CN111234063B

CN111234063B - Process for preparing solid catalyst component for olefin polymerization, olefin polymerization catalyst and use thereof

Info

Publication number: CN111234063B
Application number: CN201811443111.4A
Authority: CN
Inventors: 严立安; 黄庭; 赵惠; 郭子芳; 周俊领; 孙竹芳; 林洁; 岑为; 张军辉; 张晓帆; 付梅艳
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: 2018-11-29
Filing date: 2018-11-29
Publication date: 2021-07-30
Anticipated expiration: 2038-11-29
Also published as: CN111234063A

Abstract

The invention relates to a preparation method of a solid catalyst component for olefin polymerization, an olefin polymerization catalyst and application thereof. The preparation method comprises 1) dissolving magnesium halide in a solvent system, preferably a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent, to form a solution; 2) contacting the solution obtained in step 1) with a precipitation aid and a titanium compound to produce a mixture containing a solid precipitate. The preparation method of the invention can obtain a novel catalyst with excellent particle shape and comprehensive performance.

Description

Process for preparing solid catalyst component for olefin polymerization, olefin polymerization catalyst and use thereof

Technical Field

The invention belongs to the field of olefin polymerization catalysts, and particularly relates to a preparation method of a solid catalyst component for olefin polymerization, an olefin polymerization catalyst and application thereof.

Background

The solid granular polyolefin catalyst with magnesium, titanium, halogen and electron donor as basic components is prepared through preparing magnesium chloride into homogeneous solution, crystallizing to separate out and load active titanium-containing component. In a dissolution and precipitation system, a solid with uniform particle size can be obtained only in the presence of a precipitation aid, and the precipitation aid generally adopts organic acid anhydride, organic acid, ketone, ether and other compounds.

In CN85100997A, the titanium-containing catalyst component is prepared by dissolving magnesium halide in organic epoxy compound and organic phosphorus compound to form a homogeneous solution, mixing the solution with titanium tetrahalide or its derivative, and precipitating solid in the presence of precipitation-assisting agent such as organic acid anhydride; the solid is treated with a polycarboxylic acid ester to cause it to become attached to the solid, and then treated with a titanium tetrahalide and an inert diluent. The catalyst has obvious improvement in apparent density, regularity, particle morphology and the like. However, the productivity and catalyst performance of the catalyst prepared by this method are still to be further improved.

CN1931885A discloses a method for preparing a titanium-containing catalyst component, which comprises dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound, adding an organic alcohol electron donor to form a uniform solution, using a liquid coprecipitator, and omitting the dissolution reaction step of a precipitant, thereby obtaining a solid catalyst. However, the catalyst prepared by the method has the advantages of difficult control of particle morphology, difficult adjustment of particle size and more polymer fine powder, and is mostly suitable for an ethylene polymerization process with relaxed requirements on the fine powder.

In the method for preparing the titanium-containing catalyst component disclosed in CN101864009A, after magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound, a polyol ester compound with a special structure is introduced as a precipitation-assisting component, and a solid catalyst can be obtained. However, the performance of the catalyst prepared by the method is greatly influenced by polyol ester compounds, the activity of the catalyst is attenuated quickly, and the isotacticity and hydrogen regulation performance need to be improved.

Disclosure of Invention

The invention has found that in the preparation of the olefin polymerization catalyst, a cyclotri veratrole hydrocarbon with a special structure and a derivative thereof are introduced as precipitation-assisting components, and simultaneously, the dissolution ratio of magnesium halide, an organic epoxy compound and an organic phosphorus compound is adjusted to obtain a novel catalyst with excellent particle morphology and comprehensive performance, and simultaneously, a small amount of internal electron donor can be added to ensure that the catalyst has better stereotacticity. The catalyst has greatly raised yield, high polymerization activity and excellent hydrogen regulation sensitivity, and less polymer powder.

In a first aspect, the present invention provides a process for the preparation of a solid catalyst component for the polymerization of olefins, comprising the steps of:

1) dissolving a magnesium halide in a solvent system, preferably a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent, to form a solution, preferably a homogeneous solution;

2) contacting the solution obtained in step 1) with a precipitation aid and a titanium compound to produce a mixture containing a solid precipitate, preferably by contacting the solution obtained in step 1) with a precipitation aid to produce a first mixture and then contacting the first mixture with a titanium compound to produce a mixture containing a solid precipitate, or by contacting the solution obtained in step 1) with a titanium compound to produce a second mixture and then contacting the second mixture with a precipitation aid to produce a mixture containing a solid precipitate,

the precipitation aid comprises a compound shown as a formula A,

in the formula A, the reaction solution is prepared,

M₁to M₁₂Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C₁-C₁₀Alkylamino radical, bis-C₁-C₁₀Alkylamino, aldehyde, carboxyl, R_aC(O)-、R_aO-、C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl, 4-12 membered heterocycloalkyl and C₅-C₂₀Heteroaryl, when two groups adjacent to each other on the phenyl ring are each selected from R_aC(O)-、R_aO-、C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl, 4-12 membered heterocycloalkyl and C₅-C₂₀In the case of heteroaryl, two adjacent groups may optionally form a ring with each other, the ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof,

wherein R is_aIs selected from C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₂₀Aralkyl, 4-12 membered heterocycloalkyl and C₅-C₂₀A heteroaryl group;

R₁to R₆The same or different, each is independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₂₀Aralkyl, 4-12 membered heterocycloalkyl andC₅-C₂₀(ii) a heteroaryl group, wherein,

any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocycloalkyl, and heteroaryl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C₁-C₁₀Alkylamino radical, bis-C₁-C₁₀Alkylamino groups, aldehyde groups, carboxyl groups and heteroatoms.

