CN114478868A - Late transition metal catalyst for olefin polymerization and preparation method and application thereof - Google Patents
Late transition metal catalyst for olefin polymerization and preparation method and application thereof Download PDFInfo
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- CN114478868A CN114478868A CN202011165677.2A CN202011165677A CN114478868A CN 114478868 A CN114478868 A CN 114478868A CN 202011165677 A CN202011165677 A CN 202011165677A CN 114478868 A CN114478868 A CN 114478868A
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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
- 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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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) a chlorine-containing silicon-containing compound; (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 easily-adjusted size, and has high polymerization activity and narrow molecular weight distribution when being used for olefin polymerization.
Description
Technical Field
The invention belongs to the field of olefin polymerization, and particularly relates to a supported 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 (WO9623010, WO9827124), 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, 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 slurry or gas phase polymerization process.
Currently, in the research on the loading of late transition metal catalysts, few studies have been reported on the loading of late transition metal catalysts by using magnesium chloride compounds alone (Macromolecules 2004,37(17), 6258-. However, this method has the disadvantages that the removal of the polar solvent used for dissolving magnesium chloride requires a relatively high temperature and/or a large amount of an organoaluminum reagent, and the carrier preparation process is complicated, which is not favorable for industrial mass production. In addition, there are also those using silica gel having a good particle form as a carrier, for example, Shih Keng-Yu uses a silica gel-activated late transition metal catalyst carrying aluminum alkyl as in WO01/32723, and aluminum alkyl as a co-catalyst having a good catalytic activity can be used. 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; CN 101173012; CN101531724) by a chemical bonding way 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 the molecular weight and degree of branching of the polymers can be controlled over a wide range. 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, US 6,103,658, US 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 late transition metal catalyst 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 at higher temperature and has higher loading efficiency, and the polymer obtained by olefin polymerization has higher molecular weight and narrower molecular weight distribution.
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 at least one compound selected from the group consisting of compounds represented by the formula (I),
in the formula (I), R1And R2The same or different, independently selected from C1-C30 hydrocarbyl containing or not containing substituent; r5-R8The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r5-R8Optionally forming a ring with each other; r11Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl containing substituent or no substituent, and C1-C10 alkoxy containing substituent or no substituent.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R1And R2Independently selected from a substituted or unsubstituted C1-C20 alkyl group and/or a substituted or unsubstituted C6-C20 aryl group.
According to a preferred embodiment of the catalyst of the invention, R1And/or R2Is a group of formula (II):
in the formula (II), R1-R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C1-C20 alkoxy with or without substituent, or C1-C20 alkoxy with or without substituentC2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, and substituted or unsubstituted C7-C20 alkaryl, the alkyl being a straight-chain alkyl, branched-chain alkyl, or cycloalkyl, the alkoxy being a straight-chain alkoxy, branched-chain alkoxy, or cycloalkoxy; r is1-R5Optionally forming a ring with each other.
According to a preferred embodiment of the catalyst of the invention, in formula (II), R1-R5The aryl group is the same or different and 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, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.
According to a preferred embodiment of the catalyst of the invention, in formula (I), R11Is selected from C1-C20 alkyl with or without substituent, preferably C1-C10 alkyl with or without substituent, more preferably C1-C6 alkyl with or without substituent.
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, substituted or unsubstituted C1-C10 alkyl and substituted or unsubstituted C1-C10 alkoxy, preferably from the group consisting of halogen, substituted or unsubstituted C1-C6 alkyl and substituted or unsubstituted C1-C6 alkoxy.
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), R1-R10、R21、R22The alkyl is a linear alkyl, branched alkyl or cycloalkyl, and the alkoxy is a linear alkoxy, branched alkoxy or cycloalkoxy, each independently selected from the group consisting of hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, and substituted or unsubstituted C7-C20 alkaryl; r1-R10Optionally forming a ring with each other; r21-R22Optionally forming a ring with each other;
R11y, M and X have the same definitions as formula (I).
According to a preferred embodiment of the catalyst of the invention, in formula (III), R1-R10、R21-R22The aryl group is 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, C3-C10 cycloalkyl 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, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent and C7-C15 alkaryl with or without substituent.
According to a preferred embodiment of the catalyst of the invention, in formula (III), R1-R10、R21-R22The same or different, each independentlyIs selected from the group consisting of hydrogen, C1-C10 alkyl, halogenated C1-C10 alkyl, C1-C10 alkoxy, halogenated C1-C10 alkoxy and halogen, more preferably from the group consisting of 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, the substituents are selected from 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 invention, the substituents are selected from 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, 3-dimethylbutoxy.
