CN111072809B

CN111072809B - Catalyst component and catalyst for olefin polymerization, application thereof and olefin polymerization method

Info

Publication number: CN111072809B
Application number: CN201811223651.1A
Authority: CN
Inventors: 赵瑾; 夏先知; 刘月祥; 凌永泰; 谭扬; 陈龙; 李威莅; 任春红; 高富堂; 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: 2022-05-24
Anticipated expiration: 2038-10-19
Also published as: CN111072809A

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 contains an internal electron donor compound a and an internal electron donor compound b; the internal electron donor compound a is a malonate compound, and the internal electron donor compound b is a glycol ester compound. The catalyst component has high stereospecificity, does not contain phthalate compounds (plasticizers), and can be used for obtaining olefin polymers with higher isotactic index when the catalyst prepared from the catalyst component is used for olefin polymerization.

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, polymer isotacticity, molecular weight and molecular weight distribution, and the polyolefin catalyst is continuously updated along with the development of the internal electron donor compound.

The phthalate ester compound is the most commonly used electron donor of the polypropylene catalyst at present, and researches show that the phthalate ester compound can cause serious damage to the growth and development of animals and reproductive systems and can also have similar influence on human beings. In addition, when the catalyst using the phthalate ester compound as the internal electron donor is used for olefin polymerization, the obtained polymer has narrow molecular weight distribution, and the toughness and the processability are not satisfactory, so that the application range of the polymer is limited. Therefore, it is an urgent problem to find an internal electron donor compound that can replace it.

In the research, the carboxylic diol ester compound is used as an internal electron donor, and the prepared catalyst is used for propylene polymerization and has the characteristics of high polymerization activity and wide polymer molecular weight distribution. For example, CN1436766A and CN1552740A disclose a carboxylic acid glycol ester compound and a catalyst thereof, respectively. However, when the spherical catalyst (magnesium chloride alcoholate as carrier) of the carboxylic acid glycol ester internal electron donor is used for propylene polymerization, the stereotacticity is poor, and the isotacticity of the obtained polypropylene is low.

In addition, the use of certain malonate compounds as internal electron donors for propylene polymerization catalysts is known in the art, for example: EP0045977, EP0086473, EP 0086644. As can be seen from the polymerization results reported in the above applications, the disadvantage of using malonate based internal electron donors is the lower polymerization yield and/or the lower isotactic index obtained.

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 prepared but are also widely used in a variety of polymerization processes.

Therefore, it is of great importance to develop a novel catalyst support for olefin polymerization which overcomes the above-mentioned drawbacks of the prior art.

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 catalyst component obtained by using the sulfur-containing magnesium compound shown in the formula I as a carrier and compounding the malonate compound shown in the formula II and/or the malonate compound shown in the formula III and the glycol ester compound shown in the formula IV according to a specific proportion as an internal electron donor has high stereospecificity and does not contain a phthalate compound (plasticizer), and when the catalyst prepared from the catalyst component is used for olefin polymerization, an olefin polymer with a high isotactic index can be obtained.

In a first aspect 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 (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;

wherein the internal electron donor compound contains an internal electron donor compound a and an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.005-2.5: 1, preferably 0.007-2: 1, more preferably 0.05 to 1.5: 1; the internal electron donor compound a is a malonate compound shown in a formula II and/or a formula III, the internal electron donor compound b is a diol ester compound shown in a formula IV,

in formula II, R₄And R₅The same or different, each independently is hydrogen, 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; or, R₄And R₅Bonding to form a ring;

in the formula III, R₁' is C₁-C₂₀Alkoxy group of (a);

in formulae II and III, R₆、R₇、R₈And R₉Identical or different, each independently is C₁-C₂₀Straight or branched alkyl of (2), C₂-C₂₀Linear or branched alkenyl of (C)₃-C₂₀Substituted or unsubstituted cycloalkyl of (1), C₆-C₂₀Substituted or unsubstituted aryl of (1), C₇-C₂₀Substituted or unsubstituted aralkyl and C₇-C₂₀One of substituted or unsubstituted alkaryl groups; or, R₆And R₇Bonded to each other to form a ring and/or R₈And R₉Bonding to form a ring;

in the formula IV, R₁₀And R₁₁Identical or different, each independently of the others, halogen, C₁-C₂₀Straight or branched alkyl of (2), C₂-C₂₀Linear or branched alkenyl of (C)₃-C₂₀Substituted or unsubstituted cycloalkyl of (1), 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);

