CN114456290B - Catalyst system for olefin polymerization and prepolymerized catalyst composition - Google Patents
Catalyst system for olefin polymerization and prepolymerized catalyst composition Download PDFInfo
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- CN114456290B CN114456290B CN202011140491.1A CN202011140491A CN114456290B CN 114456290 B CN114456290 B CN 114456290B CN 202011140491 A CN202011140491 A CN 202011140491A CN 114456290 B CN114456290 B CN 114456290B
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention provides a catalyst system for olefin polymerization and a prepolymerized catalyst composition. The catalyst system for olefin polymerization of the present invention comprises the following components or the reaction product of the following components: 1) A solid catalyst component comprising magnesium element, titanium element, halogen and an internal electron donor; 2) A cocatalyst component selected from alkyl aluminum compounds; 3) An external electron donor comprising a compound represented by formula (I). The invention can improve the molecular weight and isotactic index of a polymerization product and slow down the activity decay rate of the catalyst system by introducing a ketoester compound as an external electron donor into a Ziegler-Natta type polyolefin catalyst system.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a catalyst system for olefin polymerization and a prepolymerized catalyst composition.
Background
It is well known that in order to meet the demands of industrial production, the stereospecificity, activity decay, copolymerization properties of Ziegler-Natta type polyolefin catalysts are important technical parameters for producing polyolefin products with excellent properties. Catalyst systems having excellent combination properties have been the target of efforts of polyolefin resin manufacturers and research and development institutions.
The Ziegler-Natta catalyst as the core of polyolefin technology mainly comprises magnesium element, titanium element and an internal electron donor, and the catalyst is often matched with aluminum alkyl and an external electron donor together to form a complete catalyst system. The external electron donor has the remarkable characteristics of rich types, 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 system by selecting a proper external electron donor is an important direction for the research and development of the catalyst.
Disclosure of Invention
In view of the problems of the prior art described above, it is an object of the present invention to provide a catalyst system for olefin polymerization, which can increase the molecular weight, isotactic index of a polymerization product and slow down the rate of activity decay of the catalyst system by introducing a ketoester compound as an external electron donor into a Ziegler-Natta type polyolefin catalyst system, and can increase the ethylene content of the product for ethylene-propylene copolymerization systems.
It is a second object of the present invention to provide a prepolymerized catalyst composition for olefin polymerization.
It is a further object of the present invention to provide a catalyst system and the use of a prepolymerized catalyst composition corresponding to the first object and the second object.
It is a fourth object of the present invention to provide a process for polymerizing olefins corresponding to the above object.
In order to achieve one of the above purposes, the technical scheme adopted by the invention is as follows:
a catalyst system for olefin polymerization comprising the following components or the reaction product of the following components:
1) A solid catalyst component comprising magnesium element, titanium element, halogen and an internal electron donor;
2) A cocatalyst component selected from alkyl aluminum compounds;
3) An external electron donor comprising a ketoester compound represented by formula (I),
in the formula (I) of the present invention,
M 1 and M 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl group wherein M 1 ，M 2 Optionally containing substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 One or more of alkylamino, aldehyde, carboxyl and heteroatom;
R 1 and R is 2 The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 Alkylamino, carboxyl, R a C(O)-、R a O-、C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 3 -C 12 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl, 4-12 membered heterocycloalkyl and C 5 -C 20 Heteroaryl, wherein R a Selected from C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 3 -C 8 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 20 Aralkyl, 4-12 membered heterocycloalkyl and C 5 -C 20 Heteroaryl;
M 1 ，M 2 ，R 1 and R is 2 Optionally forming a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof.
In the present application, the term substituent means a substituent selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 One or more of alkylamino, aldehyde, carboxyl and heteroatom may be selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy and halogen, preferably selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, fluoro, chloro, bromo and iodo.
The inventor of the application finds that the ketone ester compound shown in the formula (I) is introduced into a Ziegler-Natta type polyolefin catalyst system as an external electron donor, so that the activity attenuation rate of a polymerization system can be slowed down, and the molecular weight and the isotactic index of a polymerization product can be improved; in the impact copolymerization, the activity is improved, and the ethylene content of the obtained product is obviously improved.
According to some preferred embodiments of the invention, M 1 、R 1 Together with the carbon atoms to which they are attached, form a 3-6 membered ring, preferably the 3-6 membered ring is a 3-6 membered aliphatic ring.
According to some preferred embodiments of the invention, in formula (I), M 1 And M 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C 7 -C 15 Aralkyl and C 7 -C 15 Alkylaryl group wherein M 1 And M 2 Optionally containing substituents.
According to some of the inventionPreferred embodiments, R 1 And R is 2 The same or different are each independently selected from hydrogen, C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy and C 6 -C 10 Aryloxy groups, preferably selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, unsubstituted or substituted phenyl.
According to some preferred embodiments of the invention, in formula (I), M 1 And M 2 Each independently selected from C 1 -C 10 Alkyl, C 6 -C 15 Aryl, C 7 -C 15 Aralkyl and C 7 -C 15 Alkylaryl group wherein M 1 And M 2 Optionally containing substituents, or M 1 、R 1 Together with the carbon atoms to which they are attached, form a 3-6 membered ring, optionally containing oxygen and/or sulfur, preferably the 3-6 membered ring is a five membered aliphatic ring; r is R 1 And R is 2 Each independently selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, unsubstituted or substituted phenyl; the substituents are selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, fluoro, chloro, bromo and iodo.
According to some preferred embodiments of the invention, in formula (I), M 1 And M 2 Selected from C 1 -C 10 Alkyl, C 6 -C 15 Aryl, C 7 -C 15 Aralkyl and C 7 -C 15 An alkylaryl group; r is R 1 And R is 2 Each independently selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, unsubstituted or substituted phenyl; the substituents are selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, fluoro, chloro, bromo and iodo. According to some embodiments, M 1 Is methyl, ethyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, phenyl, halogen and/or C 1 -C 6 Alkyl substituted phenyl, and the like. According to some embodiments, M 2 Methyl, ethyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, phenylHalogen and/or C 1 -C 6 Alkyl substituted phenyl, and the like.
According to other preferred embodiments of the invention, in formula (I), M 1 、R 1 Together with the carbon atoms to which they are attached form a 3-6 membered ring, said 3-6 membered ring optionally containing oxygen and/or sulfur, R 1 And R is 2 Each independently selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, unsubstituted or substituted phenyl; the substituents are selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, fluoro, chloro, bromo and iodo. According to some embodiments, M 1 、R 1 Together with the carbon atoms to which they are attached, form a five-membered aliphatic ring, with or without heteroatoms, which are oxygen or sulfur.