According to a second aspect of the present invention there is provided a catalyst for the polymerisation of olefins comprising the reaction product of:

1) the solid catalyst component obtained by the production method provided in the first aspect of the present invention,

2) an organoaluminum compound which is a compound selected from the group consisting of,

3) optionally, an external electron donor compound.

According to a third aspect of the present invention, there is provided a process for polymerizing an olefin having the general formula CH, by polymerizing the olefin in the presence of the solid catalyst component obtained by the above-mentioned production process and/or the catalyst as described above₂Wherein R is hydrogen or C₁-C₆An alkyl group.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

1) dissolving a magnesium halide in a solvent system, preferably a solvent system consisting of an organic epoxy compound, an organic phosphorous compound and an inert diluent, to form a solution;

2) contacting the solution obtained in step 1) with a precipitation aid and a titanium compound to produce a mixture containing a solid precipitate,

the precipitation aid comprises a compound shown as a formula A,

in the formula A, the reaction solution is prepared,

R₁to R₆The same or different, each is independently selected from hydrogen and C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₈Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₂₀Aralkyl, 4-12 membered heterocycloalkyl and C₅-C₂₀(ii) a heteroaryl group, wherein,

According to some embodiments of the invention, M₁To M₁₂Identical or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆Alkylamino, aldehyde, carboxyl, R_aC(O)-、R_aO-、C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₆Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl, 4-6 membered heterocycloalkyl and C₅-C₁₀Heteroaryl, wherein R_aIs selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₆Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl, 4-6 membered heterocycloalkyl and C₅-C₁₀A heteroaryl group.

According to some embodiments of the invention, M₁To M₁₂Selected from hydrogen, hydroxy, amino, halogen, aldehyde group, C₁-C₆Alkoxy and halogen substituted C₁-C₆An alkoxy group.

According to some embodiments of the invention, M₁To M₁₂Not hydrogen at the same time.

According to some embodiments of the solid catalyst component provided herein, M₁、M₄、M₅、M₈、M₉And M₁₂Each independently selected from hydrogen and C₁-C₆An alkyl group.

According to the inventionSome embodiments of (1), M₂、M₃、M₆、M₇、M₁₀And M₁₁Selected from hydroxyl, amino, halogen, aldehyde group, C₁-C₆Alkoxy and halogen substituted C₁-C₆An alkoxy group.

According to some embodiments of the invention, M₁、M₅And M₉The same is true.

According to some embodiments of the invention, M₂、M₆And M₁₀The same is true.

According to some embodiments of the invention, M₃、M₇And M₁₁The same is true.

According to some embodiments of the invention, M₄、M₈And M₁₂The same is true.

According to some embodiments of the invention, R_aIs selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₆Cycloalkyl radical, C₆-C₁₀Aryl and C₇-C₁₀Aralkyl, wherein any of the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, and aralkyl groups may be optionally substituted with one or more substituents selected from the group consisting of hydroxy, halo, cyano, nitro, amino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆Alkylamino groups, aldehyde groups (-CHO), and carboxyl groups.

According to some embodiments of the invention, R in formula A₁To R₆Each independently selected from hydrogen and C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₆Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl, 4-6 membered heterocycloalkyl and C₅-C₁₀Heteroaryl, any of said alkyl, alkenyl, alkynyl, cycloalkyl, aryl and aralkyl groups may be optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitroAmino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆Alkylamino groups, aldehyde groups, carboxyl groups (-COOH), and heteroatoms.

According to some embodiments of the invention, R in formula A₁To R₆Are the same or different and are each independently selected from hydrogen and C₁-C₆Alkyl radical, C₁-C₆Alkyl groups may be optionally substituted with one or more substituents selected from hydroxy (-OH), halogen, cyano (-CN), nitro (-NO)₂) Amino (-NH-)₂) mono-C₁-C₆Alkylamino radical, bis-C₁-C₆Alkylamino groups, aldehyde groups (-CHO), carboxyl groups (-COOH) and heteroatoms.

According to some embodiments of the invention, R₁To R₆Independently selected from hydrogen and C₁-C₆An alkyl group.

According to some embodiments of the invention, R₁、R₃And R₅The same is true.

According to some embodiments of the invention, R₂、R₄And R₆The same is true.

According to some embodiments of the invention, R₁To R₆Are all the same.

According to some embodiments of the invention, the compound of formula a has the structure of formula a1, a2, or A3.

