Olefin polymerization catalyst component, catalyst system and application thereof and olefin polymerization method

Abstract

The present invention provides an olefin polymerization catalyst component, a catalyst system and an olefin polymerization method. The catalyst component contains magnesium, titanium, halogen and an internal electron donor, wherein the internal electron donor comprises a compound A, a compound B and a compound C, wherein the compound A is selected from a hydroxybenzoyl compound as shown in formula (I), the compound B is selected from an ester or ether compound other than the compound A, and the compound C is selected from a compound as shown in formula R n Si(OR6) 4‑n The alkoxysilane shown. When the catalyst component of the present invention is used together with the co-catalyst component for copolymerization of olefins (especially ethylene and propylene), it shows excellent olefin copolymerization ability while maintaining good polymerization activity, orientation ability and hydrogen adjustment sensitivity. In addition, the morphology of the polymer particles obtained by the catalyst component and the catalyst system catalyzing olefins is very good. #imgabs0#

Description

Technical Field

[0001] The invention relates to an olefin polymerization catalyst component and a catalyst system and application thereof and an olefin polymerization method. Background Art

[0002] It is well known in the prior art that a titanium compound and an electron donor compound are supported on an active magnesium halide to prepare a Ziegler-Natta catalyst. In particular, when used for olefin (especially propylene) polymerization, the electron donor compound is one of the essential components of the catalyst component in order to improve the polymerization activity, stereospecificity, hydrogen sensitivity and olefin copolymerization ability of the catalyst.

[0003] With the development of electron donor compounds, polyolefin catalysts are constantly updated. So far, many patents have disclosed a large number of electron donor compounds suitable for preparing Ziegler-Natta catalysts, mainly including: phthalate compounds (EP0045977), 1,3-diether compounds (EP0361493, EP0728724), 1,3-diketone compounds (CN1105671A), special substituted malonate compounds (CN1236732A, CN1236733A, CN1236734A, C N1292800A), succinate compounds (WO0063261, US6825309B2, US7005487B2), β-substituted glutaric acid ester compounds (WO0055215), cyano ester compounds (CN1242780A), diamine compounds (CN1087918A), maleic acid diester compounds (WO03022894) and special polyester compounds (CN1436766A, CN1436796A), etc.

[0004] The use of different internal electron donor compounds will make the prepared catalysts have different properties, such as some catalysts have higher polymerization activity, some catalysts have better hydrogen sensitivity, and some catalysts prepare polyolefin resins with wider molecular weight distribution (such as the diol ester compounds and catalysts disclosed in CN1436766A and CN1552740A). However, in the industrial production of polyolefins, it is very necessary for the catalyst used in polymerization to have very good comprehensive performance. In the prior art, people usually use the method of adding multiple internal electron donor compounds in the catalyst preparation process to improve the comprehensive performance of the catalyst. For example, in the technology disclosed in US6825309 B2, the catalyst prepared by compounding succinate and phthalate not only maintains the characteristics of the wide molecular weight distribution of the polymer obtained by using the succinate single internal electron donor catalyst for propylene polymerization, but also further improves the stereospecificity of the catalyst; the catalyst component and catalyst disclosed in CN1743346A, using the catalyst prepared by compounding 1,3-diol ester with dibutyl phthalate and ethyl benzoate for propylene polymerization, the polymer obtained has higher isotacticity and wider molecular weight distribution.

[0005] With the needs of social development, catalysts with good olefin copolymerization performance have become a very important research direction in this field. CN102796213B selects a catalyst prepared by compounding hydroxybenzoyl compounds with phthalate compounds or diether compounds, and shows high polymerization activity, good hydrogen adjustment sensitivity and high directional ability when used for propylene homopolymerization. However, practical applications show that when such catalysts are used for olefin copolymerization reactions, the olefin copolymerization ability of the catalyst is relatively insufficient. In this field, alkoxysilane compounds are usually used as external electron donors to improve the hydrogen adjustment sensitivity of the catalyst system. CN103509137A found that alkoxysilane compounds can effectively shorten the preparation time of the catalyst component when used for the precipitation method to prepare olefin polymerization catalyst components, and have an improving effect on the particle morphology and polymer fine powder content of the catalyst.

[0006] The applicant unexpectedly discovered that the catalyst prepared by using alkoxysilane compounds as internal electron donors and compounding them with hydroxybenzoyl compounds, ester compounds or with hydroxybenzoyl compounds and diether compounds can significantly improve the olefin copolymerization ability while maintaining good polymerization activity, directional ability and hydrogen regulation performance. Summary of the invention

[0007] The present invention aims to provide a catalyst component for olefin polymerization, which, when used together with an alkyl aluminum and an optional external electron donor compound for olefin (especially ethylene and propylene) copolymerization, exhibits excellent olefin copolymerization ability while maintaining good polymerization activity, orientation ability and hydrogen sensitivity. In addition, the morphology of polymer particles obtained by catalyzing olefins by the catalyst component and the catalyst system is very good.

[0008] The present invention provides an olefin polymerization catalyst component, which contains magnesium, titanium, halogen and an internal electron donor. The internal electron donor comprises a compound A, a compound B and a compound C. The compound A is selected from a hydroxybenzoyl compound as shown in formula (I), the compound B is selected from an ester or ether compound other than the compound A, and the compound C is selected from a compound as shown in formula R n Si(OR6) 4-n The alkoxysilane shown,

[0009]

[0010] In formula (I), R1 is selected from hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 R2, R3, R4 and R5 are each independently selected from hydrogen, halogen, nitro, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 or two or more of R2, R3, R4 and R5 are bonded to each other to form a ring;

[0011] Formula R n Si(OR6) 4-n In which R and R6 are each independently selected from hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups, wherein n is an integer of 0-3.

[0012] According to the present invention, the catalyst component may be formed by reacting a titanium-containing compound and an internal electron donor supported on a magnesium halide, which is a magnesium dihalide in an activated state.

[0013] The present invention also provides a catalyst system for olefin polymerization, wherein the catalyst system comprises the following components or the reaction product of the following components:

[0014] a. the above-mentioned catalyst component;

[0015] b. Alkyl aluminum compounds;

[0016] c. Optionally, at least one external electron donor compound.

[0017] The present invention also provides a use of the catalyst system according to the present invention in olefin polymerization.

