CN108250340A - A kind of method of metallocene catalyst system and its catalysis in olefine polymerization - Google Patents
A kind of method of metallocene catalyst system and its catalysis in olefine polymerization Download PDFInfo
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- CN108250340A CN108250340A CN201611231860.1A CN201611231860A CN108250340A CN 108250340 A CN108250340 A CN 108250340A CN 201611231860 A CN201611231860 A CN 201611231860A CN 108250340 A CN108250340 A CN 108250340A
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- 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
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- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
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Abstract
The present invention relates to olefin polymerization technology field, a kind of method that metallocene catalyst system and its catalysis in olefine polymerization are provided；The catalyst system includes：Component A, component B, optionally further include component C, wherein：Component A is metallocene compound, and component B is aikyiaiurnirsoxan beta or modified alumoxane, and component C is alkyl aluminum compound；The general formula of the metallocene compound is L1L2L3MX, L1Selected from cyclopentadienyl group or cyclopentadienyl derivative；L2With L1It is identical or for Monodentate anionic ligands；L3Selected from C4~C20Alkoxy anion, carboxylic acid anion, phosphate anion or sulfuric ester anion.Method using the catalyst system catalyzed alkene class monomer polymerization includes：Catalyst system with monomer solution is contacted and carries out polymerisation.Catalyst system and polymerization using the present invention, it is environmentally protective；While high catalytic activity and monomer conversion is kept, co-catalyst dosage can be greatly reduced.
Description
Technical field
The present invention relates to olefin polymerization technology field, more particularly, to a kind of metallocene catalyst system and its catalysis
The method of olefinic polymerization.
Background technology
Metallocene catalyst is because its catalytic activity is high, Polymer Molecular Weight narrowly distributing, the polymer architecture of generation
The advantages that controllable, have in olefin polymerization extensively using (referring to Chem.Rev., 2000,1205-1220；
Prog.Polym.Sci.,2008,33,797-819).Metallocene catalyst is by metallocene compound (major catalyst) and aluminium methyl
Oxygen alkane (MAO), modified methyl alcoxyl aluminium (MMAO) or organoboron compound (co-catalyst) two parts composition.The knot of major catalyst
The structure of structure especially ligand has great influence to the structure of catalytic activity and polymerizate, therefore, is synthesized by designing
The ligand of different structure can obtain the metallocene catalyst with different catalytic performances.Due to containing in most metallocene compounds
Metal-chlorine key, it is difficult to be dissolved in fat alkane class solvent, the common co-catalyst MAO of metallocene catalyst, [Ph in addition3C][B
(C6F5)4] etc. be also insoluble in saturated alkane class solvent (referring to Angew.Chem.Int.Ed., 2014,53,9722-9744.),
Therefore, the metallocene catalyst system of high activity makees solvent frequently with toluene.However, compared with saturated alkane class solvent, toluene
Toxicity is big, pollution environment, price height, and difficulty is removed from polymer, limits its development and further applies.
Ji etc. reports a kind of metallocene catalysis system soluble in saturated alkane, by contain phenol negative oxygen ion ligand and
Two kinds of component compositions of single luxuriant titanium complex major catalyst and MAO co-catalysts of di (isooctyl) phosphate (P204), highest catalysis are lived
Property is only 1.1 × 106g polymer·mol-1of Ti·h-1, catalytic activity it is low (referring to Procedia Engineering,
2011,18,422–426)。
Invention content
The object of the present invention is to provide a kind of metallocene catalyst system, which includes：Component A, component B,
Component C is optionally further included, wherein：Component A is metallocene compound, and component B is aikyiaiurnirsoxan beta or modified alumoxane, and component C is
Alkyl aluminum compound；
The general formula of the metallocene compound is L1L2L3MX, in formula,
L1Selected from cyclopentadienyl group or cyclopentadienyl derivative；L2With L1It is identical or for Monodentate anionic ligands；L3
Selected from C4~C20Alkoxy anion, carboxylic acid anion, phosphate anion or sulfuric ester anion；X is selected from alkyl, ring
Alkyl, aryl, aralkyl or halogen；M is selected from transition metals Ti, zirconium or hafnium.
According to catalyst system provided by the invention, it is preferable that in terms of metal in every molar constituent A, the content of component B is
200~3000 moles, more preferably 250~2500 moles, further preferably 280~2300 moles；The content of component C is 0
~300 moles, more preferably 0~200 mole, further preferably 0~150 mole.
