Catalyst systems and prepolymerization catalyst compositions for olefin polymerization and their applications

Abstract

This invention relates to the field of olefin polymerization catalysts, specifically to catalyst systems for olefin polymerization, prepolymerization catalyst compositions for olefin polymerization, and their application in olefin polymerization reactions. The catalyst system comprises: a solid catalyst component containing a titanium compound, a magnesium compound, and an internal electron donor; an alkylaluminum compound; and an external electron donor; the internal electron donor contains a diether compound of Formula I, and the external electron donor contains a lactone compound of Formula II. This invention uses a lactone compound as an external electron donor and an alkylaluminum compound as a co-catalyst, in combination with a solid catalyst component containing a diether compound as an internal electron donor. When used for olefin polymerization, this catalyst system exhibits not only high catalytic activity and stereospecific orientation but also good hydrogen-modulated sensitivity, resulting in improved copolymerization ability.

Description

Technical Field

[0001] This invention relates to the field of olefin polymerization catalysts, and more specifically, to catalyst systems for olefin polymerization, prepolymerization catalyst compositions for olefin polymerization, and their applications in olefin polymerization reactions. Background Technology

[0002] As is well known, the core Ziegler-Natta catalyst in polyolefin technology mainly comprises magnesium / titanium / internal electron donor. US4971937 first disclosed that when 1,3-diether compounds are used as internal electron donors, the catalyst exhibits high activity and orientation. Subsequently, CN1143651, CN1539857, CN1636023, CN101724102, and CN102040690A, among others, disclosed catalyst systems developed with specific structures of diethers or diethers combined with other compounds as internal electron donors, exhibiting characteristics such as improved hydrogen regulation and enhanced stereotactic orientation.

[0003] The applications of polyolefin products are becoming increasingly diversified. For certain applications, not only are good catalyst activity and stereospecific orientation required, but higher demands are also placed on other catalyst properties, such as copolymerization performance. Catalysts are often used in combination with alkylaluminum compounds and external electron donors to form complete catalyst systems. External electron donors are characterized by their wide variety, flexible and controllable addition, and significant impact on various catalyst properties. Therefore, selecting suitable external electron donors to regulate the overall performance of catalysts is an important direction in catalyst research and development. When selecting external electron donors, it is necessary to comprehensively consider factors such as the improvement of catalyst performance by the external electron donor compound, cost, and environmental factors. Summary of the Invention

[0004] The purpose of this invention is to provide a catalyst system for olefin polymerization that exhibits high activity and hydrogen sensitivity when used for olefin polymerization, and good ability to copolymerize polyethylene when used for ethylene / propylene copolymerization.

[0005] To achieve the above objectives, the present invention provides a catalyst system for olefin polymerization, the catalyst system comprising:

[0006] (1) A solid catalyst component, wherein the solid catalyst component contains a titanium compound, a magnesium compound and an internal electron donor;

[0007] (2) Alkyl aluminum compounds; and

[0008] (3) External electron donor;

[0009] The internal electron donor contains a diether compound represented by Formula I.

[0010]

[0011] In Formula I:

[0012] R Ⅰ R Ⅱ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ Whether the atoms are the same or different, they are each independently selected from hydrogen, halogen atoms, and straight-chain or branched C1-C atoms. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl and C7-C 20 One of the aryl groups, R Ⅶ and R Ⅷ Whether the C1-C molecules are the same or different, they are independently selected from either straight or branched chains. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 One of the aryl alkyl groups; wherein, R Ⅰ -R Ⅵ The groups are optionally bonded together to form a ring;

[0013] The external electron donor contains a lactone compound represented by Formula II.

[0014]

[0015] In Formula II:

[0016] R is the group represented by Formula III.

[0017]

[0018] In Formula III:

[0019] 2≤n≤11, R1' and R n Both are CR1"R2", where R1" and R2" are the same or different, and are independently selected from single bonds, double bonds, hydrogen atoms, halogen atoms, straight chains or branched chains of C1-C. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 One of the aryl groups.

[0020] Another aspect of the present invention provides a prepolymerization catalyst composition for olefin polymerization, the composition comprising a prepolymer obtained by polymerization of an olefin using the catalyst system described above;

[0021] The prepolymerization ratio of the prepolymer is 0.1-1000g olefin polymer / g solid catalyst component.

[0022] In another aspect, the present invention provides the use of the catalyst system described above and / or the prepolymerization catalyst composition described above in olefin polymerization reactions.

[0023] In another aspect, the present invention provides an olefin polymerization method, the method comprising: contacting one or more olefins with a catalyst system as described above and / or a prepolymerization catalyst composition as described above under olefin polymerization reaction conditions; wherein the olefin is preferably propylene.

[0024] This invention employs a lactone compound as an external electron donor and alkyl aluminum as a co-catalyst, in combination with a solid catalyst component containing a diether compound as an internal electron donor, to form a catalyst system. This catalyst system, when used for olefin polymerization, especially propylene polymerization, exhibits not only high catalytic activity and stereospecific orientation but also good hydrogen-modulated sensitivity. Furthermore, this catalyst system demonstrates good copolymerization ability in ethylene / propylene copolymerization, which is beneficial for developing high-impact polypropylene products. In addition, the lactone compound used in this invention is inexpensive and environmentally friendly, showing promising application prospects. Detailed Implementation

[0025] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0026] A first aspect of the present invention provides a catalyst system for olefin polymerization, the catalyst system comprising:

[0027] (1) A solid catalyst component, wherein the solid catalyst component contains a titanium compound, a magnesium compound and an internal electron donor;

[0028] (2) Alkyl aluminum compounds; and

[0029] (3) External electron donor;

[0030] The internal electron donor contains a diether compound represented by Formula I.

