CN115260357B

CN115260357B - Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer

Info

Publication number: CN115260357B
Application number: CN202110473860.7A
Authority: CN
Inventors: 高榕; 苟清强; 赖菁菁; 李昕阳; 安京燕; 马冬
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2021-04-29
Filing date: 2021-04-29
Publication date: 2023-08-15
Anticipated expiration: 2041-04-29
Also published as: CN115260357A

Abstract

The invention discloses a copolymerization method of a spherical or spheroidal copolymer of olefin-terminal alkenyl silane/siloxane and the copolymer obtained by the copolymerization method. The copolymerization method comprises contacting an olefin and an alkenylsilane/siloxane represented by formula (1) or a derivative thereof with a catalyst in the presence of an alkane solvent,according to the invention, through selecting the reacted terminal alkenyl silane/siloxane monomer, the catalyst and a proper polymerization process, the spherical and/or spheroidal polymer with good morphology is directly prepared without the subsequent processing steps of pelleting and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.

Description

Copolymerization method of olefin-terminal alkenyl silane/siloxane spherical or spheroid copolymer and copolymer

Technical Field

The invention relates to the field of high molecular polymer preparation, in particular to a copolymerization method of a spherical or spheroidal copolymer of olefin-terminal alkenyl silane/siloxane and the copolymer obtained by the copolymerization method.

Background

The polyolefin product has low price, excellent performance and wide application range. Under the condition of retaining the original excellent physical and chemical properties of polyolefin, polar groups are introduced into polyolefin molecular chains by a chemical synthesis method, so that the chemical inertness, dyeing property, wettability and compatibility with other materials of the polyolefin can be improved, and the novel properties which are not possessed by raw materials of the polyolefin can be endowed. High pressure free radical polymerization is currently used in most industries to facilitate the direct copolymerization of olefins with polar monomers, such as ethylene-vinyl acetate, ethylene-methyl methacrylate, ethylene-acrylic acid copolymers, using this method. Although the copolymerization of the polar monomer can be directly introduced into the polyolefin chain by high-pressure radical copolymerization, the method requires high-temperature and high-pressure conditions, and is high in energy consumption and expensive in equipment cost.

Olefin copolymers containing vinylsilane or siloxane derivative groups can be used in a variety of applications, such as in various types of cable materials, tubing, adhesives, gaskets, and crosslinked foams. The vinylsilane groups may be linked to the olefin polymer by two methods: one method is to copolymerize olefin and vinyl silane compound under the catalysis of free radical initiator at high temperature and high pressure (as in US 3225018), the polymerization process is similar to high pressure homopolymerization of ethylene, and the obtained copolymer has a structure similar to that of low density polyethylene; another approach is to graft an allyl-or vinyl-silane onto an existing polyolefin (e.g. US 3646155), which has the advantage that it can be grafted either with low density polyethylene or with high density polyethylene, but has the disadvantage that the grafting requires the additional use of free radical initiators, which also complicates the preparation process. Furthermore, too little free radical initiator usage results in too low a grafting level; too much free radical initiator can result in excessive crosslinking of the polymer. If ethylene can be catalyzed to coordinate polymerization with the terminal alkenylsilane/siloxane groups, the polymerization process can be simplified and the content of terminal alkenylsilane/siloxane groups on the polymer chain can be controlled.

At present, only a few documents report the use of transition metal complexes for the copolymerization of olefins with silicon-containing polar monomers (alkenylsilanes/siloxanes). For example, WO 03/044066 A2 discloses that ethylene can be copolymerized with allyl-or vinyl-silanes using late transition metal complexes of bidentate or tridentate ligands, however, this process requires the use of expensive Modified Methylaluminoxane (MMAO) as cocatalyst and polymerization at relatively high ethylene polymerization pressures of 4.0 to 6.0MPa, the resulting polymers having relatively low molecular weights and low branching degrees. Dalton Transaction,2015, 44 (47) 20745-20752 adopts iron pyridine diimine series catalyst to catalyze the copolymerization of propylene and silicon-containing polar monomer, and the method still adopts MMAO as cocatalyst, needs 30 ℃ or even lower temperature 0 ℃ to carry out polymerization reaction for 16 hours, and has lower polymerization activity. When the catalyst is not loaded to catalyze the olefin homopolar monomer to copolymerize, the obtained polymer is easy to form viscous massive solid, scale is easy to form in polymerization equipment, and difficulties are brought to the transportation of the polymer, solvent removal, granulation and the like.

Disclosure of Invention

In order to overcome the defects existing in the prior art, the invention provides a spherical or spheroid polar polyolefin with silane or siloxane groups and higher melting point, which can realize the introduction of crosslinkable silane or siloxane polar groups and simultaneously maintain the chain rigidity.

It is an object of the present invention to provide a method for copolymerizing a spherical or spheroidal copolymer of an olefin-alkenylsilane/siloxane, comprising reacting an olefin and alkenylsilane/siloxane represented by formula (1) or derivatives thereof in contact with a catalyst in the presence of an alkane solvent to obtain the copolymer,

in the formula (1), L ₁ -L ₃ Independently selected from H, C with or without substituents ₁ -C ₃₀ Alkyl, L ₄ Is C containing substituent ₁ -C ₃₀ Alkylene, R' ₁ -R’ ₃ C being halogen, with or without substituents ₁ -C ₁₀ Alkyl, C with or without substituents ₁ -C ₁₀ An alkoxy group.

Preferably L ₁ And L ₂ All are H.

Preferably L ₃ H, C of a shape of H, C ₁ -C ₂₀ Substituted or unsubstituted alkyl; more preferably L ₃ H, C of a shape of H, C ₁ -C ₁₀ Alkyl or C ₁ -C ₁₀ Alkyl haloalkyl; most preferably L ₃ Is H or C ₁ -C ₆ An alkyl group.

Preferably L ₄ Is C containing substituent ₁ -C ₂₀ Alkylene, more preferably L ₄ Is C containing substituent ₁ -C ₁₀ An alkylene group. For example L ₄ Is a methylene group having a substituent, an ethylene group having a substituent, a propylene group having a substituent, a butylene group having a substituent, a C group having a substituent ₅ Alkylene group, substituent-containing C ₆ Alkylene group, substituent-containing C ₇ Alkylene group, substituent-containing C ₈ Alkylene group, substituent-containing C ₉ Alkylene group, substituent-containing C ₁₀ Alkylene group, substituent-containing C ₁₂ Alkylene group, substituent-containing C ₁₄ Alkylene group, substituent-containing C ₁₈ Alkylene group, substituent-containing C ₂₀ An alkylene group.

Preferably, in formula (1), L ₁ -L ₄ Wherein the substituents are selected from halogen, C ₆ -C ₁₀ Aromatic radicals, C ₁ -C ₂₀ Alkyl, C ₁ -C ₂₀ Alkoxy, hydroxy, ester groups, preferably from halogen, phenyl, C ₁ -C ₆ Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), C ₁ -C ₁₀ Alkoxy, hydroxy, ester groups.

The carbon number of the alkylene group refers to the number of C in the straight chain, and does not include the number of C in the side group, e.g., isopropylidene (-CH) ₂ -CH(CH ₃ ) (-) is referred to herein as C with pendant (methyl) groups ₂ An alkylene group.

In the present invention, "terminal alkenyl" includes vinyl, alpha-olefin groups, and the double bond on the group is located at one end of the molecular chain. "alkenylsilane/siloxane" refers to "alkenylsilane terminated" and/or "alkenylsiloxane terminated".

According to a preferred embodiment of the present invention, specific examples of the alkenylsilane/siloxane include, but are not limited to, trimethyl (1-methyl-2-propen-1-yl) silane, trimethyl (1-methyl-3-buten-1-yl) silane, (1-ethyl-2-propen-1-yl) trimethylsilane, trimethyl (1, 2-tetramethyl-3-buten-1-yl) silane, [1- (trimethylsilyl) -3-buten-1-yl ] benzene, methoxydimethyl (1-methyl-2-propen-1-yl) silane, 2- (trimethylsilyl) -4-penten-1-ol, vinyldimethyl (1-methylethyl) silane, (chloromethyl) dimethyl-2-propen-1-yl silane, hexyldimethyl-2-propen-1-yl silane, dichlorohexyl-2-propen-1-yl silane, dichloro-5-hexen-1-ylmethyl silane, (chloromethyl) dimethyl (1-methyl-2-propen-1-yl) silane, 2- (trimethylsilyl) -4-propen-1-yl) silane, trimethyl-2-trimethylpenten-3-trisila-yl silane Diethyl methyl (2-methyl-3-buten-1-yl) silane, methoxy dimethyl (1-methyl-2-propen-1-yl) silane, 1-vinyl-3- (trimethylsilyl) cyclopentane, chlorodimethyl (1-methyl-2-propen-1-yl) silane, 3-buten-1-ylmethoxy-dimethyl silane, 3-buten-1-yl chlorodimethyl silane, allyl tert-butyldimethylsilane, trichloro-10-undecen-1-ylsilane, (7-oct-1-yl) trimethoxysilane, dimethoxymethyl-2-propen-1-ylsilane, 7-octen-2-ol-2-methyl-4- (trimethylsilyl), (1, 1-dimethylethyl) dimethyl [ (1-methyl-2-propen-1-yl) oxy ] silane, 1- (trimethylsilyl) -4-penten-1-ol, 5- (trimethylsilyl) -1-penten-3-ol, 3- (3-buten-1-methyldimethylsilyl) -1-propanol, 1- (trimethylbuten-1-yl) -1-propanol, 1- (trimethylpropen-1-yl) -1-yl, 1-buten-1-yl) 1-yl, 1- (dimethyl-2-propen-1-yl-silyl) -2-propanol, methyl 3-trimethylsilyl-4-pentenoate, 2-propenoic acid (trimethylsilyl) methyl ester, triethoxy (2-methyl-3-buten-1-yl) silane, and the like.

