CN108250340B - Metallocene catalyst system and method for catalyzing olefin polymerization by using same - Google Patents
Metallocene catalyst system and method for catalyzing olefin polymerization by using same Download PDFInfo
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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
- 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
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
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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
- 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
Abstract
The invention relates to the technical field of olefin polymerization, and provides a metallocene catalyst system and a method for catalyzing olefin polymerization by using the same; the catalyst system comprises: component a, component B, optionally further comprising component C, wherein: the component A is metallocene compound, the component B is aluminoxane or modified aluminoxane, and the component C is alkyl aluminum compound; the metallocene compound has a general formula L1L2L3MX，L1Selected from cyclopentadienyl or cyclopentadienyl derivatives; l is2And L1The same, or a monodentate anionic ligand; l is3Is selected from C4～C20Alkoxy anions, carboxylic acid anions, phosphate anions or sulfate anions. The method for catalyzing the polymerization of the olefin monomers by adopting the catalyst system comprises the following steps: and (3) contacting the catalyst system with a monomer solution to carry out polymerization reaction. The catalyst system and the polymerization method are adopted, so that the environment is protected; the amount of the cocatalyst can be greatly reduced while high catalytic activity and monomer conversion rate are maintained.
Description
Technical Field
The invention relates to the technical field of olefin polymerization, in particular to a metallocene catalyst system and a method for catalyzing olefin polymerization by using the same.
Background
Metallocene catalysts have been widely used in olefin polymerization because of their high catalytic activity, narrow molecular weight distribution of the resulting polymer, and controllable polymer structure (see chem. Rev.,2000, 1205-. The metallocene catalyst consists of two parts of metallocene compound (main catalyst) and Methylaluminoxane (MAO), Modified Methylaluminoxane (MMAO) or organoboron compound (cocatalyst). The structure of the procatalyst, particularly the ligand, has a significant effect on the catalytic activity and the structure of the polymer product, and thus metallocenes with different catalytic properties can be obtained by designing and synthesizing ligands of different structuresA metal catalyst. Most metallocene compounds are hardly soluble in aliphatic alkane solvents due to their metal-chlorine bonds, and the cocatalyst MAO, [ Ph ] commonly used for metallocene catalysts3C][B(C6F5)4]And the like are also difficult to dissolve in saturated alkane solvents (see Angew. chem. int. Ed.,2014,53,9722-9744.), and therefore, toluene is often used as a solvent for high-activity metallocene catalyst systems. However, compared with saturated alkane solvents, toluene has high toxicity, environmental pollution and high price, and is difficult to remove from polymers, thereby limiting the development and further application of the toluene.
Ji et al report a metallocene catalyst system soluble in saturated alkane, which is composed of single metallocene titanium complex main catalyst containing phenoxide anion ligand and diisooctyl phosphate (P204) and MAO cocatalyst, and its highest catalytic activity is only 1.1X 106g polymer·mol-1of Ti·h-1Low catalytic activity (see Procedia Engineering,2011,18, 422-.
Disclosure of Invention
It is an object of the present invention to provide a metallocene catalyst system comprising: component a, component B, optionally further comprising component C, wherein: the component A is metallocene compound, the component B is aluminoxane or modified aluminoxane, and the component C is alkyl aluminum compound;
the metallocene compound has a general formula L1L2L3MX, wherein in the formula,
L1selected from cyclopentadienyl or cyclopentadienyl derivatives; l is2And L1The same, or a monodentate anionic ligand; l is3Is selected from C4～C20Alkoxy anions, carboxylic acid anions, phosphate anions or sulfate anions of (a); x is selected from alkyl, cycloalkyl, aryl, aralkyl or halogen; m is selected from transition metals of titanium, zirconium or hafnium.
According to the catalyst system provided by the invention, the content of the component B is preferably 200 to 3000 mol, more preferably 250 to 2500 mol, and even more preferably 280 to 2300 mol based on each mol of the metal in the component A; the content of the component C is 0 to 300 mol, more preferably 0 to 200 mol, and further preferably 0 to 150 mol.