According to some preferred embodiments of the present invention, the ketoester compound represented by the formula (I) may be specifically selected from ethyl 2-ethyl acetoacetate, ethyl fluoropropionate, ethyl 2-isobutyl acetoacetate, dimethyl 3-oxoglutarate, methyl 1-methyl-4-piperidone-3-carboxylate, methyl 2-n-hexyl acetoacetate, ethyl 2-octyl acetoacetate, methyl 3-cyclopropyl-3-oxopropionate, ethyl 1-benzyl-4-piperidone-3-carboxylate, isopropyl acetoacetate, ethyl 2-oxocyclopentane carboxylate, ethyl 2-methoxyethyl acetoacetate, ethyl 2-ethyl-2-methyl acetoacetate, ethyl 4, 4-trichloroacetoacetate, methyl 4, 4-dimethyl-3-pentanoate, methyl 2-oxocyclopentane carboxylate, methyl 4-methoxyacetoacetate, t-butyl acetoacetate, methyl 4-oxotetrahydrothiophene-3-carboxylate, ethyl benzoyl acetate, ethyl beta-oxophenylpropionate, ethyl 2-phenyl acetoacetate, and the like.
In some preferred embodiments of the present invention, the molar ratio of the external electron donor to the titanium element in the solid catalyst component is (0-500): 1, preferably (0.01-200): 1, more preferably (0.1-100): 1.
in some preferred embodiments of the present invention, the internal electron donor is selected from one or more of a diether compound, an alkoxide compound, an aromatic carboxylate compound, or a succinate compound.
In some preferred embodiments of the present invention, the diether compound is a 1, 3-diether compound, and more preferably a 1, 3-diether compound represented by formula (II).
In the formula (II), R' 1 、R' 2 、R' 3 、R' 4 、R' 5 And R'. 6 The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 An alkylaryl group; r's' 7 And R'. 8 Identical or different, each independently selected from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl, wherein R' 1 、R' 2 、R' 3 、R' 4 、R' 5 、R' 6 、R' 7 And R'. 8 Optionally containing substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 One or more of alkylamino, aldehyde, carboxyl and heteroatom; optionally, R' 1 、R' 2 、R' 3 、R' 4 、R' 5 And R'. 6 Are bonded to each other to form a saturated or unsaturated single or multiple ring.
In some preferred embodiments of the present invention, 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- (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-dimethoxy-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dimethoxy-1, 3-dimethoxypropane, 2-dimethyl-1, 3-dimethoxypropane, 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-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-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 1-dimethyl-cyclopentadiene (1, 3-dimethyl) -bis (4, 5-tetramethyl) -cyclopentadiene (4, 4-dimethyl-1, 5-tetramethyl) -cyclopentadiene, -tetraphenylcyclopentadiene, 1-bis (methoxymethyl) -2,3,4,5, -tetrafluorocyclopentadiene, 1-bis (methoxymethyl) -3, 4-dicyclopentadienyl, 1, 1-bis (methoxymethyl) indene, 1-bis (methoxymethyl) -2, 3-dimethoxyindene, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene, 1-bis (methoxymethyl) -4,5,6, 7-tetrafluoroindene 1, 1-bis (methoxymethyl) 4, 7-dimethylindene, 1-bis (methoxymethyl) -3, 6-dimethylindene, 1-bis (methoxymethyl) -4-phenylindene, 1-bis (methoxymethyl) -4-phenyl-2-methylindene 1, 1-bis (methoxymethyl) 4, 7-dimethylindene, 1-bis (methoxymethyl) -3, 6-dimethylindene 1, 1-bis (methoxymethyl) -4-phenylindene, 1-bis (methoxymethyl) -4-phenyl-2-methylindene, 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, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene, 9-bis (methoxymethyl) -4-tert-butylfluorene, 1-bis- (methoxymethyl) -2, 5-cyclohexadiene, 1-bis- (methoxymethyl) -benzonaphthalene one or more of 7, 7-bis- (methoxymethyl) -2, 5-norbornadiene, 9-bis- (methoxymethyl) -1, 4-methane dihydronaphthalene, 9-bis- (methoxymethyl) -1, 4-methane dihydroanthracene, 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.
In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (III),
in the formula (III), R 1 And R is 2 Identical or different, each independently selected from C containing or not containing substituents 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 2 -C 20 Alkynyl, C with or without substituents 3 -C 20 Cycloalkyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl and C with or without substituents 10 -C 20 Condensed ring aryl groups, preferably each independently selected from C with or without substituents 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 3 -C 10 Cycloalkyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl and C with or without substituents 10 -C 15 Condensed ring aryl groups, the substituents being selected from hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, bis-C 1 -C 6 One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is a divalent linking group, preferably selected from C with or without substituents 1 -C 20 Alkylene, C with or without substituents 3 -C 20 Cycloalkylene and C with or without substituents 6 -C 20 Arylene groups, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C 1 -C 20 Alkyl, where the substituents are a plurality of C 1 -C 20 When alkyl, the substituents are optionally bonded to form one or more rings.
In some preferred embodiments of the present invention, the alcohol ester compound is selected from the group consisting of glycol ester compounds represented by formula (a),
in the formula (a), R' 1 And R'. 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl groups, preferably selected from C 1 -C 6 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Aralkyl and C 7 -C 10 Alkylaryl, said alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkylaryl groups optionally being selected from halogen, C 1 -C 6 Alkyl and C 1 -C 6 One or more substituents in the alkoxy group; r's' 3 、R’ 4 、R’ 5 、R’ 6 And R'. 1 -'R’ 2n The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Alkylaryl, C 7 -C 20 Aralkyl and C 10 -C 20 Condensed ring aryl groups, preferably selected from hydrogen, halogen, C 1 -C 10 Alkyl, C 2 -C 6 Alkenyl, C 2 -C 6 Alkynyl, C 3 -C 10 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 10 Alkylaryl, C 7 -C 10 Aralkyl and C 10 -C 15 Condensed ring aryl groups, the alkyl, alkenyl, alkynyl, cycloalkyl, aryl, alkylaryl, arylalkyl, and condensed ring aryl groups optionally being selected from halogen, C 1 -C 6 Alkyl and C 1 -C 6 One or more substituents in the alkoxy group; r's' 3 、R’ 4 、R’ 5 、R’ 6 And R'. 1 -R’ 2n Optionally containing heteroatoms which are one or more of nitrogen, oxygen, sulfur, silicon, halogen and phosphorus; alternatively, R' 3 、R’ 4 、R’ 5 、R’ 6 And R'. 1 -R’ 2n To form a saturated or unsaturated single ring or a saturated or unsaturated multiple ring; wherein n is an integer of 0 to 10, preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and when n is 0, the substituent is R' 3 And R'. 4 Is R 'as carbon atom and substituent' 5 And R'. 6 Is bonded to a carbon atom of (c).
