CN114478865B - Late transition metal catalyst for olefin polymerization, preparation method and application thereof - Google Patents
Late transition metal catalyst for olefin polymerization, preparation method and application thereof Download PDFInfo
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- CN114478865B CN114478865B CN202011163267.4A CN202011163267A CN114478865B CN 114478865 B CN114478865 B CN 114478865B CN 202011163267 A CN202011163267 A CN 202011163267A CN 114478865 B CN114478865 B CN 114478865B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a late transition metal catalyst for olefin polymerization, which comprises the reaction product of the following components: (1) a late transition metal compound; (2) chlorine-containing silicon-containing compounds; (3) an organoaluminum compound; (4) Silica gel, wherein the post-transition metal compound is selected from compounds shown in a formula (I). The invention also discloses a preparation method of the catalyst. The late transition metal catalyst has high loading rate, good catalyst particle shape and easy size adjustment. Has high polymerization activity and narrow molecular weight distribution when used for olefin polymerization.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a supported diimine late transition metal catalyst for olefin polymerization, and a preparation method and application thereof.
Background
During the development of olefin polymerization catalysts, late transition metal catalysts developed in the nineties of the twentieth century have received great development and attention. In particular to Ni, pd and Fe, co diimine catalyst systems (WO 9623010, WO 9827124), wherein the Ni and Pd catalysts can generate branched or even hyperbranched high molecular weight polyethylene with narrow molecular weight distribution through ethylene homogeneous polymerization, and the Fe and Co catalysts generate linear polyethylene with wide molecular weight distribution. However, the olefin polymerization is carried out in a homogeneous phase, and the resulting polymer is in an amorphous state and cannot be used in a widely used polymerization process by a slurry method or a gas phase method.
At present, in the research of loading late transition metal catalyst, the carrier can be SiO 2 、Al 2 O 3 、MgCl 2 Inorganic materials such as molecular sieve, organic materials such as cyclodextrin, polystyrene and polysiloxane, and different carriersA composite carrier with the same function. The loading mode can be physical adsorption, and the catalyst can also be connected on the carrier through the bonding action of functional groups, so that the physical adsorption acting force is weak, and the catalyst is easy to fall off from the carrier in the polymerization process; the chemical bond bonding effect is tight in connection and high in bonding strength, and the catalyst can be effectively prevented from falling off in the polymerization process. In the prior art, silica gel with good particle morphology is used as a carrier, for example, shih Keng-Yu in WO01/32723 uses a silica gel-activated transition metal catalyst loaded with aluminum alkyl, which can use aluminum alkyl as a cocatalyst and has good catalytic activity. However, a large amount of aluminum alkyl still needs to be used in the preparation of the carrier, and the loading efficiency of the catalyst is low. The catalyst ligand structure is functionalized, and the late transition metal catalyst is loaded on silica gel (CN 10169111; CN101173012; CN 101531724) in a chemical bonding mode to improve the loading efficiency of the catalyst, but the preparation cost of the catalyst is greatly improved by the method, and the defects limit the industrial application of the silica gel loaded late transition metal catalyst.
The alpha-diimine late transition metal catalysts are of great interest because of their high activity and because of the wide range of polymer molecular weights and branching that can be manipulated. Du Pont et al have filed a number of patents (WO 96/23010, WO 98/03521, WO 98/40374, WO 99/05189, WO 99/62968, WO 00/06620, U.S. Pat. No. 6,103,658, U.S. Pat. No. 6,660,677). The alpha-nickel diimine catalyst can catalyze oligomerization or polymerization of ethylene with high activity at normal temperature or low temperature under the action of methylaluminoxane or alkylaluminium. However, when the reaction temperature is increased to be higher than 50 ℃, the activity of the alpha-nickel diimine catalyst is rapidly reduced, and the molecular weight of the prepared polyethylene is rapidly reduced along with the increase of the polymerization temperature. The existing ethylene gas-phase polymerization process requires the polymerization temperature to be more than 85 ℃, the ethylene solution polymerization process requires the polymerization temperature to be 150-250 ℃, and the original late transition metal catalyst can not meet the requirements of the existing gas-phase and solution-method ethylene polymerization device.
Disclosure of Invention
The invention provides a post-transition metal catalyst of supported diimine for olefin polymerization and a preparation method thereof, aiming at the problems in the prior art, the preparation method is simple and easy to implement, the prepared catalyst can still keep higher polymerization activity and has higher loading efficiency at higher temperature, and the molecular weight distribution of the polymer obtained by olefin polymerization is narrower.
