CN111072810A

CN111072810A - Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method

Info

Publication number: CN111072810A
Application number: CN201811223652.6A
Authority: CN
Inventors: 赵瑾; 夏先知; 刘月祥; 凌永泰; 李威莅; 谭扬; 陈龙; 高富堂; 任春红; 刘涛
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: 2018-10-19
Filing date: 2018-10-19
Publication date: 2020-04-28
Anticipated expiration: 2038-10-19
Also published as: CN111072810B

Abstract

The invention belongs to the field of catalysts, and relates to a catalyst component and a catalyst for olefin polymerization, application thereof and an olefin polymerization method. The catalyst component comprises the reaction product of: (1) a solid component; (2) at least one titanium compound; and (3) an internal electron donor compound; wherein the solid component is at least one sulfur-containing magnesium compound; the internal electron donor compound comprises an internal electron donor compound a, an internal electron donor compound b and an internal electron donor compound c, wherein the internal electron donor compound a is a glycol ester compound, the internal electron donor compound b is a diether compound, and the internal electron donor compound c is a monocarboxylic ester compound. When the catalyst is used for olefin polymerization, the catalyst has high stereotacticity, and can obtain olefin polymers with high isotactic index under the condition of not using or using a small amount of external electron donor.

Description

Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method

Technical Field

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

Background

It is known that a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor compound as essential components is used in olefin polymerization, and particularly has high polymerization activity and stereospecificity in propylene polymerization. The electron donor compound is one of essential components in the solid titanium catalyst component, plays a decisive role in important indexes such as polymerization activity, isotactic index of polymer, molecular weight distribution and the like, and the continuous updating of the polyolefin catalyst is carried out along with the development of the internal electron donor compound.

Catalysts containing different internal electron donors have different characteristics, for example, some catalysts have higher polymerization activity, some catalysts have better hydrogen response, and some catalysts have wider molecular weight distribution. In the industrial production of polyolefins, there is a great demand for catalysts having an excellent balance of properties, in particular catalysts having high activity, high hydrogen response and at the same time high directing properties.

The isotactic index of the polymer is determined by the stereospecificity of the catalyst, the isotactic index is an important performance index of the polymer, the higher the isotactic index of the polypropylene is, the higher the regularity and the crystallinity are, the mechanical properties such as hardness, rigidity, modulus, fracture and yield strength of the product are increased, and the melting point, the thermal stability, the aging resistance and the radiation resistance are correspondingly improved. Therefore, in order to improve the stereospecificity of the catalyst, many studies have been made by researchers. In some researches, a catalyst containing two (or more) internal electron donors is adopted to make up the performance deficiency of the catalyst containing a single internal electron donor, so that the performance of the catalyst is improved. But the compounded effect is not a simple superposition of several electron donor properties. For example, polypropylene produced by using a catalyst comprising a monocarboxylic acid ester as an internal electron donor generally has a low isotacticity, and the product requires a atactic compound. WO03002617 discloses a catalyst component and catalyst for olefin polymerization, which is obtained by using monocarboxylic acid ester and dicarboxylic acid ester together, and the catalyst has good hydrogen regulation sensitivity, but its stereospecificity and polymerization activity are not very high.

The catalyst component and the catalyst disclosed in CN101724102A adopt a glycol ester compound and a diether compound to be compounded as an internal electron donor, and the catalyst containing the internal electron donor has ultrahigh polymerization activity and higher stereospecificity when being used for olefin polymerization. Compared with the similar catalyst, the activity and the stereospecificity of the catalyst are both at a higher level. Therefore, if the stereospecificity of the olefin polymerization catalyst is further increased, the catalyst is particularly expensive and is also very beneficial for producing some polypropylene with high isotacticity.

Due to the morphological characteristics of the spherical polypropylene catalyst and the existence of the phenomenon of 'duplication' from the catalyst to the polymer (namely, only the spherical catalyst can obtain the spherical polymer), the spherical catalyst has great advantages in the polymerization production process and the subsequent processing process of the polymer, and is particularly beneficial to the production of high molecular alloy. Therefore, in the polypropylene catalysts currently used in industry, the proportion of spherical catalysts is very large. The spherical carrier and the internal electron donor are two important components of the spherical polypropylene catalyst. The spherical carrier is mainly from a magnesium chloride alcohol compound carrier, magnesium chloride and alcohol react at high temperature to form the magnesium chloride alcohol compound, the magnesium chloride alcohol compound is melted and dispersed in an inert component, then emulsion is formed through high shearing, and the alcohol compound is solidified and formed after the emulsion is transferred into a low-temperature medium to obtain the carrier. In the production process of the carrier, melting at high temperature and solidification at low temperature are required, and thus, a large amount of energy is consumed. In order to solve the problem, CN102040683A discloses a method for preparing a carrier by reacting a magnesium halide alcoholate with an oxirane compound, and specifically discloses adding the oxirane compound after melting and dispersing the magnesium halide alcoholate; or the magnesium halide alcoholate is directly added into a reactor containing the ethylene oxide compound after being melted and dispersed. However, the catalyst carrier prepared by the method has the defects of unstable preparation process, easy carrier adhesion, poor carrier forming effect and wide particle size distribution.

The magnesium chloride alcoholate carrier cannot prepare a spherical carrier having a particle size of less than 20 μm due to its characteristics, and the above method cannot obtain a carrier having the same particle size. In general, small particle size supports not only reduce the fines of polymer from the catalyst produced but are also widely used in various gas phase polymerization processes.

Therefore, there is an urgent need to develop a small-particle-size spherical polyolefin catalyst having high stereospecificity.

Disclosure of Invention

The object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a catalyst component for olefin polymerization, a catalyst for olefin polymerization containing the catalyst component, the use of the catalyst component and the catalyst, and a process for olefin polymerization.

The inventor of the present invention has unexpectedly found in the research that sulfur is added in the preparation process of the olefin polymerization catalyst carrier, so that a carrier shown in formula I with a novel composition can be obtained, the carrier has good particle shape, smooth surface and basically no special-shaped particles, and the particle size can be realized to be less than 20 microns, and the particle size distribution is narrow. The sulfur-containing spherical magnesium compound is used as a carrier, and a small amount of monocarboxylic ester is added on the basis of adopting the compounding of a glycol ester compound and a diether compound as an internal electron donor, so that the stereospecificity of the olefin polymerization catalyst can be further improved. Therefore, when the catalyst component is used for preparing olefin polymers, the olefin polymers with high isotactic index can be obtained under the condition of not using or using a small amount of external electron donor.