R₁₂、R₁₃、R₁₄、R₁₅and 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), R₁₂、R₁₃、R₁₄、R₁₅And R¹-R²ⁿOptionally substituted with heteroatoms, which are one or more of halogen, nitrogen, oxygen, sulfur, silicon and phosphorus; or, R₁₂、R₁₃、R₁₄、R₁₅And R¹-R²ⁿTwo or more of them are mutually bonded to form a ring;

n is an integer of 0 to 10.

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-propylcyclohexylHexyl, 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 (2), 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 alkyl group having an aryl substituent and having 7 to 20 carbon atoms. 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, n-pentylphenyl.

In the present invention, C₁-C₂₀Examples 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, R in formula II is preferably₄And R₅The same or different, each independently is hydrogen, C₁-C₁₀Straight or branched alkyl of (2), C₂-C₁₀Linear or branched alkenyl of (C)₃-C₁₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₁₀Substituted or unsubstituted aryl of (1), C₇-C₁₀Substituted or unsubstituted aralkyl and C₇-C₁₀One of substituted or unsubstituted alkaryl groups; in the formula III, R₁' is C₁-C₁₀Alkoxy group of (a); in formulae II and III, R₆、R₇、R₈And R₉Identical or different, each independently is C₁-C₁₀Straight or branched alkyl of (2), C₂-C₁₀Linear or branched alkenyl of (C)₃-C₁₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₁₀Substituted or unsubstituted aryl of (1), C₇-C₁₀Substituted or unsubstituted aralkyl and C₇-C₁₀Is one of substituted or unsubstituted alkaryl groups.

More preferably, in formula II, R₄And R₅The same or different, each independently is hydrogen, C₁-C₆And C is a straight or branched alkyl group₂-C₆One of the linear or branched alkenyl groups of (a); in the formula III, R₁' is C₁-C₆Alkoxy of (2); in formulae II and III, R₆、R₇、R₈And R₉Identical or different, each independently is C₁-C₃Linear or branched alkyl.

Specifically, examples of the internal electron donor compound a may include, but are not limited to: di-n-butyl 2-isopropylmalonate, diisobutyl 2-isopropylmalonate, dipentyl 2-isopropylmalonate, di-n-butyl 2-decylmalonate, diethyl 2- (2-pentyl) malonate, diethyl 2-cyclohexylmalonate, diethyl 2-cyclohexylmethylmalonate, dimethyl 2-cyclohexylmethylmalonate, diethyl 2, 2-dibenzylmalonate, dimethyl 2-n-butyl-2-isobutylmalonate, diethyl 2-isopropyl-2-n-butylmalonate, diethyl ethoxymethylenemalonate, dimethyl ethoxymethylenemalonate, diethyl methoxymethylenemalonate, dimethyl methoxymethylenemalonate.

Most preferablyIn the case of (1), the internal electron donor compound a is a malonate compound represented by the formula III in which R is₁' is ethoxy, R₈And R₉Respectively is ethyl, and the internal electron donor compound a is ethoxymethylene diethyl malonate.

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

The middle bracket of the formula IV [ alpha ], [ alpha]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 IV₁₂、R₁₃The carbon atom directly bonded to the substituent is R₁₄、R₁₅Is bonded to the carbon atom(s) of (a).