In a first aspect the present invention provides a late transition metal catalyst for the polymerisation of olefins comprising the reaction product of:
(1) A late transition metal compound;
(2) A chlorine-containing silicon-containing compound;
(3) An organoaluminum compound;
(4) Silica gel;
the late transition metal compound is selected from compounds shown in a formula (I),
formula (I), R 1 And R 2 The same or different, independently selected from C1-C30 alkyl containing substituent or not containing substituent; r 3 And R 4 The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, R 3 -R 4 Optionally forming a ring with each other; r 11 Selected from C1-C20 alkyl containing substituent or not containing substituent; y is selected from nonmetal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R 1 And R 2 Is selected from C1-C20 alkyl containing substituent or not containing substituent and C6-C20 aryl containing substituent or not containing substituent.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R 1 And/or R 2 Is a group of formula (II):
in the formula (II), the reaction solution is shown in the specification,R 1 -R 5 the alkyl is a linear alkyl, branched alkyl or cycloalkyl, the alkoxy is a linear alkoxy, branched alkoxy or cycloalkoxy, the alkyl is a linear alkoxy, branched alkoxy or cycloalkoxy, the alkenyl is a substituted or unsubstituted C2-C20 alkenyl, the alkynyl is a substituted or unsubstituted C2-C20 alkynyl, the alkoxy is a substituted or unsubstituted C1-C20 alkoxy, the alkenyloxy is a substituted or unsubstituted C2-C20 alkenyloxy, the alkynyloxy is a substituted or unsubstituted C2-C20 alkynyloxy, the aryl is a substituted or unsubstituted C6-C20 aryl, the aralkyl is a substituted or unsubstituted C7-C20 aralkyl, and the alkylaryl is a substituted or unsubstituted C7-C20 alkaryl; r 1 -R 5 Optionally forming a ring with each other.
According to a preferred embodiment of the catalyst of the invention, in formula (II), R 1 -R 5 The same or different, each is independently selected from hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl, and substituted or unsubstituted C7-C15 alkaryl.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R 3 And R 4 The alkyl groups are the same or different and are respectively and independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl groups containing substituent or no substituent, C2-C20 alkenyl groups containing substituent or no substituent, C2-C20 alkynyl groups containing substituent or no substituent, C1-C20 alkoxy groups containing substituent or no substituent, C2-C20 alkenyloxy groups containing substituent or no substituent, C2-C20 alkynyloxy groups containing substituent or no substituent, C6-C20 aryl groups containing substituent or no substituent, C7-C20 aralkyl groups containing substituent or no substituent and C7-C20 alkaryl groups containing substituent or no substituent, the alkyl groups are linear alkyl groups, branched alkyl groups or cyclic alkyl groups, and the groups areThe alkoxy is linear alkoxy, branched alkoxy or cycloalkoxy.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R 3 And R 4 Each independently selected from the group consisting of hydrogen, halogen, hydroxy, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyloxy, substituted or unsubstituted C2-C10 alkynyloxy, substituted or unsubstituted C6-C15 aryl, substituted or unsubstituted C7-C15 aralkyl, and substituted or unsubstituted C7-C15 alkaryl.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R 3 And R 4 Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy and halogen.
According to a preferred embodiment of the catalyst of the invention, R 11 Is selected from C1-C20 alkyl containing substituent or not, preferably C1-C10 alkyl containing substituent or not, more preferably C1-C6 alkyl containing substituent or not.
According to a preferred embodiment of the catalyst of the invention, Y is O or S.
According to a preferred embodiment of the catalyst of the invention, M is nickel or palladium.
According to a preferred embodiment of the catalyst of the present invention, X is selected from the group consisting of halogen, C1-C10 alkyl with or without substituents and C1-C10 alkoxy with or without substituents, preferably from the group consisting of halogen, C1-C6 alkyl with or without substituents and C1-C6 alkoxy with or without substituents.
According to a preferred embodiment of the catalyst of the present invention, the substituents are selected from the group consisting of halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy and halogenated C1-C10 alkoxy.
According to a preferred embodiment of the catalyst of the present invention, the substituents are preferably selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy.
In the present invention, the substitution may be performed by substituting carbon in the main chain or by substituting hydrogen in carbon.
According to a preferred embodiment of the catalyst of the invention, the substituent is fluorine, chlorine, bromine or iodine.
According to a preferred embodiment of the catalyst of the present invention, examples of said C1-C6 alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or 3, 3-dimethylbutyl.
According to a preferred embodiment of the catalyst of the present invention, examples of said C1-C6 alkoxy group include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3-dimethylbutoxy.
According to a preferred embodiment of the catalyst of the invention, the late transition metal compound is selected from compounds represented by formula (III):
in the formula (III), R 1 -R 5 The group is shown as formula (II), R 3 、R 4 、R 11 The groups denoted by M, Y and O are shown in the formula (I).
According to a preferred embodiment of the catalyst of the invention, the chlorine-containing silicon-containing compound is selected from the general formula Cl m Si(R 5 ) 4-m At least one of the compounds shown in the specification, wherein R 5 Is selected from C 1 -C 20 A hydrocarbon group of (a); m represents an integer of 1 to 4.
According to some preferred embodiments of the invention, R 5 Is selected from C 1 -C 10 Alkyl of (C) 3 -C 10 Cycloalkyl of, C 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl and C 7 -C 10 An alkylaryl group of (a).
According to some preferred embodiments of the invention, R 5 Is selected from C 1 -C 6 Alkyl of (C) 3 -C 6 Cycloalkyl of, C 6 -C 10 Aryl of (C) 7 -C 10 Aralkyl and C 7 -C 10 An alkylaryl group of (a).
According to some preferred embodiments of the present invention, the chlorine-containing silicon-containing compound is selected from at least one of trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, dimethylethylchlorosilane, diethylpropylchlorosilane, dipropylmethylchlorosilane, dichlorodimethylsilane, dichlorodiethylsilicon, dichlorodiphenylsilicon, dichloromethyl-n-propylsilane, dichloromethylphenylsilane, trichloromethylsilane, trichloroethylsilane, phenyltrichlorosilane, and silicon tetrachloride, preferably from at least one of trimethylchlorosilane, triethylchlorosilane, dichlorodimethylsilane, dichlorodiethylsilicon, dichlorodiphenylsilicon, trichloromethylsilane, trichloroethylsilane, and silicon tetrachloride.