[0018] The present invention further provides an olefin polymerization process, which comprises contacting one or more olefins with the above-mentioned catalyst system of the present invention under olefin polymerization conditions.

[0019] The inventors of the present invention unexpectedly discovered through repeated experiments and studies that the catalyst components and catalyst systems of the present invention, which are synthesized by using alkoxysilane compounds in combination with hydroxybenzoyl compounds and other esters or ethers as internal electron donors, show better olefin copolymerization ability when used for olefin (especially ethylene and propylene) copolymerization, and their polymerization activity is also high, and the morphology of the polymer particles obtained by polymerization is also very good. DETAILED DESCRIPTION

[0020] The present invention provides an olefin polymerization catalyst component, which contains magnesium, titanium, halogen and an internal electron donor. The internal electron donor comprises a compound A, a compound B and a compound C. The compound A is selected from a hydroxybenzoyl compound as shown in formula (I), the compound B is selected from an ester or ether compound other than the compound A, and the compound C is selected from a compound as shown in formula R n Si(OR6) 4-n The alkoxysilane shown,

[0021]

[0022] In formula (I), R1 is selected from hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 R2, R3, R4 and R5 are each independently selected from hydrogen, halogen, nitro, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C20 or two or more of R2, R3, R4 and R5 are bonded to each other to form a ring;

[0023] Formula R n Si(OR6) 4-n In the formula (a), R and R6 are each independently hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups, wherein n is an integer of 0-3.

[0024] According to the present invention, preferably, in formula (I), R1 is hydrogen, a C1-C6 straight-chain alkyl, a C3-C6 branched-chain alkyl, a C3-C6 cycloalkyl, a C6-C 10 The aromatic and C7-C 10 R2, R3, R4 and R5 are each independently hydrogen, C1-C8 straight chain alkyl, C3-C8 branched chain alkyl, C3-C6 cycloalkyl, C6-C 10 The aromatic and C7-C 10 One of the aralkyl groups.

[0025] According to the present invention, preferably, in formula (I), R1 is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, benzyl and phenethyl; R2, R3, R4 and R5 are each independently one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl.

[0026] According to the present invention, when compound A is a hydroxybenzoyl compound represented by formula (I), compound A is preferably one of 4-hydroxybenzoic acid compounds, 4-hydroxybenzoic acid ester compounds, 2-hydroxybenzoic acid compounds and 2-hydroxybenzoic acid ester compounds; more preferably one of 2-hydroxybenzoic acid compounds and 2-hydroxybenzoic acid ester compounds.

[0027] According to the present invention, specific examples of compound A may include, but are not limited to: methyl 2-hydroxybenzoate, ethyl 2-hydroxybenzoate, n-propyl 2-hydroxybenzoate, isopropyl 2-hydroxybenzoate, n-butyl 2-hydroxybenzoate, isobutyl 2-hydroxybenzoate, n-pentyl 2-hydroxybenzoate, n-hexyl 2-hydroxybenzoate, methyl 2-hydroxy-3-methylbenzoate, methyl 2-hydroxy-4-methylbenzoate, methyl 2-hydroxy-5-methylbenzoate, methyl 2-hydroxy-3-ethylbenzoate, methyl 2-hydroxy-4-ethylbenzoate. Methyl formate, methyl 2-hydroxy-5-ethylbenzoate, ethyl 2-hydroxy-3-methylbenzoate, ethyl 2-hydroxy-4-methylbenzoate, ethyl 2-hydroxy-5-methylbenzoate, ethyl 2-hydroxy-3-ethylbenzoate, ethyl 2-hydroxy-4-ethylbenzoate, ethyl 2-hydroxy-5-ethylbenzoate, n-propyl 2-hydroxy-3-methylbenzoate, n-propyl 2-hydroxy-4-methylbenzoate, n-propyl 2-hydroxy-5-methylbenzoate, n-propyl 2-hydroxy-3-ethylbenzoate, n-propyl 2-hydroxy-4-methylbenzoate Ethyl benzoate, n-propyl 2-hydroxy-5-ethyl benzoate, isopropyl 2-hydroxy-3-methyl benzoate, isopropyl 2-hydroxy-4-methyl benzoate, isopropyl 2-hydroxy-5-methyl benzoate, isopropyl 2-hydroxy-3-ethyl benzoate, isopropyl 2-hydroxy-4-ethyl benzoate, isopropyl 2-hydroxy-5-ethyl benzoate, isobutyl 2-hydroxy-3-methyl benzoate, isobutyl 2-hydroxy-4-methyl benzoate, isobutyl 2-hydroxy-5-methyl benzoate, 2-hydroxy-3-ethyl benzoate 2-hydroxy-4-isobutylbenzoate, ethyl 2-hydroxy-4-tert-butylbenzoate, ethyl 2-hydroxy-4-n-pentylbenzoate, ethyl 2-hydroxy-4-isopentylbenzoate, ethyl 2-hydroxy-4-tert-butylbenzoate, ethyl 2-hydroxy-4-n-pentylbenzoate, ethyl 2-hydroxy-4-isopentylbenzoate and ethyl 2-hydroxy-4-cyclopentylbenzoate.

[0028] According to the present invention, the compound B is selected from one or more of ester and diether compounds other than compound A.

[0029] In the present invention, the ester can be one or more of monoaliphatic carboxylic acid esters, polyaliphatic carboxylic acid esters, monoaliphatic carboxylic acid esters, polyaliphatic carboxylic acid esters and diol ester compounds; preferably polyaliphatic carboxylic acid esters; more preferably polyaliphatic carboxylic acid alkyl esters; further preferably dialiphatic carboxylic acid alkyl esters.

[0030] According to the present invention, the dibasic aromatic carboxylic acid alkyl ester is an alkyl phthalate, preferably a C1-C1 alkyl phthalate. 10Straight chain alkyl esters of phthalic acid, C3-C 10 Branched chain alkyl esters and C3-C 10 One or more of the cycloalkyl esters.

[0031] In the present invention, the term "monoaliphatic carboxylic acid ester" refers to a compound formed by an esterification reaction between a monoaliphatic carboxylic acid and a monohydric alcohol. The term "polyaliphatic carboxylic acid ester" refers to a compound formed by an esterification reaction between a polyaliphatic carboxylic acid and a monohydric alcohol. The term "monoaliphatic aromatic carboxylic acid ester" refers to a compound formed by an esterification reaction between a monoaliphatic carboxylic acid and a monohydric alcohol. The term "polyaliphatic aromatic carboxylic acid ester" refers to a compound formed by an esterification reaction between a polyaliphatic carboxylic acid and a monohydric alcohol.