According to the catalyst system provided by the present invention, preferably, the cyclopentadienyl derivative is selected from indenyl, fluorenyl, substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl; the substituent in the substituted cyclopentadienyl, the substituted indenyl or the substituted fluorenyl is C1～C10Alkyl of (C)3～C8Cycloalkyl of, C6～C10Aryl or substituted aryl and C7～C12One or more of aralkyl or substituted aralkyl groups of (a); the number of the substituent groups in the substituted cyclopentadienyl group is 1-5, the number of the substituent groups in the substituted indenyl group is 1-7, and the number of the substituent groups in the substituted fluorenyl group is 1-9.
Preferably, L1Selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, 1, 2-dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, tetramethyl-n-propylcyclopentadienyl, tetramethylphenylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, pentaphenylcyclopentadienyl, perfluorocyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, n-butylindenyl, or fluorenyl; more preferably from cyclopentadienyl, pentamethylcyclopentadienyl, tetramethyln-propylcyclopentadienyl or tetramethylphenylcyclopentadienyl.
Preferably, the monodentate anionic ligand is an organic compound containing oxygen, sulfur, nitrogen anions, more preferably selected from the group consisting of phenol anions, thiophenol anions, ketimine anions, phosphinimine anions, guanidine anions, and imidazolinine anions.
Preferably, L3Is selected from C4～C15More preferably selected from the group consisting of carboxylic acid anions and phosphoric acid ester anions of (1)5～C12Carboxylic acid anion of (a).
Preferably, X is selected from C1～C10Alkyl of (C)3～C8Cycloalkyl of, C6～C10Aryl or substituted aryl of、C7～C12More preferably selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl or chloro.
Preferably, M is selected from titanium or zirconium, more preferably titanium.
The component A can be used directly or after being diluted by a diluent. The diluent is selected from C4～C15Preferably at least one selected from the group consisting of pentane, hexane, cyclohexane, heptane, methylcyclohexane, octane and nonane. The concentration of the component A solution does not greatly affect the polymerization reaction, and is generally 5.0X 10-4～2.5×10-3mol/L. In the polymerization system, the polymerization conversion rate can be improved by increasing the amount of the component A. The addition of a proper amount of the component A is necessary in the invention, if the dosage of the component A is too small, the number of active centers is small, the polymerization conversion rate is low, and the monomer utilization rate is low; if component A is used in excess, the catalyst utilization efficiency is low, the catalyst cost is increased, and the polymer molecular weight is reduced.
According to the catalytic system provided by the present invention, preferably, the alkylaluminoxane or modified alkylaluminoxane is selected from one or more of methylaluminoxane, triisobutylaluminum modified methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane and isobutylaluminoxane, and more preferably is selected from methylaluminoxane and/or triisobutylaluminum modified methylaluminoxane.
In a metallocene catalyst polymerization system, a component B is usually required to be ensured within a certain range to ensure that the catalyst system has activity, and the increase of the using amount of the component B has little influence on the catalytic activity, but can increase the chain transfer probability, reduce the molecular weight of a polymer and increase the catalyst cost; however, if component B is used in an excessively low amount, the catalytic activity is lowered or even no polymerization is caused.
According to the process provided by the invention, preferably, the alkyl aluminum compound has the general formula R3Al; wherein R is selected from C1～C10Alkyl of (C)3～C8Cycloalkyl of, C6～C10Aryl or substituted aryl of and C7～C12Or substituted aralkyl group.
The aluminum alkyl compound is preferably selected from one or more of triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tri-n-pentylaluminum, triisopentylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, and tri-p-tolylaluminum; more preferably one or more selected from triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tricyclopentylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, trihexyloctylaluminum, and tri-n-octylaluminum; further preferred is one or more selected from the group consisting of tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum.
The invention also provides a method for catalyzing olefin polymerization by using the catalyst system, which comprises the following steps: and (3) contacting the catalyst system with a monomer solution to carry out polymerization reaction.
