CN117430732A - Catalyst component for propylene polymerization, preparation method thereof, catalyst and application - Google Patents

Catalyst component for propylene polymerization, preparation method thereof, catalyst and application Download PDF

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Publication number
CN117430732A
CN117430732A CN202210823337.7A CN202210823337A CN117430732A CN 117430732 A CN117430732 A CN 117430732A CN 202210823337 A CN202210823337 A CN 202210823337A CN 117430732 A CN117430732 A CN 117430732A
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Prior art keywords
dibenzoate
compound
heptanediol
catalyst component
methyl
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蔡晓霞
刘海涛
庄庄
马吉星
何世雄
李昌秀
胡建军
许景琦
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene

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

Abstract

The invention belongs to the technical field of catalysts, and discloses a catalyst component for propylene polymerization, a preparation method, a catalyst and application thereof, wherein the catalyst component comprises magnesium, titanium, halogen and an electron donor, and the electron donor contains a compound X and a compound Y; the general formula of the compound X is R a ‑O‑R b Wherein R is a 、R b Identical or different, selected from C 1 ‑C 20 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not; the compound Y is a glycol ester compound. The catalyst of the invention has good fluidity, good particle morphology and uniform particle size distribution, and has high performance when being used for propylene polymerizationThe activity and hydrogen regulation sensitivity are good, and the obtained polymer does not contain phthalate compounds.

Description

Catalyst component for propylene polymerization, preparation method thereof, catalyst and application
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst component for propylene polymerization and a preparation method thereof, a catalyst containing the catalyst component, and application of the catalyst component and the catalyst.
Background
Olefin polymerization catalysts can be divided into three broad categories, namely traditional Ziegler-Natta catalysts, metallocene catalysts, and non-metallocene catalysts. For traditional Ziegler-Natta catalysts, polyolefin catalysts are continually updated as electron donor compounds in the catalysts develop. Catalyst development was carried out from the first generation TiCl 3 AlCl 3 /AlEt 2 Cl system and TiCl of the second generation 3 /AlEt 2 Cl system, tiCl with third generation magnesium chloride as carrier, monoester or aromatic dibasic acid ester as internal electron donor and silane as external electron donor 4 ·ED·MgCl 2 /AlR 3 The ED system, the catalytic polymerization activity of the catalyst and the isotacticity of the obtained polypropylene are greatly improved.
In the prior art, titanium catalyst systems for propylene polymerization mostly use magnesium, titanium, halogen and an electron donor (internal electron donor) as basic components, wherein the electron donor is one of indispensable components in the catalyst components, plays a crucial role in improving the catalyst performance, and is one of key factors influencing the catalyst performance.
At present, various electron donor compounds have been disclosed, such as phthalates, diethers, glycol esters, succinates, see patent documents US4784983, US4971937, EP0728769, WO98/56830, WO98/56834, CN1436766A, CN1453298, etc.
Different electron donor compounds have respective advantages and disadvantages. For example, glycol ester compounds are used as internal electron donor catalysts, the activity of the catalyst is high, the molecular weight distribution of the polymer obtained by polymerization is wide, but the hydrogen regulation sensitivity of the catalyst is poor, and the catalyst is unfavorable for producing polymers with high melt indexes. The monoether compounds have very low internal electron donor activity as catalysts for propylene polymerization.
Disclosure of Invention
In view of the above, the inventors of the present invention have unexpectedly found that when a monoether is compounded with a glycol ester compound in the preparation of a catalyst component for propylene polymerization, a catalyst having high activity, good hydrogen-regulating sensitivity and excellent comprehensive properties can be obtained, and a phthalate ester compound is not contained in the polymer. Based on this, it is an object of the present invention to provide a catalyst component for propylene polymerization, a process for its preparation, a catalyst and its use.
The first aspect of the present invention provides a catalyst component for propylene polymerization, comprising magnesium, titanium, halogen and an electron donor, said electron donor containing a compound X and a compound Y;
the general formula of the compound X is R a -O-R b Wherein R is a 、R b Identical or different, selected from C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not;
the compound Y is a glycol ester compound.