[0032] In the present invention, examples of the monobasic aliphatic carboxylates, polybasic aliphatic carboxylates, monobasic aromatic carboxylates and polybasic aromatic carboxylates may be: benzoates, phthalates, malonates, succinates, glutarates, pivalates and carbonates; preferably alkyl benzoates, alkyl phthalates, alkyl malonates, alkyl succinates, alkyl glutarates, alkyl pivalates and alkyl carbonates.

[0033] Specifically, in the present invention, examples of the monobasic aliphatic carboxylates, polybasic aliphatic carboxylates, monobasic aromatic carboxylates and polybasic aromatic carboxylates may include, but are not limited to, ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diisobutyl malonate, diethyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, di-n-butyl 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, 2,3-diisopropylsuccinate, dimethyl 2,3-diisopropylsuccinate, diisobutyl ...isobutyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisooctyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisooctyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisooctyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisooctyl 2,3-diisopropylsuccinate, diisobutyl 2,3-diisopropylsuccinate, diisooctyl diisobutyl 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl glutarate, di-n-butyl glutarate, diisobutyl glutarate, dimethyl carbonate, diethyl carbonate, diisobutyl carbonate, diethyl adipate, di-n-butyl adipate, diethyl sebacate, di-n-butyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalene dicarboxylate, di-n-butyl naphthalene dicarboxylate, triethyl trimellitate, tri-n-butyl trimellitate, triethyl biphenyl trimellitate, tri-n-butyl biphenyl trimellitate, tetraethyl pyromellitate and tetra-n-butyl pyromellitate.

[0034] In the present invention, the term "diol ester" refers to a compound formed by esterification of a diol with a monocarboxylic acid or a polycarboxylic acid. For example, the diol ester may be a compound represented by formula (II):

[0035]

[0036] In formula (II), R I , R II , R III , R IV , R V and R VI are independently hydrogen, C1-C 10 Aliphatic hydrocarbon groups, C6-C 10 The aromatic and C7-C 10 One of the aralkyl groups; or, R I , R II , R III , R IV , R V and R VI Two or more of R are bonded to each other to form a ring; VII and R VIII Each independently is C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aromatic aliphatic hydrocarbon groups.

[0037] Preferably, in formula (II), R I , R II , R III , R IV , R V and R VI are independently hydrogen, C1-C6 straight chain alkyl, C1-C6 branched chain alkyl, C2-C6 straight chain alkenyl, C3-C6 branched chain alkenyl, C3-C6 cycloalkyl, C6-C 10 The aromatic and C7-C 10 One of the aralkyl groups; or, R I , R II , R III , R IV , R V and R VI Two or more of R are bonded to each other to form a ring; VII and R VIII Each is independently a C1-C6 straight chain alkyl, a C3-C6 branched chain alkyl, a C3-C6 cycloalkyl, a C6-C 10 Aryl, C7-C 10 Arylalkyl and C7-C 10 One of the aromatic alkenyl groups.

[0038] More preferably, in formula (II), R I , R II, R V and R VI At least one of is hydrogen, and R I , R II , R V and R VI Not hydrogen at the same time.

[0039] More preferably, in formula (II), R I and R II At least one of them is hydrogen, and in R I and R II When only one of them is hydrogen, R I and R II The other group in is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl and halogenated phenyl; R V and R VI At least one of them is hydrogen, and in R V and R VI When only one of them is hydrogen, R V and R VI The other group in is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl and halogenated phenyl; R III and R IV Each of them is one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, allyl, n-pentyl, isopentyl and n-hexyl, or, R III and R IV bonded to each other to form a substituted or unsubstituted fluorenyl group; R VII and R VIII Each is one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, neopentyl, cyclopentyl, cyclohexyl, phenyl, halogenated phenyl, tolyl, halogenated methylphenyl, benzyl, phenethyl and styryl.

[0040] Specifically, examples of the diol ester compound may include, but are not limited to:

[0041] 1,3-Propanediol dibenzoate, 2-methyl-1,3-propanediol dibenzoate, 2-ethyl-1,3-propanediol dibenzoate, 2,2-dimethyl-1,3-propanediol dibenzoate, (R)-1-phenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol di-n-propionate, 1,3-diphenyl-2-methyl-1,3-propanediol di-n-propionate, 1,3-diphenyl-2-methyl-1,3-propanediol diacetate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-2,2-dimethyl-1,3-propanediol di-n-propionate, 1,3- Di-tert-butyl-2-ethyl-1,3-propanediol dibenzoate, 1,3-diphenyl-1,3-propanediol diacetate, 1,3-diisopropyl-1,3-propanediol di(4-n-butylbenzoate), 1-phenyl-2-amino-1,3-propanediol dibenzoate, 1-phenyl-2-methyl-1,3-butanediol dibenzoate, 1-phenyl-2-methyl-1,3-butanediol dipivalate, 3-n-butyl-2,4-pentanediol dibenzoate, 3,3-dimethyl-2,4-pentanediol dibenzoate, (2S,4S)-(+)-2,4-pentanediol dibenzoate, (2R,4R)-(+)-2,4-pentanediol dibenzoate, 2,4-pentanediol di(p-chlorobenzoate) 、2,4-pentanediol di(m-chlorobenzoate), 2,4-pentanediol di(p-bromobenzoate), 2,4-pentanediol di(o-bromobenzoate), 2,4-pentanediol di(p-methylbenzoate), 2,4-pentanediol di(p-tert-butylbenzoate), 2,4-pentanediol di(p-n-butylbenzoate), 2-methyl-1,3-pentanediol di(p-chlorobenzoate), 2-methyl-1,3-pentanediol di(p-methylbenzoate), 2-n-butyl-1,3-pentanediol di(p-methylbenzoate), 2-methyl-1,3-pentanediol di(p-tert-butylbenzoate), 2-methyl-1,3-pentanediol dipivalate, 2-methyl-3-cinnamoyloxy-1-n-pentanol benzoate, 2,2-di Methyl-1,3-pentanediol dibenzoate, 2,2-dimethyl-3-cinnamoyloxy-1-n-pentanediol benzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-n-butyl-1,3-pentanediol dibenzoate, 2-allyl-1,3-pentanediol dibenzoate, 2-methyl-1,3-pentanediol dibenzoate, 2-ethyl-1,3-pentanediol dibenzoate, 2-n-propyl-1,3-pentanediol dibenzoate, 2-n-butyl-1,3-pentanediol dibenzoate, 2,2-di-n-propyl-1,3-pentanediol dibenzoate, 1,3-pentanediol di(p-chlorobenzoate), 1,3-pentanediol di(m-chlorobenzoate), 1,3-pentanediol di(p-bromobenzoate), 1,3-Pentanediol di(o-bromobenzoate), 1,3-Pentanediol di(p-methylbenzoate), 1,3-Pentanediol di(p-tert-butylbenzoate), 1,3-Pentanediol di(p-butylbenzoate), 3-Cinnamoyloxy-1-n-pentylbenzoate, 1,3-Pentanediol dicinnamate, 1,3-Pentanediol dipropionate, 2-Ethyl-1,3-pentanediol dibenzoate, 2-n-butyl-1,3-pentanediol dibenzoate, 2-allyl-1,3-pentanediol dibenzoate, 2,2,4-trimethyl-1,3-pentanediol diisopropylcarboxylate, 1-trifluoromethyl-3-methyl-2,4-pentanediol dibenzoate, 2,4-pentanediol di-p-fluoromethylbenzoate, 2,4-pentanediol di 2-Methyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3-methyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 4-methyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 5-methyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 6-methyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3-ethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 4-ethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 5-ethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 6-ethyl- 6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3-n-propyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 4-n-propyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 5-n-propyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 6-n-propyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 3-n-butyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 4-n-butyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 5-n-butyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate, 6-n-butyl-6-(1-n-heptene)-2,4-heptanediol dibenzoate 3,5-dimethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,5-diethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,5-di-n-propyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,5-di-n-butyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,3-dimethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,3-diethyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,3-di-n-propyl-6-(1-n-heptenyl)-2,4-heptanediol dibenzoate, 3,3-di-n-butyl-6-(1-n-heptyl)-2,4-heptanediol dibenzoate, 3-ethyl-3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 3-n-propyl-3,5-heptanediol dibenzoate, 4-n-propyl-3,5-heptanediol dibenzoate, 3-n-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, 3,5-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 4,5-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 6,6-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, 4-methyl-3-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3,5-heptanediol dibenzoate Benzoate, 9,9-bis(benzoyloxymethyl)fluorene, 9,9-bis((m-methoxybenzoyloxy)methyl)fluorene, 9,9-bis((m-chlorobenzoyloxy)methyl)fluorene, 9,9-bis((p-chlorobenzoyloxy)methyl)fluorene, 9,9-bis(cinnamoyloxymethyl)fluorene, 9-(benzoyloxymethyl)-9-(propionyloxymethyl)fluorene, 9,9-bis(propionyloxymethyl)fluorene, 9,9-bis(acryloyloxymethyl)fluorene and 9,9-bis(pivaloyloxymethyl)fluorene.

[0042] The above-mentioned diol ester compounds are disclosed in CN1213080C, CN1169845C, WO 03 / 068828 and WO03 / 068723, and the relevant contents thereof are hereby incorporated into the present invention by reference.

[0043] According to the present invention, the diether compound is preferably a 1,3-diether compound as shown in formula (III),

[0044]

[0045] In formula (III), R 1 , R 2 , R 3 , R 4 , R 5 and R6 are independently hydrogen, halogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups; or, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two or more of R are bonded to each other to form a ring; 7 and R 8 Each independently is C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups.

[0046] Preferably, in formula (III),

[0047] R 1 , R 2 , R 5 and R 6 is hydrogen;

[0048] R 7 and R 8 Each is a C1-C4 straight chain or branched alkyl group, more preferably a methyl group;

[0049] R 3 is one of methyl, ethyl, n-propyl and isopropyl, R 4 is one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl and benzyl; or, R 3 is hydrogen, R 4 is one of ethyl, n-butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl and 1-decalinyl; or, R 3 and R 4 are the same and are one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl and cyclopentyl; or, R 3 and R 4 They are bonded to each other to form a cyclopentadienyl group, a fluorenyl group or an indenyl group.

[0050] The 1,3-diether compounds mentioned above in the present invention are disclosed in CN1015062B and CN1121368C, and all the relevant contents disclosed therein are incorporated herein by reference.

[0051] According to the present invention, the alkoxysilane R n Si(OR6) 4-n In the formula (a), R and R6 are each independently hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 Preferably, R and R6 are each independently hydrogen, a C1-C6 straight chain alkyl, a C3-C6 branched chain alkyl, a C3-C6 cycloalkyl, a C6-C 10 The aromatic and C7-C 10 More preferably, R and R6 are each independently one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl, 2-hydroxyethyl, 3-hydroxypropyl, and n is 0 or 1.

[0052] Specifically, the alkoxysilane R n Si(OR6) 4-n Examples may include, but are not limited to, one or more of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra-n-pentoxysilane, tetraisopentoxysilane, diethoxydimethoxysilane, tetra(2-hydroxyethoxy)silane and tetra(3-hydroxypropoxy)silane, diphenyldimethoxysilane, diphenyldiethoxysilane, propyltrimethoxysilane, and propyltriethoxysilane.

[0053] The catalyst component according to the present invention, in addition to the above three types of electron donor compounds, also comprises titanium, magnesium and halogen. Preferably, the catalyst component is a reaction product of a titanium-containing compound and compound A, compound B, and compound C loaded on a magnesium halide, wherein the magnesium halide preferably has an activated magnesium dihalide, more preferably activated magnesium dichloride. This magnesium dichloride is well known in the art as a carrier of a Ziegler-Natta catalyst. Typically, this magnesium dichloride with an activated state is characterized in that, in an X-ray diffraction pattern, the intensity of the strongest diffraction peak that appears in the diffraction pattern of inactive magnesium dichloride is reduced and expanded into a halo.