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

in formula V, R₁₆、R₁₇、R₁₈、R₁₉、R₂₀And R₂₁Are 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 b 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 dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-methyl-2-methyl-diol, 3-dibenzoate, 2-methyl-2-methyl-diol, 2-methyl-diol, 3-diol, 2-dibenzoate, 2-diol, 2-diol, 2-and/or a mixture, 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, and 3-pentanediol dibenzoate, 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 thereof, 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, 6-methyl-3, 5-heptanediol dibenzoate, and mixtures thereof, 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 b is 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate.

According to the present invention, the internal electron donor comprises a malonate compound and a glycol ester compound, which are capable of generating a certain synergistic effect, and the total amount of the malonate compound and the glycol 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 may vary within a wide range, and preferably the content of the internal electron donor is 6 to 23% by weight based on the total weight of the catalyst component, and more preferably the content of the internal electron donor is 10 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 C of₁-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 the general formula MgX₁Based on magnesium halide of Y, the surface is aliveThe amount of the sex agent is preferably 1 to 20 g.

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 components in the spherical support of the olefin polymerization catalyst can be selected and varied within a wide rangePreferably, 1mol of MgX is used₁The 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 OH compound is 6-20mol, and the dosage of 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 alpha-sulfur, beta-sulfur, gamma-sulfur, and polymeric sulfur. The elemental sulphur may be anhydrous elemental sulphur or elemental sulphur containing bound water. The above elemental sulphur is commercially available.

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: at least one of ethanol, n-propanol, isopropanol, 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 Sizer 2000 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, and the internal electron donor compound b 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 invention adopts the sulfur-containing magnesium compound as a carrier, and uses the internal electron donor compound a and the internal electron donor compound b as internal electron donors in a specific ratio to improve the stereotacticity and the polymer isotactic index of the olefin polymerization catalyst.

According to the invention, in the catalyst component, diethyl ethoxymethylenemalonate is used as an internal electron donor compound a, 2, 4-pentanediol dibenzoate and/or 3, 5-heptanediol dibenzoate is used as an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.005-2.5: 1, a catalyst having a higher stereodirecting ability can be obtained, thereby making the isotactic index of the olefin polymer higher.

In the olefin polymerization catalyst component, the contents of titanium, magnesium, halogen and an internal electron donor are not particularly limited and may be appropriately selected according to the amounts conventionally used in the art. Preferably, the weight ratio of titanium calculated as titanium element, magnesium calculated as magnesium element, halogen calculated as halogen element and internal electron donor is 1: 3-15: 8-30: 2-12; more preferably, the weight ratio of titanium in terms of titanium element, magnesium in terms of magnesium element, halogen in terms of halogen element and internal electron donor is 1: 5-12: 10-25: 4-11.

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 formula XI which is shown in the specification,

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

in 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 compound contains the internal electron donor compound a and the internal electron donor compound b.

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. Adding an internal electron donor compound a and an internal electron donor compound b 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, an internal electron donor 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 and the internal electron donor compound b may be added to the mixture of the magnesium compound and the titanium compound in several times or simultaneously when preparing the catalyst component. When the internal electron donor compound a and the internal electron donor compound b are added to the mixture of the magnesium compound and the titanium compound for several times, the internal electron donor compound a and the internal electron donor compound b can be added first; or the internal electron donor compound b can be added firstly, and then the internal electron donor compound a can be added.

According to the present invention, when the catalyst component is prepared, the amount of the magnesium compound, the titanium compound and the internal electron donor is not particularly limited, and the amount of each component may be varied within a wide range, and preferably, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor is 1: 20-140: 0.1 to 0.8, and more preferably, the molar ratio of the magnesium compound, the titanium compound and the internal electron donor is 1: 30-120: 0.2-0.6.

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.

More preferably, the aluminum alkyl compound is triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydrochloride, diisobutylaluminum monohydrochloride, diethylaluminum monochloride, diisobutylaluminum 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.

