CN107936156B - Olefin polymerization catalyst spherical component, preparation method and application thereof, olefin polymerization catalyst and application thereof, and olefin polymerization method - Google Patents
Olefin polymerization catalyst spherical component, preparation method and application thereof, olefin polymerization catalyst and application thereof, and olefin polymerization method Download PDFInfo
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Abstract
The invention relates to the field of catalysts for olefin polymerization, and discloses a spherical component of an olefin polymerization catalyst, a preparation method and application thereof, the olefin polymerization catalyst, the application thereof and a polymerization method of olefin, in particular to a preparation method of the spherical component of the olefin polymerization catalyst, the spherical component of the olefin polymerization catalyst obtained by the method, the catalyst for olefin polymerization and the application thereof in olefin polymerization reaction; and a process for olefin polymerization using the catalyst system for olefin polymerization of the present invention. The method for preparing the spherical catalyst component for olefin polymerization reaction does not need complex equipment, has simple process, can greatly save the production cost, and most importantly, compared with the spherical catalyst component prepared by the prior art, the catalyst component prepared by the method has higher activity, and the olefin polymerization obtained by catalyzing the catalyst system prepared by the method when the catalyst system is used for olefin polymerization reaction has higher bulk density and isotacticity.
Description
Technical Field
The invention relates to the field of catalysts for olefin polymerization, in particular to a preparation method of a spherical catalyst component for olefin polymerization, and the spherical catalyst component for olefin polymerization obtained by the method; and catalysts for the polymerization of olefins and their use in olefin polymerization reactions; and an olefin polymerization process using the catalyst system for olefin polymerization of the present invention.
Background
The methods for preparing the olefin polymerization solid titanium catalyst component disclosed at present are classified into two types, namely a supported catalyst, namely a method for supporting a titanium-containing active component on a carrier with a certain shape, wherein the main raw material used by the carrier is generally magnesium chloride or silica gel, the shape of the carrier is mostly spherical, such as the methods disclosed in patents of U.S. Pat. No. 4,4399054, EP-B-65700 and the like, and a granular catalyst, wherein magnesium chloride powder is prepared into a uniform solution, and then the uniform solution is crystallized to precipitate and support the titanium-containing active component, such as the methods disclosed in patents of CN85100997A, Z L89107878 and the like.
The spherical catalyst component is generally obtained by chemical dealcoholation of spherical supports, and such catalysts may be generally referred to as supported catalysts or supported catalysts. The conventional methods for preparing a high-activity supported catalyst are generally classified into a co-milling method, a milling and dipping method, a spray carrier forming method, a high-speed stirring carrier forming method, and the like. The catalyst prepared by adopting the grinding method has the main defects that the obtained catalyst has poor particle shape and wide particle size distribution, so that the obtained polymer has poor particle shape, more fine powder and low apparent density, is difficult to increase a production device, and has poor catalytic activity and orientation capability; the catalyst prepared by a spray carrier forming method, a high-speed stirring carrier forming method and the like has the advantages that the particle form of the catalyst is greatly improved, but the carrier forming equipment and process are complex, and the production cost is high.
In recent years, there are patent documents disclosing the preparation of spherical catalysts by a chemical reaction method.
Chinese patent Z L99816964.1 discloses a solid complex titanium catalyst for homo-and co-polymerization of α -olefin, which is obtained by (i) preparing a magnesium compound solution by dissolving a magnesium compound and a compound of group IIIA of the periodic Table in a mixed solvent of a cyclic ether, one or more alcohols, a phosphorus compound, and an organosilane, (ii) reacting the magnesium solution with a transition metal compound, a silicon compound, or a mixture thereof to precipitate solid particles, and (iii) reacting the precipitated solid particles with a titanium compound and an electron donor.
Chinese application No. 200780052352X discloses a method for obtaining a spherical catalyst component by dissolving magnesium chloride in alcohol and tetrahydrofuran and then precipitating out titanium tetrachloride, the method comprising: dissolving magnesium chloride in an oxygen-containing solvent to form a uniform solution, wherein the oxygen-containing solvent is a mixed solvent consisting of cyclic ether and at least one alcohol; the magnesium chloride solution is in contact reaction with a titanium compound to separate out magnesium chloride particles; and (3) carrying an electron donor on the particles, and activating and washing to obtain the solid catalyst component. The method can obtain spherical particles with the particle size of less than 100 microns, has smooth surface morphology and good particle shape, but has low activity when used for olefin polymerization, and the obtained polymer has low bulk density and isotacticity and does not have industrial application value.
Therefore, it is urgently needed to develop a preparation method of a spherical catalyst with simple process and low cost, and the prepared catalyst component has high activity, and the olefin polymer obtained by catalysis has higher bulk density and isotacticity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a spherical catalyst for olefin polymerization, which has simple process, low cost, high activity of the obtained catalyst component and high bulk density and isotacticity of the olefin polymer obtained by catalysis, and the spherical catalyst component for olefin polymerization obtained by the method; and catalysts for the polymerization of olefins and their use in olefin polymerization reactions; and an olefin polymerization process using the catalyst system for olefin polymerization of the present invention.