The second aspect of the present invention provides a process for preparing the above catalyst component for propylene polymerization, which comprises:
1) Dissolving a magnesium compound in a system containing a compound X, adding a precipitation aid and a precipitation agent, and precipitating a solid;
2) The solid precipitated in step 1) is treated with a titanium compound and the compound Y is added during and/or before the treatment of the solid with the titanium compound.
In a third aspect the present invention provides a catalyst for propylene polymerization comprising the reaction product of:
a. the catalyst component described above, or a catalyst component produced by the above production method;
b. alkylaluminum compounds of the formula AlR' n X’ 3-n In the general formula, R' is hydrogen or C 1 -C 20 X' is halogen, n is more than 0 and less than or equal to 3;
c. optionally, an external electron donor.
In a fourth aspect the present invention provides the use of the above catalyst component, the catalyst component prepared by the above preparation method, or the above catalyst in propylene polymerization.
In the preparation process of the catalyst component, the monoether and glycol ester compound are compounded, so that the catalyst has good synergistic effect, and can be obtained with good fluidity, good particle morphology, uniform particle size distribution and excellent comprehensive performance. In addition, the invention can further improve the performance of the catalyst by adjusting the adding mode, the content proportion and the like of the electron donor. When the catalyst is used for propylene polymerization, the catalyst has high activity and good hydrogen regulation sensitivity, and the obtained polymer does not contain phthalate compounds.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention there is provided a catalyst component for propylene polymerization comprising magnesium, titanium, halogen and an electron donor, said electron donor comprising a compound X and a compound Y;
the general formula of the compound X is R a -O-R b Wherein R is a 、R b Identical or different, selected from C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not;
the compound Y is a glycol ester compound.
Preferably, R a 、R b Identical or different, selected from C 1 -C 10 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not.
More preferably, R a 、R b Identical or different, selected from C 1 -C 10 Unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not.
The compound X in the present invention may be selected from, but is not limited to, at least one of the following compounds: methyl ether, ethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, n-pentyl ether, methyl n-pentyl ether, cyclohexyl ether, ethylcyclohexyl ether, cyclohexylvinyl ether, n-heptyl ether, n-octyl ether, n-nonyl ether, n-decyl ether, ethylene oxide, propylene oxide, and tetrahydrofuran.
The compound Y in the present invention may be at least one selected from compounds represented by the general formula (I),
in the formula (I), R 1 And R is 2 Identical or different, selected from C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched chain alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, and fused ring aryl groups; a is a divalent supporting group of alkyl, cycloalkyl or aryl having 1 to 20 carbon atoms, and the divalent supporting group is optionally C 1 -C 20 Wherein the divalent radicals are substituted by straight-chain or branched alkyl radicalsAnd the carbon atoms or/and hydrogen atoms in the substituents thereof may optionally be replaced by heteroatoms, which are nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms, the substituents on the divalent radicals being optionally bonded to form saturated and/or unsaturated rings or rings.
Preferably, R 1 And R is 2 Identical or different, selected from C 1 -C 20 Substituted or unsubstituted aryl, alkylaryl; a comprises formula (III), formula (IV) or formula (V),
in the formula (III), R' 3 -R′ 8 Identical or different, selected from hydrogen, halogen and C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, fused ring aryl, ester, R' 7 And R'. 8 Optionally bonded to form a ring or not;
in the formula (IV), R 1 -R 4 Identical or different, selected from C 1 -C 20 Straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, and fused ring aryl radicals, R 1 -R 4 Optionally bonded to one or more rings that are saturated and/or unsaturated;
in the formula (V), R is selected from hydrogen, halogen and C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched chain alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, fused ring aryl.