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 aluminium in the aluminium alkyl compound and the external electron donor compound is 2-200: 1, more preferably 2.5 to 100: 1.

according to the present invention, the use of the external electron donor compound in combination with the internal electron donor compound a and the internal electron donor compound b can further improve the isotactic index of the olefin polymer obtained by the method of the present invention. 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 shown in formula XIV,

(R₂₉)_m’(R₃₀)_p’Si(OR₃₁)_q’the compound of the formula XIV is shown 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; r is₃₁Is 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 the 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 used for adding propylene into the polymerization reactor after prepolymerization 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. By adopting the catalyst carrier, the malonate compound shown in the formula II and/or the formula III and the diol ester compound shown in the formula IV are compounded in a specific ratio to be used as an internal electron donor, the obtained catalyst component has high stereospecificity and does not contain a phthalate compound (plasticizer), and when the catalyst prepared from the catalyst component is used for olefin polymerization, an olefin polymer with a high isotactic index can be obtained.

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.

The test methods used in the following examples are as follows:

1. the average particle diameter and the particle size distribution of the olefin polymerization catalyst and the carrier were measured using a Masters Sizer 2000 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 alpha-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 epoxy chloropropane, continuing to react 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 carrying out vacuum drying on the product to obtain the olefin polymerization catalyst spherical carrier Z1.

The olefin polymerization catalyst spherical carrier Z1 has an average particle diameter (D50) of 15 micrometers 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 beta-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 epoxy chloropropane, continuing to react at constant temperature of 100 ℃ for 20 minutes, carrying out pressure filtration, washing a 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 olefin polymerization catalyst spherical carrier Z2 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 alpha-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 epoxy chloropropane, continuing to react at constant temperature of 100 ℃ for 20 minutes, carrying out pressure filtration, washing a 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 Z3.

The olefin polymerization catalyst spherical carrier Z3 has an average particle diameter (D50) of 20 micrometers 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 beta-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 for 20 minutes at 60 ℃, 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 olefin polymerization catalyst spherical carrier Z4 has an average particle diameter (D50) of 25 micrometers 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 alpha-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 olefin polymerization catalyst spherical carrier Z5 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, carrying out pressure filtration, washing a pressure filtration product with hexane for 5 times, and finally drying the product in vacuum 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 is intended to illustrate the catalyst component for olefin polymerization, the olefin polymerization catalyst and the olefin polymerization process of the present invention.

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

adding 90mL of titanium tetrachloride into a 300mL glass reaction bottle with a stirrer, fully replacing with high-purity nitrogen, cooling to-20 ℃, adding 8g of carrier Z1 while stirring, gradually heating to 110 ℃, and respectively adding ethoxy during heatingMethylene diethyl malonate (internal electron donor compound a, formula III, R'₁Is ethoxy, R₈And R₉Ethyl) 3mmol and 2, 4-pentanediol dibenzoate (internal electron donor compound b)7mmol, keeping the temperature at 110 ℃ for 0.5h, filtering the liquid, adding 80mL of titanium tetrachloride into the solid phase obtained by filtering, washing with hexane, and drying in vacuum to obtain the spherical catalyst component A1.

(2) Propylene polymerization reaction:

in a 5L high-pressure reaction vessel purged with a nitrogen stream, 2.5mmol of triethylaluminum, 0.1mmol of Cyclohexylmethyldimethoxysilane (CHMMS), 10mL of anhydrous hexane and 8mg of the above spherical catalyst component A1 were introduced into the reaction vessel in a nitrogen stream, the autoclave was closed, and 1.5NL of hydrogen and 2.3L of liquid propylene were introduced. The temperature is raised to 70 ℃ and the polymerization is carried out for 1 hour, thus obtaining the polypropylene. The isotactic index of the obtained polypropylene was 98.5%, and the average particle diameter of the catalyst was 13 μm.

Example 2

An olefin polymerization catalyst component was prepared by the method of example 1, except that 5mmol of ethoxymethylenediethyl malonate and 6.5mmol of 2, 4-pentanediol dibenzoate were added to obtain catalyst component A2.