According to a preferred embodiment of the catalyst of the present invention, the organoaluminum compound comprises at least one of an alkylaluminoxane compound, an alkylaluminum compound or an alkylaluminum chloride compound.
According to a preferred embodiment of the catalyst of the present invention, the alkylalumoxane has the general formula:
wherein R represents C 1 -C 12 Is preferably C 1 -C 6 Alkyl groups of (a);
a represents an integer of 4 to 30, preferably an integer of 10 to 30.
According to a preferred embodiment of the catalyst of the invention, the alkylaluminum compound is chosen from trialkylaluminum compounds, such as trialkylaluminum, for example one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum.
According to a preferred embodiment of the catalyst of the invention, the alkylaluminum chloride compound is selected from one or more of diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride and the like.
According to a preferred embodiment of the catalyst of the present invention, the alkylalumoxane is Methylalumoxane (MAO) and/or Modified Methylalumoxane (MMAO).
According to a preferred embodiment of the catalyst of the present invention, the aluminum content in the late transition metal catalyst is 1 to 20% by weight, preferably 1 to 15% by weight.
According to a preferred embodiment of the catalyst of the present invention, in the late transition metal catalyst, the late transition metal compound is contained in an amount of 0.05 to 10% by weight, based on the metal M.
According to some embodiments of the invention, the method of preparing the late transition metal compound of formula (I) comprises:
1) Will be of the formula R 1 -NH 2 And/or R 2 -NH 2 Reacting the compound with a diketone compound shown as a following formula (IV) to prepare an alpha-diimine ligand, wherein the structure of the alpha-diimine ligand is shown as a formula (V):
R 1 -R 4 the indicated groups are the same as formula (I);
2) The alpha-diimine ligand prepared in the step 1) and MXn or MXn derivatives selected from the group consisting of compounds with the general formula R 11 YH to obtain a compound shown as the formula (I) of the invention; m, X, R 11 And Y is the same as formula (I), and n is an integer satisfying the valence of the metal M.
According to some embodiments of the invention, the MXn is nickel bromide and/or nickel chloride.
According to some embodiments of the invention, the derivative of MXn is of formula LMX 2 The compound shown in the specification, wherein M is selected from metal elements in a VIII group, and is preferably nickel or palladium; x is halogen, preferably fluorine, chlorine, bromine or iodine, more preferably chlorine or bromine, and n is an integer conforming to the valence of the metal M; l is a ligand capable of coordinating with M metal, such as ethylene glycol dimethyl ether.
According to some embodiments of the invention, the derivatives of MXn include 1, 2-dimethoxyethane nickel halides, such as 1, 2-dimethoxyethane nickel bromide and 1, 2-dimethoxyethane nickel chloride.
According to some embodiments of the invention, the R is 11 The compound YH is an alcohol solvent, preferably an alcohol compound having 1 to 10 carbon atoms, preferably an alcohol compound having 1 to 6 carbon atoms, for example, ethanol or 2-methyl-1-propanol.
According to some embodiments of the invention, in step 1), the reaction is carried out in a dispersion medium, such as dichloromethane, for example, to enable the dissolution and effective dispersion of the reaction components. According to the present invention, the alpha-diimine ligand may be first dissolved in the dispersion medium.
In a second aspect, the present invention provides a method for preparing a late transition metal catalyst according to the first aspect of the present invention, comprising the steps of:
(1) Carrying out a first reaction on silica gel and a compound containing chlorine and silicon to obtain a first reaction product;
(2) Carrying out a second reaction on the first reaction product in the step (1) and an organic aluminum compound to obtain a second reaction product;
(3) And (3) carrying out a third reaction on the second reaction product obtained in the step (2) and a late transition metal compound to obtain the late transition metal catalyst.
According to some embodiments of the invention, the reaction temperature of the first reaction is between 0 ℃ and 120 ℃, preferably between 20 ℃ and 100 ℃, more preferably between 30 ℃ and 100 ℃.
According to some embodiments of the invention, the reaction temperature of the second reaction is between 30 and 120 ℃, preferably between 30 and 100 ℃, more preferably between 50 and 100 ℃.
According to some embodiments of the invention, the reaction temperature of the third reaction is between 0 and 120 ℃, preferably between 20 and 100 ℃.
According to the present invention, the reaction time of the first, second and/or third reaction is not particularly limited, and may be 0.5 to 24 hours, based on the reaction components being sufficiently reacted.
In some embodiments, the reaction time of the first reaction is 3 to 24 hours, for example, 4 hours.
In some embodiments, the reaction time of the second reaction is 3 to 24 hours, for example, 4 hours.
In some embodiments, the reaction time of the second reaction is 0.5 hours.
According to some embodiments of the invention, the first, second and/or third reaction is carried out in the presence of a dispersant. According to the present invention, the dispersant is not particularly limited, so long as it can effectively disperse the reaction components.
According to some embodiments of the present invention, the dispersant of the first reaction may be selected from one or more of toluene, benzene, xylene and saturated hydrocarbons such as hexane, heptane and cyclohexane, preferably toluene or saturated alkanes.
According to some embodiments of the invention, the dispersant of the second reaction is selected from one or more of toluene, benzene, xylene, hexane, heptane and cyclohexane, preferably toluene.