In the present invention, the compound Y may be selected from 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol dimethyl benzoate, 3, 5-heptanediol diphemethyl benzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol diphemethoxybenzoate, 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-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-4, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-heptanediol dibenzoate, 4-dimethyl-5-heptanediol dibenzoate, 6, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 6-methyl-2, 4-heptanediol di (p-chlorobenzoic 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-2, 4-octanediol di (m-methylbenzoic acid) ester, 2, 6-tetramethyl-3, 5-octanediol dibenzoate, 4-methyl-3, 5-octanediol dibenzoate, 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-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, 1, 8-naphthalate di-4-methylbenzoic acid, 1, 8-naphthalate di-3-methylbenzoic acid, 1, 8-naphthalate di-2-methylbenzoic acid, 1, 8-naphthalate di-4-ethylbenzoic acid, 1, 8-naphthalate di-4-n-propylbenzoic acid, 1, 8-naphthalate di-4-isopropylbenzoic acid, 1, 8-naphthalate di-4-n-butylbenzoic acid, 8-naphthalene ester, di-4-isobutylbenzoic acid-1, 8-naphthalene ester, di-4-tert-butylbenzoic acid-1, 8-naphthalene ester, di-4-phenylbenzoic acid-1, 8-naphthalene ester, di-4-fluorobenzoic acid-1, 8-naphthalene ester, di-3-fluorobenzoic acid-1, 8-naphthalene ester, di-2-fluorobenzoic acid-1, 8-naphthalene ester.
According to the invention, the molar ratio of the compound X to the compound Y is r,0 < r < 5, preferably 0 < r.ltoreq.3, more preferably 0 < r.ltoreq.2.
According to a second aspect of the present invention, there is provided a process for preparing the above-mentioned catalyst component for propylene polymerization, which is obtainable by contacting a magnesium compound, a titanium compound, a compound X and a compound Y.
The preparation method of the catalyst component includes but is not limited to the following methods:
1) Dissolving a magnesium compound in a system containing a compound X, adding a precipitation aid and a precipitation agent, and precipitating a solid;
2) The solid precipitated in step 1) is treated with a titanium compound and the compound Y is added during and/or before the treatment of the solid with the titanium compound.
According to the invention, in step 1) the "dissolving magnesium compound in the system containing compound X" may be that the magnesium compound is first dissolved in a solvent system to obtain a solution, and then compound X is added; the magnesium compound may be dissolved in a system comprising the compound X and a solvent system.
In the present invention, the solvent system may be a solvent system conventionally used in the prior art for dissolving a magnesium compound. For example, the solvent system may be a solvent system containing an organic epoxy compound, an organic phosphorus compound, and optionally an inert diluent, or may be a solvent system containing an organic alcohol compound and optionally an inert diluent.
According to the present invention, the organic epoxy compound, the organic phosphorus compound, etc. may be conventionally selected according to the prior art. The organic epoxy compound may be selected from aliphatic olefins, diolefins or halogenated aliphatic olefins having 2 to 8 carbon atoms substituted with hetero atoms, and may be epichlorohydrin, epibromohydrin, etc. The organophosphorus compound may be selected from hydrocarbyl or halogenated hydrocarbyl esters of orthophosphoric acid or phosphorous acid; specifically, the organic phosphorus compound may be selected from at least one of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and benzyl phosphite.
In the invention, the general formula of the organic alcohol compound is R 8 OH, wherein R is 8 C being a substituted or unsubstituted straight or branched chain 1 -C 20 Alkyl, C 2 -C 20 Alkylene, C 3 -C 20 Cycloalkyl, C 6 -C 20 Aryl, C 7 -C 20 Alkylaryl or C 7 -C 20 Aralkyl groups, preferably selected from linear or branched C 2 -C 10 Alkyl groups, further preferably at least one selected from ethanol, butanol and isooctyl alcohol.
According to the invention, the inert diluent may be any of the various solvents customary in the art for dissolving Ziegler-Natta catalyst components, preferably selected from C 6 -C 10 More preferably at least one selected from the group consisting of hexane, heptane, octane, decane, benzene, toluene, xylene and derivatives thereof.
In the present invention, the magnesium compound may be selected from magnesium dihalide, magnesium alkoxide, magnesium alkyl, a hydrate or an alkoxide of magnesium dihalide, and a derivative in which one halogen atom in the formula of magnesium dihalide is replaced with an alkoxy group or a haloalkoxy group; preferred are magnesium dihalides or magnesium dihalide alkoxides such as magnesium dichloride, magnesium dibromide, magnesium diiodide and their alkoxides.
According to the invention, the titanium compound can be selected from TiX m (OR″ 1 ) 4-m Wherein R', is a compound of formula (I) 1 Is C 1 -C 20 X is halogen, m is more than or equal to 1 and less than or equal to 4. Specifically, the titanium compound may be selected from: titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxide, preferably titanium tetrachloride.