In this regard, a first aspect of the present invention provides a catalyst component for the polymerisation of olefins, the catalyst component comprising the reaction product of:

(1) a solid component;

(2) at least one titanium compound; and

(3) an internal electron donor compound;

wherein the solid component is at least one sulfur-containing magnesium compound represented by formula I;

in the formula I, R₁Is C₁-C₈Linear or branched alkyl of, or C₃-C₈Cycloalkyl groups of (a);

R₂and R₃Identical or different, each independently of the others, is hydrogen or C₁-C₅The linear or branched alkyl group of (a),wherein the hydrogen on the alkyl group is optionally substituted with a halogen atom;

x is halogen, preferably chlorine or bromine;

m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0< q is less than or equal to 0.5;

the internal electron donor compound comprises an internal electron donor compound a, an internal electron donor compound b and an internal electron donor compound c, wherein the internal electron donor compound a is a diol ester compound shown as a formula II, the internal electron donor compound b is a diether compound shown as a formula III, and the internal electron donor compound c is a monocarboxylic ester compound;

in the formula II, R₄And R₅Identical or different, each independently is halogen, C₁-C₂₀Straight or branched alkyl of (2), C₂-C₂₀Linear or branched alkenyl of (C)₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀Is optionally substituted by halogen, C₁-C₆And C is a straight or branched alkyl group₁-C₆Substituted with one or more of alkoxy groups of (a);

R₆、R₇、R₈、R₉and R¹-R²ⁿThe same or different, each independently is hydrogen, halogen, C₁-C₂₀Straight or branched alkyl of (2), C₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted alkylaryl of, C₇-C₂₀Substituted or unsubstituted aralkyl of (1), C₂-C₁₀And C is a linear or branched alkylene group₂-C₂₀One of the ester groups of (1)，R₆、R₇、R₈、R₉And R¹-R²ⁿOptionally substituted with heteroatoms, which are one or more of halogen, nitrogen, oxygen, sulfur, silicon and phosphorus; or, R₆、R₇、R₈、R₉And R¹-R²ⁿTwo or more of them are mutually bonded to form a ring;

n is an integer of 0 to 10;

in the formula III, R₁’、R₂’、R₃’、R₄’、R₅' and R₆' same or different, each independently hydrogen, halogen, C₁-C₂₀Straight or branched alkyl of (2), C₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀One of substituted or unsubstituted alkaryl groups; or, R₁’、R₂’、R₃’、R₄’、R₅' and R₆' two or more of which are bonded to each other to form a ring;

R₇' and R₈' same or different, each independently C₁-C₂₀Straight or branched alkyl of (2), C₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀One of substituted or unsubstituted alkaryl groups;

the monocarboxylic acid ester compound is a monocarboxylic aromatic carboxylic acid ester and/or a monocarboxylic aliphatic carboxylic acid ester.

In the present invention, C₁-C₂₀Examples of the linear or branched alkyl group of (a) may include, but are not limited to: 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, n-eicosyl.

In the present invention, C₂-C₂₀Examples of the linear or branched alkenyl groups of (a) may include, but are not limited to: vinyl, allyl, isopropenyl, 1-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 1-octenyl, phenylvinyl, phenyl-n-butenyl, geranyl, 1-decenyl, 1-tetradecenyl, 1-octadecenyl, 9-octadecenyl, 1-eicosenyl, 1-octadecenyl, 3,7,11, 15-tetramethyl-1-hexadecenyl.

In the present invention, C₃-C₂₀Examples of the substituted or unsubstituted cycloalkyl group of (a) may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl, cyclododecyl.

In the present invention, C₆-C₂₀The substituted or unsubstituted aryl group of (1) includes C₆-C₂₀Substituted or unsubstituted phenyl of, also including C₁₀-C₂₀Examples of the substituted or unsubstituted fused ring aryl group of (a) may include, but are not limited to: phenyl, naphthyl, methylnaphthyl, ethylnaphthyl, anthryl, methylanthryl, ethylanthryl, phenanthryl, methylphenanthyl and ethylphenanthryl, pyrenyl, indenyl.

In the present invention, C₇-C₂₀The substituted or unsubstituted aralkyl group of (2) means an aryl group having 7 to 20 carbon atomsAlkyl groups of substituents. C₇-C₂₀Examples of the substituted or unsubstituted aralkyl group of (a) may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-tert-butyl, phenyl-isopropyl, phenyl-n-pentyl.

In the present invention, C₇-C₂₀The substituted or unsubstituted alkylaryl group of (2) means an aryl group having an alkyl substituent and having 7 to 20 carbon atoms. C₇-C₂₀Examples of substituted or unsubstituted alkaryl groups of (a) may include, but are not limited to: methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, tert-butylphenyl, isopropylphenyl and n-pentylphenyl.

In the present invention, C₁-C₆Examples of alkoxy groups of (a) may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, hexoxy.

In the present invention, the above-mentioned groups in other carbon number ranges can be selected correspondingly within the carbon number range defined, and are not described in detail herein.

According to the invention, the internal electron donor compound a is a diol ester compound shown as a formula II,

the middle bracket of the formula II]The term "in" denotes that n carbon atoms are bonded in succession and that each carbon atom is further bonded to 2 substituents, i.e. there are n carbon atoms and R in total in the parenthesis¹、R²、R³…R²ⁿAnd 2n substituents. Wherein n is an integer of 0 to 10, and when n is 0, the substituent is R in the diol ester compound shown in the formula II₆、R₇The carbon atom directly bonded to the substituent is R₈、R₉Is bonded to the carbon atom(s) of (a).

Preferably, the internal electron donor compound a is a diol ester compound shown in formula IV,

in the formula IV, R₁₀、R₁₁、R₁₂、R₁₃、R₁₄And R₁₅Are the same or different and are each independently hydrogen or C₁-C₂₀Linear or branched alkyl.

According to the present invention, examples of the internal electron donor compound a may include, but are not limited to: 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-butyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, 2-ethyl-2-butyl-1, 3-propanediol dibenzoate, 2-diethyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol, 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 3-, 2,2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-dimethyl-1, 5-pentanediol dibenzoate, 1, 6-hexanediol dibenzoate, 6-heptene-2, 4-heptanediol dibenzoate, 2-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-methyl-6-heptene-2, 4-heptanediol dibenzoate, 4-methyl-6-heptene-2, 4-heptanediol dibenzoate, 5-methyl-6-heptene-2, 4-heptanediol dibenzoate, a salt thereof, and a salt, 6-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 4-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 5-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 6-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-propyl-6-heptene-2, 4-heptanediol dibenzoate, 4-propyl-6-heptene-2, 4-heptanediol dibenzoate, 5-propyl-6-heptene-2, 4-heptanediol dibenzoate, a salt thereof, and a salt thereof, 6-propyl-6-heptene-2, 4-heptanediol dibenzoate, 3-butyl-6-heptene-2, 4-heptanediol dibenzoate, 4-butyl-6-heptene-2, 4-heptanediol dibenzoate, 5-butyl-6-heptene-2, 4-heptanediol dibenzoate, 6-butyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 3-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 5-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3, 4-dimethyl-3, 5-heptanediol dibenzoate, 3, 5-dimethyl-3, 5-heptanediol dibenzoate, 3, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-propyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 2-methyl-5-propyl-3, 5-heptanediol dibenzoate, 3-methyl-3-propyl-3, 5-heptanediol dibenzoate, 3-methyl-4-propyl-3, 5-heptanediol dibenzoate, a salt thereof, and a salt thereof, 3-methyl-5-propyl-3, 5-heptanediol dibenzoate, 4-methyl-3-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-5-propyl-3, 5-heptanediol dibenzoate.

Most preferably, the internal electron donor compound a is 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate.

According to the invention, preferably, the internal electron donor compound b is a1, 3-diether compound shown in formula V,

in formula V, R₉' and R₁₀' same or different, each independently hydrogen, halogen, C₁-C₁₈Straight or branched alkyl of (2), C₃-C₁₈Substituted or unsubstituted cycloalkyl of (A), C₆-C₁₈Substituted or unsubstituted aryl and C₇-C₁₈Or one of substituted or unsubstituted aralkyl, or R₉' and R₁₀' bonding to each other to form a ring; r₁₁' and R₁₂' same or different, each independently C₁-C₁₀Linear or branched alkyl.