Polypropylene was prepared according to the method of example 1, except that an equal amount of catalyst component A2 was used in place of catalyst component A1, to obtain polypropylene having an isotactic index of 98.3% and a catalyst average particle diameter of 12 μm.

Example 3

An olefin polymerization catalyst component was prepared by following the procedure of example 1, except that 3.7mmol of ethoxymethylenediethyl malonate was added, and 9mmol of 4-ethyl-3, 5-heptanediol dibenzoate (internal electron donor compound b) was added in place of 2, 4-pentanediol dibenzoate, to obtain catalyst component A3.

Polypropylene was prepared according to the method of example 1, except that an equal amount of catalyst component A3 was used in place of catalyst component A1, to obtain polypropylene having an isotactic index of 98.2% and a catalyst average particle diameter of 13 μm.

Example 4

An olefin polymerization catalyst component was prepared by the method of example 1, except that 0.35mmol of ethoxymethylenediethyl malonate and 6.6mmol of 2, 4-pentanediol dibenzoate were added to obtain catalyst component A4.

Polypropylene was prepared by the method of example 1, except that an equal amount of catalyst component A4 was used in place of catalyst component A1, to obtain polypropylene having an isotactic index of 98.3% and a catalyst average particle diameter of 13 μm.

Example 5

An olefin polymerization catalyst component was prepared by the same procedure as in example 1 except that 7.8mmol of ethoxymethylenediethyl malonate and 5.1mmol of 2, 4-pentanediol dibenzoate were added to give catalyst component A5.

Polypropylene was prepared according to the method of example 1, except that an equal amount of catalyst component A5 was used in place of catalyst component A1, to obtain polypropylene having an isotactic index of 98.1% and a catalyst average particle diameter of 14 μm.

Comparative example 1

This comparative example is illustrative of a reference olefin polymerization catalyst component, a reference olefin polymerization catalyst, and an olefin polymerization process of the present invention.

Preparing a catalyst: into a 300mL stirred glass reaction flask fully substituted with high purity nitrogen gas was charged 90mL of titanium tetrachloride, cooled to-20 ℃ and added under stirring 8g of an alcohol adduct of spherical magnesium dichloride (MgCl)₂·2.6C₂H₅OH, synthesized by using magnesium dichloride and ethanol according to the method disclosed in CN 1330086A), gradually raising the temperature to 110 ℃, adding 7mmol of 2, 4-pentanediol dibenzoate (an internal electron donor compound B) in the process of raising the temperature, keeping the temperature at 110 ℃ for 0.5h, filtering out liquid, adding 80mL of titanium tetrachloride into the solid phase obtained by filtering, treating the titanium tetrachloride, washing the titanium tetrachloride with hexane, and drying the titanium tetrachloride in vacuum to obtain the catalyst component B1.

Polypropylene was prepared by the method of example 1 using the above catalyst component B1 in place of the olefin polymerization catalyst component A1. The isotactic index of the obtained polypropylene was 96.1%, and the average particle diameter of the catalyst was 41 μm.

Comparative example 2

An olefin polymerization catalyst component was prepared by following the procedure of comparative example 1, except that in the preparation of the catalyst component, 7.8mmol of diethyl ethoxymethylenemalonate was added without adding 2, 4-pentanediol dibenzoate, to obtain catalyst component B2.

The above catalyst component B2 was used in place of the olefin polymerization catalyst component A1 and polypropylene was produced by the method of example 1. The isotactic index of the obtained polypropylene was 79.1%, and the average particle diameter of the catalyst was 40 μm.

Comparative example 3

An olefin polymerization catalyst component was prepared by the method of comparative example 1, except that 0.01mmol of ethoxymethylenediethyl malonate and 7mmol of 2, 4-pentanediol dibenzoate were added to obtain catalyst component B3.