In order to accomplish the above objects, in one aspect, the present invention provides a method for preparing a spherical catalyst component for olefin polymerization, the method comprising:
(1) in the presence of an inert solvent, carrying out first contact on a magnesium compound, a cyclic ether compound and an alcohol compound to obtain a uniform solution;
(2) carrying out second contact on the uniform solution obtained in the step (1) and a titanium compound to separate out a solid precipitate;
(3) and (3) in the presence of an inert solvent, carrying out third contact on the product obtained in the step (2), a titanium compound and an internal electron donor at the temperature of 120-150 ℃ to obtain a suspension containing the catalyst component.
Preferably, in the step (2), the homogeneous solution obtained in the step (1) and the titanium compound are mixed at-30 ℃ to 60 ℃, and then heated to 85 ℃ to 100 ℃ and contacted for 0.5 to 2 hours.
Preferably, the rate of temperature rise is 0.1-1 deg.C/min, more preferably 0.3-0.8 deg.C/min.
Preferably, the temperature of the first contacting is 50-100 ℃ above the temperature of said mixing and the rate of reduction from the temperature of the first contacting to the temperature of said mixing is 0.5-8 ℃/min, more preferably 1-4 ℃/min.
Preferably, step (3) further comprises:
(31) contacting the mixture containing the precipitate obtained in the step (2) with a titanium compound at a temperature of 120-150 ℃ for 0.5-1.5 hours in the presence of an inert solvent, followed by filtration to obtain a solid precipitate;
(32) and (2) in the presence of an inert solvent, contacting the solid precipitate obtained in the step (31) with a titanium compound and an internal electron donor at the temperature of 120-150 ℃ for 1-3 hours again to obtain a suspension containing the catalyst component.
In a second aspect, the present invention provides a spherical catalyst component for olefin polymerization prepared by the process as described above.
In a third aspect, the present invention provides a catalyst for the polymerization of olefins, the catalyst comprising:
(i) a catalyst component which is a catalyst component for olefin polymerization as described above;
(ii) at least one alkyl aluminum compound; and
(iii) optionally, at least one external electron donor.
In a fourth aspect, the present invention provides the use of a spherical catalyst component for olefin polymerization prepared by the process as described above or a catalyst for olefin polymerization as described above in an olefin polymerization reaction.
In a fifth aspect, the invention also provides an olefin polymerisation process comprising contacting one or more olefins with a catalyst as described above under olefin polymerisation conditions.
The preparation method of the spherical catalyst component for olefin polymerization or copolymerization reaction does not need complex equipment, and has a simple process, so that the production cost can be greatly saved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
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 one aspect, the present invention provides a method for preparing a spherical catalyst component for olefin polymerization, the method comprising:
(1) in the presence of an inert solvent, carrying out first contact on a magnesium compound, a cyclic ether compound and an alcohol compound to obtain a uniform solution;
(2) carrying out second contact on the uniform solution obtained in the step (1) and a titanium compound to separate out a solid precipitate;
(3) and (3) in the presence of an inert solvent, carrying out third contact on the product obtained in the step (2), a titanium compound and an internal electron donor at the temperature of 120-150 ℃ to obtain a suspension containing the catalyst component.
The preparation method according to the present invention, wherein each raw material for preparing the spherical catalyst component may be used in an amount that is conventional in the art, but preferably, the alcohol compound is used in an amount of 0.5 to 20 moles, more preferably 2 to 10 moles, per mole of the magnesium compound; the amount of the titanium compound to be used is 0.5 to 20 mol, more preferably 1 to 15 mol; the amount of the internal electron donor is 0.06 to 10 mol, more preferably 0.06 to 10 mol.
The inventors of the present invention have found in the course of their studies that the object of the present invention can be more preferably achieved when the cyclic ether compound is used in an amount of 1 to 20 moles, more preferably 2 to 10 moles, per mole of the magnesium compound, specific to the production method of the present invention.
According to the production method of the present invention, the amount of the inert solvent used in each step is not particularly limited as long as each component necessary for the reaction can be sufficiently dissolved to allow the reaction to proceed smoothly, and preferably, the amount of the inert solvent used in step (1) is 1 to 5L, preferably 3 to 4L, per mole of the magnesium compound, and the amount of the inert solvent used in step (3) is 1 to 5L, preferably 2 to 3L, per mole of the magnesium compound.
According to the preparation method of the present invention, the conditions of the first contacting may be those conventional in the art, and preferably, the components in step (1) are contacted at a temperature of 50 to 110 ℃, preferably 80 to 110 ℃ for 0.5 to 4 hours to form a uniform solution.
