CN110938163A - Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof - Google Patents

Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof Download PDF

Info

Publication number
CN110938163A
CN110938163A CN201811119459.8A CN201811119459A CN110938163A CN 110938163 A CN110938163 A CN 110938163A CN 201811119459 A CN201811119459 A CN 201811119459A CN 110938163 A CN110938163 A CN 110938163A
Authority
CN
China
Prior art keywords
dimethoxypropane
methoxymethyl
bis
dibenzoate
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811119459.8A
Other languages
Chinese (zh)
Inventor
张晓帆
张军辉
林洁
赵惠
赵瑾
夏先知
张天一
马长友
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201811119459.8A priority Critical patent/CN110938163A/en
Publication of CN110938163A publication Critical patent/CN110938163A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The present invention relates to the field of olefin polymerization catalysts, in particular to catalyst systems for olefin polymerization, prepolymerized catalyst compositions for olefin polymerization, and their use in olefin polymerization reactions. The catalyst system comprises: a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor; an alkyl aluminum compound; and an external electron donor; the internal electron donor contains a diether compound shown as a formula I, the external electron donor contains a lactone compound shown as a formula II, and the internal electron donor adopts the lactone compound as the external electron donorThe catalyst system is used for olefin polymerization, and has high catalytic activity and stereospecificity, good hydrogen regulation sensitivity and improved ethylene copolymerization capability.