According to a preferred embodiment of the catalyst of the invention, the late transition metal compound is selected from one or more of the following compounds:
1) a complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
2) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
3) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
4) A complex of formula (III) wherein R1-R6＝Me，R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
5) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
6) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
7) A complex of formula (III) wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
8) A complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
9) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
10) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
11) a complex of formula (III) wherein R1-R6＝Me，R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
12) a complex of formula (III), wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
13) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
14) a complex of formula (III) wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
15) a complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝H R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
16) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
17) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
18) A complex of formula (III) wherein R1-R6＝Me，R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
19) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
20) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
21) A complex of formula (III) wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
22) A complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝H，R31＝R32＝R11＝Et，M＝Ni，Y＝O，X＝Br；
23) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
24) a complex of formula (III), wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
25) a complex of formula (III) wherein R1-R6＝Me，R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
26) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
27) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
28) a complex of formula (III), wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11I.e., isobutyl, M ═ Ni, Y ═ O, and X ═ Br.
According to a preferred embodiment of the catalyst of the invention, the chlorine-containing silicon-containing compound is selected from the general formula ClmSi(R3)4-mAt least one of the compounds shown, wherein R3Is selected from C1-C20A hydrocarbon group of (a); m represents an integer of 1 to 4.
According to some preferred embodiments of the invention, R3Is selected from C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Aralkyl and C7-C10An alkylaryl group of (a).
According to some preferred embodiments of the invention, R3Is selected from C1-C6Alkyl of (C)3-C6Cycloalkyl of, C6-C10Aryl of (C)7-C10Aralkyl and C7-C10An alkylaryl group of (2).
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 alkylaluminoxane has the general formula:
wherein R represents C1-C12Is preferably C1-C6Alkyl 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 alkylaluminoxane is Methylaluminoxane (MAO) and/or Modified Methylaluminoxane (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.
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 comprises:
mixing alpha-diimine ligand shown in formula (IV) with MXn or MXn derivative and a compound selected from compounds with general formula R11YH to obtain a compound shown as the formula (I) of the invention; r1、R2、R5-R8、M、X、R11And Y is the same as formula (I), n is an integer conforming to 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 LMX2The 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 that can coordinate to the 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 compound of formula i is selected from the group consisting of11The compound YH is an alcohol compound of C1-C10, preferably an alcohol compound of C1-C6, for example, ethanol, 2-methyl-1-propanol, etc.
According to some embodiments of the invention, the alpha-diimine ligand of formula (IV) is a compound of formula (V),
wherein R is1-R10、R21、R22Have the same definition as formula (III).
According to some embodiments of the invention, the reaction is carried out in a dispersion medium, such as an aprotic solvent, such as methylene chloride, for example, to enable 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 fact that the reaction components can be 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 present invention, the organoaluminum compound is added in an amount of 0.01 to 30mmol 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.
In a third aspect, the present invention provides a process for the polymerisation of olefins comprising polymerising an olefin, preferably of the formula CH, in the presence of a catalyst as described in the first aspect of the invention or prepared by a process according to the second aspect of the invention2Wherein R is hydrogen or C1-C6Alkyl 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 is present at a concentration of 1 × 10 during polymerization－8mol/l-1X 10－3Mol/l, preferably 1X 10－8Mole/liter－1-10－5Mol/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 2.0 MPa.
In a fourth aspect, the present invention provides a catalyst according to the first aspect of the present invention and/or a catalyst obtainable by a process according to the second aspect of the present invention and/or a process according to the third aspect of the present invention for use 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 is given in conjunction with the examples which are given for purposes of illustration only and are not to be construed as limiting the scope of the invention. The examples, in which specific conditions are not specified, were conducted under 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 ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The test method comprises the following steps:
1. nuclear magnetic resonance apparatus: bruker DMX 300(300MHz), 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. Characterization of polymer molecular weight and molecular weight distribution: the molecular weight and the distribution thereof are determined by Gel Permeation Chromatography (GPC), the 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 1.0 ml/min; the measurement temperature was 150 ℃. Each sample was measured twice.
Example 1
(1) Preparation of the Complex
1) Complex L1Preparation of
Reference Organometallics, 2013,32, 2291-2299.