During the polymerization, the component C and the component A may be used after being mixed in a solvent. The solvent is C4～C15Aliphatic alkanes or cycloalkanes. The mixing temperature and mixing time of the component C and the component A have little influence on the catalytic activity center and the polymerization reaction effect. In general, the mixing temperature is preferably 0 ℃ to 80 ℃ and the mixing time is preferably 30 seconds to 3 hours. The catalyst activity can be further improved by an appropriate amount of the aluminum alkyl compound, but the amount of the aluminum alkyl compound is not excessively large. Too much amount of the catalyst causes severe chain transfer agent and decrease of polymer molecular weight on one hand, and increases catalyst cost on the other hand.
According to the method provided by the invention, preferably, the mode of contacting each component in the catalyst system formed by the component A and the component B with the monomer solution is one of the following modes:
(1) adding the component A into the monomer solution and then adding the component B;
(2) adding the component B into the monomer solution and then adding the component A;
(3) simultaneously adding the component A and the component B into the monomer solution;
(4) pre-mixing the component A and the component B and then adding the mixture into a monomer solution;
(5) the two streams, component A and component B, are mixed separately with the monomer solution stream.
According to the method provided by the invention, preferably, the component C in the catalyst system formed by the component A, the component B and the component C is added in one of the following modes:
(1) simultaneously adding the component A, the component B and the component C into the monomer solution;
(2) mixing the component C and the component A, and then adding the mixture into the monomer solution; the order of addition of component B is not limited;
(3) mixing the component C and the component B, and then adding the mixture into the monomer solution; the order of addition of component A is not limited;
(4) the three streams, component a, component B and component C, are mixed separately with the monomer solution stream.
According to the process provided by the present invention, preferably, the monomer suitable for use is an olefin, more preferably one or more selected from the group consisting of α -olefins, cyclic olefins and non-conjugated dienes. The alpha-olefin is preferably selected from one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene or 4-methyl-1-pentene; the cyclic olefin is preferably selected from one or more of cyclopentene, cyclohexene or norbornene; the non-conjugated diene is preferably selected from one or more of 5-ethylidene-2-norbornene (ENB), dicyclopentadiene, 5-vinyl-2-norbornene (VNB), 1, 4-hexadiene and 1, 6-octadiene.
According to the method provided by the invention, the molar ratio of the metal in the component A to the monomer is preferably 5.0X 10-7～1.0×10-4: 1, more preferably 8.0X 10-7～8.0×10-5: 1, more preferably 1.0X 10-6～5.5×10-5：1。
According to the method provided by the invention, preferably, the polymerization mode of the polymerization reaction is gas-phase polymerization, suspension polymerization or solution polymerization.
If suspension polymerization is employed, the diluent used is C3～C10Alkane or C3～C10Preferably selected from propylene, 1-butene, 1-hexene, butane, pentane or hexane, more preferably from propylene, 1-butene or butane.
If solution polymerization is used, the solvent used is selected from C3～C10Saturated alkanes or C3～C10At least one of cycloalkanes, preferably at least one selected from propane, butane, pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, nonane.
The concentration of the monomer solution is 1-8 mol/L, and the selection of the monomer concentration is related to the monomer type.
Carrying out olefin monomer polymerization reaction in the presence of the catalyst system, wherein the polymerization reaction temperature is preferably-30-130 ℃, more preferably-10-115 ℃, and further preferably-5-100 ℃; the polymerization reaction time is 1 minute to 2 hours, more preferably 2 minutes to 1.5 hours, and still more preferably 5 minutes to 1 hour.
Reacting at polymerization temperature for a certain time, terminating the polymerization reaction by using water, methanol, ethanol, amine and other substances, treating the obtained solution in hydrochloric acid ethanol solution or aqueous solution containing NaOH, separating out a polymer, removing the solvent, separating the polymer, and drying to constant weight.