According to a preferred embodiment of the invention, the olefin comprises an olefin having 2 to 16 carbon atoms, in some embodiments of the invention the olefin comprises ethylene or an alpha-olefin having 3 to 16 carbon atoms. In other embodiments of the invention, the olefin is C ₃ -C ₁₆ Cycloolefins, preferably 5-membered ringsOr a 6 membered ring. Preferably, the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms, more preferably ethylene or C ₂ -C ₁₀ Alpha-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and the like.

The catalyst comprises a main catalyst and a cocatalyst, wherein the main catalyst is selected from at least one of metal complexes shown in a formula (I),

in the formula (I), R ₁ 、R ₂ Independently selected from substituent-containing or substituent-free C ₁ -C ₃₀ A hydrocarbon group; r is R ₃ 、R ₄ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Hydrocarbyl radicals, adjacent R ₃ And R is ₄ Optionally interconnected to form a ring or ring system; r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ A hydrocarbon group; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C with substituent or without substituent ₁ -C ₁₀ Hydrocarbyl, C with or without substituents ₁ -C ₁₀ Hydrocarbyloxy groups.

According to some embodiments of the metal complexes of the invention, in formula (I), R ₁ 、R ₂ Independently selected from substituent-containing or substituent-free C ₁ -C ₂₀ Alkyl, C with or without substituents ₆ -C ₂₀ Aryl, preferably R ₁ 、R ₂ Is a group of formula (II):

in the formula (II), R ¹ ～R ⁵ Identical or different, each independently selected from hydrogen, halogen, hydroxy, C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ An alkylaryl group; r is R ¹ ～R ⁵ Optionally interconnected to form a ring or ring system;

preferably, in formula (II), R ¹ ～R ⁵ Each independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₁₀ Alkyl, C with or without substituents ₂ -C ₁₀ Alkenyl, C with or without substituents ₂ -C ₁₀ Alkynyl, substituted or unsubstituted C ₃ -C ₁₀ Cycloalkyl, C with or without substituents ₁ -C ₁₀ Alkoxy, C with or without substituents ₂ -C ₁₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₁₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₁₀ C having or not having a substituent ₆ -C ₁₅ Aryl, C with or without substituents ₇ -C ₁₅ Aralkyl, C with or without substituents ₇ -C ₁₅ Alkylaryl groups.

According to some embodiments of the metal complexes of the invention, in formula (I), M is selected from nickel or palladium.

According to some embodiments of the metal complexes of the invention, in formula (I), Y is selected from O or S;

according to some embodiments of the metal complexes of the invention, in formula (I), X is selected from the group consisting of halogensC with or without substituents ₁ -C ₁₀ Alkyl, C with or without substituents ₁ -C ₁₀ Alkoxy, preferably selected from halogen, substituted or unsubstituted C ₁ -C ₆ Alkyl, C with or without substituents ₁ -C ₆ An alkoxy group.

According to some embodiments of the metal complexes of the invention, in formula (I), R' is selected from C with or without substituents ₁ -C ₂₀ Alkyl, preferably C with or without substituents ₁ -C ₁₀ Alkyl, more preferably C with or without substituents ₁ -C ₆ An alkyl group.

According to some embodiments of the metal complexes of the invention, in formula (I), R ₃ And R is ₄ Identical or different, each independently selected from hydrogen, halogen, hydroxy, C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Alkylaryl groups.

According to some embodiments of the metal complexes of the invention, the metal complex has a structure as shown in formula (IX):

in the formula (IX), R ¹ ～R ⁵ Each independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₁₀ Alkyl, C with or without substituents ₃ -C ₁₀ Cycloalkyl, C with or without substituents ₁ -C ₁₀ Alkoxy, C with or without substituents ₃ -C ₁₀ C having or not having a substituent ₆ -C ₁₅ Aryl, C with or without substituents ₇ -C ₁₅ Aralkyl, C with or without substituents ₇ -C ₁₅ An alkylaryl group;

R ₃ 、R ₄ independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, halogenated C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, halogenated C ₁ -C ₁₀ Alkoxy, halogen, preferably independently selected from hydrogen, C ₁ -C ₆ Alkyl, halogenated C ₁ -C ₆ Alkyl, C ₁ -C ₆ Alkoxy, halogenated C ₁ -C ₆ Alkoxy, halogen;

m is nickel; y is O; x is selected from fluorine, chlorine and bromine;

r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ Alkyl, preferably C with or without substituents ₁ -C ₁₀ Alkyl, more preferably C with or without substituents ₁ -C ₆ An alkyl group.

The metal complex shown in the formula (I) can be prepared by the following steps: bringing a diimine compound represented by the formula (A) into contact with MX _n And R' YH are reacted with each other,

in the formula (A), R ₁ 、R ₂ 、R ₃ And R is ₄ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1,2 or 3; y and R 'in R' YH have the same definition as in formula (I).

The above reaction is carried out in an organic solvent, preferably the organic solvent is a haloalkane, more preferably the organic solvent is selected from one or more of dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.

The MXn comprises a nickel halide, such as nickel bromide or nickel chloride; and 1, 2-dimethoxyethane nickel halides such as 1, 2-dimethoxyethane nickel bromide or 1, 2-dimethoxyethane nickel chloride.

The related structure and preparation method of the metal complex shown in the formula (I) or the formula (IX) can be seen in Chinese patent application CN201911049039.1, and Chinese patent application CN201911049039.1 is fully incorporated into the present invention.

According to some embodiments of the metal complexes of the invention, the metal complexes have a structure as shown in formula (III):

in the formula (III), R ₅ ～R ₈ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ Hydrocarbyl radicals, R ₅ ～R ₈ Optionally interconnected to form a ring or ring system; preferably, R ₅ ～R ₈ Independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, halogenated C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, halogenated C ₁ -C ₁₀ Alkoxy, halogen.

In the formula (III), R ₁ 、R ₂ Identical or different, independently selected from the group consisting of C containing substituents or C not containing substituents ₁ -C ₃₀ A hydrocarbon group; r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ A hydrocarbon group; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C with substituent or without substituent ₁ -C ₁₀ Hydrocarbyl, C with or without substituents ₁ -C ₁₀ Hydrocarbyloxy groups.

According to the invention Some embodiments of the metal complexes of formula (III), R ₁ 、R ₂ Independently selected from substituent-containing or substituent-free C ₁ -C ₂₀ Alkyl, C with or without substituents ₆ -C ₂₀ Aryl, preferably R ₁ 、R ₂ Is a group represented by the above formula (II).

According to some embodiments of the metal complexes of the invention, the metal complexes have a structure as shown in formula (IV):

in the formula (IV), R ¹ ～R ¹¹ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₆ -C ₂₀ Aryloxy, substituted or unsubstituted C ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Aralkoxy, C with or without substituents ₇ -C ₂₀ Alkylaryl, substituted or unsubstituted C ₇ -C ₂₀ An alkylaryl group.

Preferably, R ¹ ～R ¹¹ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₁₀ Alkyl, C with or without substituents ₂ -C ₁₀ Alkenyl group,C with or without substituents ₂ -C ₁₀ Alkynyl, substituted or unsubstituted C ₃ -C ₁₀ Cycloalkyl, C with or without substituents ₁ -C ₁₀ Alkoxy, C with or without substituents ₂ -C ₁₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₁₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₁₀ C having or not having a substituent ₆ -C ₁₅ Aryl, C with or without substituents ₇ -C ₁₅ Aralkyl and C with or without substituents ₇ -C ₁₅ Alkylaryl groups.

The metal complex as shown in formula (III) can be prepared by the following steps: reacting a diimine compound represented by the formula (B) with MXn and R' YH,

in the formula (B), R ₅ ～R ₈ Having the same definition as formula (III); r is R ₁ And R is ₂ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1,2 or 3; y and R 'in R' YH have the same definition as in formula (I).