According to some embodiments of the invention, the dispersant of the third reaction is selected from one or more of toluene, benzene, xylene, hexane, heptane, cyclohexane, preferably toluene, hexane or a mixture of both.
According to some embodiments of the invention, the first, second and/or third reaction is carried out under the protection of an inert gas such as nitrogen.
According to some embodiments of the present invention, the late transition metal catalyst obtained in step (3) is in a slurry state, and the slurry can be used for polymerization directly, or can be used for polymerization after removing the solvent, washing and drying to obtain a solid catalyst.
According to some embodiments of the invention, the chlorine-containing silicon-containing compound is added in an amount of 0.01 to 3mmol per gram of silica gel.
According to some embodiments of the invention, the late transition metal compound is added in an amount of 1 to 1000. Mu. Mol, calculated as metal M, per gram of silica gel.
According to some embodiments of the present invention, the organoaluminum compound is added in an amount of 0.01 to 30mmol per gram of silica gel.
In a third aspect, the present invention provides a process for the polymerisation of olefins, which process comprises polymerising an olefin, preferably of the formula CH, in the presence of a catalyst according to the first aspect of the present invention or prepared according to the second aspect of the present invention 2 = CHR where R is hydrogen or C 1 -C 6 Alkyl groups of (a); more preferably, the olefin is one or more of ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene.
The catalyst prepared by the invention can be used in different polymerization methods, such as gas phase polymerization, slurry polymerization and the like. Can be used for homopolymerization or copolymerization of olefin, in particular for homopolymerization of ethylene or copolymerization of ethylene and other alpha-olefin.
The catalyst prepared by the invention can be directly used for olefin polymerization, such as in a gas-phase polymerization process; the catalyst can also be used for olefin polymerization by adding aluminum alkyl as a cocatalyst, and particularly, the aluminum alkyl added in a slurry process can remove impurities in a system and improve the polymerization activity to a certain extent without adding expensive MAO as the cocatalyst.
The solvent used in the polymerization of the present invention is selected from alkanes, aromatic hydrocarbons or halogenated hydrocarbons, preferably one or a mixture of hexane, pentane, heptane, benzene, toluene, dichloromethane, chloroform and dichloroethane, and most preferably one or a mixture of hexane, toluene and heptane.
According to some embodiments of the invention, the late transition metal catalyst has a concentration of 1 at the time of polymerization×10 －8 mol/l-1X 10 －3 Mol/l, preferably 1X 10 －8 Mole/liter －1 -10 －5 Mol/l.
According to some embodiments of the invention, the temperature of the polymerization is from-78 ℃ to 150 ℃, preferably from 0 ℃ to 90 ℃, more preferably from 55 ℃ to 90 ℃.
According to some embodiments of the invention, the polymerization pressure is from 0.01 to 10.0MPa, preferably from 0.01 to 2.0MPa.
In a fourth aspect the present invention provides the use of a catalyst according to the first aspect of the invention and/or a catalyst obtainable by a process according to the second aspect of the invention and/or a process according to the third aspect of the invention in the polymerisation of olefins.
Compared with the prior art, the invention has the following advantages:
1. the complex synthesis method provided by the invention is simple and feasible, and the trinuclear complex can be directly prepared from the ligand;
2. the preparation method of the modified silica gel carrier is simple, the loading efficiency of the late transition metal complex is high, the obtained catalyst has good particle shape, and the size of the catalyst particles is adjustable.
3. The supported late transition metal catalyst is used for ethylene polymerization or copolymerization and has higher polymerization activity at higher temperature.
4. The catalyst prepared by the invention is used for olefin polymerization to obtain resin powder, has good particle shape and high bulk density, and can be suitable for polymerization processes of a slurry method and a gas phase method.
Detailed Description
In order that the invention may be more readily understood, the following detailed description of the invention refers to the accompanying examples which are intended to be illustrative of the invention only and are not to be taken as limiting the scope of the invention. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used are not indicated by the manufacturer, and are conventional products which are commercially available or obtainable by conventional methods.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
The test method comprises the following steps:
1. nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz), tetramethylsilicon (TMS) as an internal standard.
2. ICP (plasma emission spectroscopy) characterization: the weight percent of metal in the supported catalyst was determined quantitatively. The instrument is a P1000 type ICP-AES plasma emission spectrometer produced by PE company in America.
3. The molecular weight and the molecular weight distribution of the polymer are characterized in that the molecular weight and the molecular weight distribution are determined by Gel Permeation Chromatography (GPC), an instrument adopts Waters Alliance GPCV 2000, the solvent is 1,2, 4-trichlorobenzene, the sample concentration is lmg/ml, and the solvent flow rate is 1.0ml/min; the measurement temperature was 150 ℃. Each sample was measured twice.
In the following examples, DME refers to ethylene glycol dimethyl ether.
Example 1
(1) Complex Ni 1 Preparation of (R in the formula (III)) 1 、R 3 Is methyl, R 2 、R 4 -R 5 Is hydrogen, R 3 、R 4 Is methyl, R 11 Is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9 mmol) of (DME) NiBr 2 To a solution containing 0.175g (0.6 mmol) of ligand L 1 In dichloromethane solution. Stirring for 6h at room temperature, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain yellow powdery solid Ni 1 . Yield: 70.2 percent. Elemental analysis (C) 44 H 58 Br 6 N 4 Ni 3 O 2 ): c,39.72; h,4.39; n,4.21; experimental values (%): c,39.38; h,4.60; and N,3.96.