According to the invention, in formula (a), the bracket part represents that n carbon atoms are bonded in turn and each carbon atom is also bonded to 2 substituents, i.e. n carbon atoms and R 'are shared in the bracket' 1 、R’ 2 、R’ 3 …R’ 2n And 2n substituents.
According to the present invention, the glycol ester compound may be specifically selected from 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol dimethyl benzoate, 3, 5-heptanediol diphosven methyl benzoate, 3, 5-heptanediol dichloro benzoate, 3, 5-heptanediol diphenoxybenzoate, 3, 5-heptanediol dimethoxy benzoate, 2-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-heptanediol-2, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 6-dimethyl-4-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-methyl-5-heptanediol dibenzoate, 4-ethyl-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-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, 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, 3, 6-dimethyl-1, 2-phenylene dibenzoate, 4-tert-butyl-1, 2-phenylene dibenzoate, 1, 2-naphthalene dibenzoate, 2, 3-naphthalene dibenzoate, dibenzoate-1, 8-naphthalene, di-4-methylbenzoic acid-1, 8-naphthalene, di-4-ethylbenzoic acid-1, 8-naphthalene, di-4-n-propyl-benzoic acid, 1, 8-naphthalene, 4-diphenyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-isopropyl-benzoic acid, 4-isopropyl-4-naphthalene, 4-diphenyl-4-isopropyl-benzoic acid, 4-isopropyl-4-phenyl-4, 8-naphthalene, 1, 8-naphthalene di-3-fluorobenzoate and 1, 8-naphthalene di-2-fluorobenzoate.
In some preferred embodiments of the present invention, the aromatic carboxylic acid ester compound is selected from the group consisting of compounds represented by formula (IV),
in the formula (IV), each R 3 The same or different, each independently selected from the group consisting of C 1 -C 6 C of substituents on alkyl and halogen atoms 1 -C 8 Alkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 5 -C 10 Cycloalkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 6 -C 15 With or without aryl groups, selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 15 Alkylaryl groups optionally containing a member selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 15 Aralkyl of (a); r is R 4 -R 7 May be the same or different and are each independently selected from hydrogen, halogen, with or without C 1 -C 6 C of substituents on alkyl and halogen atoms 1 -C 8 Alkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 5 -C 10 Cycloalkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 6 -C 20 With or without aryl groups, selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 20 Alkylaryl groups optionally containing a member selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 20 Aralkyl groups.
According to the present invention, the aromatic carboxylic acid ester compound is preferably a phthalate carboxylic acid ester; more preferably, the aromatic carboxylic acid ester compound is at least one selected from the group consisting of diethyl phthalate, dipropyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, dipentyl phthalate, dihexyl phthalate, diheptyl phthalate and dioctyl phthalate, and still more preferably, the aromatic carboxylic acid ester compound is diisobutyl phthalate.
In some preferred embodiments of the present invention, the succinate compound is selected from the group consisting of compounds represented by formula (V),
in the formula (V), R' 1 、R" 2 、R" 3 、R" 4 、R" 5 And R'. 6 Identical or different, each independently selected from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl or C 7 -C 20 Alkylaryl, R'. 1 、R" 2 、R" 3 、R" 4 、R" 5 And R'. 6 Optionally containing heteroatoms; r' R " 3 、R" 4 、R" 5 And R'. 6 The groups may optionally be linked to form a ring.
According to the present invention, the succinic acid ester compound is selected from the group consisting of diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropyl succinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2,3- (bistrimethylsilyl) succinate, diethyl 2- (3, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisoamyl succinate, diethyl 2,3- (1-trifluoromethyl-ethyl) succinate, diethyl 2-isopropyl-3-isobutyl succinate, diethyl 2-tert-butyl-3-isopropyl succinate, diethyl 2-isopropyl-3-cyclohexyl succinate, diethyl 2, 3-dimethyl-3-cyclohexyl succinate, diethyl 2, 3-dimethyl-3-ethyl-succinate, 2, 3-diisopropyl-2, 3-diethyl 2-isopropyl-3-isobutyl succinate, diethyl 2, 2-isopropyl-3-diisopropyl-2, 3-diethyl-isopropyl-2, 3-diisopropyl-2, 3-dibutyl-2, 3-diisopropyl-succinate, diethyl 2, 3-diisopropyl-2, 3-dibutyl-2, 3-diisopropyl-succinate, diisobutyl 2,3- (bistrimethylsilyl) succinate, diisobutyl 2- (3, 3-trifluoropropyl) -3-methylsuccinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisoamyl succinate, diisobutyl 2,3- (1-trifluoromethyl-ethyl) succinate, diisobutyl 2-isopropyl-3-isobutylsuccinate diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate diisobutyl 2, 3-tetramethylsuccinate, diisobutyl 2, 3-tetraethylsuccinate diisobutyl 2, 3-tetrapropylsuccinate, diisobutyl 2, 3-diethyl-2, 3-diisopropyldisuccinate; preferably one or more selected from diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate and diisobutyl2, 3-diisopropylsuccinate.
According to the present invention, the solid catalyst component comprises titanium element, magnesium element and internal electron donor, and is a reaction product of titanium compound, magnesium compound and internal electron donor. Since the present invention is to improve the performance of the olefin polymerization catalyst by changing the external electron donor, the method for preparing the solid catalyst component in the present invention may be carried out according to a method conventionally used in the art, for example, the method disclosed in CN1506384, CN1091748, CN85100997, CN102399326A, US4540679, etc., the disclosure of which is incorporated herein by reference.
The preparation method of the solid catalyst component in the present invention includes, but is not limited to, the following methods:
method 1: adding an inert solvent into a magnesium compound, adding an organic epoxy compound and an organic phosphorus compound, dissolving, and then adding a precipitation aid and a titanium compound to precipitate a solid; adding internal electron donor, loading on solid, and treating with titanium tetrahalide and inert diluent.
Method 2: dissolving solid magnesium compound in organic alcohol compound such as 2-ethylhexanol in inert solvent such as decane or toluene, adding precipitation aid and titanium compound after dissolving, and separating out solid; adding internal electron donor, loading on solid, and treating with titanium compound and inert diluent.
Method 3: dispersing magnesium halide alcohol compound into titanium compound at low temperature (below-5 deg.c), raising temperature to high temperature (above 50 deg.c), adding internal electron donor compound during raising temperature, filtering, treating the precipitate with titanium compound, and washing the precipitate to obtain the solid catalyst component.