In the present invention, the precipitating agent may be a metal halide such as titanium halide, iron halide, zinc halide, etc., of which titanium halide such as titanium tetrachloride or titanium tetrabromide, etc. is preferable; titanium tetrachloride is more preferred.
According to the invention, the precipitation aid may be selected from oxygen-containing compounds, preferably from acid anhydrides and diesters, more preferably from acid anhydrides and malonates. Specifically, the organic acid is selected from acetic anhydride, phthalic anhydride (phthalic anhydride), succinic anhydride, maleic anhydride, pyromellitic dianhydride, diethyl diisobutylmalonate, diethyl di-n-butylmalonate, diethyl di-t-butylmalonate, dipropyl di-isobutyl malonate, dipropyl di-n-butylmalonate, dibutyl di-i-butylmalonate, dibutyl di-n-butylmalonate, dibutyl di-t-butylmalonate, dipentyl di-n-butylmalonate, dipentyl di-t-butylmalonate, dihexyl di-n-butylmalonate, dihexyl di-t-butylmalonate, and the like.
The solid catalyst component of the present invention can be prepared according to the method described below, but the preparation method of the catalyst component according to the present invention is not limited thereto.
Firstly, dissolving a magnesium compound in a system consisting of a compound X, an organic epoxy compound, an organic phosphorus compound and an inert diluent to form a uniform solution, and then mixing the uniform solution with a precipitation agent (such as a titanium compound) in the presence of a precipitation aid, heating the uniform solution to precipitate a solid; the solid is then treated with an electron donor compound Y to be supported on the solid, and the solid is then treated with titanium tetrahalide or titanium tetrahalide and an inert diluent.
According to a third aspect of the present invention there is provided a catalyst for propylene polymerization comprising the reaction product of:
a. the catalyst component described above, or a catalyst component produced by the above production method;
b. alkylaluminum compounds of the formula AlR' n X’ 3-n In the general formula, R' is hydrogen or C 1 -C 20 X' is halogen, n is more than 0 and less than or equal to 3;
c. optionally, an external electron donor.
In the present invention, the alkylaluminum compound may be specifically selected from triethylaluminum, tripropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-octylaluminum, triisobutylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, preferably triethylaluminum, triisobutylaluminum.
According to the present invention, the "optionally, external electron donor" means that the external electron donor is selected with or without addition according to necessity. For applications requiring olefin polymers with high stereoregularity, an external electron donor is added, which may be conventionally selected according to the prior art, and may be selected, for example, from the general formula (R) 3 ) k Si(OR 4 ) 4-k The organic silicon compound is shown in the specification, wherein k is more than or equal to 0 and less than or equal to 3, R 3 Selected from halogen, hydrogen atom and C 1 -C 20 Alkyl, cycloalkyl, aryl, haloalkyl or amino, R 4 Is C 1 -C 20 Alkyl, cycloalkyl, aryl, haloalkyl or amino.
Specific examples of external electron donors include, but are not limited to: trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, cyclohexylmethyldimethoxysilane, methyl tert-butyldimethoxysilane; preferred are cyclohexylmethyldimethoxysilane and diphenyldimethoxysilane.
In the invention, the molar ratio of the component a to the component b is titanium: the aluminum is 1:5-1000, preferably 1:25-100; the molar ratio of the component c to the component a is the external electron donor: titanium is 0-500:1, preferably 25-100:1. When the external electron donor of the component c is the organic silicon compound, the molar ratio of the component c to the component a is as follows: titanium is present in a ratio of 0-500:1, preferably 25-100:1.
According to a fourth aspect of the present invention there is provided the use of the above catalyst component, the catalyst component prepared by the above preparation method or the above catalyst in propylene polymerization.
The catalyst component or catalyst of the present invention may be used directly in propylene polymerization or may be pre-polymerized before being used in propylene polymerization.
The prepolymerization is to prepolymerize the above catalyst component or catalyst with olefin (propylene) to obtain a prepolymer having a prepolymerization multiple of 0.1 to 1000g of olefin polymer per g of solid catalyst component, preferably 0.2 to 500g of olefin polymer per g of solid catalyst component.
The prepolymerization can be carried out in liquid or in gas phase at a temperature of from-20 to 80 ℃, preferably from 0 to 50 ℃. The step of prepolymerizing can be carried out in-line as part of a continuous polymerization process or separately in a batch operation.
The propylene polymerization of the present invention is carried out according to a known polymerization method, and may be carried out in a liquid phase or a gas phase, or may be carried out in a combination of liquid phase and gas phase polymerization stages. Propylene polymerization includes homo-polymerization of propylene or copolymerization of propylene with other olefins using conventional techniques such as slurry processes, gas-phase fluidized beds, and the like. The following reaction conditions are preferably employed: the polymerization temperature is 0 to 150 ℃, preferably 60 to 90 ℃; the polymerization pressure is 0.01-10MPa.
The substances and parameters not defined in the present invention can be selected according to the prior art, and are conventional in the art.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
In the following examples and comparative examples, the data were obtained as follows:
1. melt index MI of polymer: the melt flow rate was measured using a melt flow meter at 230℃under a pressure of 2.16kg according to ASTM D1238-99, standard test method for measuring thermoplastic melt flow Rate with an extrusion plastometer.
2. Electron donor content in the catalyst: the electron donor content of the catalyst was determined using a waters 600E high performance liquid chromatograph. Firstly, pretreating a sample by using an ethyl acetate-dilute hydrochloric acid solution system, extracting an electron donor compound, separating by a high performance liquid chromatograph, measuring the peak area of the electron donor compound, correcting by using an external standard curve, and calculating the percentage content of the electron donor compound in the sample. And then converted into a molar ratio of the electron donor.
Examples 1 to 8
To a reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 98mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate were added in this order, and the temperature of the compound X was raised to 50℃with stirring, maintained for 2.5 hours, and 1.4g of phthalic anhydride was added, and the reaction was continued for 1 hour. Cooling the solution to below-25 ℃, and dropwise adding TiCl in 1h 4 56mL, slowly warm to 80 ℃, and precipitate solid. Then, compound Y was added to the solid, the temperature was maintained for 1 hour, and after filtration, the solid was washed twice with 70mL of toluene, respectively, to obtain a solid precipitate. TiCl is then added to the precipitate 4 Toluene solution, heating to 110 ℃, maintaining for 1h, and filtering; the same operation was repeated four times. The filtered precipitate was washed three times with 70mL of toluene at 110℃for 10min each and twice with 60mL of hexane to obtain (solid) catalyst components, the specific substances used for Compound X and Compound Y in each example, and the compounds X and Compound in the catalyst componentsThe molar ratio of the substance Y is shown in Table 1.
Polymerization of propylene: the stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mmol, methylcyclohexyldimethoxy silane (CHMMS) 0.1mmol, 8-10mg of the solid catalyst component prepared in each example and 7.2L of hydrogen were added, 2.3L of liquid propylene was introduced, and the temperature was raised to 70℃and maintained at that temperature for 1 hour. Cooling and decompressing to obtain PP powder. The data are shown in Table 1.
Example 9
Under the protection of nitrogen, adding 4.8g of anhydrous magnesium chloride, 19.5g of isooctanol, a compound X and 19.5g of decane solvent into a 500mL reactor with a stirrer, heating to 130 ℃, reacting for 1.5 hours until the magnesium chloride is completely dissolved, adding 2.0g of diethyl diisobutylmalonate, and continuously maintaining the temperature of 130 ℃ for reacting for 1 hour to obtain an alkoxide; the alcohol was cooled to room temperature. Under the protection of nitrogen, dropwise adding the alcohol compound into 120mL of titanium tetrachloride solution precooled to the temperature of minus 22 ℃, slowly heating to the temperature of 100 ℃, adding the compound Y, heating to the temperature of 110 ℃ for 2 hours, filtering while the mixture is hot, adding 120mL of titanium tetrachloride, reacting for 1 hour at the temperature of 110 ℃, and filtering. The solid particles were washed with anhydrous hexane 4 times and dried to obtain a solid catalyst component. The specific materials used for compound X, compound Y, and the molar ratio of compound X to compound Y in the catalyst component are shown in Table 1.
