CN118852499A - Olefin polymerization catalyst carrier and preparation method thereof, catalyst component, catalyst and olefin polymerization method - Google Patents
Olefin polymerization catalyst carrier and preparation method thereof, catalyst component, catalyst and olefin polymerization method Download PDFInfo
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- CN118852499A CN118852499A CN202310485742.7A CN202310485742A CN118852499A CN 118852499 A CN118852499 A CN 118852499A CN 202310485742 A CN202310485742 A CN 202310485742A CN 118852499 A CN118852499 A CN 118852499A
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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
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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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- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
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Abstract
The invention relates to the technical field of catalysts, and provides an olefin polymerization catalyst carrier, a preparation method thereof, a catalyst component, a catalyst and an olefin polymerization method. The catalyst support comprises a magnesium compound and a phosphorus compound represented by the following formula,Wherein R 1 is a linear alkyl of C 1～C12 or a branched alkyl of C 3～C12; r 2 and R 3 are each independently selected from hydrogen, a linear alkyl group of C 1～C5 or a branched alkyl group of C 3～C5, a linear alkyl group of C 1～C5 substituted by a halogen atom or a branched alkyl group of C 3～C5; x is selected from halogen; m is 0.1-1.9; n is 0.1 to 1.9; m+n=2; the phosphorus compound is derived from polyphosphate shown in a general formula L K+2PKO3K+1, wherein L is a metal element, and K is an integer of 3-5; the content of the phosphorus compound in the catalyst carrier is 0< p <3wt% based on the weight of phosphorus element. According to the invention, the catalyst carrier with good particle morphology can be obtained without adding a high molecular dispersion stabilizer by adding the polyphosphate, and the prepared catalyst has higher polymerization activity when being used for olefin polymerization.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an olefin polymerization catalyst carrier and a preparation method thereof, a catalyst component, a catalyst and an olefin polymerization method.
Background
Catalysts for olefin polymerization are mostly prepared by supporting titanium halides on active anhydrous magnesium chloride. Further research shows that the catalyst solid component with controllable particle morphology can be obtained by adopting a method of firstly preparing a magnesium compound carrier with better particle morphology and then loading an active component. Wherein the particle morphology and particle size of the support determine the particle morphology and particle size of the catalyst. Currently, more magnesium compound carriers are used as magnesium chloride alkoxide carriers (such as carriers disclosed in US4421674A、US4469648A、WO8707620A1、WO9311166A1、US5100849A、US6020279A、US4399054A、US6127304A、US6323152B1、CN1463990A、CN1580136A and the like) and alkoxymagnesium carriers (such as carriers disclosed in patent CN101134789A, US4727051A, CN101190953a and the like).
In order to further simplify the carrier preparation process and improve the polymerization performance of the catalyst, researchers develop a new process for preparing the spherical magnesium compound carrier by utilizing a reaction precipitation method. Patent CN200910235565.7 discloses a compound useful as a carrier for olefin polymerization catalysts and a process for preparing the same, which comprises heating a magnesium halide, an alcohol compound and an inert dispersion medium to form a magnesium halide alkoxide solution, and then reacting the solution with an ethylene oxide compound to form a spherical carrier. The patent CN201310491393.6 adds the macromolecule dispersion stabilizer in the preparation process of the carrier, thereby obtaining solid particles with good particle morphology and narrow particle size distribution without adding inert dispersion medium, improving the yield of a single kettle and reducing the recovery cost of the solvent. However, the addition of the polymer dispersion stabilizer not only increases the production cost of the carrier, but also has adverse effects on the recovery treatment of byproducts and increases the difficulty of solvent recovery treatment.
Therefore, it is important to develop a novel catalyst support for olefin polymerization which can overcome the above-mentioned drawbacks of the prior art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an olefin polymerization catalyst carrier, a preparation method thereof, a catalyst component, a catalyst and an olefin polymerization method.
The technical scheme adopted by the invention comprises the following steps:
In a first aspect, the present invention provides an olefin polymerization catalyst support comprising a magnesium compound and a phosphorus compound as shown in formula (I),
Wherein R 1 is a linear alkyl of C 1～C12 or a branched alkyl of C 3～C12; r 2 and R 3 are the same or different and are each independently selected from hydrogen, a linear alkyl group of C 1～C5 or a branched alkyl group of C 3～C5, the hydrogen on the linear alkyl group of C 1～C5 or the branched alkyl group of C 3～C5 being optionally substituted by a halogen atom; x is selected from halogen; m is 0.1 to 1.9, preferably 0.8 to 1.2; n is 0.1 to 1.9, preferably 0.8 to 1.2; m+n=2;
the phosphorus compound is derived from polyphosphate shown in a general formula L K+2PKO3K+1, wherein L is a metal element, and K is an integer of 3-5;
the content of the phosphorus compound in the catalyst carrier is 0< p <3wt%, preferably 0.01wt% < p <1wt%, such as 0.02wt％、0.05wt％、0.08wt％、0.10wt％、0.15wt％、0.20wt％、0.25wt％、0.35wt％、0.40wt％、0.50wt％、0.60wt％、0.70wt％、0.80wt％、0.90wt％, etc., based on the weight of phosphorus element.