Method 4: preparing a suspension by using an alkoxy magnesium carrier and an inert diluent, then reacting with a mixture formed by a titanium compound and the inert diluent, filtering, performing contact reaction on the obtained precipitate, the titanium compound and an internal electron donor compound, and washing the precipitate to obtain the solid catalyst component.
According to a preferred embodiment of the present invention, a titanium compound or a mixture of a titanium compound and an inert solvent (inert solvent such as hexane, heptane, octane, decane, toluene, etc.) precooled to-15 ℃ to-40 ℃ is mixed with a magnesium compound, and 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 and the solid phase obtained is treated at least 2 times again with titanium compound and washed with solvent, finally vacuum drying to obtain the solid catalyst component.
According to the present invention, the magnesium compound may be various magnesium compounds conventionally used in the art for preparing olefin polymerization catalysts, for example, the magnesium compound may be selected from at least one of magnesium dihalide, alkoxymagnesium, alkyl magnesium, hydrate of magnesium dihalide, alkoxide of magnesium dihalide, and derivative in which one halogen atom in the magnesium dihalide molecule is substituted with hydrocarbyloxy or halohydrocarbonyloxy. According to a preferred embodiment of the present invention, the magnesium compound is an alkoxide of magnesium dihalide.
According to a preferred embodiment of the present invention, the magnesium dihalide alkoxide has a spherical magnesium alkoxide represented by the formula (VI),
MgX 2 ·m(R’OH)·nE·qH 2 o type (VI)
In formula (VI): x is chlorine or bromine; r' is C 1 -C 4 Alkyl (e.g., methyl, ethylRadical, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl) m is 0.5 to 4.0; e is an ether or ester electron donor compound, and n is 0-1.0, wherein the ether or ester can be ether or ester which is known in the art and can be used as an electron donor, and can also be an internal electron donor and/or an external electron donor used in the invention; q is 0-0.8.
According to a preferred embodiment of the invention, in formula (VI), X is chloro or bromo; r' is C1-C4 alkyl, m is 1.5-3.5; n and q are both 0.
According to a preferred embodiment of the invention, the magnesium compound is MgCl 2 ·m(CH 3 CH 2 OH), m is 1.5-3.5.
According to some embodiments of the present invention, the method of preparing the magnesium dihalide alkoxide may be prepared according to methods well known in the art, for example, with reference to the method disclosed in CN1330086 a.
According to a preferred embodiment of the present invention, the method for preparing an alkoxide of magnesium dihalide comprises: (1) Mixing anhydrous magnesium dihalide with an alcohol compound (R' OH) and reacting at 90-140 ℃ to obtain an alcohol compound of magnesium halide; (2) Shearing the magnesium halide alkoxide in a dispersion medium, and cooling in an inert medium after shearing to obtain the spherical magnesium halide alkoxide. The ratio of the anhydrous magnesium dihalide to the alcohol compound may be determined according to the ratio of the alcohol compound to be supported on the anhydrous magnesium dihalide as required. Wherein, the dispersion medium can adopt hydrocarbon inert solvents such as kerosene, white oil, silicone oil, paraffin oil, vaseline oil and the like. The inert medium may be selected from pentane, hexane, heptane, petroleum ether, raffinate, and the like. Wherein the shearing refers to shearing the magnesium halide alkoxide by external shearing force, such as high-speed stirring (such as CN 1330086), spraying (such as US 6020279), and high-gravity rotating bed (such as CN 1580136A) and emulsifying machine (CN 1463990A).
According to a preferred embodiment of the present invention, in order to further improve the purity of the magnesium compound, the obtained spherical magnesium halide alkoxide is further subjected to washing and drying steps.
According to the invention, the alkoxy magnesium is prepared by reacting metal magnesium, ethanol, isooctanol (2-ethylhexanol) and a mixed halogenating agent under inert atmosphere. The mixed halogenating agent is a combination of a halogen and a halogen compound, a non-limiting selection of which: iodine, bromine, chlorine, magnesium chloride, magnesium bromide, magnesium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, calcium bromide, calcium iodide, mercury chloride, mercury bromide, mercury iodide, magnesium ethoxyiodide, magnesium methoxyiodide, magnesium isopropyliodide, hydrogen chloride, chloroacetyl chloride, and the like.
The titanium compound according to the present invention may be various titanium compounds conventionally used in the art for preparing olefin polymerization catalysts. According to a preferred embodiment of the present invention, the titanium compound has a structure represented by formula (VII),
Ti(OR”) 4-k X k (VII)
In formula (VII): r' is C 1 -C 20 X is F, cl or Br; k is an integer of 0 to 4.
According to a preferred embodiment of the invention, in formula (VII): r' is a C1-C10 alkyl group.
According to a preferred embodiment of the invention, in formula (VII): r' is a C1-C5 alkyl group.
According to a preferred embodiment of the invention, for example, in formula (VII): r' is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl.
According to a preferred embodiment of the invention, in formula (VII): x is Cl.
According to a preferred embodiment of the present invention, the titanium compound is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium tributoxide monochloride, titanium dibutoxide dichloride, titanium tributoxide monochloride, titanium triethoxide monochloride, titanium diethoxide dichloride, titanium monoethoxide trichloride and titanium trichloride.
According to a preferred embodiment of the invention, the titanium compound is titanium tetrachloride.
According to some embodiments of the invention, the weight ratio of titanium element, magnesium element and internal electron donor in the solid catalyst component is 1 (5-25): 2-15.
In some preferred embodiments of the present invention, the alkyl aluminum compound is selected from the group consisting of compounds represented by formula (b),
AlR 3 (b),
in the formula (b), R is C with or without halogen atom substituent 1 -C 20 Alkyl groups, preferably C with or without halogen atom substituents 1 -C 6 An alkyl group.
In some preferred embodiments of the present invention, the alkyl aluminum compound is selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum dichloride, al (n-C) 6 H 13 ) 3 And Al (n-C) 8 H 17 ) 3 One or more of the following.
In some preferred embodiments of the present invention, the molar ratio of the external electron donor to the aluminum element in the alkyl aluminum compound is 1 (0.1 to 1000), preferably 1 (1 to 500).
According to the invention, the molar ratio of the solid catalyst component, calculated as titanium element, to the alkylaluminum compound, calculated as aluminum element, in the catalyst system is 1 (5-5000), preferably 1 (20-2000).
In order to achieve the second purpose, the technical scheme adopted by the invention is as follows:
a prepolymerized catalyst composition for the polymerization of olefins comprising a prepolymer obtained by polymerizing an olefin with the catalyst system according to the first aspect of the invention.