The above reaction to form the metal complex represented by the formula (III) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.

The preparation of the diimine compound represented by the formula (B) comprises reacting a diketone compound represented by the formula (B') with R ₁ NH ₂ And R is ₂ NH ₂ And (c) reacting to produce the diimine compound represented by the formula (B).

In the above reaction for producing the diimine compound represented by the formula (B), the reaction is carried out in the presence of an aluminum alkyl and an aprotic solvent, preferably one or more of toluene, benzene and xylene. The alkyl aluminum compound is C ₁ -C ₆ The alkylaluminum compound, such as trimethylaluminum, triethylaluminum, tripropylaluminum, etc., is preferably trimethylaluminum.

The related structure and preparation method of the metal complex shown in the formula (III) or the formula (IV) can be seen in Chinese patent application CN201911048975.0, and Chinese patent application CN201911048975.0 is fully incorporated into the present invention.

According to some embodiments of the metal complexes of the invention, the metal complexes have a structure as shown in formula (V):

in the formula (V), R ₅ ～R ₇ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ Hydrocarbyl radicals, R ₅ ～R ₇ Optionally interconnected to form a ring or ring system; preferably, R ₅ ～R ₇ Independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, halogenated C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, halogenated C ₁ -C ₁₀ Alkoxy, halogen, more preferably selected from hydrogen, C ₁ -C ₆ Alkyl, halogenated C ₁ -C ₆ Alkyl, C ₁ -C ₆ Alkoxy, halogenated C ₁ -C ₆ Alkoxy, halogen.

In the formula (V), R ₁ 、R ₂ Identical or different, independently selected from the group consisting of C containing substituents or C not containing substituents ₁ -C ₃₀ A hydrocarbon group; r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ A hydrocarbon group; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C with substituent or without substituent ₁ -C ₁₀ Hydrocarbyl, C with or without substituents ₁ -C ₁₀ Hydrocarbyloxy groups.

According to some embodiments of the metal complexes of the invention, in formula (V), R ₁ 、R ₂ Independently selected from substituent-containing or substituent-free C ₁ -C ₂₀ Alkyl, C with or without substituents ₆ -C ₂₀ Aryl, preferably R ₁ 、R ₂ Is a group represented by the above formula (II).

According to some embodiments of the metal complexes of the invention, the metal complexes have a structure as shown in formula (VI):

in the formula (VI), R ¹ ～R ⁵ Independently selected from hydrogen, halogen, substituted or unsubstituted C ₁ -C ₆ Alkyl, C with or without substituents ₁ -C ₆ An alkoxy group; r is R ₅ ～R ₁₀ Independently selected from hydrogen, halogen, C ₁ -C ₆ Alkyl, C ₁ -C ₆ An alkoxy group; m is nickel; y is O; x is selected from halogen; r' is selected from substituent-containing or substituent-free C ₁ -C ₆ An alkyl group.

The metal complex of formula (V) is prepared by the steps of: bringing a diimine compound represented by the formula (C) into contact with MX _n And R' YH are reacted with each other,

in the formula (C), R ₅ 、R ₆ 、R ₇ Has the same definition as formula (V); r is R ₁ And R is ₂ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1,2 or 3; y and R 'in R' YH have the same definition as in formula (I).

The above reaction to form the metal complex of formula (V) is carried out in an organic solvent, preferably the organic solvent is a haloalkane, more preferably the organic solvent is selected from one or more of dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.

The preparation of the diimine compound represented by the formula (C) comprises reacting a diketone compound represented by the formula (C') with R ₁ NH ₂ And R is ₂ NH ₂ And (C) reacting to produce the diimine compound represented by the formula (C).

Wherein R is ₁ 、R ₂ 、R ₅ -R ₇ Has the same definition as formula (V).

In the reaction for producing the diimine compound shown in (C), the catalyst used in the reaction is selected from organic acids such as formic acid, acetic acid and p-toluenesulfonic acid, and the solvent is preferably one or more of methanol, ethanol and acetonitrile.

The related structure and preparation method of the metal complex shown in the formula (V) or the formula (VI) can be seen in Chinese patent application CN201911049899.5, and Chinese patent application CN201911049899.5 is fully incorporated into the present invention.

According to some embodiments of the metal complexes of the invention, the metal complexes have a structure as shown in formula (VII):

in the formula (VII), R ₂₁ ～R ₂₄ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Hydrocarbyl, C with or without substituents ₁ -C ₂₀ Hydrocarbyloxy radicals R ₂₁ ～R ₂₄ Optionally interconnected to form a ring or ring system; preferably, R ₂₁ ～R ₂₄ Each independently selected from hydrogen, halogen, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₆ -C ₂₀ Aryloxy, substituted or unsubstituted C ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Aralkoxy, C with or without substituents ₇ -C ₂₀ Alkylaryl, substituted or unsubstituted C ₇ -C ₂₀ An alkylaryl group.

In the formula (VII), R ₁ 、R ₂ Identical or different, independently selected from the group consisting of C containing substituents or C not containing substituents ₁ -C ₃₀ A hydrocarbon group; r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ A hydrocarbon group; y is selected from group VIA nonmetallic atoms; m is a group VIII metal; x is selected from halogen, C with substituent or without substituent ₁ -C ₁₀ Hydrocarbyl and C with or without substituents ₁ -C ₁₀ Hydrocarbyloxy groups.

According to some embodiments of the metal complexes of the invention, in formula (VII), R ₁ 、R ₂ Independently selected from substituent-containing or substituent-free C ₁ -C ₂₀ Alkyl, C with or without substituents ₆ -C ₂₀ Aryl, preferably R ₁ 、R ₂ Is a group represented by the above formula (II).

According to some embodiments of the metal complexes of the invention, the metal complex has a structure as shown in formula (VIII):

In the formula (VIII), R ¹ ～R ¹⁰ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₆ -C ₂₀ Aryloxy, substituted or unsubstituted C ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Aralkoxy, C with or without substituents ₇ -C ₂₀ Alkylaryl, substituted or unsubstituted C ₇ -C ₂₀ An alkylaryl group.

The metal complex shown in the formula (VII) is prepared through the following steps: bringing a diimine compound represented by the formula (D) into contact with MX _n And R' YH are reversedIt should be noted that,

in the formula (D), R ₂₁ ～R ₂₄ Has the same definition as formula (VII); r is R ₁ 、R ₂ Has the same definition as formula (I), MX _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (I).

The above reaction to form the metal complex represented by the formula (VII) is carried out in an organic solvent, preferably the organic solvent is a halogenated alkane, more preferably the organic solvent is one or more selected from dichloromethane, chloroform and 1, 2-dichloroethane. The reaction is preferably carried out at a temperature of 15-40 ℃.

The preparation of the diimine compound represented by the formula (D) comprises reacting a diketone compound represented by the formula (D') with R ₁ NH ₂ And R is ₂ NH ₂ And (c) reacting to produce the diimine compound represented by the formula (D).

In the above reaction for producing the diimine compound represented by the formula (D), the reaction is carried out in the presence of p-toluenesulfonic acid and an aprotic solvent, preferably one or more of toluene, benzene and xylene.

The related structure and preparation method of the metal complex shown in the formula (VII) or the formula (VIII) can be seen in Chinese patent application CN201911049898.0, and Chinese patent application CN201911049898.0 is fully incorporated into the present invention.

In some embodiments of the invention, in the above metal complexes Wherein the substituents are selected from halogen, hydroxy, C ₁ -C ₁₀ Alkyl, halogenated C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, halogenated C ₁ -C ₁₀ An alkoxy group; the substituents are preferably selected from halogen, hydroxy, C ₁ -C ₆ Alkyl, halogenated C ₁ -C ₆ Alkyl, C ₁ -C ₆ Alkoxy, halogenated C ₁ -C ₆ An alkoxy group.

In some embodiments, the C ₁ -C ₆ The alkyl group is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, isohexyl, 3-dimethylbutyl, and the like.

In some embodiments, the C ₁ -C ₆ The alkoxy group is selected from methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentoxy, isopentoxy, n-hexoxy, isohexoxy, 3-dimethylbutoxy and the like.

In the above technical solution, preferably, the halogen is selected from fluorine, chlorine, bromine and iodine.

The cocatalyst is selected from an organoaluminum compound and/or an organoboron compound; wherein the organic aluminum compound is selected from at least one of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide, and the organic boron compound is selected from aromatic boron and/or borate.

