CN109705240B - Granular catalyst component, preparation method and application thereof - Google Patents
Granular catalyst component, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of olefin polymerization catalyst components, and discloses a granular catalyst component, a preparation method and application thereof, wherein the method comprises the following steps: (1) carrying out first contact on a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound in a solvent to form a uniform solution; (2) in the presence of a precipitation assistant, carrying out second contact on the uniform solution and a titanium compound in a dropwise manner to obtain a mixture; (3) carrying out third contact on the mixture obtained in the step (2) and ester to obtain a solid-liquid mixture; (4) optionally, contacting the solid-liquid mixture obtained in the step (3) with an internal electron donor compound to obtain the granular catalyst component; wherein the temperature of the third contact is higher than the temperature of the second contact and increases from the temperature of the second contact to the temperature of the third contact under the condition of standing.
Description
Technical Field
The invention relates to the field of olefin polymerization catalysts, in particular to a preparation method of a granular catalyst component, the granular catalyst component prepared by the method and application of the granular catalyst component in olefin polymerization or copolymerization reaction.
Background
The methods for preparing the solid titanium catalyst component for olefin polymerization disclosed at present are classified into two types, one is a supported catalyst component, namely, a titanium-containing active component is supported on a carrier with a certain shape, the main raw material used by the carrier is generally magnesium chloride or silica gel, and the shape is mostly spherical, such as the methods disclosed in patents of US4399054, EP-B-65700 and the like; the other type is a granular catalyst component, which is prepared by preparing magnesium chloride powder into a uniform solution, and then crystallizing to separate out and load the titanium-containing active component, such as the method disclosed in patents CN85100997A and ZL 89107878.
The two catalyst components have different average particle sizes, the supported catalyst component has an average particle size of 40 microns or more, and the particulate catalyst component has an average particle size of 25 microns or less.
Generally, the particle size of the polyolefin catalyst component is within a certain range. From the viewpoint of preparing the catalyst component, a larger particle size is desired to simplify the preparation process and reduce the cost; from the viewpoint of polymerization process control and polymer product quality, it is desirable that the particle size is suitable and not too large to reduce breakage during polymerization. In general, the particle size of the polyolefin catalyst component based on magnesium chloride is 100 μm or less, and the catalyst component exceeding this particle size range is liable to be crushed and to generate fine powder during the polymerization, which is disadvantageous for the production in an industrial apparatus. The catalyst components having a particle size of 40 to 100 μm are generally prepolymerized before the olefin polymerization is carried out, whereas the catalyst components having a particle size of less than 30 μm are generally directly subjected to the polymerization.
At present, the catalyst components produced by the two methods are used on a large scale on industrial equipment and are suitable for different polymerization process equipment. As for the supported catalyst component, the obtained polymer has better fluidity because the particle size is larger and the shape is similar to a sphere, and the polymer is widely applied to a loop industrial device with a prepolymerization process unit; and for the granular catalyst component, the strength of the granules is higher because of crystallization, the granules are less broken in the polymerization process, and the granular catalyst component is widely applied to gas phase industrial devices without prepolymerization, including gas phase fluidized bed and stirred bed processes.
In view of the above, if a particle-type catalyst component for olefin polymerization having a particle size of more than 30 μm is prepared, the application field of the particle-type catalyst component will be greatly expanded and it is possible to directly apply to a loop industrial apparatus without prepolymerization.
In recent years, there have been many attempts to prepare catalyst components of large particle size particle type for olefin polymerization.
CN1258683A discloses a method for obtaining larger particles by increasing the amount of toluene added as a solvent in a magnesium chloride dissolution system, and mentions that non-spheroidal particles such as rods, needles, date pits and the like are liable to occur when the particle size is larger, and discloses a method for solving these problems, with which particles below 25 μm can be prepared, but when the particle size is made larger by further increasing toluene, the probability of occurrence of non-spheroidal particles is greatly increased, and thus the method cannot be used for preparing particles above 25 μm.
US8344079 also discloses a method of obtaining larger particles by increasing the amount of toluene solvent added to the magnesium chloride dissolution system and prolonging the particle growth time after crystallization out, but the bulk density of the resulting polymer is significantly reduced and the particle shape is not spheroidal when the particle size is larger than 35 microns.
Korean samsung corporation, patent ZL99816964.1 in chinese application, discloses a method of obtaining a catalyst component having a large particle size by dissolving magnesium chloride in alcohol and tetrahydrofuran and precipitating titanium tetrachloride, and spherical particles having a surface morphology of 100 μm or less, which is good in smooth particle shape, but has low activity when used for olefin polymerization, and the obtained polymer has low bulk density and isotacticity, and thus has no industrial application value.
In summary, the use of the prior art for the preparation of catalyst components in the form of particles having a particle size in the range of more than 50 μm is not satisfactory at present, nor is the production of catalyst components in this particle size range satisfactory.
Disclosure of Invention
The object of the present invention is to overcome the above drawbacks of the prior art by providing a process for preparing a catalyst component in the form of spheroidal particles having a median particle diameter in the range of about 50 μm or more, a small distribution coefficient and no reduction in bulk density and isotacticity of the olefin polymer produced by the process.