In some preferred embodiments of the invention, the prepolymer has a prepolymer fold of from 0.1 to 1000g prepolymer per g solid catalyst component, preferably from 0.2 to 500g prepolymer per g solid catalyst component, more preferably from 0.5 to 20g prepolymer per g solid catalyst component.
According to the present invention, the term "prepolymerized catalyst" refers to a catalyst which has undergone a polymerization step at a lower degree of conversion. In the present invention, the same olefin as that used for polymerization can be used for the prepolymerization.
According to some preferred embodiments of the invention, the olefin has the general formula CH 2 =chr, wherein R is hydrogen or C 1 -C 7 An alkyl group.
According to some preferred embodiments of the invention, the olefin that is prepolymerized is propylene.
According to some preferred embodiments of the present invention, propylene or a mixture thereof with one or more alpha-olefins in a molar amount of up to 20% is used for the prepolymerization.
According to some embodiments of the invention, the temperature of the prepolymerization is from-20 to 80℃and the polymerization pressure is preferably from 0 to 5MPa.
According to some preferred embodiments of the invention, the temperature of the prepolymerization is 0-50 ℃.
According to some embodiments of the invention, the prepolymerization is carried out in liquid or in gas phase.
According to some embodiments of the invention, the pre-polymerization step may be performed in-line as part of a continuous polymerization process or separately in a batch operation.
According to some preferred embodiments of the present invention, to prepare 0.1 to 1000g of olefin prepolymer per g of polymer of solid catalyst component, the prepolymerization of the catalyst according to the invention with olefin is carried out independently in a batch operation, the polymerization pressure being 0 to 5MPa.
In order to achieve the third purpose, the technical scheme adopted by the invention is as follows:
the use of the catalyst system described above or the prepolymerized catalyst composition described above in the field of olefin polymerization, in particular propylene polymerization.
According to the invention, the olefins have the general formula CH 2 =chr, wherein R is hydrogen or C 1 -C 7 Alkyl, said olefin polymerization may be a homo-polymerization of a single said olefin or a co-polymerization of a plurality of said olefins, or may beTo be a combination of a single olefin homo-polymerization process and a multiple olefin co-polymerization process.
According to some preferred embodiments of the invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
According to some preferred embodiments of the invention, the olefin is ethylene, propylene and/or 1-butene.
In order to achieve the fourth purpose, the technical scheme adopted by the invention is as follows:
a process for the polymerization of olefins comprising: the olefin is polymerized in the presence of the above-described catalyst system and/or the above-described prepolymerized catalyst composition.
In some preferred embodiments of the invention, the polymerization conditions include: the temperature is 0 ℃ to 150 ℃, preferably 50 ℃ to 90 ℃; the pressure is 0.01MPa to 10MPa, preferably 0.1MPa to 5MPa; the time is 0.1 to 5 hours, preferably 0.2 to 3 hours.
According to some embodiments of the invention, both the catalyst system and the prepolymerized catalyst composition may be used for the polymerization of olefins.
According to some preferred embodiments of the present invention, both the catalyst system and the prepolymerized catalyst composition may be used in the homo-polymerization of propylene or in the copolymerization of other olefins.
According to the invention, the catalyst system of the invention can be added directly to the reactor for use in the polymerization process or can be added to the reactor after the catalyst system has been prepolymerized with the olefin to obtain a prepolymerized catalyst composition.
According to the present invention, the olefin polymerization may be carried out according to a known polymerization method, in a liquid phase or a gas phase, or in a combination of liquid and gas phase polymerization stages, or by a conventional technique such as a slurry method, a gas phase fluidized bed, or the like.
According to the invention, the polymerization may be carried out in the presence of a solvent. Wherein the concentration of the catalyst system in the solvent, based on the titanium element in the solid catalyst component, may be 0.1×10 -5 -5×10 -5 Moles/liter.
According to some preferred embodiments of the present invention, the concentration of the catalyst system in the solvent may be 0.2X10, based on the titanium element in the solid catalyst component -5 -2×10 -5 Moles/liter.
In the present invention, alkyl refers to straight chain alkyl or branched alkyl, non-limiting examples of which include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, n-heptyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, tetrahydrogeranyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl n-hexadecyl, n-octadecyl, n-nonadecyl and n-eicosyl.
In the present invention, examples of alkenyl groups may include, but are not limited to: ethenyl, propenyl, butenyl, pentenyl, octenyl.
In the present invention, examples of alkynyl groups may include, but are not limited to: ethynyl and propargyl.
Examples of cycloalkyl groups in the present invention may include, but are not limited to: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-n-propylcyclohexyl, 4-n-butylcyclohexyl, cycloundecyl and cyclododecyl.
Examples of halogens in the present invention include, but are not limited to, fluorine, chlorine, bromine, and iodine.
In the present invention, examples of aryl groups may include, but are not limited to: phenyl, methylphenyl, ethylphenyl, 4-tert-butylphenyl, naphthyl.
In the present invention, aralkyl refers to an alkyl group having an aryl substituent, examples may include, but are not limited to: phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl and phenyl-isopropyl.
In the present invention, alkylaryl refers to an aryl group having an alkyl substituent with a carbon number of 7 to 20, examples of which may include, but are not limited to: methylphenyl, ethylphenyl.
In the present invention, examples of alkoxy groups may include, but are not limited to: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, isopentoxy, tert-pentoxy and hexoxy.
In the present invention, the hetero atom means an atom commonly contained in a molecular structure other than a halogen atom, a carbon atom and a hydrogen atom, for example, O, N, S, P, si, B and the like.
The invention adopts the ketoester compound shown in the formula (I) or the derivative thereof as an external electron donor, takes alkyl aluminum as a cocatalyst and is matched with a solid catalyst component for use, and the catalyst system can improve the stereospecificity of the catalyst system, slow down the activity decay rate of the catalyst system and improve the molecular weight of a polymerization product under the condition of keeping higher activity, so that a high-isotactic high-rigidity polyolefin product can be prepared; the catalyst system can simultaneously improve the yield and the ethylene content of the product during the impact copolymerization of the ethylene and the propylene.
Detailed Description
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.
1. Polymerization activity of the catalyst: the amount of polymer obtained (in kg) over a period of time divided by the amount of catalyst added (in g).
2. Weight average molecular weight: high temperature gel permeation chromatography, measured with reference to standard GB/T36214.4-2018.
3. Polymer isotactic index: reference standard GB/T2412-2008.
4. Ethylene content: and measuring by an infrared spectrometer.
Preparation example 1
This preparation example is used to illustrate the preparation of the solid catalyst component.