According to an embodiment of the present invention, the cyclotri-veratryl hydrocarbon or derivative thereof represented by formula a is selected from at least one of the following compounds:

a compound A: m₂＝M₃＝M₆＝M₇＝M₁₀＝M₁₁＝OCH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound B: m₂＝M₃＝M₆＝M₇＝M₁₀＝M₁₁＝OCH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound C: m₂＝M₃＝M₆＝M₇＝M₁₀＝M₁₁＝OCH₂CH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound D: m₂＝M₃＝M₆＝M₇＝M₁₀＝M₁₁＝OCH(CH₃)₂，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound E: m₂＝M₃＝M₆＝M₇＝M₁₀＝M₁₁＝OCH₂CH₂CH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound F: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝OCH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound G: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝OCH₂CH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound H: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝OCH₂CH₂CH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

a compound I: m₂＝M₃＝M₆＝M₇＝M₁₀＝M₁₁＝OH，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound J: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝OH，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound K: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝NH₂，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

a compound L: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝Cl，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound M: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝Br，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound N: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝I，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound O: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝CHO，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

compound P: m₂＝M₆＝M₁₀＝OCH₃；M₃＝M₇＝M₁₁＝OCH₂CH₂CH₂Br，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H structural formula is:

compound Q: m₂＝M₆＝M₁₀＝＝OH，M₃＝M₇＝M₁₁＝OCH₂CH₃，M₁＝M₄＝M₅＝M₈＝M₉＝M₁₂＝H，R₁＝R₂＝R₃＝R₄＝R₅＝R₆H, structural formula:

according to some embodiments of the invention, in step 2), the mixture comprising the solid precipitate is produced by contacting the solution obtained in step 1) with a precipitation aid to obtain a first mixture, and then contacting the first mixture with a titanium compound.

According to further embodiments of the present invention, in step 2), the mixture containing the solid precipitate is produced by contacting the solution obtained in step 1) with a titanium compound to obtain a second mixture, and then contacting the second mixture with a precipitation aid.

According to some embodiments of the invention, in step 2) the first mixture is contacted with the titanium compound at a temperature of-30 to 60 ℃, preferably-30 to 5 ℃, and/or the solution obtained in step 1) is contacted with the titanium compound at a temperature of-30 to 60 ℃, preferably-30 to 5 ℃, to obtain a second mixture.

According to some embodiments of the invention, the method of preparing further comprises the steps of:

3) contacting the mixture containing the solid precipitate obtained in the step 2) with an internal electron donor compound to obtain a solid containing magnesium and titanium;

optionally, 4) treating the magnesium and titanium containing solid obtained in step 3) with a mixture of a titanium compound and an inert diluent, followed by washing with an inert diluent to obtain the solid catalyst component.

According to some embodiments of the present invention, in step 3), the mixture containing the solid precipitate is first heated to 60-110 ℃, an internal electron donor compound is added during the heating process or after the heating to 60-110 ℃, preferably after the heating to 60-110 ℃, the reaction is continued for 0.2-8 hours, then solid-liquid separation is performed, and the solid is washed with an inert diluent to obtain a solid containing magnesium and titanium.

According to some embodiments of the present invention, the amount ratio of the components is 0.2 to 10 moles, preferably 0.5 to 4 moles, of the organic epoxy compound per mole of the magnesium halide; 0.1 to 3 moles, preferably 0.3 to 1.5 moles of an organic phosphorus compound; 0.5 to 20 mol, preferably 5 to 15 mol, of a titanium compound; 0.01-0.3 mol of precipitation assistant, preferably 0.02-0.2 mol; 0 to 10 mol of the internal electron donor compound, preferably 0.02 to 0.3 mol.

According to some embodiments of the invention, the organic epoxy compound is selected from the group consisting of oxides, glycidyl ethers and internal ether compounds of aliphatic olefins, diolefins or halogenated aliphatic olefins or diolefins having a number of carbon atoms ranging from 2 to 8, preferably from ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.

According to some embodiments of the invention, the organophosphorus compound is selected from the group consisting of hydrocarbyl orthophosphates, halogenated hydrocarbyl orthophosphates, hydrocarbyl phosphites, and halogenated hydrocarbyl phosphites, preferably at least one selected from the group consisting of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite.

According to some embodiments of the invention, the magnesium halide is selected from the group consisting of magnesium dihalides, water and alcohol complexes of magnesium dihalides, and derivatives of magnesium dihalides of which formula one halogen atom is replaced by a hydrocarbyl or hydrocarbyloxy group. The magnesium dihalide is specifically: magnesium dichloride, dibromide and/or diiodo, preferably magnesium dichloride.

According to some embodiments of the invention, the titanium compound has the formula Ti (OR)_4-nX_nWherein R is C₁-C₁₄An aliphatic hydrocarbon group or an aromatic hydrocarbon group, X is a halogen atom, n is an integer of 0 to 4, and is preferably one selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, or a mixture thereof.

According to some embodiments of the present invention, the internal electron donor compound comprises at least one selected from the group consisting of glycol esters, alkyl esters of aliphatic monocarboxylic acids, alkyl esters of aromatic monocarboxylic acids, alkyl esters of aliphatic polycarboxylic acids, alkyl esters of aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers, and aliphatic ketones. Different internal electron donors are selected, and the catalyst shows different orientation performance and hydrogen regulation performance.