Description

Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof
Technical Field
The present invention relates to the field of olefin polymerization catalysts, in particular to catalyst systems for olefin polymerization, prepolymerized catalyst compositions for olefin polymerization, and their use in olefin polymerization reactions.
Background
It is well known that the core Ziegler-Natta catalysts as polyolefin technology mainly comprise magnesium/titanium/internal electron donor. US4971937 first disclosed that 1, 3-diether compounds have a high activity and directionality when used as internal electron donors. Then, CN1143651, CN1539857, CN1636023, CN101724102, CN102040690A, etc. respectively disclose that the developed diether or diether with specific structure is compounded with other compounds to be used as a catalyst system of an internal electron donor, and has the characteristics of improving hydrogen regulation, improving stereospecificity, etc.
At present, polyolefin products tend to be diversified in application, and for some specific application occasions, the catalyst is required to have good activity, stereospecificity and the like, and higher requirements are provided for other properties of the catalyst, such as copolymerization property. The catalyst is often used in combination with an aluminum alkyl and an external electron donor to form a complete catalyst system. The external electron donor has the obvious characteristics of rich varieties, flexible and controllable addition, large influence on various performances of the catalyst and the like, so that the regulation and control of the overall performance of the catalyst by selecting a proper external electron donor is an important direction for the research and development of the catalyst, and when the external electron donor is selected, the improvement of the external electron donor compound on the performance of the catalyst, cost, environmental factors and the like need to be comprehensively considered.
Disclosure of Invention
The invention aims to provide a catalyst system for olefin polymerization, which has high activity and hydrogen regulation sensitivity when used for olefin polymerization and has better capability of copolymerizing ethylene when used for ethylene/propylene copolymerization.
In order to achieve the above object, one aspect of the present invention provides a catalyst system for olefin polymerization, the catalyst system comprising:
(1) a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor;
(2) an alkyl aluminum compound; and
(3) an external electron donor;
wherein the internal electron donor contains a diether compound shown as a formula I,
Figure BDA0001810308090000021
in formula I:
RⅠ、RⅡ、RⅢ、RⅣ、RⅤand RⅥIdentical or different, each independently selected from hydrogen, halogen atoms, linear or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl and C7-C20One of the aralkyl radicals, RⅦAnd RⅧIdentical or different, each independently selected from linear or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl groups; wherein R isⅠ-RⅥOptionally linked to form a ring;
wherein the external electron donor contains a lactone compound shown as a formula II,
Figure BDA0001810308090000022
in formula II:
r is a group of the formula III,
Figure BDA0001810308090000031
in formula III:
2≤n≤11，R1' and RnAre all CR1”R2", wherein R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, a double bond, hydrogen, a halogen atom, a straight or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20One of aralkyl groups.
Another aspect of the present invention provides a prepolymerized catalyst composition for olefin polymerization, said composition comprising a prepolymer obtained by polymerizing an olefin using the catalyst system as described above;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
In a further aspect the present invention provides the use of a catalyst system as described above and/or a prepolymerised catalyst composition as described above in the polymerisation of olefins.
In yet another aspect, the present invention provides an olefin polymerization process comprising: contacting one or more olefins with a catalyst system as described above and/or a prepolymerized catalyst composition as described above under olefin polymerization conditions; the olefin is preferably propylene.
The invention adopts the lactone compound as an external electron donor, adopts the alkyl aluminum as a cocatalyst, and is matched with the solid catalyst component containing the diether compound as an internal electron donor for use to form a catalyst system, and the catalyst system is used for olefin polymerization, particularly propylene polymerization, and has high catalytic activity and stereospecificity and good hydrogen regulation sensitivity. And when the catalyst system is used for ethylene/propylene copolymerization, the ethylene copolymerization capability is better, which is beneficial to developing polypropylene products with high impact resistance. In addition, the lactone compound used in the invention has the characteristics of low price and environmental friendliness, and has a good application prospect.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect of the present invention, there is provided a catalyst system for the polymerisation of olefins, the catalyst system comprising:
(1) a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor;
(2) an alkyl aluminum compound; and
(3) an external electron donor;
wherein the internal electron donor contains a diether compound shown as a formula I,
Figure BDA0001810308090000041
in formula I:
RⅠ、RⅡ、RⅢ、RⅣ、RⅤand RⅥIdentical or different, each independently selected from hydrogen, halogen atoms, linear or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl and C7-C20One of the aralkyl radicals, RⅦAnd RⅧIdentical or different, each independently selected from linear or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl groups; wherein R isⅠ-RⅥOptionally linked to form a ring;
wherein the external electron donor contains a lactone compound shown as a formula II,
Figure BDA0001810308090000042
in formula II:
r is a group of the formula III,
Figure BDA0001810308090000051
in formula III:
2≤n≤11，R1' and RnAre all CR1”R2", wherein R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, a double bond, hydrogen, a halogen atom, a straight or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20One of aralkyl groups.
According to the invention, in formula I, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥIdentical or different, each independently selected from hydrogen, halogen atoms, linear or branched C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl of (C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl of, C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl and C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20One of the aralkyl groups of (1).
RⅦAnd RⅧIdentical or different, each independently selected from linear or branched C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl of (C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl of, C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkylaryl and C of7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20One of the aralkyl groups of (a); wherein R isⅠ-RⅥOptionally bonded to form a ring.
Preferably, RⅠ、RⅡ、RⅢ、RⅣ、RⅤAnd RⅥIdentical or different, each independently selected from hydrogen, linear or branched C1-C8More preferably selected from hydrogen, linear or branched C1-C5Alkyl of (e.g. C)1、C2、C3、C4、C5The alkyl group of (a) includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, neopentyl.
Preferably, RⅦAnd RⅧIdentical or different, each independently selected from linear or branched C1-C8More preferably a straight or branched C1-C5Alkyl of (e.g. C)1、C2、C3、C4、C5Including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.
According to a particular embodiment of the invention, the diether compound is chosen 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, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 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-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 1-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene, 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-bis (methoxymethyl) -4-phenylindene, 2-methylindene, 2-dimethylindene, 1, 1-bis (methoxymethyl) -4-phenylindene, 1,1, 1-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylindene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -2-phenylindene, 9, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.
Preferably, the diether compound is selected from the group consisting of 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-di-neopentyl-1, 3-dimethoxypropane, 2-di-tert-butyl-1, 3-dimethoxypropane, 2-di-neopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane and 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane.