(2) Preparation of alkyl silicon chloride/silica gel carrier
Under the protection of nitrogen, 10.0g of dry silica gel carrier is taken and added into a glass reactor, 100 ml of dry hexane is added and dispersed into suspension, 1 ml of SiCl is added 2 (n-Bu) 2 Stirring, heating to 30 deg.C, reacting for 4 hr, and vacuum drying to obtain solid powder with good fluidity.
(3) Preparation of organoaluminum/alkylsilylchloride/silica gel support
Under the protection of nitrogen, 5.0g of the solid powder obtained in the step (2) is taken and added into a glass reactor, 60 ml of dried toluene is added to be dispersed into suspension, 18 ml of 10wt% MAO (methyl aluminoxane) toluene solution is added, the temperature is raised to 50 ℃, the reaction is stirred for 4 hours, and then the solid powder with good fluidity, namely the silica gel carrier containing the methyl aluminoxane, is obtained by washing three times with toluene, 50 ml each time, then washing with hexane and drying in vacuum.
(4) Preparation of Supported late transition Metal catalyst A
Under the protection of nitrogen, 2.00g of the silica gel carrier containing methylaluminoxane obtained in the step (3) is added into a glass reactor, 30 ml of dried toluene is added to prepare slurry, and 0.133g (0.1 mmol) of complex Ni is added 1 Dissolving in 20 ml of toluene, dropwise adding the toluene solution of the obtained complex into a reactor, reacting at 30 ℃ for 30 minutes, washing with 30 ml of toluene, and drying in vacuum to obtain the supported late transition metal catalyst A. The catalyst A has Ni content of 0.70 wt% and Al content of 9.88 wt% as shown by ICP.
(5) Experiment of ethylene polymerization
In a 1-liter stainless steel high-pressure polymerizer, the autoclave was purged with nitrogen and ethylene three times, then 500 ml of a hexane solvent was added, and 2 ml of a 1 mol/l Triethylaluminum (TEA) hexane solution was added with the addition of hexane, followed by addition of 20 to 50 mg of the supported late transition metal catalyst prepared above, heating to 80 ℃ and raising and maintaining the pressure to and at 1.0MPa for 1 hour. After the polymerization reaction is finished, cooling, collecting polyethylene particle powder, and weighing. The polymerization results are shown in Table 1.
Comparative example 1
(1) Preparation of silicon alkyl chloride/silica gel carrier
Same as example 1, step (2).
(2) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(3) Preparation of Supported transition Metal catalyst A
Under the protection of nitrogen, 2.00g of the prepared organoaluminum/silicon hydrocarbyl chloride/silica gel carrier was charged into a glass reactor, 30 ml of dried toluene was added to prepare a slurry, 0.153g (0.3 mmol) of complex 1 (see the structure below, for the synthesis thereof, J.Am.chem.Soc.1995,117, 6414-6415) was dissolved in 20 ml of toluene and reacted at 30 ℃ for 30 minutes, followed by washing with 30 ml of toluene and vacuum drying to obtain a supported transition metal catalyst A. By ICP characterization, catalyst a contained 0.60% Ni and 10.11% Al by weight.
(4) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
Example 2
(1) Complex Ni 2 Preparation of (R in the formula (III)) 1 、R 3 Is isopropyl, R 2 、R 4 -R 5 Is hydrogen, R 3 、R 4 Is methyl, R 11 Is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9 mmol) of (DME) NiBr 2 To a solution containing 0.243g (0.6 mmol) of ligand L 2 In dichloromethane solution. Stirring at room temperature for 6h, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain yellow powdery solid Ni 2 . The yield was 74.0%. Elemental analysis (C) 60 H 90 Br 6 N 4 Ni 3 O 2 ): c,46.35; h,5.83; n,3.60; experimental values (%): c,46.48; h,6.12; and N,3.50.
(2) Preparation of silicon alkyl chloride/silica gel carrier
Same as example 1, step (2).
(3) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(4) Preparation of Supported late transition Metal catalyst B
Similar to step (4) in example 1, only 0.133g (0.1 mmol) of Ni complex in example 1 was added 1 Replacement with 0.155 g (0.1 mmol) of complex Ni 2 And obtaining the loaded transition metal catalyst B. The catalyst B has a Ni content of 0.71 wt% and an Al content of 10.26 wt% according to ICP characterization.
(5) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
Comparative example 2
(1) Preparation of silicon alkyl chloride/silica gel carrier
Same as example 2, step (2).
(2) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 2, step (3).
(3) Preparation of Supported transition Metal catalyst B
2.00g of the organoaluminum/silicon hydrocarbonyl/silica gel prepared above was charged into a glass reactor under nitrogen atmosphere, 30 ml of dried toluene was added to prepare a slurry, 0.187g (0.3 mmol) of the complex 2 was dissolved in 20 ml of toluene (see the structure below, for the synthesis thereof, J.Am. Chem. Soc.1995,117, 6414-6415), reacted at 30 ℃ for 30 minutes, washed with 30 ml of toluene, and vacuum-dried to obtain a supported transition metal catalyst B. By ICP characterization, catalyst B contained 0.55% by weight Ni and 10.16% by weight Al.