The inventors of the present invention have surprisingly found that, during a large number of experiments, a polyphosphate having the general formula L K+2PKO3K+1 is introduced into a system for preparing a carrier for an olefin polymerization catalyst, a carrier having a good morphology can be obtained without using a polymer dispersion stabilizer, and the catalyst prepared by the method has a high catalytic activity.
The term "carrier" as used herein means a material having no olefin polymerization activity, i.e., a carrier containing no active component, such as a titanium compound, which can form a polymer having olefin polymerization activity.
According to some embodiments of the invention, the polyphosphate comprises at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, and hydrates thereof.
According to some embodiments of the invention, the R 1 is a C 1～C8 linear alkyl or a C 3～C8 branched alkyl; preferably, the R 1 is selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl and 2-ethylhexyl.
According to some embodiments of the invention, R 2 and R 3 are the same or different and are each independently selected from hydrogen, linear alkyl or isopropyl of C 1～C3 or linear alkyl or isopropyl of halogen substituted C 1-C3; preferably, each of R 2 and R 3 is independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, bromoethyl.
According to some embodiments of the invention, the halogen is selected from chlorine, bromine and iodine, preferably chlorine.
According to some embodiments of the invention, the catalyst support is a spherical particle.
According to some embodiments of the invention, the catalyst support has an average diameter of 10-100 μm, preferably 30-70 μm, and a particle size distribution of less than 1.2, preferably 0.6-0.9.
In a second aspect, the present invention provides a process for preparing an olefin polymerization catalyst support comprising:
(a) Reacting magnesium halide shown in a general formula of MgX 2, an alcohol compound shown in a general formula of R 1 OH and a polyphosphate shown in a general formula of L K+ 2PKO3K+1 to form suspension, wherein X is halogen, R 1 is C 1～C12 straight-chain alkyl or C 3～C12 branched-chain alkyl, L is a metal element, and K is an integer of 3-5;
(b) Reacting the suspension formed in step (a) with an epoxy compound to form an olefin polymerization catalyst support;
Preferably, the epoxy compound is represented by the general formula (II),
Wherein R 2 and R 3 are the same or different and are each independently selected from hydrogen, a linear alkyl group of C 1～C5 or a branched alkyl group of C 3～C5, the hydrogen on the linear alkyl group of C 1～C5 or the branched alkyl group of C 3～C5 being optionally substituted with a halogen atom.
In the preparation method provided by the invention, the magnesium halide, the alcohol compound and the polyphosphate are added in the step (a) in different orders.
According to some embodiments of the invention, the polyphosphate comprises at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, and hydrates thereof.
According to some embodiments of the invention, R 1 is a C 1～C8 straight chain alkyl or a C 3～C8 branched alkyl.
According to some embodiments of the invention, the alcohol compound represented by the general formula R 1 OH comprises at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-pentanol, isoamyl alcohol, n-hexanol, n-octanol, 2-ethyl-1-hexanol.
According to some embodiments of the invention, R 2 and R 3 are the same or different and are each independently selected from hydrogen, linear alkyl or isopropyl of C 1～C3 or linear alkyl or isopropyl of halogen substituted C 1-C3.
According to some embodiments of the invention, each of R 2 and R 3 is independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, bromoethyl.
According to some embodiments of the invention, the epoxy compound comprises at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide.
According to some embodiments of the invention, the magnesium halide represented by the general formula MgX 2 comprises at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, preferably magnesium dichloride.
According to some embodiments of the invention, the molar ratio of the alcohol compound to magnesium halide is (3-30): 1, preferably (4 to 25): 1, for example, can be 5:1, 8:1, 10:1, 12:1, 14:1, 17:1, 20:1, 23:1, etc.; the molar ratio of the polyphosphate to the magnesium halide is 1: (10-300), for example, can be 1:12, 1:20, 1:40, 1:60, 1:88, 1:100, 1:122, 1:150, 1:179, 1:180, 1:182, 1:190, 1:220, 1:250, 1:270, 1:290, etc., preferably 1: (20-200).
According to some embodiments of the invention, the reaction temperature in step (a) is 30 to 160 ℃, preferably 40 to 120 ℃, e.g. 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ etc., and the reaction time is 0.1 to 5 hours, preferably 0.5 to 2 hours, e.g. 1 hour.