According to the invention, in the formula III, R1' and RnAre all CR1”R2”，R1"and R2"identical or different, each independently selected from the group consisting of a single bond, hydrogen, a halogen atom, a linear or branched C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl of (C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl of, C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20One of the aralkyl groups of (1).
Preferably, R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, hydrogen, straight or branched C1-C8More preferably selected from the group consisting of a single bond, hydrogen, straight or branched C1-C5Alkyl of (e.g. C)1、C2、C3、C4、C5Including, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.
According to a specific embodiment of the present invention, the lactone compound is at least one selected from the group consisting of β -propiolactone, γ -butyrolactone, α -methyl- γ -butyrolactone, α -methylene- γ -butyrolactone, α -ethyl- γ -butyrolactone, α 2-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, 580-cyclohexylmethyl- α -ethoxymethyl- γ -butyrolactone, α -cyclohexylmethyl- γ -cyclohexyl- α 3-methoxymethyl- γ -butyrolactone, α -benzyl- α -methoxymethyl- γ -butyrolactone, α -isopropyl- α -methoxymethyl- γ -butyrolactone, 8672-cyclohexyl- γ -butyrolactone, delta-heptyl- γ -butyrolactone, delta-nonyl- γ -lactone, delta-valerolactone, delta- γ -lactone, delta-nonyl- γ -lactone, delta- γ -butyrolactone, delta-valerolactone, delta- γ -lactone, delta-nonyl-lactone, delta- γ -butyrolactone, delta-valerolactone, delta- γ -valerolactone, delta- α -lactone, delta-valerolactone, and delta- γ -lactone.
Preferably, the lactone compound is at least one selected from the group consisting of gamma-butyrolactone, gamma-caprolactone, gamma-nonalactone, gamma-decalactone, gamma-undecalactone, gamma-dodecalactone, and gamma-angelactone.
According to the present invention, in order to further improve the catalytic activity and stereospecificity and hydrogen response of the catalyst system, it is preferable that the internal electron donor further comprises an additional internal electron donor compound (i.e., the internal electron donor is a complex of a diether compound and an additional internal electron donor compound), and more preferably, the additional internal electron donor compound is at least one of an ester compound (which may be, for example, an alcohol ester compound and/or a phenol ester compound) and a ketone compound.
More preferably, the additional internal electron donor compound is an alcohol ester compound, and even more preferably, the alcohol ester compound comprises a diol ester compound shown in formula IV,
Figure BDA0001810308090000091
wherein R is1And R2Same or different, selected from substituted or unsubstituted, linear or branched C1-C20Alkyl (e.g., straight or branched C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl group of (1), C2-C20Alkylene (e.g. C)2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkenyl group of (2), C3-C20Cycloalkyl (e.g. C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl) of (C)6-C20Aryl (e.g. aryl)，C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (2), C7-C20Alkaryl radicals (e.g. C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkylaryl group of (a), C7-C20Aralkyl (e.g., C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aralkyl of) or C10-C20Condensed ring aryl (e.g. C)10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20A condensed ring aryl group of (b);
wherein M is selected from C1-C20Divalent alkylene radical of alkyl (e.g. C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Divalent alkylene group of alkyl group) C3-C20Divalent alkylene radical of cycloalkyl (e.g., C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Divalent alkylene group of cycloalkyl) and C6-C20Divalent alkylene radical of aryl radical (e.g. C)6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Divalent alkylene group of an aryl group) optionally substituted by C1-C20Linear or branched alkyl (e.g. C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Straight or branched alkyl groups of (a) and the substituents are optionally bonded to one or more rings,
wherein the carbon atoms or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.
According to a preferred embodiment of the present invention, M is selected from at least one of the groups represented by formula (VII), formula (VIII), formula (IX), formula (X) and formula (XI);
Figure BDA0001810308090000101
formula (VII), R'3-R′8Same or different, selected from hydrogen, halogen, substituted or unsubstituted, linear or branched C1-C20Alkyl (e.g. C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl group of (1), C2-C20Alkylene (e.g. C)2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkenyl group of (2), C3-C20Cycloalkyl (e.g. C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl) of (C)6-C20Aryl (e.g. C)6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (2), C7-C20Alkaryl radicals (e.g. C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkylaryl group of (a), C7-C20Aralkyl (e.g., C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aralkyl group of (2), C10-C20Condensed ring aryl (e.g. C)10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Condensed ring aryl) or C1-C20Ester group (C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Ester group of (b), R'7And R'8Optionally bonded to form a ring;
formula (VIII), R1-R4Identical or different, each independently selected from substituted or unsubstituted, linear or branched C1-C20Alkyl (e.g. C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl group of (1), C2-C20Alkylene (e.g. C)2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkenyl group of (2), C3-C20Cycloalkyl (e.g. C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl) of (C)6-C20Aryl (e.g. C)6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (2), C7-C20Alkaryl radicals (e.g. C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkylaryl group of (a), C7-C20Aralkyl (e.g., C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aralkyl of) or C10-C20Condensed ring aryl (e.g. C)10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Condensed ring aryl group of (3), R1-R4Optionally bonded into one or more rings;
in the formulae (IX), (X) and (XI), R3、R4And R5Each independently selected from hydrogen, halogen, substituted or unsubstituted straight or branched C1-C20Alkyl (e.g. C)1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkyl group of (1), C2-C20Alkylene (e.g. C)2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkenyl group of (2), C3-C20Cycloalkyl (e.g. C)3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Cycloalkyl) of (C)6-C20Aryl (e.g. C)6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aryl of (2), C7-C20Alkaryl radicals (e.g. C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Alkylaryl group of (a), C7-C20Aralkyl (e.g., C)7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20Aralkyl of) or C10-C20Condensed ring aryl (e.g. C)10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20A condensed ring aryl group of (ii).
Preferably, the glycol ester compound is selected from the group consisting of 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-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, and mixtures thereof, 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-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 4-dimethyl-3, 5-heptanediol dibenzoate, 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-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-3, 5-heptanediol di (m-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenz, 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-dimethyl-3, 5-octanediol dibenzoate, 4-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-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-phenylene dibenzoate, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, methyl-4, 6-nonanediol dibenzoate, 5-dimethyl-4, 6-nonanediol dibenzoate, 5-methyl-4-ethyl-4, 6-, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 1, 8-naphthyl di-4-n-butylbenzoate, 8-naphthyl ester, di-4-isobutylbenzoic acid-1, 8-naphthyl ester, di-4-tert-butylbenzoic acid-1, 8-naphthyl ester, di-4-phenylbenzoic acid-1, 8-naphthyl ester, di-4-fluorobenzoic acid-1, 8-naphthyl ester, di-3-fluorobenzoic acid-1, 8-naphthyl ester and di-2-fluorobenzoic acid-1, 8-naphthyl ester.
Preferably, the diol ester compound is 2, 4-pentanediol dibenzoate.