According to some more specific embodiments, the internal electron donor compound comprises a glycol ester compound represented by formula Z:

in the formula Z, R₁And R₂Same or different, selected from C₁-C₂₀Alkyl radical, C₂-C₂₀Alkenyl radical, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Aralkyl and C₁₀-C₂₀A fused ring aryl, said alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl being optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; m is a divalent linking group, preferably selected from C₁-C₂₀Alkylene radical, C₃-C₂₀Cycloalkylene and C₆-C₂₀Arylene radical, said alkylene, cycloalkylene and/or arylene radical being substituted by C₁-C₂₀Alkyl substituted and the substituents are optionally bonded to one or more rings, the carbon or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms;

more preferably, the internal electron donor compound comprises a glycol ester compound represented by formula B:

in the formula B, R₁And R₂Are the same or different and are each independently selected from C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl and C₇-C₂₀Alkylaryl, preferably selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl and C₇-C₁₀Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C₁-C₆Alkyl and C₁-C₆In alkoxy radicalSubstituted with one or more substituents of (a);

R₃、R₄、R₅、R₆and R¹-R²ⁿThe same or different, each is independently selected from hydrogen, halogen and C₁-C₂₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Aralkyl and C₁₀-C₂₀Condensed ring aryl, preferably selected from hydrogen, halogen, C₁-C₁₀Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Alkylaryl group, C₇-C₁₀Aralkyl and C₁₀-C₁₅A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C₁-C₆Alkyl and C₁-C₆One or more substituents in alkoxy;

R₃、R₄、R₅、R₆and R¹-R²ⁿOptionally containing heteroatoms, which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus;

or, R₃、R₄、R₅、R₆And R¹-R²ⁿTwo or more of which are bonded to each other to form a saturated or unsaturated monocyclic ring or a saturated or unsaturated polycyclic ring;

wherein n is an integer of 0 to 10, preferably 1 to 8, more preferably 2 to 6, and when n is 0, the substituent is R₃And R₄The carbon atom and substituent of (A) is R₅And R₆Is bonded to the carbon atom(s) of (a).

According to some embodiments of the invention, the inert diluent is selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene.

2) the organoaluminum compounds, such as alkyl aluminum compounds,

3) optionally, an external electron donor compound.

In the present invention, the organoaluminum compound is an alkylaluminum compound which is commonly used in the field of olefin polymerization and which can be used as a cocatalyst for an olefin polymerization catalyst. Preferably, the alkyl aluminum compound is a compound represented by formula (V),

AlR’_n'X’_3-n'the compound of the formula (V),

in the formula V, R' is C₁-C₂₀Alkyl or halo C₁-C₂₀Alkyl, preferably C₁-C₈Alkyl or halo C₁-C₈Alkyl, X 'is halogen, and n' is an integer of 1 to 3. In the formula (V), X' is preferably one or more of chlorine, bromine and iodine, and more preferably chlorine.

More preferably, the aluminum alkyl compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, Al (n-C)₆H₁₃)₃And Al (n-C)₈H₁₇)₃One or more of (a). Most preferably, the alkyl aluminium compound is triethyl aluminium and/or triisobutyl aluminium.

According to some embodiments, the molar ratio of aluminum in the organoaluminum compound to titanium in component 1) is from 5 to 5000, preferably from 20 to 500.

The external electron donor is preferably an organosilicon compound. Preferably, the organosilicon compound has the formula R_nSi(OR′)_4-nWherein n is more than 0 and less than or equal to 3, R and R' in the general formula are the same or different alkyl, cycloalkyl, aryl, halogenated alkyl and the like, and R can also be halogen or hydrogen atom. The inventionThe organosilicon compound includes trimethyl methoxysilane, trimethyl ethoxysilane, trimethyl phenoxysilane, dimethyl dimethoxysilane, dimethyl diethoxysilane, methyl tert-butyl dimethoxysilane, diphenoxydimethoxysilane, diphenyl diethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, vinyl trimethoxysilane, cyclohexyl methyldimethoxysilane, dicyclopentyl dimethoxysilane, 2-ethylpiperidinyl-2-tert-butyl dimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyl dimethoxysilane, and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane.

The amount of external electron donor (3) is: the molar ratio of the organic aluminum compound to the external electron donor compound is 0.1 to 500, preferably 1 to 300, and more preferably 3 to 100.

According to a third aspect of the present invention, there is also provided the use of a catalyst for the polymerisation of olefins as described above in the polymerisation of olefins.

According to the invention, the olefin polymerization is carried out according to known methods, operating in the liquid phase of the monomer or of a solution of the monomer in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas-liquid phase. The polymerization temperature is generally from 0 ℃ to 150 ℃ and preferably from 60 ℃ to 100 ℃. The polymerization pressure is normal pressure or higher.

The improvement of the present invention is that a new catalyst for olefin polymerization is used, and the specific kind of olefin, the polymerization reaction method and conditions of olefin can be the same as those in the prior art.

According to the present invention, there is provided a process for olefin polymerization comprising contacting one or more olefins, at least one of which is represented by the formula CH, with the solid catalyst component and/or catalyst obtained by the above preparation process under olefin polymerization conditions₂Olefins represented by ═ CHR, where R is hydrogen or C₁-C₆An alkyl group.

The olefin polymerization catalyst can be used for olefin homopolymerization and can also be used for copolymerization of a plurality of olefins. At least one of the olefins is of the formula CH₂Olefins represented by ═ CHR, where R is hydrogen or C₁-C₆An alkyl group. The general formula CH₂Specific examples of olefins represented by ═ CHR may include: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the general formula CH₂The olefins represented by ═ CHR are one or more of ethylene, propylene, 1-n-butene, 1-n-hexene, and 4-methyl-1-pentene. More preferably, the general formula CH₂The olefin represented by ═ CHR is propylene, or copolymerization of propylene with other olefins.