Sequentially adding the components into a reactor fully replaced by high-purity nitrogenMagnesium chloride 6.0g, toluene 119mL, epichlorohydrin 5mL, tributyl phosphate (TBP) 15.6mL, and the solid was completely dissolved while stirring and heating to 50℃and maintaining for 2.5 hours; phthalic anhydride 1.7g was added and continued for 1 hour; cooling the solution to below-25 ℃, and dripping TiCl in 1 hour 4 70mL, slowly heating to 80 ℃, and gradually precipitating solid matters in the heating process; 6mmol of 3-methyl-2, 4-pentanediol dibenzoate was added as an internal electron donor, the temperature was maintained for 1 hour, and after filtration, 80mL of toluene was added and washed twice to obtain a solid precipitate. 60mL of toluene and TiCl are then added 4 40mL, heating to 100deg.C, treating for 2 hours, removing filtrate, adding 60mL toluene, tiCl 4 40mL, heating to 100 ℃, treating for 2 hours, and discharging filtrate; 60mL of toluene is added, the mixture is washed three times in a boiling state, 60mL of hexane is added, the mixture is washed twice in a boiling state, 60mL of hexane is added, and the mixture is washed twice at normal temperature, so that a solid catalyst component Z1 with the titanium content of 2.4wt% is obtained.
Preparation example 2
This preparation example is used to illustrate the preparation of magnesium compounds.
Mixing anhydrous magnesium chloride and ethanol according to the molar ratio of 1:2.6, heating to 120 ℃ for reaction to generate magnesium chloride alkoxide melt, stirring at high speed in dispersion medium white oil and silicone oil, then placing into cooled hexane to form spherical magnesium chloride alkoxide particles, washing and drying to obtain the spherical carrier.
Preparation example 3
This preparation example is used to illustrate the preparation of the solid catalyst component.
In a 300mL glass reaction flask with stirring, which is fully replaced by high-purity nitrogen, 100mL of titanium tetrachloride is added, the mixture is cooled to-20 ℃, 8g of spherical magnesium chloride alkoxide prepared in preparation example 2 is added, the temperature is slowly raised to 110 ℃, 3mmol of 2, 4-pentanediol dibenzoate and 3mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane are added as internal electron donors in the heating process, after the temperature is kept constant at 110 ℃ for 0.5h, the liquid is filtered, the titanium tetrachloride is added for two times, then the mixture is washed with hexane for five times, and the titanium-containing solid catalyst component Z2 with the titanium content of 2.7 weight percent is obtained after vacuum drying.
Preparation example 4
This preparation example is used to illustrate the preparation of the solid catalyst component.
In a 300mL glass reaction flask with stirring, which is fully replaced by high-purity nitrogen, 100mL of titanium tetrachloride is added, the mixture is cooled to-20 ℃, 8g of spherical magnesium chloride alkoxide prepared in preparation example 2 is added, the temperature is slowly raised to 110 ℃, 6mmol of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane is added as an internal electron donor in the heating process, after the temperature is kept constant at 110 ℃ for 0.5h, liquid is filtered, titanium tetrachloride is added for treatment twice, then hexane is used for washing for five times, and the titanium-containing solid catalyst component Z3 with the titanium content of 2.4wt% is obtained after vacuum drying.
Preparation example 5
This preparation example is used to illustrate the preparation of the solid catalyst component.
In a 300mL glass reaction bottle with stirring, which is fully replaced by high-purity nitrogen, 100mL of titanium tetrachloride is added, the mixture is cooled to-20 ℃, 8g of spherical magnesium chloride alkoxide prepared in preparation example 2 is added, the temperature is slowly raised to 110 ℃, 3mmol of diisobutyl phthalate and 3mmol of 3-methyl-2, 4-pentanediol dibenzoate are added as internal electron donors in the heating process, after the temperature is kept constant for 0.5h at 110 ℃, the liquid is filtered, the titanium tetrachloride is added for treatment twice, then the mixture is washed with hexane for five times, and the titanium-containing solid catalyst component Z4 with the titanium content of 2.5wt% is obtained after vacuum drying.
The compounds KE1-KE9 and carbofuran are used after the molecular sieve is soaked.
Examples 1 to 17 and comparative examples 1 to 7
Examples 1-17 and comparative examples 1-7 are provided to illustrate the catalyst systems provided by the present invention and their use.
A 48-channel parallel pressure reactor (reaction volume 20 mL) was charged with a certain amount of hydrogen; charging propylene gas to about 1MPa, and adding 5mL of liquid propylene; as triethylaluminum (as elemental aluminum): external electron donor: adding triethylaluminum, an external electron donor and a heptane solution of the solid catalyst component (calculated by titanium element) in a molar ratio of 500:20:1 to prepare a mixed solution; taking a certain amount of mixed solution (containing 0.02mg of solid catalyst component by mass) and injecting the mixed solution into a reactor; the reaction was carried out at 70℃for 1 hour.
Discharging, and calculating the activity of the catalyst; the isotactic index and weight average molecular weight of the polymer were also measured, and the results are shown in Table 1.
TABLE 1
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Note that: c-donor: cyclohexyl methyl dimethoxy silane;
KE1: isopropyl acetoacetate;
KE2: ethyl 2-oxocyclopentanecarboxylate;
KE3: 2-methoxyethyl acetoacetate;
KE4: methyl 4, 4-dimethyl-3-pentanoate;
KE5: methyl 2-oxocyclopentane carboxylate;
KE6: 4-methoxy acetoacetic acid methyl ester;
KE7: tert-butyl acetoacetate;
KE8: 4-oxotetrahydrothiophene-3-carboxylic acid methyl ester;
KE9: ethyl benzoylacetate.
As can be seen from Table 1, when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the isotactic index of the polymer is improved, and the weight average molecular weight is obviously improved. Compared with the common catalyst system, the catalyst system containing the ketoester is added, the isotacticity index of the product is improved, the weight average molecular weight of the product is improved, and the catalyst system is favorable for producing high-rigidity polypropylene products with high stereoregularity.
Examples 18 to 25 and comparative examples 8 to 11
This example is intended to illustrate the attenuation properties of a catalyst system comprising a ketoester compound as an external electron donor.
In a 48-channel parallel pressure reactor (reaction volume 20 mL), the autoclave was purged with hydrogen; charging propylene gas to about 1MPa, and adding 5mL of liquid propylene; as triethylaluminum (as elemental aluminum): external electron donor: adding triethylaluminum, an external electron donor and a heptane solution of the solid catalyst component (calculated by titanium element) in a molar ratio of 250:25:1 to prepare a mixed solution; taking a certain amount of mixed solution (containing 0.02mg of solid catalyst component by mass) and injecting the mixed solution into a reactor; the reaction is carried out at 70 ℃ for a certain time. And discharging, and calculating the activity of the catalyst.