According to the present invention, the content of the additional internal electron donor compound may vary within a wide range, preferably the molar ratio of the diether compound and the additional internal electron donor compound is 1 (0.1-50), preferably 1 (0.1-10).
According to the present invention, in order to further improve the catalytic activity, the stereospecificity and the hydrogen response of the catalyst system, it is preferable that 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 additional external electron donor compound is a silane-based compound.
Further preferably, the silane-based compound is selected from the group consisting of an alkoxysilane, an alkenylsilane, and an aminosilane; more preferably, the silane compound is selected from tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-t-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxysilane, vinyldimethoxysilane, vinyldimethoxy, At least one of vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-butylsilane, aminotriiisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane, and ethylaminotriisobutylsilane.
According to the present invention, the content of the silane compound may be varied within a wide range, and it is preferable that the molar ratio of the lactone compound to the silane compound is (1-100): (100-1), preferably (1-10): (10-1).
According to the 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 the olefin polymerization catalyst by changing the kinds of the internal electron donor and the external electron donor, the method for preparing the solid catalyst component by the above reaction in the present invention may be performed according to a method conventionally used in the art, for example, methods disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, etc., the disclosure of which is incorporated herein by reference.
According to a specific embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (such as hexane, heptane, octane, decane, toluene, etc.) pre-cooled to-15 ℃ to-40 ℃ is mixed with a magnesium compound, the temperature of the mixture is raised to 90 ℃ to 110 ℃ in stages and maintained for 0.1 to 2 hours, and an internal electron donor is added during the raising of the temperature. Then solid-liquid separation is carried out, the obtained solid phase is treated for at least 2 times by using the titanium compound again, and is washed by using a solvent, and finally, the solid catalyst component is obtained by vacuum drying.
According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, and for example, the magnesium compound may be selected from at least one of magnesium dihalides, alkoxy magnesium, alkyl magnesium, hydrates of magnesium dihalides, alcoholates of magnesium dihalides, and derivatives in which one halogen atom in the molecule of magnesium dihalide is substituted with hydrocarbyloxy group or halohydrocarbyloxy group.
According to a preferred embodiment of the invention, the magnesium compound is an alcoholate of magnesium dihalide. More preferably, the alcoholate of a magnesium dihalide has the form of a spherical magnesium alcoholate represented by formula V,
MgX2·m(R’OH)·nE·qH2o formula V
In formula V:
x is chlorine or bromine;
r' is C1-C4Alkyl (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl) of (a), m is 0.5 to 4.0;
e is an ether or ester electron donor compound, n is 0-1.0, wherein the ether or ester can be an ether or ester which can be used as an electron donor and is known in the art, and can also be an internal electron donor and/or an external electron donor used in the invention;
q is 0 to 0.8.
According to a further preferred embodiment of the present invention, in formula V, X is chloro or bromo; r' is C1-C4M is 1.5 to 3.5; n and q are both 0, and more preferably, the magnesium compound is MgCl2·m(CH3CH2OH), m is 1.5-3.5.
According to the present invention, said alcoholate of magnesium dihalide can be prepared by referring to the processes disclosed in chinese patent applications CN1091748 and CN101050245, the relevant disclosures of which are incorporated herein by reference in their entirety. The following provides a specific preparation method of the magnesium dihalide alcoholate:
(1) mixing anhydrous magnesium dihalide with an alcohol compound (R' OH), optionally adding an ether or ester electron donor compound, and reacting at 90-140 ℃ to obtain an alcohol compound of magnesium halide;
(2) shearing the magnesium halide alcohol compound in a dispersion medium, cooling the sheared magnesium halide alcohol compound in an inert medium to obtain the spherical magnesium halide alcohol compound, and washing and drying the spherical magnesium halide alcohol compound to obtain the spherical carrier.
The mixing ratio of the anhydrous magnesium dihalide and the alcohol compound may be determined according to the actual need of the alcohol compound supported on the anhydrous magnesium dihalide.
Wherein, the dispersion medium can adopt hydrocarbon inert solvent, such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil, etc. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate oil, and the like.
Wherein the shearing means shearing the alcoholic product of the magnesium halide by external shearing force, for example, high-speed stirring method (e.g. CN1330086), spraying method (e.g. US6020279) and super-gravity rotating bed (e.g. CN1580136A) and emulsifier method (CN1463990A) and the like.
According to the present invention, the titanium compound may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. Preferably, the titanium compound has a structure represented by formula VI,
Ti(OR”)4-kXkformula VI
In formula VI:
r' is C1-C20Is preferably C1-C10Is preferably C1-C5Alkyl of (a), for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl;
x is F, Cl or Br, preferably Cl;
k is an integer of 0 to 4.
Preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride; more preferably, the titanium compound is titanium tetrachloride.
According to a preferred embodiment of the present invention, the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
According to the invention, the alkylaluminum compound has the general formula AlR3R are identical or different C1-C8One or two of the alkyl groups of (2) may be substituted with halogen, and one or more alkyl aluminum groups may be selectedCan be used together. The alkyl aluminum compound is preferably triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, alkyl aluminum chloride, or the like.
According to the invention, it is preferred that in said catalyst system the molar ratio of the catalyst component, calculated as titanium element, to the aluminium of the alkylaluminium compound is 1: (5-1000), preferably 1: (20-500).
According to the present invention, it is preferred that in the catalyst system, the molar ratio of the external electron donor to the aluminum in the alkyl aluminum compound is 1: (0.1-200); preferably 1: (1-100).
According to a second aspect of the present invention, there is provided a prepolymerized catalyst composition for olefin polymerization, characterized in that said composition comprises a prepolymer obtained by polymerizing an olefin using the catalyst system as described above;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
According to the present invention, the "prepolymerized catalyst" means a catalyst which has been subjected to a polymerization step at a relatively low conversion, and in the present invention, the prepolymerization may be carried out using the same α -olefin as the olefin used for the polymerization, wherein the olefin to be subjected to the prepolymerization is preferably propylene, and specifically, it is particularly preferred that the prepolymerization is carried out using propylene or a mixture thereof with one or more α -olefins in a molar amount of up to 20%.
According to the invention, the prepolymerization conditions can be carried out at temperatures of-20 to 80 ℃, preferably 0 to 50 ℃, in liquid or gas phase. The pre-polymerization step may be carried out in-line as part of a continuous polymerization process or separately in a batch operation.
In the present invention, to prepare a polymer of 0.1 to 1000g of an olefin polymer per g of a solid catalyst component, preferably 0.2 to 500g of an olefin polymer per g of a solid catalyst component, more preferably 0.5 to 20g of an olefin polymer per g of a solid catalyst component, it is particularly preferred that the prepolymerization of the catalyst of the present invention with an olefin is carried out independently in a batch operation, and the polymerization pressure is preferably 0.01 to 5 MPa.
According to a third aspect of the present invention there is provided the use of a catalyst system as described above and/or a prepolymerised catalyst composition as described above in the polymerisation of olefins.