In the present invention, the hydrocarbon group may be selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl and alkaryl groups.

In the present invention, alkyl means a straight or branched alkyl group, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.

In the present invention, examples of the alkenyl group may include, but are not limited to: ethenyl, propenyl, butenyl, pentenyl, octenyl.

In the present invention, examples of alkynyl groups may include, but are not limited to: ethynyl and propynyl.

In the present invention, examples of the cycloalkyl group may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl and cyclododecyl.

In the present invention, examples of the halogen include, but are not limited to, fluorine, chlorine, bromine and iodine.

In the present invention, examples of the aryl group may include, but are not limited to: phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, naphthyl.

In the present invention, aralkyl means an alkyl group having an aryl substituent, and examples may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.

In the present invention, the alkylaryl group means an aryl group having an alkyl substituent group with a carbon number of 7 to 20, and examples thereof may include, but are not limited to: methylphenyl, ethylphenyl.

In the present invention, examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, and hexoxy.

In the present invention, examples of the condensed ring aryl group may include, but are not limited to: naphthyl, anthryl, phenanthryl, pyrenyl.

In the present invention, the hetero atom means an atom usually contained in a molecular structure other than a halogen atom, a carbon atom and a hydrogen atom, for example, O, N, S, P, Si and B, etc.

Compared with the prior art, the invention has the following obvious advantages: in the preparation process of the catalyst, a cyclotriveratrum hydrocarbon compound with a special structure is selected as a precipitation-assisting component to replace a conventional precipitation-assisting agent compound, namely phthalic anhydride or glycol ester precipitation-assisting agent, so that the yield of the catalyst is greatly improved while the perfect particle form of the catalyst is maintained, and meanwhile, the compound is added before the catalyst is precipitated, so that the internal structure of the catalyst is more effectively improved, the obtained catalyst has higher polymerization activity and excellent hydrogen regulation performance and stereospecificity when used for propylene polymerization, and the polymer has less fine powder content.

The present invention will be described in detail below by way of examples. However, the present invention is not limited to the following examples.

The test methods referred to in the following examples are as follows:

1. polymer isotacticity was determined by heptane extraction (6 hours of heptane boil extraction): two grams of the dried polymer sample were extracted with boiling heptane in an extractor for 6 hours, and the ratio of the weight (g) of the polymer to 2(g) of the residue was dried to constant weight, which was the isotacticity.

2. Determination of the melt index of the Polymer: measured according to GB/T3682-2000.

3. The particle size distribution of the catalyst is as follows: measured according to the malvern 2000 n-hexane dispersant laser diffraction method.

4. Titanium content in catalyst: tested according to 721 spectrophotometer.

5. Yield of catalyst: the yield of the catalyst is defined as the mass of catalyst obtained/mass of magnesium chloride used x 100%

Preparation of catalyst

Example 1

Sequentially adding 0.05 mol of anhydrous magnesium chloride, 0.75 mol of toluene, 0.1 mol of epichlorohydrin and 0.033 mol of tributyl phosphate into a reaction kettle repeatedly replaced by high-purity nitrogen, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 55 ℃, adding 2.5 mmol of compound A diluted by 0.1 mol of toluene, reacting for 1 hour, cooling to-28 ℃, dropwise adding 0.51 mol of titanium tetrachloride, continuing to react for one hour, gradually heating to 85 ℃, separating out solid particles in the heating process, adding 4.0 mmol of DNBP, keeping the temperature for one hour, filtering out mother liquor, washing and filtering out liquid for multiple times by using an inert diluent of toluene, adding 0.44 mol of titanium tetrachloride, keeping the temperature of 0.7 mol of toluene at 110 ℃ for 2 hours, filtering, then repeatedly processing for two times, washing for 5 times by using hexane, and drying the residual solid product in vacuum to obtain the solid titanium catalyst component.

Example 2

In the same manner as in example 1, 2.5 mmol of the compound A diluted with 0.1 mol of toluene was added instead of 1.5 mmol of the compound B diluted with 0.1 mol of toluene.

Example 3

In the same manner as in example 1, 2.5 mmol of Compound A diluted with 0.1 mol of toluene was added instead of 4.0 mmol of Compound F diluted with 0.1 mol of toluene.

Example 4

In the same manner as in example 1, 0.05 mol of epichlorohydrin and 0.05 mol of tributyl phosphate were added instead of 0.1 mol of epichlorohydrin and 0.033 mol of tributyl phosphate.

Example 5

In the same manner as in example 1, the sequence of two steps was changed only by "lowering the temperature to-28 ℃ and adding 0.51 mol of titanium tetrachloride" and "adding 2.5 mmol of Compound A diluted with 0.1 mol of toluene and reacting for 1 hour".

Example 6

Just as in example 1, 4 mmol of DNBP was changed to 2.0 mmol of 4-ethyl-3, 5-heptanediol dibenzoate.