According to the present invention, examples of the internal electron donor compound b may include, but are not limited to: 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2-isopropylphenyl-1, 3-dimethoxypropane, 2-isopropyl, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-methyl, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene.

Most preferably, the internal electron donor compound b is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene.

In the present invention, the 1, 3-diether compound can be synthesized by the methods disclosed in CN1020448C, CN100348624C and CN 1141285A. The disclosure of which is incorporated herein by reference in its entirety. This is not described in detail herein.

According to the present invention, it is preferable that the aliphatic monocarboxylic acid ester is a monoester comprising an aliphatic monocarboxylic acid having 2 to 10 carbon atoms and a monohydric or polyhydric aliphatic alcohol having 1 to 15 carbon atoms or an aromatic alcohol having 6 to 15 carbon atoms; the monobasic aromatic carboxylic ester is formed by monobasic aromatic carboxylic acid with 7-10 carbon atoms and monobasic or polybasic aliphatic alcohol with 1-15 carbon atoms or aromatic alcohol with 6-15 carbon atoms.

More preferably, the monovalent aromatic carboxylic acid ester is at least one of benzoate, orthohydroxybenzoate, orthomethoxybenzoate and orthoethoxybenzoate.

Most preferably, the internal electron donor compound c is ethyl o-anisate and/or ethyl benzoate.

In the research process, the inventor of the present invention finds that when 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate is used as an internal electron donor compound a, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and/or 9, 9-dimethoxymethylfluorene is used as an internal electron donor compound b, and ethyl o-methoxybenzoate and/or ethyl benzoate is used as an internal electron donor compound c, the obtained catalyst has high stereospecificity when used for olefin polymerization, and can obtain olefin polymers with high isotactic index under the condition of not using or using a small amount of external electron donor.

According to the present invention, the internal electron donor comprises a diol ester compound, a diether compound and a monocarboxylic acid ester compound, which can generate a certain synergistic effect, and the total amount of the diol ester compound, the diether compound and the monocarboxylic acid ester compound is preferably 70 to 100 wt%, more preferably 80 to 100 wt%, even more preferably 90 to 100 wt%, and most preferably 100 wt%, based on the amount of the internal electron donor.

The olefin polymerization catalyst component according to the present invention is not particularly limited, and the content of the internal electron donor component may vary within a wide range, and preferably the content of the internal electron donor is 4 to 25% by weight based on the total weight of the catalyst component, and more preferably the content of the internal electron donor is 7 to 22% by weight based on the total weight of the catalyst component.

According to the present invention, preferably, the raw material for synthesizing the spherical carrier of the olefin polymerization catalyst comprises elemental sulfur and has a general formula of MgX₁Magnesium halide of Y, formula R₁OH compounds, ethylene oxide compounds;

general formula MgX₁In Y, X₁Is halogen, Y is halogen, C₁-C₅Alkyl of (C)₁-C₅Alkoxy group of (C)₆-C₁₀Aryl or C of₆-C₁₀An aryloxy group of (a);

general formula R₁In OH, R₁Is C₁-C₈Alkyl or C₃-C₈Cycloalkyl groups of (a);

the structure of the oxirane compound is shown as a formula X:

in the formula X, R₂₅And R₂₆Each independently is hydrogen, C₁-C₅Alkyl or C₁-C₅A haloalkyl group of (a).

According to a preferred embodiment of the present invention, the sulfur-containing magnesium compound is prepared by a method comprising the steps of:

(1) elemental sulfur with the general formula of MgX₁Magnesium halide of Y, formula R₁Mixing and heating an OH compound, an optional inert liquid medium, and an optional surfactant to obtain a liquid mixture;

(2) and (2) carrying out contact reaction on the liquid mixture obtained in the step (1) and an ethylene oxide compound.

According to the present invention, the inert liquid medium may be any of various liquid media commonly used in the art that do not chemically interact with the reactants and reaction products. For example:the inert liquid medium may be a silicone oil type solvent and/or a hydrocarbon type solvent. Specifically, the inert liquid medium may be at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil, and methyl phenyl silicone oil. The inert liquid medium according to the invention is particularly preferably white oil. The inert liquid medium may be used in an amount according to the formula MgX₁The amount of the magnesium halide of Y is determined. Generally, 1mol of MgX is represented by the formula₁The inert liquid medium may be used in an amount of 0.8 to 10L, preferably 2 to 8L, based on the magnesium halide of Y.

According to the present invention, a surfactant such as at least one of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol, polyacrylic acid salt, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkylacrylate copolymer-modified polyethyleneimine, a polymer of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethyleneoxide-propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenylpolyoxyethylene ether, and polyalkylmethacrylate may be used in the reaction, and preferably at least one of polyvinylpyrrolidone, polyvinylpyrrolidone vinyl acetate copolymer, and polyethylene glycol. 1mol of MgX₁The amount of the surfactant is preferably 1 to 20g based on the magnesium halide of Y.

According to the invention, in step (1), elemental sulfur is reacted with a compound of the general formula MgX₁Magnesium halide of Y, formula R₁The conditions under which the compound of OH, optionally in admixture with an inert liquid medium and/or a surfactant, is heated are not particularly limited, provided that the heating conditions are such as to give a compound of formula MgX₁The magnesium halide of Y is melted and fully reacted with sulfur. Generally, the conditions of heating include: the temperature is 80-120 ℃, and the time is 0.5-5 hours; preferably, the temperature is 80-100 ℃ and the time is 0.5-3 hours.

According to the present invention, the conditions for contacting the liquid mixture with the ethylene oxide in step (2) may be any of the existing conditions capable of forming a carrier for an olefin polymerization catalyst, for example, the conditions for contacting include: the temperature is 40-120 ℃, and the time is 15-60 minutes; preferably, the conditions of the contact reaction include: the temperature is 60-100 ℃, and the time is 20-50 minutes.

According to the invention, the method can also comprise the steps of carrying out solid-liquid separation on the product obtained by the contact reaction, washing the solid-phase product obtained by the separation and drying the solid-phase product. The solid-liquid separation may be any of various conventional methods for separating a solid phase from a liquid phase, such as suction filtration, pressure filtration, or centrifugal separation, and preferably, the solid-liquid separation is a pressure filtration method. In the present invention, the conditions for the pressure filtration are not particularly limited, and it is considered that the separation of the solid phase and the liquid phase is sufficiently achieved as much as possible. The washing may be carried out by washing the obtained solid phase product by a method known to those skilled in the art, and for example, the obtained solid phase product may be washed by an inert hydrocarbon solvent (e.g., pentane, hexane, heptane, petroleum ether and gasoline). In the present invention, the drying conditions are not particularly limited, and examples thereof include: the drying temperature can be 20-70 ℃, and the drying time can be 0.5-10 hours. According to the invention, the drying can be carried out under atmospheric or reduced pressure.