(4) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
Example 3
(1) Preparation of silicon alkyl chloride/silica gel carrier
The same procedure as in step (2) of example 1 was repeated except that SiCl in example 1 was used 2 (n-Bu) 2 Is replaced by SiCl 4 。
(2) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(3) Preparation of Supported late transition Metal catalyst C
The same procedure as in step (4) of example 2 gave a supported late transition metal catalyst C. The catalyst C was characterized by ICP, and had a Ni content of 0.72% by weight and an Al content of 10.33% by weight.
(4) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
Example 4
(1) Complex Ni 3 Preparation of (R in the formula (III)) 1 、R 3 Is isopropyl, R 2 、R 4 -R 5 Is hydrogen, R 3 、R 4 Is methyl, R 11 Is isobutyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9 mmol) of (DME) NiBr 2 To a solution of 2-methyl-1-propanol (10 mL) containing 0.243g (0.6 mmol) of ligand L 2 To a solution of dichloromethane (10 mL), stirred at room temperature for 6h, and precipitated by addition of anhydrous ether. Filtering to obtain filter cake, washing with anhydrous diethyl etherVacuum drying the filter cake to obtain brownish red powdery solid Ni 3 . The yield was 74.5%. Elemental analysis (C) 64 H 98 Br 6 N 4 Ni 3 O 2 ): c,47.71; h,6.13; n,3.48; experimental values (%): c,47.48; h,6.42; and N,3.29.
(2) Preparation of silicon hydrocarbyl chloride/silica gel carrier
Same as example 1, step (2).
(3) Preparation of alkylaluminoxane/silicon alkyl chloride/silica gel carrier
Same as example 1, step (3).
(4) Preparation of Supported late transition Metal catalyst D
Similar to step (4) in example 1, only 0.133g (0.1 mmol) of Ni complex in example 1 was added 1 Replacement by 0.161 g (0.1 mmol) of complex Ni 3 And obtaining the loaded transition metal catalyst D. According to ICP characterization, in the catalyst D, the weight content of Ni is 0.69%, and the weight content of Al is 10.04%.
(5) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
Example 5
(1) Preparation of silicon alkyl chloride/silica gel carrier
The same procedure as in step (2) of example 1 was repeated except that SiCl in example 1 was used 2 (n-Bu) 2 By SiCl 4 。
(2) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(3) Preparation of Supported late transition Metal catalyst E
Similar to step (4) in example 1, only 0.133g (0.1 mmol) of Ni complex in example 1 was added 1 Replacement by 0.161 g (0.1 mmol) of complex Ni 3 To obtain the loaded transition metal catalyst E. ICP representation shows that in the catalyst E, the weight content of Ni is 0.71%, and the weight content of Al is 10.21%.
(4) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
Example 6
(1) Complex Ni 4 Preparation of (R in the formula (III)) 1 、R 3 Is methyl, R 2 、R 4 -R 5 Is hydrogen, R 3 、R 4 Is p-fluorophenyl, R 11 Is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9 mmol) of (DME) NiBr 2 To a solution containing 0.272g (0.6 mmol) of ligand L was slowly added dropwise 3 In dichloromethane (10 mL). The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and adding anhydrous ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni 4 . The yield was 74.1%. Elemental analysis (C) 64 H 62 Br 6 F 4 N 4 Ni 3 O 2 ): c,46.57; h,3.79; n,3.39; experimental values (%): c,46.72; h,3.97; and N,3.48.
(2) Preparation of silicon alkyl chloride/silica gel carrier
The same preparation method as that of the step (2) in example 1 was used except that SiCl in example 1 was used 2 (n-Bu) 2 Is replaced by SiCl 4 。
(3) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(4) Preparation of Supported late transition Metal catalyst F
Similar to step (4) in example 1, only 0.133g (0.1 mmol) of Ni complex in example 1 was added 1 Replacement with 0.165 g (0.1 mmol) of complex Ni 4 And obtaining the loaded transition metal catalyst F. The catalyst F was characterized by ICP, and had a Ni content of 0.70% by weight and an Al content of 10.24% by weight.
(5) Experiment of ethylene polymerization
The same procedure as in step (5) of example 1 was repeated, and the polymerization results are shown in Table 1.
TABLE 1 polymerization results of the Supported late transition Metal catalysts
As can be seen from Table 1, compared with the complex of the comparative example, the supported transition metal catalyst of the invention has higher loading rate, the catalyst has higher polymerization activity, and the molecular weight distribution of the obtained polymer is obviously higher than that of the polymer of the comparative example.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (34)
1. A late transition metal catalyst for the polymerization of olefins, said catalyst comprising the reaction product of:
(1) A late transition metal compound;
(2) A chlorine-containing silicon-containing compound;
(3) An organoaluminum compound;
(4) Silica gel;
the late transition metal compound is selected from compounds shown in a formula (I),
in the formula (I), R 1 And R 2 Is the same as orAnd is independently selected from the group represented by formula (II):
in the formula (II), R 1 -R 5 The alkyl is a linear alkyl, branched alkyl or cycloalkyl, the alkoxy is a linear alkoxy, branched alkoxy or cycloalkoxy, the alkyl is a linear alkoxy, branched alkoxy or cycloalkoxy, the alkenyl is a substituted or unsubstituted C2-C20 alkenyl, the alkynyl is a substituted or unsubstituted C2-C20 alkynyl, the alkoxy is a substituted or unsubstituted C1-C20 alkoxy, the alkenyloxy is a substituted or unsubstituted C2-C20 alkenyloxy, the alkynyloxy is a substituted or unsubstituted C2-C20 alkynyloxy, the aryl is a substituted or unsubstituted C6-C20 aryl, the aralkyl is a substituted or unsubstituted C7-C20 aralkyl, or the alkylaryl is a substituted or unsubstituted C7-C20 alkaryl; r is 1 -R 5 Optionally forming a ring with each other;
in the formula (I), R 3 And R 4 Identical or different, are each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, R 3 -R 4 Optionally forming a ring with each other; r is 11 Selected from C1-C20 alkyl containing substituent or not containing substituent; m is selected from nickel or palladium; y is selected from O or S; x is selected from halogen, C1-C10 alkyl containing substituent or no substituent or C1-C10 alkoxy containing substituent or no substituent.