According to a preferred embodiment of the invention, the organoaluminium compound is selected from alkylaluminoxane or an aluminium oxide of formula AlR _n X ¹ _3-n An organoaluminum compound (alkylaluminum or alkylaluminum halide) of the formula AlR _n X ¹ _3-n Wherein R is H, C ₁ -C ₂₀ Saturated or unsaturated hydrocarbon radicals, C ₁ -C ₂₀ Saturated or unsaturated hydrocarbyloxy, preferably C ₁ -C ₂₀ Alkyl, C ₁ -C ₂₀ Alkoxy, C ₇ -C ₂₀ Aralkyl or C ₆ -C ₂₀ An aryl group; x is X ¹ Halogen, preferably chlorine or bromine; 0<n is less than or equal to 3. Specific examples of the organoaluminum compounds include, but are not limited to: trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane (MAO) and Modified Methylaluminoxane (MMAO). Preferably, the organoaluminum compound is Methylaluminoxane (MAO).

According to a preferred embodiment of the invention, the organoboron compound is selected from the group consisting of aromatic boron and/or borates. The arylboron is preferably substituted or unsubstituted phenylboron, more preferably tris (pentafluorophenyl) boron. The borates are preferably N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate and/or triphenylmethyl tetrakis (pentafluorophenyl) borate.

According to a preferred embodiment of the present invention, the concentration of the metal complex main catalyst in the reaction system is 0.00001 to 100mmol/L, for example, 0.00001mmol/L, 0.00005mmol/L, 0.0001mmol/L, 0.0005mmol/L, 0.001mmol/L, 0.005mmol/L, 0.01mmol/L, 0.05mmol/L, 0.1mmol/L, 0.3mmol/L, 0.5mmol/L, 0.8mmol/L, 1mmol/L, 5mmol/L, 8mmol/L, 10mmol/L, 20mmol/L, 30mmol/L, 50mmol/L, 70mmol/L, 80mmol/L, 100mmol/L and any value therebetween, preferably 0.0001 to 1mmol/L, more preferably 0.001 to 0.5mmol/L.

According to a preferred embodiment of the present invention, when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to M in the procatalyst metal complex is (10 to 10000000): 1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1, 1000000:1, 10000000:1 and any value therebetween, preferably (10 to 100000): 1, more preferably (100 to 10000): 1.

When the cocatalyst comprises an organoboron compound and an organoaluminum compound, the molar ratio of boron in the organoboron compound to metal complex M in the procatalyst is (0.1-1000): 1, e.g., 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 3:1, 5:1, 8:1, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 500:1, 700:1, 800:1, 1000:1 and their combinationsAny value between (0.1-500): 1 is preferable; the molar ratio of the aluminum in the organic aluminum compound to the metal complex M in the main catalyst is (10-10) ⁵ ) 1, for example, 10:1, 20:1, 50:1, 100:1, 200:1, 300:1, 400:1, 500:1, 600:1, 700:1, 800:1, 1000:1, 2000:1, 3000:1, 5000:1, 10000:1, 100000:1 and any value therebetween, preferably (10 to 5000): 1, more preferably (10 to 1000): 1.

According to a preferred embodiment of the invention, the polymerization is carried out in an alkane solvent selected from C ₃ -C ₂₀ One or more of the alkanes, preferably selected from C ₃ -C ₁₀ Alkanes, for example, may be selected from one or more of butane, isobutane, pentane, hexane, heptane, octane and cyclohexane, preferably one or more of hexane, heptane and cyclohexane.

According to a preferred embodiment of the invention, the reaction is carried out under anhydrous and anaerobic conditions.

According to a preferred embodiment of the invention, the reaction conditions include: the reaction temperature is-50℃to 80 ℃, preferably-20℃to 60 ℃, more preferably 10℃to 60 ℃, and may be, for example, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 70 ℃, 80 ℃ or any value therebetween; the reaction time is 10 to 200min, preferably 20 to 60min.

In the present invention, the pressure of the reaction is not particularly limited as long as the monomer can be subjected to the coordination copolymerization reaction. When the olefin is ethylene, for example, the pressure of ethylene in the reactor is preferably 1 to 1000atm, more preferably 1 to 200atm, still more preferably 1 to 50atm, from the viewpoints of cost reduction and simplification of the polymerization process.

In the present invention, the term "reaction system" refers to a system comprising a solvent, an olefin, a polar monomer of an alkenylsilane/siloxane or a derivative thereof, and a catalyst.

The average particle diameter of the spherical or spheroidal copolymer obtained by the copolymerization method is 0.02 to 50.0mm, preferably 0.2 to 20.0mm.

The method provided by the invention can directly obtain the spherical and/or spheroidal copolymer without subsequent processing such as granulation and the like, and the polymer has good morphology, so that the method provided by the invention has good industrial application prospect.

It is a further object of the present invention to provide olefin-terminal alkenylsilane/siloxane copolymers prepared by the above process, which comprise spherical and/or spheroidal polymers.

According to a preferred embodiment of the invention, the at least partially spherical and/or spheroidal polymer in the copolymer has a hollow structure.

According to a preferred embodiment of the present invention, the olefin-alkenylsilane/siloxane copolymer comprises structural units derived from an olefin and structural units derived from alkenylsilane/siloxane represented by formula (2),

in the formula (2), L ₁ -L ₃ Each independently selected from H, C with or without substituents ₁ -C ₃₀ Alkyl, L ₄ Is C containing substituent ₁ -C ₃₀ Alkylene, R' ₁ -R’ ₃ C being halogen, with or without substituents ₁ -C ₁₀ Alkyl, C with or without substituents ₁ -C ₁₀ An alkoxy group.

According to a preferred embodiment of the invention, in formula (2), L ₁ And L ₂ Is H, L ₃ Is H, C with or without substituents ₁ -C ₂₀ Alkyl, L ₄ Is C containing substituent ₁ -C ₂₀ An alkylene group.

According to a preferred embodiment of the invention, in formula (2), L ₁ And L ₂ Is H, L ₃ Is H or C ₁ -C ₆ An alkyl group; l (L) ₄ Is C containing substituent ₁ -C ₁₀ Alkylene groups, said substituents being selected from halogen, C ₆ -C ₁₀ Aromatic radicals, C ₁ -C ₂₀ Alkyl, C ₁ -C ₂₀ Alkoxy, hydroxy, ester groups, preferably from halogen, benzeneRadical, C ₁ -C ₆ Alkyl (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl), C ₁ -C ₁₀ One or more of alkoxy, hydroxy, ester groups.

According to a preferred embodiment of the present invention, in the olefin-terminal alkenylsilane/siloxane copolymer, the content of the structural unit represented by the formula (2) is 0.2 to 10.0mol%, for example, may be 0.2mol%, 0.4mol%, 0.6mol%, 0.8mol%, 1.0mol%, 1.5mol%, 2.0mol%, 3.0mol%, 4.0mol%, 5.0mol%, 6.0mol%, 7.0mol%, 8.0mol%, 9.0mol%, 10.0mol% and any value therebetween, and preferably 0.5 to 5.0mol%.

According to a preferred embodiment of the invention, the structural units derived from olefins comprise structural units derived from C ₂ -C ₁₆ Structural units of olefins, preferably derived from C ₂ -C ₁₆ Alpha-olefins or C ₃ -C ₁₆ Structural units of cycloolefins.

According to a preferred embodiment of the invention, the density of the spherical and/or spheroidal polymer is from 0.3000 to 0.8500g/cm ³ For example, it may be 0.3000g/cm ³ 、0.3500g/cm ³ 、0.4000g/cm ³ 、0.4500g/cm ³ 、0.5000g/cm ³ 、0.5500g/cm ³ 、0.6000g/cm ³ 、0.6500g/cm ³ 、0.7000g/cm ³ 、0.7500g/cm ³ 、0.8000g/cm ³ 、0.8500g/cm ³ And any value therebetween, preferably 0.4000 to 0.7500g/cm ³ The density was measured using the method in GB/T6343-2009.

According to a preferred embodiment of the present invention, the average particle size of the spherical and/or spheroidal polymer is 0.02 to 50.0mm, and may be, for example, 0.02mm, 0.05mm, 0.1mm, 0.5mm, 1.0mm, 1.5mm, 2.0mm, 3.0mm, 5.0mm, 8.0mm, 10.0mm, 15.0mm, 20.0mm, 25.0mm, 30.0mm, 35.0mm, 40.0mm, 45.0mm, 50.0mm and any value therebetween, preferably 0.2 to 20.0mm.

According to a preferred embodiment of the invention, the wall thickness of the spherical and/or spheroidal polymer having a hollow structure is 1 to 95% of the radius of the spherical and/or spheroidal polymer, which may be, for example, 1%, 2%, 5%, 8%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80%, 90%, 95% and any value in between, preferably 5 to 70%, more preferably 10 to 50%.

According to a preferred embodiment of the application, the olefin-terminal alkenylsilane/siloxane copolymer has a melting point of 70 to 125 ℃, for example 70 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 120 ℃, 125 ℃ and any value in between.

According to a preferred embodiment of the application, the weight average molecular weight of the olefin-terminal alkenylsilane/siloxane copolymer is 5,000 ～ 500,000, preferably 10,000 ～ 300,000.

