CN110938162A - 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 PDFInfo
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- CN110938162A CN110938162A CN201811115855.3A CN201811115855A CN110938162A CN 110938162 A CN110938162 A CN 110938162A CN 201811115855 A CN201811115855 A CN 201811115855A CN 110938162 A CN110938162 A CN 110938162A
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- 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
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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 diol ester compound shown as a formula I, the external electron donor contains a lactone compound shown as a formula II, and the lactone compound is used as the external electron donorThe catalyst system is used for olefin polymerization, and has high catalytic activity and stereospecificity and good hydrogen regulation sensitivity.
Description
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 known that the core Ziegler-Natta catalyst used in polyolefin technology mainly comprises magnesium/titanium/halogen/internal electron donor, and the catalyst is often used in combination with aluminum alkyl and external electron donor to form a complete catalyst system. Among them, the internal electron donor and the external electron donor have been developed in recent decades from none to many, from single structure and variety to rich variety, diverse functions, excellent performance, and have made great progress in technology, and thus have gradually become important components of polyolefin catalyst technology. At present, a large number of electron donor compounds have been disclosed, such as internal electron donor mono-or polycarboxylic esters, ketones, mono-or polyethers, amines, etc. and their derivatives, external electron donor mono-or polycarboxylic esters, amines, silanes, aminosilanes, etc. and their derivatives.
Patent publications CN1213080, CN1241954, CN1319062, CN1319063 and CN1310964 respectively use diol ester compounds with different carbon atoms as internal electron donor to prepare polyolefin catalyst, and use silane compounds as external electron donor.
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. As is known, the external electron donor has the remarkable characteristics of abundant species, flexible and controllable addition, large influence on various performances of the catalyst, and the like, so that the regulation 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 diol ester compound shown in a formula I,
in formula I:
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;
wherein the external electron donor contains a lactone compound shown as a formula II,
in formula II:
r is a group of the formula III,
in formula III:
2≤n≤11，R1' and RnIs' 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 the external electron donor, the alkyl aluminum as the cocatalyst and the diol ester compound as the solid catalyst component of the internal electron donor for matching use, and the catalyst system is used for olefin polymerization, particularly propylene polymerization, not only has higher catalytic activity and better stereospecificity of the catalyst, but also has better hydrogen regulation sensitivity of the catalyst and wider molecular weight distribution of the product, which is very favorable for improving the processing performance of the product; 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 common industrial external electron donor, the catalyst has better overall performance when the lactone compound is added as the external electron donor. The lactone compound 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 diol ester compound shown in a formula I,
in formula I:
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;
wherein the external electron donor contains a lactone compound shown as a formula II,
in formula II:
r is a group of the formula III,
in formula III:
2≤n≤11，R1' and RnIs' 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, R1And 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. 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 (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) 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 (V), formula (VI), formula (VII), formula (VIII) and formula (IX);
formula (V), 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 (A), (B) andVI)，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 (VII), (VIII) and (IX), 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-C20Alkyl arylRadical (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 3-methyl-2, 4-pentanediol dibenzoate.
According to the invention, in the formula III, 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 γ -caprolactone, γ -decalactone, γ -dodecalactone and γ -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 external electron donor further comprises an additional external electron donor compound (i.e., the external electron donor is a complex of a lactone compound and an additional 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 of 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 present invention, the magnesium compound is a magnesium dihalide and/or an alcoholate of a magnesium dihalide. More preferably, the magnesium compound is at least one of magnesium dichloride, magnesium dibromide, an alcoholate of magnesium dichloride and an alcoholate of magnesium dibromide.
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 IV,
Ti(OR”)4-kXkformula IV
In formula IV:
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 (1) may be substituted with halogen, and one or more kinds of alkylaluminums may be used in combination. 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. Polymer isotactic index: the assay was performed with reference to the standard GB/T2412-.
3. Weight average molecular weight (M)w): measured by high temperature sol-gel chromatography with reference to standard GB/T36214.4-2018.
4. Molecular weight distribution (weight average molecular weight M)wNumber average molecular weight Mn): measured by high temperature sol-gel chromatography with reference to standard GB/T36214.4-2018.
5. Ethylene content in the polymer (wt%): measured by fourier infrared spectrometer VERTEX 70.
Preparation example 1
This preparation example is intended to illustrate the preparation of the solid catalyst component
Adding 6.0g of magnesium chloride, 119ml of toluene, 5ml of epichlorohydrin and 15.6ml of tributyl phosphate (TBP) into a reactor fully replaced by high-purity nitrogen in sequence, and heating to 50 ℃ under stirringAfter 2.5 hours, the solid is completely dissolved; 1.7g of phthalic anhydride is added and the mixture is maintained for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl within 1 hour4Slowly heating to 80 ℃ at 70ml, and gradually separating out solids in the heating process; adding 6mmol of 3-methyl-2, 4-pentanediol dibenzoate as an internal electron donor, maintaining the temperature for 1 hour, filtering, adding 80ml of toluene, and washing twice to obtain a solid precipitate.
Then 60ml of toluene, TiCl are added440ml, heating to 100 ℃, processing for 2 hours, discharging the filtrate, then adding 60ml of toluene and TiCl440ml, heating to 100 ℃, treating for 2 hours, and discharging the filtrate; 60ml of toluene was added, and boiling washing was carried out three times, 60ml of hexane was further added, boiling washing was carried out twice, 60ml of hexane was added, and washing was carried out at normal temperature twice thereafter to obtain a solid catalyst component.