Example 7

Sequentially adding 0.05 mol of anhydrous magnesium chloride, 0.66 mol of toluene, 0.1 mol of epichlorohydrin and 0.033 mol of tributyl phosphate into a reaction kettle repeatedly replaced by high-purity nitrogen, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 55 ℃, cooling to-5 ℃, dropwise adding 0.51 mol of titanium tetrachloride, adding 1.0 mmol of compound Q diluted by 0.1 mol of toluene, continuously reacting for one hour, gradually heating to 110 ℃, keeping the temperature for one hour, filtering out mother liquor, washing the filtered liquid for many times by using an inert diluent of toluene, washing the filtered liquid for 5 times by using hexane, and drying the residual solid product in vacuum to obtain the solid titanium catalyst component.

Comparative example 1

Adding 0.05 mol of anhydrous magnesium chloride, 0.88 mol of toluene, 0.05 mol of epoxy chloropropane and 12.5 ml of tributyl phosphate into a reaction kettle, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 0.01 mol of phthalic anhydride, continuing to react for one hour, cooling to-28 ℃, dropwise adding 0.51 mol of titanium tetrachloride, gradually heating to 85 ℃, adding 8.0 mmol of DNBP at 80 ℃, keeping the temperature of 85 ℃ for one hour, filtering out mother liquor, washing twice with 0.95 mol of toluene, filtering, adding 0.57 mol of toluene, 0.36 mol of titanium tetrachloride, keeping the temperature of 110 ℃ for 2 hours, filtering, repeatedly processing once again, washing 5 times with hexane and drying to obtain a solid titanium catalyst component.

Comparative example 2

Sequentially adding 0.05 mol of anhydrous magnesium chloride, 0.9 mol of toluene, 0.05 mol of epichlorohydrin and 12.5 ml of tributyl phosphate into a reaction kettle repeatedly replaced by high-purity nitrogen, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 60 ℃, adding 0.01 mol of phthalic anhydride, continuing to react for one hour, cooling to-28 ℃, dropwise adding 0.51 mol of titanium tetrachloride, gradually heating to 85 ℃, adding 2.5 mmol A and 4.0 mmol DNBP at 75 ℃, keeping the temperature for one hour after the temperature of 85 ℃ is reached, filtering out mother liquor, washing twice by using 0.95 mol of toluene, filtering, adding 0.57 mol of toluene, 0.36 mol of titanium tetrachloride, keeping the temperature for 2 hours at 110 ℃, filtering, repeatedly processing once again, washing 5 times by using hexane, and drying to obtain a solid titanium catalyst component.

Comparative example 3

Sequentially adding 0.05 mol of anhydrous magnesium chloride, 0.75 mol of toluene, 0.1 mol of epichlorohydrin and 0.033 mol of tributyl phosphate into a reaction kettle repeatedly replaced by high-purity nitrogen, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 55 ℃, cooling to-28 ℃, dropwise adding 0.51 mol of titanium tetrachloride, adding 2.0 mmol of 4-ethyl-3, 5-heptanediol dibenzoate diluted by 0.1 mol of toluene, continuously reacting for one hour, gradually heating to 85 ℃, and separating out solid particles in the heating process. Adding 4.0 millimole of dibutyl phthalate at 85 ℃, keeping the temperature constant for one hour, filtering out mother liquor, washing the filtered liquid for multiple times by using an inert diluent toluene, adding 0.44 mole of titanium tetrachloride, keeping the temperature constant for 2 hours at 110 ℃ by using 0.7 mole of toluene, repeating the treatment for two times after filtering, washing for 5 times by using hexane, and drying the residual solid product in vacuum to obtain the solid titanium catalyst component.

Comparative example 4

Sequentially adding 0.04 mol of anhydrous MgCl into a reaction kettle repeatedly replaced by high-purity nitrogen₂0.47 mol of toluene, 2.0 ml of epichlorohydrin and 3.0 ml of tributyl phosphate, heating to 50 ℃ under stirring, maintaining for 15 minutes, adding 6.0 ml of ethanol, continuing to react for 15 minutes, cooling the solution to-5 ℃, dripping a mixed solution of 30 ml of titanium tetrachloride and 30 ml of heptane into the solution, heating to 40 ℃, filtering, washing with hexane for 4 timesAnd vacuum drying to obtain the solid catalyst.

Comparative example 5

Sequentially adding 0.05 mol of anhydrous magnesium chloride, 0.75 mol of toluene, 0.1 mol of epichlorohydrin and 0.033 mol of tributyl phosphate into a reaction kettle repeatedly replaced by high-purity nitrogen, reacting for 2 hours under the conditions of stirring speed of 450rpm and temperature of 55 ℃, cooling to-5 ℃, dropwise adding 0.51 mol of titanium tetrachloride, adding 3.0 mmol of 2, 4-pentanediol dibenzoate diluted by 0.1 mol of toluene, continuously reacting for one hour, gradually heating to 110 ℃, keeping the temperature for one hour, filtering out mother liquor, washing the filtered liquid for many times by using an inert diluent toluene, washing the filtered liquid for 5 times by using hexane, and vacuum-drying the residual solid product to obtain the solid titanium catalyst component.