According to the invention, the content of the above-mentioned components in the spherical support of the olefin polymerization catalyst can be selected and varied within wide limits, preferably 1mol of MgX₁The magnesium halide of Y is taken as a reference, the dosage of the elemental sulfur is 0.0001 to 0.5mol, and the general formula is R₁The dosage of OH compound is 4-30mol, and the dosage of ethylene oxide compound is 1-10 mol; further preferably, MgX is present in an amount of 1mol₁Based on magnesium halide of Y, the general formula is R₁The dosage of the OH compound is 6-20mol, and the dosage of the ethylene oxide compound is 2-6 mol.

In the present invention, the elemental sulfur may be any subtype of elemental sulfur, including but not limited to at least one of α -sulfur, β -sulfur, γ -sulfur, and polymeric sulfur.

According to the invention, of the formula MgX₁In Y, X₁Preferably chlorine or bromine, Y is preferably chlorine, bromine, C₁-C₅Alkoxy or C₆-C₁₀An aryloxy group of (1). Said C is₁-C₅The alkyl group of (A) may be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl, C₁-C₅The alkoxy group of (C) may be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, C₆-C₁₀The aryl group of (A) may be, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, an o-ethylphenyl group, an m-ethylphenyl group, a p-ethylphenyl group or a naphthyl group, said C₆-C₁₀The aryloxy group of (a) may be, for example, a phenoxy group or a naphthoxy group. A general formula of MgX₁The magnesium halide of Y may be one kind of magnesium halide or a mixture of plural kinds of magnesium halides. A general formula of MgX₁Specific examples of magnesium halides of Y may be, but are not limited to: at least one of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride. Magnesium chloride is preferred from the viewpoint of availability of raw materials.

According to the invention, of the formula R₁In OH, R₁Can be C₁-C₈Alkyl or C₃-C₈In which C is₃-C₈The carbon atoms in the cycloalkyl group(s) may be all or part of them may participate in the ring formation, and C is₃-C₈The cycloalkyl group of (b) may be, for example, a cyclopentyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexyl group or a cyclohexylmethyl group. R₁Preferably C₁-C₈Alkyl groups of (a); said C is₁-C₈The alkyl group of (b) may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, an octyl group or an isooctyl group. Has the general formula R₁Specific examples of compounds of OH may be, but are not limited to: ethanol, n-propanol, iso-propanolAt least one of propanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, 2-ethylhexanol, and n-octanol.

According to the invention, in the oxirane compound with the structure shown as the formula X, R₂₅And R₂₆Preferably each independently hydrogen, C₁-C₃Alkyl or C₁-C₃A haloalkyl group of (a); specific examples of the oxirane compound may be, but are not limited to: at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide, and butylene bromide oxide.

The average particle size of the spherical support for the olefin polymerization catalyst of the present invention can be controlled in a wide range and may be, for example, 10 to 100 μm. According to a preferred embodiment of the present invention, the average particle diameter (D50) of the spherical support for olefin polymerization catalyst can be controlled to 30 μm or less, preferably to 20 μm or less, and the particle size distribution ((D90-D10)/D50) is less than 1.2; the particle size distribution is preferably 0.8 or less. In the preferred embodiment, the catalyst prepared from the spherical support of the olefin polymerization catalyst can give an olefin polymer having a higher bulk density. In the present invention, the average particle diameter and the particle size distribution of the spherical support for an olefin polymerization catalyst can be measured using a Master Sizer2000 laser particle Sizer (manufactured by Malvern Instruments Ltd.).

When the solid component (olefin polymerization catalyst support) is spherical particles, the catalyst component obtained by reacting the support with the titanium compound, the internal electron donor compound a, the internal electron donor compound b, and the internal electron donor compound c is also spherical particles. Further, since the spherical carrier has a small particle diameter and a narrow particle diameter distribution, the catalyst component obtained is also small in particle diameter and narrow in particle diameter distribution.

According to the invention, the spherical support of the olefin polymerization catalyst may contain water originating from traces of water carried by the synthesis raw materials and the reaction medium. According to the present invention, a slight amount of water in each of the above reactants may also participate in the reaction for forming the spherical support of the olefin polymerization catalyst.

The preparation method adopts a sulfur-containing magnesium compound as a carrier, and uses the combination of an internal electron donor compound a, an internal electron donor compound b and an internal electron donor compound c as an internal electron donor component to improve the stereotacticity and the polymer isotactic index of an olefin polymerization catalyst, wherein in the catalyst component, the molar ratio of the internal electron donor compound a to the internal electron donor compound b to the internal electron donor compound c is 0.5-15: 1.5-20: 1 under the preferable condition; more preferably, the molar ratio of the internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c is 0.6-10: 2-13: 1.

In the present invention, the contents of the magnesium, titanium, halogen and internal electron donor in the olefin polymerization catalyst component are not particularly limited and may be appropriately selected according to the amounts conventionally used in the art. Preferably, in the catalyst component, the weight ratio of titanium calculated by titanium element, magnesium calculated by magnesium element, halogen calculated by halogen element and internal electron donor is 1: 5-15: 10-30: 2-10; preferably 1: 8-12: 15-25: 3-8.

In the present invention, the titanium compound may be a titanium compound commonly used in the art. Preferably, the titanium compound is a compound represented by formula XI and/or formula XII:

TiX_p(OR₂₇)_4-pa compound of the formula XI,

TiX_q(OR₂₈)_3-qin the formula XII, the reaction mixture is,

in the formulae XI and XII, X is halogen and R₂₇、R₂₈Each independently is C₁-C₂₀P is an integer of 1 to 4, and q is an integer of 1 to 3.

Further preferably, the titanium compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tributoxy titanium chloride, dibutoxy titanium dichloride, butoxytitanium trichloride, triethoxy titanium chloride, diethoxy titanium dichloride, ethoxytitanium trichloride, and titanium trichloride. Most preferably, the titanium compound is titanium tetrachloride.

The method for preparing the catalyst component for olefin polymerization of the present invention may comprise the steps of: reacting a sulfur-containing magnesium compound shown as a formula I with a titanium compound, and adding an internal electron donor in one or more time periods before, during and after the reaction of the magnesium compound and the titanium compound, wherein the internal electron donor comprises the internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c.

In the present invention, the reaction of the magnesium compound with the titanium compound can be carried out according to the methods disclosed in the prior art, for example, the titanium compound can be cooled to 0 ℃ or less (preferably-5 ℃ to-25 ℃), then the magnesium compound is added and stirred and mixed at that temperature for 10 to 60 minutes, and then heated to the reaction temperature (preferably 60 to 130 ℃) and maintained at that reaction temperature for 0.5 to 10 hours. An internal electron donor compound a, an internal electron donor compound b and an internal electron donor compound c are added in the temperature rising process. Then adding a titanium compound for one or more treatments, and finally, washing with an inert solvent for a plurality of times, thereby obtaining the catalyst component. Examples of the inert solvent may include, but are not limited to: hexane, heptane, octane, decane, toluene.

In the preparation method of the catalyst component for olefin polymerization, the internal electron donor component may be added in one or more periods of time before, during, and after the reaction of the magnesium compound and the titanium compound. The period of time before the reaction of the magnesium compound with the titanium compound means a period of time after the magnesium compound is added to the reactor and before the temperature is raised to the reaction temperature.