According to some embodiments of the invention, step (a) is performed in a closed vessel.
According to some embodiments of the invention, the polyphosphate of step (a) is formulated as an aqueous polyphosphate solution and then reacted.
According to some embodiments of the invention, the concentration of the aqueous polyphosphate solution is 10 to 60wt%, preferably 30 to 60wt%.
According to some embodiments of the invention, the molar ratio of the epoxy compound to magnesium halide is (1-10): 1, preferably (2 to 6): 1, for example, may be 3:1, 4:1, 5:1, etc.
According to some embodiments of the invention, the reaction temperature in step (b) is 30 to 160 ℃, preferably 40 to 120 ℃, e.g. 60 ℃, and the reaction time is 0.1 to 5 hours, preferably 0.2 to 1 hour, e.g. 0.5 hour.
According to some embodiments of the invention, the suspension of step (a) may or may not be prepared with the addition of an inert dispersing medium. The inert dispersion medium may be selected from at least one of liquid aliphatic, aromatic, cycloaliphatic hydrocarbons, silicone oils. The volume ratio of the inert dispersion medium to the alcohol compound is (0-5): 1, preferably (0 to 2): 1.
According to some embodiments of the invention, the trace amount of water in each of the raw materials added in step (a) may participate in the reaction to form the suspension.
According to some embodiments of the invention, the method further comprises step (c) recovering the catalyst support produced.
In the present invention, the recovery in the step (c) means that the solid-liquid separation technique known in the art, such as filtration, decantation, centrifugal separation, etc., is used to obtain the solid granular catalyst carrier, and the obtained catalyst carrier is also washed with an inert hydrocarbon solvent and dried. Among them, the inert hydrocarbon solvent is preferably a linear or branched liquid alkane having a carbon chain length of more than 4 carbons, aromatic hydrocarbon such as hexane, heptane, octane, decane, toluene, etc.
According to a preferred embodiment of the present invention, the method for preparing the catalyst carrier comprises:
(1) In a closed container, reacting magnesium halide MgX 2, an alcohol compound R 1 OH and an aqueous solution of polyphosphate with a structure L K+2PKO3K+1 for 0.1-5 hours (preferably 0.5-2 hours) at 30-160 ℃ (preferably 40-120 ℃) to form a suspension;
(2) Reacting the suspension with an epoxy compound represented by the above formula (II) at 30-160 ℃ (preferably 40-120 ℃) for 0.1-5 hours (preferably 0.2-1 hour) to precipitate solid particles;
(3) And recovering the solid particles through a solid-liquid separation technology to obtain the catalyst carrier.
According to a more preferred embodiment of the present invention, the method for preparing a catalyst carrier comprises:
(1) Heating an aqueous solution of magnesium halide MgX 2, an alcohol compound R 1 OH and a polyphosphate with a structure L K+2PKO3K+1 to 30-160 ℃ (preferably 40-120 ℃) in a closed container under stirring, and reacting for 0.1-5 hours (preferably 0.5-2 hours) to form a mixture suspension; wherein the amount of the alcohol compound is 3 to 30 moles, preferably 4 to 25 moles, per mole of magnesium; the polyphosphate is used in an amount of 0.002 to 0.1 mole, preferably 0.004 to 0.05 mole.
(2) Adding an epoxy compound represented by the above formula (II) to the above mixture suspension under stirring, and reacting at 30-160 ℃ (preferably 40-120 ℃) for 0.1-5 hours (preferably 0.2-1 hour) to form solid particles, wherein the epoxy compound is used in an amount of 1-10 moles, preferably 2-6 moles, per mole of magnesium;
(3) And recovering the solid particles through a solid-liquid separation technology to obtain the catalyst carrier.
In a third aspect, the present invention provides an olefin polymerization catalyst support prepared by the preparation method of the second aspect.
According to some embodiments of the invention, the catalyst support is a spherical particle.
According to some embodiments of the invention, the catalyst support has an average diameter of 10-100 μm, preferably 30-70 μm, and a particle size distribution of less than 1.2, preferably 0.6-0.9.
In a fourth aspect, the present invention provides an olefin polymerization catalyst component comprising the reaction product of the catalyst support of the first aspect or the catalyst support of the third aspect with a titanium compound and optionally an internal electron donor compound.
According to some embodiments of the invention, the titanium compound is used in an amount of 5 to 200 moles, preferably 10 to 100 moles, per mole of magnesium compound of formula (I) in the catalyst support; the internal electron donor is used in an amount of 0 to 0.5 mol, preferably 0.08 to 0.4 mol.
According to some embodiments of the invention, the titanium compound is selected from titanium compounds of general formula Ti (OR 4)4-aXa, wherein R 4 is an aliphatic hydrocarbon group of C 1-C14, X is halogen, a is an integer from 0 to 4.