TABLE 2
Note that: c-donor: cyclohexyl methyl dimethoxy silane;
AC 90 、AC 60 、AC 30 distribution represents 90min, 60min, 30min reactivity.
As can be seen from Table 2, when the catalyst system provided by the invention is used for olefin polymerization, especially propylene polymerization, the activity attenuation is obviously slowed down, and compared with the conventional catalyst system, the catalyst system added with the catalyst system containing ketoester as an external electron donor has longer activity life, thereby being beneficial to industrial production.
Examples 26 to 28 and comparative examples 12 to 14
This example illustrates the application of a ketoester compound as an external electron donor in impact copolymerization.
In a 48-channel parallel pressure reactor (reaction volume 20 ml), the autoclave was purged with hydrogen; charging propylene gas to about 1MPa, and adding 5ml of liquid propylene; as triethylaluminum (as elemental aluminum): external electron donors in table 2: adding triethylaluminum, an external electron donor and a solid catalyst component in a molar ratio of 250:25:1 (calculated by titanium element) to prepare a mixed solution; taking a certain amount of mixed solution (containing 0.02mg of solid catalyst component by mass) and injecting the mixed solution into a reactor; the reaction is carried out for 40 minutes at 70 ℃, the system is replaced by ethylene-propylene mixed gas (the volume ratio of ethylene to propylene is 1:1), and the pressure is controlled at 80 ℃ for 0.7Mpa for 20 minutes.
Discharging, weighing the polymer by using a weighing device of the PPR, and calculating to obtain the activity of the catalyst; the ethylene content of the polymer was also measured, and the results are shown in Table 3.
TABLE 3 Table 3
| Examples | Solid catalyst component | External electron donor | Activity (kgPP/gCat) | Ethylene content (wt%) |
| Example 26 | Z1 | KE4 | 62 | 7.9 |
| Comparative example 12 | Z1 | C-donor | 31 | 6.7 |
| Example 27 | Z2 | KE9 | 77 | 5.2 |
| Comparative example 13 | Z2 | C-donor | 62 | 4.7 |
| Example 28 | Z3 | KE7 | 69 | 6.7 |
| Comparative example 14 | Z3 | C-donor | 42 | 6.4 |
Note that: c-donor: cyclohexylmethyldimethoxysilane.
As can be seen from Table 3, when the catalyst system provided by the invention is used for olefin copolymerization, especially ethylene-propylene copolymerization, compared with the catalyst system in which C-Donor is used as an external electron Donor, the ethylene content of a copolymer obtained by the catalyst system in which the external electron Donor contains a ketoester compound shown as the formula (I) is improved, and the polymerization activity is improved. According to the characteristics of the catalyst provided by the invention, the catalyst system provided by the invention is also suitable for a copolymerization system, and is beneficial to improving the copolymerization productivity.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (22)
1. A catalyst system for olefin polymerization comprising the following components or the reaction product of the following components:
1) A solid catalyst component comprising magnesium element, titanium element, halogen and an internal electron donor;
2) A cocatalyst component selected from alkyl aluminum compounds;
3) An external electron donor comprising a ketoester compound represented by formula (I),
formula (I)
In the formula (I) of the present invention,
M 1 and M 2 Identical or different, each independently selected from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl group wherein M 1 ，M 2 Optionally containing substituents selected from C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 One or more of alkylamino, aldehyde, and carboxyl;
R 1 and R is 2 The same or different, each independently selected from hydrogen, hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 Alkylamino, carboxyl, R a C(O)-、R a O-、C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 3 -C 12 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl, 4-12 membered heterocycloalkyl and C 5 -C 20 Heteroaryl, wherein R a Selected from C 1 -C 10 Alkyl, C 2 -C 10 Alkenyl, C 2 -C 10 Alkynyl, C 3 -C 8 Cycloalkyl, C 6 -C 10 Aryl, C 7 -C 20 Aralkyl, 4-12 membered heterocycloalkyl and C 5 -C 20 Heteroaryl;
M 1 ，M 2 ，R 1 And R is 2 Optionally forming a ring with each other, said ring being selected from the group consisting of a saturated or unsaturated monocyclic ring, a saturated or unsaturated polycyclic ring, and combinations thereof;
the internal electron donor is selected from one or more of diether compounds, alcohol ester compounds, aromatic carboxylic acid ester compounds or succinic acid ester compounds.
2. The catalyst system of claim 1, wherein in formula (I), M 1 And M 2 Identical or different, each independently selected from C 1 -C 10 Alkyl, C 3 -C 10 Cycloalkyl, C 6 -C 15 Aryl, C 7 -C 15 Aralkyl and C 7 -C 15 Alkylaryl group wherein M 1 And M 2 Optionally containing substituents; or M 1 、R 1 Together with the carbon atoms to which they are attached form a 3-6 membered ring.
3. The catalyst system of claim 2, wherein the 3-6 membered ring is a 3-6 membered aliphatic ring.
4. The catalyst system of claim 1, wherein in formula (I), R 1 And R is 2 The same or different are each independently selected from hydrogen, C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy and C 6 -C 10 An aryloxy group.
5. The catalyst system of claim 4, wherein in formula (I), R 1 And R is 2 The same or different are each independently selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 An alkoxy group.
6. The catalyst system of claim 1 wherein the substituents are selected from the group consisting of C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, fluoro, chloro, bromo and iodo.
7. The catalyst system according to claim 1 or 2, characterized in that,
in the formula (I), M 1 And M 2 Each independently selected from C 1 -C 10 Alkyl, C 6 -C 15 Aryl, C 7 -C 15 Aralkyl and C 7 -C 15 Alkylaryl group wherein M 1 And M 2 Optionally containing substituents, or M 1 、R 1 Together with the carbon atoms to which they are attached, form a 3-6 membered ring, said 3-6 membered ring optionally containing oxygen and/or sulfur; r is R 1 And R is 2 Each independently selected from hydrogen, C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, unsubstituted or substituted phenyl; the substituents are selected from C 1 -C 6 Alkyl, C 1 -C 6 Alkoxy, fluoro, chloro, bromo and iodo.