(II) propylene polymerization step

In a 5 l autoclave, after sufficient displacement by vapor phase propylene, 5 ml of a hexane solution of triethylaluminum (concentration of triethylaluminum 0.5 mmol/ml), l ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration of CHMMS 0.1 mmol/ml), 10 ml of anhydrous hexane and 10 mg of the solid catalyst component were added at room temperature. The autoclave was closed, 1.0NL of hydrogen and 1.15Kg of liquid propylene were introduced; the temperature was raised to 70 ℃ over 10 minutes with stirring. The polymerization reaction is carried out for 2 hours at 70 ℃, and the polymerization result is shown in a second table;

(III) ethylene polymerization step

After a stainless steel kettle with the volume of 2 liters is fully replaced by hydrogen, 1000 ml of hexane, 1.5 ml of triethylaluminum and a measured (5-6 mg) of hexane solution with the concentration of l mol/l are added into the stainless steel kettle, the prepared solid catalyst component is heated to 70 ℃ and hydrogenated to 0.18MPa (gauge pressure), ethylene is introduced into the kettle to make the pressure in the kettle reach 0.73MPa (gauge pressure), and the polymerization is carried out for 2 hours at the temperature of 80 ℃, and the polymerization result is shown in the table III.

Table-comparison of experimental results

The data in the table show that the catalyst prepared by the method has stable control of titanium content, higher yield than a benzoic anhydride precipitation aid, equivalent yield to a glycol ester precipitation aid, good particle size adjustability and narrow distribution.

TABLE comparison of propylene polymerization Properties

The data in the table show that the catalyst prepared by the method has high polymerization activity, less polymer fine powder, good performances of isotacticity, melt index and bulk density and excellent comprehensive performance.

Comparison of polymerization Properties of ethylene

The data in table three show that when the catalyst prepared by the method is used for ethylene polymerization, polymer fine powder is reduced, the bulk density is high, and the comprehensive performance is excellent.

Claims

1. A method for preparing a solid catalyst component for olefin polymerization, comprising the steps of:

1) dissolving magnesium halide in a solvent system to form a solution;

the precipitation aid comprises a compound shown as a formula A,

in the formula A, the reaction solution is prepared,

M₁、M₄、M₅、M₈、M₉and M₁₂Each independently selected from hydrogen and C₁-C₁₀An alkyl group; m₂、M₃、M₆、M₇、M₁₀And M₁₁Selected from hydroxy, halogen and R_aO-, in which R_aIs selected from C₁-C₁₀An alkyl group;

R₁to R₆Are the same or different and are each independently selected from hydrogen and C₁-C₁₀An alkyl group.

2. The method according to claim 1, wherein the solvent system in step 1) is a solvent system consisting of an organic epoxy compound, an organic phosphorus compound and an inert diluent.

3. The method of claim 1, wherein step 2) comprises: producing a mixture containing a solid precipitate by contacting the solution obtained in step 1) with a precipitation aid to obtain a first mixture and then contacting the first mixture with a titanium compound, or by contacting the solution obtained in step 1) with a titanium compound to obtain a second mixture and then contacting the second mixture with a precipitation aid to obtain a mixture containing a solid precipitate.

4. The process according to claim 1, wherein in the formula A, M is₁、M₄、M₅、M₈、M₉And M₁₂Each independently selected from hydrogen and C₁-C₆An alkyl group; m₂、M₃、M₆、M₇、M₁₀And M₁₁Selected from hydroxy and C₁-C₆An alkoxy group; r₁To R₆Each independently selected from hydrogen and C₁-C₆An alkyl group.

5. The method of claim 2, further comprising the steps of:

6. The process according to claim 3, wherein in step 2) the first mixture is contacted with the titanium compound at a temperature of-30 to 60 ℃ and/or the solution obtained in step 1) is contacted with the titanium compound at a temperature of-30 to 60 ℃ to obtain the second mixture.

7. The process according to claim 3, wherein in step 2) the first mixture is contacted with the titanium compound at a temperature of-30 to 5 ℃ and/or the solution obtained in step 1) is contacted with the titanium compound at a temperature of-30 to 5 ℃ to obtain the second mixture.

8. The preparation method of claim 5, wherein in step 3), the mixture containing the solid precipitate is heated to 60-110 ℃, an internal electron donor compound is added during the heating process or after the temperature is raised to 60-110 ℃, then solid-liquid separation is carried out, and the solid is washed by an inert diluent to obtain a solid containing magnesium and titanium.

9. The preparation method of claim 5, wherein in the step 3), the mixture containing the solid precipitate is heated to 60-110 ℃, the internal electron donor compound is added in the heating process or after the temperature is raised to 60-110 ℃, the reaction is continued for 0.2-8 hours after the temperature is raised to 60-110 ℃, then solid-liquid separation is carried out, and the solid is washed by inert diluent to obtain the solid containing magnesium and titanium.

10. The preparation method according to claim 5, wherein the amount ratio of the components is 0.2 to 10 moles of the organic epoxy compound per mole of the magnesium halide; 0.1 to 3 moles of an organic phosphorus compound; 0.5-20 mol of titanium compound; 0.01-0.3 mol of precipitation aid; 0-10 mol of internal electron donor compound.

11. The preparation method according to claim 5, wherein the amount ratio of the components is 0.5 to 4 mol of the organic epoxy compound per mol of the magnesium halide; 0.3-1.5 mol of organic phosphorus compound; 5-15 mol of titanium compound; 0.02-0.2 mol of precipitation aid; 0.02-0.3 mol of internal electron donor compound.