The above catalyst component B3 was used in place of the olefin polymerization catalyst component A1 and polypropylene was produced by the method of example 1. The isotactic index of the obtained polypropylene was 96.3%, and the average particle diameter of the catalyst was 40 μm.

Comparative example 4

An olefin polymerization catalyst component was prepared by the method of comparative example 1, except that 8.2mmol of ethoxymethylenediethyl malonate and 3mmol of 2, 4-pentanediol dibenzoate were added to obtain catalyst component B4.

The above catalyst component B4 was used in place of the olefin polymerization catalyst component A1 and polypropylene was produced by the method of example 1. The isotactic index of the obtained polypropylene was 86.7%, and the average particle diameter of the catalyst was 41 μm.

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 carrier DZ1 to obtain 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 isotactic index of the obtained polypropylene was 96.8%, and the average particle diameter of the catalyst was 57 μm.

It can be seen from the results of examples 1-5 and comparative examples 1-4 that the stereospecificity of the catalyst can be significantly improved by using the sulfur-containing magnesium compound of the present invention as a carrier, compounding the malonate compound and the glycol ester compound as components of the internal electron donor, and controlling the molar ratio of the two within a certain range, so that the isotactic index of the obtained polymer is significantly improved.

As can be seen from the results of comparing example 1 with comparative example 5, the catalyst of the present invention, which uses a sulfur-containing magnesium compound as a carrier, has a stereospecificity significantly higher than that of a catalyst using a sulfur-free magnesium compound as a 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;

x is halogen;

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;

wherein the internal electron donor compound contains an internal electron donor compound a and an internal electron donor compound b, and the molar ratio of the internal electron donor compound a to the internal electron donor compound b is 0.005-2.5: 1; the internal electron donor compound a is a malonate compound shown in a formula II and/or a formula III, the internal electron donor compound b is a diol ester compound shown in a formula IV,

in the formula III, R₁' is C₁-C₂₀Alkoxy group of (a);

in formulae II and III, R₆、R₇、R₈And R₉Identical or different, each independently is C₁-C₂₀Straight or branched alkyl of (2), C₂-C₂₀Linear or branched alkylene 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, R₆And R₇Bonded to each other to form a ring and/or R₈And R₉Bonding to form a ring;

in the formula IV, R₁₀And R₁₁Identical 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 of (1), 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);

n is an integer of 0 to 10.

2. The catalyst component according to claim 1 in which X is chlorine or bromine.

3. The catalyst component according to claim 1 in which the molar ratio of the internal electron donor compound a to the internal electron donor compound b is from 0.007 to 2: 1.

4. the catalyst component according to claim 3 in which the molar ratio of the internal electron donor compound a to the internal electron donor compound b is between 0.05 and 1.5: 1.

5. 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;

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 (1);

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).

6. The catalyst component according to claim 5 in which the sulphur-containing magnesium compound is obtained by a process comprising the steps of:

7. The catalyst component according to claim 6 in which the inert liquid medium is a silicone-oil type solvent and/or a hydrocarbon type solvent; 1mol of MgX₁Based on the magnesium halide of Y, toThe dosage of the inert liquid medium is 0.8-10L.

8. The catalyst component according to claim 7 in which 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.

9. The catalyst component according to claim 6 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.

10. The catalyst component according to claim 6 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; in the step (2), the contact reaction conditions include: the temperature is 40-120 ℃ and the time is 15-60 minutes.

11. The catalyst component according to claim 10 in which in step (1) the heating is carried out at a temperature of 80 to 100 ℃ for a time of 0.5 to 3 hours.

12. The catalyst component according to claim 10 in which in step (2) the conditions of the contact reaction comprise: the temperature is 60-100 ℃, and the time is 20-50 minutes.

13. According to claimThe catalyst component according to any of claims 5 to 12 in which 1mol of MgX is present₁The 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 the OH compound is 4-30mol, and the dosage of the ethylene oxide compound is 1-10 mol.

14. The catalyst component according to claim 13 in which MgX is present in 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.