[0054] According to the present invention, the preparation method of the activated magnesium dihalide is well known in the art. Generally, it can be obtained by grinding inactive magnesium dihalide by a grinder; it can also be obtained by reacting alkyl magnesium halide, alkyl magnesium, alkoxy magnesium or inactive magnesium dihalide with a halide (such as aluminum halide, halosilane or titanium halide) in a solvent system; it can also be obtained by reacting inactive magnesium dihalide with one or more of ester, alcohol and ether electron donor compounds to form a magnesium halide adduct, the magnesium halide adduct selectively contains trace water, and then by chemical reaction or heating treatment under negative pressure, the coordinated electron donor is removed to obtain activated magnesium dihalide. According to the different preparation methods of the activated magnesium dihalide, compared with the preparation of olefin polymerization catalyst components, the activated magnesium dihalide can be prepared in advance, or it can be obtained simultaneously during the preparation process of olefin polymerization catalyst components.

[0055] According to the present invention, the titanium-containing compound is a titanium trihalide and a general formula Ti(OR′) 4－m X′ m One or more of the titanium compounds shown in the formula, wherein R' is C1-C 10 Straight chain alkyl and C3-C 10 wherein X′ is a halogen, and m is an integer of 0-4. Preferably, the titanium-containing compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium trichloride, titanium tributoxide, titanium trichloride, titanium trichloride, titanium triethoxide, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium tetra ... trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium trichloride, titanium tri

[0056] The preparation of the olefin polymerization catalyst component of the present invention can be carried out according to various known methods. For example, the preparation method of the solid catalyst component described in CN1006071B can be used, firstly, inactive magnesium halide is dissolved in a solvent system to form a solution, then titanium-containing compound and compound A, compound B and compound C of the present invention are added, and in the presence of a precipitation aid, the olefin polymerization catalyst component containing active centers is separated out again by heating. The activated magnesium halide is generated simultaneously in the above reaction. The relevant contents described in CN1006071B are hereby incorporated into the present invention as a reference.

[0057] Alternatively, a magnesium halide adduct may be prepared first, preferably a magnesium halide adduct of the general formula MgX 1 X 2 ·m(R″OH)·nE·qH2O, and the adduct particles are spherical, wherein m is 1.0-5.0, n is 0-1.0, and q is 0-0.8; X 1 and X 2Each is one of chlorine and bromine; R″ is one of a C1-C4 straight-chain alkyl group and a C3-C4 branched-chain alkyl group; E is an electron donor compound, which can be an ether or an ester. Preferably, m is 1.5-3.5, and n is 0-0.5. The magnesium halide adduct particles are then reacted with a titanium-containing compound, compound A, compound B, and compound C to finally obtain an olefin polymerization catalyst component containing activated magnesium halide. The preparation of this olefin polymerization catalyst component can be carried out with reference to the methods disclosed in CN1036011C, CN1151183C, CN101565475A, CN101486776B and CN102796213B, and the relevant contents disclosed therein are fully introduced into the present invention as a reference.

[0058] In any preparation method, compound A, compound B and compound C can be added before, during or after the reaction of magnesium halide or magnesium halide adduct with titanium-containing compound; preferably, they are added during the reaction with titanium-containing compound. According to the present invention, compound A, compound B and compound C can also be added simultaneously or in steps, and compound A, compound B and compound C can also be added in multiple times, and the order of adding compound A, compound B and compound C can be irrelevant.

[0059] In the preparation process of the catalyst component of the present invention, the molar ratio of compound A, compound B, compound C and the titanium-containing compound to the magnesium halide can be 0.005-0.4:0.01-0.5:0.005-0.4:5-100:1 per mol of magnesium; preferably, the molar ratio of compound A, compound B, compound C and the titanium-containing compound to the magnesium halide is 0.01-0.25:0.05-0.35:0.01-0.25:15-90:1; more preferably, the molar ratio of compound A, compound B, compound C and the titanium-containing compound to the magnesium halide is 0.02-0.18:0.05-0.25:0.015-0.15:25-80:1.

[0060] In addition, the present invention also provides a catalyst system for olefin polymerization, characterized in that the catalyst system comprises the following components:

[0061] a. the above-mentioned catalyst component;

[0062] b. Alkyl aluminum compounds;

[0063] c. Optionally, at least one external electron donor compound.

[0064] Compared with the catalyst system for olefin polymerization in the prior art, the olefin polymerization catalyst system of the present invention using the catalyst components according to the present invention not only maintains high polymerization activity, good hydrogen regulation sensitivity and high directional ability when used for olefin polymerization reactions, but also unexpectedly shows excellent olefin copolymerization ability.

[0065] According to the olefin polymerization catalyst system of the present invention, the alkyl aluminum compound can be various alkyl aluminum compounds commonly used in the art. For example, the alkyl aluminum compound can be alkyl aluminum sesquichloride and the general formula AlR I R II R III One or more of the compounds shown, R in the general formula I , R II and R III Each of them can be one of chlorine, C1-C8 straight chain alkyl and C3-C8 branched chain alkyl, and R I , R II and R III At least one of the following is one of a C1-C8 straight-chain alkyl group and a C3-C8 branched-chain alkyl group. Preferably, the alkyl aluminum compound is one or more of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octylaluminum, diethyl aluminum monochloride, diisobutyl aluminum monochloride, di-n-butyl aluminum monochloride, di-n-hexyl aluminum monochloride, ethyl aluminum dichloride, diisobutyl aluminum dichloride, di-n-butyl aluminum dichloride, di-n-hexyl aluminum dichloride and Al2Et3Cl3.

[0066] Generally, according to the catalyst system for olefin polymerization of the present invention, the molar ratio of the alkyl aluminum compound calculated as aluminum to the catalyst component calculated as titanium may be 1-2000:1, preferably 20-700:1.

[0067] According to the olefin polymerization catalyst system of the present invention, the external electron donor compound can be various electron donor compounds commonly used in the art. For example, the external electron donor compound can be one or more of carboxylic acid, anhydride, ester, ketone, ether, alcohol, organophosphorus and organosilicon compounds; preferably an organosilicon compound.

[0068] According to the olefin polymerization catalyst system of the present invention, the external electron donor is more preferably a general formula R a x R b y Si(OR c ) z The organosilicon compound shown in the general formula, R a , R b and R c Each is C1-C 18 A hydrocarbon group or a C1-C18 x and y are each an integer of 0-2, z is an integer of 1-3, and x+y+z=4. Further preferably, the general formula R a x R b y Si(OR c ) z In, R a and R b At least one selected from C3-C 10 branched alkyl with or without heteroatoms, C3-C 10 Cycloalkyl and C6-C 10 One of the aromatic groups, R c C1-C 10 Straight chain alkyl and C3-C 10 One of the branched alkyl groups, preferably methyl, x is 1, y is 1, and z is 2; or, R b C3-C 10 Branched alkyl or C3-C 10 A cycloalkyl group, and R c is methyl, x is 0, y is 1, and z is 3.