2. The late transition metal catalyst according to claim 1, wherein in formula (II), R 1 -R 5 The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, or C1-C10 alkynyloxy with or without substituentA C6-C15 aryl group which does not contain a substituent, a C7-C15 aralkyl group which does not contain a substituent or a C7-C15 alkaryl group which does not contain a substituent or a substituent.
3. The late transition metal catalyst according to claim 1, wherein in formula (I), X is selected from the group consisting of halogen, substituted or unsubstituted C1-C10 alkyl, or substituted or unsubstituted C1-C10 alkoxy;
and/or R 11 Selected from C1-C20 alkyl containing or not containing substituent.
4. The late transition metal catalyst of claim 3, wherein in formula (I), X is selected from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl, and substituted or unsubstituted
C1-C6 alkoxy;
and/or R 11 Selected from C1-C10 alkyl containing or not containing substituent.
5. The late transition metal catalyst according to claim 4, wherein in formula (I), R 11 Selected from C1-C6 alkyl containing substituent or not containing substituent.
6. The late transition metal catalyst of claim 1, wherein in formula (I), R 3 And R 4 The alkyl is a straight chain alkyl, branched chain alkyl or cycloalkyl, the alkoxy is a straight chain alkoxy, branched chain alkoxy or cycloalkoxy, the alkyl is a straight chain alkoxy, branched chain alkoxy or cycloalkoxy, the C1-C20 alkyl is substituted or not substituted, the C2-C20 alkenyl is substituted or not substituted, the C2-C20 alkynyl is substituted or not substituted, the C1-C20 alkoxy is substituted or not substituted, the C2-C20 alkenyloxy is substituted or not substituted, the C6-C20 aryl is substituted or not substituted, the C7-C20 aralkyl is substituted or not substituted, or the C7-C20 alkaryl is substituted or not substituted.
7. The late transition metal catalyst according to claim 6, wherein in formula (I), R 3 And R 4 Each independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, C2-C10 alkenyl with or without substituent, C2-C10 alkynyl with or without substituent, C1-C10 alkoxy with or without substituent, C2-C10 alkenyloxy with or without substituent, C2-C10 alkynyloxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent, or C7-C15 alkaryl with or without substituent.
8. The late transition metal catalyst of claim 7, wherein in formula (I), R 3 And R 4 Each independently selected from hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy or halogen.
9. The late transition metal catalyst of claim 8, wherein in formula (I), R 3 And R 4 Each independently selected from hydrogen, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, halogenated C1-C6 alkoxy or halogen.
10. Late transition metal catalyst according to any of claims 1 to 9, characterized in that the substituents are selected from halogen, hydroxy, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy or halogenated C1-C10 alkoxy.
11. The late transition metal catalyst of claim 10, wherein the substituent is selected from the group consisting of halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy, and halogenated C1-C6 alkoxy.
12. The late transition metal catalyst of claim 11, wherein the C1-C6 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, or 3, 3-dimethylbutyl;
and/or the C1-C6 alkoxy is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy or 3, 3-dimethylbutoxy;
and/or the halogen is selected from fluorine, chlorine, bromine or iodine.
13. Late transition metal catalyst according to claim 1, characterized in that the late transition metal compound is selected from compounds according to formula (III):
in the formula (III), R 1 -R 5 The group is shown as formula (II), R 3 、R 4 、R 11 The groups denoted by M, Y and O are shown in the formula (I).
14. The late transition metal catalyst according to any one of claims 1 to 9, 11 to 12, wherein the late transition metal compound of formula (I) is prepared by a method comprising:
1) Will be of the formula R 1 -NH 2 And/or R 2 -NH 2 Reacting the compound with a diketone compound shown as the following formula (IV) to prepare an alpha-diimine ligand, wherein the structure of the alpha-diimine ligand is shown as the formula (V):
R 1 -R 4 the indicated groups are the same as formula (I);
2) The alpha-diimine ligand prepared in the step 1) and MXn or MXn derivativeAnd is selected from the group consisting of those of the formula R 11 YH to obtain a compound shown as the formula (I) of the invention; m, X, R 11 And Y is the same as formula (I), and n is an integer conforming to the valence of the metal M.
15. The late transition metal catalyst of any of claims 1-9, 11-13, wherein the chlorine-containing silicon-containing compound is selected from the group consisting of compounds of the general formula Cl m Si(R 5 ) 4-m At least one of the compounds shown is a compound,
wherein R is 5 Is selected from C 1 -C 20 A hydrocarbon group of (a); m represents an integer of 1 to 4.