According to some embodiments of the 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 trichloride, titanium triethoxide monochloride, titanium diethoxide dichloride, titanium monoethoxide trichloride.
According to some embodiments of the invention, the internal electron donor is selected from the group consisting of esters, ethers, ketones, amines, and silanes.
According to some embodiments of the invention, the internal electron donor is selected from mono-or poly-aliphatic carboxylic acid esters or aromatic carboxylic acid esters, glycol ester compounds, diether compounds.
According to some embodiments of the invention, the mono-or poly-aliphatic carboxylic acid ester or aromatic carboxylic acid ester is selected from ethyl benzoate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl adipate, dibutyl adipate, diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, triethyl biphenyl, tributyl benzene and tetra-n-butyl pyromellitate.
According to some embodiments of the invention, the glycol ester compound is selected from the group consisting of 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-dimethyl-1, 3-propanediol dibenzoate, (R) -1-phenyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol di-n-propionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol dipropionate, 1, 3-diphenyl-2-methyl-1, 3-propanediol diacetate, and, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-2, 2-dimethyl-1, 3-propanediol dipropionate, 1, 3-di-tert-butyl-2-ethyl-1, 3-propanediol dibenzoate, 1, 3-diphenyl-1, 3-propanediol diacetate, 1, 3-diisopropyl-1, 3-propanol bis (4-butylbenzoic acid) ester, 1-phenyl-2-amino-1, 3-propanediol dibenzoate, 1-phenyl-2-methyl-1, 3-butanediol dibenzoate, phenyl-2-methyl-1, 3-butanediol dipivalate, 3-butyl-2, 4-pentanediol dibenzoate, and the like, 3, 3-dimethyl-2, 4-pentanediol dibenzoate, (2S, 4S) - (+) -2, 4-pentanediol dibenzoate, (2R, 4R) - (+) -2, 4-pentanediol dibenzoate, 2, 4-pentanediol di (p-chlorobenzoic acid) ester, 2, 4-pentanediol di (m-chlorobenzoic acid) ester, 2, 4-pentanediol di (p-bromobenzoic acid) ester, 2, 4-pentanediol di (o-bromobenzoic acid) ester, 2, 4-pentanediol di (p-methylbenzoic acid) ester, 2, 4-pentanediol di (p-tert-butylbenzoic acid) ester, 2, 4-pentanediol di (p-butylbenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-chlorobenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-methylbenzoic acid) ester, 2-butyl-1, 3-pentanediol di (p-methylbenzoic acid) ester, 2-methyl-1, 3-pentanediol di (p-tert-butylbenzoic acid) ester, 2-methyl-1, 3-pentanediol pivalate, 2-methyl-1, 3-pentanediol benzoic acid cinnamic acid ester, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol benzoic acid cinnamic acid ester, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-allyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 1, 3-pentanediol bis (p-chlorobenzoic acid) ester, 1, 3-pentanediol bis (m-chlorobenzoic acid) ester, 1, 3-pentanediol bis (p-bromobenzoic acid) ester, 1, 3-pentanediol bis (o-bromobenzoic acid) ester, 1, 3-pentanediol bis (p-methylbenzoic acid) ester, 1, 3-pentanediol bis (p-t-butylbenzoic acid) ester, 1, 3-pentanediol bis (p-butylbenzoic acid) ester, 1, 3-pentanediol benzoic acid cinnamic acid ester, 1, 3-pentanediol di-cinnamic acid ester, 1, 3-pentanediol dipropionate, 2-methyl-1, 3-pentanediol benzoic acid cinnamic acid ester, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol benzoic acid cinnamic acid ester, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-allyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol benzoic acid cinnamic acid ester, 2, 4-trimethyl-1, 3-pentanediol diisopropyl formate, 1-trifluoromethyl-3-methyl-2, 4-pentanediol dibenzoate, 2, 4-pentanediol di-p-fluoromethyl benzoate, 2, 4-pentanediol di (2-furancarboxylic acid) ester, 2-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-methyl-6-heptene-2, 4-heptanediol dibenzoate, 4-methyl-6-heptene-2, 4-heptanediol dibenzoate, 5-methyl-6-heptene-2, 4-heptanediol dibenzoate, 6-methyl-6-heptene-2, 4-heptanediol dibenzoate, 3-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 4-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 5-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 6-ethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-propyl-6-heptene-2, 4-heptanediol dibenzoate, 4-propyl-6-heptene-2, 4-heptanediol dibenzoate, 5-propyl-6-heptene-2, 4-heptanediol dibenzoate, 6-propyl-6-heptene-2, 4-heptanediol dibenzoate, 3-butyl-6-heptene-2, 4-heptanediol dibenzoate, 4-butyl-6-heptene-2, 4-heptanediol dibenzoate, 5-butyl-6-heptene-2, 4-heptanediol dibenzoate, 6-butyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dimethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-diethyl-6-heptene-2, 4-heptanediol dibenzoate, 3-dipropyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 3-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3-ethyl-3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, 5-ethyl-3, 5-heptanediol dibenzoate, 3-propyl-3, 5-heptanediol dibenzoate, 4-propyl-3, 5-heptanediol dibenzoate, 3-butyl-3, 5-heptanediol dibenzoate, 2, 3-dimethyl-3, 5-heptanediol dibenzoate, 2, 4-dimethyl-3, 5-heptanediol dibenzoate, 2, 5-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3, 3-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 4, 5-dimethyl-3, 5-heptanediol dibenzoate, 4, 6-dimethyl-3, 5-heptanediol dibenzoate, 4-dimethyl-3, 5-heptanediol dibenzoate, 6-dimethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 3-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-3-ethyl-3, 5-heptanediol dibenzoate, 4-methyl-4-ethyl-3, 5-heptanediol dibenzoate, 9-bis (benzylcarboxymethyl) fluorene, 9-bis ((m-methoxybenzylcarboxymethyl) fluorene, 9-bis ((m-chlorobenzenecarboxymethyl) fluorene, 9-bis ((p-chlorobenzenecarboxymethyl) methyl) fluorene, 9-bis (cinnamylcarboxymethyl) fluorene, 9- (benzylcarboxymethyl) -9- (propylcarboxymethyl) fluorene, 9, 9-bis (propylcarboxymethyl) fluorene, 9-bis (propylcarboxymethyl) fluorene and 9, 9-bis (neopentylcarboxymethyl) fluorene.
According to some embodiments of the present invention, the diether compound is selected from 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-1, 3-dimethoxypropane, 2-phenyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane, 2-diisopropyl-1, 3-dimethoxypropane, 2-dibutyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-bis (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-isopropyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-isopropyl-1, 3-dimethoxypropane, 2-phenyl-2-sec-butyl-1, 3-dimethoxypropane, 2-benzyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-sec-butyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclohexyl-2-sec-butyl-1, 3-dimethoxypropane, 2-isopropyl-2-sec-butyl-1, 3-dimethoxypropane and 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane.
The present invention thus further provides the use of the catalyst support according to the first aspect or the catalyst support according to the third aspect in the preparation of an olefin polymerisation catalyst.
In the present invention, the synthesis of the catalyst component may be carried out by methods conventional in the art, such as described in chinese patent CN1091748A, by reacting spherical magnesium-containing composition particles directly with titanium halide; OR by adopting the method described in Chinese patent CN104558274A, firstly reacting a spherical magnesium-containing composition with an alkoxy titanium compound with a structural formula of Ti (OR) 4 to obtain an intermediate product, and then reacting with titanium halide. In the above catalyst preparation process, some internal electron donor compounds known in the industry can be optionally added according to the actual application requirements.
In a fifth aspect, the present invention provides an olefin polymerization catalyst comprising the catalyst component of the fourth aspect, an alkyl aluminum compound and optionally an external electron donor compound.
According to some embodiments of the present invention, in the catalyst for olefin polymerization, the molar ratio of the alkylaluminum compound in aluminum to the catalyst component for olefin polymerization in titanium is 1 to 2000:1, preferably 20 to 500:1; the molar ratio of the external electron donor compound to the alkylaluminum compound, calculated as aluminum, is 0.005-0.5:1, preferably 0.01-0.4:1.
In the present invention, the alkyl aluminum compound may be selected from various alkyl aluminum compounds commonly used in the art.
According to some embodiments of the invention, the alkylaluminum compound is at least one of triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, di-n-butylaluminum chloride, di-n-hexylaluminum chloride, monoethylaluminum dichloride, monoisobutylaluminum dichloride, mono-n-butylaluminum dichloride, and mono-n-hexylaluminum dichloride.
In the present invention, the external electron donor compound may be selected from various external electron donor compounds commonly used in the art.
According to some embodiments of the invention, the external electron donor is selected from at least one of carboxylic acids, anhydrides, esters, ketones, ethers, alcohols, organophosphorus compounds and silicon compounds.
According to some embodiments of the invention, the external electron donor is an organosilicon compound of the general formula R a xRb ySi(ORc)z, wherein R a、Rb and R c are each a C 1-C18 hydrocarbon group or a heteroatom-containing C 1-C18 hydrocarbon group; x and y are each integers from 0 to 2, z is an integer from 1 to 4, and x+y+z=4.