[0069] Specifically, examples of the organic silicon compound may be, but are not limited to, cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-2-ethylpiperidinyldimethoxysilane, (1,1,1-trifluoro-2-propyl)-methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane and tert-hexyltrimethoxysilane.

[0070] Generally, according to the catalyst system for olefin polymerization of the present invention, the amount of the external electron donor compound is 0.005-0.5 mole, preferably 0.01-0.4 mole, relative to 1 mole of the alkyl aluminum compound calculated as aluminum.

[0071] In the present invention, the alkyl aluminum compound and the optional external electron donor compound may be contacted and reacted with the catalyst component alone or as a mixture of the two components.

[0072] The above-mentioned olefin polymerization catalyst system according to the present invention is suitable as a catalyst system for olefin polymerization.

[0073] The present invention also provides an olefin polymerization method, which comprises contacting one or more olefins with the catalyst system provided by the present invention under olefin polymerization conditions.

[0074] The olefin polymerization method according to the present invention can prepare a polymer having high ethylene content and high rubber content and having perfect particle morphology by using the catalyst system according to the present invention. The olefin polymerization method according to the present invention has no particular limitation on olefin polymerization conditions and the olefin used.

[0075] Generally, according to the olefin polymerization method of the present invention, the olefin may be an olefin represented by the general formula CH2=CHR, wherein R may be hydrogen, C1-C 12 Straight chain alkyl, C3-C 12 Branched alkyl and C6-C 12 According to the olefin polymerization method of the present invention, the olefin may contain a small amount of diene if necessary. According to the olefin polymerization method of the present invention, the olefin is preferably propylene, or a mixture of propylene and an olefin represented by CH2=CHR, wherein R is one of hydrogen, a C1-C6 straight-chain alkyl group and a C3-C6 branched-chain alkyl group.

[0076] According to the olefin polymerization method of the present invention, the polymerization of the olefin can be either homopolymerization or copolymerization. The polymerization of the olefin can be carried out according to methods known in the art, for example, the polymerization can be bulk polymerization, gas phase polymerization, slurry polymerization or liquid bulk-gas phase combined polymerization. According to the olefin polymerization method of the present invention, the olefin polymerization temperature can be conventional conditions in the art, for example, the polymerization temperature can be 0°C-150°C, preferably 60°C-90°C; the polymerization reaction pressure can be normal pressure or pressurized.

[0077] The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention.

[0078] In the following embodiments, the test methods involved are as follows:

[0079] 1. Polymer melt index (MI): measured according to ASTM D1238-99.

[0080] 2. Polymer isotactic index (II): It is determined by the n-heptane extraction method (n-heptane boiling extraction for 6 hours), that is, 2 grams of dry polymer sample is placed in a Soxhlet extractor and extracted with boiling n-heptane for 6 hours. Then, the residue is dried to constant weight. The ratio of the obtained residue weight (g) to 2 is the isotactic index.

[0081] 3. Xylene soluble content (XS): Place the copolymer in a vacuum drying oven and bake at 75°C for 30 minutes, then quickly put it into a desiccator and cool it to room temperature; weigh about 2g of the copolymer, put it into a 500ml conical flask, add 200ml of xylene and heat to dissolve, cool the dissolved sample at room temperature for 12-14 minutes, then place it in a constant temperature water bath at 25°C for cooling and crystallization for 60 minutes, filter the crystals, heat, bake, weigh and calculate the content of the soluble matter.

[0082] 4. Ethylene content: measured using Nicolet Magna-IR760 infrared spectrometer, hot pressing film forming method, 170°C, 20MPa.

[0083] 5. Use spectrophotometry to determine the titanium content in the catalyst component.

[0084] Example 1

[0085] (1) Preparation of olefin polymerization catalyst components

[0086] In a 300mL glass reaction bottle with stirring that has been fully replaced with high-purity nitrogen, add 90mL of titanium tetrachloride and 18mL of anhydrous hexane, cool to -20°C, add 8.0g of spherical magnesium chloride adduct MgCl2·2.7CH3CH2OH·0.02E (E is ethyl o-methoxybenzoate) (preparation method see CN101486722A), and maintain -20°C stirring for 30min. Then, slowly heat to 110°C, and add 0.4mL of ethyl 2-hydroxybenzoate, 1.5mL of diisobutyl phthalate and 0.2mL of tetraethoxysilane during the heating process. After isothermal reaction at 110°C for 30min, filter out the liquid. Add 80mL of titanium tetrachloride, heat to 120°C, maintain at 120°C for 30min, and filter out the liquid; repeat the above operation once. Finally, the solid was washed five times with 60°C hexane (80 mL / times), and the solid was vacuum dried to obtain a spherical catalyst component. The titanium content in the catalyst component was 2.2 wt%.

[0087] (2) Olefin homopolymerization

[0088] The bulk polymerization of propylene in liquid phase was carried out in a 5L stainless steel autoclave. Under nitrogen protection, 5mL of triethylaluminum hexane solution (concentration of 0.5mmol / mL), 1mL of cyclohexylmethyldimethoxysilane hexane solution (concentration of 0.1mmol / mL) and 9mg of the above-mentioned spherical catalyst component were added to the autoclave in sequence. The autoclave was closed, and 6.5L of hydrogen (standard volume) and 2.3L of liquid propylene were added. The temperature was raised to 70°C and the reaction was carried out for 1 hour. Then, the temperature was lowered, the pressure was released, the material was discharged, and it was dried to obtain polypropylene. The polymerization results are shown in Table 1.

[0089] (3) Olefin copolymerization

[0090] The reaction was carried out in a 400mL stainless steel autoclave. After the reactor was fully replaced by gas phase propylene, 100g propylene and 800mL hydrogen (controlled by a gas mass flowmeter) were added, the temperature was raised to 20°C, and the pre-complexed triethylaluminum, cyclohexylmethyldimethoxysilane and catalyst mixture (aluminum: propylene = 0.13g / kg, aluminum: silicon = 16mol / mol, catalyst 1mg) were automatically injected and added by the robotic arm, stirring was started and timing was started. After 10 minutes of prepolymerization, the temperature was quickly raised to 69°C for bulk polymerization. After 100 minutes, the remaining propylene in the reactor was emptied, and the ethylene / propylene mixed gas (ethylene: propylene = 2:3mol / mol) configured in proportion in advance was quickly added, and the temperature was quickly raised to 80°C. During the gas phase polymerization, the ratio of propylene / ethylene was controlled in real time by gas chromatography. After 30 minutes of reaction, the termination gas was introduced, the heating was stopped, the stirring was stopped, the pressure was released, the material was discharged, and the polymer was dried to obtain polypropylene. The polymerization results are shown in Table 2.

