CN108117617B - Solid catalyst component and catalyst for olefin polymerization - Google Patents
Solid catalyst component and catalyst for olefin polymerization Download PDFInfo
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- CN108117617B CN108117617B CN201611062232.5A CN201611062232A CN108117617B CN 108117617 B CN108117617 B CN 108117617B CN 201611062232 A CN201611062232 A CN 201611062232A CN 108117617 B CN108117617 B CN 108117617B
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Abstract
The invention provides a solid catalyst component and a catalyst for olefin polymerization, which contain Mg, Ti, halogen and optionally an electron donor, wherein the C value of the solid catalyst component particle is more than or equal to 0.7, and the C value is the average sphericity. The solid catalyst component and the catalyst have the preferable particle form, and the obtained polymer product has the characteristics of good fluidity, high bulk density, no stickiness, less fine powder and lump material, good polymerization production stability and high productivity of the unit volume of a reaction kettle.
Description
Technical Field
The invention relates to an olefin polymerization catalyst component and a catalyst and application thereof, in particular to a solid catalyst component and a catalyst for olefin polymerization, belonging to the field of polyolefin catalysts.
Background
The production process of polypropylene mainly includes five major processes of solution process, slurry process, bulk process, gas phase process and bulk-gas phase process combination process. The gas-phase polypropylene production process is favored because of simple process flow, simple operation, good production flexibility, large single-line production capacity, higher safety and less equipment investment. The gas phase reactor may be divided into a stirred bed and a fluidized bed according to the state of motion of solids therein. The small range of motion of the solids in the stirred bed, in the form of micromotion, and the high bulk density of the particles, allows the production of large quantities of polyolefin product in a small reactor volume.
Innovene polypropylene technology from Ineos is an important production technology in the polypropylene industry today. The process is mainly characterized in that a unique horizontal stirred bed reactor close to plug flow is adopted, an internal baffle is arranged, a specially designed horizontal stirrer is arranged, and blades of the stirrer form 45 degrees with a stirring shaft, so that the whole bed layer can be slowly and regularly stirred. The bed has a plurality of gas and liquid phase feed points from which catalyst, liquid propylene and gas are fed. The main catalyst is directly added into the gas phase reactor under the carrying of fresh propylene, and has the characteristics of high activity, good stability, low fine powder content and the like. However, in the production process, the problems of temperature fluctuation in the reactor, high fine powder content, polymer agglomeration and the like caused by nonuniform dispersion of the main catalyst particles, and the like are often caused, which is not favorable for long-period stable operation of the device.
Chinese patent CN102030841 discloses a propylene gas phase polymerization method, which comprises pre-complexing a cocatalyst with or without an external electron donor, and then performing a small amount of propylene continuous or intermittent prepolymerization, wherein the pre-complexing and the prepolymerization improve the dispersibility of a main catalyst, reduce the temperature fluctuation frequency caused by uneven dispersion of the main catalyst in a reactor, simultaneously alleviate the agglomeration problem of the polymer in the reactor, and effectively reduce the content of fine powder in the polymer.
However, for many existing polymerization plants, the addition of a prepolymerization plant means new investment and relatively large modification, and the prepolymerization also has some limitations, and the prepolymerization improves the activity of the catalyst and reduces the generation of fine powder in the polymerization process by controlling the initial reaction of the catalyst and propylene under low temperature conditions, which is also a difficult control problem of the technical process. Due to the high initial activity of the catalyst, once the process is improperly controlled, the agglomeration is easily caused in the prepolymerization reactor, when the agglomeration blocks a discharge line, the pressure of the prepolymerization reactor is increased, and when the agglomeration blocks the discharge line, the chain shutdown of the prepolymerization reactor is caused, so that the whole polypropylene device is shut down. When the prepolymerization is not controlled properly, the biological material is easy to back mix, which affects the polymerization stability.
Therefore, it is desirable to provide a solid catalyst component having a regular particle shape and a high bulk density to improve the production stability of olefin polymerization.
Disclosure of Invention
The present invention has been made in view of the above-mentioned background art, and an object thereof is to provide a solid catalyst component suitable for olefin polymerization, which has characteristics of regular particle shape and suitable particle sphericity.
It is another object of the present invention to provide a method for preparing the solid catalyst component.
It is still another object of the present invention to provide a catalyst comprising the solid catalyst component.
It is a further object of the present invention to provide a process for the preparation of the catalyst.
It is a further object of the present invention to provide the above solid catalyst component and the use of the solid catalyst in the polymerization of olefins.
In order to achieve the above object, the present invention provides a solid catalyst component for olefin polymerization, which contains Mg, Ti, halogen and optionally an electron donor compound, wherein the C value of the particles of the solid catalyst component is not less than 0.7, wherein the C value is the average sphericity, which is the arithmetic average of the values of the sphericity C' of the individual particles, and the number of the sampled particles is 200 to 500000.
The sphericity c 'value of a single particle is obtained by a shape factor definition method (see circulation in ISO 9276-6-2008) based on two-dimensional image analysis by applying a microscopic or digital imaging technology, and the calculation formula of the c' value is as follows:
wherein A is the measured projected area of the single particle, and P is the measured projected perimeter of the single particle;
the number of the solid catalyst component, the c' value of which is not less than 0.7, is preferably not less than 60% of the total number of the particles.
Preferably, the number of particles having a c' value of 0.8 or more is not less than 30% of the total number of particles.
The sample for sphericity test can be directly selected from solid catalyst component, and particle morphology test is carried out under the protection of inert gas or inert liquid. Since the polymer obtained by bulk polymerization of propylene under certain conditions has better reproducibility to the morphology of the solid catalyst, for the polypropylene catalyst, any polymerization mode and polymerization conditions that can maintain the particle shape of the catalyst component can be used to perform the test, and the measured sphericity is regarded as the sphericity of the particles of the polypropylene catalyst component. Polymerization conditions that can maintain the catalyst component in particulate form include, but are not limited to: the polymerization temperature is 60-70 ℃, the propylene is subjected to bulk polymerization at a constant speed of raising the temperature from 20 ℃ to 70 ℃ for at least 15 minutes, and the catalytic activity of the selected catalyst component under the polymerization conditions per hour is not lower than 25Kg of polypropylene/g of catalyst. When polypropylene particles are used for the test, the original polymer particles obtained directly from the polymerization of the solid catalyst component without any treatment step for altering the particle morphology (e.g., granulation, etc.) are selected and screened to remove a portion of particles smaller than 300 μm for particle shape analysis.
The average sphericity C of the particles of the solid catalyst component and the value of the sphericity C' of the individual particles can be determined using various instruments suitable for the analysis of the morphology of the particle appearance, preferably a granulometer, the model of which includes, but is not limited to, the Marvin Morphogi G3 dry particle size and particle shape analyzer, Retsch
An X2 particle size analyzer, an XPT-C laser particle size analyzer, a Kangta FC200 full-automatic image method particle size analyzer, a Jinan micro-nano Winner100 dynamic particle image analyzer, and the like.
In the solid catalyst component of the present invention, Mg is derived from a dialkoxymagnesium compound selected from the group consisting of dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium.
The Ti in the invention is derived from the general formula of TiXN(OR)4-NWherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and N is 0 < N < 4.
The titanium compound of the present invention includes, but is not limited to, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide or an alkyl titanium halide, wherein the alkyl titanium halide includes, but is not limited to, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride or tri-n-butoxytitanium chloride; among them, these alkyltitanium halides may be used in combination of one or more. Titanium tetrachloride is preferably used as the titanium compound of the present invention.
The electron donor compound is a Lewis base containing one or more electronegative groups, wherein the electron donor atom is selected from the group consisting of N, O, S, P, As or Sn.
The electron donor compound is an ester, an ether or a polyoxy functional compound, and preferably the following compounds: aromatic monoester compounds; aromatic diester compounds; a succinate compound; 1, 3-diethers; glycol ester compounds; a ring-substituted compound containing one ether group and one ester group, wherein the ring-substituted group is preferably a cyclopentadiene substituent and a fluorene substituent; a diacid ester compound; a glycidyl ester compound; and citrate compounds, and these electron donor compounds may be used alone or in combination of two or more.
Specifically, the electron donor compound may be selected from monocarboxylic acid ester or polycarboxylic acid ester compounds, such as aromatic dicarboxylic acid compound or aliphatic dicarboxylic acid ester compound, wherein the aromatic dicarboxylic acid compound may be a diester compound of aromatic dicarboxylic acid represented by general formula (I):
R1and R2The alkyl groups may be the same or different and represent a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkylaryl group or arylalkyl group having 7 to 20 carbon atoms.
Specifically, it is a phthalate diester or a terephthalate diester, wherein the phthalate diester may include but is not limited to: dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, methyl ethyl phthalate, methyl isopropyl phthalate, methyl n-propyl phthalate, ethyl n-butyl phthalate, ethyl isobutyl phthalate, di-n-pentyl phthalate, diisopentyl phthalate, dihexyl phthalate, di-n-heptyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, 2-dimethylhexyl phthalate, 2-ethylhexyl phthalate, di-n-nonyl phthalate, diisodecyl phthalate, 2-dimethylheptyl phthalate, n-hexyl phthalate, n-butyl (2-ethylhexyl) phthalate, n-hexyl phthalate, n-nonyl isononyl phthalate, isopentyl n-decyl phthalate, n-undecyl phthalate, isopentyl isohexyl phthalate, n-hexyl phthalate (2-methylhexyl phthalate), n-hexyl (2-ethylhexyl) phthalate, n-hexyl (isononyl) phthalate, n-hexyl (n-decyl) phthalate, n-heptyl (2-ethylhexyl) phthalate, n-heptyl (isononyl) phthalate, n-heptyl (nonyl) phthalate, and 2-ethylhexyl (isononyl) phthalate. These esters may be used alone or in combination of two or more. The terephthalic acid diesters include, but are not limited to: dimethyl terephthalate, diethyl terephthalate, di-n-propyl terephthalate, diisopropyl terephthalate, di-n-butyl terephthalate, diisobutyl terephthalate, ethyl methyl terephthalate, methyl isopropyl terephthalate, ethyl (n-propyl) terephthalate, ethyl (n-butyl) terephthalate, ethyl (isobutyl) terephthalate, di-n-pentyl terephthalate, diisopentyl terephthalate, dihexyl terephthalate, di-n-heptyl terephthalate, di-n-octyl terephthalate, diison-octyl terephthalate, di-2, 2-dimethylhexyl terephthalate, di-2-ethylhexyl terephthalate, di-n-nonyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, di-n-butyl terephthalate, di-isobutyl terephthalate, di-n-butyl terephthalate, di-hexyl terephthalate, di, Di (2, 2-dimethylethylheptyl) terephthalate, n-butyl isohexyl terephthalate, n-butyl (2-ethylhexyl) terephthalate, n-hexyl n-pentyl terephthalate, n-pentyl isohexyl terephthalate, isopentyl (heptyl) terephthalate, terephthalic acid, n-pentyl (2-ethylhexyl) terephthalate, n-pentyl (isononyl) terephthalate, isopentyl (n-decyl) terephthalate, n-pentyl (undecyl) terephthalate, isopentyl (isohexyl) terephthalate, n-hexyl (2-ethylhexyl) terephthalate, n-hexyl (isononyl) terephthalate, n-hexyl (n-decyl) terephthalate, n-heptyl (2-ethylhexyl) terephthalate, n-heptyl (isononyl) terephthalate, n-heptyl (neodecyl) terephthalate, n-hexyl (iso-hexyl) terephthalate, n-hexyl (iso-nonyl) terephthalate, n-hexyl (n-decyl) terephthalate, n-hexyl (iso-decyl) terephthalate, n-hexyl (neo, And 2-ethylhexyl (isononyl) terephthalate. These esters may be used alone or in combination of two or more.
Among the diester-based compounds of the aromatic dicarboxylic acids, at least one of diethyl phthalate, dipropyl phthalate, diisopropyl terephthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, di-n-butyl terephthalate, diisobutyl terephthalate, di-n-octyl terephthalate, diisooctyl terephthalate, di-2-ethylhexyl terephthalate and diisodecyl phthalate is preferable.
Specifically, the electron donor compound may be selected from 1, 3-diethers as shown in the general formula (II):
in the formula (II), R, R1、R2、R3、R4And R5Which may be the same or different, represent H or a linear or branched alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl group having from 1 to 18 carbon atoms; r6And R7The alkyl groups may be the same or different and represent a straight-chain or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 5 to 20 carbon atoms, an alkylaryl group or arylalkyl group having 7 to 20 carbon atoms; r to R7One or more of the groups in (a) may beThe linkages form cyclic structures, and may each contain one or more heteroatoms selected from halogen, N, O, S, P, and Si.
Specifically, the 1, 3-diethers include, but are not limited to: 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-tert-butyl-1, 3-dimethoxypropane, 2-cumyl-1, 3-dimethoxypropane, 2- (2-phenylethyl) -1, 3-dimethoxypropane, 2- (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2- (p-chlorophenyl) -1, 3-dimethoxypropane, 2- (diphenylmethyl) -1, 3-dimethoxypropane, 2 (1-naphthyl) -1, 3-dimethoxypropane, 2 (p-fluorophenyl) -1, 3-dimethoxypropane, 2 (1-decahydronaphthyl) -1, 3-dimethoxypropane, 2 (p-tert-butylphenyl) -1, 3-dimethoxypropane, 2, 2-dicyclohexyl-1, 3-dimethoxypropane, 2, 2-diethyl-1, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-dimethoxypropane, 2, 2-dibutyl-1, 3-dimethoxypropane, 2, 2-diethyl-1, 3-diethoxypropane, 2, 2-dicyclopentyl-1, 3-dimethoxypropane, 2, 2-dipropyl-1, 3-diethoxypropane, 2, 2-dibutyl-1, 3-diethoxypropane, 2-methyl-2-ethyl-1, 3-dimethoxypropane, 2-methyl-2-propyl-1, 3-dimethoxypropane, 2-methyl-2-benzyl-1, 3-dimethoxypropane, 2-methyl-2-phenyl-1, 3-dimethoxypropane, 2-methyl-2-cyclohexyl-1, 3-dimethoxypropane, 2-methyl-2-methylcyclohexyl-1, 3-dimethoxypropane, 2, 2-bis (p-chlorophenyl) -1, 3-dimethoxypropane, 2, 2-bis (2-phenylethyl) -1, 3-dimethoxypropane, 2, 2-bis (2-cyclohexylethyl) -1, 3-dimethoxypropane, 2-methyl-2-isobutyl-1, 3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1, 3-dimethoxypropane, 2, 2-bis (p-methylphenyl) -1, 3-dimethoxypropane, 2-methyl-2-isopropyl-1, 3-dimethoxypropane, 2, 2-diisobutyl-1, 3-dimethoxypropane, 2, 2-diphenyl-1, 3-dimethoxypropane, 2, 2-dibenzyl-1, 3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1, 3-dimethoxypropane, 2, 2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2, 2-diisobutyl-1, 3-diethoxypropane, 2, 2-diisobutyl-1, 3-dibutoxypropane, 2-isobutyl-2-isopropyl-1, 3-dimethoxypropane, 2, 2-di-sec-butyl-1, 3-dimethoxypropane, 2, 2-di-tert-butyl-1, 3-dimethoxypropane, 2, 2-dineopentyl-1, 3-dimethoxypropane, 2-isopropyl-2-isopentyl-1, 3-dimethoxypropane, 2-phenyl-2-benzyl-1, 3-dimethoxy __ -ylpropane, 2-cyclohexyl-2-cyclohexylmethyl-1, 3-dimethoxypropane. 1, 1-bis (methoxymethyl) -cyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetramethylcyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetraphenylcyclopentadiene; 1, 1-bis (methoxymethyl) -2,3,4, 5-tetrafluorocyclopentadiene; 1, 1-bis (methoxymethyl) -3, 4-dicyclopentylcyclopentadiene; 1, 1-bis (methoxymethyl) indene; 1, 1-bis (methoxymethyl) -2, 3-dimethylindene; 1, 1-bis (methoxymethyl) -4,5,6, 7-tetrahydroindene; 1, 1-bis (methoxymethyl) -2,3,6, 7-tetrafluoroindene; 1, 1-bis (methoxymethyl) -4, 7-dimethylindene; 1, 1-bis (methoxymethyl) -3, 6-dimethylindene; 1, 1-bis (methoxymethyl) -4-phenylindene; 1, 1-bis (methoxymethyl) -4-phenyl-2-methylindene; 1, 1-bis (methoxymethyl) -4-cyclohexylindene; 1, 1-bis (methoxymethyl) -7- (3,3, 3-trifluoropropyl) indene; 1, 1-bis (methoxymethyl) -7-trimethylsilylindole; 1, 1-bis (methoxymethyl) -7-trifluoromethylindene; 1, 1-bis (methoxymethyl) -4, 7-dimethyl-4, 5,6, 7-tetrahydroindene; 1, 1-bis (methoxymethyl) -7-methylindene; 1, 1-bis (methoxymethyl) -7-cyclopentylindole; 1, 1-bis (methoxymethyl) -7-isopropylindene; 1, 1-bis (methoxymethyl) -7-cyclohexylindene; 1, 1-bis (methoxymethyl) -7-tert-butylindene;
1, 1-bis (methoxymethyl) -7-tert-butyl-2-methylindene; 1, 1-bis (methoxymethyl) -7-phenylindene; 1, 1-bis (methoxymethyl) -2-phenylindene; 1, 1-bis (methoxymethyl) -1H-benzo [ e ] indene; 1, 1-bis (methoxymethyl) -1H-2-methylbenzo [ e ] indene; 9, 9-bis (methoxymethyl) fluorene; 9, 9-bis (methoxymethyl) -2,3,6, 7-tetramethylfluorene; 9, 9-bis (methoxymethyl) -2,3,4,5,6, 7-hexafluorofluorene; 9, 9-bis (methoxymethyl) -2, 3-benzofluorene; 9, 9-bis (methoxymethyl) -2,3,6, 7-dibenzofluorene; 9, 9-bis (methoxymethyl) -2, 7-diisopropylfluorene; 9, 9-bis (methoxymethyl) -1, 8-dichlorofluorene; 9, 9-bis (methoxymethyl) -2, 7-dicyclopentylfluorene; 9, 9-bis (methoxymethyl) -1, 8-difluorofluorene; 9, 9-bis (methoxymethyl) -1,2,3, 4-tetrahydrofluorene; 9, 9-bis (methoxymethyl) -1,2,3,4,5,6,7, 8-octahydrofluorene; 9, 9-bis (methoxymethyl) -4-tert-butylfluorene.
In the present invention, the polycarboxylic acid ester compound may be selected from succinic acid ester compounds represented by the general formula (III):
in the general formula (III), the radical R1And R2Which may be identical to or different from each other, is C1～C20A linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl group, optionally comprising heteroatoms; r3～R6Wherein at least two radicals are different from hydrogen and are selected from C1～C20Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl radicals, optionally containing hetero atoms, and, in addition, the radicals R3-R6May be joined together to form a ring. Preferably, R1And R2Is C1～C8Alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups. Particularly preferred are compounds wherein R is1And R2Selected from primary alkyl groups, in particular branched primary alkyl groups. Suitable R1And R2Examples of (B) are methyl, ethyl, n-propyl, n-butyl, isobutyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl and neopentyl.
Preferably, formula (III) is a compound of the type: wherein R is3～R5Is hydrogen and R6Are branched alkyl, cycloalkyl, aryl, aralkyl and alkaryl groups having 3 to 10 carbon atoms. Particularly preferred are compounds of the general formula (III) wherein R6Is a branched primary alkyl group or cycloalkyl group having 3 to 10 carbon atoms. In particular, mono-substituted succinate compounds may include, but are not limited to: diethyl sec-butylsuccinate, diethyl hexylsuccinate and cyclopropylDiethyl sulfosuccinate, diethyl norbornyl succinate, diethyl perhydrosuccinate, diethyl trimethyl succinate, diethyl methoxysuccinate, diethyl p-methoxyphenylsuccinate, diethyl p-chlorophenylsuccinate, diethyl phenylsuccinate, diethyl cyclohexylsuccinate, diethyl benzylsuccinate, diethyl cyclohexylmethylsuccinate, diethyl tert-butylsuccinate, diethyl isobutylsuccinate, diethyl isopropylsuccinate, diethyl neopentylsuccinate, diethyl isopentylsuccinate, diethyl (1-trifluoromethylethyl) succinate, diethyl fluorenylsuccinate, 1-ethoxycarbonyldiisobutyl phenylsuccinate (1- (ethoxycarbonyldiisobutyl), diisobutyl sec-butylsuccinate, diisobutyl hexylsuccinate, diisobutyl cyclopropylsuccinate, diisobutyl norbornyl succinate, Diisobutyl perhydrosuccinate, diisobutyl trimethylsilylsuccinate, diisobutyl methoxysuccinate, diisobutyl p-methoxyphenylsuccinate, diisobutyl p-chlorophenoxysuccinate, diisobutyl cyclohexylsuccinate, diisobutyl benzylsuccinate, diisobutyl cyclohexylmethylsuccinate, diisobutyl t-butylsuccinate, diisobutyl isobutylsuccinate, diisobutyl isopropylsuccinate, diisobutyl neopentylsuccinate, diisobutyl isopentylsuccinate, diisobutyl (1-trifluoromethylethyl) succinate, diisobutyl fluorenylsuccinate, dipentyl sec-butylsuccinate, dipentyl hexylsuccinate, dipentyl cyclopropylsuccinate, dineopentyl norbornylsuccinate, dineopentyl perhydrosuccinate, dineopentyl trimethylsilylsuccinate, dineopentyl methoxysuccinate, Dipentyl p-methoxyphenyl succinate, dipentyl p-chlorophenyl succinate, dipentyl phenylsuccinate, dipentyl cyclohexylsuccinate, dipentyl benzylsuccinate, dipentyl cyclohexylmethylsuccinate, dipentyl t-butylsuccinate, dipentyl isobutylsuccinate, dipentyl isopropylsuccinate, dipentyl neopentylsuccinate, dipentylsuccinate isopentylsuccinate, (1-trifluoromethylethyl) dipentyl succinate, and dipentyl fluorenylsuccinate.
As another preferred embodiment, the compound represented by the general formula (III) may be a compound of the following class: wherein R is3～R6Wherein at least two radicals are different from hydrogen and are selected from C1～C20Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl or alkaryl groups, optionally containing heteroatoms. Particular preference is given to those in which two radicals other than hydrogen are bonded to the same carbon atom. Specifically, the disubstituted succinate compounds shown in the general formula (III) can include, but are not limited to: diethyl 2, 2-dimethylsuccinate, diethyl 2-ethyl-2-methylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylmethyl-2-isobutylsuccinate diethyl __, 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, diethyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diethyl 2-isopentyl-2-isobutylsuccinate, diethyl 2-isopropylsuccinate, diethyl 2-ethylsuccinate, diethyl 2-ethyl-2-isobutylsuccinate, diethyl 2-benzyl-2-isopropylsuccinate, diethyl 2-cyclohexylsuccinate, diethyl 2-isobutylsuccinate, diethyl 2-isopropylsuccinate, Diethyl 2-phenyl-2-n-butylsuccinate, diisobutyl 2, 2-dimethylsuccinate, diisobutyl 2-ethyl-2-methylsuccinate, diisobutyl 2-benzyl-2-isopropylsuccinate, diisobutyl 2-cyclohexylmethyl-2-isobutylsuccinate, diisobutyl 2-cyclopentyl-2-n-butylsuccinate, diisobutyl 2, 2-diisobutylsuccinate, diisobutyl 2-cyclohexyl-2-ethylsuccinate, diisobutyl 2-isopropyl-2-methylsuccinate, diisobutyl 2-tetradecyl-2-ethylsuccinate, diisobutyl 2-isobutyl-2-ethylsuccinate, diisobutyl 2- (1-trifluoromethylethyl) -2-methylsuccinate, diisobutyl 2-isobutyl-2-methylsuccinate, Diisobutyl 2-isopentyl-2-isobutylsuccinate, diisobutyl 2-phenyl-2-n-butylsuccinate, dipentyl 2, 2-dimethylsuccinate, dipentyl 2-ethyl-2-methylsuccinate, dipentyl 2-benzyl-2-isopropylsuccinate, dipentyl 2-cyclohexylmethyl-2-isobutylsuccinate, dipentyl 2-cyclopentyl-2-n-butylsuccinate, dipentyl 2, 2-diisobutylsuccinate, dipentyl 2-cyclohexyl-2-ethylsuccinate, dipentyl 2-isopropyl-2-methylsuccinate, dipentyl 2-tetradecyl-2-ethylsuccinate2-isobutyl-2-ethylsuccinate, 2- (1-trifluoromethylethyl) -2-methylsuccinate, 2-isopentyl-2-isobutylsuccinate, and 2-phenyl-2-n-butylsuccinate.
Further, according to another embodiment of the present invention, in the compound represented by the general formula (III), wherein at least two groups other than hydrogen are bonded to different carbon atoms, i.e., R3And R5Or R4And R6. Specifically, such compounds may include, but are not limited to: diethyl 2, 3-bis (trimethylsilyl) succinate, diethyl 2-sec-butyl-3-methylsuccinate, diethyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diethyl 2, 3-bis (2-ethylbutyl) succinate, diethyl 2, 3-diethyl-2-isopropylsuccinate, diethyl 2, 3-diisopropyl-2-methylsuccinate, diethyl 2, 3-dicyclohexyl-2-methylsuccinate, diethyl 2, 3-dibenzylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-bis (cyclohexylmethyl) succinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2, 3-diisobutylsuccinate, diethyl 2, 3-diisopropylsuccinate, diethyl 2, 3-di-tert-butylsuccinate, diethyl 2-diisopropylsuccinate, diethyl 2-sec-butylsuccinate, diethyl-2-3-diisopropylsuccinate, diethyl-2-, Diethyl 2, 3-dineopentylsuccinate, diethyl 2, 3-diisopentylsuccinate, diethyl 2, 3-bis (1-trifluoromethylethyl) succinate, diethyl 2, 3-ditetradecylsuccinate, diethyl 2, 3-difluorenylsuccinate, 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-cyclohexylsuccinate, diethyl 2-cyclohexyl-3-cyclopentylsuccinate, diethyl 2,2, 3, 3-tetramethylsuccinate, diethyl 2, 3-dimethylsuccinate, diethyl, Diethyl 2,2, 3, 3-tetraethylsuccinate, diethyl 2,2, 3, 3-tetrapropylsuccinate, diethyl 2, 3-diethyl-2, 3-diisopropylsuccinate, diethyl 2,2, 3, 3-tetrafluorosuccinate, diisobutyl 2, 3-bis (trimethylsilyl) succinate, diisobutyl 2-sec-butyl-3-methylsuccinate, diisobutyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, diisobutyl 2, 3-bis (2-ethylbutyl) succinate, diisobutyl 2, 3-diethyl-2-isopropylsuccinate, diisobutyl 2, 3-diisopropyl-2-methylsuccinateIsobutyl ester, 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-bis (1-trifluoromethylethyl) succinate, diisobutyl 2, 3-bis (tetradecyl) succinate, diisobutyl 2, 3-difluorenylsuccinate, 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, diisobutyl 2,2, 3, 3-tetramethylsuccinate, diisobutyl 2,2, 3, 3-tetraethylsuccinate, diisobutyl 2,2, 3, 3-tetrapropylsuccinate, diisobutyl 2, 3-diethyl-2, 3-dipropylsuccinate, diisobutyl 2,2, 3, 3-tetrafluorosuccinate, dipentyl 2, 3-bis (trimethylsilyl) succinate, dipentyl 2-sec-butyl-3-methylsuccinate, dipentyl 2, 3-butylsuccinate, and mixtures thereof, Dipentyl 2- (3,3, 3-trifluoropropyl) -3-methylsuccinate, dipentyl 2, 3-bis (2-ethylbutyl) succinate, dipentyl 2, 3-diethyl-2-isopropylsuccinate, dipentyl 2, 3-diisopropyl-2-methylsuccinate, dipentyl 2, 3-dicyclohexyl-2-methylsuccinate, dipentyl 2, 3-dibenzylsuccinate, dipentyl 2, 3-diisopropylsuccinate, dipentyl 2, 3-bis (cyclohexylmethyl) succinate, dipentyl 2, 3-di-tert-butylsuccinate, dipentyl 2, 3-diisobutylsuccinate, dipentyl 2, 3-dineopentylsuccinate, dipentyl 2, 3-diisopentylsuccinate, Dipentyl 2,3- (1-trifluoromethylethyl) succinate, dipentyl 2, 3-ditetradecyl succinate, dipentyl 2, 3-difluorenylsuccinate, dipentyl 2-isopropyl-3-isobutylsuccinate, dipentyl 2-tert-butyl-3-isopropylsuccinate, dipentyl 2-isopropyl-3-cyclohexylsuccinate, dipentyl 2-isopentyl-3-cyclohexylsuccinate, dipentyl 2-tetradecyl-3-cyclohexylmethylDipentyl sulfosuccinate, 2-cyclohexyl-3-cyclopentylsuccinate, 2,3, 3-tetramethylsuccinate, 2,3, 3-tetraethylsuccinate, 2,3, 3-tetrapropylsuccinate, 2, 3-diethyl-2, 3-diisopropylsuccinate, and 2,2, 3, 3-tetrafluorosuccinate.
As discussed above, the groups R attached to the same carbon atom3-R6Also preferred are compounds of formula (III) in which two or four are linked together to form a ring. Such suitable compounds may include, but are not limited to: 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 6-dimethylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetyl) -2, 5-dimethylcyclopentane, 1- (ethoxycarbonyl) -1- (ethoxyacetylmethyl) -2-methylcyclohexane, 1- (ethoxycarbonyl) -1- (ethoxyacetylcyclohexyl) cyclohexane.
Each of the compounds discussed above may be used in the form of a pure isomer or in the form of a mixture of enantiomers, or in the form of a mixture of positional isomers and enantiomers. When a pure isomer is to be used, it is generally isolated and purified by separation techniques well known in the art. In particular, some of the succinate compounds of the present invention may be used as pure racemic or meso form, or alternatively as a mixture of the two forms.
In particular, the electron donor compound may also be selected from glycol ester compounds of general formula (IV):
in the general formula (IV), R1～R6、R1～R2May be the same or different hydrogen, halogen or substituted or unsubstituted straight or branched C1～C20Alkyl radical, C3～C20Cycloalkyl radical, C6～C20Aryl radical, C7～C20Alkylaryl group, C7～C20Aralkyl radical, C2～C10Alkylene or C10～C20A fused ring aryl group; but R is1And R2Not being hydrogen, R3～R6And R1～R2Optionally looped or not looped.
The diol ester compounds represented by the general formula (IV) include, but are not limited to: 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-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-methyl-1, 3-propanediol, 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-dimethyl-1, 3-pentanediol dibenzoate, 2-ethyl-1, 3-pentanediol dibenzoate, 2-butyl-1, 3-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 3-propanediol dibenzoate, 3-, 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, 2-butyl-1, 3-pentanediol dibenzoate, 2, 4-trimethyl-1, 3-pentanediol dibenzoate, 3-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-propyl-1, 3-pentanediol dibenzoate, 2-methyl-3-butyl-2, 4-pentanediol dibenzoate, 2-methyl-1, 3-pentanediol dibenzoate, 2-methyl-2, 3-, 2, 2-dimethyl-1, 5-pentanediol dibenzoate, 3, 5-heptanediol dibenzoate, 4-ethyl-3, 5-heptanediol dibenzoate, and the like. Pentanediol esters and heptanediol esters are preferred.
The solid catalyst component of the present invention can be prepared by the following method:
reacting alcohol (A) and magnesium metal powder (B) in the presence of halogen or a halogen-containing compound (C) under the protection of nitrogen to obtain a dialkoxy magnesium compound, wherein the molar ratio of (A) to (B) is 2-10, and the molar ratio of (C) to (B) is 0.002-0.01; and (B) and (A) or an inert organic solvent (D) or a mixed solution of (A) and (D) are added for multiple times when the viscosity of the reaction solution rises sharply, the molar ratio of the total amount of the added (A) to the added (B) is 2-10, the adding times are 4-10 times, the adding amounts of the added materials can be the same or different, and the time interval of each adding is within the time range of 10-120 minutes. The dialkoxy magnesium compound is contacted with a titanium compound and reacts with an electron donor compound for 1-3 hours, then the solid product obtained after the reaction is treated for 1-4 times by using the titanium compound or a mixed solution of the titanium compound and an inert organic solvent, and then the solid product is washed for 1-7 times by using the inert organic solvent and dried.
Preferably, the times of supplementing the total amount of (A) and (B) are 5-10 times, the adding amount of each time is increased gradually, the time interval of each time is within the time range of 20-80 minutes, and the total adding time is not more than 800 minutes.
The alcohol (A) is a lower alcohol having 1-6 carbon atoms, and is used singly or in combination of two or more, wherein ethanol is preferred, and a solid catalyst for olefin polymerization having better polymerization activity, polymer particle size distribution and particle morphology can be obtained. The invention has no strict requirement on the purity of alcohol, and the water content is generally controlled below 2000 ppm.
The particle size of the metal magnesium powder (B) is preferably less than 350 microns, preferably within the range of 80-350 microns, the active magnesium content is not less than 98 percent, and the metal magnesium powder can be in a spherical shape or a strip shape or other shapes.
The halogen in the halogen or the halogen-containing compound (C) is chlorine, bromine and iodine, preferably iodine; the halogen atom of the halogen-containing compound is chlorine, bromine and iodine; among the halogen-containing compounds, halogen-containing metal compounds are preferred, such as MgCl2、MgBr2、MgI2、Mg(OEt)Cl、Mg(OEt)I、CaCl2NaCl, KBr; particular preference is given to MgCl2. The form, particle size, and the like of these compounds are not particularly limited, and may be any. These halogens or halogen-containing compoundsThese compounds may be used alone or in combination of two or more.
The inert organic solvent (D) is aromatic hydrocarbon or alkane which is liquid at room temperature, and the aromatic hydrocarbon is as follows: benzene, toluene, xylene, ethylbenzene, propylbenzene or trimethylbenzene, preferably toluene or xylene; the alkane is hexane, heptane or cyclohexane; the aromatic hydrocarbon and the alkane may be used alone or in combination.
The preparation method of the invention has the following technical conditions:
(A) the order of contacting (A), (B) and (C) may be arbitrary, wherein (A) is contacted with (C) first, and then with (B); (A) the components (B), (B) and (C) may be added singly or simultaneously at a time, or may be added in portions or continuously, wherein the portions or continuous addition is preferable; (A) the contact temperature of (A), (B) and (C) is from 30 ℃ to 90 ℃, preferably from 40 ℃ to 80 ℃.
When the viscosity of the reaction solution rises sharply, adding (B) and (A) or an inert organic solvent (D) or a mixed solution of (A) and (D) for multiple times, wherein the molar ratio of the added amount to (B) is 2-10; when a mixed solution of (A) and (D) is used, the ratio of (A) to (D) is arbitrary; the temperature of the mixture of (A) or (D) or (A) and (D) is 30 to 90 ℃, preferably 40 to 80 ℃. The frequency of supplementing (A) and (B) is 4-10 times, preferably 5-10 times, the adding amount of each time is equal or increased, preferably increased each time, the time interval of each time is in the time range of 20-80 minutes, and the total adding time is not more than 800 minutes.
After the reaction is completed, the obtained solid can be washed by (D), or the solid can be not washed to obtain suspension containing the solid, or the dialkoxy magnesium compound can be obtained after the solvent is removed by pressure filtration; .
The dialkoxy magnesium compound is contacted with a titanium compound at a temperature of between 25 ℃ below zero and 20 ℃, and is reacted with an electron donor compound for 1 to 3 hours at a temperature higher than 20 ℃, then the solid product obtained after the reaction is treated for 1 to 4 times at a temperature of between 60 and 130 ℃ by using the titanium compound or a mixed solution of the titanium compound and an inert organic solvent, and then the solid product is washed for 1 to 7 times by using the inert organic solvent and dried. The solid catalyst component obtained by the invention can be used for preparing an olefin polymerization catalyst, and the olefin polymerization catalyst comprises the following components or the reaction product of the following components:
a) the solid catalyst component of the present invention;
b) at least one compound of the general formula AlRnX(3-n)The organic aluminum compound of (1) is an organic aluminum compound, wherein R is hydrogen or a hydrocarbon group having 1-20 carbon atoms; x is halogen, n is an integer of more than or equal to 0 and less than or equal to 3; and, optionally,
c) an external electron donor compound.
The organic aluminum compound is at least one selected from trialkyl aluminum compound, trialkyl aluminum and alkyl aluminum halide, alkyl aluminum hydride and alkyl aluminum sesquichloride.
Preferably, the organoaluminum compound may be selected from trialkyl compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, trioctylaluminum, and the like. The organoaluminum compounds may also be used trialkylaluminums with alkylaluminum halides, alkylaluminum hydrides or compounds such as AlEt2Cl and Al2Et3Cl3Such as alkylaluminum sesquichlorides, alkyl chloroalkoxanes may also be used.
For applications where good isotacticity is required, the catalyst may also include an external electron donor compound. The external electron donor compound can be selected from compounds with a general formula of RnSi(OR1)4-nSiloxane compound of the formula (I), wherein R and R1Is C1～C18Optionally a heteroatom; n is an integer of 0-3.
Specifically, the siloxane compounds include, but are not limited to: trimethylmethoxysilane, trimethylethoxysilane, tri-n-propylmethoxysilane, tri-n-propylethoxysilane, tri-n-butylmethoxysilane, triisobutylethoxysilane, tricyclohexylmethylsilane, tricyclohexylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di-n-propyldimethoxysilane, diisopropyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldiethoxysilane, di-n-butyldiethoxysilane, diisobutyldiethoxysilane, di-t-butyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldiethoxysilane, di-n-butyldiethoxysilane, n-butylmethyldimethoxysilane, di (2-ethylhexyl) dimethoxysilane, di (n-butyldimethoxysilane), di (n, Bis (2-ethylhexyl) diethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylisopropyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylethyldiethoxysilane, cyclopentylisopropyldiethoxysilane, cyclopentylisobutyldimethoxysilane, cyclohexyl-n-propyldimethoxysilane, cyclohexyl-n-propyldiethoxysilane, cyclohexyl-n-butyldiethoxysilane, pentylmethyldimethoxysilane, pentylmethyldiethoxysilane, pentylethyldimethoxysilane, pentylethyldiethoxysilane, cyclohexyldimethylmethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyldiethylmethoxysilane, cyclohexyldiethylethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyldimethoxysilane, cyclohexyldiethoxysilane, 2-ethylhexyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, tert-butyltrimethoxysilane, n-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclopentyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclopentyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-ethylhexyltrimethoxysilane, vinyltrimethoxysilane, 2-ethylhexyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, 3, 5-dimethylcyclohexylcyclopentyldimethoxysilane, 3-methylcyclohexylcyclohexyldimethoxysilane, bis (3-methylcyclohexyl) dimethoxysilane, 4-methylcyclohexylcyclohexyldimethoxysilane, bis (4-methylcyclohexyl) dimethoxysilane, 3, 5-dimethylcyclohexylcyclohexyldimethoxysilane, bis (3, 5-dimethylcyclohexyl) dimethoxysilane, pentakis (, Tetrapropoxysilane and tetrabutoxysilane. Among these organosilicon compounds, the following are preferred: di-n-propyldimethoxysilane, di-isopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, di-t-butyldimethoxysilane, di-n-butyldiethoxysilane, t-butyltrimethoxysilane, dicyclohexyldimethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, cyclopentylmethyl-dimethoxysilane, cyclopentylmethyl-diethoxysilane, cyclopentylethyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane and 3, 5-dimethylcyclopentyldimethoxysilane, and the like. These compounds may be used alone or in admixture thereof.
The solid catalyst component and the solid catalyst of the present invention are applied to olefin CH2The preparation of ═ CHR polymers comprises homopolymerization, prepolymerization and copolymerization, wherein R is hydrogen or a hydrocarbyl group containing 1-12 carbon atoms, and olefin CH2CHR is a linear olefin, branched olefin, or diolefin; wherein: the linear olefin is preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-nonene, 1-decene or 1-octene; the branched olefin is preferably 3-methyl-1-butene or 4-methyl-1-pentene; the diene is preferably butadiene, vinylcyclopentene or vinylcyclohexene.
The use is preferably gas phase polymerization. The gas phase polymerization may occur in a gas phase fluidized bed, a vertical gas phase stirred tank, a horizontal gas phase stirred tank, of which a horizontal gas phase stirred tank is preferred.
The shape and size of the solid particles of the catalyst component determine many important characteristics of the particulate material, not only affecting the viscosity, heat transfer, mass transfer, flowability, agglomeration, catalysis, etc. of the catalyst particles, but also the unit processes of mixing, flowing, transporting, etc. of the catalyst and polymer fines in the polymerization apparatus are directly related to the shape of the catalyst particles. The properties of the catalyst components such as particle size, particle shape and the like not only directly influence the application process of the catalyst in a polymerization reaction device, but also directly influence the operation of powder materials such as polypropylene and the like in the device because the morphology of the products such as polypropylene and the like is the copy of the morphology of the catalyst. Controlling the particle shape of the solid particles of the catalyst component is therefore important for the use of the catalyst in production plants and for the control of product properties.
The invention adds magnesium and alcohol for a plurality of times in batches within a certain time interval and time range in the process of preparing the dialkoxy magnesium compound carrier, in particular adds the magnesium and the alcohol in an increasing mode, so that the reaction is stably carried out, the regular and uniform carrier is favorable to be formed, the particle shape of the carrier can be improved, the average sphericity of the prepared solid catalyst component is more than or equal to 0.7, the particle number of the single particle with the sphericity c 'value of more than or equal to 0.7 is not less than 60 percent of the total number of the particles, and the particle number of the single particle with the value c' of more than or equal to 0.8 is not less than 30 percent of the total number of the particles, the solid particle shape of the catalyst is regular, the stacking density is high, the invention is particularly suitable for being applied to a gas phase horizontal stirring reactor, and can effectively solve the problems of temperature fluctuation in the reactor caused by uneven dispersion of main catalyst particles, no stickiness, less fine powder and block material, good stability of polymerization production and high productivity of the reaction kettle in unit volume.
Detailed Description
The present invention will be further described with reference to the following examples, which are provided for the purpose of illustration and are not intended to limit the scope of the present invention.
Determination of the isotacticity of the Polymer
Measured by heptane extraction (6 hours boiling extraction with heptane). Two grams of dried polymer samples were extracted in an extractor with boiling heptane for 6 hours, and the ratio of the weight of the polymer (g) to 2, which was obtained by drying the residue to constant weight, was the isotacticity.
Determination of the content of fines
Fines were defined below an 80 mesh screen (corresponding to a particle size of less than 180um) for polypropylene as measured by astm e 1187.
Bulk density of the Polymer
GB/T 1636-2008
Determination of the sphericity of the catalyst
The polypropylene catalyst component was polymerized as follows: after a 5L stainless steel reactor was sufficiently purged with nitrogen, 5mL of a triethylaluminum hexane solution having a concentration of 0.5mol/L and 1mL of a methylcyclohexyldimethoxysilane (CMMS) hexane solution having a concentration of 0.1mol/L and 10mg of the prepared catalyst were added, 10mL of hexane was added to flush the feed line, 2L (in a standard state) of hydrogen and 2.5L of purified propylene were added, and the reaction was prepolymerized at 20 ℃ for 5 minutes, and the temperature was uniformly raised to 70 ℃ for 15 minutes, and polymerized at this temperature for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging a reaction product, and drying to obtain the polymer. The polymer obtained was screened to remove particles smaller than 300 μm and then used for particle shape analysis to determine sphericity, and the determined sphericity value was regarded as the sphericity of the polypropylene catalyst component.
Gas phase polymerization
The catalysts prepared in the following examples and comparative examples were used for propylene polymerization using a horizontal gas phase polymerization reactor having basic dimensions: 400mm inside diameter, 1100mm long and 138L volume. Controlling the concentration of each component in the reactor as follows: 1 vol% of hydrogen, 95 vol% of propylene and 4 vol% of nitrogen. Controlling the reaction temperature to be 66-68 ℃, the pressure of the reactor to be 2.5MPa, and the retention time to be 50 minutes. The external electron donor adopts methyl cyclohexyl dimethoxy silane, and the flow rate is 0.6 g/h; the catalyst feed was 2g/h (30% white oil slurry) and the triethylaluminium feed was 3.6 g/h. The results are shown in tables 1 and 2.
Example 1
In a four-neck flask equipped with a stirrer, a reflux condenser was installed and an accumulative gas meter was connected to the reflux condenser, and 70.8mL of absolute ethanol and 1.26g of iodine were added to the vessel after the entire reaction apparatus was sufficiently replaced with nitrogen gas to dissolve it. 6g of magnesium powder is added into the mixture, the mixture is heated to the reflux temperature of the ethanol under the stirring condition, and 40mL of absolute ethanol and 5g of magnesium powder are added into the mixture every 15 minutes from the beginning of the reflux for 5 times. And (3) after the fifth addition is finished, the liquid viscosity begins to sharply rise within about 1-2 hours, at this time, 259mL of ethanol is added into the reaction system, the reaction is continued until no hydrogen is generated any more after the reaction is finished, the whole reaction time is about 6 hours, and the diethoxy magnesium carrier is obtained after filter pressing and drying.
Adding 960mL of toluene into the diethoxymagnesium carrier, starting stirring, cooling to 0 ℃, then adding 240mL of titanium tetrachloride, heating to enable the reaction liquid to be heated to 80 ℃, adding 43.2mL of di-n-butyl phthalate, continuing heating to 100 ℃, reacting for 2 hours, then performing pressure filtration on the liquid, washing for 2 times at 80 ℃ by 1200mL of toluene, treating the obtained solid for 60 minutes at 110 ℃ by 1200mL of toluene solution of titanium tetrachloride with the volume ratio of 20%, then washing for 5 times by 1200mL of hexane at 40 ℃, and drying the obtained solid to obtain the solid catalyst component.
Example 2
The preparation steps of the catalyst components are the same as example 1, except that 30mL of absolute ethyl alcohol and 4g of magnesium powder are added in turn every 30 minutes from the beginning of reflux; 35mL of absolute ethyl alcohol and 4.5g of magnesium powder; 40mL of absolute ethyl alcohol and 5g of magnesium powder; 45mL of absolute ethyl alcohol and 5.5g of magnesium powder; 50mL of absolute ethyl alcohol and 6g of magnesium powder. And the di-n-butyl phthalate was replaced by equimolar amounts of 9, 9-bismethoxymethylfluorene.
Example 3
The preparation steps of the catalyst components are the same as example 1, except that 30mL of absolute ethyl alcohol and 4g of magnesium powder are added in turn every 20 minutes from the beginning of reflux; 35mL of absolute ethyl alcohol and 4.5g of magnesium powder; 40mL of absolute ethyl alcohol and 5g of magnesium powder; 45mL of absolute ethyl alcohol and 5.5g of magnesium powder; 50mL of absolute ethyl alcohol and 6g of magnesium powder; 55mL of absolute ethyl alcohol and 6.5g of magnesium powder; 60mL of absolute ethyl alcohol and 7g of magnesium powder.
Comparative example 1
A1-liter reactor equipped with mechanical stirring was purged with nitrogen and charged with a mixture of 150g of magnesium ethoxide, 275mL of 2-ethyl-1-hexanol and 300mL of toluene. The mixture was stirred at 450rpm and carbon dioxide pressure at 30psig and heated at 93 ℃ for three hours. The resulting solution was transferred to a 2L bottle and diluted with 400mL of toluene and 400mL of n-decane to give a total solution volume of 1520 mL. The solution contained 0.10g equivalents of magnesium ethoxide per ml.
100mL of toluene, 30mL of chlorobenzene, 9mL of tetraethoxysilane, 8.5mL of titanium tetrachloride and 100mL of decane were charged in a 1L reactor under nitrogen protection. The mixture was stirred at 26-30 ℃ at 600rpm for five minutes, and then 50mL of the above prepared solution was added to the reactor by syringe, and solid particles were precipitated.
After stirring the mixture containing the precipitate for a further 5 minutes, 22mL of Tetrahydrofuran (THF) are added rapidly by syringe, the stirring speed is then immediately increased to 1500rpm, the temperature is raised to 60 ℃ in 15 minutes, the starting solid is dissolved in the THF solution, after about 10 minutes of addition of THF, stirring is continued at 60 ℃ for 45 minutes, stirring is stopped and the mixture is left to stand. The supernatant was decanted and the solid was washed twice with 250mL portions of toluene.
The solid obtained above was placed in a 1L reactor, 200mL of chlorobenzene and 100mL of titanium tetrachloride were added, the mixture was heated to 135 ℃ over 30 minutes, stirred at 1500rpm for one hour, after the stirring was stopped, the solid was allowed to stand, the supernatant liquid was decanted, 250mL of chlorobenzene, 100mL of titanium tetrachloride and 2.1mL of di-n-butyl phthalate were added to the obtained solid, the mixture was stirred at 135 ℃ at 600rpm for 90 minutes, the supernatant liquid was decanted, and the residue was washed 4 times with 200mL of decane and twice with 200mL of hexane, to obtain a solid catalyst component.
Comparative example 2
A2 liter flask equipped with a polytetrafluoroethylene stirring rod was charged with 39.6g of 95% strength titanium tetraethoxide, 81.2g of magnesium ethoxide, 9.4g of cresol, 52.5g of ethanol and 800g of chlorobenzene. The mixture was rapidly charged with a solution of titanium tetrachloride in chlorobenzene (18g in 200g) under nitrogen at 300rpm, heated to 60-65 ℃ for about 2 hours until the solid was completely dissolved. The temperature was raised to 92 ℃ and the system was purged with nitrogen gently, and the escaped ethanol was collected by a nitrogen bubbler. After stirring for 10 hours, the solution volume decreased by 5% and became cloudy. The suspension was filtered while hot, washed once with chlorobenzene, twice with isooctane and dried under nitrogen flow to give the procatalyst. 8g of the above procatalyst was added to 150mL of a 1: 1 to a solution of chlorobenzene and titanium tetrachloride, heated to 110 ℃, 2g of diisobutylphthalate is added, the mixture is kept at 110 ℃ for 1 hour, and 150mL of a solution prepared by mixing the components in a volume ratio of 1: 1 chlorobenzene and titanium tetrachloride, and 1mmol phthaloyl chloride, at 110 ℃ for 1 hour, removing the supernatant and adding 150mL of a mixture of 1: 1 chlorobenzene and titanium tetrachloride were kept at 110 ℃ for 30 minutes. The solid obtained is washed once with decane at 90 ℃ and twice at room temperature. Drying at 50 ℃ under nitrogen to obtain the solid catalyst component.
TABLE 1
TABLE 2
Activity ofa: units kg polymer/g catalyst
BD: bulk Density, Unit g/ml
T: range of reactor temperature fluctuation
As can be seen from tables 1 and 2, the average sphericity C of the solid component of the catalyst in examples 1 to 3 is greater than 0.7, the percentage of particles having a sphericity C '> 0.7 is greater than 70%, and the percentage of particles having a sphericity C' >0.8 is greater than 60%, compared with comparative examples 1 and 2, the obtained polymer has higher bulk density, less fine powder content, no polymer lumps, and a small temperature fluctuation range in the reactor, and is more suitable for being applied to a horizontal gas phase polymerization reactor.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined generally in dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Claims (16)
1. A method for preparing a solid catalyst component for olefin polymerization, comprising the steps of:
1) reacting alcohol (A) and magnesium metal powder (B) in the presence of halogen or a halogen-containing compound (C) under the protection of nitrogen to obtain a dialkoxy magnesium compound, wherein the molar ratio of (A) to (B) is 2-10, and the molar ratio of (C) to (B) is 0.002-0.01; when the temperature is raised to the reflux temperature of the alcohol (A) under the stirring condition, the mixed solution of the (B) and the (A) is supplemented for multiple times, the molar ratio of the total amount of the supplemented (A) to the supplemented (B) is 2-10, the supplementing times are 5-10 times, the adding amount of each time is increased progressively, the time interval of each time of addition is within the time range of 20-80 minutes, and the total adding time is not more than 800 minutes;
2) the dialkoxy magnesium compound is contacted with a titanium compound and optionally reacted with an electron donor compound for 1-3 hours, then the solid product obtained after the reaction is treated for 1-4 times by using the titanium compound or a mixed solution of the titanium compound and an inert organic solvent, and then the solid product is washed for 1-7 times by using the inert organic solvent and dried.
2. The process for preparing a solid catalyst component according to claim 1, characterized in that the dialkoxymagnesium compound is selected from dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, or butoxyethoxymagnesium.
3. The process for the preparation of a solid catalyst component according to claim 1, characterized in that the titanium compound is selected from the group consisting of compounds of the general formula TiXN(OR)4-NA titanium compound, wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and 0 < N < 4.
4. The process for the preparation of the solid catalyst component according to claim 1, characterized in that the electron donor compound is a Lewis base containing one or more electronegative groups, wherein the electron donor atom is selected from the group consisting of N, O, S, P, As or Sn.
5. The method for preparing the solid catalyst component according to claim 4, wherein the electron donor compound is an aromatic monoester compound; 1, 3-diethers; glycol ester compounds; a ring-substituted compound containing one ether group and one ester group; a diacid ester compound; a glycidyl ester compound; a citrate compound, and these electron donor compounds are used alone or in combination of two or more.
6. The method for preparing a solid catalyst component according to claim 5, wherein the diacid ester compound is an aromatic diester-based compound or a succinate-based compound.
7. The process for preparing a solid catalyst component according to any one of claims 1 to 6, characterized in that the particles of the solid catalyst component have a C value of 0.7 or more, wherein the C value is the average sphericity.
8. Process for the preparation of the solid catalyst component according to claim 7, characterized in that the solid catalyst component, which isc’The number of particles with value of 0.7 is not less than 60% of the total number of particles, whereinc’The value is the individual particle sphericity.
9. The process for preparing a solid catalyst component according to claim 8, wherein the number of particles having a c' value of 0.8 or more is not less than 30% of the total number of particles.
10. An olefin polymerization catalyst characterized by: comprising the following components or the reaction product of the following components:
a) a solid component of the catalyst obtained by the process according to any one of claims 1 to 9;
b) at least one compound of the general formula AlRnX(3-n)The organic aluminum compound of (1) is an organic aluminum compound, wherein R is hydrogen or a hydrocarbon group having 1-20 carbon atoms; x is halogen, n is an integer of more than or equal to 0 and less than or equal to 3; and, optionally,
c) an external electron donor compound.
11. The olefin polymerization catalyst according to claim 10, characterized in that: the organic aluminum compound is at least one selected from trialkyl aluminum compound, trialkyl aluminum and alkyl aluminum halide, alkyl aluminum hydride and alkyl aluminum sesquichloride.
12. The olefin polymerization catalyst according to claim 10, characterized in that: the external electron donor compound is selected from the general formula RnSi(OR1)4-nThe siloxane compound of (a), wherein: r and R1Is C1~C18Optionally containing heteroatoms; n is an integer of 0-3.
13. Use of a catalyst according to any of claims 10 to 12 for the preparation of the alkene CH2= applications in CHR polymersThe method is characterized by comprising homopolymerization, prepolymerization and copolymerization, wherein R is hydrogen or a hydrocarbyl group containing 1-12 carbon atoms, and olefin CH2= CHR linear olefin, branched olefin or diolefin; wherein: the linear olefin is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-nonene, 1-decene or 1-octene; the branched olefin is 3-methyl-1-butene or 4-methyl-1-pentene; the diene is butadiene, vinyl cyclopentene or vinyl cyclohexene.
14. Use according to claim 13, wherein the use is a gas phase polymerisation.
15. Use according to claim 14, wherein the gas phase polymerization takes place in a gas phase fluidized bed, a vertical gas phase stirred tank, a horizontal gas phase stirred tank.
16. Use according to claim 15, wherein the gas phase polymerization takes place in a horizontal gas phase stirred tank.
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