According to a preferred embodiment of the present application, the olefin-terminal alkenylsilane/siloxane copolymer may have a molecular weight distribution of 4.5 or less, for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5 and any value therebetween, and preferably has a molecular weight distribution of 1.0 to 4.0.

In the present application, the particle size of a spherical or spheroidal polymer is herein considered to be equal to the diameter of a sphere of equal volume to the volume of the particle.

It is a further object of the present application to provide the use of the copolymers obtained by the copolymerization process as polyolefin materials.

The symbols used in the different formulae or formulae in the present application are, for example, R ₁ ～R ₈ 、R ₂₁ ～R ₂₄ 、R ¹ ～R ¹¹ 、R’、X、M、Y、L ₁ -L ₄ 、R’ ₁ -R’ ₃ And the like, unless otherwise specified, are defined as the same as those of the general formula or structural formula.

In the present application, alkyl means a straight chain alkyl group, a branched alkyl group or a cycloalkyl group. For example, C ₁ -C ₂₀ Alkyl means C ₁ -C ₂₀ Straight chain alkyl, C ₃ -C ₂₀ Branched alkyl or C ₃ -C ₂₀ Cycloalkyl groups. Examples of straight or branched alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-Butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and n-decyl.

C ₃ -C ₂₀ Examples of cycloalkyl groups include, but are not limited to: cyclopropyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl and 4-n-butylcyclohexyl.

C ₆ -C ₂₀ Examples of aryl groups include, but are not limited to: phenyl, 4-methylphenyl, 4-ethylphenyl, dimethylphenyl, vinylphenyl.

Alkenyl refers to straight chain alkenyl, branched alkenyl, or cycloalkenyl. For example, C ₂ -C ₂₀ Alkenyl means C ₁ -C ₂₀ Straight chain alkenyl, C ₃ -C ₂₀ Branched alkenyl or C of (2) ₃ -C ₂₀ Is a cycloalkenyl group of (a). Examples of alkenyl groups include, but are not limited to: vinyl, allyl, butenyl.

C ₇ -C ₂₀ Examples of aralkyl groups include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenylisopropyl, phenyl-n-butyl and phenyl-tert-butyl.

C ₇ -C ₂₀ Examples of alkylaryl groups include, but are not limited to: tolyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl and tert-butylphenyl.

The present invention provides a novel catalyst comprising a trinuclear metal complex for use in the preparation of olefin-terminal alkenylsilane/siloxane copolymers.

By screening the catalyst structure, polymerization conditions and alkenylsilane/siloxane monomers, a polymerization process is found that can directly prepare spherical polyolefin. The catalyst can directly prepare polyolefin with silane or siloxane without loading, so that the catalyst can be used for avoiding complex loading process, directly preparing spherical particles, avoiding the post-processing procedure of polymer granulation and bringing great convenience to the industrial production of the method.

Further, in the preparation method of the olefin-terminal alkenyl silane/siloxane copolymer, the spherical and/or spheroidal polymer with good morphology is directly prepared by selecting the reacted terminal alkenyl silane/siloxane monomer, the catalyst and a proper polymerization process without the subsequent processing steps of granulation and the like, and the obtained polymerization product is not easy to scale in a reactor and is convenient to transport.

Drawings

FIG. 1 is a photograph of a copolymer obtained in example 7.

Detailed Description

The present invention will be described in detail with reference to the following examples and drawings, but it should be understood that the examples and drawings are only for illustrative purposes and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.

The raw materials used in examples and comparative examples, if not particularly limited, are all as disclosed in the prior art, and are, for example, available directly or prepared according to the preparation methods disclosed in the prior art.

The analytical characterization instrument used in the present invention is as follows:

the polymer is washed by dilute acid solution before measurement, so that the metal content in the polymer is less than or equal to 50ppm.

1. Nuclear magnetic resonance apparatus: bruker DMX 300 (300 MHz), tetramethyl silicon (TMS) as an internal standard, was used to test the structure of the complex ligand at 25 ℃.

2. Comonomer content of the polymer: wavelength dispersive X-ray fluorescence spectrometry (XRF): the composition of the elements in the polymer sample is qualitatively determined according to the X-ray fluorescence spectrum by using an Axios-Advanced type wavelength dispersion X-ray fluorescence spectrometer of PANalytical company of Netherlands, and the content of the elements in the polymer is semi-quantitatively determined according to the peak intensity of the elements in the X-ray fluorescence spectrum.

2. Molecular weight and molecular weight distribution PDI of polymer (pdi=mw/Mn): by PL-GPC ₂ 20, measured at 150℃in trichlorobenzene as solvent (standard: PS, flow rate: 1.0mL/min, column: 3 XPlgel 10um M1×ED-B300×7.5 nm).

3. The activity measurement method comprises the following steps: gravimetric analysis. The activity is expressed as polymer weight (g). Times.60/(nickel (mol). Times.reaction time (min)).

4. Polymer density test: the density was measured using GB/T6343-2009.

Example 1

Complex Ni ₁ Is prepared from

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ To a solution of ligand L1 in methylene chloride (10 mL) containing 0.175g (0.6 mmol) of the solution was slowly added dropwise, and the mixture was stirred at room temperature for 6 hours, and then dehydrated ether was added to precipitate. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain yellow powdery solid Ni ₁ . Yield: 70.2%. 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; n,3.96.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe were injected into the polymerization system ₃ (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L in toluene) complex Ni were added ₁ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 3.34×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 16.7 ten thousand, the molecular weight distribution was 3.26, and the si monomer molar content was 3.45%. The average particle size of the spheroidal polymer was 0.78mm.

Example 2

A 7mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130 c for 2 hours,vacuum while hot and use N ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L (0.24 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 124. Mu.L of AliBu were injected into the polymerization system ₃ (95％)，50μL AlMe ₃ (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were added ₁ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 4.23×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 16.4 ten thousand, the molecular weight distribution was 3.42, and the si monomer molar content was 3.50%. The average particle diameter of the spheroidal polymer was 0.68mm.

Example 3

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2hrs, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlEt are injected ₃ (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L in toluene) complex Ni were added ₁ . The reaction was vigorously stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralizing with 10wt% hydrochloric acid acidified ethanol solution to obtain polymer with polymerization activity of 1.96×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 8.2 ten thousand, the molecular weight distribution was 4.14, and the si monomer molar content was 3.01%. The average particle size of the spheroidal polymer was 0.72mm.

Example 4

Complex Ni ₂ Is prepared from

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ Ethanol solution (10 mL)) Slowly added dropwise to a dichloromethane solution (10 mL) containing 0.272g (0.6 mmol) of ligand L2. The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₂ . 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; n,3.48.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlMe were injected into the polymerization system ₃ (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were added simultaneously ₂ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 1.96×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 12.6 ten thousand, the molecular weight distribution was 4.43, and the si monomer molar content was 3.01%. The average particle size of the spheroidal polymer was 0.70mm.

Comparative example 1

This comparative example 1 differs from example 3 in that: the amount of catalyst A (shown as formula (I') was 0.025. Mu. Mol) for the comparative catalyst.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. To the polymerization system, 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 25. Mu.L of MAO (1.53 mol/L of toluene solution) and 25.0. Mu.L (1.0 mmol/L of toluene solution) of the complex A were injected, and the reaction was stirred at 30℃under an ethylene pressure of 10atm for 30 minutes. Finally, the mixture is neutralized by ethanol solution acidified by 10wt percent hydrochloric acid to obtain polymer . Polymerization Activity was 1.04X 10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 6.8 ten thousand, the molecular weight distribution was 3.82, and the si monomer molar content was 2.06%.

Example 5

1) Ligand L ₃ Is prepared from the following steps:

under the protection of nitrogen, 2,4, 6-trimethylaniline (1.7 mL,12 mmol) is dissolved in 20mL of toluene, 12mL (1.0M, 12 mmol) of trimethylaluminum is dripped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to the room temperature, camphorquinone (0.831 g,5 mmol) is added, and the system is refluxed for 6 hours. Neutralizing the reaction product with sodium hydroxide aqueous solution, extracting with dichloromethane, drying, and column chromatography to obtain yellow ligand L ₃ The yield was 62.5%. ¹ HNMR(300MHz,CDCl ₃ ),δ(ppm)[an isomer ratio of 1.2:1]:major isomer:6.72(s,4H,Ar-H),2.26-2.13(m,12H,C _Ar -CH ₃ ),1.87(s,6H,C _Ar -CH ₃ ),1.79(m,4H,CH ₂ ),1.42(m,1H),1.26(s,3H,CH ₃ ),1.07(s,6H,CH ₃ )。Minor isomer:6.67(s,4H,Ar-H),2.09-2.01(m,12H,C _Ar -CH ₃ ),1.85(s,6H,C _Ar -CH ₃ ),1.79(m,4H,CH ₂ ),1.40(m,1H),1.26(s,3H,CH ₃ ),0.94(s,6H,CH ₃ )。

2) Complex Ni ₃ (R in the formula IV) ¹ -R ³ Is methyl, R ⁴ -R ⁷ 、R ¹⁰ Is hydrogen, R ⁸ 、R ⁹ And R is ¹¹ Methyl, R' is ethyl, M is nickel, Y is O, X is Br).

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ Is slowly added dropwise to an ethanol solution (10 mL) containing 0.240g (0.6 mmol) of ligand L ₃ In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₃ . Production ofThe rate was 78.6%. Elemental analysis (C) ₆₀ H ₈₂ Br ₆ N ₄ Ni ₃ O ₂ ): c,46.59; h,5.34; n,3.62; experimental values (%): c,46.24; h,5.67; n,3.21.

3) Polymerization:

a7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. Into the polymerization system, 4.0mL of heptane, 50. Mu.L (0.24 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 62. Mu.L of AliBu3 (95%), 50. Mu.L of AlMe3 (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were injected ₃ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 5.42×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 9.33 ten thousand, the molecular weight distribution was 3.54, and the si monomer molar content was 4.85%. The average particle diameter of the spheroidal polymer was 0.69mm.

Example 6

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2hrs, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlEt are injected ₃ (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L in toluene) complex Ni were added ₃ . The reaction was vigorously stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralizing with 10wt% hydrochloric acid acidified ethanol solution to obtain polymer with polymerization activity of 3.72X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 7.26 ten thousand, the molecular weight distribution was 3.49, and the si monomer molar content was 4.76%. The average particle diameter of the spheroidal polymer was 0.77mm.

Example 7

Continuously drying 1L stainless steel polymerization kettle with mechanical stirring at 130deg.C for 2 hr, vacuumizing while it is hot, and using N ₂ The air was replaced 3 times. 450mL of hexane, 5mL (24.1 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 6.2mL of AliBu3 (95%), 0.5mL of AlMe3 (1.0 mol/L of heptane), 6.4mg (12.5. Mu. Mol) of tris (pentafluorophenyl) borane, 11.5mg (12.5. Mu. Mol) of triphenylmethyl tetrakis (pentafluorophenyl) borate, and 1.9mg (1.25. Mu. Mol) of complex Ni were injected into the polymerization system ₂ Ethylene pressure of 10atm was maintained at 20℃and the reaction was stirred for 30min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 7.82X 10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 18.72 ten thousand, the molecular weight distribution was 3.42, and the si monomer molar content was 4.47%. The average particle diameter of the spheroidal polymer in the copolymer was 3.2mm, and the density of the resulting polymer was 0.5724g/cm ³ 。

Comparative example 2

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. To the polymerization system was injected 4.0mL of heptane, 50. Mu.L (0.30 mmol) of allyltrimethoxysilane, 25. Mu.L of MAO (1.53 mol/L of toluene solution), and 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni ₃ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 2.56X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 7.42 ten thousand, the molecular weight distribution was 3.73, and the si monomer molar content was 3.34%. The polymer obtained is free of spherical particles.

Example 8

1) Ligand L ₄ Is prepared from the following steps:

under the protection of nitrogen, 2, 6-dimethyl-4-bromo-aniline (2.45 g,12 mmol) is dissolved in 20mL of toluene, 12mL (1.0M, 12 mmol) of trimethylaluminum is dripped at normal temperature, the reaction is refluxed for 2 hours, the system is cooled to the room temperature, camphorquinone (0.831 g,5 mmol) is added, and the system is refluxed for 6 hours. Neutralizing the reaction product with sodium hydroxide aqueous solution, extracting with dichloromethane, drying, and column chromatography to obtain yellow ligand L ₄ The yield is 60.7%. ¹ HNMR(300MHz,CDCl ₃ ),δ(ppm)[an isomer ratio of 1.1:1]:major isomer:7.05(s,4H,Ar-H),2.18(m,12H,CAr-CH ₃ ),1.85(m,4H,CH ₂ ),1.37(m,1H),1.26(s,3H,CH ₃ ),1.06(s,6H,CH ₃ ).Minor isomer:7.02(s,4H,Ar-H),2.04(m,12H,CAr-CH ₃ ),1.85(m,4H,CH ₂ ),1.37(m,1H),1.26(s,3H,CH ₃ ),0.96(s,6H,CH ₃ )。

2) Complex Ni ₄ (R in the formula IV) ¹ 、R ³ Is methyl, R ² Bromine, R ⁴ -R ⁷ 、R ¹⁰ Is hydrogen, R ⁸ 、R ⁹ And R is ¹¹ Methyl, R' is ethyl, M is nickel, Y is O, X is Br).

Will contain 0.278g (0.9 mmol) (DME) NiBr ₂ Is slowly added dropwise to an ethanol solution (10 mL) containing 0.318g (0.6 mmol) of ligand L ₄ In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₄ . The yield was 74.1%. Elemental analysis (C) ₅₆ H ₇₀ Br ₁₀ N ₄ Ni ₃ O ₂ ): c,37.24; h,3.91; n,3.10; experimental values (%): c,37.38; h,4.30; n,3.03.

3) Polymerization:

a7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe were injected into the polymerization system ₃ (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were added ₄ Ethylene pressure of 15atm was maintained at 50℃and the reaction was stirred for 20min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 6.27X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 12.32 ten thousand, the molecular weight distribution was 3.62, and the si monomer molar content was 4.51%. The average particle size of the spheroidal polymer was 0.70mm.

Example 9

Complex Ni ₅ Is prepared from

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ Is slowly added dropwise to an ethanol solution (10 mL) containing 0.249g (0.6 mmol) of ligand L ₅ In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₅ . The yield was 84.3%. Elemental analysis (C) ₆₄ H ₆₆ Br ₆ N ₄ Ni ₃ O ₂ ): c,48.69; h,4.21; n,3.55; experimental values (%): c,48.54; h,4.47; n,3.21.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe were injected into the polymerization system ₃ (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L in toluene) complex Ni were added ₅ The reaction was stirred at 30℃for 60min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 5.69×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 12.34 ten thousand, the molecular weight distribution was 4.27, and the si monomer molar content was 4.12%. The average particle size of the spheroidal polymer was 0.79mm.

Example 10

1L stainless steel with mechanical stirringThe polymerization vessel was dried continuously at 130℃for 2h, evacuated while hot and with N ₂ The air was replaced 3 times. 450mL of hexane, 5mL (24.1 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 12.3mL of AliBu were injected into the polymerization system ₃ (95％)，0.5mL AlMe ₃ (1.0 mol/L in heptane), 6.4mg (12.5. Mu. Mol) of tris (pentafluorophenyl) borane, 11.5mg (12.5. Mu. Mol) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 2.0mg (1.25. Mu. Mol) of complex Ni were added ₅ Ethylene pressure of 10atm was maintained at 20℃and the reaction was stirred for 30min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 5.24X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 9.07 ten thousand, the molecular weight distribution was 3.84, and the si monomer molar content was 4.14%. The average particle diameter of the spheroidal polymer in the copolymer was 3.8mm, and the density of the resulting polymer was 0.5517g/cm ³ 。

Example 11

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2hrs, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L (0.26 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlEt are injected ₃ (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L in toluene) complex Ni were added ₅ . The reaction was vigorously stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Neutralizing with 10wt% hydrochloric acid acidified ethanol solution to obtain polymer with polymerization activity of 4.23×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 8.31 ten thousand, the molecular weight distribution was 3.24, and the si monomer molar content was 4.26%. The average particle size of the spheroidal polymer was 0.72mm.

Comparative example 3

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. To the polymerization system was injected 4.0mL of heptane, 50. Mu.L (0.30 mmol) of allyltrimethoxysilane, 25. Mu.L of MAO (1.53 mol/L in toluene) and 12.5. Mu.L of the mixture was addedL (1.0 mmol/L toluene solution) complex Ni ₅ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 2.24X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 5.27 ten thousand, the molecular weight distribution was 4.34, and the si monomer molar content was 3.17%. The polymer obtained is free of spherical particles.

Example 12

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ To a solution of ligand L6 in methylene chloride (10 mL) containing 0.389g (0.6 mmol) of the ligand L6 was slowly dropped (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₆ . The yield was 74.1%. Elemental analysis (C) ₅₂ H ₃₄ Br ₁₄ N ₄ Ni ₃ O ₂ ): c,30.59; h,1.68; n,2.74; experimental values (%): c,30.72; h,1.97; n,2.48.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol), 50. Mu.L of AlMe were injected into the polymerization system ₃ (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were added ₆ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 10 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 4.22×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 5.14 ten thousand, the molecular weight distribution was 4.24, and the si monomer molar content was 4.33%. Average particle of spheroidal polymerThe diameter is 0.68mm.

Example 13

Preparation of ligand L7 reference Organometallics 2013,32,2291-2299.