According to some embodiments of the invention, in formula R a xRb ySi(ORc)z, at least one of R a and R b is selected from any one of C 3-C10 branched alkyl group with or without heteroatoms, C 3-C10 cycloalkyl group with or without heteroatoms, and C 6-C10 aryl group, R c is any one of C 1-C10 linear alkyl group and C 3-C10 branched alkyl group, preferably methyl, ethyl; x is 1, y is 1, z is 2; or R b is branched alkyl of C 3-C10 or cycloalkyl of C 3-C10, and R c is methyl, x is 0, y is 1, and z is 3.
According to some embodiments of the invention, examples of the organosilicon compound may be, but are not limited to: cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, n-butylcyclohexyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidyl-2-tert-butyldimethoxysilane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidyl-dimethoxysilane, (1, 1-trifluoro-2-propyl) -methyldimethoxysilane, cyclohexyltrimethoxysilane, tert-butyltrimethoxysilane and tert-hexyltrimethoxysilane.
In a sixth aspect, the present invention provides a process for the polymerization of olefins comprising: contacting at least one olefin with the catalyst of the fifth aspect under olefin polymerization conditions.
According to some embodiments of the invention, the olefin has the formula CH 2 =chr, wherein R is hydrogen or C 1-C7 alkyl.
According to some embodiments of the invention, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene, and 1-hexene.
The invention has the advantages that:
(1) The catalyst carrier with good particle morphology can be obtained without adding a high molecular dispersion stabilizer by adding polyphosphate;
(2) The catalyst prepared by the catalyst carrier prepared by the invention has higher polymerization activity when being used for olefin polymerization.
Drawings
FIG. 1 is an optical micrograph of the catalyst support prepared in example 1.
FIG. 2 is an optical micrograph of the catalyst support prepared in comparative example 1.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the present invention in any way.
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the raw materials, instruments, equipment, etc. used in the following examples are all commercially available or available by existing methods; the reagent dosage is the reagent dosage in the conventional experimental operation if no special description exists; the experimental methods are conventional methods unless otherwise specified.
In each of the examples and comparative examples of the present invention, each performance data was tested according to the following test method:
1. polymer melt index: measured according to ASTM D1238-99.
2. Polymer isotactic index: the measurement was carried out by heptane extraction (boiling extraction with heptane for 6 hours), i.e. 2g of a dried polymer sample was taken, placed in an extractor and extracted with boiling heptane for 6 hours, after which the residue was dried to constant weight, and the ratio of the weight (g) of the obtained polymer to 2 was the isotactic index.
3. Particle size distribution testing: the average particle diameter and particle size distribution of the carrier particles were measured by a Master Sizer 2000 particle size machine (manufactured by Malvern Instruments Ltd). Wherein the particle size distribution value span= (D90-D10)/D50.
4. The apparent morphology of the catalyst support for olefin polymerization was observed by means of an optical microscope commercially available from Nikon under the model Eclipse E200.
5. Phosphorus content in the carrier: and (5) measuring by an inductively coupled plasma mass spectrometer.
6. Catalyst activity = weight of polymer obtained/weight of catalyst used.
Example 1
Into a 1.0L reactor, 2.8mol of ethanol, 0.2mol of magnesium chloride and 1.6g of an aqueous solution of sodium tripolyphosphate having a concentration of 25wt% were added, and the temperature was raised to 60℃with stirring (450 rpm). After reacting at constant temperature for 1 hour, adding epichlorohydrin 0.6mol, maintaining the temperature for 0.5 hour, filtering out liquid, washing solid with hexane for 5 times, and drying in vacuum to obtain solid component particles.
The structure of the carrier body was analyzed by nuclear magnetic resonance as follows:
the inductively coupled plasma mass spectrometer determines that the carrier contains 0.25wt% of phosphorus element.
The carrier particle size distribution d50=51.6 μm, span=0.6, and the particle morphology is shown in fig. 1.
Example 2
Into a 1.0L reactor, 2.4mol of ethanol, 0.2mol of magnesium chloride and 1.0g of 50wt% strength aqueous potassium tripolyphosphate were added, and the temperature was raised to 70℃with stirring (450 rpm). After reacting at constant temperature for 1 hour, adding epichlorohydrin 0.6mol, maintaining the temperature for 0.5 hour, filtering out liquid, washing solid with hexane for 5 times, and drying in vacuum to obtain solid component particles.
The structure of the carrier body was analyzed by nuclear magnetic resonance as follows:
the inductively coupled plasma mass spectrometer determines that the carrier contains 0.3wt% of phosphorus element.
Carrier particle size distribution d50=45.8 μm, span=0.6.
Example 3
The preparation process is described with reference to example 1, with the only difference that 1g of an aqueous sodium tripolyphosphate solution having a concentration of 25% by weight is added.
