 1,1,1- trichloroethanes, 1,1,1- Trichloropropane, tri- chlorobutane of 1,1,1-, the chloro- 2- methylpropane of 1,1,1- tri-, tri- chloropentane of 1,1,1-, the chloro- 2,2- of 1,1,1- tri- Dimethylpropane, the chloro- 2- methybutane of 1,1,1- tri-, the chloro- 3- methybutane of 1,1,1- tri-, bis- trimethylewne chlorohydrin 3- of 2,2-, 2,2- bis- Chloro- n-butyl alcohol, the chloro- 1- ethyl alcohol of 2,2,2- tri-, tri- trimethylewne chlorohydrin 3- of 3,3,3-, 1,1,1- trichloro-2-propanol, the chloro- 2- of 1,1,1- tri- Methyl-2-propanol, the chloro- 2- butanol of 1,1,1- tri-, tri- chloro-2-methyl -2- butanol of 1,1,1-, 2- chlorobenzyl alcohol, the chloro- 1- of 2,2,2- tri- O-tolyl ethyl alcohol, 2- trichloromethyl -4- bromobenzyl alcohol.
2. vanadium-based catalyst systems according to claim 1, it is characterized in that: the molar ratio of co-catalyst and major catalyst be 8~ 150；The molar ratio of regulator and major catalyst is 0.4~35.
3. vanadium-based catalyst systems according to claim 1, it is characterized in that: applicable alkene be ethylene, it is propylene, 1- butylene, different Butylene, 1- amylene, 1- hexene, 1- heptene, 1- octene, 1- decene, 1- hendecene, 1- laurylene, 1- tridecylene, 1-tetradecylene, Ten pentaene of 1-, 1- hexadecylene, norbornene, cyclopentene, cyclohexene, cyclopentadiene, 1,3- cyclohexadiene, 1,4- cyclohexadiene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, dicyclopentadiene, 1,4- hexadiene, 2- methyl-1,4- oneself two Alkene, 1,6- octadiene.
4. vanadium-based catalyst systems according to claim 1, it is characterized in that:
Major catalyst general formula is VOClnL3-nVfanadium compound in n be 2, L be phenol anion or containing 1~20 carbon atom The position of the phenol anion of alkyl or aryl substituent group, substituent group can be ortho position, any position of meta or para position, substituent group Number be 1~5 integer.
5. vanadium-based catalyst systems according to claim 4, it is characterized in that:
Major catalyst general formula is VOClnL3-nVfanadium compound in, L be phenol anion, 4- methylphenol anion, 2- methylbenzene Phenol anion, 2,6- xylenol anion, 2,6 di tert butyl 4 methyl phenol anion or 2,4,6- tri-butyl benzene Phenol anion.
6. vanadium-based catalyst systems according to claim 1, it is characterized in that: alkyl aluminum described in co-catalyst is selected from trimethyl Aluminium, triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, triisobutyl aluminium, three n-pentyl aluminium, three n-hexyls One of aluminium, thricyclohexyl aluminium or their mixture；The alkyl aluminium halide is selected from a Chlorodimethyl aluminium, a chlorine diethyl Base aluminium, a chlorine di-n-butyl aluminium, a chloro-di-isobutyl aluminum, dichloromethyl aluminium, ethyl aluminum dichloride, dichloro n-butylaluminum, dichloro are different Butyl aluminium, two aluminium of trichlorine trimethyl, two aluminium of ethylaluminum, three normal-butyl of trichlorine, two aluminium, one in two aluminium of trichlorine triisobutyl Kind or their mixture；Alkylaluminoxane be selected from one of methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide or it Mixture.
7. vanadium-based catalyst systems according to claim 2, it is characterized in that: the molar ratio of co-catalyst and major catalyst be 10~ 120；The molar ratio of regulator and major catalyst is 0.5~28.
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