The technical scheme of the invention has the beneficial effects that: (1) by adopting the catalyst system and the polymerization method, the environment-friendly alkane solvent can be completely adopted, the use of toxic aromatic hydrocarbon solvent is avoided, and the environment is protected; (2) the catalyst can copolymerize ethylene and alpha-olefin or efficiently copolymerize ethylene, alpha-olefin and non-conjugated diene, the activity of the catalyst is greatly improved, and the using amount of a cocatalyst can be greatly reduced while high catalytic activity and monomer conversion rate are kept, so that the production cost can be reduced, the catalyst component residue is reduced, and the quality of a polymer product is improved; (3) the olefin polymerization product has high molecular weight and the product performance is improved.
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 weight average molecular weight (M) of the polymer was determined by gel chromatography at 150 ℃w) And molecular weight distribution (M)w/Mn) Trichlorobenzene is used as solvent and mobile phase.
The catalyst activity is in gpolymer mol per mol of procatalyst per hour of polymer production-1of Ti·h-1。
Example 1
To a monomer solution (ethylene: propylene ═ 1:2) at a concentration of 140g/L, a 10 wt% MMAO/heptane solution (component B) and a 1, 3-bis (2, 6-diisopropylphenyl) -imidoimidazoline-isooctanoic acid-cyclopentadienyl titanium chloride (component a)/hexane solution were added at 50 ℃, wherein the molar ratio of Al in component B to Ti in component a was 2000: 1, after carrying out polymerization reaction for 30 minutes, adding a 5% hydrochloric acid ethanol solution to terminate the reaction, and carrying out vacuum drying on the obtained copolymer at 40 ℃ until the weight is constant, thereby obtaining 3.7g of binary copolymer. The catalyst activity was 1.5X 106g polymer·mol-1of Ti·h-1Weight average molecular weight (M) of the copolymerw) Is 3.2X 105Molecular weight distribution index (M)w/Mn) Is 2.1; the ethylene content of the copolymer was 61 wt% and the propylene content was 39 wt%.
Example 2
To a monomer solution (ethylene: propylene ═ 1:2) having a concentration of 140g/L at 50 ℃, a 10 wt% MMAO/heptane solution (component B) was added and component a was mixed with triisobutylaluminum (component C) for 1 minute, the molar ratio of Al in component B to Ti in component a being 1000: 1, the molar ratio of the component C to the Ti in the component A is 20: 1 polymerization time 30 minutes, and termination of the procedure in example 1 gave 2.8g of a bipolymer. The catalytic activity was 1.1X 106gpolymer·mol-1of Ti·h-1(ii) a M of the copolymerwIs 3.8X 105，Mw/MnIs 2.0; the ethylene content of the copolymer was 66 wt% and the propylene content was 34 wt%.
Example 3
The polymerization process was as described in example 2, except that the molar ratio of Al in component B to Ti in component a was 300: 1, the molar ratio of the component C to the Ti in the component A is 100: 1, 5.4g of a binary copolymer was obtained. The catalytic activity was 2.2X 106g polymer·mol-1of Ti·h-1. M of the copolymerwIs 2.7X 105，Mw/MnIs 2.3; the ethylene content of the copolymer was 56% by weight and the propylene content was 44% by weight.
Example 4
The polymerization process was as described in example 2, except that the molar ratio of component C to Ti in component a was 100: 1, polymerization temperature 15 ℃ to give 5.03g of a copolymer having a catalytic activity of 5.0X 106g polymer·mol-1of Ti·h-1. M of the copolymerwIs 1.3X 105，Mw/MnIs 2.3; the ethylene content of the copolymer was 45 wt% and the propylene content was 55 wt%.
Example 5
The polymerization was carried out as described in example 4, except that the start-up temperature was 90 ℃ and the temperature was increased to 95 ℃ during the polymerization. 3.6g of a binary copolymer was obtained. The catalytic activity was 3.6X 106g polymer·mol-1of Ti·h-1. M of the copolymerwIs 2.0X 105，Mw/MnIs 2.6; the ethylene content of the copolymer was 58 wt% and the propylene content was 42 wt%.