In the present invention, the internal electron donor compound a, the internal electron donor compound b, and the internal electron donor compound c may be added to the mixture of the magnesium compound and the titanium compound several times or simultaneously when preparing the catalyst component. When the internal electron donor compound a, the internal electron donor compound b and the internal electron donor c are added to the mixture of the magnesium compound and the titanium compound in several times, the internal electron donor compound a and the internal electron donor compound b may be added first, and then the internal electron donor compound c may be added; or adding the internal electron donor compound c, and then adding the internal electron donor compound a and the internal electron donor compound b.

According to the present invention, in the preparation of the catalyst component, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor component is not particularly limited, and the amount of each component used may be varied within a wide range, and preferably, the molar ratio of the magnesium compound in terms of magnesium element, the titanium compound in terms of titanium element and the internal electron donor is 1: 20 to 200: 0.04 to 0.8, more preferably, the molar ratio of the magnesium compound in terms of magnesium element, the titanium compound in terms of titanium element and the internal electron donor is 1: 50 to 180: 0.05 to 0.5, and most preferably, the molar ratio of the magnesium compound in terms of magnesium element, the titanium compound in terms of titanium element and the internal electron donor is 1: 70 to 150: 0.1 to 0.4.

A second aspect of the present invention provides the use of a catalyst component as described above in the preparation of a catalyst for the polymerisation of olefins.

A third aspect of the present invention provides a catalyst for olefin polymerization, the catalyst comprising:

(1) the above catalyst components;

(2) an alkylaluminum compound as a cocatalyst; and

(3) optionally an external electron donor compound.

According to the present invention, in the above-mentioned catalyst for olefin polymerization, the aluminum alkyl compound may be any of various aluminum alkyl compounds commonly used in the field of olefin polymerization, which can be used as a cocatalyst for an olefin polymerization catalyst. Preferably, the alkyl aluminum compound is a compound represented by formula XIII,

AlR’_n'X’_3-n'the compound of the formula XIII is shown in the specification,

in the formula XIII, R' is C₁-C₈X 'is halogen, preferably one or more of chlorine, bromine and iodine, more preferably chlorine, and n' is an integer of 1 to 3.

Go toIn a preferred case, the aluminum alkyl compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum 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 the invention, the alkyl aluminium compound may be used in amounts conventional in the art. Preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 1 to 2000: 1. further preferably, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the catalyst component is from 10 to 500: 1. Most preferably, the molar ratio of aluminum in the aluminum alkyl compound to titanium in the catalyst component is from 20 to 200: 1.

The present invention is not particularly limited with respect to the kind and content of the external electron donor in the catalyst for olefin polymerization. Preferably, the molar ratio of the aluminum in the aluminum alkyl compound to the external electron donor compound is 2-200: 1, more preferably 2.5-100: 1.

According to the invention, the external electron donor compound is combined with the compounded internal electron donor compound to further improve the isotactic index of the olefin polymer obtained by the method. The external electron donor compound may be any of various external electron donor compounds commonly used in the art to achieve the above-mentioned objects, such as: one or more of carboxylic acids, carboxylic acid anhydrides, carboxylic acid esters, ketones, ethers, alcohols, lactones, organophosphorus compounds, and organosilicon compounds. Preferably, the external electron donor compound is an organosilicon compound represented by formula XIV,

(R₂₉)_m’(R₃₀)_p’Si(OR₃₁)_qthe formula (XIV) is defined in the specification,

in the formula XIV, R₂₉、R₃₀And R₃₁Each independently is C₁-C₁₈Optionally containing heteroatoms, said heteroatoms being one or more of F, Cl, Br, N and I; m 'and p' are each independently an integer from 0 to 2, q 'is an integer from 1 to 3, and the sum of m', p ', and q' is 4.

Preferably, R₂₉And R₃₀Each independently is C₃-C₁₀Straight-chain or branched alkyl of C₃-C₁₀Linear or branched alkenyl of (C)₃-C₁₀Substituted or unsubstituted alkylene of (A), C₃-C₁₀Substituted or unsubstituted cycloalkyl and C₆-C₁₀Optionally containing heteroatoms which are one or more of F, Cl, Br, N and I; r₃₁Is C₁-C₁₀More preferably methyl.

According to the present invention, specific examples of the external electron donor compound may include, but are not limited to: one or more of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, t-hexyltrimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane, and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.

More preferably, the external electron donor compound is cyclohexylmethyldimethoxysilane and/or dicyclopentyldimethoxysilane.

According to the present invention, in the preparation process of the catalyst for olefin polymerization, the alkylaluminum and the optional external electron donor compound may be respectively mixed with the catalyst component for olefin polymerization and then reacted, or the alkylaluminum and the optional external electron donor compound may be mixed in advance and then mixed with the catalyst component for olefin polymerization and reacted.

According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor may be added into the polymerization reactor separately, or may be added into the polymerization reactor after mixing, or may be added into the polymerization reactor after olefin prepolymerization by a prepolymerization method known in the art.

A fourth aspect of the invention provides the use of a catalyst as described above in the polymerisation of olefins.

A fifth aspect of the present invention provides an olefin polymerization process comprising: one or more olefins are contacted with the above-described catalyst under olefin polymerization conditions. The improvement of the present invention is that a new catalyst component and catalyst for olefin polymerization are used, so that the specific kind of olefin, the polymerization reaction method and conditions of olefin can be the same as those in the prior art. The olefin is at least one olefin represented by the formula CH2 ═ CHR, where R is hydrogen or C₁-C₆Linear or branched alkyl. 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, 4-methyl-1-pentene. Preferably, the general formula CH₂The olefins represented by ═ CHR are ethylene, propylene, 1-n-butene, 1-n-hexene, 4-methyl-1-pentene. More preferably, the general formula CH₂The olefin represented by ═ CHR is propylene.

The olefin polymerization method of the present invention may be homopolymerization of a single olefin or copolymerization of a plurality of olefins.

According to the olefin polymerization process of the present invention, the olefin polymerization conditions may be conventional in the art. In liquid phase monomer or inert solvent containing polymerized monomer, or in gas phase, or by combined polymerization processes in gas and liquid phase. In general, the olefin polymerization conditions may include: the temperature is 0-150 ℃, the time is 0.1-8 hours, and the pressure is 0.01-10 MPa. Preferably, the olefin polymerization conditions comprise: the temperature is 50-100 ℃, the time is 0.5-3 hours, and the pressure is 0.5-5 MPa. The amount of the catalyst for olefin polymerization may be various conventional amounts of olefin polymerization catalysts of the prior art. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen can be used as a polymer molecular weight regulator to be added into the polymerization reactor to regulate the molecular weight and melt index of the polymer. The alkyl aluminum compound and the optional external electron donor compound can be contacted and reacted with the active component singly or as a mixture of two components. The catalyst component, the alkyl aluminum and the external electron donor compound can be respectively added into a polymerization reactor, can be mixed and then added into the polymerization reactor, and can also be added into the polymerization reactor after propylene is prepolymerized by adopting a prepolymerization method known in the industry.

The olefin polymerization catalyst carrier used in the invention is added with sulfur in the preparation process, and the sulfur can reduce the collision probability among unformed particles and reduce the adhesion among carrier particles, so that the obtained carrier particles have small particle size, narrow distribution and good shape. The olefin polymerization catalyst component adopts a sulfur-containing magnesium compound as a carrier, and a glycol ester compound, a diether compound and a monocarboxylic ester compound are compounded to serve as an internal electron donor component (the internal electron donor does not contain a phthalate ester compound), so that the prepared catalyst has high stereoregularity when being used for olefin polymerization, and can obtain an olefin polymer with high isotactic index under the condition of not using or using a small amount of external electron donor.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.