2) Complex Ni1Preparation of (R in the formula (III))1、R3、R4、R6Is isopropyl, R2、R5、R7-R10、R21、R22Is hydrogen, and R11Is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.332g (0.6mmol) of ligand L1In dichloromethane solution. The color of the solution immediately turned red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain red powdery solid Ni1. Yield: 78.2 percent. Elemental analysis (C)84H98Br6N4Ni3O2): c, 54.50; h, 5.34; n, 3.03; experimental values (%): c, 54.38; h, 5.72; and N, 3.16.
(2) Preparation of alkyl silicon chloride/silica gel carrier
Under the protection of nitrogen, 10.0g of dry silica gel carrier is added into a glass reactor, 100 mL of dry hexane is added to be dispersed into suspension, and 1mL of SiCl is added2(n-Bu)2Stirring, 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, 60mL of dried toluene is added to be dispersed into suspension, 18 mL of 10 wt% MAO (methylaluminoxane) 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 methylaluminoxane, is obtained by washing with toluene three times, 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, 30mL of dried toluene is added to prepare slurry, and 0.185g (0.1mmol) of complex Ni is added1Dissolving in 20mL of toluene, dropwise adding the toluene solution of the obtained complex into a reactor, reacting at 30 ℃ for 30 minutes, washing with 30mL of toluene, and drying in vacuum to obtain the supported late transition metal catalyst A. The catalyst A has Ni content of 0.68 wt% and Al content of 10.42 wt% as shown by ICP.
(5) Experiment of ethylene polymerization
In a 1L stainless steel autoclave, each of nitrogen and ethylene was substituted three times, 500 mL of a hexane solvent was added, 2 mL of a 1 mol/L Triethylaluminum (TEA) hexane solution was added with the addition of hexane, 20 to 50 mg of the supported transition metal catalyst prepared above was added, the temperature was raised to 80 ℃, the pressure was raised to and maintained at 1.0MPa, and the reaction was carried out 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 alkylaluminoxane/magnesium chloride/silica gel carrier is added into a glass reactor, 30ml of dried toluene is added to prepare slurry, 0.231g (0.3mmol) of a comparative complex is dissolved in 20ml of toluene (the structure is shown in the specification, the synthesis is shown in Organometallics, 2013,32,2291 and 2299), the reaction is carried out for 30 minutes at 30 ℃, then 30ml of toluene is used for washing, and vacuum drying is carried out to obtain the supported transition metal catalyst A, and the supported transition metal catalyst A is characterized by ICP, wherein the weight content of Ni in the catalyst A is 0.54 percent, and the weight content of Al in the catalyst A is 10.27 percent.
(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) Ligand L2Is referred to patent CN 10639264
Complex Ni2Preparation of (R in the formula (III))1、R3、R4、R6Is ethyl, R2、R5、R7-R10、R22Is hydrogen, R21Is tert-butyl, and R11Is ethyl, M is nickel, Y is O, X is Br)
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.365g (0.6mmol) of ligand L2In dichloromethane solution. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish redSolid Ni powder2. The yield was 82.0%. Elemental analysis (C)92H114Br6N4Ni3O2): c, 56.28; h, 5.85; n, 2.85; experimental values (%): c, 56.43; h, 6.12; and N, 3.08.
(2) Preparation of silicon alkyl chloride/silica gel carrier
The same as example 1, step (2), except that SiCl was used in example 12(n-Bu)2Is replaced by SiCl4。
(3) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(4) Preparation of Supported late transition Metal catalyst B
Like example 1 step (4), only 0.185g (0.1mmol) of complex Ni from example 11Replacement with 0.196 g (0.1mmol) of complex Ni2And obtaining the loaded transition metal catalyst B. The catalyst B has a Ni content of 0.70 wt% and an Al content of 10.27 wt%, which are characterized by ICP.
(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 3
(1) Preparation of the Complex
1) Ligand L3Is referred to patent CN 10639264
2) Complex Ni3Preparation of (R in the formula (III))1、R3、R4、R6Is methyl, R2、R5Is bromine, R7-R10、R22Is hydrogen, R21Is tert-butyl, and R11Is ethyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.426g (0.6mmol) of ligand L3In dichloromethane solution. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni3. The yield was 82.0%. Elemental analysis (C)84H94Br10N4Ni3O2): c, 46.56; h, 4.37; n, 2.59; experimental values (%): c, 46.43; h, 4.72; and N, 2.98.