In order to achieve the above object, the present invention provides a method for preparing a catalyst component in the form of particles, wherein the method comprises:
(1) carrying out first contact on a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound in a solvent to form a uniform solution;
(2) in the presence of a precipitation assistant, reacting the uniform solution with a titanium compound under stirring at a first temperature to obtain a mixture;
(3) mixing the mixture obtained in the step (2) with ester, heating to a second temperature under a standing condition, and reacting at the second temperature to obtain a solid-liquid mixture;
(4) optionally, contacting the solid-liquid mixture obtained in the step (3) with an internal electron donor compound to obtain the granular catalyst component.
In a second aspect, the present invention also provides a catalyst component in the form of particles prepared by the process as described above.
In a third aspect, the present invention also provides the use of a catalyst component in the form of particles prepared by a process as described above in the polymerisation or copolymerisation of olefins.
In the preparation process of the granular catalyst component, the magnesium compound, the organic phosphorus compound, the organic alcohol compound and the organic epoxy compound are firstly contacted in the solvent to form a uniform solution, reacting the obtained homogeneous solution with titanium halide or its derivative in the presence of a precipitation assistant, adding esters before precipitating magnesium/titanium-containing solid, simultaneously, the reaction speed of crystallization is controlled by controlling the reaction speed and controlling the stirring speed and the standing time, so that the crystallization is separated out to form spheroidal particles with larger particle size, an electron donor is loaded or not loaded on the solid precipitate after the solid precipitate is formed, the olefin polymerization catalyst component with the medium particle size of more than 50 microns can be prepared after the solid precipitate is washed by an inert diluent, and the prepared olefin polymerization catalyst component is spherical-like, so that better fluidity can be ensured. In addition, when the particulate catalyst component prepared by the process of the present invention is used in the polymerization or copolymerization of olefins, there is no occurrence of a situation that leads to a decrease in bulk density and isotacticity of the produced polymer.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a process for the preparation of a catalyst component in particulate form, wherein the process comprises:
(1) carrying out first contact on a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound in a solvent to form a uniform solution;
(2) in the presence of a precipitation assistant, reacting the uniform solution with a titanium compound under stirring at a first temperature to obtain a mixture;
(3) mixing the mixture obtained in the step (2) with ester, heating to a second temperature under a standing condition, and reacting at the second temperature to obtain a solid-liquid mixture;
(4) optionally, contacting the solid-liquid mixture obtained in the step (3) with an internal electron donor compound to obtain the granular catalyst component.
The inventors of the present invention have found, in the course of their research, that, in the course of preparing a catalyst component in the form of particles, firstly, contacting a magnesium compound, an organic phosphorus compound, an organic alcohol compound and an organic epoxy compound in a solvent to form a uniform solution, reacting the obtained homogeneous solution with titanium halide or its derivative in the presence of a precipitation assistant, adding esters before precipitating magnesium/titanium-containing solid, meanwhile, the reaction speed of crystallization is controlled by controlling the reaction speed and controlling the stirring speed and the standing time, so that the crystallization is separated out to form spheroidal particles with larger particle size, an electron donor is loaded or not loaded on the solid precipitate after the solid precipitate is formed, the olefin polymerization catalyst component with the medium particle size of more than 50 microns can be prepared after the solid precipitate is washed by an inert diluent, and the prepared olefin polymerization catalyst component is spheroidal. When the olefin polymerization catalyst component particles having such characteristics are used in the polymerization or copolymerization of olefins, the bulk density and isotacticity of the resulting polymer are not lowered, and the present invention has been completed.
According to the present invention, in step (1), the organic alcohol compound is preferably an organic alcohol compound having a carbon number of between C2 and C10 and a derivative thereof. More preferably C3-C6 organic alcohol compounds and derivatives thereof, for example, 3 carbon alcohols, 4 carbon alcohols, 5 carbon alcohols, and 6 carbon alcohols and derivatives thereof; most preferably, the organic alcohol compound is selected from butanol and pentanol. Wherein the term "derivative" refers to an alcohol in which one or more groups of the organic alcohol compound are substituted with other substituents. The substituents may be various substituents known in the art, and methyl, ethyl, propyl, isopropyl and butyl are preferred in the present invention.
According to the invention, the organic epoxide compound may be any of various organic epoxides commonly used in the art, for example, one or more of aliphatic olefins having 2 to 8 carbon atoms, oxidation products of halogenated aliphatic olefins, dienes, oxides of dienes, glycidyl ethers and internal ethers, specifically, for example, one or more of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether, and particularly, epichlorohydrin is preferable.
According to the present invention, the organophosphorus compound can be various organophosphorus compounds commonly used in the art, for example, can be orthophosphoric acid, hydrocarbyl esters of phosphorous acid and/or halogenated hydrocarbyl esters of orthophosphoric acid, phosphorous acid, and specifically can be one or more of trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite, wherein tributyl phosphate and/or tributyl phosphite is preferred.
The solvent may be any solvent commonly used in the art capable of dissolving a mixture of a magnesium compound, an organic alcohol compound, an organic epoxy compound, an organic phosphorus compound, the ester, and an internal electron donor compound, and specifically, may be one or more of toluene, ethylbenzene, benzene, xylene, chlorobenzene, hexane, heptane, octane, and decane, and among them, toluene is preferable.
According to the present invention, it is preferable that at least one of the magnesium compound and the titanium compound is a halogen-containing compound.
Preferably, in the present invention, the magnesium compound is at least one of a magnesium compound represented by formula (I), a hydrate of the magnesium compound represented by formula (I), and an alcohol adduct of the magnesium compound represented by formula (I),
MgR4R5(Ⅰ)
in the formula (I), R4And R5Each is one of halogen, linear or branched alkoxy of C1-C5 and linear or branched alkyl of C1-C5; preferably at least one of a magnesium halide, a magnesium alcoholate and a magnesium haloalcoholate; more preferably at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, an alcohol adduct of magnesium dichloride, an alcohol adduct of magnesium dibromide and an alcohol adduct of magnesium diiodide, particularly preferably one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, and particularly preferably magnesium dichloride.
Preferably, the titanium compound is a compound represented by the formula (II),
TiXm(OR6)4-mformula (II)
In the formula (II), X is halogen, R6Is a C1-C20 hydrocarbyl group, m is an integer of 1-4; at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium and trichloromonoethoxytitanium is preferred, among them, one or more of titanium tetrachloride, titanium tetrabromide and titanium tetraiodide are preferred, and titanium tetrachloride is particularly preferred.
The precipitation aid can be various precipitation aids commonly used in the field, and can be one or more of organic acid, organic acid anhydride, organic ether and organic ketone, preferably one or more of C2-C20 organic acid anhydride, organic acid, organic ether and organic ketone; specifically, for example, one or more of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, ethyl ether, propyl ether, butyl ether, and pentyl ether may be mentioned, and phthalic anhydride is particularly preferable.
According to the present invention, although the object of the present invention can be achieved as long as the preparation is carried out in accordance with the above procedure in the preparation of the catalyst component. However, the inventors of the present invention have found that the above characteristics of the produced olefin polymerization catalyst component can be further improved when the ester is selected from at least one of alkyl esters of aliphatic monocarboxylic acids, alkyl esters of aromatic monocarboxylic acids, alkyl esters of aliphatic polycarboxylic acids, and alkyl esters of aromatic polycarboxylic acids.
Among them, it is further preferred that the ester is at least one selected from the group consisting of alkyl esters of straight or branched C1-C4 saturated aliphatic monocarboxylic acids, alkyl esters of straight or branched C1-C4 saturated aliphatic polycarboxylic acids, alkyl esters of C7-C8 aromatic monocarboxylic acids, and alkyl esters of C7-C8 aromatic polycarboxylic acids. For example, alkyl esters of C1, C2, C3 or C4 straight or branched chain saturated aliphatic monocarboxylic acids, alkyl esters of C1, C2, C3 or C4 straight or branched chain saturated aliphatic polycarboxylic acids, alkyl esters of C7 or C8 aromatic monocarboxylic acids, alkyl esters of C7 or C8 aromatic polycarboxylic acids. Still more preferably, the alkyl ester may be a C1-C6 straight or branched chain alkyl ester, such as methyl, ethyl, propyl, butyl, pentyl, octyl. The various isomers of these esters are also understood to be included within the scope of the present invention.
Specifically, the ester may be selected from at least one of diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 1, 3-diamyl phthalate, methyl formate, ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, and butyl butyrate; preferably, the ester may be selected from at least one of methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, more preferably, the ester is diisobutyl phthalate and/or di-n-butyl phthalate.
According to the present invention, as long as the catalyst component is prepared according to the above steps, the purpose of the present invention can be achieved, and the amount of each substance is not particularly limited, and the amount can be adjusted according to the conventional amount in the art, preferably, the amount of the organic epoxy compound is 0.2 to 10 mol, preferably 0.5 to 4 mol, per mol of the magnesium element; the amount of the organic phosphorus compound to be used is 0.1 to 3 mol, preferably 0.3 to 1 mol; the amount of the organic alcohol compound to be used is 0.005 to 15 mol, preferably 0.06 to 10 mol; the precipitation assistant is used in an amount of 0.03 to 1 mol, preferably 0.05 to 0.4 mol; the amount of the ester to be used is 0.005 to 15 mol, preferably 0.06 to 10 mol; the amount of the titanium compound to be used is 0.5 to 20 mol, preferably 1 to 15 mol; the electron donor compound is preferably used in an amount of 0.005 to 15 mol, more preferably 0.06 to 10 mol.
According to the present invention, since the ester added in step (3) can serve as a certain amount of internal electron donor, when the amount of the added ester is large, no or little internal electron donor may be added, as long as the sum of the amount of the ester and the amount of the internal electron donor is such that the content of the internal electron donor in the finally prepared catalyst component is in the range of 5 to 25 wt%.
According to the present invention, the internal electron donor may be any of various internal electron donors commonly used in the art, for example, esters as described above, and one or more of aliphatic ethers, cycloaliphatic ethers, and aliphatic ketones.
The aliphatic ether, cycloaliphatic ether, aliphatic ketone can be any of the compounds conventionally used in the art, and can be chosen, for example, from C2-C6Fatty ethers, C3-C4Cyclic ether, C3-C6A saturated aliphatic ketone. Specifically, for example, the following may be mentioned: one or more of diethyl ether, propyl ether, butyl ether, pentyl ether, hexyl ether, Tetrahydrofuran (THF), acetone, butanone, 2-pentanone, and methyl isobutyl ketone.
Preferably, the internal electron donor of the present invention is one or more of diisobutyl phthalate, di-n-butyl phthalate, 1, 3-diamyl phthalate, ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyl butyrate, and particularly preferably di-n-butyl phthalate and/or diisobutyl phthalate.
According to the present invention, the conditions of the step (1) contacting, the step (2) first temperature and the step (3) second temperature are not particularly required, and can be performed with reference to the prior art, and preferably, the step (1) contacting conditions include: the contact temperature is 10-100 ℃, preferably 30-80 ℃, and the contact time is 0.5-6 hours, preferably 1-4 hours; the conditions of the first temperature of the step (2) include: the contact temperature is-50 to 10 ℃, preferably-30 to 5 ℃, and the time is 0.1 to 5 hours, preferably 0.2 to 4 hours; the stirring conditions are as follows: the stirring speed is 50-800 r/min; the conditions of the second temperature of the step (3) include: the contact temperature is 10-110 deg.C, and the contact time is 0.5-8 hr. And wherein the second temperature of step (3) is higher than the first temperature of step (2); preferably, the temperature difference between the second temperature and the first temperature is 30-80 ℃; more preferably, the temperature difference between the second temperature and the first temperature is 40-60 ℃.
And (3) under the condition that the internal electron donor is required to be added, adding the internal electron donor after a solid precipitate is formed in the heating process after the alcohol is added in the step (3).
According to the present invention, the temperature raising condition in step (3) may further include: (a) standing for 1-2 hours at constant temperature of-30 to-10 ℃; (b) standing for 1-2 hours at a constant temperature of-5 ℃ to 5 ℃; in the present invention, the reaction rate of crystal precipitation is controlled by controlling the reaction rate and by controlling the stirring rate and the standing time, so that the crystals are precipitated as spheroidal particles having a large particle diameter.
According to the invention, the heating rate can be 10-100 ℃/h, specifically, for example, the heating rate can be 90-100 ℃/h, 25-35 ℃/h or 5-15 ℃/h, in the invention, the reaction speed of crystallization can be controlled by controlling the heating rate in the heating process, so that the crystallization can be precipitated into spheroidal particles with larger particle size, preferably, the heating rate is controlled to be 25-35 ℃/h when the temperature is raised to 0 ℃ at-30 ℃, the heating rate is controlled to be 5-15 ℃/h when the temperature is raised to 30 ℃ at 0 ℃, and the heating rate is controlled to be 90-100 ℃/h when the temperature is raised to 80 ℃ at 30 ℃, so that the effect is better; more preferably, the heating rate is controlled to be 29-31 ℃/h when the temperature is raised to 0 ℃ from minus 30 ℃, the heating rate is controlled to be 9-11 ℃/h when the temperature is raised to 30 ℃, and the heating rate is controlled to be 99-100 ℃/h when the temperature is raised to 80 ℃ from 30 ℃, so that the effect is better.
According to the present invention, the temperature rise from the temperature of the second contact to the temperature of the third contact may be performed under the condition of standing, preferably, the temperature rise process at-30 to 5 ℃ is performed under the condition of standing, and the temperature rise process at the temperature of 5 ℃ to the third contact, for example, the temperature rise process at 5 to 60 ℃ is preferably performed under the condition of stirring; particularly preferably, the mixture is stirred at a constant temperature of 25 ℃ to 35 ℃ for 1 to 2 hours. In the present invention, by controlling the stirring rate and the standing time, the reaction rate of the crystal precipitation can be controlled, and the crystal is precipitated into spheroidal particles having a larger particle diameter.
According to the invention, under the condition that no internal electron donor needs to be loaded, the solid-liquid mixture obtained in the step (3) can be filtered, washed and dried to obtain the olefin polymerization catalyst component. And (3) under the condition that an internal electron donor is required to be loaded, filtering, washing and drying the solid-liquid mixture obtained in the step (3) and a material in contact with the internal electron donor compound to obtain the olefin polymerization catalyst component.
The method and conditions for filtering, washing and drying have no special requirements, and can be carried out by referring to the prior art, and are not described again.
According to a preferred embodiment of the present invention, the process for preparing the catalyst component of the present invention comprises the steps of:
dissolving magnesium compound in solvent solution of organic epoxy compound, organic alcohol compound and organic phosphorus compound under stirring, and contacting at 10-100 deg.C for 0.5-6 hr, preferably at 30-80 deg.C for 1-4 hr under stirring to form uniform solution; in the presence of a precipitation assistant, under the stirring condition, at the temperature of-30 to 60 ℃, preferably at the temperature of-30 to 5 ℃, dripping a titanium compound into the uniform solution or dripping the uniform solution into the titanium compound, before a solid precipitate is formed in a solution system, adding ester, then stopping stirring, and raising the temperature under the standing condition, preferably, standing for 1 to 2 hours at the constant temperature of-30 to-10 ℃, standing for 1 to 2 hours at the constant temperature of-5 ℃ to 5 ℃, more preferably, raising the temperature at-30 to 5 ℃ under the standing condition, raising the temperature at 5 to 60 ℃ under the stirring condition, and stirring for 1 to 2 hours at the constant temperature of 25 ℃ to 35 ℃; then heating to 60-110 ℃, optionally adding an internal electron donor compound after solid precipitate is formed in the heating process, contacting for 0.5-8 hours, preferably 1-6 hours, under the stirring state, filtering out mother liquor, washing with a washing agent (such as toluene), treating for 3-4 times with a mixture of a transition metal titanium halide and the washing agent (such as toluene), filtering out liquid, and washing solid with the washing agent (such as hexane and toluene) to obtain the olefin polymerization catalyst component.
In a second aspect, the present invention also provides a catalyst component in the form of particles prepared by a process as described above.
The olefin polymerization catalyst component provided by the invention has a medium particle size of more than 50 microns and is spherical-like.
In a third aspect, the present invention also provides the use of a catalyst component in the form of particles, prepared as above, in the polymerization or copolymerization of olefins.
According to the present invention, the olefin polymerization process may be any of various processes for polymerizing olefins, which are conventional in the art, and for example, comprises contacting under olefin polymerization conditions in one of the following two ways:
(A) contacting one or more olefins with an olefin polymerization catalyst component and an alkyl aluminum compound, wherein the molar ethylene content of the one or more olefins is greater than 80%;
(B) contacting one or more olefins with an olefin polymerization catalyst component, an aluminum alkyl compound, and an organosilicon compound;
wherein the olefin polymerization catalyst component is the olefin polymerization catalyst component of the invention.
Although there is no limitation on the olefin when contacted in the manner of (B), for the polymerization mainly used for ethylene, if only a part of the olefin is contacted at this time in the manner of (A), the object of the present invention can be achieved, and therefore, it is preferable that the molar content of ethylene in the olefin(s) when contacted in the manner of (B) is 80% or less.
According to the invention, the molar ratio of aluminium in the aluminium alkyl compound to titanium in the olefin polymerization catalyst component is generally between 5 and 5000: 1, preferably 20 to 500: 1. the dosage of the organic silicon compound can be adjusted according to specific requirements, and the invention has no special requirements.
According to the invention, the alkyl aluminium compound is a compound of formula (III),
AlR'n'X'3-n'(Ⅲ)
in the formula (III), R ' is hydrogen, alkyl with 1-20 carbon atoms or aryl with 6-20 carbon atoms, X ' is halogen, and n ' is an integer of 1-3. Among them, at least one of trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichloride is preferable, and triethylaluminum is preferable.
Wherein the organosilicon compound has a general formula of Rn Si(OR1)4-nWherein n is an integer of 0 to 3, R is one or more of alkyl, cycloalkyl, aryl, halogenated alkyl, halogen and hydrogen atom, R is1Is one or more of alkyl, cycloalkyl, aryl and halogenated alkyl;preferably trimethylmethoxysilane, trimethylethoxysilane, trimethylphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyl-tert-butyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, at least one of dicyclohexyldimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, methylcyclohexyldimethoxysilane, dicyclopentyldimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyldimethoxysilane and (1,1, 1-trifluoro-2-propyl) -methyldimethoxysilane, preferably methylcyclohexyldimethoxysilane.
According to the present invention, the olefin may be any of various commonly used olefins, for example, at least one of 1-olefins having 2 to 6 carbon atoms, preferably at least one of ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. The olefin polymerization method is particularly suitable for propylene homopolymerization, propylene and ethylene random copolymerization and heterogeneous impact copolymerization.
According to the invention, the olefin polymerization conditions may be those conventionally used in the art, generally at a temperature of from 0 to 150 ℃ for a time of from 0.5 to 5 hours and at a pressure of from 0.1 to 10 MPa.
Preferably, the olefin polymerization process of the invention is carried out in the presence of a solvent, said contacting being carried out in the presence of a solvent, said olefin polymerization conditions comprising: the olefin polymerization catalyst may be used in a concentration in the solvent which is conventional in the art, for example, in a range of from 0.0001 to 1 mol/liter, in terms of titanium in the olefin polymerization catalyst, at a temperature of from 0 to 150 ℃ for a period of from 0.5 to 5 hours and a pressure of from 0.1 to 10 MPa. Preferably, the contacting is carried out in the presence of hydrogen, which may be added in an amount conventional in the art, generally in the range of from 0.01 to 20 liters (under standard conditions).
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited thereto. In the following example, it is shown that,
the particle size of the prepared olefin polymerization catalyst component was determined using a malvern 2000 laser particle sizer in british; wherein, the distribution coefficient is (D90-D10)/D50;
observing the shape of the prepared olefin polymerization catalyst component using an optical microscope and a scanning electron microscope;
the Melt Index (MI) of the polymer was determined using a melt index determinator (model 6932, CEAST, Italy) according to GB/T3682-2000;
the bulk density of the polymer is determined by reference to ASTM D1895-96;
the method for testing the isotacticity of the polymer comprises the following steps: after a 2 gram sample of the dried polymer was extracted in an extractor with boiling heptane for 6 hours, the residue was dried to constant weight and the isotacticity was calculated by the following formula:
isotacticity (%). mass of polymer after extraction/2 × 100.
Example 1
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Sequentially adding 4.8 g of anhydrous magnesium chloride, 145 ml of toluene, 4.0 ml of epichlorohydrin, 12.5 ml of tributyl phosphate and 1.0 ml of butanol into a reaction kettle repeatedly replaced by high-purity nitrogen, reacting for 2 hours at the temperature of 60 ℃, adding 1.4 g of phthalic anhydride, continuously reacting for one hour, cooling to-28 ℃, dropwise adding 56 ml of titanium tetrachloride, adding 1.1 ml of di-n-butyl phthalate (DNBP), stopping stirring and standing, heating to 0 ℃ for 1 hour, keeping the temperature for 1 hour, stirring, heating to 30 ℃ within 3 hours, heating to 80 ℃ within 0.5 hour after keeping the temperature for 1 hour, adding 1.1 ml of di-n-butyl phthalate (DNBP), keeping the temperature for one hour, filtering out mother liquor, washing twice with toluene, adding 48 ml of titanium tetrachloride, keeping the temperature of a toluene solution for 72 ml, keeping the temperature for 0.5 hour at 110 ℃, filtering, and repeatedly treating twice, then washed 5 times with hexane and the remaining solid product was dried under vacuum to give a granular catalyst component. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Example 2
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that the stirring was stopped and left to stand for 1 hour (at-28 ℃ C.), the temperature was raised to-5 ℃ at a temperature raising rate of 29 ℃ per hour, the temperature was kept constant for 1 hour, the stirring was started, the temperature was raised to 25 ℃ at a temperature raising rate of 9 ℃ per hour, the temperature was kept constant for 1 hour under stirring, and the temperature was raised to 60 ℃ at a temperature raising rate of 99 ℃ per hour. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Example 3
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that the stirring was stopped and left to stand for 1 hour (at-28 ℃ C.), the temperature was raised to-5 ℃ at a temperature rise rate of 31 ℃ per hour, the temperature was kept constant for 1 hour, then the stirring was started, the temperature was raised to 25 ℃ at a temperature rise rate of 11 ℃ per hour, the temperature was kept constant for 1 hour under stirring, and then the temperature was raised to 60 ℃ at a temperature rise rate of 100 ℃ per hour. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Example 4
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that the stirring was stopped and left to stand for 1 hour (at-28 ℃ C.), the temperature was raised to 5 ℃ at a temperature raising rate of 30 ℃ per hour, the temperature was kept constant for 1 hour, then the stirring was started, the temperature was raised to 35 ℃ at a temperature raising rate of 10 ℃ per hour, the temperature was kept constant for 1 hour under stirring, and then the temperature was raised to 60 ℃ at a temperature raising rate of 100 ℃ per hour. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Example 5
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that the stirring was stopped and left to stand for 1 hour (at-28 ℃ C.), the temperature was raised to 0 ℃ at a temperature raising rate of 29 ℃ per hour, the temperature was kept constant for 1 hour, then the stirring was started, the temperature was raised to 30 ℃ at a temperature raising rate of 9 ℃ per hour, the temperature was kept constant for 1 hour under stirring, and then the temperature was raised to 90 ℃ at a temperature raising rate of 100 ℃ per hour. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Example 6
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that the stirring was stopped and left to stand for 1 hour (at-28 ℃ C.), the temperature was raised to 2 ℃ at a temperature raising rate of 30 ℃ per hour, the temperature was kept constant for 1 hour, then the stirring was started, the temperature was raised to 32 ℃ at a temperature raising rate of 10 ℃ per hour, the temperature was kept constant for 1 hour under stirring, and then the temperature was raised to 70 ℃ at a temperature raising rate of 100 ℃ per hour. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Example 7
This example illustrates the particle-type catalyst component provided by the present invention and the preparation method thereof
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that the stirring was stopped and left to stand for 1 hour (at-28 ℃ C.), the temperature was raised to 2 ℃ at a temperature raising rate of 31 ℃ per hour, the temperature was kept constant for 1 hour, then the stirring was started, the temperature was raised to 28 ℃ at a temperature raising rate of 10 ℃ per hour, the temperature was kept constant for 1 hour under stirring, and then the temperature was raised to 80 ℃ at a temperature raising rate of 100 ℃ per hour. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Comparative example 1
Comparative example to illustrate a reference granular catalyst component and method for its preparation
The preparation of the catalyst component in the form of granules was carried out in the same manner as in example 1, except that the stirring was not stopped, i.e., there was no standing period. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Comparative example 2
Comparative example to illustrate a reference granular catalyst component and method for its preparation
The preparation of the granular catalyst component was carried out according to the method of example 1, except that the standing was continued after the constant temperature of 0 ℃ until the mother liquor was filtered without stirring. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Comparative example 3
Comparative example to illustrate a reference granular catalyst component and method for its preparation
The preparation of the granular catalyst component was carried out in the same manner as in example 1, except that no butanol was added. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Comparative example 4
Comparative example to illustrate a reference granular catalyst component and method for its preparation
Preparation of a particulate catalyst component was carried out in the same manner as in example 1 except that 56 ml of titanium tetrachloride was added dropwise without adding 1.1 ml of di-n-butyl phthalate (DNBP). The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Comparative example 5
Comparative example to illustrate a reference granular catalyst component and method for its preparation
Preparation of a granular catalyst component was carried out in the same manner as in example 1 except that butanol was not added, and 1.1 ml of di-n-butyl phthalate (DNBP) was not added after 56 ml of titanium tetrachloride was added dropwise. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
Comparative example 6
Comparative example to illustrate a reference granular catalyst component and method for its preparation
Preparation of a particulate type catalyst component was carried out in the same manner as in example 1 except that butanol was not added, and 1.1 ml of di-n-butyl phthalate (DNBP) was not added after 56 ml of titanium tetrachloride was added dropwise, and stirring was not stopped, that is, no standing stage was carried out. The particle diameter, distribution coefficient and particle shape of the obtained particulate catalyst component are shown in Table 1.
TABLE 1
| D10 (micron) | D50 (micron) | D90 (micron) | Coefficient of distribution | Granule shape | |
| Example 1 | 37 | 51 | 72 | 0.69 | Sphere-like shape |
| Example 2 | 35 | 48 | 68 | 0.71 | Sphere-like shape |
| Example 3 | 34 | 49 | 67 | 0.67 | Sphere-like shape |
| Example 4 | 39 | 53 | 80 | 0.77 | Sphere-like shape |
| Example 5 | 32 | 58 | 78 | 0.79 | Sphere-like shape |
| Example 6 | 37 | 52 | 75 | 0.73 | Sphere-like shape |
| Example 7 | 35 | 50 | 71 | 0.72 | Sphere-like shape |
| Comparative example 1 | 19 | 59 | 112 | 1.58 | Bar shape |
| Comparative example 2 | 4 | 24 | 44 | 1.67 | Bar shape |
| Comparative example 3 | 12 | 62 | 140 | 2.06 | Rod-like |
| Comparative example 4 | 38 | 62 | 99 | 0.98 | Rod-like |
| Comparative example 5 | 26 | 71 | 122 | 1.35 | Rod-like |
| Comparative example 6 | 14 | 72 | 130 | 1.61 | Rod-like |
As can be seen from table 1, the preparation method of the olefin polymerization catalyst component provided herein can prepare the catalyst component having a medium particle size of 50 μm or more and a spheroidal shape, whereas the olefin polymerization catalyst components prepared in comparative examples 1 to 6 cannot simultaneously combine both of these characteristics. And the particle size of the prepared olefin polymerization catalyst component can be further improved by reducing the addition amount of the ester and selecting the organic alcohol compound of C3-C6. In addition, it can be seen from the distribution coefficient that the distribution coefficient of the catalyst component can be effectively controlled within the range of 0.5 to 0.8 with the embodiment of the present invention, and when the preferred embodiment is adopted, the range of the distribution coefficient can be further narrowed to the range of 0.6 to 0.7 (note that in the above range, the smaller the distribution coefficient, the more concentrated the particle size of the catalyst component is).
Test example
After a 5-liter stainless steel autoclave was sufficiently purged with nitrogen, 5 ml of a hexane solution of triethylaluminum having a concentration of 0.5 mol/liter and 1 ml of a hexane solution of methylcyclohexyldimethoxysilane (CMMS) having a concentration of 1 mol/liter were charged, 10 mg of the catalyst components prepared in examples 1 to 7 and comparative examples 1 to 4 were added, respectively, 10 ml of hexane was then added to flush the feed line, 1 liter (in a standard state) of hydrogen and 2 liters of purified propylene were added, and polymerization was carried out at this temperature for 1 hour. After the reaction was completed, the reaction vessel was cooled and stirred to discharge the reaction product, thereby obtaining olefin polymers polymerized using the catalyst components prepared in examples 1 to 7 and comparative examples 1 to 4, respectively, and the melt index, isotacticity and bulk density of the obtained polymers are shown in Table 2, respectively.
TABLE 2
| Melt index (g/10min) | Bulk Density (g/ml) | Degree of isotacticity (%) | |
| Example 1 | 4.8 | 0.45 | 99.1 |
| Example 2 | 4.5 | 0.45 | 99.3 |
| Example 3 | 4.2 | 0.46 | 99.1 |
| Example 4 | 4.5 | 0.44 | 99.2 |
| Example 5 | 3.9 | 0.44 | 99.2 |
| Example 6 | 4.2 | 0.45 | 99.1 |
| Example 7 | 3.5 | 0.45 | 99.1 |
| Comparative example 1 | 4.5 | 0.36 | 98.8 |
| Comparative example 2 | 4.3 | 0.38 | 99.0 |
| Comparative example 3 | 3.8 | 0.35 | 99.1 |
| Comparative example 4 | 4.2 | 0.35 | 98.7 |
| Comparative example 5 | 4.1 | 0.38 | 98.9 |
| Comparative example 6 | 3.6 | 0.38 | 98.6 |
Typically, the polyolefin has a melt index in the range of 2 to 6 and a bulk density in the range of 0.42 to 0.47 under such polymerization conditions. As can be seen from the above Table 2, the olefin polymerization catalyst components prepared by the process of the present invention can ensure that the melt index and bulk density of the olefin are in the optimum ranges as described above, whereas the olefin polymerization catalyst components prepared in comparative examples 1 to 4 cannot. Furthermore, the catalyst component prepared by the invention can further improve the isotacticity of the obtained polymer.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (20)
1. A process for the preparation of a catalyst component in the form of particles, characterized in that it comprises:
(1) contacting a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an organic alcohol compound in a solvent to form a uniform solution;
(2) in the presence of a precipitation assistant, reacting the uniform solution with a titanium compound under stirring at a first temperature to obtain a mixture;
(3) mixing the mixture obtained in the step (2) with ester, heating to a second temperature under a standing condition, and reacting at the second temperature to obtain a solid-liquid mixture;
(4) optionally, contacting the solid-liquid mixture obtained in the step (3) with an internal electron donor compound to obtain the granular catalyst component.
2. The production method according to claim 1, wherein, in step (1), the organic alcohol compound is selected from C2-C10Alcohol and derivatives thereof.
3. According to the claimsThe method according to claim 2, wherein the organic alcohol compound is selected from the group consisting of C3-C6Alcohol and derivatives thereof.
4. The production method according to claim 3, wherein the organic alcohol compound is selected from butanol and pentanol.
5. The production method according to claim 1, wherein at least one of the magnesium compound in the step (1) and the titanium compound in the step (2) is a halogen-containing compound.
6. The production method according to claim 5, wherein the magnesium compound is at least one of a magnesium compound represented by formula (I), a hydrate of a magnesium compound represented by formula (I), and an alcohol adduct of a magnesium compound represented by formula (I),
MgR4R5 (I)；
in the formula (I), R4And R5Each is halogen, C1-C5Linear or branched alkoxy and C1-C5Is one of linear or branched alkyl.
7. The production method according to claim 5, wherein the titanium compound is a compound represented by the formula (II),
TiXm(OR6)4-mformula (II);
in the formula (II), X is halogen, R6Is C1-C20M is an integer of 1 to 4.
8. The production method according to claim 1, wherein the ester is at least one selected from the group consisting of alkyl esters of aliphatic monocarboxylic acids, alkyl esters of aromatic monocarboxylic acids, alkyl esters of aliphatic polycarboxylic acids, and alkyl esters of aromatic polycarboxylic acids.
9. The method of claim 8, wherein the ester is selected from C1-C4Saturated fatC of aliphatic monocarboxylic acid1-C6Alkyl ester of (1), C1-C4C of saturated aliphatic polycarboxylic acids1-C6Alkyl ester of (1), C7-C8C of aromatic monocarboxylic acids1-C6Alkyl esters and C7-C8C of aromatic polycarboxylic acids1-C6At least one of alkyl esters of (a).
10. The production method according to claim 9, wherein the ester is selected from at least one of diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, 1, 3-diamyl phthalate, methyl formate, ethyl formate, n-propyl formate, isopropyl formate, butyl formate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, and butyl butyrate.
11. The preparation method according to claim 1, wherein the organic epoxy compound is used in an amount of 0.2 to 10 moles, the organic phosphorus compound is used in an amount of 0.1 to 3 moles, the organic alcohol compound is used in an amount of 0.005 to 15 moles, the precipitation assistant is used in an amount of 0.03 to 1 mole, the ester is used in an amount of 0.005 to 15 moles, the titanium compound is used in an amount of 0.5 to 20 moles, and the internal electron donor is used in an amount of 0.005 to 15 moles, per mole of the magnesium element.
12. The preparation method according to claim 1, wherein the contacting conditions of step (1) include: the contact temperature is 10-100 ℃ and the contact time is 0.5-6 hours;
the conditions of the first temperature of the step (2) include: the contact temperature is-50 to 10 ℃ and the contact time is 0.1 to 5 hours; the stirring conditions are as follows: the stirring speed is 50-800 r/min;
the conditions of the second temperature of the step (3) include: the contact temperature is 10-110 ℃ and the contact time is 0.5-8 hours;
and the second temperature is higher than the first temperature.
13. The production method according to claim 12, wherein the temperature difference between the second temperature and the first temperature is 30 to 80 ℃.
14. The preparation method according to claim 1, wherein in the step (4), the internal electron donor is added during the heating process after the ester is added to the mixture obtained in the step (2).
15. The production method according to claim 1, wherein the temperature-elevating condition of step (3) includes:
(a) standing for 1-2 hours at constant temperature of-30 to-10 ℃;
(b) standing for 1-2 hours at a constant temperature of-5 ℃ to 5 ℃;
wherein the heating rate is 10-100 ℃/h.
16. The production method according to claim 15, wherein the temperature raising process at-30 to 5 ℃ is performed under a condition of standing, and the temperature raising process at 5 to 60 ℃ is performed under a condition of stirring.
17. The method of claim 16, wherein the stirring is carried out at a constant temperature of 25 ℃ to 35 ℃ for 1 to 2 hours.
18. The preparation method of any one of claims 1 to 17, wherein the method further comprises filtering, washing and drying the solid-liquid mixture obtained in step (3) or the material obtained by contacting the solid-liquid mixture obtained in step (3) with the internal electron donor compound to obtain the granular catalyst component.
19. A catalyst component in the form of particles prepared by the process of any one of claims 1 to 18.
20. Use of a catalyst component in the form of particles prepared by the process according to any one of claims 1 to 18 in the polymerization of olefins.
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