Polymerization of propylene: the stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mmol, methylcyclohexyldimethoxy silane (CHMMS) 0.1mmol, 8-10mg of the solid catalyst component prepared in each example and 7.2L of hydrogen were added, 2.3L of liquid propylene was introduced, and the temperature was raised to 70℃and maintained at that temperature for 1 hour. Cooling and decompressing to obtain PP powder. The data are shown in Table 1.
Example 10
To a reactor fully replaced with high-purity nitrogen, 4.8g of magnesium chloride, 98mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate were added in this order, and the temperature of the compound X was raised to 50℃with stirring, and the reaction was maintained for 2.5 hours, 8mmol of diethyl diisobutylmalonate was added, and the reaction was continued for 1 hour. The solution was cooled to-25℃TiCl was added dropwise over 1h 4 35mL, slowly warm to 80 ℃, solid precipitation. Then, compound Y was added to the solid, the temperature was maintained for 1 hour, and after filtration, the solid was washed twice with 70mL of toluene, respectively, to obtain a solid precipitate. TiCl is then added to the precipitate 4 Toluene solution, heating to 110 ℃, maintaining for 1h, and filtering; the same operation was repeated four times. The filtered precipitate was washed three times with 70mL of toluene at 110℃for 10min each and twice with 60mL of hexane to obtain (solid) catalyst components, specific substances used for the compound X and the compound Y, and the molar ratio of the compound X to the compound Y in the catalyst components, as shown in Table 1.
Polymerization of propylene: the stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mmol, methylcyclohexyldimethoxy silane (CHMMS) 0.1mmol, 8-10mg of the solid catalyst component prepared in this example and 7.2L of hydrogen were further added, 2.3L of liquid propylene was introduced, and the temperature was raised to 70℃and maintained at this temperature for 1 hour. Cooling and decompressing to obtain PP powder. The data are shown in Table 1.
Comparative example 1
To the reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 98mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate were added in this order, the temperature was raised to 50℃with stirring, and the reactor was maintained for 2.5 hours, 8mmol of diethyl diisobutylmalonate was added, and the reaction was continued for 1 hour. Cooling the solution to below-25 ℃, and dropwise adding TiCl in 1h 4 56mL, slowly warm to 80 ℃, and precipitate solid. Then, compound Y was added to the solid, the temperature was maintained for 1 hour, and after filtration, the solid was washed twice with 70mL of toluene, respectively, to obtain a solid precipitate. TiCl is then added to the precipitate 4 Toluene solution, heating to 110 ℃, maintaining for 1h, and filtering; the same operation was repeated four times. The filtered precipitate was washed three times with 70mL of toluene at 110℃for 10min each, and twice with 60mL of hexane to obtain a (solid) catalyst component. The specific substances and contents used for the compound Y are the same as in example 2.
Polymerization of propylene: the stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mmol, methylcyclohexylDimethoxysilane (CHMMS) 0.1mmol, 8-10mg of the solid catalyst component prepared in the comparative example and 7.2L of hydrogen were further added, 2.3L of liquid propylene was introduced, and the temperature was raised to 70℃and maintained at that temperature for 1 hour. Cooling and decompressing to obtain PP powder. The data are shown in Table 1.
Comparative example 2
To a reactor fully replaced with high purity nitrogen, 4.8g of magnesium chloride, 98mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate were added in this order, and the temperature of the compound X was raised to 50℃with stirring, maintained for 2.5 hours, and 1.4g of phthalic anhydride was added, and the reaction was continued for 1 hour. Cooling the solution to below-25 ℃, and dropwise adding TiCl in 1h 4 56mL, slowly warm to 80 ℃, and precipitate solid. The temperature was maintained for 1h, and after filtration, the mixture was washed twice with 70mL of toluene, respectively, to obtain a solid precipitate. TiCl is then added to the precipitate 4 Toluene solution, heating to 110 ℃, maintaining for 1h, and filtering; the same operation was repeated four times. The filtered precipitate was washed three times with 70mL of toluene at 110℃for 10min each, and twice with 60mL of hexane to obtain a (solid) catalyst component. The specific substances and amounts used for compound X are the same as in example 2.