(2) Preparation of silicon alkyl chloride/silica gel carrier
The same procedure as in step (2) of example 1.
(3) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
The same procedure as in step (3) of example 1, except that 18 mL of 10% MAO in example 1 was replaced with 13 mL of 2M diethylaluminum chloride.
(4) Preparation of Supported late transition Metal catalyst C
As in step (4) of example 1, only 0.185g (0.1mmol) of Ni complex of example 1 was added1Replacement with 0.217 g (0.1mmol) of complex Ni3And obtaining the loaded transition metal catalyst C. The catalyst C was characterized by ICP, and had a Ni content of 0.68 wt% and an Al content of 10.13 wt%.
(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 4
(1) Complex Ni4Preparation of (R in the formula (III))1、R3、R4、R6Is ethyl, R2、R5、R7-R10、R22Is hydrogen, R21Is tert-butyl, and R11Is isobutyl, M is nickel, Y is O, X is Br):
will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.365g (0.6mmol) of ligand L2In dichloromethane solution. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni4. The yield was 83.0%. Elemental analysis (C)96H122Br6N4Ni3O2)：C,57.09；H,6.09；N,2.77(ii) a Experimental values (%): c, 57.24; h, 6.32; and N, 3.04.
(2) Preparation of silicon hydrocarbyl chloride/silica gel carrier
The same as example 1, step (2), except that SiCl was used in example 12(n-Bu)2Conversion to CH3SiCl3。
(3) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 1, step (3).
(4) Preparation of Supported late transition Metal catalyst D
As in step (4) of example 1, only 0.185g (0.1mmol) of Ni complex of example 1 was added1Replacement by 0.202 g (0.1mmol) of complex Ni4And obtaining the loaded transition metal catalyst D. According to ICP characterization, in the catalyst D, the weight content of Ni is 0.71%, and the weight content of Al is 10.24%.
(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 the Complex
1) Ligand L4Is referred to patent CN 1063939261
2) Complex Ni5Preparation of
Will contain 0.277g (0.9mmol) of (DME) NiBr2To a solution containing 0.358g (0.6mmol) of ligand L4In dichloromethane solution. The color of the solution immediately turned deep red and a large amount of precipitate formed. Stirring at room temperature for 6h, and precipitating with anhydrous diethyl ether. Filtering to obtain a filter cake, washing the filter cake with anhydrous ether, and vacuum drying to obtain brownish red powdery solid Ni5. The yield was 84.3%. Elemental analysis (C)92H90Br6N4Ni3O2): c, 56.98; h, 4.68; n, 2.89; experimental values (%): c, 56.78; h, 4.62; and N, 3.18.
(2) Preparation of silicon alkyl chloride/silica gel carrier
The same procedure as in step (2) of example 2 was repeated.
(3) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
The same procedure as in step (3) of example 2 was repeated.
(4) Preparation of Supported late transition Metal catalyst E
As in step (4) of example 2, only 0.196 g (0.1mmol) of Ni complex in example 2 was added2Replacement with 0.194 g (0.1mmol) of complex Ni5To obtain the supported late transition metal catalyst E. The catalyst E was characterized by ICP, and had a Ni content of 0.72 wt% and an Al content of 10.30 wt%.
(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 5, step (2).
(2) Preparation of organoaluminum/silicon hydrocarbonchloride/silica gel carrier
Same as example 5, step (3).
(3) Preparation of Supported transition Metal catalyst E
As in step (4) of example 5, only 0.194 g (0.1mmol) of Ni complex of example 5 was added5Substitution was made with 0.244 g (0.3mmol) of complex 5 to give the supported transition metal catalyst E. By ICP characterization, catalyst E contained 0.57% Ni and 10.52% 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.
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 (15)
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), R1And R2The same or different, independently selectedA C1-C30 hydrocarbon group containing or not containing a substituent; r5-R8The same or different, each independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent; r5-R8Optionally forming a ring with each other; r11Selected from C1-C20 substituted or unsubstituted hydrocarbon groups; y is selected from non-metal atoms of group VIA; m is a group VIII metal; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent.