15. The catalyst component according to any of claims 5-12 in which the elemental sulphur is selected from at least one of alpha sulphur, beta sulphur, gamma sulphur and polymeric sulphur.

16. The catalyst component according to any of claims 5 to 12 in which the general formula MgX₁In Y, X₁Is chlorine or bromine, Y is chlorine, bromine, C₁-C₅Alkoxy or C₆-C₁₀An aryloxy group of (1).

17. The catalyst component according to claim 16 in which 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.

18. The catalyst component according to any of claims 5 to 12 in which R is of the general formula₁In OH, R₁Is C₁-C₈The alkyl group of (1).

19. The catalyst component according to claim 18 in which R is of formula₁The 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.

20. The catalyst component according to any of claims 5-12 in which in the oxirane compound of formula X, R is₂₅And R₂₆Each independently is hydrogen, C₁-C₃Alkyl or C₁-C₃A haloalkyl group of (a).

21. The catalyst component according to claim 20 in which the oxirane is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, chlorobutylene oxide, propylene bromide oxide and butylene bromide oxide.

22. 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 and a particle size distribution of less than 1.2.

23. The catalyst component according to claim 22 in which the sulphur-containing magnesium compound has an average particle diameter of less than or equal to 20 microns.

24. The catalyst component according to claim 22 in which the particle size distribution is 0.8 or less.

25. The catalyst component according to any of claims 1 to 12 and 22 to 24 in which in formula II R₄And R₅The same or different, each independently is hydrogen, C₁-C₁₀Straight or branched alkyl of (2), C₂-C₁₀Linear or branched alkenyl of (C)₃-C₁₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₁₀Substituted or unsubstituted aryl of (1), C₇-C₁₀Substituted or unsubstituted aralkyl and C₇-C₁₀One of substituted or unsubstituted alkaryl groups;

in the formula III, R₁' is C₁-C₁₀Alkoxy group of (a);

in formulae II and III, R₆、R₇、R₈And R₉Identical or different, each independently is C₁-C₁₀Straight or branched alkyl of (2), C₂-C₁₀Linear or branched alkenyl of (C)₃-C₁₀Substituted or unsubstituted cycloalkyl of (A), C₆-C₁₀Substituted or unsubstituted aryl of (1), C₇-C₁₀Substituted or unsubstituted aralkyl and C₇-C₁₀Is one of substituted or unsubstituted alkaryl groups.

26. The catalyst component according to claim 25 in which in formula II R₄And R₅The same or different, each independently is hydrogen, C₁-C₆And C is a straight or branched alkyl group₂-C₆One of the linear or branched alkenyl groups of (a); in the formula III, R₁' is C₁-C₆Alkoxy group of (a); in formulae II and III, R₆、R₇、R₈And R₉Identical or different, each independently is C₁-C₃Linear or branched alkyl.

27. The catalyst component according to any of claims 1-12 and 22-24 in which the internal electron donor compound b is a diol ester compound of formula v,

28. The catalyst component according to any of claims 1 to 12 and 22 to 24 in which the weight ratio of titanium, magnesium, halogen and internal electron donor, calculated as titanium element, magnesium element, halogen element and internal electron donor in the catalyst component for olefin polymerization is 1: 3-15: 8-30: 2-12.

29. The catalyst component according to claim 28 in which the weight ratio of titanium, magnesium, halogen and internal electron donor, calculated as halogen, is 1: 5-12: 10-25: 4-11.

30. Use of the catalyst component according to any one of claims 1 to 29 for the preparation of a catalyst for the polymerization of olefins.

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

(1) the catalyst component of any one of claims 1 to 29;

(2) an alkyl aluminum compound; and

(3) optionally an external electron donor compound.

32. Use of the catalyst of claim 31 in olefin polymerization reactions.

33. An olefin polymerization process, comprising: contacting one or more olefins with the catalyst of claim 31 under olefin polymerization conditions.