[0091] Example 2

[0092] (1) Preparation of olefin polymerization catalyst components

[0093] The spherical catalyst component was prepared in the same manner as in Example 1 (1), except that the amount of tetraethoxysilane used was 0.4 mL. The titanium content in the catalyst component was 2.4 wt%.

[0094] (2) Olefin homopolymerization

[0095] Propylene polymerization was carried out in the same manner as in Example 1 (2), except that the catalyst component was the catalyst component prepared in step (1) above. The polymerization results are shown in Table 1.

[0096] (3) Olefin copolymerization

[0097] The olefin copolymerization was carried out in the same manner as in Example 1 (3), except that the catalyst component was the catalyst component prepared in the above step (1). The polymerization results are shown in Table 2.

[0098] Example 3

[0099] (1) Preparation of olefin polymerization catalyst components

[0100] The spherical catalyst component was prepared in the same manner as in Example 1 (1), except that the amount of tetraethoxysilane used was 1.0 mL. The titanium content in the catalyst component was 2.2 wt%.

[0101] (2) Olefin homopolymerization

[0102] Propylene polymerization was carried out in the same manner as in Example 1 (2), except that the catalyst component was the catalyst component prepared in step (1) above. The polymerization results are shown in Table 1.

[0103] (3) Olefin copolymerization

[0104] The olefin copolymerization was carried out in the same manner as in Example 1 (3), except that the catalyst component was the catalyst component prepared in the above step (1). The polymerization results are shown in Table 2.

[0105] Comparative Example 1

[0106] (1) Preparation of olefin polymerization catalyst components

[0107] The spherical catalyst component was prepared in the same manner as in Example 1 (1), except that tetraethoxysilane was not used. The titanium content in the catalyst component was 2.3 wt%.

[0108] (2) Olefin homopolymerization

[0109] Propylene polymerization was carried out in the same manner as in Example 1 (2), except that the catalyst component was the catalyst component prepared in step (1) above. The polymerization results are shown in Table 1.

[0110] (3) Olefin copolymerization

[0111] The olefin copolymerization was carried out in the same manner as in Example 1 (3), except that the catalyst component was the catalyst component prepared in the above step (1). The polymerization results are shown in Table 2.

[0112] Example 4

[0113] (1) Preparation of olefin polymerization catalyst components

[0114] The spherical catalyst component was prepared in the same manner as in Example 1 (1), except that 1.5 mL of diisobutyl phthalate was replaced with 1.2 mL of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane. The titanium content in the catalyst component was 2.5 wt%.

[0115] (2) Olefin homopolymerization

[0116] Propylene polymerization was carried out in the same manner as in Example 1 (2), except that the catalyst component was the catalyst component prepared in step (1) above. The polymerization results are shown in Table 3.

[0117] (3) Olefin copolymerization

[0118] The olefin copolymerization was carried out in the same manner as in Example 1 (3), except that the catalyst component was the catalyst component prepared in the above step (1). The polymerization results are shown in Table 4.

[0119] Example 5

[0120] (1) Preparation of olefin polymerization catalyst components

[0121] The spherical catalyst component was prepared in the same manner as in Example 4 (1), except that the amount of tetraethoxysilane was changed to 0.4 mL. The titanium content in the catalyst component was 2.5 wt%.

[0122] (2) Olefin homopolymerization

[0123] Propylene polymerization was carried out in the same manner as in Example 4 (2), except that the catalyst component was the catalyst component prepared in step (1) above. The polymerization results are shown in Table 3.

[0124] (3) Olefin copolymerization

[0125] The olefin copolymerization was carried out in the same manner as in Example 4 (3), except that the catalyst component was the catalyst component prepared in the above step (1). The polymerization results are shown in Table 4.

[0126] Comparative Example 2

[0127] (1) Preparation of olefin polymerization catalyst components

[0128] The spherical catalyst component was prepared in the same manner as in Example 4 (1), except that tetraethoxysilane was not used. The titanium content in the catalyst component was 2.6 wt%.

[0129] (2) Olefin homopolymerization

[0130] Propylene polymerization was carried out in the same manner as in Example 4 (2), except that the catalyst component was the catalyst component prepared in step (1) above. The polymerization results are shown in Table 3.

[0131] (3) Olefin copolymerization

[0132] The olefin copolymerization was carried out in the same manner as in Example 4 (3), except that the catalyst component was the catalyst component prepared in the above step (1). The polymerization results are shown in Table 4.

[0133] Table 1

[0134]

[0135] Table 2

[0136]

[0137] Table 1 and Table 2 respectively list the polymerization results when the catalyst components and catalyst systems obtained by Examples 1-3 and Comparative Example 1 are used for olefin polymerization. As can be seen from Table 1, compared with the catalyst system of the prior art, the catalyst system of the present invention comprising the catalyst component of the present invention still has high polymerization activity, good hydrogen adjustment sensitivity and high directional ability under the same hydrogen partial pressure conditions. As can be seen from Table 2, when the catalyst system of the present invention prepared by the catalyst component of the present invention containing compound C catalyzes the copolymerization of ethylene and propylene, the ethylene content in the resin is significantly increased, which shows that the catalyst component of the present invention and the catalyst system prepared by the catalyst component of the present invention have significantly improved olefin copolymerization ability. In addition, the morphology of the polymer particles obtained by polymerizing propylene with the catalyst system of the present invention comprising the catalyst component of the present invention is very good, and the amount of fine powder is very small.

[0138] Table 3

[0139]

[0140] Table 4

[0141]

[0142] Tables 3 and 4 list the polymerization results of the catalyst components and catalyst systems obtained by Examples 4-5 and Comparative Example 2 when used for olefin polymerization. It can also be clearly seen from Tables 3 and 4 that when the present invention uses an alkoxysilane compound with a 2-hydroxybenzoyl compound and a 1,3-diether compound as an internal electron donor, the obtained catalyst system of the present invention comprising the catalyst component of the present invention also exhibits excellent comprehensive performance, that is, compared with the catalyst system of the prior art, the catalyst system of the present invention comprising the catalyst component of the present invention shows significantly improved olefin copolymerization ability while maintaining high polymerization activity, good hydrogen adjustment sensitivity and high directional ability. Similarly, when the catalyst component and catalyst system of the present invention using an alkoxysilane compound with a 2-hydroxybenzoyl compound and a 1,3-diether compound as an internal electron donor are used for olefin polymerization, the morphology of the obtained polymer particles is very good and the amount of fine powder is very small.

Claims

1. An olefin polymerization catalyst component, the catalyst component comprising magnesium, titanium, halogen and an internal electron donor, the internal electron donor comprising compound A, compound B and compound C, the compound A being selected from hydroxybenzoyl compounds as shown in formula (I), the compound B being selected from one or more of ester and ether compounds other than compound A, and the compound C being selected from compounds of the general formula R n Si(OR6) 4-n The alkoxysilane shown, In formula (I), R1 is selected from hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 R2, R3, R4 and R5 are each independently selected from hydrogen, halogen, nitro, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 or two or more of R2, R3, R4 and R5 are bonded to each other to form a ring; Formula R n Si(OR6) 4-n In which R and R6 are each independently selected from hydrogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups, wherein n is an integer of 0-3.

2. The catalyst component according to claim 1, characterized in that Compound A is selected from one or more of 4-hydroxybenzoic acid compounds, 4-hydroxybenzoic acid ester compounds, 2-hydroxybenzoic acid compounds and 2-hydroxybenzoic acid ester compounds.

3. The catalyst component according to claim 2, characterized in that Compound A is one of 2-hydroxybenzoic acid compounds and 2-hydroxybenzoic acid ester compounds.

4. The catalyst component according to any one of claims 1 to 3, characterized in that In formula (I), R1 is hydrogen, C1-C6 straight chain alkyl, C3-C6 branched chain alkyl, C3-C6 cycloalkyl, C6-C 10 The aromatic and C7-C 10 R2, R3, R4 and R5 are each independently selected from hydrogen, C1-C8 straight chain alkyl, C3-C8 branched chain alkyl, C3-C6 cycloalkyl, C6-C 10 The aromatic and C7-C 10 One of the aralkyl groups.

5. The catalyst component according to claim 4, characterized in that In formula (I), R1 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, benzyl or phenethyl; R2, R3, R4 and R5 are each independently selected from one of hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, n-heptyl and tolyl.

6. The catalyst component according to claim 1, characterized in that The ester other than compound A is selected from one or more of monobasic aliphatic carboxylic acid esters, polybasic aliphatic carboxylic acid esters, monobasic aromatic carboxylic acid esters, polybasic aromatic carboxylic acid esters and diol ester compounds as shown in formula (II): In formula (II), R I , R II , R III , R IV , R V and R VI are independently hydrogen, C1-C 10 Aliphatic hydrocarbon groups, C6-C 10 The aromatic and C7-C 10 One of the aralkyl groups; or, R I , R II , R III , R IV , R V and R VI Two or more of R are bonded to each other to form a ring; VII and R VIII Each independently is C1-C 10 Straight chain alkyl, C3-C 10 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aromatic aliphatic hydrocarbon groups.

7. The catalyst component according to claim 6, characterized in that The ester is a dibasic aromatic carboxylic acid alkyl ester.

8. The catalyst component according to claim 1, characterized in that The ether compound is a 1,3-diether compound represented by formula (III), In formula (III), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are independently hydrogen, halogen, C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups; or, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 Two or more of R are bonded to each other to form a ring; 7 and R 8 Each independently is C1-C 20 Straight chain alkyl, C3-C 20 Branched alkyl, C3-C 20 Cycloalkyl, C6-C 20 The aromatic and C7-C 20 One of the aralkyl groups.

9. The catalyst component according to claim 8, characterized in that In formula (III), R 1 , R 2 , R 5 and R 6 is hydrogen; R 7 and R 8 Each is a C1-C4 straight chain or C3-C4 branched chain alkyl group; R 3 is one of methyl, ethyl, n-propyl and isopropyl, R 4 is one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, isopentyl, 2-ethylhexyl, cyclopentyl, cyclohexyl, methylcyclohexyl, phenyl and benzyl; Or, R 3 is hydrogen, R 4 is one of ethyl, n-butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexylethyl, diphenylmethyl, p-chlorophenyl, 1-naphthyl and 1-decalinyl; Or, R 3 and R 4 are the same and are one of ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, neopentyl, phenyl, benzyl, cyclohexyl and cyclopentyl; Or, R 3 and R 4 They are bonded to each other to form a cyclopentadienyl group, a fluorenyl group or an indenyl group.

10. The catalyst component according to claim 1, characterized in that The alkoxysilane R n Si(OR6) 4-n In the formula (a), R and R6 are each independently hydrogen, a C1-C6 straight chain alkyl, a C3-C6 branched chain alkyl, a C3-C6 cycloalkyl, a C6-C 10 The aromatic and C7-C 10 One of the aralkyl groups, wherein n is an integer of 0-2.

11. The catalyst component according to claim 10, characterized in that The alkoxysilane R n Si(OR6) 4-n In the above, R and R6 are each independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, phenyl, 2-hydroxyethyl or 3-hydroxypropyl, and n is 0 or 1.

12. An olefin polymerization catalyst system comprising the following components or the reaction product of the following components: a. The catalyst component according to any one of claims 1 to 11; b. Alkyl aluminum compounds; c. Optionally, at least one external electron donor compound.

13. An olefin polymerization process comprising contacting one or more olefins with the catalyst system according to claim 12 under olefin polymerization conditions.

14. The olefin polymerization method according to claim 13, characterized in that The one or more olefins are selected from the olefins represented by CH2=CHR, wherein R is hydrogen, C1-C 12 Straight chain alkyl, C3-C 12 Branched alkyl and C6-C 12 One of the aromatic groups.

15. The olefin polymerization method according to claim 14, characterized in that The olefin is propylene, or a mixture of propylene and an olefin represented by CH2=CHR, wherein R is one of hydrogen, a C1-C6 straight-chain alkyl group and a C3-C6 branched-chain alkyl group.

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