FIG. 1 is an optical microscope photograph of a spherical support of an olefin polymerization catalyst prepared in preparation example 1;

FIG. 2 is an optical micrograph of an olefin polymerization catalyst support prepared in comparative preparation example 1.

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.

In the following examples and comparative examples:

1. the average particle diameter and the particle size distribution of the olefin polymerization catalyst component and the carrier were measured using a Masters Sizer2000 particle Sizer (manufactured by Malvern Instruments Ltd.);

2. the apparent morphology of the olefin polymerization catalyst support was observed by means of an optical microscope, commercially available from Nikon, under the model Eclipse E200;

3. the polymer isotacticity index was determined by heptane extraction (6 hours of heptane boil extraction): a2 g sample of the dried polymer was 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 a constant weight, which was the isotactic index.

Preparation example 1

This preparation example is intended to illustrate the spherical support for the olefin polymerization catalyst used in the present invention and the process for preparing the same.

Adding 8.0g (0.08mol) of magnesium chloride, 56mL (0.96mol) of ethanol, 1g (0.03mol) of α -sulfur and 1g of PVP (polyvinylpyrrolidone) as surfactants into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epichlorohydrin, reacting at constant temperature of 90 ℃ for half an hour, carrying out pressure filtration, washing the pressure filtration product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z1.

The spherical carrier Z1 for the olefin polymerization catalyst has an average particle diameter (D50) of 15 microns and a particle size distribution ((D90-D10)/D50) of 0.6. As shown in FIG. 1, the spherical support Z1 for olefin polymerization catalyst has regular particle morphology, smooth surface, substantially spherical shape, concentrated particle size distribution and substantially no irregular particles.

According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z1 is as follows:

preparation example 2

Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.3g (0.009mol) of β -sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epichlorohydrin, continuing to react at constant temperature for 20 minutes at 100 ℃, carrying out pressure filtration, washing the pressure filtration product for 5 times by using hexane, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z2.

The spherical carrier Z2 for the olefin polymerization catalyst has an average particle diameter (D50) of 18 microns and a particle size distribution ((D90-D10)/D50) of 0.7. The spherical carrier Z2 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.

According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z2 is as follows:

preparation example 3

Adding 300mL of white oil, 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.2g (0.006mol) of α -sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 100 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epichlorohydrin, continuing to react at constant temperature for 20 minutes at 100 ℃, performing pressure filtration, washing the pressure filtration product for 5 times by using hexane, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z3.

The spherical carrier Z3 for the olefin polymerization catalyst has an average particle diameter (D50) of 20 microns and a particle size distribution ((D90-D10)/D50) of 0.8. The spherical carrier Z3 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.

According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z3 is as follows:

preparation example 4

Adding 8.0g (0.08mol) of magnesium chloride, 59mL (0.48mol) of cyclohexylmethanol, 0.3g (0.009mol) of β -sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant into a 0.6L reaction kettle, heating to 60 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature of 60 ℃ for 20 minutes, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z4.

The spherical carrier Z4 for the olefin polymerization catalyst had an average particle diameter (D50) of 25 μm and a particle size distribution ((D90-D10)/D50) of 0.9. The spherical carrier Z4 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.

According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z4 is as follows:

preparation example 5

In a 0.6L reaction kettle, adding 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol, 0.3g (0.009mol) of α -sulfur and 1g of PVP (polyvinylpyrrolidone) as a surfactant, heating to 70 ℃ under stirring, reacting at constant temperature for 1 hour, adding 11.2mL (0.16mol) of propylene oxide, continuing to react at constant temperature of 70 ℃ for 20 minutes, carrying out pressure filtration, washing the pressure filtration product with hexane for 5 times, and finally carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z5.

The spherical carrier Z5 for the olefin polymerization catalyst has an average particle diameter (D50) of 26 microns and a particle size distribution ((D90-D10)/D50) of 0.9. The spherical carrier Z5 for olefin polymerization catalyst has regular particle shape, smooth surface, basically spherical shape, concentrated particle size distribution and basically no special-shaped particle.

According to gas chromatography-mass spectrometry, elemental analysis and nuclear magnetic characterization, the structural formula of Z5 is as follows:

comparative preparation example 1

This comparative preparation example is intended to illustrate a reference olefin polymerization catalyst support and a method for preparing the same.

Adding 0.08mol of magnesium chloride, 0.96mol of ethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 90 ℃ under stirring, reacting at constant temperature for 2 hours, adding 38mL (0.48mol) of epoxy chloropropane, continuing reacting at constant temperature of 90 ℃ for half an hour, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally drying the product in vacuum to obtain the catalyst carrier DZ1 for olefin polymerization.

The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ1 was 60 μm, and the particle size distribution ((D90-D10)/D50) was 1.3. The particle morphology observed with an optical microscope is shown in fig. 2. As can be seen from fig. 2, the catalyst carrier for olefin polymerization DZ1 had irregular particles and a rough surface.

Comparative preparation example 2

Adding 8.0g (0.08mol) of magnesium chloride, 59mL (0.48mol) of cyclohexylmethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 60 ℃ under stirring, reacting at constant temperature for 1 hour, adding 12.5mL (0.16mol) of epoxy chloropropane, continuing to react at constant temperature for 20 minutes at 60 ℃, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier DZ 2.

The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ2 was 80 μm, and the particle size distribution ((D90-D10)/D50) was 1.5. The particle morphology is observed by an optical microscope, and special-shaped particles exist in DZ2, and the surface is rough.

Comparative preparation example 3

Adding 8.0g (0.08mol) of magnesium chloride, 28mL (0.48mol) of ethanol and 1g of PVP (polyvinylpyrrolidone) serving as a surfactant into a 0.6L reaction kettle, heating to 70 ℃ under stirring, reacting at constant temperature for 1 hour, adding 11.2mL (0.16mol) of propylene oxide, continuing to react at constant temperature of 70 ℃ for 20 minutes, performing pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally performing vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier DZ 3.

The average particle diameter (D50) of the olefin polymerization catalyst carrier DZ3 was 88 μm, and the particle size distribution ((D90-D10)/D50) was 1.7. The particle morphology is observed by an optical microscope, and special-shaped particles exist in DZ3, and the surface is rough.

Example 1

This example illustrates the preparation of the catalyst component and catalyst for olefin polymerization and the propylene polymerization process provided by the present invention.

(1) Preparation of the catalyst component for olefin polymerization:

adding 90mL of titanium tetrachloride and 10mL of hexane into a 300mL stirred glass reaction bottle fully replaced by high-purity nitrogen, cooling to-20 ℃, adding 8g of carrier Z1, stirring, slowly heating in stages, adding 1.8mmol of ethyl o-methoxybenzoate (internal electron donor compound c), 2.3mmol of 2, 4-pentanediol dibenzoate (internal electron donor compound a) and 7.3mmol of 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane (internal electron donor compound b) during heating, continuously heating to 110 ℃, keeping the temperature for 0.5h after heating, removing liquid by suction filtration, and adding titanium tetrachloride into the filtered solid phase for treatment. Then washed five times with hexane and dried in vacuo to give spherical catalyst A1.