2. The late transition metal catalyst of claim 1, wherein R is1And R2Independently selected from substituted or unsubstituted C1-C20 alkyl and/or substituted or unsubstituted C6-C20 aryl, preferably R1And/or R2Is a group of formula (II):
in the formula (II), R1-R5The alkyl is a linear alkyl, branched alkyl or cycloalkyl, and the alkoxy is a linear alkoxy, branched alkoxy or cycloalkoxy, each independently selected from the group consisting of hydrogen, halogen, hydroxyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 alkenyloxy, substituted or unsubstituted C2-C20 alkynyloxy, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C7-C20 aralkyl, and substituted or unsubstituted C7-C20 alkaryl; r1-R5Optionally forming a ring with each other;
preferably, in formula (II), R1-R5The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C10 alkyl with or without substituent, and substituentC2-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.
3. Late transition metal catalyst according to claim 1 or 2, characterized in that M is selected from nickel and palladium; y is selected from O and S; x is selected from halogen, C1-C10 alkyl with or without substituent and C1-C10 alkoxy with or without substituent, preferably selected from halogen, C1-C6 alkyl with or without substituent and C1-C6 alkoxy with or without substituent;
and/or in the formula (I), R11Is selected from C1-C20 alkyl with or without substituent, preferably C1-C10 alkyl with or without substituent, more preferably C1-C6 alkyl with or without substituent.
4. Late transition metal catalyst according to any of claims 1 to 3, characterized in that the late transition metal compound is selected from compounds of formula (III):
in the formula (III), R1-R10、R21、R22The same or different, each is independently selected from hydrogen, halogen, hydroxyl, C1-C20 alkyl with or without substituent, C2-C20 alkenyl with or without substituent, C2-C20 alkynyl with or without substituent, C1-C20 alkoxy with or without substituent, C2-C20 alkenyloxy with or without substituent, C2-C20 alkynyloxy with or without substituent, C6-C20 aryl with or without substituent, C7-C20 aralkyl with or without substituent, and CC7-C20 alkylaryl with or without substituent, wherein the alkyl is linear alkyl, branched alkyl or cycloalkyl, and the alkoxy is linear alkoxy, branched alkoxy or cycloalkoxy; r is1-R10Optionally forming a ring with each other; r21-R22Optionally forming a ring with each other;
R11y, M and X have the same definitions as formula (I);
preferably, R1-R10、R21-R22The 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, C3-C10 cycloalkyl 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, C3-C10 cycloalkoxy with or without substituent, C6-C15 aryl with or without substituent, C7-C15 aralkyl with or without substituent, and C7-C15 alkaryl with or without substituent;
preferably, R1-R10、R21-R22The substituents are the same or different and are 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.
5. The late transition metal catalyst of any one of claims 1-4, wherein 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; the substituents are preferably selected from halogen, hydroxy, C1-C6 alkyl, halogenated C1-C6 alkyl, C1-C6 alkoxy and halogenated C1-C6 alkoxy;
preferably, the C1-C6 alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3, 3-dimethylbutyl;
preferably, the C1-C6 alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3, 3-dimethylbutoxy;
preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.
6. Late transition metal catalyst according to claim 4, characterized in that the late transition metal compound is selected from one or more of the following compounds:
1) a complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
2) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
3) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
4) A complex of formula (III) wherein R1-R6＝Me，R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
5) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
6) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
7) A complex of formula (III) wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝R21＝R22＝H，R11＝Et，M＝Ni，Y＝O，X＝Br；
8) A complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
9) a complex of formula (III), wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
10) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
11) a complex of formula (III) wherein R1-R6＝Me，R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
12) a complex of formula (III), wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
13) a complex of formula (III), wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
14) a complex of formula (III) wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝R21＝R22＝H，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
15) a complex of formula (III) wherein R1＝R3＝R4＝R6Is isopropyl, R2＝R5＝R7-R10＝HR21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
16) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
17) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
18) A complex of formula (III) wherein R1-R6＝Me，R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
19) A complex of formula (III), wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
20) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
21) A complex of formula (III) wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝H，R21＝R22＝R11＝Et，M＝Ni，Y＝O，X＝Br；
22) A complex of formula (III) wherein R1＝R3＝R4＝R6Is ═ isopropyl, R2＝R5＝R7-R10＝H，R31＝R32＝R11＝Et，M＝Ni，Y＝O，X＝Br；
23) A complex of formula (III) wherein R1＝R3＝R4＝R6＝Et，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
24) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Me，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
25) a complex of formula (III), wherein R1-R6＝Me，R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
26) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Br，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
27) a complex of formula (III) wherein R1＝R3＝R4＝R6＝Cl，R2＝R5＝R7-R10＝H，
R21＝R22＝Et，R11Isobutyl, M ═ Ni, Y ═ O, X ═ Br;
28) a complex of formula (III), wherein R1＝R3＝R4＝R6＝F，R2＝R5＝R7-R10＝H，R21＝R22＝Et，R11I.e., isobutyl, M ═ Ni, Y ═ O, and X ═ Br.