Example 6
The polymerization was carried out as described in example 2, except that the monomer solution contained ENB (1% of the total moles of ethylene/propylene), the molar ratio of component C to Ti in component a was 100: 1, mixing time of component C with component A was 30min, yielding 6.1g of terpolymer. The catalyst activity was 2.4X 106g polymer·mol-1of Ti·h-1. M of the copolymerwIs 2.5 multiplied by 105，Mw/MnIs 2.6. Ethylene content in the copolymer45 wt%, propylene content 51.5 wt%, ENB content 3.5 wt%.
Example 7
The polymerization was carried out as described in example 5, except that the polymerization temperature was 30 ℃ and the polymerization time was 10 minutes, to obtain 4.41g of a bipolymer. The catalytic activity was 1.3X 107g polymer·mol-1of Ti·h-1. M of the copolymerwIs 3.3X 105，Mw/MnIs 2.4; the ethylene content of the copolymer was 51% by weight and the propylene content was 49% by weight.
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 (28)
1. A metallocene catalyst system, characterized in that the catalyst system comprises: component a, component B and component C, wherein: the component A is metallocene compound, the component B is aluminoxane or modified aluminoxane, and the component C is alkyl aluminum compound;
the metallocene compound has a general formula L1L2L3MX, wherein in the formula,
L1selected from cyclopentadienyl or cyclopentadienyl derivatives; l is2And L1The same, or a monodentate anionic ligand; l is3Is selected from C4～C20Alkoxy anions, carboxylic acid anions, phosphate anions or sulfate anions of (a); x is selected from alkyl, cycloalkyl, aryl, aralkyl or halogen; m is selected from transition metals of titanium, zirconium or hafnium.
2. The catalyst system of claim 1 wherein component B is present in an amount of 200 to 3000 moles per mole of metal in component a; the content of the component C is 20-300 mol.
3. The catalyst system according to claim 2, wherein the content of component B is 250 to 2500 mol.
4. The catalyst system according to claim 3, wherein the content of component B is 280 to 2300 mol.
5. The catalyst system according to claim 2, wherein the content of component C is 20 to 200 mol.
6. The catalyst system according to claim 5, wherein the content of component C is 20 to 150 mol.
7. The catalyst system according to claim 1, wherein the cyclopentadienyl derivative is selected from indenyl, fluorenyl, substituted cyclopentadienyl, substituted indenyl or substituted fluorenyl; the substituent in the substituted cyclopentadienyl, the substituted indenyl or the substituted fluorenyl is C1～C10Alkyl of (C)3～C8Cycloalkyl of, C6～C10Aryl or substituted aryl and C7～C12One or more of aralkyl or substituted aralkyl groups of (a); the number of the substituent groups in the substituted cyclopentadienyl group is 1-5, the number of the substituent groups in the substituted indenyl group is 1-7, and the number of the substituent groups in the substituted fluorenyl group is 1-9;
the monodentate anionic ligand is an organic compound containing oxygen, sulfur and nitrogen anions; preferably selected from the group consisting of phenol anions, thiophenol anions, ketimine anions, phosphinimine anions, guanidine anions, and imidazolinine anions;
L3is selected from C4～C15Carboxylic acid anions, phosphoric acid ester anions of (a);
x is selected from C1～C10Alkyl of (C)3～C8Cycloalkyl of, C6～C10Aryl or substituted aryl of, C7～C12Aralkyl or substituted aralkyl of (a) or halogen;
m is selected from titanium or zirconium.
8. The catalyst system of claim 1, wherein L1Selected from the group consisting of cyclopentadienyl, methylcyclopentadienyl, 1, 2-dimethylcyclopentadienyl, tetramethylcyclopentadienyl, pentamethylcyclopentadienyl, tetramethyl-n-propylcyclopentadienyl, tetramethylphenylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, tert-butylcyclopentadienyl, pentaphenylcyclopentadienyl, perfluorocyclopentadienyl, indenyl, methylindenyl, dimethylindenyl, n-butylindenyl or fluorenyl, more preferably from the group consisting of cyclopentadienyl, pentamethylcyclopentadienyl, tetramethyl-n-propylcyclopentadienyl or tetramethylphenylcyclopentadienyl.