16. The late transition metal catalyst of claim 15, wherein said general formula Cl m Si(R 5 ) 4-m In R 5 Is selected from C 1 -C 10 Alkyl of (C) 3 -C 10 Cycloalkyl of, C 6 -C 10 Aryl of, C 7 -C 10 Aralkyl or C 7 -C 10 An alkylaryl group of (a);
or R 5 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl or phenyl.
17. The late transition metal catalyst of claim 15, wherein the chlorine-containing silicon-containing compound is selected from at least one of trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, dimethylethylchlorosilane, diethylpropylchlorosilane, dipropylmethylchlorosilane, dichlorodimethylsilane, dichlorodiethylsilicon, dichlorodiphenylsilicon, dichloromethyl-n-propylsilane, dichloromethylphenylsilane, trichloromethylsilane, trichloroethylsilane, phenyltrichlorosilane, and silicon tetrachloride.
18. The late transition metal catalyst of any of claims 1-9, 11-13, 16-17, wherein the organoaluminum compound comprises at least one of an alkylaluminoxane compound, an alkylaluminum compound, or an alkylaluminum chloride compound.
19. The late transition metal catalyst of claim 18, wherein the alkylalumoxane is of the formula:
wherein R represents C 1 -C 12 A hydrocarbon group of (a); a represents an integer of 4 to 30.
20. The late transition metal catalyst of claim 19, wherein R represents C in the general formula of alkylalumoxane 1 -C 6 Alkyl groups of (a);
and/or a represents an integer of 10 to 30.
21. The late transition metal catalyst of claim 18, wherein the organoaluminum compound is selected from one or more of trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, methylaluminoxane, and MMAO.
22. The late transition metal catalyst of any one of claims 1-9, 11-13, 16-17, 19-21, wherein the late transition metal catalyst has an aluminum content of 1-20% by weight; and/or the content by weight of the late transition metal compound is 0.05-10% based on the metal M.
23. The late transition metal catalyst of claim 22, wherein the aluminum is present in the late transition metal catalyst in an amount of 1-15% by weight.
24. The method of preparing a late transition metal catalyst according to any one of claims 1 to 23, comprising the steps of:
(1) Carrying out a first reaction on silica gel and a compound containing chlorine and silicon to obtain a first reaction product;
(2) Carrying out a second reaction on the first reaction product in the step (1) and an organic aluminum compound to obtain a second reaction product;
(3) And (3) carrying out a third reaction on the second reaction product obtained in the step (2) and a late transition metal compound to obtain the late transition metal catalyst.
25. The method of claim 24, wherein the first, second and/or third reaction is carried out in the presence of a dispersant selected from at least one of toluene, benzene, xylene, hexane, heptane and cyclohexane.
26. The production method according to claim 25, wherein the reaction temperature of the first reaction is 0 to 120 ℃, and the reaction time of the first reaction is 0.5 to 24 hours;
and/or the reaction temperature of the second reaction is 30-120 ℃, and the reaction time of the second reaction is 0.5-24 hours;
and/or the reaction temperature of the third reaction is 0-120 ℃, and the reaction time of the third reaction is 0.5-24 hours.
27. The method of claim 26, wherein the reaction temperature of the first reaction is 20 to 100 ℃;
and/or the reaction time of the first reaction is 3 to 24 hours;
and/or the reaction temperature of the second reaction is 30-100 ℃;
and/or the reaction time of the second reaction is 3-24 hours;
and/or the reaction temperature of the third reaction is 20-100 ℃.
28. The method of claim 27, wherein the reaction temperature of the first reaction is 30 to 100 ℃;
and/or the reaction temperature of the second reaction is 50-100 ℃.
29. The production method according to any one of claims 24 to 28, wherein the chlorine-containing silicon-containing compound is added in an amount of 0.01 to 3mmol, and/or the late transition metal compound is added in an amount of 1 to 1000 μmol, and/or the organoaluminum compound is added in an amount of 0.01 to 30mmol, per gram of silica gel.
30. A process for the polymerization of olefins comprising polymerizing olefins in the presence of a catalyst as claimed in any of claims 1 to 23 or prepared according to the preparation process of any of claims 24 to 29.
31. The method of claim 30, wherein the olefin has the formula CH 2 = CHR, wherein R is hydrogen or C 1 -C 6 Alkyl groups of (a);
and/or the late transition metal catalyst has a concentration of 1X 10 during polymerization －8 mol/l-1X 10 －3 Mol/l;
and/or the temperature of the polymerization is-78 ℃ to 150 ℃;
and/or the pressure of the polymerization is 0.01 to 10.0MPa.
32. The process of claim 31, wherein the olefin is one or more of ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene;
and/or the late transition metal catalyst is present in a concentration of 1X 10 at the time of polymerization －8 Mole/liter －1 -10 －5 Mol/l;
and/or the temperature of the polymerization is from 0 ℃ to 90 ℃;
and/or the pressure of the polymerization is 0.01 to 2.0MPa.
33. The process of claim 32, wherein the temperature of the polymerization is from 55 ℃ to 90 ℃.
34. Use of a catalyst according to any one of claims 1 to 23 or a catalyst prepared according to the process of any one of claims 24 to 29 or a process according to any one of claims 30 to 33 in the polymerisation of olefins.
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