7. The late transition metal catalyst according to any one of claims 1 to 6, wherein the late transition metal compound is prepared by a method comprising: mixing alpha-diimine ligand shown in formula (IV) with MXn or MXn derivative and a compound selected from compounds with general formula R11YH to obtain a compound shown as the formula (I) of the invention; r1、R2、R5-R8、M、X、R11And Y is the same as formula (I), n is an integer conforming to the valence of the metal M,
8. the late transition metal catalyst of any of claims 1-7, wherein the chlorine-containing silicon-containing compound is selected from the group consisting of compounds of the general formula ClmSi(R3)4-mAt least one of the compounds shown is a compound,
wherein R is3Is selected from C1-C20Preferably selected from C1-C10Alkyl of (C)3-C10Cycloalkyl of, C6-C10Aryl of (C)7-C10Aralkyl and C7-C10An alkylaryl group of (a); m represents an integer of 1 to 4;
preferably, said R is3Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, and phenyl;
more preferably, 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.
9. The late transition metal catalyst of any of claims 1-8, wherein the organoaluminum compound comprises at least one of an alkylaluminoxane compound, an alkylaluminum compound, or an alkylaluminum chloride compound; preferably, the alkylaluminoxane has the general formula:
wherein R represents C1-C12Is preferably C1-C6Alkyl groups of (a); a represents an integer of 4 to 30, preferably an integer of 10 to 30;
preferably, 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, methylalumoxane and MMAO.
10. The late transition metal catalyst according to any one of claims 1 to 9, wherein the aluminum content in the late transition metal catalyst is 1 to 20% by weight; and/or the content by weight of the late transition metal compound is 0.05-10% in terms of the metal M.
11. The method of preparing a late transition metal catalyst according to any one of claims 1 to 10, 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) carrying out a third reaction on the second reaction product obtained in the step (2) and a late transition metal compound to obtain a late transition metal catalyst;
preferably, 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.
12. The production method according to claim 11, wherein the reaction temperature of the first reaction is 0 to 120 ℃, preferably 20 to 100 ℃, more preferably 30 to 100 ℃, and the reaction time of the first reaction is 0.5 to 24 hours, preferably 3 to 24 hours;
and/or the reaction temperature of the second reaction is 30-120 ℃, preferably 30-100 ℃, more preferably 50-100 ℃, and the reaction time of the second reaction is 0.5-24 hours, preferably 3-24 hours;
and/or the reaction temperature of the third reaction is 0-120 ℃, preferably 20-100 ℃, and the reaction time of the third reaction is 0.5-24 hours.
13. The production method according to claim 11 or 12, wherein the chlorine-containing silicon-containing compound is added in an amount of 0.01 to 3mmol, and/or the organoaluminum compound is added in an amount of 0.01 to 30mmol, and/or the late transition metal compound is added in an amount of 1 to 1000. mu. mol, in terms of the metal M, per gram of the silica gel.
14. A process for the polymerization of olefins, comprising polymerizing an olefin, preferably of the general formula CH, in the presence of a catalyst according to any one of claims 1 to 10 or prepared according to the process of any one of claims 11 to 132Wherein R is hydrogen or C1-C6Alkyl groups of (a); more preferably, the olefin is one or more of ethylene, propylene, butene, pentene, hexene, octene, 4-methyl-1-pentene,
preferably, the late transition metal catalyst is present at a concentration of 1X 10 during polymerization－8mol/l-1X 10－3Mol/l, preferably 1X 10－8Mole/liter－1-10－5Mol/l;
more preferably, the temperature of the polymerization is from-78 ℃ to 150 ℃, preferably from 0 ℃ to 90 ℃, more preferably from 55 ℃ to 90 ℃, and/or the pressure of the polymerization is from 0.01 to 10.0MPa, preferably from 0.01 to 2.0 MPa.
15. Use of a catalyst according to any of claims 1-10 or a catalyst prepared according to the process of any of claims 11-13 or a process according to claim 14 in the polymerisation of olefins.
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