8. The catalyst system of claim 7 wherein the 3-6 membered ring is a five membered aliphatic ring.
9. The catalyst system of any of claims 1-6, wherein the diether compound is a 1,3 diether compound;
the alcohol ester compound is selected from glycol ester compounds shown in a formula (III),
formula (III),
in the formula (III), R 1 And R is 2 Identical toOr different, each independently selected from C containing or not containing substituents 1 -C 20 Alkyl, C with or without substituents 2 -C 20 Alkenyl, C with or without substituents 2 -C 20 Alkynyl, C with or without substituents 3 -C 20 Cycloalkyl, C with or without substituents 6 -C 20 Aryl, C with or without substituents 7 -C 20 Alkylaryl, C with or without substituents 7 -C 20 Aralkyl and C with or without substituents 10 -C 20 Condensed ring aryl groups, the substituents being selected from hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, bis-C 1 -C 6 One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is a divalent linking group;
the aromatic carboxylic ester compound is selected from compounds shown in a formula (IV),
the compound of formula (IV),
in the formula (IV), each R 3 The same or different, each independently selected from the group consisting of C 1 -C 6 C of substituents on alkyl and halogen atoms 1 -C 8 Alkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 5 -C 10 Cycloalkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 6 -C 15 With or without aryl groups, selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 15 Alkylaryl groups optionally containing a member selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 15 Aralkyl of (a); r is R 4 -R 7 May be the same or different and are each independently selected from hydrogen, halogen, with or without C 1 -C 6 C of substituents on alkyl and halogen atoms 1 -C 8 Alkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 5 -C 10 Cycloalkyl, with or without radicals selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 6 -C 20 With or without aryl groups, selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 20 Alkylaryl groups optionally containing a member selected from C 1 -C 6 C of substituents on alkyl and halogen atoms 7 -C 20 An aralkyl group;
the succinate compound is selected from compounds shown in a formula (V),
(V)
In the formula (V), R' 1 、R" 2 、R" 3 、R" 4 、R" 5 And R'. 6 Identical or different, each independently selected from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl or C 7 -C 20 Alkylaryl, R'. 1 、R" 2 、R" 3 、R" 4 、R" 5 And R'. 6 Optionally containing heteroatoms; r' R " 3 、R" 4 、R" 5 And R'. 6 The groups may optionally be linked to form a ring.
10. The catalyst system of claim 9, wherein the diether compound is a 1, 3-diether compound of formula (II),
formula (II)
In the formula (II), R' 1 、R' 2 、R' 3 、R' 4 、R' 5 And R'. 6 The same or different, each independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 An alkylaryl group; r's' 7 And R'. 8 Identical or different, each independently selected from C 1 -C 20 Alkyl, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Aralkyl and C 7 -C 20 Alkylaryl, wherein R' 1 、R' 2 、R' 3 、R' 4 、R' 5 、R' 6 、R' 7 And R'. 8 Optionally containing substituents selected from hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 10 Alkylamino, bis-C 1 -C 10 One or more of alkylamino, aldehyde, and carboxyl; optionally, R' 1 、R' 2 、R' 3 、R' 4 、R' 5 And R'. 6 Two or more of which are bonded to each other to form a saturated or unsaturated single or multiple ring;
in the formula (III), R 1 And R is 2 Identical or different, each independently selected from C containing or not containing substituents 1 -C 10 Alkyl, C with or without substituents 2 -C 10 Alkenyl, C with or without substituents 3 -C 10 Cycloalkyl, C with or without substituents 6 -C 10 Aryl, C with or without substituents 7 -C 10 Alkylaryl, C with or without substituents 7 -C 10 Aralkyl and C with or without substituents 10 -C 15 Condensed ring aryl groups, the substituents being selected from hydroxy, halogen, cyano, nitro, amino, mono-C 1 -C 6 Alkylamino, bis-C 1 -C 6 One or more of alkylamino, aldehyde, carboxyl and heteroatom; m is selected from C with or without substituents 1 -C 20 Alkylene, C with or without substituents 3 -C 20 Cycloalkylene and C with or without substituents 6 -C 20 Arylene groups, the substituents being selected from nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms and C 1 -C 20 Alkyl, where the substituents are a plurality of C 1 -C 20 When alkyl, the substituents are optionally bonded to form one or more rings.
11. The catalyst system of any of claims 1-6, wherein the alkyl aluminum compound has the formula AlR 3 Wherein each R is independently selected from hydrogen, halogen, C 1 -C 20 Alkyl, C 1 -C 20 Alkoxy or halo C 1 -C 20 Alkyl, at least one of three R is C 1 -C 20 An alkyl group.
12. The catalyst system of claim 11 wherein said alkyl aluminum compound has the formula AlR 3 Wherein each R is independently selected from hydrogen, halogen, C 1 -C 10 Alkyl, C 1 -C 10 Alkoxy or halo C 1 -C 10 Alkyl, at least one of three R is C 1 -C 10 An alkyl group.
13. The catalyst system of claim 12, wherein the alkyl aluminum compound is one or more of triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monohydride, and ethylaluminum dichloride.
14. The catalyst system of any one of claims 1 to 6, wherein the molar ratio of the external electron donor to the aluminum element in the alkyl aluminum compound is 1 (0.1 to 1000),
the molar ratio of the external electron donor to the titanium element in the solid catalyst component is (0.01-200): 1;
in the catalyst system, the molar ratio of the solid catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1 (5-5000).
15. The catalyst system of claim 14 wherein the molar ratio of said external electron donor to aluminum element in said alkyl aluminum compound is 1 (1-500),
the molar ratio of the external electron donor to the titanium element in the solid catalyst component is (0.1-100): 1, a step of;
in the catalyst system, the molar ratio of the solid catalyst component calculated as titanium element to the alkyl aluminum compound calculated as aluminum element is 1 (20-2000).
16. A prepolymerized catalyst composition comprising a prepolymer obtained by polymerizing an olefin with the catalyst system according to any one of claims 1 to 15.
17. The prepolymerized catalyst composition according to claim 16, characterized in that the prepolymer has a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of solid catalyst component.
18. The prepolymerized catalyst composition according to claim 16, characterized in that the olefin is propylene.
19. Use of the catalyst system of any one of claims 1-15 or the prepolymerized catalyst composition of any one of claims 16-18 in olefin polymerization.
20. A process for the polymerization of olefins comprising: polymerizing an olefin under olefin polymerization conditions in the presence of the catalyst system of any one of claims 1-15 or the prepolymerized catalyst composition of claim 16 or 17.
21. The process for the polymerization of olefins according to claim 20 wherein said olefins are of the formula CH 2 =chr, wherein R is hydrogen or C 1 -C 7 An alkyl group.
22. The olefin polymerization process of claim 21 wherein said olefin is selected from one or more of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
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| US9777084B2 (en) * | 2016-02-19 | 2017-10-03 | Formosa Plastics Corporation, Usa | Catalyst system for olefin polymerization and method for producing olefin polymer |
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