According to catalyst system provided by the invention, it is preferable that the cyclopentadienyl derivative be selected from indenyl, fluorenyl,
Substituted cyclopentadienyl group, the indenyl of substitution or substituted fluorenyl；The substituted cyclopentadienyl group, the indenyl of substitution or substitution
Fluorenyl in substituent group be C1~C10Alkyl, C3~C8Cycloalkyl, C6~C10Aryl or substituted aryl and C7~C12Virtue
It is one or more in alkyl or substituted aralkyl；The number of substituent group is 1~5 in the substituted cyclopentadienyl group, described
The number of substituent group is 1~7 in substituted indenyl, and the number of substituent group is 1~9 in the substituted fluorenyl.
Preferably, L1Selected from cyclopentadienyl group, methyl cyclopentadienyl, 1,2- dimethylcyclo-pentadienyls, tetramethyl-ring
Pentadienyl, pentamethylcyclopentadiene base, tetramethyl n-propyl cyclopentadienyl group, durol cyclopentadienyl group, ethyl ring
Pentadienyl, n-propyl cyclopentadienyl group, isopropylcyclopentadienyl, n-butyl cyclopentadienyl, t-butyl cyclopentadienyl,
Pentaphenylcyclopentadiene base, perfluor cyclopentadienyl group, indenyl, methylindenyl, dimethylindenyl, normal-butyl indenyl or fluorenyl；More
It is preferably selected from cyclopentadienyl group, pentamethylcyclopentadiene base, tetramethyl n-propyl cyclopentadienyl group or durol basic ring penta 2
Alkenyl.
Preferably, the Monodentate anionic ligands are the organic compound containing aerobic, sulphur, nitrogen anion, are more preferably selected from
Phenol anion, aryl thiolate ions, ketimide anion, phosphinimine anion, guanidine anion or imidazoline imines anion.
Preferably, L3Selected from C4~C15Carboxylic acid anion, phosphate anion, be more preferably selected from C5~C12Carboxylic acid bear
Ion.
Preferably, X is selected from C1~C10Alkyl, C3~C8Cycloalkyl, C6~C10Aryl or substituted aryl, C7~C12
Aralkyl or substituted aralkyl or halogen, be more preferably selected from methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, pungent
Base, benzyl or chlorine.
Preferably, M is selected from titanium or zirconium, more preferably titanium.
Component A can be used directly, can also with dilution dilution agent after use.Diluent is selected from C4~C15Alkane or ring
At least one of alkane, at least one be preferably selected from pentane, hexane, hexamethylene, heptane, hexahydrotoluene, octane, nonane
Kind.The concentration of component solution A influences polymerisation less, and generally 5.0 × 10-4~2.5 × 10-3mol/L.In condensate
In system, the dosage of increase component A can improve polymerisation conversion.It is necessary to add in suitable component A in the present invention, if
Component A dosages are very little, then activated centre number is few, and polymerisation conversion is low, and monomer utilization ratio is low；If component A dosages are excessive, urge
Agent utilization ratio is low, increases catalyst cost, and can reduce polymer molecular weight.
According to catalyst system and catalyzing provided by the invention, it is preferable that the alkylaluminoxane or modified alkylaluminoxanes are selected from first
Base aikyiaiurnirsoxan beta, triisobutyl aluminum modified methylaluminoxane, ethylaluminoxane, propylaluminoxane, butyla-luminoxane and isobutyl group
It is one or more in aikyiaiurnirsoxan beta, it is more preferably selected from methylaluminoxane and/or triisobutyl aluminum modified methylaluminoxane.
In metallocene catalyst polymerisation system, component B usually requires to ensure to cause catalytic body in a certain range
It is active, the dosage of increase component B is smaller on catalytic activity influence, but can increase chain tra nsfer probability, reduces polymer point
Son amount, and catalyst cost can be increased；But if component B dosages are too low, can reduce catalytic activity and not polymerize even.
According to method provided by the invention, it is preferable that the general formula of the alkyl aluminum compound is R3Al；In formula, R is selected from C1
~C10Alkyl, C3~C8Cycloalkyl, C6~C10Aryl or substituted aryl and C7~C12Aralkyl or substituted aralkyl
In it is one or more.
The alkyl aluminum compound is preferably selected from triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, three
Aluminium isobutyl, three sec-butyl aluminium, three cyclopenta aluminium, three n-pentyl aluminium, triisopentyl aluminium, tri-n-hexyl aluminum, thricyclohexyl aluminium, three
One kind in octyl aluminum, three positive decyl aluminium, ethyl dimethyl aluminium, methyl diethyl aluminum, triphenyl aluminum and three p-methylphenyl aluminium
It is or a variety of；More preferably selected from triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, triisobutyl aluminium, tricyclic
It is one or more in amyl aluminium, tri-n-hexyl aluminum, thricyclohexyl aluminium, three own octyl group aluminium and tri-n-octylaluminium；Further preferably
It is one or more in three n-butylaluminums, triisobutyl aluminium, tri-n-hexyl aluminum and tri-n-octylaluminium.
The present invention also provides a kind of method using above-mentioned catalyst system catalysis in olefine polymerization, this method includes：It will urge
Agent system is contacted with monomer solution carries out polymerisation.
In the course of the polymerization process, component C is used after being mixed in a solvent with component A.The solvent is C4~C15Fat
Race's alkane or cycloalkane.The mixing temperature and incorporation time of component C and component A, to catalytic active center and polymerisation effect
It influences little.In general, it is preferably 30 seconds~3 hours that mixing temperature, which is preferably 0 DEG C~80 DEG C incorporation times,.Suitable alkyl calorize
Catalyst activity can be further improved, but alkyl aluminum compound dosage should not be excessive by closing object.On the one hand its dosage excessively causes
Chain-transferring agent is serious, and polymer molecular weight declines, and catalyst cost on the other hand can be caused to improve.
According to method provided by the invention, it is preferable that each component and list in the catalyst system that component A and component B is formed
The mode of liquid solution contact is one of in the following manner：
(1) component A is first added in into monomer solution and adds component B；
(2) component B is first added in into monomer solution and adds component A；
(3) component A and component B are added in simultaneously into monomer solution；
(4) it is added in monomer solution after being pre-mixed component A and component B；
(5) component A and component B two fluids mix respectively with monomer solution stream.
According to method provided by the invention, it is preferable that component C in the catalyst system that component A, component B and component C are formed
The mode of addition is one of in the following manner：
(1) component A, component B and component C are added in simultaneously into monomer solution；
(2) component C is added after being mixed with component A in monomer solution；The order of addition of component B is unrestricted；
(3) component C is added after being mixed with component B in monomer solution；The order of addition of component A is unrestricted；
(4) component A, component B and tri- fluid streams of component C mix respectively with monomer solution stream.
According to method provided by the invention, it is preferable that applicable monomer is alkene, is more preferably selected from alpha-olefin, cycloolefin
With it is one or more in non-conjugated diene hydrocarbon.The alpha-olefin be preferably selected from ethylene, propylene, 1- butylene, 1- amylenes, 1- oneself
It is one or more in alkene, 1- octenes or 4- methyl-1 amylenes；The cycloolefin is preferably selected from cyclopentene, cyclohexene or norborneol
Alkene it is one or more；The non-conjugated diene hydrocarbon is preferably selected from 5- ethylidene -2- norbornene (ENB), dicyclopentadiene, 5-
It is one or more in vinyl -2- norbornene (VNB), 1,4- hexadienes and 1,6- octadienes.
According to method provided by the invention, it is preferable that the molar ratio of metal and monomer is 5.0 × 10 in component A-7~1.0
×10-4：1, more preferably 8.0 × 10-7~8.0 × 10-5：1, further preferably 1.0 × 10-6~5.5 × 10-5：1.
According to method provided by the invention, it is preferable that the polymerization methods of the polymerisation are gas-phase polymerization, suspension polymerisation
Or polymerisation in solution.
According to suspension polymerisation, diluent used is C3~C10Alkane or C3~C10Alkene, be preferably selected from propylene, 1-
Butylene, 1- hexenes, butane, pentane or hexane are more preferably selected from propylene, 1- butylene or butane.
According to polymerisation in solution, solvent used is selected from C3~C10Saturated alkane or C3~C10At least one in cycloalkane
Kind is preferably selected from at least one of propane, butane, pentane, hexane, heptane, octane, hexamethylene, hexahydrotoluene, nonane.
A concentration of 1~8mol/L of the monomer solution, the selection of monomer concentration are related with monomeric species.
Polymerizing olefin monomers reaction is carried out in the presence of the catalyst system, it is preferable that polymeric reaction temperature is -30 DEG C
~130 DEG C, more preferably -10 DEG C~115 DEG C, further preferably -5 DEG C~100 DEG C；Polymerization reaction time is small for 1 minute~2
When, more preferably 2 minutes~1.5 hours, further preferably 5 minutes~1 hour.
It reacts at the polymerization temperature after a certain period of time, terminates polymerisation with substances such as water, methanol, ethyl alcohol, amine, will obtain
Solution handled in ethanol solution hydrochloride or with aqueous solution containing NaOH, polymer be precipitated, remove solvent, post-consumer polymer
Separation, drying to constant weight.
The advantageous effect that technical scheme of the present invention is brought is：(1) catalyst system using the present invention and polymerization side
Method can use environmental-friendly alkane solvents completely, avoid using toxic aromatic hydrocarbon solvent, environmentally protective；It (2) can be with
Make ethylene and alpha-olefin copolymer or ethylene, alpha-olefin and non-conjugated diene is made to realize efficiently copolymerization, catalyst activity is significantly
It improves, and while high catalytic activity and monomer conversion is kept, co-catalyst dosage can be greatly reduced, so as to reduce life
Cost is produced, catalytic component residual is reduced, improves polymeric articles quality；(3) molecular weight of Olefins Product Streams is high, improves production
Moral character energy.
Specific embodiment
The preferred embodiment of the present invention is described in more detail below, further illustrates the present invention, but does not form to this
The limitation of invention protection domain.
According to ASTM-D3900-95, ethylene in ethylene-propylene copolymer is measured using Fourier infrared spectrograph (FTIR)
Or propylene content.
According to GB/T21464-2008, ethylene, propylene or ENB in ethylene-propylene-ENB copolymers are measured using FTIR and contained
Amount.
Weight average molecular weight (the M of polymer is measured at 150 DEG C using gel permeation chrommatographw) and molecular weight distribution (Mw/Mn),
Trichloro-benzenes is solvent and mobile phase.
Catalyst activity generates polymer gauge per hour with every mole of major catalyst, and unit is gpolymer mol-1of
Ti·h-1。
Embodiment 1
At 50 DEG C, to the monomer solution (ethylene of a concentration of 140g/L：Propylene=1:2) add in a concentration of 10wt%'s in
MMAO/ n-heptane solutions (component B) and bis- (2,6- the diisopropyl phenyls)-imine imidazole quinoline-isooctyl acid-cyclopentadienyl groups of 1,3-
The molar ratio of Ti is 2000 in Al and component A in titanium chloride (component A)/hexane solution, wherein component B：1, polymerisation 30 is divided
Zhong Hou adds in the ethanol solution hydrochloride that mass fraction is 5% and terminates reaction, and obtained copolymer is dried under vacuum to perseverance at 40 DEG C
Weight, obtains 3.7g bipolymers.Catalyst activity is 1.5 × 106g polymer·mol-1of Ti·h-1, the weight of copolymer
Average molecular weight (Mw) it is 3.2 × 105, molecular weight distributing index (Mw/Mn) it is 2.1；In copolymer ethylene contents be 61wt%, third
Alkene content is 39wt%.
Embodiment 2
At 50 DEG C, to the monomer solution (ethylene of a concentration of 140g/L：Propylene=1:2) add in a concentration of 10wt%'s in
MMAO/ n-heptane solutions (component B) and component A are added to after mixing 1 minute with triisobutyl aluminium (component C) in polymerization system,
The molar ratio of Ti is 1000 in Al and component A in component B：The molar ratio of 1, component C and Ti in component A are 20：1, polymerization time
It it is 30 minutes, termination procedure obtains 2.8g bipolymers with embodiment 1.Catalytic activity is 1.1 × 106gpolymer·mol-1of Ti·h-1；The M of copolymerwIt is 3.8 × 105, Mw/MnIt is 2.0；Ethylene contents are 66wt% in copolymer, and propylene content is
34wt%.
Embodiment 3
As described in Example 2, the difference lies in the molar ratio of Ti is 300 to polymerization process in Al and component A in component B：
The molar ratio of 1, component C and Ti in component A are 100：1, obtain 5.4g bipolymers.Catalytic activity is 2.2 × 106g
polymer·mol-1of Ti·h-1.The M of copolymerwIt is 2.7 × 105, Mw/MnIt is 2.3；Ethylene contents are in copolymer
56wt%, propylene content 44wt%.
Embodiment 4
As described in Example 2, the difference lies in the molar ratio of Ti is 100 to polymerization process in component C and component A：1, gather
It is 15 DEG C to close temperature, obtains 5.03g copolymers, and catalytic activity is 5.0 × 106g polymer·mol-1of Ti·h-1.Copolymerization
The M of objectwIt is 1.3 × 105, Mw/MnIt is 2.3；Ethylene contents are 45wt%, propylene content 55wt% in copolymer.
Embodiment 5
As described in Example 4, the difference lies in start-up temperature is 90 DEG C to polymerization process, and temperature increases in polymerization process
To 95 DEG C.Obtain 3.6g bipolymers.Catalytic activity is 3.6 × 106g polymer·mol-1of Ti·h-1.Copolymer
MwIt is 2.0 × 105, Mw/MnIt is 2.6；Ethylene contents are 58wt%, propylene content 42wt% in copolymer.
Embodiment 6
As described in Example 2, the difference lies in (account for ethylene/propene always to rub polymerization process in monomer solution containing ENB
The 1% of your number), the molar ratio of Ti is 100 in component C and component A：The incorporation time of 1, component C and component A are 30min, are obtained
6.1g terpolymer.Catalyst activity is 2.4 × 106g polymer·mol-1of Ti·h-1.The M of copolymerwFor 2.5 ×
105, Mw/MnIt is 2.6.Ethylene contents are 45wt% in copolymer, and propylene content 51.5wt%, ENB content are 3.5wt%.
Embodiment 7
As described in Example 5, the difference lies in polymerization temperature is 30 DEG C to polymerization process, and polymerization time is 10 minutes, is obtained
To 4.41g bipolymers.Catalytic activity is 1.3 × 107g polymer·mol-1of Ti·h-1.The M of copolymerwIt is 3.3
×105, Mw/MnIt is 2.4；Ethylene contents are 51wt%, propylene content 49wt% in copolymer.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.In the case of without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes will be apparent from for the those of ordinary skill in art field.
Claims (11)
1. a kind of metallocene catalyst system, which is characterized in that the catalyst system includes：Component A, component B, are optionally also wrapped
Component C is included, wherein：Component A is metallocene compound, and component B is aikyiaiurnirsoxan beta or modified alumoxane, and component C is alkyl aluminum chemical combination
Object；
The general formula of the metallocene compound is L1L2L3MX, in formula,
L1Selected from cyclopentadienyl group or cyclopentadienyl derivative；L2With L1It is identical or for Monodentate anionic ligands；L3Selected from C4
~C20Alkoxy anion, carboxylic acid anion, phosphate anion or sulfuric ester anion；X be selected from alkyl, cycloalkyl,
Aryl, aralkyl or halogen；M is selected from transition metals Ti, zirconium or hafnium.
2. catalyst system according to claim 1, wherein, in terms of metal in every molar constituent A, the content of component B is
200~3000 moles, preferably 250~2500 moles, further preferably 280~2300 moles；The content of component C for 0~
300 moles, preferably 0~200 mole, further preferably 0~150 mole.
3. catalyst system according to claim 1, wherein, the cyclopentadienyl derivative is selected from indenyl, fluorenyl, takes
The cyclopentadienyl group in generation, the indenyl of substitution or substituted fluorenyl；The substituted cyclopentadienyl group, the indenyl or substituted of substitution
Substituent group in fluorenyl is C1~C10Alkyl, C3~C8Cycloalkyl, C6~C10Aryl or substituted aryl and C7~C12Aralkyl
It is one or more in base or substituted aralkyl；The number of substituent group is 1~5 in the substituted cyclopentadienyl group, described to take
The number of substituent group is 1~7 in the indenyl in generation, and the number of substituent group is 1~9 in the substituted fluorenyl；
L1Be preferably selected from cyclopentadienyl group, methyl cyclopentadienyl, 1,2- dimethylcyclo-pentadienyls, tetramethyl-ring pentadienyl,
Pentamethylcyclopentadiene base, tetramethyl n-propyl cyclopentadienyl group, durol cyclopentadienyl group, ethyicydopentadi etanyf group,
N-propyl cyclopentadienyl group, isopropylcyclopentadienyl, n-butyl cyclopentadienyl, t-butyl cyclopentadienyl, five benzyl rings
Pentadienyl, perfluor cyclopentadienyl group, indenyl, methylindenyl, dimethylindenyl, normal-butyl indenyl or fluorenyl, are more preferably selected from
Cyclopentadienyl group, pentamethylcyclopentadiene base, tetramethyl n-propyl cyclopentadienyl group or durol cyclopentadienyl group；
The Monodentate anionic ligands are the organic compound containing aerobic, sulphur, nitrogen anion；It is preferably selected from phenol anion, thiophenol
Anion, ketimide anion, phosphinimine anion, guanidine anion or imidazoline imines anion；
L3Selected from C4~C15Carboxylic acid anion, phosphate anion, be preferably selected from C5~C12Carboxylic acid anion；
X is selected from C1~C10Alkyl, C3~C8Cycloalkyl, C6~C10Aryl or substituted aryl, C7~C12Aralkyl or take
For aralkyl or halogen, it is preferably selected from methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl group, benzyl or chlorine；
M is selected from titanium or zirconium, preferably titanium.
4. catalyst system according to claim 1, wherein, the alkylaluminoxane or modified alkylaluminoxanes are selected from first
Base aikyiaiurnirsoxan beta, triisobutyl aluminum modified methylaluminoxane, ethylaluminoxane, propylaluminoxane, butyla-luminoxane and isobutyl group
It is one or more in aikyiaiurnirsoxan beta, it is preferably selected from methylaluminoxane and/or triisobutyl aluminum modified methylaluminoxane.
5. catalyst system according to claim 1, wherein, the general formula of the alkyl aluminum compound is R3Al；In formula, R choosings
From C1~C10Alkyl, C3~C8Cycloalkyl, C6~C10Aryl or substituted aryl and C7~C12Aralkyl or substitution aralkyl
It is one or more in base；
The alkyl aluminum compound is preferably selected from triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, three isobutyls
It is base aluminium, three sec-butyl aluminium, three cyclopenta aluminium, three n-pentyl aluminium, triisopentyl aluminium, tri-n-hexyl aluminum, thricyclohexyl aluminium, three just pungent
One kind or more in base aluminium, three positive decyl aluminium, ethyl dimethyl aluminium, methyl diethyl aluminum, triphenyl aluminum and three p-methylphenyl aluminium
Kind；More preferably selected from triethyl aluminum, tri-n-n-propyl aluminum, triisopropylaluminiuand, three n-butylaluminums, triisobutyl aluminium, three cyclopenta
It is one or more in aluminium, tri-n-hexyl aluminum, thricyclohexyl aluminium, three own octyl group aluminium and tri-n-octylaluminium；Further preferably it is selected from
It is one or more in three n-butylaluminums, triisobutyl aluminium, tri-n-hexyl aluminum and tri-n-octylaluminium.
6. a kind of method of catalyst system catalysis in olefine polymerization as described in any one of claim 1-5, which is characterized in that
This method includes：Catalyst system with monomer solution is contacted and carries out polymerisation.
7. according to the method described in claim 6, wherein, each component and monomer in the catalyst system that component A and component B are formed
The mode of solution contact is one of in the following manner：
(1) component A is first added in into monomer solution and adds component B；
(2) component B is first added in into monomer solution and adds component A；
(3) component A and component B are added in simultaneously into monomer solution；
(4) it is added in monomer solution after being pre-mixed component A and component B；
(5) component A and component B two fluids mix respectively with monomer solution stream.
8. according to the method described in claim 6, wherein, component C in the catalyst system that component A, component B and component C are formed
The mode of addition is one of in the following manner：
(1) component A, component B and component C are added in simultaneously into monomer solution；
(2) component C is added after being mixed with component A in monomer solution；
(3) component C is added after being mixed with component B in monomer solution；
(4) component A, component B and tri- fluid streams of component C mix respectively with monomer solution stream.
9. according to the method described in claim 6, wherein, monomer is alkene, selected from alpha-olefin, cycloolefin or non-conjugated diene hydrocarbon
In it is one or more；The alpha-olefin is preferably selected from ethylene, propylene, 1- butylene, isobutene, 1- amylenes, 1- hexenes, 1- octenes
With it is one or more in 4- methyl-1 amylenes；The cycloolefin is preferably selected from one in cyclopentene, cyclohexene and norbornene
Kind is a variety of；The non-conjugated diene hydrocarbon is preferably selected from 5- ethylidene -2- norbornene, dicyclopentadiene, 5- vinyl -2 and drops
It is one or more in bornylene, 1,4- hexadienes and 1,6- octadienes.
10. according to the method described in claim 6, wherein, the molar ratio of metal and monomer is 5.0 × 10 in component A-7~1.0
×10-4：1, preferably 8.0 × 10-7~8.0 × 10-5：1, more preferably 1.0 × 10-6~5.5 × 10-5：1.
11. according to the method described in any one of claim 6-10, wherein, polymeric reaction temperature is -30 DEG C~130 DEG C, excellent
It is selected as -10 DEG C~115 DEG C, more preferably -5 DEG C~100 DEG C.
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