9. The catalyst system of claim 7, wherein L3Is selected from C5～C12Carboxylic acid anion of (a).
10. The catalyst system of claim 7, wherein X is selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, benzyl, or chloro.
11. The catalyst system of claim 7, wherein M is selected from titanium.
12. The catalyst system according to claim 1, wherein the alkylaluminoxane or modified alkylaluminoxane is selected from one or more of methylaluminoxane, triisobutylaluminum modified methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane and isobutylaluminoxane.
13. The catalyst system according to claim 12, wherein the alkylaluminoxane or modified alkylaluminoxane is selected from methylaluminoxane and/or triisobutylaluminum modified methylaluminoxane.
14. According to claim1, wherein the alkyl aluminum compound has the general formula of R3Al; wherein R is selected from C1～C10Alkyl of (C)3～C8Cycloalkyl of, C6～C10Aryl or substituted aryl of and C7～C12Or substituted aralkyl group.
15. The catalyst system according to claim 14, wherein the alkyl aluminum compound is selected from one or more of triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tricyclopentylaluminum, tri-n-pentylaluminum, triisopentylaluminum, tri-n-hexylaluminum, tricyclohexylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, and tri-p-tolylaluminum.
16. The catalyst system according to claim 15, wherein the alkyl aluminium compound is selected from one or more of triethylaluminium, tri-n-propylaluminium, triisopropylaluminium, tri-n-butylaluminium, triisobutylaluminium, tricyclopentylaluminium, tri-n-hexylaluminium, tricyclohexylaluminium, trihexoctylaluminium and tri-n-octylaluminium.
17. The catalyst system according to claim 16, wherein the alkyl aluminium compound is selected from one or more of tri-n-butyl aluminium, tri-iso-butyl aluminium, tri-n-hexyl aluminium and tri-n-octyl aluminium.
18. A process for the polymerization of olefins catalyzed by the catalyst system of any of claims 1 to 17, comprising: and (3) contacting the catalyst system with a monomer solution to carry out polymerization reaction.
19. The process of claim 18 wherein component a and component B form a catalyst system in which each component is contacted with the monomer solution in one of the following ways:
(1) adding the component A into the monomer solution and then adding the component B;
(2) adding the component B into the monomer solution and then adding the component A;
(3) simultaneously adding the component A and the component B into the monomer solution;
(4) pre-mixing the component A and the component B and then adding the mixture into a monomer solution;
(5) the two streams, component A and component B, are mixed separately with the monomer solution stream.
20. The process of claim 18 wherein component C is added to the catalyst system formed from component a, component B and component C in one of the following ways:
(1) simultaneously adding the component A, the component B and the component C into the monomer solution;
(2) mixing the component C and the component A, and then adding the mixture into the monomer solution;
(3) mixing the component C and the component B, and then adding the mixture into the monomer solution;
(4) the three streams, component a, component B and component C, are mixed separately with the monomer solution stream.
21. The process of claim 18, wherein the monomer is an olefin selected from one or more of an alpha-olefin, a cyclic olefin, or an unconjugated diene.
22. The process of claim 21, wherein the alpha-olefin is selected from one or more of ethylene, propylene, 1-butene, isobutylene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene;
the cycloolefin is selected from one or more of cyclopentene, cyclohexene and norbornene;
the non-conjugated diene is selected from one or more of 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 1, 4-hexadiene and 1, 6-octadiene.
23. The process of claim 18 wherein the molar ratio of metal to monomer in component a is 5.0 x 10-7～1.0×10-4：1。
24. The process of claim 23 wherein the molar ratio of metal to monomer in component a is 8.0 x 10-7～8.0×10-5：1。
25. The process of claim 24 wherein the molar ratio of metal to monomer in component a is 1.0 x 10-6～5.5×10-5：1。
26. The process of any of claims 18-25, wherein the polymerization temperature is from-30 ℃ to 130 ℃.
27. The process of claim 26, wherein the polymerization temperature is from-10 ℃ to 115 ℃.
28. The process of claim 27, wherein the polymerization temperature is from-5 ℃ to 100 ℃.
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