Polymerization of propylene: the stainless steel reactor with the volume of 5L is fully replaced by gas propylene and then AlEt is added 3 2.5mmol, methylcyclohexyldimethoxy silane (CHMMS) 0.1mmol, 8-10mg of the solid catalyst component prepared in the comparative example and 7.2L of hydrogen were further added, 2.3L of liquid propylene was introduced, and the temperature was raised to 70℃and maintained at that temperature for 1 hour. Cooling and decompressing to obtain PP powder. The data are shown in Table 1.
Comparative example 3
In a reactor fully replaced by high-purity nitrogen, 4.8g of magnesium chloride, 98mL of toluene, 4mL of epichlorohydrin and 12.5mL of tributyl phosphate are added in sequence, the temperature is raised to 50 ℃ under stirring, the mixture is maintained for 2.5h, 1.4g of phthalic anhydride is added, and the mixture is maintained for 1h continuously. Cooling the solution to below-25 ℃, and dropwise adding TiCl in 1h 4 56mL, slowly warm to 80 ℃, and precipitate solid. Then, compound X and compound Y were added to the solid, the temperature was maintained for 1 hour, and after filtration, the mixture was washed twice with 70mL of toluene, respectively, to obtain a solid precipitate. TiCl is then added to the precipitate 4 Nail (A)Heating benzene solution to 110 ℃, maintaining for 1h, and filtering; the same operation was repeated four times. The filtered precipitate was washed three times with 70mL of toluene at 110℃for 10min each and twice with 60mL of hexane to obtain (solid) catalyst components, the specific materials used for the compound X and the compound Y in this comparative example, and the molar ratio of the compound X to the compound Y in the catalyst components, as shown in Table 1.
Polymerization of propylene: a stainless steel reactor having a volume of 5L was fully replaced with gaseous propylene and then added with A1Et 3 2.5mmol, methylcyclohexyldimethoxy silane (CHMMS) 0.1mmol, 8-10mg of the solid catalyst component prepared in the comparative example and 7.2L of hydrogen were further added, 2.3L of liquid propylene was introduced, and the temperature was raised to 70℃and maintained at that temperature for 1 hour. Cooling and decompressing to obtain PP powder. The data are shown in Table 1.
TABLE 1
In addition, as can be seen from table 1, the catalyst provided by the invention is used for propylene polymerization, has higher activity and good hydrogen regulation sensitivity, and the obtained polymer does not contain phthalate compounds.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.

Claims (13)

1. A catalyst component for propylene polymerization, characterized in that it comprises magnesium, titanium, halogen and an electron donor, said electron donor containing a compound X and a compound Y;
the general formula of the compound X is R a -O-R b Wherein R is a 、R b Identical or different, selected fromC 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not;
the compound Y is a glycol ester compound.
2. The catalyst component for propylene polymerization according to claim 1 in which R a 、R b Identical or different, selected from C 1 -C 10 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not.
3. The catalyst component for propylene polymerization according to claim 2, wherein R a 、R b Identical or different, selected from C 1 -C 10 Unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene; r is R a And R is b Optionally bonded to form a ring or not.
4. The catalyst component for propylene polymerization according to claim 1 in which the compound X is selected from at least one of methyl ether, diethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, n-pentyl ether, methyl n-pentyl ether, cyclohexyl ether, ethylcyclohexyl ether, cyclohexylvinyl ether, n-heptyl ether, n-octyl ether, n-nonyl ether, n-decyl ether, ethylene oxide, propylene oxide and tetrahydrofuran.
5. The catalyst component for propylene polymerization according to claim 1, wherein the compound Y is at least one selected from the compounds represented by the general formula (I),
in the formula (I)，R 1 And R is 2 Identical or different, selected from C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched chain alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, and fused ring aryl groups; a is a divalent supporting group of alkyl, cycloalkyl or aryl having 1 to 20 carbon atoms, and the divalent supporting group is optionally C 1 -C 20 Wherein the carbon atoms or/and hydrogen atoms in the divalent radicals and substituents thereof may optionally be replaced by heteroatoms, which are nitrogen, oxygen, sulfur, silicon, phosphorus, halogen atoms, the substituents on the divalent radicals optionally being bonded to form saturated/unsaturated one or more rings.