(2) Propylene polymerization reaction:

in a 5L autoclave, purged with a stream of nitrogen, 1mmol of triethylaluminum, 0.04mmol of Cyclohexylmethyldimethoxysilane (CHMMS), 10mL of anhydrous hexane and 6mg of spherical catalyst component A1 were introduced into the stream of nitrogen. The autoclave was closed and 2NL and 2.3L of liquid propylene were added. The temperature was raised to 70 ℃ and polymerization was carried out for 1.0 hour. The test results are shown in Table 1.

Example 2

An olefin polymerization catalyst component was prepared according to the method of example 1, and polypropylene was prepared according to the method of example 1, except that cyclohexylmethyldimethoxysilane was not introduced during the polymerization of propylene. The test results are shown in Table 1.

Example 3

An olefin polymerization catalyst component was prepared according to the method of example 1, except that 0.6mmol of ethyl o-methoxybenzoate, 5.1mmol of 2, 4-pentanediol dibenzoate and 6.1mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase to obtain catalyst component A3.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component A3 was used in place of catalyst component A1. The test results are shown in Table 1.

Example 4

An olefin polymerization catalyst component was prepared according to the method of example 1, except that 3.7mmol of ethyl benzoate (internal electron donor compound c), 2.4mmol of 3, 5-heptanediol dibenzoate, and 9.0mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature rise to obtain catalyst component a 4.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component A4 was used in place of catalyst component A1. The test results are shown in Table 1.

Example 5

An olefin polymerization catalyst component was prepared according to the method of example 1 except that 8g of the carrier Z2 was added, and 1.9mmol of ethyl o-methoxybenzoate, 2.4mmol of 2, 4-pentanediol dibenzoate and 9.1mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during temperature elevation to give a catalyst component A5.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component A5 was used in place of catalyst component A1. The test results are shown in Table 1.

Example 6

This example is intended to illustrate the catalyst component for olefin polymerization, the olefin polymerization catalyst and the olefin polymerization process of the present invention.

An olefin polymerization catalyst component was prepared according to the method of example 5 except that 0.8mmol of ethyl o-methoxybenzoate, 4.6mmol of 2, 4-pentanediol dibenzoate and 10.2mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added during the temperature increase to obtain catalyst component A6.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component A6 was used in place of catalyst component A1. The test results are shown in Table 1.

Example 7

An olefin polymerization catalyst component was prepared according to the method of example 5, except that 0.7mmol of ethyl benzoate, 6.1mmol of 2, 4-pentanediol dibenzoate and 3.8mmol of 9, 9-dimethoxymethylfluorene were added during the temperature increase to obtain catalyst component A7.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component A7 was used in place of catalyst component A1. The test results are shown in Table 1.

Comparative example 1

Into a 300mL stirred glass reaction flask fully purged with high purity nitrogen, 90mL of titanium tetrachloride and 10mL of hexane were added, cooled to-20 ℃ and 8g of spherical magnesium chloride alcoholate (MgCl)₂·2.6C₂H₅OH, synthesizing magnesium dichloride and ethanol according to the method disclosed in CN 1330086A), stirring, slowly heating in stages, adding 5.1mmol of 2, 4-pentanediol dibenzoate (an internal electron donor compound a) in the heating process, continuously heating to 110 ℃, keeping the temperature for 0.5h after the temperature is reached, filtering to remove liquid, and adding titanium tetrachloride into the solid phase obtained by filtering for treatment. Then washed with hexane and dried under vacuum to obtain catalyst component B1.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component B1 was used in place of catalyst component A1. The test results are shown in Table 1.

Comparative example 2

An olefin polymerization catalyst component was prepared by following the procedure of comparative example 1, except that 9.0mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was added in place of 2, 4-pentanediol dibenzoate during the preparation of the catalyst component, to obtain catalyst component B2.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component B2 was used in place of catalyst component A1. The test results are shown in Table 1.

Comparative example 3

An olefin polymerization catalyst component was prepared by the method of comparative example 1, except that 2.3mmol of 2, 4-pentanediol dibenzoate and 7.3mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane were added in place of 5.1mmol of 2, 4-pentanediol dibenzoate in the preparation of the catalyst component to obtain catalyst component B3.

And polypropylene was prepared by following the procedure of example 1, except that catalyst component B3 was used in place of catalyst component A1. The test results are shown in Table 1.

Comparative example 4

An olefin polymerization catalyst component was prepared by following the procedure of comparative example 3 to obtain catalyst component B3.

And polypropylene was prepared according to the procedure of example 1, except that cyclohexylmethyldimethoxysilane was not introduced during the polymerization of propylene. The test results are shown in Table 1.

Comparative example 5

An olefin polymerization catalyst component was prepared by following the procedure of example 1 except that the carrier Z1 was replaced with an equal amount of the carrier DZ1 to obtain a catalyst component B5.

The above catalyst component B5 was used in place of the olefin polymerization catalyst component A1 and polypropylene was produced by the method of example 1. The test results are shown in Table 1.

TABLE 1

As can be seen from the comparison of the data in examples 1 to 7 and comparative examples 1 to 5 in Table 1, the catalyst component obtained by using the sulfur-containing magnesium compound as a carrier and using the combination of the internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c as an internal electron donor has a stereospecificity significantly higher than that of a catalyst containing only a glycol ester internal electron donor or only a diether internal electron donor, and the average particle size of the catalyst is significantly reduced.

As can be seen from the comparison of the data in examples 1-2 and comparative examples 3-4 in Table 1, the catalyst prepared by compounding the sulfur-containing magnesium compound as a carrier and three internal electron donor compounds of the present invention has a further improved stereospecificity compared with the catalyst prepared by compounding the magnesium halide alcoholate as a carrier and 2, 4-pentanediol dibenzoate and/or 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, and the polymer obtained has a higher isotactic index both when the external electron donor is used and when the external electron donor is not used. This improvement of the present invention is particularly valuable since the data of comparative examples 3-4 are already at a very high level in the art.

As can be seen from the comparison of the data of example 1 and comparative example 5 in Table 1, the catalyst using the sulfur-containing magnesium compound as the carrier provided by the present invention has a stereospecificity significantly higher than that of the catalyst using the sulfur-free magnesium compound as the carrier, and the average particle size of the catalyst is greatly reduced.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A catalyst component for the polymerization of olefins, the catalyst component comprising the reaction product of:

(1) a solid component;

(2) at least one titanium compound; and

(3) an internal electron donor compound;

R₂and R₃Identical or different, each independently of the others, is hydrogen or C₁-C₅The linear or branched alkyl group of (1), wherein hydrogen on the alkyl group may be optionally substituted with a halogen atom;

x is halogen, preferably chlorine or bromine;

m is 0.1-1.9, n is 0.1-1.9, m + n is 2, 0< q is less than or equal to 0.5;

in the formula II, R₄And R₅Identical or different, each independently is halogen, C₁-C₂₀Straight or branched alkyl of (2), C₂-C₂₀Linear or branched alkenyl of (C)₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀One of substituted or unsubstituted alkaryl groups; the hydrogen atom on the aromatic ring of the aryl, aralkyl or alkaryl group being optionally substituted by halogen, C₁-C₆And C is a straight or branched alkyl group₁-C₆Substituted with one or more of alkoxy groups of (a);