The inductively coupled plasma mass spectrometer determines that the carrier contains 0.15wt% of phosphorus element.
Carrier particle size distribution d50=40 μm, span=0.65.
Example 4
The preparation process is described with reference to example 1, except that 2.4g of an aqueous sodium tripolyphosphate solution having a concentration of 25% by weight is added.
The inductively coupled plasma mass spectrometer determines that the carrier contains 0.35wt% of phosphorus element.
Carrier particle size distribution d50=60 μm, span=0.8.
Example 5
(1) Preparation of the catalyst component
In a 300mL glass reaction flask, 100mL of titanium tetrachloride was added under an inert atmosphere, cooled to-20℃and 8g of the catalyst carrier prepared in example 1 was added thereto, and the temperature was raised to 110 ℃. During the heating process, 1.5mL of diisobutyl phthalate is added, liquid is filtered, the solution is washed twice with titanium tetrachloride, three times with hexane, and the catalyst component is obtained after vacuum drying.
(2) Propylene polymerization
The propylene liquid phase bulk polymerization was carried out in a 5L stainless steel autoclave. To the reaction vessel, 5mL of a hexane solution of triethylaluminum (concentration: 0.5 mmol/mL), 1mL of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (concentration: 0.1 mmol/mL) and 9mg of the above catalyst component were successively added under nitrogen atmosphere. The autoclave was closed and 1.5L (standard volume) of hydrogen and 2.3L of liquid propylene were added. Heating to 70 ℃, reacting for 1 hour, reducing the temperature, releasing the pressure, discharging, drying the obtained propylene homopolymer, and weighing.
The results showed that the propylene polymerization activity of the catalyst was 3.5KgPP/gCat, the polymer isotactic index was 97.2% by weight, and the polymer melt index was 8.2g/10min.
Comparative example 1
The preparation process is described with reference to example 1, with the only difference that sodium tripolyphosphate is not added.
The morphology of the carrier particles is shown in figure 2. It can be seen from fig. 2 that the carrier particles adhere to form shaped particles.
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 (11)
1. An olefin polymerization catalyst carrier, characterized in that the catalyst carrier comprises a magnesium compound and a phosphorus compound as shown in formula (I),
Wherein R 1 is a linear alkyl of C 1～C12 or a branched alkyl of C 3～C12; r 2 and R 3 are the same or different and are each independently selected from hydrogen, a linear alkyl group of C 1～C5 or a branched alkyl group of C 3～C5, the hydrogen on the linear alkyl group of C 1～C5 or the branched alkyl group of C 3～C5 being optionally substituted by a halogen atom; x is selected from halogen; m is 0.1-1.9; n is 0.1 to 1.9; m+n=2;
the phosphorus compound is derived from polyphosphate shown in a general formula L K+2PKO3K+1, wherein L is a metal element, and K is an integer of 3-5;
The content of the phosphorus compound in the catalyst carrier is 0< p <3wt%, preferably 0.01wt% < p <1wt%, based on the weight of phosphorus element.
2. The catalyst support of claim 1, wherein the polyphosphate comprises at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, and hydrates thereof.
3. The catalyst support according to claim 1 or 2, characterized in that R 1 is a linear alkyl group of C 1～C8 or a branched alkyl group of C 3～C8; preferably, the R 1 is selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, n-octyl and 2-ethylhexyl;
And/or, the R 2 and R 3 are the same or different and are each independently selected from hydrogen, linear alkyl or isopropyl of C 1～C3 or linear alkyl or isopropyl of halogen substituted C 1-C3; preferably, each of R 2 and R 3 is independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, bromoethyl;
And/or the halogen is selected from chlorine, bromine and iodine, preferably chlorine.
4. A catalyst support according to any one of claims 1 to 3, wherein the catalyst support is a spherical particle;
preferably, the catalyst support has an average diameter of from 10 to 100. Mu.m, preferably from 30 to 70. Mu.m, and a particle size distribution of less than 1.2, preferably from 0.6 to 0.9.
5. A process for preparing an olefin polymerization catalyst support comprising:
(a) Reacting magnesium halide shown in a general formula of MgX 2, an alcohol compound shown in a general formula of R 1 OH and a polyphosphate shown in a general formula of L K+2PKO3K+1 to form suspension, wherein X is halogen, R 1 is C 1～C12 straight-chain alkyl or C 3～C12 branched-chain alkyl, L is a metal element, and K is an integer of 3-5;
(b) Reacting the suspension formed in step (a) with an epoxy compound to form an olefin polymerization catalyst support;
Preferably, the epoxy compound is represented by the general formula (II),
Wherein R 2 and R 3 are the same or different and are each independently selected from hydrogen, a linear alkyl group of C 1～C5 or a branched alkyl group of C 3～C5, the hydrogen on the linear alkyl group of C 1～C5 or the branched alkyl group of C 3～C5 being optionally substituted with a halogen atom.