According to a fourth aspect of the present invention, there is provided an olefin polymerisation process comprising: contacting one or more olefins with a catalyst system as described above and/or a prepolymerized catalyst composition as described above under olefin polymerization conditions.
According to the present invention, both the above catalyst system and the prepolymerized catalyst composition of the present invention can be used in the homopolymerization of olefins, preferably propylene, or in the copolymerization with other olefins, for example ethylene.
Thus, the present invention also provides a process for the polymerisation of olefins, which process comprises: the olefin is polymerized under the action of the above-mentioned catalyst system or the above-mentioned prepolymerized catalyst composition.
According to the invention, the olefin has the general formula CH2Wherein R is hydrogen or C1-C12Alkyl or aryl of (a). Preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene, more preferably, the olefin is ethylene and/or propylene.
According to the invention, the catalyst system can be directly added into a reactor for a polymerization process, or the catalyst system and olefin are prepolymerized to obtain a prepolymerized catalyst which is then added into the reactor for polymerization.
According to the invention, the olefin polymerization can be carried out according to known polymerization methods, in liquid or gas phase, or in a combination of liquid and gas phase polymerization stages, or using conventional techniques such as slurry processes, gas phase fluidized beds, etc. Preferred polymerization conditions include a temperature of from 0 to 150 ℃ for from 0.5 to 5 hours and a pressure of from 0.01 to 10MPa, more preferably a temperature of from 60 to 90 ℃ for from 0.5 to 2 hours and a pressure of from 0.05 to 1.5 MPa.
According to the invention, the polymerization can be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent may be 0.1X 10 in terms of the titanium element in the solid catalyst component-5-5×10-5Mol/l, preferably 0.5X 10-5-2×10-5Mol/l.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
1. polymerization activity of catalyst: the amount of polymer obtained in kg over time is divided by the amount of catalyst added in g.
2. Weight average molecular weight (M)w): measured by high temperature sol-gel chromatography with reference to standard GB/T36214.4-2018.
3. Polymer isotactic index: the assay was performed with reference to the standard GB/T2412-.
4. Ethylene content in the copolymer (wt%): measured by fourier infrared spectrometer VERTEX 70.
Preparation example 1
This preparation example is illustrative of the preparation of a magnesium compound
Mixing anhydrous magnesium chloride and ethanol according to a molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alcoholate melt, stirring at a high speed in white oil and silicone oil as dispersion media, then putting into cooled hexane to form spherical magnesium chloride alcoholate particles, washing and drying to obtain a spherical carrier MgCl2·2.6C2H5OH。
Preparation example 2
This preparation example is intended to illustrate the preparation of the solid catalyst component
100ml of titanium tetrachloride was charged into a 300ml stirred glass reaction flask fully substituted with high-purity nitrogen, cooled to-20 ℃ and charged with the spherical magnesium chloride alcoholate (MgCl) prepared in preparation example 12·2.6C2H5OH), slowly heating to 110 ℃, adding the internal electron donor shown in the table 1 in the heating process, keeping the temperature of 110 ℃ for 0.5h, filtering out liquid, adding titanium tetrachloride for treatment twice, and then using the titanium tetrachlorideAnd washing the alkane for five times, and drying in vacuum to obtain the titanium-containing solid catalyst component A.
Examples 1 to 8 and comparative examples 1 to 2
This example illustrates the catalyst system provided by the present invention and its applications
Purging with nitrogen at high temperature in a 48-channel parallel pressure reactor (reaction volume 20ml) (PPR), and cooling to normal temperature; replacing the reactor with propylene at normal temperature, and filling propylene with a certain pressure and a certain amount of hydrogen; filling propylene gas to about 1MPa, and adding 6ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminium (calculated as aluminium): external electron donors in table 1: the solid catalyst component prepared in preparation example 2 (by titanium element) is sequentially added with triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into the reactor; the temperature is raised to 70 ℃ for reaction for 1 hour.
Discharging, weighing the polymer by using a weighing device carried by the PPR, and calculating to obtain the catalyst activity; the isotactic index and the weight-average molecular weight of the polymer were also measured, and the results are shown in Table 1.
TABLE 1
Figure BDA0001810308090000201
Figure BDA0001810308090000211
Note: a1 is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;
b1 is 2, 4-pentanediol dibenzoate;
C-Donor: cyclohexyl methyldimethoxysilane;
mixture 1 molar ratio γ -caprolactone: C-Donor ═ 3: 1;
mixture 2 molar ratio γ -dodecalactone: C-Donor ═ 3: 1.
Examples 9 to 12 and comparative examples 3 to 4
This example illustrates the catalyst system provided by the present invention and its applications
Purging with nitrogen at high temperature in a 48-channel parallel pressure reactor (reaction volume 20ml) (PPR), and cooling to normal temperature; replacing the reactor with propylene at normal temperature, and filling propylene with a certain pressure and a certain amount of hydrogen; filling propylene gas to about 1MPa, and adding 6ml of liquid propylene; several 1ml glass bottles were placed on a shaking table and filled with triethylaluminium (calculated as aluminium): external electron donors in table 2: the solid catalyst component prepared in preparation example 2 (by titanium element) is sequentially added with triethyl aluminum, an external electron donor and a heptane solution of the solid catalyst component in a molar ratio of 500:25:1 to prepare a mixed solution; automatically extracting a certain amount of mixed liquid by using a needle head and injecting the mixed liquid into the reactor; heating to 70 ℃ and reacting for 40 minutes; the reactor is emptied, mixed gas with the mol ratio of 1 to 1 of ethylene/propylene is introduced, the temperature is raised to 80 ℃, the reaction pressure is controlled to be 0.7MPa, and the reaction is carried out for 20 minutes.
The polymer was discharged and the ethylene content of the polymer was determined and the results are shown in Table 2.
TABLE 2
Figure BDA0001810308090000221
Note: a1 is 2-isopropyl-2-isoamyl-1, 3-dimethoxypropane;
b1 is 2, 4-pentanediol dibenzoate;
C-Donor: cyclohexylmethyldimethoxysilane.
As can be seen from tables 1 and 2, when the catalyst system provided by the invention is used for olefin polymerization, particularly propylene polymerization, the stereospecificity of the catalyst can meet the requirements, and the catalytic activity and the hydrogen regulation sensitivity are good; and when the catalyst system is used for ethylene/propylene copolymerization, the ethylene copolymerization capability is better, which is beneficial to developing polypropylene products with high impact resistance. Compared with the catalyst using C-Donor as an external electron Donor, the catalyst added with the external electron Donor containing the lactone compound and combined with the internal electron Donor of the diether compound has obviously high activity and better hydrogen regulation sensitivity; and in the case of ethylene/propylene copolymerization, the ethylene copolymerization ability is improved.
According to the characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is particularly suitable for preparing polypropylene products with low ash content, high melt index and high isotactic index, and the melt index of the product can be regulated and controlled in a wider range by adjusting the hydrogenation amount, and the catalyst system can also be used for preparing products with improved impact resistance. When the catalyst system compounded by the internal electron donor or the catalyst system compounded by the external electron donor is adopted, the activity of the catalyst system is higher than that when the catalyst system is singly used, and the stereospecificity is still kept at a higher level, so that the preparation method is very favorable for keeping the high isotactic index of the polymer and reducing ash content, and is used for preparing high-purity polymers.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims (18)