R₆、R₇、R₈、R₉and R¹-R²ⁿThe same or different, each independently is hydrogen, halogen, C₁-C₂₀Straight or branched alkyl of (2), C₃-C₂₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted alkylaryl of, C₇-C₂₀Substituted or unsubstituted aralkyl of (1), C₂-C₂₀And C is a linear or branched alkylene group₂-C₂₀One of the ester groups of (1), R₆、R₇、R₈、R₉And R¹-R²ⁿOptionally substituted with heteroatoms, which are one or more of halogen, nitrogen, oxygen, sulfur, silicon and phosphorus; or, R₆、R₇、R₈、R₉And R¹-R²ⁿTwo or more of them are mutually bonded to form a ring;

n is an integer of 0 to 10;

2. The catalyst component according to claim 1 in which the starting material for the synthesis of the sulphur-containing magnesium compound comprises elemental sulphur, of general formula MgX₁Magnesium halide of Y, formula R₁OH compounds, ethylene oxide compounds;

the structure of the oxirane compound is shown as a formula X:

3. The catalyst component according to claim 2 in which the sulphur-containing magnesium compound is obtained by a process comprising the steps of:

(1) elemental sulfur with the general formula of MgX₁Magnesium halide of Y, formula R₁Mixing OH compound, optional inert liquid medium, optional surfactant, and heating to obtain liquidA mixture of phases;

4. The catalyst component according to claim 3 in which the inert liquid medium is a silicone-oil type solvent and/or a hydrocarbon type solvent; preferably, the inert liquid medium is selected from at least one of kerosene, paraffin oil, vaseline oil, white oil, methyl silicone oil, ethyl silicone oil, methyl ethyl silicone oil, phenyl silicone oil and methyl phenyl silicone oil; 1mol of MgX₁The amount of the inert liquid medium is 0.8-10L based on magnesium halide of Y.

5. The catalyst component according to claim 3 in which the surfactant is selected from at least one of polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, polyacrylic acid salts, polyacrylamide, polystyrene sulfonate, naphthalene sulfonic acid formaldehyde condensate, condensed alkylphenyl ether sulfate, condensed alkylphenol polyoxyethylene ether phosphate, oxyalkylacrylate copolymer modified polyethyleneimine, polymers of 1-dodecyl-4-vinylpyridine bromide, polyvinylbenzyltrimethylamine salt, polyethyleneoxide propylene oxide block copolymer, polyvinylpyrrolidone vinyl acetate copolymer, alkylphenyl polyoxyethylene ether, and polyalkylmethacrylate; 1mol of MgX₁The dosage of the surfactant is 1-20g based on magnesium halide of Y.

6. The catalyst component according to claim 3 in which in step (1) the heating is carried out at a temperature of from 80 to 120 ℃ for a time of from 0.5 to 5 hours; preferably, the heating temperature is 80-100 ℃ and the time is 0.5-3 hours; in the step (2), the contact reaction conditions include: the temperature is 40-120 ℃, and the time is 15-60 minutes; preferably, the conditions of the contact reaction include: the temperature is 60-100 ℃, and the time is 20-50 minutes.

7. A device according to any one of claims 2 to 6Catalyst component, wherein 1mol of the general formula is MgX₁The magnesium halide of Y is taken as a reference, the dosage of the elemental sulfur is 0.0001 to 0.5mol, and the general formula is R₁The dosage of OH compound is 4-30mol, and the dosage of ethylene oxide compound is 1-10 mol; preferably, MgX is present in 1mol of the formula₁Based on magnesium halide of Y, the general formula is R₁The dosage of the OH compound is 6-20mol, and the dosage of the ethylene oxide compound is 2-6 mol.

8. The catalyst component according to any of claims 2-6 in which the elemental sulphur is selected from at least one of α -sulphur, β -sulphur, γ -sulphur and polymeric sulphur.

9. The catalyst component according to any of claims 2 to 6 in which the general formula MgX₁In Y, X₁Is chlorine or bromine, Y is chlorine, bromine, C₁-C₅Alkoxy or C₆-C₁₀An aryloxy group of (a);

preferably, the general formula is MgX₁The magnesium halide of Y is at least one selected from the group consisting of magnesium chloride, magnesium bromide, phenoxymagnesium chloride, isopropoxymagnesium chloride and n-butoxymagnesium chloride.

10. The catalyst component according to any of claims 2 to 6 in which R is of the general formula₁In OH, R₁Is C₁-C₈Alkyl groups of (a); preferably, the general formula is R₁The compound of OH is selected from at least one of ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isopentanol, n-hexanol, 2-ethylhexanol, and n-octanol.

11. The catalyst component according to any of claims 2-6 in which in the oxirane compound of formula X, R is₂₅And R₂₆Each independently is hydrogen, C₁-C₃Alkyl or C₁-C₃A haloalkyl group of (a); preferably, the oxirane is selected from ethylene oxide, propylene oxide, butylene oxide, chloropropylene oxideAt least one of an alkane, chloroepoxybutane, bromoepoxypropane, and bromoepoxybutane.

12. The catalyst component according to claim 1 in which the sulphur-containing magnesium compound has an average particle diameter of less than or equal to 30 microns, preferably less than or equal to 20 microns, a particle size distribution of less than 1.2, preferably less than or equal to 0.8.

13. The catalyst component according to any of claims 1-6 and 12 in which the internal electron donor compound a is a diol ester compound of formula IV,

14. The catalyst component according to any of claims 1 to 6 and 12 in which the internal electron donor compound b is a1, 3-diether compound of formula V,

15. The catalyst component according to any of claims 1 to 6 and 12 in which the monoaliphatic carboxylic acid ester is a monoaliphatic ester formed from a monoaliphatic carboxylic acid having from 2 to 10 carbon atoms and a monohydric or polyhydric aliphatic alcohol having from 1 to 15 carbon atoms or an aromatic alcohol having from 6 to 15 carbon atoms;

the monobasic aromatic carboxylic ester is formed by monobasic aromatic carboxylic acid with 7-10 carbon atoms and monobasic or polybasic aliphatic alcohol with 1-15 carbon atoms or aromatic alcohol with 6-15 carbon atoms.

16. The catalyst component according to any of claims 1 to 6 and 12, wherein the molar ratio of the internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c in the catalyst component is from 0.5 to 15: 1.5-20: 1; preferably, the molar ratio of the internal electron donor compound a, the internal electron donor compound b and the internal electron donor compound c is 0.6-10: 2-13: 1.

17. the catalyst component according to any of claims 1 to 6 and 12 in which the weight ratio of titanium, magnesium, halogen and internal electron donor, calculated as halogen, in the catalyst component is 1: 5-15: 10-30: 2-10; preferably 1: 8-12: 15-25: 3-8.

18. Use of the catalyst component according to any one of claims 1 to 17 in the preparation of a catalyst for the polymerization of olefins.

19. A catalyst for the polymerization of olefins, the catalyst comprising:

(1) the catalyst component of any one of claims 1 to 17;

(2) an alkyl aluminum compound; and

(3) optionally an external electron donor compound.

20. Use of the catalyst of claim 19 in olefin polymerization reactions.

21. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of claim 19 under olefin polymerization conditions.