6. The method according to claim 5, wherein the polyphosphate comprises at least one of sodium tripolyphosphate, potassium tripolyphosphate, sodium tetrapolyphosphate, and hydrates thereof;
And/or, the R 1 is a C 1～C8 linear alkyl or a C 3～C8 branched alkyl; preferably, the alcohol compound shown in the general formula R 1 OH comprises at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, n-amyl alcohol, isoamyl alcohol, n-hexanol, n-octanol and 2-ethyl-1-hexanol;
And/or, the R 2 and R 3 are the same or different and are each independently selected from hydrogen, linear alkyl or isopropyl of C 1～C3 or linear alkyl or isopropyl of halogen substituted C 1-C3; preferably, each of R 2 and R 3 is independently selected from methyl, ethyl, chloromethyl, chloroethyl, bromomethyl, bromoethyl; more preferably, the epoxy compound includes at least one of ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, butylene oxide, propylene oxide, butylene oxide;
And/or the magnesium halide shown in the general formula MgX 2 comprises at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, preferably magnesium dichloride.
7. The method according to claim 5 or 6, wherein the molar ratio of the alcohol compound to magnesium halide is (3 to 30): 1, preferably (4 to 25): 1, a step of; the molar ratio of the polyphosphate to the magnesium halide is 1: (10 to 300), preferably 1: (20-200);
And/or the reaction temperature in step (a) is 30 to 160 ℃, preferably 40 to 120 ℃, and the reaction time is 0.1 to 5 hours, preferably 0.5 to 2 hours;
And/or, said step (a) is carried out in a closed container;
And/or, the polyphosphate in the step (a) is prepared into an aqueous polyphosphate solution and then participates in the reaction; preferably, the concentration of the aqueous polyphosphate solution is 10 to 60wt%, preferably 30 to 60wt%;
and/or the molar ratio of the epoxy compound to the magnesium halide is (1-10): 1, preferably (2 to 6): 1, a step of;
and/or the reaction temperature in step (b) is 30 to 160 ℃, preferably 40 to 120 ℃, and the reaction time is 0.1 to 5 hours, preferably 0.2 to 1 hour.
8. An olefin polymerization catalyst support prepared by the preparation method of any one of claims 5 to 7; preferably, the catalyst support is a spherical particle; more preferably, the catalyst support has an average diameter of 10 to 100. Mu.m, preferably 30 to 70. Mu.m, and a particle size distribution of less than 1.2, preferably 0.6 to 0.9.
9. An olefin polymerization catalyst component comprising the reaction product of the catalyst support of any one of claims 1-4 or the catalyst support of claim 8 with a titanium compound and optionally an internal electron donor compound.
10. An olefin polymerization catalyst comprising the catalyst component of claim 9, an alkyl aluminum compound, and optionally an external electron donor compound.
11. A process for the polymerization of olefins comprising: contacting at least one olefin with the catalyst of claim 10 under olefin polymerization conditions; preferably, the olefin has the formula CH 2 =chr, wherein R is hydrogen or C 1-C7 alkyl; more preferably, the olefin is selected from at least one of ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-hexene.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1485520A (en) * | 1973-12-26 | 1977-09-14 | Mitsui Petrochemical Ind | Process for polymerising or copolymerising olefins and catalyst therefor |
| US20060025300A1 (en) * | 2002-12-18 | 2006-02-02 | Basell Poliolefine Italia S.P.A. | Magnesium dichloride-based adducts and catalyst components obtained therefrom |
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| WO2022089423A1 (en) * | 2020-10-26 | 2022-05-05 | 中国石油化工股份有限公司 | Solid component for preparing olefin polymerization catalyst, and preparation method therefor and application thereof |
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|---|---|---|---|---|
| GB1485520A (en) * | 1973-12-26 | 1977-09-14 | Mitsui Petrochemical Ind | Process for polymerising or copolymerising olefins and catalyst therefor |
| US20060025300A1 (en) * | 2002-12-18 | 2006-02-02 | Basell Poliolefine Italia S.P.A. | Magnesium dichloride-based adducts and catalyst components obtained therefrom |
| WO2007055349A1 (en) * | 2005-11-14 | 2007-05-18 | Toyo Boseki Kabushiki Kaisha | Polyester polymerization catalyst, polyester produced by using same, method for producing polyester, and molded body composed of such polyester |
| CN107438484A (en) * | 2015-04-01 | 2017-12-05 | Gs 加德士 | Sodium polyphosphate supported catalyst with improved activity and method for preparing methyl ethyl ketone and 1,3-butadiene using 2,3-butanediol |
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