1. A catalyst system for the polymerization of olefins, the catalyst system comprising:
(1) a solid catalyst component comprising a titanium compound, a magnesium compound, and an internal electron donor;
(2) an alkyl aluminum compound; and
(3) an external electron donor;
wherein the internal electron donor contains a diether compound shown as a formula I,
Figure FDA0001810308080000011
in formula I:
RⅠ、RⅡ、RⅢ、RⅣ、RⅤand RⅥAre the same or different and are each independently selectedFrom hydrogen, halogen atoms, straight-chain or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl and C7-C20One of the aralkyl radicals, RⅦAnd RⅧIdentical or different, each independently selected from linear or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl and C7-C20One of aralkyl groups; wherein R isⅠ-RⅥOptionally linked to form a ring;
wherein the external electron donor contains a lactone compound shown as a formula II,
Figure FDA0001810308080000012
in formula II:
r is a group of the formula III,
Figure FDA0001810308080000013
in formula III:
2≤n≤11，R1' and RnAre all CR1”R2", wherein R1"and R2"identical or different" are each independently selected from the group consisting of a single bond, a double bond, hydrogen, a halogen atom, a straight or branched C1-C20Alkyl radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20One of aralkyl groups.
2. The catalyst system according to claim 1, wherein the diether compound is selected from the group consisting of 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-methyl-ethyl-1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2-methyl-2-propyl-2-ethyl-1, 3-dimethoxy, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2- (1-naphthyl) -1, 3-dimethoxypropane, 2- (2-fluorophenyl) -1, 3-dimethoxypropane, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-2-propyl-methyl-1, 3-, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-diisobutyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2- (1-methylbutyl) -2-sec-butyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-butyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl, 2, 2-di-sec-butyl-1, 3-dimethoxypropane, 2-di-tert-butyl-1, 3-dimethoxypropane, 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-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 1-bis (methoxymethyl) -cyclopentadiene, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene, 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-bis (methoxymethyl) -4-tetracyclohexylindene, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) phenylindene, 1-bis (methoxymethyl) -7-cyclopentylinndene, 1-bis (methoxymethyl) -7-isopropylindene, 1-bis (methoxymethyl) -7-cyclohexylindene, 1-bis (methoxymethyl) -7-tert-butylindene, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene, 1-bis (methoxymethyl) -7-phenylindene, 1-bis (methoxymethyl) -7-phenylindene, 1, 1-bis (methoxymethyl) -2-phenylindene, 9-bis (methoxymethyl) fluorene, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene, 9-bis (methoxymethyl) -1, 8-dichlorofluorene, 9-bis (methoxymethyl) -1, 8-difluorofluorene, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene, 7-bis- (methoxymethyl) -2, at least one of 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methanodihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methanodihydroanthracene, 4-bis- (methoxymethyl) -1-phenyl-1, 4-dihydronaphthalene, 4-bis- (methoxymethyl) -1-phenyl-3, 4-dihydronaphthalene, 5-bis- (methoxymethyl) -1,3, 6-cycloheptatriene, and 1-methoxymethyl-1- (1' -methoxyethyl) -2,3,4, 5-tetramethylcyclopentadiene.
3. The catalyst system according to claim 1 or 2, wherein the lactone compound is selected from at least one of β -propiolactone, γ -butyrolactone, α -methyl- γ -butyrolactone, α -methylene- γ -butyrolactone, α -ethyl- γ -butyrolactone, α 2-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 1-ethoxymethyl- γ -butyrolactone, 8653-cyclohexylmethyl- γ -cyclohexyl- α -methoxymethyl- γ -butyrolactone, α -benzyl- α -methoxymethyl- γ -butyrolactone, α -isopropyl-methoxymethyl- γ -butyrolactone, 8472-cyclohexylmethyl-863-methoxymethyl- γ -butyrolactone, delta-valerolactone, delta- γ -valerolactone, delta- γ -butyrolactone, delta-valerolactone, delta- γ -valerolactone, delta-decalactone, delta- γ -valerolactone, delta- γ - α - γ -valerolactone, delta-decalactone, or more.
4. The catalyst system of any one of claims 1-3, wherein the internal electron donor further comprises an additional internal electron donor compound;
preferably, the additional internal electron donor compound is at least one of an ester compound and a ketone compound;
more preferably, the additional internal electron donor compound is a diol ester compound represented by formula IV,
Figure FDA0001810308080000041
in formula IV:
wherein R is1And R2Identical or different, each independently selected from substituted or unsubstituted, linear or branched C1-C20Alkyl radical, C2-C20Alkylene radical, C3-C20Cycloalkyl radical, C6-C20Aryl radical, C7-C20Alkylaryl group, C7-C20Aralkyl or C10-C20A fused ring aryl group;
m is selected from C1-C20Divalent alkylene group of alkyl group, C3-C20Divalent alkylene radical of cycloalkyl and C6-C20A divalent alkylene group of an aryl group, wherein the divalent alkylene group is optionally substituted with C1-C20Is substituted with a straight or branched alkyl group and the substituents are optionally bonded to one or more rings;
wherein the carbon atoms or/and hydrogen atoms in M are optionally substituted by nitrogen, oxygen, sulfur, silicon, phosphorus or halogen atoms.