6. The catalyst component for propylene polymerization according to claim 5, wherein R 1 And R is 2 Identical or different, selected from C 1 -C 20 Substituted or unsubstituted aryl, alkylaryl;
a comprises formula (III), formula (IV) or formula (V),
in the formula (III), R' 3 -R′ 8 Identical or different, selected from hydrogen, halogen and C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, fused ring aryl, ester, R' 7 And R'. 8 Optionally bonded to form a ring or not;
in the formula (IV), R 1 -R 4 Identical or different, selected from C 1 -C 20 Straight-chain alkyl, branched alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, and fused ring aryl radicals, R 1 -R 4 Can be optionally bonded to be saturated and/or unsaturatedOne or more rings;
in the formula (V), R is selected from hydrogen, halogen and C 1 -C 20 Substituted or unsubstituted straight chain alkyl, branched chain alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl, alkylene, fused ring aryl.
7. The catalyst component for propylene polymerization according to claim 1, wherein, the compound Y is selected from 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 3, 5-heptanediol diphemethyl benzoate, 3, 5-heptanediol di-p-chlorobenzoate, 3, 5-heptanediol diphemethoxybenzoate, 3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 6-methyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 4-butyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-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 (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-2, 4-octanediol di (p-methylbenzoic acid) ester, 6-methyl-2, 4-heptanediol di (m-methylbenzoic acid) ester, 2, 6-tetramethyl-3, 5-octanediol dibenzoate, 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-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, 1-dimethyl-1, 8-naphthalene benzoate, 3-dimethyl-1, 8-naphthalene benzoate, 4-naphthalene benzoate, 1, 8-naphthalene benzoate, 4-naphthalene-methyl-1, 8-naphthalene benzoate, 8-naphthalene ester, di-4-n-butylbenzoic acid-1, 8-naphthalene ester, di-4-isobutylbenzoic acid-1, 8-naphthalene ester, di-4-tert-butylbenzoic acid-1, 8-naphthalene ester, di-4-phenylbenzoic acid-1, 8-naphthalene ester, di-4-monofluorobenzoic acid-1, 8-naphthalene ester, di-3-fluorobenzoic acid-1, 8-naphthalene ester, and di-2-fluorobenzoic acid-1, 8-naphthalene ester.
8. The catalyst component for propylene polymerization according to claim 1 in which the molar ratio of compound X and compound Y is r,0 < r < 5, preferably 0 < r < 3, more preferably 0 < r < 2.
9. The method for producing a catalyst component for propylene polymerization according to any one of claims 1 to 8, characterized in that the method comprises:
1) Dissolving a magnesium compound in a system containing a compound X, adding a precipitation aid and a precipitation agent, and precipitating a solid;
2) The solid precipitated in step 1) is treated with a titanium compound and the compound Y is added during and/or before the treatment of the solid with the titanium compound.
10. The method for preparing a catalyst component for propylene polymerization according to claim 9, wherein the precipitation agent is a metal halide, preferably a titanium halide, more preferably titanium tetrachloride.
11. The method for preparing a catalyst component for propylene polymerization according to claim 9, wherein the precipitation aid is an oxygen-containing compound, preferably an acid anhydride and/or a diester compound, more preferably an acid anhydride and/or a malonate diester compound.
12. A catalyst for propylene polymerization, characterized in that the catalyst comprises the reaction product of:
a. a catalyst component according to any one of claims 1 to 8 or a catalyst component obtainable by the process according to any one of claims 9 to 11;
b. alkylaluminum compounds of the formula AlR' n X’ 3-n In the general formula, R' is hydrogen or C l -C 20 X' is halogen, n is more than 0 and less than or equal to 3;
c. optionally, an external electron donor.
13. Use of the catalyst component according to any one of claims 1 to 8, the catalyst component produced by the production process according to any one of claims 9 to 11, or the catalyst according to claim 12 in propylene polymerization.
CN202210823337.7A 2022-07-13 2022-07-13 Catalyst component for propylene polymerization, preparation method thereof, catalyst and application Pending CN117430732A (en)

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