12. The production method according to any one of claims 5 and 8 to 11,

the magnesium halide is selected from one of magnesium dihalide, a complex of magnesium dihalide with water and alcohol, and a derivative of magnesium dihalide in which one halogen atom is replaced by a hydrocarbon group or a hydrocarbonoxy group;

the organic epoxy compound is selected from oxides, glycidyl ethers and internal ether compounds of aliphatic olefin, diolefin or halogenated aliphatic olefin or diolefin with the carbon number of 2-8;

said organophosphorus compound is selected from the group consisting of hydrocarbyl esters of orthophosphoric acid, halohydrocarbyl esters of orthophosphoric acid, hydrocarbyl esters of phosphorous acid and halohydrocarbyl esters of phosphorous acid;

the inert diluent is selected from at least one of hexane, heptane, octane, decane, benzene, toluene and xylene;

the titanium compound has a general formula of Ti (OR)_4-nX_nWherein R is C₁-C₁₄An aliphatic hydrocarbon group or an aromatic hydrocarbon group, X is a halogen atom, and n is an integer of 0 to 4;

the internal electron donor compound includes at least one selected from the group consisting of glycol esters, alkyl esters of aliphatic monocarboxylic acids, alkyl esters of aromatic monocarboxylic acids, alkyl esters of aliphatic polycarboxylic acids, alkyl esters of aromatic polycarboxylic acids, aliphatic ethers, cycloaliphatic ethers, and aliphatic ketones.

13. The method of any one of claims 5 and 8-11, wherein the internal electron donor compound comprises a glycol ester compound represented by formula Z:

in the formula Z, R₁And R₂Same or different, selected from C₁-C₂₀Alkyl radical, C₂-C₂₀Alkenyl radical, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Aralkyl and C₁₀-C₂₀A fused ring aryl, said alkyl, alkenyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl being optionally substituted with one or more substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C₁-C₆Alkylamino radical, bis-C₁-C₆Alkylamino groups, aldehyde groups, carboxyl groups, and heteroatoms; m is a divalent linking group.

14. The process according to claim 13, wherein in formula Z, M is selected from C₁-C₂₀Alkylene radical, C₃-C₂₀Cycloalkylene and C₆-C₂₀Arylene radical, said alkylene, cycloalkylene and/or arylene radical being substituted by C₁-C₂₀Alkyl is substituted and the substituents are optionally bonded to one or more rings, the carbon or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.

15. Preparation process according to any one of claims 5 and 8 to 11, characterized in that the organic epoxide is chosen from ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.

16. The production method according to any one of claims 5 and 8 to 11, wherein the organophosphorus compound is at least one selected from the group consisting of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite.

17. The method according to any one of claims 5 and 8 to 11, wherein the titanium compound is selected from one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloromonoethoxytitanium, or a mixture thereof.

18. The method according to any one of claims 5 and 8 to 11, wherein the internal electron donor compound comprises a glycol ester compound represented by formula B,

in the formula B, R₁And R₂Are the same or different and are each independently selected from C₁-C₁₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Aralkyl and C₇-C₂₀An alkaryl group;

R₃、R₄、R₅、R₆and R¹-R²ⁿThe same or different, each is independently selected from hydrogen, halogen and C₁-C₂₀Alkyl radical, C₂-C₁₀Alkenyl radical, C₂-C₁₀Alkynyl, C₃-C₂₀Cycloalkyl radical, C₆-C₂₀Aryl radical, C₇-C₂₀Alkylaryl group, C₇-C₂₀Aralkyl and C₁₀-C₂₀A fused ring aryl, said alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkaryl, aralkyl and fused ring aryl optionally substituted with a substituent selected from halogen, C₁-C₆Alkyl and C₁-C₆One or more substituents in alkoxy;

wherein n is an integer of 0 to 10, and when n is 0, the substituent is R₃And R₄The carbon atom and substituent of (A) is R₅And R₆Is bonded to the carbon atom(s) of (a).

19. The method according to claim 18, wherein R in the formula B₁And R₂Is selected from C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Aralkyl and C₇-C₁₀Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, arylalkyl or alkylaryl being optionally substituted by one or more substituents selected from halogen, C₁-C₆Alkyl and C₁-C₆And one or more substituents in the alkoxy group.

20. The method according to claim 18, wherein R in the formula B₃、R₄、R₅、R₆And R¹-R²ⁿThe same or different, each is independently selected from hydrogen, halogen and C₁-C₁₀Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₃-C₁₀Cycloalkyl radical, C₆-C₁₀Aryl radical, C₇-C₁₀Alkylaryl group, C₇-C₁₀Aralkyl and C₁₀-C₁₅A fused ring aryl group.

21. The method according to claim 18, wherein n in the formula B is an integer of 1 to 8.

22. The method according to claim 18, wherein n in the formula B is an integer of 2 to 6.

23. A catalyst for the polymerization of olefins comprising the reaction product of:

1) the solid catalyst component obtained by the production method according to any one of claims 1 to 22,

3) optionally, an external electron donor compound.

24. The catalyst according to claim 23, characterized in that the organoaluminum compound is an alkylaluminum compound.

25. A process for polymerizing an olefin having the general formula CH, in the presence of the solid catalyst component obtained by the production process according to any one of claims 1 to 22 and/or the catalyst according to claim 23 or 24, in which the olefin is polymerized₂Wherein R is hydrogen or C₁-C₆An alkyl group.

26. The process of claim 25, wherein the olefin is ethylene, propylene, and/or 1-butene.