5. The catalyst system according to claim 4, wherein the glycol ester compound is selected from the group consisting of 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, p-methoxybenzoate, and mixtures thereof, 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-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 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-chlorobenzoic acid) ester, 6-methyl-2, 4-heptanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 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-dimethyl-3, 5-octanediol dibenzoate, 4-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-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-phenylene dibenzoate, mixtures thereof, and mixtures thereof, 3, 5-diisopropyl-1, 2-phenylene dibenzoate, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, 1, 8-naphthyl di-4-methylbenzoate, 1, 8-naphthyl di-3-methylbenzoate, 1, 8-naphthyl di-2-methylbenzoate, 1, 8-naphthyl di-4-ethylbenzoate, 1, 8-naphthyl di-4-n-propylbenzoate, 1, 8-naphthyl di-4-isopropylbenzoate, 8-naphthyl ester, 1, 8-naphthyl di-4-n-butylbenzoate, 1, 8-naphthyl di-4-isobutylbenzoate, 1, 8-naphthyl di-4-tert-butylbenzoate, 1, 8-naphthyl di-4-phenylbenzoate, 1, 8-naphthyl di-4-fluorobenzoate, 1, 8-naphthyl di-3-fluorobenzoate, and 1, 8-naphthyl di-2-fluorobenzoate.
6. Catalyst system according to claim 4 or 5, wherein the molar ratio of the diether compound and the additional internal electron donor compound is 1 (0.1-50), preferably 1 (0.1-10).
7. The catalyst system of any one of claims 1-6, wherein the external electron donor further comprises an additional external electron donor compound;
preferably, the additional external electron donor compound is a silane compound;
preferably, the silane-based compound is selected from the group consisting of alkoxysilanes, alkenylsilanes, and aminosilanes;
more preferably, the silane compound is selected from the group consisting of tetramethoxysilane, tetraethoxysilane, diisopropyldimethoxysilane, isopropyltrimethoxysilane, di-n-propyldimethoxysilane, n-propyltrimethoxysilane, di-n-butyldimethoxysilane, di-t-butyldimethoxysilane, diisobutyldimethoxysilane, cyclopentyltrimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldimethoxysilane, cyclohexylethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, vinylmethoxysilane, vinylethoxysilane, vinylpropoxysilane, vinyldimethoxysilane, vinyldiethoxysilane, vinyldipropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxysilane, at least one of vinyltripropoxysilane, allylmethoxysilane, allylethoxysilane, allylpropoxysilane, allyldimethoxysilane, allyldiethoxysilane, allyldipropoxysilane, allyltrimethoxysilane, allyltriethoxysilane, allyltripropoxysilane, aminotrimethylsilane, aminotriethylsilane, aminotripropylsilane, aminotri-butylsilane, aminotriiisobutylsilane, methylaminotrimethylsilane, methylaminotriethylsilane, methylaminotripropylsilane, methylaminotri-n-butylsilane, methylaminotriisobutylsilane, ethylaminotrimethylsilane, ethylaminotriethylsilane, ethylaminotripropylsilane, ethylaminotri-n-butylsilane, and ethylaminotriisobutylsilane.
8. The catalyst system according to claim 7, wherein the molar ratio of the lactone compound and the silane-based compound is (1-100): (100-1), preferably (1-10): (10-1).
9. The catalyst system according to any one of claims 1-8, wherein the solid catalyst component is a reaction product of a titanium compound, a magnesium compound and the internal electron donor.
10. The catalyst system according to any one of claims 1 to 9, wherein the magnesium compound is selected from at least one of magnesium dihalide, alkoxy magnesium, alkyl magnesium, a hydrate of magnesium dihalide, an alcoholate of magnesium dihalide, and a derivative in which one halogen atom in the molecule of magnesium dihalide is substituted with hydrocarbyloxy group or halohydrocarbyloxy group;
preferably, the magnesium compound is an alcoholate of magnesium dihalide;
more preferably, the alcoholate of a magnesium dihalide has the form of a spherical magnesium alcoholate represented by formula V,
MgX2·m(R’OH)·nE·qH2o formula V
In formula V:
x is chlorine or bromine;
r' is C1-C4M is 0.5 to 4.0;
e is an ether or ester electron donor compound, and n is 0-1.0;
q is 0 to 0.8;
further preferably, the magnesium compound is MgCl2·m(CH3CH2OH)。
11. The catalyst system of any one of claims 1-10, wherein the titanium compound has a structure represented by formula VI,
Ti(OR”)4-kXkformula VI
In formula VI:
r' is C1-C20Alkyl groups of (a);
x is F, Cl or Br;
k is an integer of 0 to 4;
preferably, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotris butoxytitanium, dichlorodibutoxytitanium, trichloro monobutoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, trichloro-monoethoxytitanium and titanium trichloride; more preferably, the titanium compound is titanium tetrachloride.
12. The catalyst system according to any one of claims 1-11, wherein the alkyl aluminum compound is selected from at least one of triethylaluminum, tripropylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and alkylaluminum chloride.
13. The catalyst system according to any one of claims 1 to 13, wherein the weight ratio of the titanium element, the magnesium element and the internal electron donor in the solid catalyst component is 1: (5-25): (2-15).
14. The catalyst system according to any one of claims 1 to 13, wherein the molar ratio of titanium in the solid catalyst component to aluminum in the alkyl aluminum compound is 1: (5-1000), preferably 1: (20-500).
15. The catalyst system of any one of claims 1-14, wherein the molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1: (0.1-200); preferably 1: (1-100).
16. A prepolymerized catalyst composition for the polymerization of olefins, comprising a prepolymer obtained by polymerizing olefins using the catalyst system according to any of claims 1 to 15;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
17. Use of the catalyst system of any one of claims 1 to 15 and/or the prepolymerized catalyst composition of claim 16 in the polymerization of olefins.
18. A process for the polymerization of olefins, the process comprising: contacting one or more olefins with the catalyst system of any of claims 1 to 15 and/or the prepolymerized catalyst composition of claim 16 under olefin polymerization conditions.
CN201811119459.8A 2018-09-25 2018-09-25 Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof Pending CN110938163A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811119459.8A CN110938163A (en) 2018-09-25 2018-09-25 Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811119459.8A CN110938163A (en) 2018-09-25 2018-09-25 Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof

Publications (1)

Publication Number Publication Date
CN110938163A true CN110938163A (en) 2020-03-31

Family

ID=69905155

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811119459.8A Pending CN110938163A (en) 2018-09-25 2018-09-25 Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof

Country Status (1)

Country Link
CN (1) CN110938163A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950984A (en) * 2018-09-26 2020-04-03 中国石油化工股份有限公司 Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN114456290A (en) * 2020-10-22 2022-05-10 中国石油化工股份有限公司 Catalyst system for olefin polymerization and prepolymerized catalyst composition

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391397A (en) * 2011-09-09 2012-03-28 中国科学院化学研究所 Polypropylene catalyst containing monoester external electron donor
US20140148565A1 (en) * 2012-11-26 2014-05-29 Lummus Novolen Technology Gmbh High performance ziegler-natta catalyst systems, process for producing such supported catalysts and use thereof
CN104250316A (en) * 2013-06-28 2014-12-31 中国石油化工股份有限公司 Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method
CN104558282A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application
CN104558284A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application
CN104558274A (en) * 2013-10-10 2015-04-29 中国石油化工股份有限公司 Titanium-containing solid catalyst component for olefin polymerization reactions
CN105440180A (en) * 2014-08-15 2016-03-30 中国石油化工股份有限公司 Propylene polymer and preparation method thereof
US20160251457A1 (en) * 2013-10-18 2016-09-01 China Petroleum & Chemical Corporation Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102391397A (en) * 2011-09-09 2012-03-28 中国科学院化学研究所 Polypropylene catalyst containing monoester external electron donor
US20140148565A1 (en) * 2012-11-26 2014-05-29 Lummus Novolen Technology Gmbh High performance ziegler-natta catalyst systems, process for producing such supported catalysts and use thereof
CN104250316A (en) * 2013-06-28 2014-12-31 中国石油化工股份有限公司 Olefin polymerization catalyst component, olefin polymerization catalyst and olefin polymerization method
CN104558274A (en) * 2013-10-10 2015-04-29 中国石油化工股份有限公司 Titanium-containing solid catalyst component for olefin polymerization reactions
CN104558282A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application
CN104558284A (en) * 2013-10-18 2015-04-29 中国石油化工股份有限公司 Catalyst component used for olefin polymerization and preparation method thereof as well as catalyst used for olefin polymerization and application
US20160251457A1 (en) * 2013-10-18 2016-09-01 China Petroleum & Chemical Corporation Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor
CN105440180A (en) * 2014-08-15 2016-03-30 中国石油化工股份有限公司 Propylene polymer and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110950984A (en) * 2018-09-26 2020-04-03 中国石油化工股份有限公司 Catalyst component for olefin polymerization, catalyst and olefin polymerization method
CN114456290A (en) * 2020-10-22 2022-05-10 中国石油化工股份有限公司 Catalyst system for olefin polymerization and prepolymerized catalyst composition
CN114456290B (en) * 2020-10-22 2023-07-21 中国石油化工股份有限公司 Catalyst system for olefin polymerization and prepolymerized catalyst composition

Similar Documents

Publication Publication Date Title
CN102574939B (en) Catalytic component for olefinic polymerization and preparation method thereof
US11041028B2 (en) Non-phthalate catalyst system and its use in the polymerization of olefins
US7220696B2 (en) Solid titanium catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for olefin polymerization
CN109111539B (en) Catalyst component for olefin polymerization and catalyst thereof
CN110938163A (en) Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof
CN109694420B (en) Catalyst system for olefin polymerization, prepolymerized catalyst and olefin polymerization process
CN114716591B (en) Catalyst component for propylene polymerization, preparation method and application thereof
CN111234062B (en) Catalyst system for olefin polymerization and use thereof
CN111234068B (en) Catalyst system for olefin polymerization and use thereof
CN106543310B (en) A kind of olefin polymerization catalyst system and its application
CN112300304B (en) Catalyst system for olefin polymerization and prepolymerized catalyst composition
CN112661883B (en) Solid catalyst component for preparing polyolefin, catalyst system and application thereof
CN112661882B (en) Application of cyclohexene-1,2-dicarboxylic acid ester compound
CN112300311B (en) Catalyst for olefin polymerization and olefin polymerization method
CN108570119B (en) Solid catalyst component containing naphthalenediamine compound, catalyst and application thereof
JP2988227B2 (en) Method for producing olefin polymer and catalyst for olefin polymerization
CN113754801A (en) Solid catalyst for preparing olefin polymer and solid catalyst system
CN110938161B (en) Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof
CN110938162A (en) Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof
CN110938157B (en) Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof
CN112300303B (en) Catalyst system for olefin polymerization and application thereof
CN112300302B (en) Twelve-membered ring compound and application thereof
CN113754802B (en) Catalyst system for olefin polymerization reaction and prepolymerization catalyst composition
CN114456290B (en) Catalyst system for olefin polymerization and prepolymerized catalyst composition
CN114456286B (en) Catalyst system for olefin polymerization and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination