CN117924548A - Catalyst component for olefin polymerization, preparation method, catalyst system and olefin polymerization method - Google Patents

Abstract

The invention discloses a preparation method of an olefin polymerization catalyst component, which comprises the steps of contacting a magnesium halide compound with an organic epoxy compound, an organic phosphorus compound and optionally a hydroxyl compound in an organic solvent to form a magnesium-containing solution; contacting an inert dispersing medium, a titanium-containing compound, said magnesium-containing solution to form a mixture comprising at least two liquid phases; preparing a spherical solid object in the presence of a surfactant and a first electron donor; the first electron donor compound comprises an ether or ester compound containing oxygen or/and sulfur atoms; no organic anhydride or organic silicon compound is added in the preparation method; before the magnesium-containing solution is contacted with the titanium-containing compound, if the inert dispersion medium is contacted with the magnesium-containing solution first, the total volume of the inert dispersion medium is not more than 80 percent. The preparation method can prepare the catalyst spherical solid with perfect particle shape.

Description

Catalyst component for olefin polymerization, preparation method, catalyst system and olefin polymerization method

Technical Field

The invention relates to the technical field of olefin polymerization, in particular to a catalyst component for olefin polymerization, a preparation method, a catalyst system and an olefin polymerization method.

Background

Supported Ziegler-Natta catalysts have been widely developed because their morphology can be controlled by the morphology of the support, particularly magnesium chloride supported olefin polymerization catalysts. The preparation of catalysts with good particle morphology is advantageous for industrial plant operation and is one of the keys for catalyst development in the past. The catalyst solid is prepared by a one-step method through a solution crystallization technology, and has the advantages of simple preparation process flow, low energy consumption, higher catalyst strength, less polymer fine powder and the like. However, earlier processes such as the patent CN85100997a and CN1097597C were only capable of producing particulate catalyst solids. In recent years, as described in patent CN103619475B, CN107207657A, CN111479627A, CN02812445.6 and US11098323, a technology for controlling the precipitation of spherical catalyst solids during crystallization by emulsion technology has been developed, and the catalyst morphology has been improved greatly.

In the patent CN103619475B, magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound to form a magnesium compound solution, the magnesium compound solution is contacted with titanium tetrahalide, organic anhydride is used as a precipitation aid, a non-aromatic solvent and a surfactant are added, and an emulsion method is adopted to prepare a spherical catalyst solid. However, the catalyst is porous and fragile, and the polymer bulk density is low. Based on the patent CN107207657A, the spherical catalyst solid is prepared by adding an organic ether compound and organic anhydride as a co-precipitation aid, so that the catalyst property is improved. However, the catalyst still suffers from some drawbacks. When the emulsion method is used for preparing the catalyst component, the disperse phase containing the magnesium phase in the two-phase system is dispersed in the solvent continuous phase, and the magnesium phase has high viscosity and high concentration, so that the catalyst component is easy to separate out rod-shaped materials, large blocks and adhesion materials. The problem is particularly pronounced in scale-up preparations. In addition, the catalyst is easy to generate coarse powder during polymerization, and the coarse powder is easy to break into fine powder, so that the stable operation of a polymerization device is very unfavorable. One of the reasons why the magnesium phase has high viscosity is that the precipitation aid commonly used at present is an organic carboxylic acid or anhydride compound, and the addition of the precipitation aid increases the viscosity of the system, is unfavorable for uniform particle precipitation, and is easy to generate caking and blocking materials. In addition, carboxylic acid or anhydride-based precipitation aid materials used in these disclosed techniques have certain side effects on the catalyst system, which may lead to a decrease in catalyst activity.

Disclosure of Invention

The invention aims to provide a preparation method of an olefin polymerization catalyst component, which is characterized in that when an organic epoxy compound and an organic phosphorus compound are adopted to dissolve a magnesium halide compound and then mixed with a titanium compound to separate out a catalyst solid, an emulsion technology is adopted, a separation assisting agent such as anhydride and an organic silicon compound is not used, the separation assisting effect of the separation assisting agent is not exerted, a good catalyst particle shape can be prepared, the catalyst is spherical, the particle distribution is uniform, and the catalyst activity is higher.

According to the prior art, when no precipitation aid is used, the prepared catalyst has poor form and uniform particles cannot be obtained. The inventors have unexpectedly found that uniform spherical particles can be precipitated by controlling the crystallization formation using emulsion techniques, even without the addition of a precipitation aid. However, it is generally difficult to obtain spherical particles by contacting a titanium-containing compound with a magnesium-containing solution by a conventional method. The inventors have unexpectedly found that by optimizing the contact mode of the inert dispersion medium, the titanium-containing compound and the magnesium-containing solution, the sphericity of the precipitated catalyst component solids can be intact and the particles can be uniform.

In addition, the electron donor is added into the magnesium-containing solution, so that the electron donor does not play a role in precipitation assistance, and the stereospecificity of the catalyst is improved. The preparation method can prepare the spherical solid of the catalyst with perfect particle shape, uniform particle size distribution, excellent catalyst performance and higher activity and stereotactic capability.

It is a second object of the present invention to provide an olefin polymerization catalyst component corresponding to one of the objects.

It is a further object of the present invention to provide an olefin polymerization catalyst system corresponding to the above object.

It is a fourth object of the present invention to provide a process for the polymerization of olefins corresponding to the above object.

In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:

A process for preparing a spherical catalyst component for the polymerization of olefins comprising:

S1, contacting a magnesium halide compound with an organic epoxy compound, an organic phosphorus compound and optionally a hydroxyl-containing compound in an organic solvent to form a magnesium-containing solution;

s2, contacting an inert dispersion medium, a titanium-containing compound and the magnesium-containing solution with II to form a mixture containing at least two liquid phases;

S3, separating out solid matters containing spherical forms from the mixture in the presence of a surfactant and a first electron donor;

s4, optionally, contacting the solid and a second electron donor compound to obtain the olefin polymerization catalyst component;

the first electron donor compound comprises an ether or ester compound containing oxygen or/and sulfur atoms;

No organic anhydride or organic silicon compound is added in the preparation method;

the magnesium-containing solution is contacted with an inert dispersion medium or not before being contacted with the titanium-containing compound;

Before the magnesium-containing solution is contacted with the titanium-containing compound, when the magnesium-containing solution is contacted with the inert dispersion medium, the volume of the inert dispersion medium contacted with the magnesium-containing solution is not more than 80% of the total volume of the inert dispersion medium.

In some preferred embodiments of the present invention, the volume of the inert dispersion medium that is contacted first preferably does not exceed 70% of the total volume of the inert dispersion medium, more preferably does not exceed 60% of the total volume.

According to some embodiments of the invention, the inert dispersion medium that is contacted first may be any value between 0, 25%,50%,60%,70%,75%,80% and the total volume of the inert dispersion medium.

In the existing preparation method, the inert dispersion medium is completely mixed with the magnesium-containing solution and then is contacted with the titanium-containing compound. When the inert dispersion medium contacts with the magnesium-containing solution, the amount of the inert dispersion medium is limited, on one hand, as the inert dispersion medium has an extraction effect on the solvent and the reagent in the magnesium-containing solution, the viscosity of a dispersion phase in the contact process can be reduced by changing the contact mode, the sticky agglomeration of precipitated particles is reduced, and the precipitation of spherical particles is promoted; on the other hand, the contact process is optimized, the crystallization process can be better controlled, and the stable precipitation of particle crystals is more facilitated, and uniform spherical particles are precipitated.

According to some embodiments of the invention, in step S1, the conditions of contact I comprise: the temperature is 10-150 ℃, preferably 30-130 ℃; the contact time is 0.05 to 10 hours, preferably 0.1 to 6 hours.

According to some embodiments of the invention, in step S2, the conditions of contact II include: the time is 1 minute to 10 hours, preferably 3 minutes to 7 hours; the contact temperature is-30 to 60 ℃, preferably-10 to 40 ℃.

According to some embodiments of the invention, in step S1, the magnesium halide compound has the general formula MgX ₂, wherein X is a halogen atom, preferably bromine, chlorine or iodine; preferably, the magnesium halide compound is at least one of magnesium dichloride, magnesium dibromide and magnesium diiodide, more preferably magnesium dichloride.

According to some embodiments of the invention, the organic epoxy compound is selected from one or more of an oxidation product of a C2 to C8 aliphatic olefin, an oxidation product of a C2 to C8 halogenated aliphatic olefin; preferably, the organic epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, methyl glycidyl ether and diglycidyl ether, more preferably propylene oxide.

According to some embodiments of the invention, the organophosphorus compound is selected from one or more of compounds represented by formula (1) and formula (2):

Wherein R ₁、R₂、R₃、R₄、R₅ and R ₆ are each independently selected from a straight-chain alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a halogenated hydrocarbon having 1 to 20 carbon atoms, an aromatic hydrocarbon having 6 to 20 carbon atoms, and an aromatic hydrocarbon having a substituent.

According to some embodiments of the invention, the organophosphorus compound is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripentyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite, preferably tributyl phosphate.

According to some embodiments of the invention, the hydroxyl-containing compound has a general formula as shown in formula (3):

HOR _a (3)

In the formula (3), ra is a hydrocarbon group with 2-20 carbon atoms, preferably, the hydrocarbon group is a saturated or unsaturated straight-chain or branched alkyl, cycloalkyl or aromatic hydrocarbon group, more preferably, the hydroxyl-containing compound is an alcohol compound, and more preferably, one or more of ethanol, propanol, butanol, 2-ethylhexanol, benzyl alcohol and phenethyl alcohol.

According to some embodiments of the invention, the organic solvent is an aromatic hydrocarbon compound, preferably one or more of toluene, ethylbenzene, benzene, xylene, preferably toluene.

According to some embodiments of the present invention, the manner of contacting the magnesium-containing solution formed in step S1 is not particularly limited, and the purpose of the contacting is to form a uniform solution containing magnesium element.

According to some embodiments of the invention, in step S1, the temperature of the contacting is between 10 ℃ and 150 ℃, preferably between 30 ℃ and 130 ℃; the contact time is 0.05 to 10 hours, preferably 0.1 to 6 hours.

According to some embodiments of the invention, in step S2, the inert dispersion medium is one or more of silicone oil, kerosene, paraffinic oil, white oil, vaseline oil, methyl silicone oil, alkane and cycloalkane, preferably one or more of white oil, hexane, heptane, octane, nonane, decane, dodecane and cyclohexane, more preferably one or more of white oil, hexane, decane.

According to some embodiments of the invention, the titanium-containing compound has the general formula (4):

TiX _m(OR_b)_4-m (4)

In the formula (4), X is halogen, R _b is a hydrocarbon group of 1 to 20 carbon atoms, m is an integer of 1 to 4, and the titanium-containing compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium chlorotriethoxide, titanium dichlorodiethoxide and titanium trichloromonoethoxide, and preferably titanium tetrachloride.

According to some embodiments of the present invention, in step S2, comprising in particular adding dropwise the inert dispersion medium to the magnesium-containing solution after mixing homogeneously the inert dispersion medium with the titanium-containing compound; the method specifically comprises the steps of uniformly mixing a part of inert dispersion medium with titanium-containing compound, and then dropwise adding the mixture into a mixed solution of magnesium-containing solution and the rest of inert dispersion medium; also specifically comprising simultaneously starting to drop an inert dispersion medium and a titanium-containing compound into a magnesium-containing solution, respectively; the method may further specifically comprise that the inert dispersion medium and the titanium compound are not simultaneously and respectively dripped into the magnesium-containing solution, and the time for the different time is not the inert dispersion medium or the titanium compound is completely dripped into the magnesium-containing solution, and then the dripping of the other part is started; it may also comprise in particular the dropwise addition of the titanium-containing compound to the magnesium-containing solution, followed by the addition of the inert dispersing medium.

According to some embodiments of the invention, in step S2, the mixture comprising at least two liquid phases comprises colloids, two-phase solutions, emulsions and other forms. In this way, in the presence of the surfactant, the mixture can be caused to form a uniform emulsion by one or more of vibration, stirring, atomization, shearing and the like, so that the spherical solid matters can be solidified and separated out.

According to some embodiments of the invention, the at least two liquid phase mixtures comprise a continuous phase comprising at least an inert dispersion medium, and a dispersed phase comprising at least a product of reacting a magnesium-containing compound with a titanium-containing compound, and a product of reacting an organophosphorus compound with a titanium-containing compound, formed by reacting a magnesium halide compound with an organic epoxy compound.

According to some embodiments of the invention, step S3 further comprises the step of causing the mixture to disperse uniformly by one or more of vibration, stirring, atomizing, shearing.

According to some embodiments of the invention, the mixture is warmed to 20 ℃ to 110 ℃ and solidified to precipitate solids, resulting in a suspension.

According to some embodiments of the invention, the suspension is stirred for a further 10 minutes to 24 hours. The purpose is to make the crystal form more stable and to increase the particle strength.

According to some embodiments of the present invention, the temperature of the mixture is not particularly limited, and any known method may be used for heating, such as slow, stepwise, fast or programmed heating, and the specific heating mode is adjusted according to the specific formulation, contact temperature, etc.; in addition, the inventor researches and discovers that in the preparation method, under the condition that other conditions are the same, different heating processes can influence the particle morphology and particle size distribution of the final catalyst; specifically, a relatively slow heating process can obtain a relatively good particle shape, otherwise, the particle shape is deteriorated due to the excessively high heating speed; thus, the temperature of the mixture may be raised for 1 minute to 36 hours, preferably 3 minutes to 24 hours.

According to some embodiments of the invention, in step S3, the temperature of the mixture is raised at a temperature-raising rate of 0.01 to 4 ℃/min, more preferably 0.05 to 2 ℃/min.

According to some embodiments of the invention, the surfactant is selected from polymeric surfactants; preferably one or more of an alcoholysis product of a maleic anhydride polymer and an alcoholysis product of a maleic anhydride-based copolymer, more preferably one or more of an alcoholysis product of a polymaleic anhydride, an alcoholysis product of a maleic anhydride-styrene copolymer, an alcoholysis product of a maleic anhydride-styrene-alkyl (meth) acrylate terpolymer, and an alcoholysis product of a maleic anhydride-alkyl (meth) acrylate copolymer;

Wherein the side chain of the alkyl ester is a straight-chain alkyl group with 1-30 carbon atoms, a branched-chain alkyl group with 3-30 carbon atoms, a cyclic alkyl group with 3-30 carbon atoms or an aromatic hydrocarbon group with 6-30 carbon atoms, preferably 1-20 carbon atoms; the alcoholysis product is a polymer product obtained by reacting the alcoholysis product with an organic alcohol compound, and the structure of the organic alcohol compound is ROH, wherein R is a linear alkane group with 2-20 carbon atoms, a branched alkane group with 3-20 carbon atoms, a cyclic alkane group with 3-20 carbon atoms or an aromatic hydrocarbon group with 6-20 carbon atoms.

According to some preferred embodiments of the present invention, the surfactant according to the present invention may be further selected from at least one of a (meth) acrylic acid alkyl ester polymer and a copolymer of a (meth) acrylic acid alkyl ester, for example, may be at least one of a poly (meth) acrylic acid alkyl ester, a (meth) acrylic acid alkyl ester-maleic anhydride copolymer, a (meth) acrylic acid alkyl ester-maleic anhydride-styrene copolymer; wherein the ester side chains are straight chain alkyls of 1 to 30 carbon atoms, branched alkyls of 3 to 30 carbon atoms, cyclic alkyls of 3 to 30 carbon atoms or aromatic alkyls of 6 to 30 carbon atoms, preferably those with ester side chains of 1 to 20 carbon atoms.

According to some embodiments of the present invention, the surfactant may be a poly (meth) acrylate polymer surfactant, and may specifically be a surfactant product purchased from additive company under the trade name T602.

According to some embodiments of the invention, the surfactant is present in an amount of 0.05g to 1g per gram of magnesium halide compound.

In the preparation method of the invention, the adding position of the surfactant can be any position in the preparation method, and the surfactant can be added integrally or in a dispersing way. According to the invention, the surfactant is added at a position which is wholly or partially in or after the formation of the magnesium-containing homogeneous solution; may be added integrally to the inert dispersion medium; or may be partially added to the inert dispersion medium and the other to the homogeneous solution containing magnesium element.

According to some embodiments of the invention, the surfactant is added at a temperature of 10 ℃ to 100 ℃, preferably 10 ℃ to 80 ℃, more preferably 10 ℃ to 60 ℃.

According to some embodiments of the invention, the first electron donor compound comprises one or more of ethers, esters compounds containing oxygen and/or sulfur atoms; preferably one or more of aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol ester compounds, monoethers, diethers, polyethers, alcohol ethers, and thioethers.

According to some embodiments of the invention, the first electron donor compound may specifically include:

Dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, di-tert-butyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, dicyclohexyl ether, diheptyl ether, dioctyl ether, dibenzyl ether, methylethyl ether, methylpropyl ether, methylisopropyl ether, methylbutyl ether, methylisobutyl ether, methylpentyl ether, methylisopentyl ether, methylhexyl ether, methylheptyl ether, methyloctyl ether, ethylpropyl ether, ethylisopropyl ether, ethylbutyl ether, ethylisobutyl ether, ethyltert-butyl ether, ethylpentyl ether, ethylisopentyl ether, ethylhexyl ether, ethylheptyl ether, ethyloctyl ether, propylisopropyl ether, propylbutyl ether, propylisobutyl ether, propylpentyl ether, propylisopentyl ether, propylhexyl ether, propylheptyl ether, propyloctyl ether, isopropylbutyl ether, isopropylisobutyl ether, isopropyltert-butyl ether, isopropyl amyl ether, isopropyl isoamyl ether, isopropyl hexyl ether, isopropyl heptyl ether, isopropyl octyl ether, butyl isobutyl ether, butyl tert-butyl ether, butyl amyl ether, butyl isoamyl ether, butyl hexyl ether, butyl heptyl ether, butyl octyl ether, isobutyl tert-butyl ether, isobutyl amyl ether, isobutyl isoamyl ether, isobutyl hexyl ether, isobutyl heptyl ether, isobutyl octyl ether, tert-butyl amyl ether, tert-butyl isoamyl ether, tert-butyl hexyl ether, tert-butyl heptyl ether, tert-butyl octyl ether, amyl isoamyl ether, amyl hexyl ether, amyl heptyl ether, amyl octyl ether, isoamyl hexyl ether, isopentyl heptyl ether, isopentyl octyl ether, hexyl octyl ether, heptyl octyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, butylene glycol dimethyl ether, butanediol diethyl ether, butanediol dibutyl ether, hexanediol dimethyl ether, hexanediol diethyl ether, hexanediol dibutyl ether, 2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2-isopropyl-1, 3-dimethoxypropane, 2-butyl-1, 3-dimethoxypropane, 2-sec-yl-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-dicyclohexyl-1, 3-dimethoxypropane, 2-dicyclopentyl-1, 3-dimethoxypropane, 2-diethyl-1, 3-dimethoxypropane, 2-dipropyl-1, 3-dimethoxypropane 2, 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-diphenyl-1, 3-dimethoxypropane, 2-dibenzyl-1, 3-dimethoxypropane, 2-sec-butyl-2-isopropyl-1, 3-dimethoxypropane, 2-diphenyl-1, 3-dimethoxypropane, 2-sec-butyl-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, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene, ethylsulfide, dipropylsulfide, diisopropylsulfide, dibutylsulfide, diisobutylsulfide, di-tert-butylsulfide, dipentylsulfide, diisopentylsulfide, dihexylsulfide, dicyclohexylsulfide, diheptylsulfide, dioctylsulfide, dibenzyl sulfide, methylethylsulfide, methylpropylsulfide, methylisopropylsulfide, methylbutylsulfide, methylisobutylsulfide, methyltertibutylsulfide, methyl amyl sulfide, methyl isoamyl sulfide, methyl hexyl sulfide, methyl heptyl sulfide, methyl octyl sulfide, ethyl propyl sulfide, ethyl isopropyl sulfide, ethyl butyl sulfide, ethyl isobutyl sulfide, ethyl tertiary butyl sulfide, ethyl amyl sulfide, ethyl isoamyl sulfide, ethyl hexyl sulfide, ethyl heptyl sulfide, ethyl octyl sulfide, propyl isopropyl sulfide, propyl butyl sulfide, propyl isobutyl sulfide, propyl tertiary butyl sulfide, propyl pentyl sulfide, propyl isopentyl sulfide, propyl hexyl sulfide, propyl heptyl sulfide, propyl octyl sulfide, isopropyl butyl sulfide, isopropyl isobutyl sulfide, isopropyl tertiary butyl sulfide, isopropyl pentyl sulfide, isopropyl isopentyl sulfide, isopropyl hexyl sulfide, isopropyl heptyl sulfide, isopropyl octyl sulfide, butyl isobutyl sulfide, butyl tert-butyl sulfide, butyl pentyl sulfide, butyl isopentyl sulfide, butyl hexyl sulfide, butyl heptyl sulfide, butyl octyl sulfide, isobutyl tert-butyl sulfide, isobutyl pentyl sulfide, isobutyl isopentyl sulfide, isobutyl hexyl sulfide, isobutyl heptyl sulfide, isobutyl octyl sulfide, tert-butyl pentyl sulfide, tert-butyl isopentyl sulfide, tert-butyl hexyl sulfide, tert-butyl heptyl sulfide, tert-butyl octyl sulfide, pentyl isopentyl sulfide, pentyl hexyl sulfide, pentyl heptyl sulfide, pentyl octyl sulfide, isopentyl hexyl sulfide, isopentyl heptyl sulfide, isopentyl octyl sulfide, hexyl heptyl sulfide, hexyl octyl sulfide, heptyl octyl sulfide, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, di-n-octyl phthalate, diethyl malonate, dibutyl malonate, diethyl adipate, dibutyl adipate diethyl sebacate, dibutyl sebacate, diethyl maleate, di-n-butyl maleate, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, tributyl trimellitate, triethyl biphenyldicarboxylate tributyl biphenyltricarboxylic acid, tetraethyl pyromellitate, tetrabutyl pyromellitate, methyl formate, butyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl butyrate, isobutyl butyrate, ethyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, ethyl acrylate, methyl methacrylate, ethyl crotonate, ethyl cyclohexane formate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl p-t-butylbenzoate, ethyl naphthalate, methyl toluate, ethyl toluate, pentyl toluate, ethyl ethylbenzoate, methyl anisate, ethyl ethoxybenzoate, 1, 3-propanediol dibenzoate, 2-methyl-1, 3-propanediol dibenzoate, 2-ethyl-1, 3-propanediol dibenzoate, 2-propyl-1, 3-propanediol dibenzoate, 2-butyl-1, 3-propanediol dibenzoate 2, 2-dimethyl-1, 3-propanediol dibenzoate, 2-ethyl-2-butyl-1, 3-propanediol dibenzoate, 2-diethyl-1, 3-propanediol dibenzoate, 2-methyl-2-propyl-1, 3-propanediol dibenzoate, 2-isopropyl-2-isopentyl-1, 3-propanediol dibenzoate, 2, 4-pentanediol dibenzoate, 3-methyl-2, 4-pentanediol dibenzoate, 3-ethyl-2, 4-pentanediol dibenzoate, 3-propyl-2, 4-pentanediol dibenzoate, 3-butyl-2, 4-pentanediol dibenzoate, 3-dimethyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-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, 2-methyl-1, 3-pentanediol dibenzoate, 2-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, and 2-butyl-1, 3-pentanediol dibenzoate, 2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-dimethyl-1, 5-pentanediol dibenzoate, 1, 6-hexanediol dibenzoate, 6-heptene-2, 4-heptanediol dibenzoate, 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-dibutyl-6-heptene-2, 4-heptanediol dibenzoate, 3, 5-heptanediol dibenzoate, 2-methyl-3, 5-heptanediol dibenzoate, 3-methyl-3, 5-heptanediol dibenzoate, 4-methyl-3, 5-heptanediol dibenzoate, 5-methyl-3, 5-heptanediol dibenzoate 6-methyl-3, 5-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, 6-dimethyl-3, 5-heptanediol dibenzoate, 2, 6-dimethyl-3, 5-heptanediol dibenzoate, 3, 4-dimethyl-3, 5-heptanediol dibenzoate, 3, 5-dimethyl-3, 5-heptanediol dibenzoate, 3, 6-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, and 6, 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, and, 4-methyl-5-ethyl-3, 5-heptanediol dibenzoate, 2-methyl-3-propyl-3, 5-heptanediol dibenzoate, 2-methyl-4-propyl-3, 5-heptanediol dibenzoate, 2-methyl-5-propyl-3, 5-heptanediol dibenzoate, 3-methyl-3-propyl-3, 5-heptanediol dibenzoate, 3-methyl-4-propyl-3, 5-heptanediol dibenzoate, 3-methyl-5-propyl-3, 5-heptanediol dibenzoate, 4-methyl-3-propyl-3, 5-heptanediol dibenzoate, 4-methyl-4-propyl-3, 5-heptanediol dibenzoate, 4-methyl-5-propyl-3, 5-heptanediol dibenzoate, diethyl 2, 2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropyl succinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate, diethyl 2-cyclopentyl-2-n-butylsuccinate, diethyl 2, 2-diisobutylsuccinate, diethyl 2-cyclohexyl-2-ethylsuccinate, diethyl 2-isopropyl-2-methylsuccinate, diethyl 2-tetradecyl-2-ethylsuccinate, diethyl 2-isobutyl-2-ethylsuccinate, 2- (1-trifluoromethyl-ethyl) -2-methylsuccinic acid diethyl ester, 2-isopentyl-2-isobutylsuccinic acid diethyl ester, 2-phenyl-2-n-butylsuccinic acid diethyl ester, 2-diisobutyl dimethyl succinate, 2-ethyl-2-methylsuccinic acid diisobutyl ester, 2-benzyl-2-isopropylsuccinic acid diisobutyl ester, 2-cyclohexylmethyl-2-isobutylsuccinic acid diisobutyl ester, 2-cyclopentyl-2-n-butylsuccinic acid diisobutyl ester, 2-diisobutylsuccinic acid diisobutyl ester, 2-cyclohexyl-2-ethylsuccinic acid diisobutyl ester, 2-isopropyl-2-methylsuccinic acid diisobutyl ester diisobutyl 2-tetradecyl-2-ethylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2- (1-trifluoromethyl-ethyl) -2-methylsuccinate, diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2-phenyl-2-n-butyl-succinate, dineopentyl 2, 2-dimethylsuccinate, dineopentyl 2-ethyl-2-methylsuccinate, dineopentyl 2-benzyl-2-isopropylsuccinate, dineopentyl 2-cyclohexylmethyl-2-isobutylsuccinate, dineopentyl 2-cyclopentyl 2-n-butylsuccinate, dineopentyl 2, 2-diisobutylsuccinate, dineopentyl 2-cyclohexyl-2-ethylsuccinate, dineopentyl 2-isopropyl-2-methylsuccinate, dineopentyl 2-tetradecyl-2-ethylsuccinate, dineopentyl 2-isobutyl-2-ethylsuccinate, dineopentyl 2- (1-trifluoromethyl-ethyl) -2-methylsuccinate, dineopentyl 2-isopentyl-2-isobutylsuccinate, dineopentyl 2-phenyl-2-n-butylsuccinate, diethyl2, 3-bis (trimethylsilyl) succinate, diethyl2, 2-sec-butyl-3-methylsuccinate, 2- (3, trifluoropropyl) -3-methylsuccinic acid diethyl ester, 2, 3-bis (2-ethyl-butyl) succinic acid diethyl ester, 2, 3-diethyl-2-isopropyl succinic acid diethyl ester, 2, 3-diisopropyl-2-methylsuccinic acid diethyl ester, 2, 3-dicyclohexyl-2-methylsuccinic acid diethyl ester, 2, 3-dibenzylsuccinic acid diethyl ester, 2, 3-diisopropyl succinic acid diethyl ester, 2, 3-bis (cyclohexylmethyl) succinic acid diethyl ester, 2, 3-di-tert-butylsuccinic acid diethyl ester, 2, 3-diisobutylsuccinic acid diethyl ester, 2, 3-dineopentylsuccinic acid diethyl ester, 2, 3-diisopentylsuccinic acid diethyl ester, 2,3- (1-trifluoromethyl-ethyl) succinic acid diethyl ester, 2, 3-tetradecylsuccinic acid diethyl ester, diethyl 2, 3-fluorenylsuccinate, diethyl 2-isopropyl-3-isobutylsuccinate, diethyl 2-tert-butyl-3-isopropylsuccinate, diethyl 2-isopropyl-3-cyclohexylsuccinate, diethyl 2-isopentyl-3-cyclohexylsuccinate, diethyl 2-tetradecyl-3-cyclohexylmethylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, diisobutyl 2, 3-diethyl-2-isopropyl succinate, diisobutyl 2, 3-diisopropyl-2-methylsuccinate, diisobutyl 2, 3-dicyclohexyl-2-methylsuccinate, diisobutyl 2, 3-dibenzylsuccinate, diisobutyl 2, 3-diisopropylsuccinate diisobutyl 2, 3-bis (cyclohexylmethyl) succinate, diisobutyl 2, 3-di-tert-butylsuccinate, diisobutyl 2, 3-diisobutylsuccinate, diisobutyl 2, 3-dineopentylsuccinate, diisobutyl 2, 3-diisopentylsuccinate, diisobutyl 2,3- (1-trifluoromethyl-ethyl) succinate, diisobutyl 2, 3-tetradecylsuccinate, diisobutyl 2, 3-fluorenylsuccinate, diisobutyl 2-isopropyl-3-isobutylsuccinate, diisobutyl 2-tert-butyl-3-isopropylsuccinate, diisobutyl 2-isopropyl-3-cyclohexylsuccinate, diisobutyl 2-isopentyl-3-cyclohexylsuccinate, diisobutyl 2-tetradecyl-3-cyclohexylmethylsuccinate, diisobutyl 2-cyclohexyl-3-cyclopentylsuccinate, dineopentyl 2, 3-bis (trimethylsilyl) succinate, dineopentyl 2, 2-sec-butyl-3-methylsuccinate, dineopentyl 2- (3, 3-trifluoropropyl) -3-methylsuccinate, dineopentyl 2, 3-bis (2-ethyl-butyl) succinate, dineopentyl 2, 3-diethyl-2-isopropyl succinate, dineopentyl 2, 3-diisopropyl-2-methylsuccinate, dineopentyl 2, 3-dicyclohexyl-2-methylsuccinate, dineopentyl 2, 3-dibenzylsuccinate, dineopentyl 2, 3-diisopropyl succinate Dineopentyl 2, 3-bis (cyclohexylmethyl) succinate, dineopentyl 2, 3-di-tert-butylsuccinate, dineopentyl 2, 3-diisobutylsuccinate, dineopentyl 2, 3-dineopentylsuccinate, dineopentyl 2, 3-diisopentylsuccinate, dineopentyl 2,3- (1-trifluoromethyl-ethyl) succinate, dineopentyl 2, 3-tetradecylsuccinate, dineopentyl 2, 3-fluorenylsuccinate, dineopentyl 2-isopropyl-3-isobutylsuccinate, dineopentyl 2-tert-butyl-3-isopropylsuccinate, dineopentyl 2-isopropyl-3-cyclohexylsuccinate, dineopentyl 2-isopentyl-3-cyclohexylsuccinate, one or more of 2-tetradecyl-3-cyclohexylmethyl succinic acid dipivalyl ester and 2-cyclohexyl-3-cyclopentylsuccinic acid dipivalyl ester.

According to some embodiments of the invention, the first electron donor compound is added at a position, in whole or in part, in or after the formation of the homogeneous solution containing magnesium element; may be added in whole or in part to the mixture of step S2; it may be added in step S3, but it is necessary to add it before the solid is precipitated.

According to some embodiments of the invention, the second electron donor compound may be selected from one or more of esters, ethers, ketones, amines, silanes; preferably one or more of mono-or poly-aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol ester compounds and diether compounds; more preferably one or more of dibasic aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol esters and diether compounds; further preferred are one or more of phthalates, malonates, succinates, glutarates, glycol esters, 1, 3-diethers, pivalates or carbonates.

According to some embodiments of the invention, the second electron donor compound is at least one of di-n-butyl phthalate, diisobutyl phthalate, 2, 4-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, diethyl 2, 3-diisopropylsuccinate, diisobutyl 2, 3-diisopropylsuccinate, di-n-butyl 2, 3-diisopropylsuccinate, dimethyl 2, 2-diisobutyl dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diethyl 2-ethyl-2-methylsuccinate, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 9-dimethoxymethylfluorene.

According to some embodiments of the invention, in step S4, the conditions of contacting III include: the temperature is 10-150 ℃, preferably 10-100 ℃; the time is 0.05 to 8 hours, preferably 1 to 6 hours.

According to some embodiments of the invention, the molar ratio of the second electron donor to the magnesium halide is 0.01-1:1.

According to some embodiments of the present invention, the organic epoxy compound is 0.1 to 10 moles, the hydroxyl group-containing compound is 0.1 to 10 moles, the organic phosphorus compound is 0.1 to 10 moles, the organic solvent is 0.1 to 40 moles, the titanium compound is 0.5 to 25 moles, and the first electron donor compound is 0.01 to 10 moles per mole of the magnesium halide compound; preferably, the organic epoxy compound is 0.4 to 4 moles, the hydroxyl group-containing compound is 0 to 5 moles, the organic phosphorus compound is 0.5 to 4 moles, the organic solvent is 0.1 to 30 moles, the titanium compound is 1 to 20 moles, and the first electron donor compound is 0.01 to 2 moles.

According to some embodiments of the invention, the hydroxyl-containing compound is present in an amount of 0.1 to 5 moles.

According to some embodiments of the invention, the inert dispersion medium is added in an amount of 0.1g to 300g, preferably 1g to 150g, per gram of magnesium halide compound.

The technical scheme of the invention also comprises the following steps:

an olefin polymerization catalyst component prepared by the above preparation method.

According to some embodiments of the invention, the morphology of the catalyst component comprises a spherical structure.

According to some embodiments of the invention, the catalyst component has an average particle size of 1 to 100 μm.

The technical scheme of the invention also comprises the following steps:

an olefin polymerization catalyst system comprising:

(1) The catalyst component prepared according to the preparation method or the catalyst component;

(2) An alkyl aluminum compound; and

Optionally, (3) an external electron donor compound.

According to some embodiments of the invention, the alkyl aluminum compound has a general formula of AlR _nX_3-n, wherein R is hydrogen, a hydrocarbon group with 1-20 carbon atoms, in particular alkyl, aralkyl, aryl, etc.; x is halogen, and n is an integer of 1 to 3. In particular, it may be at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydride, diisobutylaluminum monohydride, diethylaluminum monochloride, diisobutylaluminum monochloride, sesquiethylaluminum chloride and ethylaluminum dichloride, preferably triethylaluminum and/or triisobutylaluminum.

According to some embodiments of the invention, the alkyl aluminum compound may be used in amounts conventional in the art. Preferably, the molar ratio of aluminum in the alkyl aluminum compound to titanium in the catalyst component is from 5 to 5000:1, more preferably from 20 to 800:1.

According to some embodiments of the invention, the external electron donor compound is preferably an organosilicon compound. Wherein n is an integer of 0 to 3, R is one or more of alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, and R _y is one or more of alkyl, cycloalkyl, aryl and halogenated alkyl; preferably at least one of trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl tert-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-tert-butyldimethoxysilane, (1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1, 1-trifluoro-2-propyl) -methyldimethoxysilane, preferably methylcyclohexyldimethoxysilane.

According to some embodiments of the present invention, the amount of the external electron donor compound is not particularly limited, and preferably, the molar ratio of the alkyl aluminum compound to the external electron donor compound is 0.1 to 500:1, preferably 1 to 300:1, more preferably 3 to 100:1, in terms of aluminum.

The technical scheme of the invention also comprises the following steps:

A process for polymerizing olefins, wherein the olefins are polymerized in the presence of the catalyst component prepared by the above-mentioned preparation process or the above-mentioned catalyst component or the above-mentioned catalyst system.

According to some embodiments of the invention, the olefin polymerization is a homopolymerization or a copolymerization of multiple olefins. At least one of the olefins is an olefin represented by the formula CH ₂ =chr, wherein R is hydrogen or a C1-C6 linear or branched alkyl group. Specific examples of the olefin represented by the formula CH ₂ =chr may include: ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the olefin represented by the formula CH ₂ =chr is one or more of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene. More preferably, the olefin represented by the formula CH ₂ =chr is ethylene, propylene, or the copolymerization of ethylene, propylene and other olefins.

According to some embodiments of the invention, the polymerization of olefins is carried out according to known methods, in the liquid phase of a solution of monomers or monomers in an inert solvent, or in the gas phase, or by a combined polymerization process in the gas-liquid phase.

According to some embodiments of the invention, the polymerization conditions include: the temperature is 0-150 ℃, preferably 60-100 ℃; the pressure of the polymerization reaction is 0.1 to 10MPa, preferably 0.1 to 5MPa.

Compared with the prior art, the invention has the following beneficial effects:

(1) According to the preparation method of the olefin polymerization catalyst component, when the magnesium halide compound is dissolved by adopting the organic epoxy compound and the organic phosphorus compound and then mixed with the titanium compound to separate out the catalyst solid, the precipitation aid is not needed, the emulsion technology is adopted, the uniform spherical solid can be separated out, and the catalyst activity is higher because the catalyst does not contain anhydride substances.

(2) The electron donor is added before the solid matters of the catalyst are precipitated, so that the electron donor does not play a role in precipitation assistance, but improves the stereotactic capability of the catalyst. The prepared catalyst is a spherical solid with perfect particles, uniform in particle size distribution, excellent in catalyst performance and high in activity and stereotactic capability.

Drawings

FIG. 1 is a microscopic image of the solid prepared in example 1.

FIG. 2 is a microscope image of the solid prepared in comparative example 4.

FIG. 3 is a microscope image of the solid prepared in comparative example 9.

Detailed Description

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited to the following description.

The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products available commercially without the manufacturer's knowledge.

1. Determination of titanium content in the catalyst: colorimetric determination is performed by an ultraviolet-visible spectrophotometer model 722;

2. Magnesium-containing support or catalyst particle size distribution: measured according to a laser diffraction method, a Markov 2000 particle size analyzer and a normal hexane dispersing agent are adopted, wherein the particle size distribution value SPAN= (D90-D10)/D50;

3. Measurement of polymer Bulk Density (BD) is referred to ASTM D1895-96 standard;

4. The propylene polymer Isotacticity Index (II) was determined using the heptane extraction method: after 2 g of the dried polymer sample was extracted with boiling heptane in an extractor for 6 hours, the residue was dried to constant weight and the ratio of the weight (g) of the obtained polymer to 2 (g) was isotacticity.

5. Sphericity SPHT (iso 9276-6) of the polymer was collected using Camsizer instrument, spht=4pi a/P2, P-circumference of particle projection measured, a-area covered by particle projection measured. For an ideal sphere, the SPHT value is 1.SPHT values are approximately 1, the closer the particles are to spherical.

Example 1

10.8G of anhydrous magnesium chloride, 91g of toluene, 10.6g of epichlorohydrin and 29.2g of tributyl phosphate were successively added to a reaction vessel repeatedly replaced with high-purity nitrogen, and stirred at a temperature of 60℃for 3 hours under 300 RMP. A further 3.1g of T602 was added to the reaction vessel. The temperature was maintained at 60℃for 1 hour more. Cooling to 20 ℃, adding 69.1g of hexane and 4.5ml of dibutyl ether, and continuously cooling to 0 ℃ to form a magnesium-containing solution. 207.1g of titanium tetrachloride and 69.1g of hexane were uniformly mixed to form a titanium-containing solution. The stirring rate of the reaction kettle is increased to 500RMP, the titanium-containing solution is dripped into the magnesium-containing solution, and the reaction kettle is continuously maintained for 1 hour after the dripping is finished. Gradually heating to 80 ℃ within 4 hours, and keeping for 1 hour to precipitate a solid phase to obtain a solid-liquid mixture. The liquid phase was removed by filtration, 160ml of toluene and 40ml of titanium tetrachloride were added, 3ml of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was added, and after heating to 80℃for 1 hour, the filtrate was removed. The solid was washed 2 times with 200ml toluene. 120ml of toluene, 80ml of titanium tetrachloride were added, and the mixture was treated at 110℃for 1 hour, and the filtrate was removed. The process was repeated once. And repeatedly washing with 200ml of hexane for 5 times to obtain an olefin polymerization catalyst component solid. A micrograph of the solid is shown in FIG. 1. The average particle diameter D50 of the solid was 17.4 μm and SPAN value was 0.67 as measured by particle size distribution. The catalyst composition data are shown in table 1.

Polymerization of propylene: in a 5 liter autoclave, after being sufficiently replaced with nitrogen gas, 5ml of a hexane solution of triethylaluminum (triethylaluminum concentration: 0.5 mmol/ml), 1ml of a hexane solution of Cyclohexylmethyldimethoxysilane (CHMMS) (CHMMS concentration: 0.1 mmol/ml), 10ml of anhydrous hexane and 10mg of the above-mentioned catalyst component were added at room temperature. 1 liter of hydrogen under standard conditions and 1.15 kg of liquid propylene were introduced. Heating to 70 ℃, carrying out polymerization reaction for 1 hour at 70 ℃, cooling the reaction kettle after the reaction is finished, stopping stirring, and discharging a reaction product to obtain an olefin polymer, wherein the polymerization result of the catalyst and the polymer data are shown in Table 1.

Example 2

A catalyst component was prepared in the same manner as in example 1 except that dibutyl ether was changed to 2.5ml of dibutyl sulfide to obtain an olefin polymerization catalyst component solid. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Example 3

A catalyst component was prepared in the same manner as in example 1 except that dibutyl ether was changed to 2.5ml of triethylene glycol dibutyl ether to obtain an olefin polymerization catalyst component solid. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Example 4

A catalyst component was prepared in the same manner as in example 1 except that dibutyl ether was changed to 2ml of ethyl benzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was changed to dibutyl phthalate to obtain an olefin polymerization catalyst component solid. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Example 5

A catalyst component was prepared in the same manner as in example 1 except that dibutyl ether was changed to 2ml of 2, 4-pentanediol dibenzoate and 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was changed to 2ml of 2, 4-pentanediol dibenzoate, to obtain an olefin polymerization catalyst component solid. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Example 6

10.8G of anhydrous magnesium chloride, 68.1g of toluene, 12.8g of epichlorohydrin and 29.2g of tributyl phosphate were successively added to a reaction vessel repeatedly replaced with high-purity nitrogen, and stirred at a temperature of 60℃for 3 hours under 300 RMP. 5.7g T602 are added. The temperature was maintained at 60℃for 1 hour more. Cooling to 20 ℃, adding 89.1g of hexane and 5.4ml of diisoamyl ether, and continuously cooling to 0 ℃ to form a magnesium-containing solution. Stirring was increased to 400RMP, and 207.1g of titanium tetrachloride and 89.1g of hexane were each dropped into the magnesium-containing solution, and the dropping was continued for 1 hour. The temperature was gradually increased to 80℃over 4 hours. 3ml of 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane was added during the precipitation at a temperature elevated to 80℃and maintained for 1 hour, and the filtrate was removed. Then washed 2 times with 200ml toluene. 120ml of toluene, 80ml of titanium tetrachloride were added, and the mixture was treated at 110℃for 1 hour, and the filtrate was removed. The process was repeated once. And repeatedly washing with 200ml of hexane for 5 times to obtain an olefin polymerization catalyst component solid. The average particle diameter D50 of the solid was 57.2 μm and SPAN value was 0.83 as measured by particle size distribution. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

The propylene polymerization process was the same as in example 1. The polymerization results and polymer data for the catalysts are shown in Table 1.

Example 7

A catalyst component was prepared in the same manner as in example 6 except that diisoamyl ether was changed to 3ml of dioctyl ether and that hexane was not added to the magnesium-containing solution, but 207.1g of titanium tetrachloride and 178.2g of hexane were respectively dropped into the magnesium-containing solution. To obtain the solid matter of the olefin polymerization catalyst component. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

The propylene polymerization process was the same as in example 1. The polymerization results and polymer data for the catalysts are shown in Table 1.

Example 8

A catalyst component was prepared in the same manner as in example 1 except that dibutyl ether was changed to be added after the titanium-containing solution was added dropwise to the magnesium-containing solution. To obtain the solid matter of the olefin polymerization catalyst component. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Example 9

A catalyst component was prepared in the same manner as in example 1 except that 1.2g of ethanol was added after tributyl phosphate was added. To obtain the solid matter of the olefin polymerization catalyst component. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 1

The catalyst component was prepared by the same method as in example 1 except that dibutyl ether was not used. To obtain the solid matter of the olefin polymerization catalyst component. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 2

A catalyst component was prepared in the same manner as in example 4 except that ethyl benzoate was not used, to obtain an olefin polymerization catalyst component solid. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 3

A catalyst component was prepared in the same manner as in example 5 except that 2, 4-pentanediol dibenzoate was not added to a magnesium-containing solution, and after precipitation of a solid, the added 2, 4-pentanediol dibenzoate was changed to 4ml to obtain a solid of an olefin polymerization catalyst component. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 4

The catalyst component was prepared in the same manner as in example 1 except that after T602 was added, 3g of phthalic anhydride was further added. To obtain the solid matter of the olefin polymerization catalyst component. A micrograph of the solid is shown in fig. 2, and an optical microscope shows the morphology of the solid as a part of a sphere, a part of a large rod and a lump. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 5

The catalyst component was prepared by the same method as in example 1 except that dibutyl ether was not used, and after the addition of T602, the addition of 3g of phthalic anhydride was continued. To obtain the solid matter of the olefin polymerization catalyst component. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 6

A catalyst component was prepared in the same manner as in example 1 except that dibutyl ether was changed to be added after the completion of dropwise addition of the solution containing magnesium to the solution containing titanium and after gradually raising the temperature to 80 ℃. To obtain the solid matter of the olefin polymerization catalyst component. The optical microscope showed the solid to be spherical in shape and uniform in particle size. The catalyst component data are shown in Table 1.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 7

The catalyst component was prepared by the same method as in example 3 of patent CN101643519B to obtain a solid olefin polymerization catalyst component. The optical microscope showed that the precipitated solid was in the form of particles, and non-spherical.

Propylene polymerization procedure the catalyst polymerization data and polymer data are shown in Table 1, as in example 1.

Comparative example 8

A catalyst component was prepared in the same manner as in example 3 except that 158.2g of hexane in total was added to the magnesium-containing solution, and titanium tetrachloride was dropped into the magnesium-containing solution. To obtain the solid matter of the olefin polymerization catalyst component. The optical microscope showed that the precipitated solid forms almost no spherical particles, and were both bulk and powdery.

Comparative example 9

A catalyst component was prepared in the same manner as in example 5 except that 158.2g of hexane in total was added to the magnesium-containing solution, and titanium tetrachloride was dropped into the magnesium-containing solution. To obtain the solid matter of the olefin polymerization catalyst component. As shown in fig. 3, the microscopic photograph of the solid was that the precipitated solid was in the form of a lump and a powder, and almost no spherical particles were present.

Example 10

A catalyst component was prepared in the same manner as in example 5, except that 80% of the total 158.2g of hexane was brought into contact with the magnesium-containing solution to form a new magnesium-containing solution, and that the other 20% of hexane and titanium tetrachloride were simultaneously and initially dropped into the magnesium-containing solution, respectively, to precipitate solids. The optical microscope showed that the morphology of the precipitated solids was mainly some lumps and powders, containing spherical particles.

Example 11

A catalyst component was prepared in the same manner as in example 5, except that 65% of the total 158.2g of hexane was brought into contact with the magnesium-containing solution to form a new magnesium-containing solution, and that the other 35% of hexane and titanium tetrachloride were simultaneously and initially dropped into the magnesium-containing solution, respectively, to precipitate solids. The optical microscope showed that the precipitated solids had spherical particles in morphology, with some lumps and fines present.

TABLE 1 catalyst Components and propylene polymerization Properties

From the isotacticity II data of the above examples, the catalyst stereotacticity was higher when the electron donor compound was added before the catalyst component solids precipitated, as seen from the comparison of examples 1, 2,3 and comparative example 1, the comparison of example 4 and comparative example 2, the comparison of example 5 and comparative example 3, and the comparison of example 1 and comparative example 6. According to the SPHT data of the above examples, the comparison of examples 1, 2,3 and comparative example 1, the comparison of example 4 and comparative example 2, and the comparison of example 5 and comparative example 3, it is understood that the catalyst component prepared by the preparation method of the present invention, with or without the addition of an electron donor compound, has a spherical morphology for the polymer formed by polymerization before the catalyst component is separated out, and that the catalyst component solid can maintain good spherical particles according to the replicative effect of the olefin catalyst and its polymer. Usually, an electron donor is added before the catalyst component is precipitated, and the electron donor can play a role in precipitating, so that the catalyst is precipitated in a good particle form; however, in the present invention, the electron donor does not act as an auxiliary precipitation, but rather slightly reduces the sphericity of the catalyst solid, and the main function is to improve the stereotactic ability of the catalyst.

According to example 1 and comparative examples 4 and 5, the preparation method of the present invention does not use an anhydride precipitation aid, and the catalyst activity is higher.

From the SPHT data of example 5 and comparative example 7, it was found that the preparation method according to the present invention can precipitate a uniform spherical solid by the emulsion technique, and the catalyst morphology is more excellent.

From examples 1, 3,5, 10, 11 and comparative examples 8 to 9, it was found that uniform spherical solid matters were precipitated by optimizing the contact modes of the inert dispersion medium, the titanium-containing compound, and the magnesium-containing solution in the presence of the electron donor.

According to the above examples and comparative examples, in the preparation method of the present invention, when an acid anhydride-based precipitation aid is not used, a uniform spherical solid can be precipitated by emulsion technology, the activity of the catalyst component is higher, the electron donor is added before the precipitation of the solid, and the stereospecificity of the catalyst is higher.

What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent modifications and improvements will occur to those skilled in the art, and are intended to be within the scope of the present invention, as a matter of common general knowledge in the art, in light of the technical teaching provided by the present invention.

Claims (10)

1. A process for preparing a catalyst component for olefin polymerization comprising the steps of:

S1, contacting a magnesium halide compound with an organic epoxy compound, an organic phosphorus compound and optionally a hydroxyl-containing compound in an organic solvent to form a magnesium-containing solution;

s2, contacting an inert dispersion medium, a titanium-containing compound and the magnesium-containing solution with II to form a mixture containing at least two liquid phases;

S3, separating out solid matters containing spherical forms from the mixture in the presence of a surfactant and a first electron donor;

s4, optionally, contacting the solid and a second electron donor compound with III to obtain the olefin polymerization catalyst component;

the first electron donor compound comprises an ether or ester compound containing oxygen or/and sulfur atoms;

No organic anhydride or organic silicon compound is added in the preparation method;

the magnesium-containing solution is contacted with an inert dispersion medium or not before being contacted with the titanium-containing compound;

Before the magnesium-containing solution is contacted with the titanium-containing compound, when the magnesium-containing solution is contacted with the inert dispersion medium, the volume of the inert dispersion medium contacted with the magnesium-containing solution is not more than 80% of the total volume of the inert dispersion medium.

2. The method for producing a catalyst component according to claim 1, wherein the volume amount of the inert dispersion medium to be contacted is preferably not more than 70% of the total volume amount of the inert dispersion medium, and more preferably not more than 60% of the total volume amount.

3. The preparation method according to any one of claims 1 or 2, wherein the magnesium halide compound has the general formula MgX ₂, wherein X is a halogen atom, preferably bromine, chlorine or iodine;

And/or the organic epoxy compound is selected from one or more of oxidation products of aliphatic olefins of C2-C8 and oxidation products of halogenated aliphatic olefins of C2-C8; preferably, the organic epoxy compound is one or more of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, methyl glycidyl ether and diglycidyl ether;

And/or the organophosphorus compound is selected from one or more of compounds represented by formula (1) and formula (2):

Wherein R1, R2, R3, R4, R5 and R6 are each independently selected from a straight chain alkyl group of 1 to 20 carbon atoms, a branched chain alkyl group of 3 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, a halogenated hydrocarbon of 1 to 20 carbon atoms or an aromatic hydrocarbon of 6 to 20 carbon atoms, and an aromatic hydrocarbon having a substituent; preferably, the organophosphorus compound is selected from one or more of trimethyl phosphate, triethyl phosphate, tributyl phosphate, tripentyl phosphate, triphenyl phosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite;

and/or the general formula of the hydroxyl-containing compound is shown as the formula (3):

HOR _a (3)

R _a in the formula (3) is a hydrocarbon group with 2-20 carbon atoms, preferably, the hydrocarbon group is saturated or unsaturated straight-chain or branched alkyl, naphthene group or aromatic hydrocarbon group, more preferably, the hydroxyl-containing compound is an alcohol compound, and more preferably, one or more of ethanol, propanol, butanol, 2-ethylhexanol, benzyl alcohol and phenethyl alcohol;

And/or the organic solvent is an aromatic hydrocarbon compound, preferably one or more of toluene, ethylbenzene, benzene and xylene;

and/or the inert dispersing medium is one or more of silicone oil, kerosene, paraffin oil, white oil, vaseline oil, methyl silicone oil, alkane and cycloalkane, preferably one or more of hexane, heptane, octane, nonane, decane, dodecane and cyclohexane;

and/or the general formula of the titanium-containing compound is shown as the formula (4):

TiX _m(OR_b)_4-m (4)

In the formula (4), X is halogen, R _b is alkyl of 1-20 carbon atoms, m is an integer of 1-4, and the titanium-containing compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy and titanium trichloromonoethoxy;

And/or, based on each mole of the magnesium halide compound, 0.1 to 10 moles of the organic epoxy compound, 0 to 10 moles of the hydroxyl-containing compound, 0.1 to 10 moles of the organic phosphorus compound, 0.1 to 40 moles of the organic solvent and 0.5 to 25 moles of the titanium compound; preferably, the organic epoxy compound is 0.4 to 4 moles, the hydroxyl-containing compound is 0 to 5 moles, the organic phosphorus compound is 0.5 to 4 moles, the organic solvent is 0.1 to 30 moles, and the titanium compound is 1 to 20 moles;

And/or the inert dispersion medium is added in an amount of 0.1g to 300g, preferably 1g to 150g, per gram of the magnesium halide compound.

4. A method of preparation according to any one of claims 1 to 3, wherein the surfactant is selected from polymeric surfactants; preferably one or more of an alcoholysis product of a maleic anhydride polymer and an alcoholysis product of a maleic anhydride-based copolymer, more preferably one or more of an alcoholysis product of a polymaleic anhydride, an alcoholysis product of a maleic anhydride-styrene copolymer, an alcoholysis product of a maleic anhydride-styrene-alkyl (meth) acrylate terpolymer, and an alcoholysis product of a maleic anhydride-alkyl (meth) acrylate copolymer;

Wherein the side chain of the alkyl ester is a straight-chain alkyl group with 1-30 carbon atoms, a branched-chain alkyl group with 3-30 carbon atoms, a cyclic alkyl group with 3-30 carbon atoms or an aromatic hydrocarbon group with 6-30 carbon atoms, preferably 1-20 carbon atoms; the alcoholysis product is a polymer product obtained by reacting the alcoholysis product with an organic alcohol compound, and the structure of the organic alcohol compound is ROH, wherein R is a linear alkane group with 2-20 carbon atoms, a branched alkane group with 3-20 carbon atoms, a cyclic alkane group with 3-20 carbon atoms or an aromatic hydrocarbon group with 6-20 carbon atoms;

Or the surfactant is at least one selected from the group consisting of (meth) acrylic acid alkyl ester polymers and copolymers of (meth) acrylic acid alkyl esters, preferably at least one selected from the group consisting of polyalkyl (meth) acrylates, alkyl (meth) acrylate-maleic anhydride copolymers, and copolymers of alkyl (meth) acrylate-maleic anhydride-styrene; wherein the ester side chains are straight chain alkyls of 1 to 30 carbon atoms, branched alkyls of 3 to 30 carbon atoms, cyclic alkyls of 3 to 30 carbon atoms or aromatic alkyls of 6 to 30 carbon atoms, preferably those with ester side chains of 1 to 20 carbon atoms;

Preferably, the surfactant is 0.05g to 1g per gram of magnesium halide compound;

and/or the surfactant is added at a temperature of 10 ℃ to 100 ℃, preferably 10 ℃ to 80 ℃, more preferably 10 ℃ to 60 ℃.

5. The method according to any one of claims 1 to 4, wherein the first electron donor compound comprises one or more of an ether compound and an ester compound containing oxygen and/or sulfur atoms; preferably one or more of aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol ester compounds, monoethers, diethers, polyethers, alcohol ethers and thioether compounds;

Preferably, the first electron donor compound is present in an amount of 0.01 to 10 moles per mole of magnesium halide compound; more preferably, the first electron donor compound is 0.01 to 2 moles;

and/or the second electron donor compound may be selected from one or more of esters, ethers, ketones, amines, silanes; preferably one or more of mono-or poly-aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol ester compounds and diether compounds; more preferably one or more of dibasic aliphatic carboxylic acid esters, aromatic carboxylic acid esters, glycol esters and diether compounds; further preferred are one or more of phthalates, malonates, succinates, glutarates, glycol esters, 1, 3-diethers, pivalates or carbonates;

preferably, in step S4, the conditions for contacting III include: the temperature is 10-150 ℃, preferably 10-100 ℃; the time is 0.05 to 8 hours, preferably 1 to 6 hours;

And/or the molar ratio of the addition amount of the second electron donor to the magnesium halide is 0.01-1:1.

6. An olefin polymerization catalyst component prepared by the preparation method of any one of claims 1 to 5.

7. The catalyst component according to claim 6, wherein the morphology of the catalyst component comprises a spherical structure;

and/or the catalyst component has an average particle diameter of 1 to 100 μm.

8. A catalyst system comprising:

(1) The catalyst component according to claim 6 or 7;

(2) An alkyl aluminum compound; and

Optionally, (3) an external electron donor compound.

9. A process for the polymerization of olefins by polymerizing olefins in the presence of the catalyst component of claim 6 or 7 or the catalyst system of claim 8.

10. The method of claim 9, wherein the polymerization is a homopolymerization or a copolymerization of multiple olefins;

preferably, the conditions of the polymerization reaction include: the temperature is 0-150 ℃, preferably 60-100 ℃; the pressure of the polymerization reaction is 0.1 to 10MPa, preferably 0.1 to 5MPa.