Complex Ni ₇ (R in structural formula VIII) ¹ 、R ³ 、R ⁴ 、R ⁶ Is methyl, R ² 、R ⁵ 、R ⁷ -R ¹⁰ 、R ₂₁ -R ₂₄ Hydrogen, and R' is ethyl, M is nickel, Y is O, X is Br).

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ To a solution of ligand L7 in methylene chloride (10 mL) containing 0.264g (0.6 mmol) of ligand L7 was slowly added dropwise (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₇ . Yield: 78.2%. Elemental analysis (C) ₆₈ H ₆₆ Br ₆ N ₄ Ni ₃ O ₂ ): c,50.21; h,4.09; n,3.44; experimental values (%): c,50.38; h,4.22; n,3.76.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 40. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.15 mmol), 50. Mu.L of AlMe were injected into the polymerization system ₃ (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) tris (pentafluorophenyl) borane, 12.5. Mu.L (1.0 mmol/L in toluene) complex Ni was added ₇ Ethylene pressure of 15atm was maintained at 30℃and the reaction was stirred for 30min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 2.21×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 15.17 ten thousand, the molecular weight distribution was 4.22, and the si monomer molar content was 1.08%. The average particle diameter of the spheroidal polymer was 0.71mm.

Example 14

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Preparation of ligand L8: compound A (1.77 g,5.1 mmol) and 2, 6-dimethyl-4-bromo-aniline (2.3 g,11.3 mmol) were refluxed for 1 day in 100mL of toluene, the solvent was removed after filtration, and the residue was dissolved in dichloromethane and chromatographed on a petroleum ether/ethyl acetate column to give L8 as a yellow solid in 78% yield. ¹ H NMR(CDCl3，δ，ppm):1.84(s，12H)，1.19ppm(s，18H)，4.70(s，2H)，7.04(8H)，7.12(s，2H)。

Complex Ni ₈ Preparation of (R in formula VIII) ¹ 、R ³ 、R ⁴ 、R ⁶ Is methyl, R ² 、R ⁵ Bromine, R ⁷ -R ¹⁰ 、R ₂₂ -R ₂₄ Is hydrogen, R ₂₁ Is tert-butyl, and R' is ethyl, M is nickel, Y is O, X is Br

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ Slowly (10 mL) was added dropwise to a dichloromethane solution (10 mL) containing 0.426g (0.6 mmol) of ligand L8. The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₈ . The yield was 82.0%. Elemental analysis (C) ₈₄ H ₉₄ Br ₁₀ N ₄ Ni ₃ O ₂ ): c,46.56; h,4.37; n,2.59; experimental values (%): c,46.43; h,4.72; n,2.98.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2hrs, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. 4.0mL of heptane, 50. Mu.L of triethoxysilane (2-methyl-3-butenyl) (0.19 mmol) were injected, plusInto 50. Mu.L of AlMe3 (0.1 mol/L in heptane), 12.5. Mu.L (0.01 mol/L in toluene) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L in toluene) of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, 12.5. Mu.L (1.0 mmol/L in toluene) of complex Ni were added ₈ . The reaction was vigorously stirred at 30℃for 30min while maintaining an ethylene pressure of 15 atm. Neutralization with 10wt% hydrochloric acid acidified ethanol solution with polymerization activity of 5.33X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 17.64 ten thousand, the molecular weight distribution was 4.37, and the si monomer molar content was 1.16%. The average particle size of the spheroidal polymer was 1.24mm.

Comparative example 4

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. To the polymerization system was injected 4.0mL of heptane, 50. Mu.L (0.30 mmol) of allyltrimethoxysilane, 25. Mu.L of MAO (1.53 mol/L of toluene solution), and 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni ₈ Ethylene pressure of 15atm was maintained at 30℃and the reaction was stirred for 30min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 4.21×10 ⁵ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 10.30 ten thousand, the molecular weight distribution was 4.42, and the si monomer molar content was 0.88%. The polymer obtained is free of spherical particles.

Example 15

1) Ligand L ₉ Reference CN106397264;

2) Complex Ni ₉ Preparation of (R in formula VIII) ¹ 、R ³ 、R ⁴ 、R ⁶ Is ethyl, R ² 、R ⁵ 、R ⁷ -R ¹⁰ 、R ₂₂ -R ₂₄ Is hydrogen, R ₂₁ Is tert-butyl, and R' is ethyl, M is nickel, Y is O, X is Br

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ Ethanol dissolution of (C)The solution (10 mL) was slowly added dropwise containing 0.365g (0.6 mmol) of ligand L ₉ In methylene chloride (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying to obtain brownish red powdery solid Ni ₉ . The yield was 82.0%. Elemental analysis (C) ₉₂ H ₁₁₄ Br ₆ N ₄ Ni ₃ O ₂ ): c,56.28; h,5.85; n,2.85; experimental values (%): c,56.43; h,6.12; n,3.08.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. Into the polymerization system, 4.0mL of heptane, 50. Mu.L (0.24 mmol) of methyl 3-trimethylsilyl-4-pentenoate, 62. Mu.L of AliBu3 (95%), 50. Mu.L of AlMe3 (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were injected ₉ Ethylene pressure of 15atm was maintained at 30℃and the reaction was stirred for 60min. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 1.42×10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 30.37 ten thousand, the molecular weight distribution was 4.42, and the si monomer molar content was 1.13%. The average particle size of the spheroidal polymer was 2.12mm.

Example 16

The preparation of ligand L10 is referred to in patent CN201510462932.2.

Will contain 0.277g (0.9 mmol) (DME) NiBr ₂ To a solution of ligand L10 in methylene chloride (10 mL) containing 0.341g (0.6 mmol) of ligand L10 was slowly dropped (10 mL). The color of the solution immediately changed to dark red and a large amount of precipitate was formed. Stirring at room temperature for 6h, adding anhydrous diethyl ether for precipitation. Filtering to obtain a filter cake, washing the filter cake with anhydrous diethyl ether, and vacuum drying Obtaining brownish red powdery solid Ni ₁₀ . The yield was 82.1%. Elemental analysis (C) ₈₈ H ₈₂ Br ₆ N ₄ Ni ₃ O ₂ ): c,56.13; h,4.39; n,2.98; experimental values (%): c,56.28; h,4.62; n,3.24.

A7 mL stainless steel glass liner polymerizer equipped with mechanical stirring was continuously dried at 130℃for 2h, evacuated while hot and N-terminally used ₂ The air was replaced 3 times. Into the polymerization system was injected 4.0mL of heptane, 100. Mu.L (0.51 mmol) of trimethyl (1-methyl-3-buten-1-yl) silane, 50. Mu.L of AlMe ₃ (0.1 mol/L of heptane solution), 12.5. Mu.L (0.01 mol/L of toluene solution) of tris (pentafluorophenyl) borane, 12.5. Mu.L (0.01 mol/L of toluene solution) of triphenylmethyl tetrakis (pentafluorophenyl) borate, and 12.5. Mu.L (1.0 mmol/L of toluene solution) of complex Ni were added simultaneously ₁₀ The reaction was stirred at 30℃for 30min while maintaining an ethylene pressure of 20 atm. Finally, the mixture was neutralized with an ethanol solution acidified with 10wt% hydrochloric acid to obtain a polymer. Polymerization Activity was 1.48X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The weight average molecular weight was 19.27 ten thousand, the molecular weight distribution was 4.20, and the si monomer molar content was 1.14%. The average particle size of the spheroidal polymer was 1.98mm.

The catalyst compositions employed in examples 1 to 16 have a copolymerization activity of up to 7.27X10 ⁶ g·mol ^-1 (Ni)·h ^-1 The method comprises the steps of carrying out a first treatment on the surface of the Compared with comparative examples 1-4, the catalysts of examples 1-16 have significantly improved copolymerization activity, significantly improved comonomer content, and lower molecular weight distribution, and the polymer molecular weight can be controlled over a wider range. And compared with the comparative example, the spherical polymer can not be obtained, and the spherical particle polymer with higher comonomer Si content can be obtained by adjusting the monomer structure, thereby being more beneficial to the popularization and application of the technology.

The embodiments of the present invention have been described above, the description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A process for copolymerizing a spherical or spheroidal copolymer of an olefin-alkenylsilane/siloxane which comprises reacting an olefin with an alkenylsilane/siloxane represented by the formula (1) or a derivative thereof in contact with a catalyst in the presence of an alkane solvent,

in the formula (1), L ₁ -L ₃ Independently selected from H, C with or without substituents ₁ -C ₃₀ Alkyl, L ₄ Is C containing substituent ₁ -C ₃₀ Alkylene, R' ₁ -R’ ₃ C being halogen, with or without substituents ₁ -C ₁₀ Alkyl, C with or without substituents ₁ -C ₁₀ An alkoxy group;

in the formula (I), R ₃ 、R ₄ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Hydrocarbyl radicals, adjacent R ₃ And R is ₄ Optionally interconnected to form a ring or ring system; r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ A hydrocarbon group; y is selected from group VIA nonmetallic atoms; m is selected from nickel or palladium; x is selected from halogen, C with substituent or without substituent ₁ -C ₁₀ Hydrocarbyl, C with or without substituents ₁ -C ₁₀ A hydrocarbyloxy group; r is R ₁ 、R ₂ Is a group of the formula (II) in which R ¹ ～R ⁵ Identical or different, each independently selected from hydrogen, halogen, hydroxy, C with or without substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Alkylaryl, R ¹ ～R ⁵ Optionally interconnected to form a ring or ring system;

the cocatalyst is selected from an organoaluminium compound and/or an organoboron compound.