Examples 1 to 6 and comparative example 1
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, weight average molecular weight and molecular weight distribution of the polymer were also measured, and the results are shown in Table 1.
TABLE 1
Note: C-Donor: cyclohexyl methyl dimethoxy silane
Mixture 1 molar ratio γ -caprolactone: C-Donor ═ 3: 1;
the molar ratio of the mixture 2 is gamma-decalactone: C-Donor ═ 3: 1.
Examples 7 to 12 and comparative example 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 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
| Examples | External electron donor | Amount of hydrogenation (NL 10)-3) | Ethylene content (wt%) |
| Example 7 | Gamma-caprolactone | 20 | 9.1 |
| Example 8 | Mixture 1 | 20 | 9.3 |
| Example 9 | Gamma-dodecalactone | 20 | 8.4 |
| Example 10 | Gamma-angelic lactone | 20 | 9.3 |
| Example 11 | Gamma-decalactone | 20 | 8.5 |
| Example 12 | Mixture 2 | 20 | 8.7 |
| Comparative example 2 | C-Donor | 20 | 7.1 |
Note: C-Donor: cyclohexyl methyl dimethoxy silane
Mixture 1 molar ratio γ -caprolactone: C-Donor ═ 3: 1;
the molar ratio of the mixture 2 is gamma-decalactone: C-Donor ═ 3: 1.
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. Compared with the catalyst using C-Donor as an external electron Donor, the catalyst using the C-Donor as an internal electron Donor and the diol ester mixture as an internal electron Donor has the advantages of obviously high activity and better hydrogen regulation sensitivity; and in the case of ethylene/propylene copolymerization, the ethylene copolymerization ability is improved. In addition, the molecular weight distribution of the polymer obtained by the catalysis of the catalyst provided by the invention is wider.
Meanwhile, the molecular weight of the polymer prepared by the catalyst system provided by the invention is lower than that of the polymer prepared by a comparative catalyst system under different hydrogenation amounts, and the molecular weight of the polymer prepared by the catalyst is more obviously reduced along with the addition amount of hydrogen, so that the better hydrogen regulation sensitivity of the polymer is further proved.
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 high melt index and high isotactic index, and the melt index of the products can be regulated and controlled in a wider range by adjusting the hydrogenation amount. 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.
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 (15)
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 diol ester compound shown in a formula I,
in formula I:
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;
wherein the external electron donor contains a lactone compound shown as a formula II,
in formula II:
r is a group of the formula III,
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 lactone compound is 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 3-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- α -methoxymethyl- γ -butyrolactone, delta-valerolactone, delta- γ -valerolactone, delta-nonyl- γ -butyrolactone, delta-valerolactone, delta- γ -valerolactone, delta-nonyl-lactone, delta- γ -lactone, delta-valerolactone, delta-90-gamma- γ -lactone, delta-valerolactone, delta- γ -caprolactone, delta- γ -lactone, delta- γ -caprolactone, delta- γ.
3. The catalyst system according to claim 1 or 2, 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, 2-methyl-3, 5-heptanediol, 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, 1, 8-naphthyl di-2-fluorobenzoate.
4. The catalyst system according to any one of claims 1-3, 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.
5. The catalyst system according to claim 4, wherein the molar ratio of the lactone compound and the silane-based compound is (1-100): (100-1), preferably (1-10): (10-1).
6. The catalyst system according to any one of claims 1-5, wherein the solid catalyst component is a reaction product of a titanium compound, a magnesium compound and the internal electron donor.
7. The catalyst system according to any one of claims 1 to 6, 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 a magnesium dihalide and/or an alcoholate of a magnesium dihalide.
8. The catalyst system of any one of claims 1-7, wherein the titanium compound has a structure represented by formula IV,
Ti(OR”)4-kXkformula IV
In formula IV:
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.
9. The catalyst system according to any one of claims 1-8, 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.
10. The catalyst system according to any one of claims 1 to 9, 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).
11. The catalyst system according to any one of claims 1 to 10, 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).
12. The catalyst system of any one of claims 1-11, wherein the molar ratio of the external electron donor to aluminum in the alkylaluminum compound is 1: (0.1-200); preferably 1: (1-100).
13. 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 12;
wherein the pre-polymerization multiple of the prepolymer is 0.1 to 1000g of olefin polymer per g of the solid catalyst component.
14. Use of the catalyst system of any one of claims 1 to 12 and/or the prepolymerized catalyst composition of claim 13 in the polymerization of olefins.
15. 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 12 and/or the prepolymerized catalyst composition of claim 13 under olefin polymerization conditions; the olefin is preferably propylene.
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| CN114426599A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof |
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| 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 |
| CN105524192A (en) * | 2015-12-09 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | Polypropylene catalyst composition with high-temperature activity inhibitory effect and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN105524192A (en) * | 2015-12-09 | 2016-04-27 | 大唐国际化工技术研究院有限公司 | Polypropylene catalyst composition with high-temperature activity inhibitory effect and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426599A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof |
| CN114426599B (en) * | 2020-10-15 | 2023-11-10 | 中国石油化工股份有限公司 | Catalyst component for preparing polyolefin, preparation method thereof, olefin polymerization catalyst and application thereof |
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