[0031]

[0032] In Formula I:

[0033] R Ⅰ RⅡ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ Whether the atoms are the same or different, they are each independently selected from hydrogen, halogen atoms, and straight-chain or branched C1-C atoms. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl and C7-C 20 One of the aryl groups, R Ⅶ and R Ⅷ Whether the C1-C molecules are the same or different, they are independently selected from either straight or branched chains. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 Alkyl and C7-C 20 One of the aryl alkyl groups; wherein, R Ⅰ -R Ⅵ The groups are optionally bonded together to form a ring;

[0034] The external electron donor contains a lactone compound represented by Formula II.

[0035]

[0036] In Formula II:

[0037] R is the group represented by Formula III.

[0038]

[0039] In Formula III:

[0040] 2≤n≤11, R1' and R n Both are CR1"R2", where R1" and R2" are the same or different, and are independently selected from single bonds, double bonds, hydrogen atoms, halogen atoms, straight chains or branched chains of C1-C. 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Aryl, C7-C 20 One of the aryl groups.

[0041] According to the present invention, in formula I, R Ⅰ R Ⅱ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ They may be the same or different, each independently selected from hydrogen, halogen atoms, and straight-chain or branched C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Alkyl groups, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 cycloalkyl groups, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 aryl and C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 One of the aryl groups.

[0042] R Ⅶ and R Ⅷ Whether identical or different, each is independently selected from straight or branched chains C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Alkyl groups, C3, C4, C5, C6, C7, C8, C9, C10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Cycloalkyl, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Aryl, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkylaryl and C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 One of the aryl alkyl groups; wherein, R Ⅰ -R Ⅵ The groups are optionally linked together to form a ring.

[0043] Preferred, R Ⅰ R Ⅱ R Ⅲ R Ⅳ R Ⅴ and R Ⅵ The same or different, each independently selected from hydrogen, straight-chain or branched C1-C8 alkyl groups, more preferably selected from hydrogen, straight-chain or branched C1-C5 alkyl groups, such as C1, C2, C3, C4, C5 alkyl groups, including but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl.

[0044] Preferred, R Ⅶ and R Ⅷ The same or different, each independently selected from straight-chain or branched C1-C8 alkyl groups, more preferably straight-chain or branched C1-C5 alkyl groups, such as C1, C2, C3, C4, C5 alkyl groups, including but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.

[0045] According to a specific embodiment of the present invention, the diether compound is selected from 2-(2-ethylhexyl)1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane, 2-(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-(p-chlorophenyl)-1,3-dimethoxypropane, 2-(diphenylmethyl)-1,3-dimethoxypropane, 2-(1-naphthyl)-1,3-dimethoxypropane, 2-(2-fluorophenyl)-1,3-dimethoxypropane, etc. -Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane 2,2-Bis(p-chlorophenyl)-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)- 2-sec-butyl-1,3-dimethoxypropane, 2,2-disec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-phenyl-1,3-dimethoxypropane, 2-phenyl-2-sec-butyl-1,3-dimethoxypropane, 2-isopropyl-2-benzyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane3-Dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 1,1-bis(methoxymethyl)-cyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetramethylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetraphenylcyclopentadiene, 1,1-bis(methoxymethyl)-2,3,4,5,-tetrafluorocyclopentadiene, 1,1-bis(methoxymethyl)-3,4-dicyclopentylcyclopentadiene, 1,1-bis(methoxymethyl)indene, 1,1 -bis(methoxymethyl)-2,3-dimethoxyindene, 1,1-bis(methoxymethyl)-2,3,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,5,6,7-tetrafluoroindene, 1,1-bis(methoxymethyl)-4,7-dimethylindene, 1,1-bis(methoxymethyl)-3,6-dimethylindene, 1,1-bis(methoxymethyl)-4-phenylindene, 1,1-bis(methoxymethyl)-4-phenyl-2-methylindene, 1,1-bis(methoxymethyl)-4-tetracyclohexylindene, 1,1-bis(methoxymethyl)-7-(3,3,3-trifluoropropyl)phenylindene, 1,1-bis(methoxymethyl)-7-cyclopentylindene, 1,1-bis(methoxymethyl)-2,3-dimethoxyindene, 1,1-bis(methoxymethyl)-7-cyclohexylindene, 1,1-bis(methoxymethyl)-7-tert-butylindene, 1,1-bis(methoxymethyl)-7-tert-butyl-2-methylindene, 1,1-bis(methoxymethyl)-7-phenylindene, 1,1-bis(methoxymethyl)-2-phenylindene, 9,9-di(methoxymethyl)fluorene, 9,9-di(methoxymethyl)-2,7-dicyclopentylfluorene, 9,9-di(methoxymethyl)-1,8-dichlorofluorene, 9,9-di(methoxymethyl)-1,8-difluorofluorene, 9,9-di(methoxymethyl)-1,2,3,4-tetrahydrofluorene, 9,9-di(methoxymethyl)-4-tert-butyl At least one of the following: fluorene, 1,1-bis-(methoxymethyl)-2,5-cyclohexadiene, 1,1-bis-(methoxymethyl)-benzonaphthalene, 7,7-bis-(methoxymethyl)-2,5-norbornadiene, 9,9-bis-(methoxymethyl)-1,4-methanedihydronaphthalene, 9,9-bis-(methoxymethyl)-1,4-methanedihydroanthracene, 4,4-bis-(methoxymethyl)-1-phenyl-1,4-dihydronaphthalene, 4,4-bis-(methoxymethyl)-1-phenyl-3,4-dihydronaphthalene, 5,5-bis-(methoxymethyl)-1,3,6-cycloheptatriene, and 1-methoxymethyl-1-(1'-methoxyethyl)-2,3,4,5-tetramethylcyclopentadiene.

[0046] Preferably, the diether compound is selected from 2-isopropyl-1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-di ... At least one of 3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-sec-butyl-1,3-dimethoxypropane, 2,2-disec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane.

[0047] According to the present invention, in formula III, R1' and R n All are CR1"R2", where R1" and R2" are the same or different, and are independently selected from single bonds, hydrogen, halogen atoms, and straight or branched C1, C2, C3, C4, C5, C6, C7, C8, C9, C6. 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Alkyl groups, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 cycloalkyl groups, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C14 C 15 C 16 C 17 C 18 C 19 C 20 Aryl groups, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 One of the aryl groups.

[0048] Preferably, R1” and R2” are the same or different, and are each independently selected from single-bonded, hydrogen, straight-chain or branched C1-C8 alkyl groups, more preferably from single-bonded, hydrogen, straight-chain or branched C1-C5 alkyl groups, such as C1, C2, C3, C4, C5 alkyl groups, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.

[0049] According to a specific embodiment of the present invention, the lactone compound is selected from β-propiolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, α-methylene-γ-butyrolactone, α-ethyl-γ-butyrolactone, α-butyl-γ-butyrolactone, α-bromo-γ-butyrolactone, α-hydroxy-γ-butyrolactone, β-hydroxy-γ-butyrolactone, α-methyl-α-methoxymethyl-γ-butyrolactone, α-hexyl-α-methoxymethyl-γ-butyrolactone, α-cyclohexylmethyl-α-methoxymethyl-γ-butyrolactone, α-cyclohexylmethyl-α-ethoxymethyl-γ-butyrolactone, α-cyclohexylmethyl-γ-cyclohexyl-α-methoxymethyl At least one of γ-butyrolactone, α-benzyl-α-methoxymethyl-γ-butyrolactone, α-isopropyl-α-methoxymethyl-γ-butyrolactone, α-cyclohexyl-α-methoxymethyl-γ-butyrolactone, α-pentyl-α-methoxymethyl-γ-butyrolactone, γ-pentylactone, γ-caprolactone, γ-heptylactone, γ-octylactone, γ-nonylactone, γ-decylactone, γ-undecanolactone, γ-dodecylactone, δ-butyrolactone, δ-pentylactone, δ-caprolactone, δ-heptylactone, δ-octylactone, δ-nonylactone, δ-decylactone, δ-undecanolactone, δ-dodecylactone, ε-caprolactone, dihydrocoumaryl, and γ-angelicolactone.

[0050] Preferably, the lactone compound is selected from at least one of γ-butyrolactone, γ-caprolactone, γ-nonanolactone, γ-decanolactone, γ-undecaprolactone, γ-dodecanolactone and γ-angelicinolone.

[0051] According to the present invention, in order to further improve the catalytic activity, stereoregulation, and hydrogen-modulated sensitivity of the catalyst system, preferably, the internal electron donor further contains another internal electron donor compound (i.e., the internal electron donor is a complex of a diether compound and another internal electron donor compound), more preferably, the other internal electron donor compound is at least one of an ester compound (e.g., an alcohol ester compound and / or a phenolic ester compound) and a ketone compound.

[0052] More preferably, the additional internal electron-donating compound is an alcohol ester compound; even more preferably, the alcohol ester compound includes a diol ester compound represented by Formula IV.

[0053]

[0054] R1 and R2 may be the same or different, and are selected from substituted or unsubstituted straight or branched C1-C. 20 Alkyl groups (e.g., straight-chain or branched C1, C2, C3, C4, C5, C6, C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkyl groups), C2-C 20 Alkenyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (olefin group), C3-C 20 Cycloalkyl groups (e.g., C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C20 cycloalkyl), C6-C 20 Aryl groups (e.g., C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 aryl), C7-C 20 Alkyl aryl (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkylaryl), C7-C 20 Araneyl groups (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (aryl) or C 10 -C 20 Fused ring aryl (e.g., C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (Fused ring aryl);

[0055] Wherein, M is selected from C1-C 20 Divalent spar groups of alkyl groups (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C1) 10 C 11 C 12 C 13 C 14 C15 C 16 C 17 C 18 C 19 C 20 (alkyl divalent styrene), C3-C 20 Divalent spar groups of cycloalkyl groups (e.g., C3, C4, C5, C6, C7, C8, C9, C10, C11, C20, C30, C40, C50, C60, C70, C80, C90, C10, C110, C120, C130, C140, C150, C160, C170, C180, C190, 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (divalent styrene of cycloalkyl groups) and C6-C 20 Aryl divalent striations (e.g., C6, C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (of aryl divalent support groups), wherein the divalent support group is optionally C1-C 20 Straight-chain or branched alkyl groups (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 ...1, C1, C1, C1, C1, C1, C1, 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (A straight-chain or branched alkyl group) is substituted, and the substituents are optionally bonded to one or more rings.

[0056] In M, carbon atoms and / or hydrogen atoms are optionally replaced by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.

[0057] According to a preferred embodiment of the present invention, M is selected from at least one of the groups shown in formula (VII), formula (VIII), formula (IX), formula (X) and formula (XI);

[0058]

[0059] Formula (VII), R′3-R′8 may be the same or different, and are selected from hydrogen, halogens, substituted or unsubstituted straight-chain or branched C1-C atoms. 20 Alkyl groups (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkyl groups), C2-C 20 Alkenyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (olefin group), C3-C 20 Cycloalkyl groups (e.g., C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 cycloalkyl), C6-C 20 Aryl groups (e.g., C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 aryl), C7-C 20 Alkyl aryl (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C14 C 15 C 16 C 17 C 18 C 19 C 20 alkylaryl), C7-C 20 Araneyl groups (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Aryl groups), C 10 -C 20 Fused ring aryl (e.g., C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Fused ring aryl) or C1-C 20 Ester group (C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (The ester group), R′7 and R′8 are optionally bonded into a ring;

[0060] Equation (VIII), R 1 -R 4 The C1-C molecules, whether identical or different, are independently selected from substituted or unsubstituted straight or branched chains. 20 Alkyl groups (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C17 C 18 C 19 C 20 alkyl groups), C2-C 20 Alkenyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (olefin group), C3-C 20 Cycloalkyl groups (e.g., C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 cycloalkyl), C6-C 20 Aryl groups (e.g., C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 aryl), C7-C 20 Alkyl aryl (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkylaryl), C7-C 20 Araneyl groups (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C14 C 15 C 16 C 17 C 18 C 19 C 20 (aryl) or C 10 -C 20 Fused ring aryl (e.g., C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 Fused ring aryl), R 1 -R 4 Optionally, they can be keyed into one or more rings;

[0061] In formulas (IX), (X), and (XI), R3, R4, and R5 are each independently selected from hydrogen, halogens, substituted or unsubstituted straight-chain or branched C1-C atoms. 20 Alkyl groups (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkyl groups), C2-C 20 Alkenyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (olefin group), C3-C 20 Cycloalkyl groups (e.g., C3, C4, C5, C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C15 C 16 C 17 C 18 C 19 C 20 cycloalkyl), C6-C 20 Aryl groups (e.g., C6, C7, C8, C9 ... 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 aryl), C7-C 20 Alkyl aryl (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 alkylaryl), C7-C 20 Araneyl groups (e.g., C7, C8, C9, C6) 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (aryl) or C 10 -C 20 Fused ring aryl (e.g., C 10 C 11 C 12 C 13 C 14 C 15 C 16 C 17 C 18 C 19 C 20 (Fused ring aryl group).

[0062] Preferably, the diol ester compound is selected from 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4-ethyl-3 5-Heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-Heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-chlorobenzoate), 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl-3,5-octanediol dibenzoate, 4-methyl- 4-Ethyl-3,5-octanediol dibenzoate, 2-Methyl-4-ethyl-3,5-octanediol dibenzoate, 2-Methyl-6-ethyl-3,5-octanediol dibenzoate, 5-Methyl-4,6-nonanediol dibenzoate, 5-Ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate and 4-butyl-3,5-heptanediol dibenzoate, 1,2-phenylene dibenzoate, 3-methyl-5-tert-butyl-1,2-Phenylidene benzoate, 3,5-diisopropyl-1,2-phenylene benzoate, 3,6-dimethyl-1,2-phenylene benzoate, 4-tert-butyl-1,2-phenylene benzoate, 1,2-naphthalene benzoate, 2,3-naphthalene benzoate, 1,8-naphthalene dibenzoate, 1,8-naphthalene dibenzoate, 1,8-naphthalene di-4-methylbenzoate, 1,8-naphthalene di-3-methylbenzoate, 1,8-naphthalene di-2-methylbenzoate, 1,8-naphthalene di-4-ethylbenzene 1,8-Naphthyl formate, 1,8-naphthyl di-4-n-propylbenzoic acid, 1,8-naphthyl di-4-isopropylbenzoic acid, 1,8-naphthyl di-4-n-butylbenzoic acid, 1,8-naphthyl di-4-isobutylbenzoic acid, 1,8-naphthyl di-4-tert-butylbenzoic acid, 1,8-naphthyl di-4-phenylbenzoic acid, 1,8-naphthyl di-4-fluorobenzoic acid, 1,8-naphthyl di-3-fluorobenzoic acid, and 1,8-naphthyl di-2-fluorobenzoic acid.

[0063] Preferably, the diol ester compound is 2,4-pentanediol dibenzoate.

[0064] According to the present invention, the content of the additional internal electron donor compound can vary within a wide range. Preferably, the molar ratio of the diether compound to the additional internal electron donor compound is 1:(0.1-50), more preferably 1:(0.1-10).

[0065] According to the present invention, in order to further improve the catalytic activity, stereoregulation, and hydrogen-modulated sensitivity of the catalyst system, preferably, the external electron donor further comprises another external electron donor compound, that is, the external electron donor is a complex of a lactone compound and another external electron donor compound. More preferably, the other external electron donor compound is a silane compound.

[0066] More preferably, the silane compound is selected from alkoxysilanes, alkenylsilanes, and aminosilanes; more preferably, the silane compound is selected from tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-tert-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyldipropoxysilane, vinyldimethoxysilane, vinyldiprop ... The first of the following: silane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-n-butylsilane, aminotriisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane, and ethylaminotriisobutylsilane.

[0067] According to the present invention, the content of the silane compound can vary within a wide range. Preferably, the molar ratio of the lactone compound to the silane compound is (1-100):(100-1), more preferably (1-10):(10-1).

[0068] According to the present invention, the solid catalyst component contains titanium, magnesium, and an internal electron donor, and is a reaction product of a halogen-containing titanium compound, a halogen-containing magnesium compound, and an internal electron donor. Since the present invention improves the performance of olefin polymerization catalysts by changing the types of internal and external electron donors, the method for preparing the solid catalyst component through the above reaction can be carried out according to methods conventionally used in the art. For example, methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, and US4540679 can be referenced, the contents of which are incorporated herein by reference.

[0069] According to a specific embodiment of the present invention, a titanium compound pre-cooled to -15°C to -40°C, or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.), is mixed with a magnesium compound. The temperature of the mixture is then raised to 90-110°C in stages and maintained for 0.1-2 hours, during which an internal electron donor is added. Solid-liquid separation is then performed, and the resulting solid phase is treated at least twice with the titanium compound, washed with a solvent, and finally vacuum dried to obtain the solid catalyst component.

[0070] According to the present invention, the magnesium compound can be any of the magnesium compounds conventionally used in the preparation of olefin polymerization catalysts in the art. For example, the magnesium compound can be selected from at least one of magnesium dihalides, magnesium alkoxyides, alkyl magnesium, magnesium dihalides hydrates, magnesium dihalides alcohols, and derivatives in which one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbon oxygen or a halohydroxyl oxygen.

[0071] According to a preferred embodiment of the present invention, the magnesium compound is an alkoxide of magnesium dihalide. More preferably, the magnesium dihalide alkoxide has a spherical magnesium alkoxide as shown in Formula V.

[0072] MgX2·m(R'OH)·nE·qH2O (Formula V)

[0073] In formula V:

[0074] X is chlorine or bromine;

[0075] R' is a C1-C4 alkyl group (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl), and m is 0.5-4.0;

[0076] E is an ether or ester electron donor compound, and n is 0-1.0. The ether or ester can be an ether or ester known in the art that can serve as an electron donor, or it can be an internal electron donor and / or an external electron donor used in this invention.

[0077] q is 0-0.8.

[0078] According to a further preferred embodiment of the present invention, in formula V, X is chlorine or bromine; R' is a C1-C4 alkyl group, m is 1.5-3.5; n and q are both 0. More preferably, the magnesium compound is MgCl2·m(CH3CH2OH), m is 1.5-3.5.

[0079] According to the present invention, the magnesium dihalide ethanolate can be prepared by referring to the methods disclosed in Chinese patent applications CN1091748 and CN101050245, all of which are incorporated herein by reference. The following provides a specific method for preparing the magnesium dihalide ethanolate:

[0080] (1) Anhydrous magnesium dihalide is mixed with an alcohol compound (R'OH), and optionally an ether or ester electron-donating compound is added. The mixture is reacted at 90-140℃ to obtain an alcohol of magnesium halide.

[0081] (2) The magnesium halide ethanolate is sheared in a dispersion medium and then cooled in an inert medium to obtain the spherical magnesium halide ethanolate. After washing and drying, a spherical carrier is obtained.

[0082] The ratio of the anhydrous magnesium dihalide to the alcohol compound can be determined according to the actual needs of the ratio of the alcohol compound loaded on the anhydrous magnesium dihalide.

[0083] The dispersion medium can be a hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, petrolatum oil, etc. The inert medium can be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, etc.

[0084] The shearing refers to the shearing of the magnesium halide alcohol by external shearing force, such as high-speed stirring (e.g., CN1330086), spraying (e.g., US6020279), high-gravity rotating bed (e.g., CN1580136A), and emulsifier (CN1463990A).

[0085] According to the present invention, the titanium compound can be any of the various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. Preferably, the titanium compound has the structure shown in Formula VI.

[0086] Ti(OR”) 4-k X k Style VI

[0087] In formula VI:

[0088] R” is C1-C 20 Alkyl groups, preferably C1-C 10 The alkyl group is preferably a C1-C5 alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl;

[0089] X is F, Cl, or Br, preferably Cl;

[0090] k is an integer between 0 and 4.

[0091] Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichlorobutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloroethoxy, and titanium trichloride; more preferably, the titanium compound is titanium tetrachloride.

[0092] According to a preferred embodiment of the present invention, the weight ratio of titanium, magnesium and internal electron donor in the solid catalyst component is 1:(5-25):(2-15).

[0093] According to the present invention, the alkylaluminum compound has the general formula AlR3, where R is the same or different C1-C8 alkyl group, one or two of which may be substituted with a halogen, and one or more alkylaluminum compounds may be used in combination. Preferably, the alkylaluminum compound is triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, alkylaluminum chloride, etc.

[0094] According to the present invention, preferably, in the catalyst system, the molar ratio of the catalyst component based on titanium to aluminum in the alkylaluminum compound is 1:(5-1000), more preferably 1:(20-500).

[0095] According to the present invention, preferably, in the catalyst system, the molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1:(0.1-200); more preferably, it is 1:(1-100).

[0096] According to a second aspect of the present invention, a prepolymerization catalyst composition for olefin polymerization is provided, characterized in that the composition contains a prepolymer obtained by polymerizing an olefin using the catalyst system described above;

[0097] The prepolymerization ratio of the prepolymer is 0.1-1000g olefin polymer / g solid catalyst component.

[0098] According to the present invention, a "prepolymerization catalyst" refers to a catalyst that undergoes a polymerization step with a low degree of conversion. In the present invention, the same α-olefin as the olefin used in the polymerization can be used for prepolymerization, wherein the olefin used for prepolymerization is preferably propylene. Specifically, it is particularly preferred to use propylene or a mixture thereof with one or more α-olefins in a molar amount of up to 20% for prepolymerization. Preferably, the degree of conversion (prepolymerization multiple) of the prepolymerization catalyst component is about 0.2-500 g olefin polymer / g solid catalyst component, more preferably 0.5-20 g olefin polymer / g solid catalyst component.

[0099] According to the present invention, the prepolymerization conditions can be carried out in a liquid or gas phase at a temperature of -20 to 80°C, preferably 0 to 50°C. The prepolymerization step can be carried out online as part of a continuous polymerization process or independently in a batch operation.

[0100] In this invention, to prepare a polymer with a content of 0.1-1000 g olefin polymer / g solid catalyst component, preferably 0.2-500 g olefin polymer / g solid catalyst component, more preferably 0.5-20 g olefin polymer / g solid catalyst component, and particularly preferably the prepolymerization of the catalyst of this invention with olefins is carried out independently in a batch operation, with a polymerization pressure preferably of 0.01-5 MPa.

[0101] According to a third aspect of the invention, the application of the catalyst system described above and / or the prepolymerization catalyst composition described above in olefin polymerization reactions is provided.

[0102] According to a fourth aspect of the present invention, an olefin polymerization method is provided, the method comprising: contacting one or more olefins with a catalyst system as described above and / or a prepolymerization catalyst composition as described above under olefin polymerization reaction conditions.

[0103] According to the present invention, the above-described catalyst system and prepolymer catalyst composition can both be used in the homopolymerization of olefins, preferably propylene, or in copolymerization reactions with other olefins, such as ethylene.

[0104] Therefore, the present invention also provides a method for polymerizing olefins, the method comprising: polymerizing the olefins under the action of the above-described catalyst system or the above-described prepolymerization catalyst composition.

[0105] According to the present invention, the general formula of the olefin is CH2=CHR, wherein R is hydrogen or C1-C. 12 The olefin is a hydrocarbon or aryl group. Preferably, the olefin is selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, and more preferably, the olefin is ethylene and / or propylene.

[0106] According to the present invention, the catalyst system described above can be directly added to the reactor for use in the polymerization process, or the catalyst system can be prepolymerized with olefins to obtain a prepolymerized catalyst and then added to the reactor for polymerization reaction.

[0107] According to the present invention, the olefin polymerization reaction can be carried out according to known polymerization methods, in the liquid phase or gas phase, or in a combination of liquid-phase and gas-phase polymerization stages, and conventional techniques such as slurry polymerization and gas-phase fluidized bed polymerization can also be used. Preferred polymerization conditions include a temperature of 0-150°C, a time of 0.5-5 hours, and a pressure of 0.01-10 MPa; more preferably, a temperature of 60-90°C, a time of 0.5-2 hours, and a pressure of 0.05-1.5 MPa.

[0108] According to the present invention, the polymerization can be carried out in the presence of a solvent. Specifically, the concentration of the catalyst system in the solvent, based on titanium in the solid catalyst component, can be 0.1 × 10⁻⁶. -5 -5×10 -5 Moles per liter, preferably 0.5 × 10⁻⁶. -5 -2×10 -5 Moles per liter.

[0109] The present invention will be described in detail below through embodiments. In the following embodiments,

[0110] 1. Catalyst polymerization activity: The amount of polymer obtained in a certain time (in kg) divided by the amount of catalyst added (in g).

[0111] 2. Weight-average molecular weight (M) w The result was obtained by high-temperature sol-gel chromatography, in accordance with standard GB / T36214.4-2018.

[0112] 3. Polymer isotactic index: determined according to standard GB / T 2412-2008.

[0113] 4. Ethylene content (wt%) in the copolymer: measured by a VERTEX70 Fourier transform infrared spectrometer.

[0114] Preparation Example 1

[0115] This preparation example illustrates the preparation of magnesium compounds.

[0116] Anhydrous magnesium chloride and ethanol were mixed at a molar ratio of 1:2.6 and heated to 120°C to react and generate a magnesium chloride alcohol melt. After being stirred at high speed in a dispersion medium of white oil and silicone oil, the melt was placed in cooled hexane to form spherical magnesium chloride alcohol particles. After washing and drying, spherical carrier MgCl2·2.6C2H5OH was obtained.

[0117] Preparation Example 2

[0118] This preparation example illustrates the preparation of solid catalyst components.

[0119] In a 300ml glass reaction flask equipped with a stirrer and fully purged with high-purity nitrogen, 100ml of titanium tetrachloride was added, and the mixture was cooled to -20℃. The spherical magnesium chloride alcohol (MgCl2·2.6C2H5OH) prepared in Preparation Example 1 was added, and the mixture was slowly heated to 110℃. During the heating process, the internal electron donors shown in Table 1 were added. After maintaining the temperature at 110℃ for 0.5h, the liquid was filtered off, and the mixture was treated twice with titanium tetrachloride. Then, it was washed five times with hexane and dried under vacuum to obtain titanium-containing solid catalyst component A.

[0120] Examples 1-8 and Comparative Examples 1-2

[0121] This embodiment is used to illustrate the catalyst system provided by the present invention and its application.

[0122] In a 48-channel parallel pressure reactor (reaction volume 20 ml) (PPR), nitrogen was used for high-temperature purging, followed by cooling to room temperature. The reactor was then replaced with propylene at room temperature, and propylene and hydrogen were introduced at a certain pressure. The pressure of propylene gas was increased to approximately 1 MPa, and 6 ml of liquid propylene was added. Several 1 ml glass bottles were placed on a shaking table, and a solution of triethylaluminum (calculated as aluminum): the external electron donor from Table 1: the solid catalyst component prepared in Example 2 (calculated as titanium) in heptane was added sequentially to prepare a mixture. A certain amount of the mixture was automatically drawn using a needle and injected into the reactor. The temperature was raised to 70 degrees Celsius, and the reaction was carried out for 1 hour.

[0123] The polymer was discharged and weighed using the built-in weighing equipment of the PPR to calculate the catalyst activity; at the same time, the isotactic index and weight-average molecular weight of the polymer were determined, and the results are shown in Table 1.

[0124] Table 1

[0125]

[0126]

[0127] Note: a1 is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0128] b1 is 2,4-pentanediol dibenzoate;

[0129] C-Donor: Cyclohexylmethyldimethoxysilane;

[0130] The molar ratio of the mixture is γ-caprolactone:C-Donor = 3:1;

[0131] The molar ratio of the mixture was γ-dodecyl lactone:C-Donor = 3:1.

[0132] Examples 9-12 and Comparative Examples 3-4

[0133] This embodiment is used to illustrate the catalyst system provided by the present invention and its application.

[0134] In a 48-channel parallel pressure reactor (20 ml reaction volume) (PPR), nitrogen was used for high-temperature purging, followed by cooling to room temperature. At room temperature, the reactor was replaced with propylene, and propylene and hydrogen were introduced at a certain pressure. The pressure was increased to approximately 1 MPa, and 6 ml of liquid propylene was added. Several 1 ml glass bottles were placed on a shaking table, and a solution of triethylaluminum (calculated as aluminum): the external electron donor from Table 2: the solid catalyst component prepared in Example 2 (calculated as titanium) in heptane was added sequentially to prepare a mixture. A certain amount of the mixture was automatically drawn using a needle and injected into the reactor. The temperature was raised to 70 degrees Celsius and the reaction was carried out for 40 minutes. The reactor was then vented, and a mixture of ethylene / propylene in a 1:1 molar ratio was introduced. The temperature was raised to 80 degrees Celsius, the reaction pressure was controlled at 0.7 MPa, and the reaction was carried out for 20 minutes.

[0135] The polymer was discharged, and its ethylene content was measured. The results are shown in Table 2.

[0136] Table 2

[0137]

[0138] Note: a1 is 2-isopropyl-2-isopentyl-1,3-dimethoxypropane;

[0139] b1 is 2,4-pentanediol dibenzoate;

[0140] C-Donor: Cyclohexylmethyldimethoxysilane.

[0141] As shown in Tables 1 and 2, the catalyst system provided by this invention, when used for olefin polymerization, especially propylene polymerization, not only meets the requirements for stereoregulation but also exhibits good catalytic activity and hydrogen sensitivity. Furthermore, this catalyst system demonstrates good copolymerization ability in ethylene / propylene copolymerization, which is beneficial for developing high-impact polypropylene products. Compared to using C-Donor as an external electron donor, the catalyst with an external electron donor containing a lactone compound and an internal electron donor combined with a diether compound exhibits significantly higher activity and better hydrogen sensitivity; and its copolymerization ability is improved in ethylene / propylene copolymerization.

[0142] Based on the above-described characteristics of the catalyst provided by this invention, the catalyst system provided by this invention is particularly suitable for preparing polypropylene products with low ash content, high melt index, and high isotactic index. Furthermore, the melt index of the product can be controlled over a wide range by adjusting the hydrogenation amount. It can also be used to prepare products with improved impact resistance. When using a catalyst system with internal or external electron donors, the catalyst system exhibits higher activity than when using either alone, while maintaining a high level of stereotactic orientation. This is highly beneficial for maintaining a high isotactic index and reducing ash content in the polymer, thus enabling the preparation of high-purity polymers.

[0143] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalyst system for olefin polymerization, characterized in that, This catalyst system contains: (1) A solid catalyst component, wherein the solid catalyst component contains a titanium compound, a magnesium compound and an internal electron donor; (2) Alkyl aluminum compounds; as well as (3) External electron donor; The internal electron donor is a diether compound and optionally a diol ester compound, wherein the diether compound is selected from 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, etc. 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-bis( Cyclohexylmethyl)-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-isopropyl-1,3-dimethoxypropane, 2-(1-methylbutyl)-2-sec-butyl-1,3-dimethoxypropane, 2,2-disec-butyl-1,3-dimethoxypropane, 2,2-di-tert-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1 At least one of the following: 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-sec-butyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene;The diol ester compound is selected from 2,4-pentanediol dibenzoate, 3-methyl-2,4-pentanediol dibenzoate, 3,5-heptanediol dibenzoate, 4-ethyl-3,5-heptanediol dibenzoate, 3,5-heptanediol di-p-methylbenzoate, 3,5-heptanediol di-o-methylbenzoate, 3,5-heptanediol di-p-chlorobenzoate, 3,5-heptanediol di-o-chlorobenzoate, 3,5-heptanediol di-p-methoxybenzoate, 3,5-heptanediol di-o-methoxybenzoate, 3,5-heptanediol di-m-methoxybenzoate, 2-methyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-heptanediol dibenzoate, 6-methyl-3,5-heptanediol dibenzoate, 4- Ethyl-3,5-heptanediol dibenzoate, 5-ethyl-3,5-heptanediol dibenzoate, 4-propyl-3,5-heptanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate, 2,4-dimethyl-3,5-heptanediol dibenzoate, 2,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 4,6-dimethyl-3,5-heptanediol dibenzoate, 4,4-dimethyl-3,5-heptanediol dibenzoate, 6,6-dimethyl-3,5-heptanediol dibenzoate, 2-methyl-4-ethyl-3,5-heptanediol dibenzoate, 4 4-Methyl-4-ethyl-3,5-heptanediol dibenzoate, 2-methyl-4-propyl-3,5-heptanediol dibenzoate, 4-methyl-4-propyl-3,5-heptanediol dibenzoate, 6-methyl-2,4-heptanediol di(p-chlorobenzoate), 6-methyl-2,4-heptanediol di(p-methylbenzoate), 6-methyl-2,4-heptanediol di(m-methylbenzoate), 2,2,6,6-tetramethyl-3,5-heptanediol dibenzoate, 4-methyl-3,5-octanediol dibenzoate, 4-ethyl-3,5-octanediol dibenzoate, 4-propyl-3,5-octanediol dibenzoate, 4-butyl-3,5-octanediol dibenzoate, 4,4-dimethyl -3,5-Octanediol dibenzoate, 4-Methyl-4-ethyl-3,5-octanediol dibenzoate, 2-Methyl-4-ethyl-3,5-octanediol dibenzoate, 2-Methyl-6-ethyl-3,5-octanediol dibenzoate, 5-Methyl-4,6-nonanediol dibenzoate, 5-Ethyl-4,6-nonanediol dibenzoate, 5-propyl-4,6-nonanediol dibenzoate, 5-butyl-4,6-nonanediol dibenzoate, 5,5-dimethyl-4,6-nonanediol dibenzoate, 5-methyl-4-ethyl-4,6-nonanediol dibenzoate, 5-phenyl-4,6-nonanediol dibenzoate, 4,6-nonanediol dibenzoate, 4-butyl-3,5-heptanediol dibenzoate; Wherein, the external electron donor is a lactone compound and optionally a silane compound, wherein the lactone compound is selected from at least one of γ-butyrolactone, γ-valactone, γ-caprolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-butyrolactone, δ-valactone, δ-caprolactone, δ-heptanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, and δ-dodecanolactone; and the silane compound is selected from at least one of tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-tert-butyldimethoxysilane, diisobutyldimethoxysilane, and cyclopentyltrimethoxysilane. At least one of the following: oxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltriethoxysilane, and allyltripropoxysilane.

2. The catalyst system according to claim 1, wherein, The molar ratio of the diether compound to the diol ester compound is 1:(0.1-50).

3. The catalyst system according to claim 1, wherein, The molar ratio of the diether compound to the diol ester compound is 1:(0.1-10).

4. The catalyst system according to claim 1, wherein, The molar ratio of the lactone compound to the silane compound is (1-100):(100-1).

5. The catalyst system according to claim 1, wherein, The molar ratio of the lactone compound to the silane compound is (1-10):(10-1).

6. The catalyst system according to any one of claims 1-5, wherein, The solid catalyst is composed of titanium compounds, magnesium compounds, and the reaction products of the internal electron donor.

7. The catalyst system according to any one of claims 1-5, wherein, The magnesium compound is selected from at least one of magnesium dihalides, magnesium alkoxy compounds, alkyl magnesium compounds, magnesium dihalides hydrates, magnesium dihalides alcohols, and derivatives of magnesium dihalides in which one halogen atom is replaced by a hydrocarbon or a halohydroxyl group.

8. The catalyst system according to any one of claims 1-5, wherein, The magnesium compound is an ethanolate of magnesium dihalide.

9. The catalyst system according to claim 8, wherein, The magnesium dihalide alkoxides have spherical magnesium alkoxides as shown in Formula V. MgX2·m(R'OH) ·nE·qH2O (Formula V) In formula V: X is chlorine or bromine; R' is a C1-C4 alkyl group, and m is 0.5-4.0; E is an ether or ester electron-donating compound, and n is 0-1.0; q is 0-0.

8.

10. The catalyst system according to any one of claims 1-5, wherein, The magnesium compound is MgCl2·m(CH3CH2OH).

11. The catalyst system according to any one of claims 1-5, wherein, The titanium compound has the structure shown in Formula VI. Ti(OR’’) 4-k X k Formula VI In formula VI: R'' is C1-C 20 Alkyl groups; X is F, Cl, or Br; k is an integer between 0 and 4.

12. The catalyst system according to any one of claims 1-5, wherein, The titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxy, titanium tetraethoxy, titanium monochlorotributoxy, titanium dichlorodibutoxy, titanium trichlorobutoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloroethoxy, and titanium trichloride.

13. The catalyst system according to any one of claims 1-5, wherein, The titanium compound is titanium tetrachloride.

14. The catalyst system according to any one of claims 1-5, wherein, The alkylaluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and alkylaluminum chloride.

15. The catalyst system according to any one of claims 1-5, wherein, The weight ratio of titanium, magnesium and internal electron donor in the solid catalyst component is 1:(5-25):(2-15).

16. The catalyst system according to any one of claims 1-5, wherein, The molar ratio of titanium in the solid catalyst component to aluminum in the alkylaluminum compound is 1:(5-1000).

17. The catalyst system according to any one of claims 1-5, wherein, The molar ratio of titanium in the solid catalyst component to aluminum in the alkylaluminum compound is 1:(20-500).

18. The catalyst system according to any one of claims 1-5, wherein, The molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1:(0.1-200).

19. The catalyst system according to any one of claims 1-5, wherein, The molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1:(1-100).

20. A prepolymerization catalyst composition for olefin polymerization, characterized in that, The composition contains a prepolymer obtained by polymerizing an olefin using the catalyst system described in any one of claims 1-19; The prepolymerization ratio of the prepolymer is 0.1-1000g olefin polymer / g solid catalyst component.

21. The use of the catalyst system according to any one of claims 1-19 and / or the prepolymerization catalyst composition according to claim 20 in olefin polymerization reactions.

22. A method for olefin polymerization, characterized in that, The method includes contacting one or more olefins with the catalyst system of any one of claims 1-19 and / or the prepolymerization catalyst composition of claim 20 under olefin polymerization reaction conditions.

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