2. The copolymerization process according to claim 1, wherein,

y is selected from O or S; x is selected from halogen, C with substituent or without substituent ₁ -C ₁₀ Alkyl, C with or without substituents ₁ -C ₁₀ An alkoxy group; r' is selected from substituent-containing or substituent-free C ₁ -C ₂₀ An alkyl group; r is R ₃ And R is ₄ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ An alkylaryl group; l (L) ₁ And L ₂ Are all H, L ₃ Is H, C with or without substituents ₁ -C ₂₀ Alkyl, L ₄ Is C containing substituent ₁ -C ₂₀ An alkylene group.

3. The copolymerization process according to claim 1, characterized in that the metal complex is prepared by the following steps: bringing a diimine compound represented by the formula (A) into contact with MX _n And R' YH are reacted with each other,

in the formula (A), R ₁ 、R ₂ 、R ₃ And R is ₄ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (I).

4. The copolymerization method according to claim 1, wherein the metal complex has a structure represented by the formula (III):

in the formula (III), R ₅ ～R ₈ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ Hydrocarbyl radicals, R ₅ ～R ₈ Optionally interconnected to form a ring or ring system.

5. The copolymerization process according to claim 4, wherein,

R ₅ ～R ₈ independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, halogenated C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy group,Halogenated C ₁ -C ₁₀ Alkoxy, halogen.

6. The copolymerization process according to claim 4, wherein the metal complex has a structure represented by the formula (IV):

7. The copolymerization process according to any one of claims 4 to 6, characterized in that the metal complex is prepared by: bringing a diimine compound represented by the formula (B) into contact with MX _n And R' YH are reacted with each other,

in the formula (B), R ₅ ～R ₈ Having the same definition as formula (III); r is R ₁ And R is ₂ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (I).

8. The copolymerization method according to claim 1, wherein the metal complex has a structure represented by the formula (V):

in the formula (V), R ₅ ～R ₇ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₃₀ Hydrocarbyl radicals, R ₅ ～R ₇ Optionally interconnected to form a ring or ring system.

9. The copolymerization process according to claim 8, wherein,

R ₅ ～R ₇ independently selected from hydrogen, C ₁ -C ₁₀ Alkyl, halogenated C ₁ -C ₁₀ Alkyl, C ₁ -C ₁₀ Alkoxy, halogenated C ₁ -C ₁₀ Alkoxy, halogen.

10. The copolymerization process according to claim 8, wherein the metal complex has a structure represented by the formula (VI):

11. The copolymerization process according to claim 8 or 10, characterized in that the metal complex is prepared by the following steps: bringing a diimine compound represented by the formula (C) into contact with MX _n And R' YH are reacted with each other,

in the formula (C), R ₅ 、R ₆ 、R ₇ Has the same definition as formula (V); r is R ₁ And R is ₂ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (I).

12. The copolymerization method according to claim 1, wherein the metal complex has a structure represented by the formula (VII):

in the formula (VII), R ₂₁ ～R ₂₄ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Hydrocarbyl, C with or without substituents ₁ -C ₂₀ Hydrocarbyloxy radicals R ₂₁ ～R ₂₄ Optionally interconnected to form a ring or ring system.

13. The copolymerization process according to claim 12, wherein,

R ₂₁ ～R ₂₄ each independently selected from hydrogen, halogen, substituted or non-substitutedC containing substituents ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstituted C ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₆ -C ₂₀ Aryloxy, substituted or unsubstituted C ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Aralkoxy, C with or without substituents ₇ -C ₂₀ Alkylaryl, substituted or unsubstituted C ₇ -C ₂₀ An alkylaryl group.

14. The copolymerization process according to claim 12, wherein the metal complex has a structure represented by formula (VIII):

in the formula (VIII), R ¹ ～R ¹⁰ Independently selected from hydrogen, halogen, hydroxy, substituted or unsubstituted C ₁ -C ₂₀ Alkyl, C with or without substituents ₂ -C ₂₀ Alkenyl, C with or without substituents ₂ -C ₂₀ Alkynyl, substituted or unsubstituted C ₃ -C ₂₀ Cycloalkyl, C with or without substituents ₁ -C ₂₀ Alkoxy, C with or without substituents ₂ -C ₂₀ Alkenyloxy, substituted or unsubstituted C ₂ -C ₂₀ Alkynyloxy, substituted or unsubstitutedC ₃ -C ₂₀ C having or not having a substituent ₆ -C ₂₀ Aryl, C with or without substituents ₆ -C ₂₀ Aryloxy, substituted or unsubstituted C ₇ -C ₂₀ Aralkyl, C with or without substituents ₇ -C ₂₀ Aralkoxy, C with or without substituents ₇ -C ₂₀ Alkylaryl, substituted or unsubstituted C ₇ -C ₂₀ An alkylaryl group.

15. The copolymerization process according to claim 12 or 14, characterized in that the metal complex is prepared by the following steps: bringing a diimine compound represented by the formula (D) into contact with MX _n And R' YH are reacted with each other,

in the formula (D), R ₂₁ ～R ₂₄ Has the same definition as formula (VII); r is R ₁ And R is ₂ Having the same definition as formula (I); MX (MX) _n Wherein M and X have the same definition as the formula (I), n is the number of X satisfying the valence state of M, and n is 1, 2 or 3; y and R 'in R' YH have the same definition as in formula (I).

16. The copolymerization method according to claim 1, wherein:

the concentration of the metal complex in the reaction system is 0.00001-100 mmol/L.

17. The copolymerization method according to claim 1, wherein:

the organic aluminum compound is selected from one or more of alkyl aluminoxane, alkyl aluminum and alkyl aluminum halide; the organoboron compound is selected from an aromatic boron and/or borate.

18. The copolymerization method according to claim 17, wherein:

when the cocatalyst is an organoaluminum compound, the molar ratio of aluminum in the organoaluminum compound to M in the metal complex is (10 to 10 ⁷ )：1；

When the cocatalyst comprises an organoboron compound and an organoaluminum compound, the molar ratio of boron in the organoboron compound to M in the metal complex is (0.1-1000): 1, the molar ratio of aluminum in the organoaluminum compound to M in the metal complex is (10 to 10 ⁵ )：1。

19. The copolymerization method according to claim 18, wherein:

the molar ratio of aluminum in the organoaluminum compound to M in the metal complex is (10 to 100000): 1.

20. the copolymerization method according to claim 1, wherein:

The concentration of the terminal alkenyl silane/siloxane or the derivative reaction system thereof is 0.01-6000 mmol/L.

21. The copolymerization method according to claim 20, wherein:

the concentration of the terminal alkenyl silane/siloxane or the derivative reaction system thereof is 0.1-1000 mmol/L.

22. The copolymerization method according to claim 1, wherein:

the olefin is an olefin having 2 to 16 carbon atoms.

23. The copolymerization method according to claim 22, wherein:

the olefin is ethylene or an alpha-olefin having 3 to 16 carbon atoms.

24. The copolymerization method according to claim 1, wherein:

the reaction temperature is-50-80 ℃, and the reaction time is 10-200 min.

25. The copolymerization method according to claim 1, wherein:

the average particle diameter of the spherical or spheroidal copolymer is 0.02-50.0 mm.

26. The copolymerization method according to claim 25, wherein:

the average particle diameter of the spherical or spheroidal copolymer is 0.2-20.0 mm.

27. A copolymer obtained by the copolymerization method according to any one of claims 1 to 26.

28. The copolymer of claim 27, wherein:

At least part of the sphere or sphere-like copolymer has cavities and holes inside.

29. The copolymer of claim 27, wherein:

the density of the copolymer is 0.3000-0.8500 g/cm ³ The density was measured using GB/T6343-2009; and/or the number of the groups of groups,

the weight average molecular weight of the copolymer was 5,000 ～ 500,000.

30. The copolymer of claim 29, wherein:

the density of the copolymer is 0.4000-0.7500 g/cm ³ The method comprises the steps of carrying out a first treatment on the surface of the And/or the number of the groups of groups,

the weight average molecular weight of the copolymer was 10,000 ～ 300,000.

31. Use of a copolymer obtained by a copolymerization process according to any one of claims 1 to 26 as polyolefin material.