According to the preparation method of the present invention, the conditions of the second contacting can also be the contacting conditions conventional in the art, but the inventors of the present invention found that the activity of the prepared catalyst component is higher by mixing the homogeneous solution obtained in step (1) with the titanium compound at a lower temperature and then heating to a higher temperature. Preferably, the homogeneous solution obtained in step (1) is first mixed with the titanium compound at-30 ℃ to 60 ℃, preferably-10 ℃ to 40 ℃, more preferably 0 to 30 ℃, and then heated to 85 ℃ to 100 ℃, preferably at a rate of 0.1 ℃/min to 1 ℃/min, more preferably 0.3 ℃/min to 0.8 ℃/min, and contacted for 0.5 to 2 hours, to allow the solid precipitate to be more sufficiently precipitated. And the temperature rising rate can make the particle type of the finally obtained catalyst component more uniform and the activity higher.
According to the preparation method of the present invention, after the second contact precipitates a solid precipitate, the method of the present invention further comprises a step of subjecting the mixture containing the precipitate obtained in step (2) to solid-liquid separation, and washing the obtained solid precipitate. Wherein the solid-liquid separation method is a conventional choice in the art, such as a filtration method. The washing is preferably carried out by washing the obtained precipitate with an inert solvent to an extent that impurities such as unreacted raw materials are sufficiently removed.
According to the production method of the present invention, it is preferable that the temperature of the first contact is higher than the temperature of mixing the homogeneous solution with the titanium compound, and therefore, the production method of the present invention further comprises a step of cooling the obtained homogeneous solution after the first contact. Preferably, the temperature of the first contacting is 50-100 ℃ above the temperature of said mixing and the rate of reduction from the temperature of the first contacting to the temperature of said mixing is 0.5-8 ℃/min, more preferably 1-4 ℃/min. The cooling rate can make the particle type of the finally obtained catalyst component more uniform and the activity higher.
In the course of research, the inventors of the present invention found that by performing step (3) in two steps, the activity of the obtained catalyst component can be significantly improved, and the isotacticity and bulk density of the finally catalyzed olefin polymer can also be significantly improved within a reasonable range. The method comprises the following specific steps:
(31) in the presence of an inert solvent, firstly, contacting the mixture containing the precipitate obtained in the step (2) with a titanium compound at the temperature of 120-150 ℃ for 0.5-1.5 hours, and then filtering to obtain a solid precipitate;
(32) then in the presence of an inert solvent, the solid precipitate obtained in the step (31) is contacted with a titanium compound and an internal electron donor for 1 to 3 hours again at the temperature of 120-150 ℃ to obtain a suspension containing the catalyst component.
As described above, in the production process of the present invention, the titanium compound may be added in 2 stages or 3 stages, and when the titanium compound is added in 2 stages, that is, once in step (2) and once in step (3), the ratio of the amount of the titanium compound in step (2) to the amount of the titanium compound in step (3) is 1 (15-25), preferably 1 (18-22). Preferably, when the titanium compound is added in 3 times, that is, one addition is made in step (2) and 2 additions are made in step (3), the ratio of the amount of the titanium compound used in step (2) to each amount of the titanium compound added 2 times after that in step (3) is 1 (7.5-12.5) to (7.5-12.5), preferably 1 (9-11) to (9-11).
As described above, the inert solvent is preferably added in two portions in step (3), and in this preferred case, the ratio of the amounts of the inert solvent used in two portions is 1 (0.5-2), more preferably 1 (0.8-1.2).
According to the production method of the present invention, preferably, 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),
MgXR1(Ⅰ)
R1is one of halogen and straight chain or branched chain alkyl of C1-C5, and X is halogen; preferably at least one of magnesium halide, alkyl magnesium halide, and haloalcoholate of enzyme; 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.
According to the preparation method of the present invention, the alcohol compound may be one or more of aliphatic alcohol, alicyclic alcohol and aromatic alcohol. Wherein the aliphatic alcohol is preferably a monohydric alcohol or a polyhydric alcohol having 1 to 12 carbon atoms, more preferably 2 to 12 carbon atoms; the alicyclic alcohol is preferably an alicyclic alcohol with 3-12 carbon atoms; the aromatic alcohol is preferably an aryl alcohol having 6 to 20 carbon atoms or an alkylaryl alcohol having 7 to 20 carbon atoms. Specific examples of the alcohol compound may be one or more of ethanol, propanol, butanol, 2-ethylhexanol, benzyl alcohol, and phenethyl alcohol, and butanol is preferable.
According to the preparation method of the invention, the cyclic ether compound is preferably a cyclic ether compound with 3-6 carbon atoms or a derivative thereof, and in the invention, the cyclic ether compound is preferably tetrahydrofuran and/or 2-methyltetrahydrofuran, and most preferably tetrahydrofuran. Wherein the term "derivative" refers to a cyclic ether in which one or more groups are substituted with other substituents in the cyclic ether compound. 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 present invention, the internal electron donor may be any of various internal electron donors commonly used in the art, for example, alkyl esters of aliphatic or aromatic monocarboxylic acids, alkyl esters of aliphatic or aromatic polycarboxylic acids, and one or more of aliphatic ethers, cycloaliphatic ethers, and aliphatic ketones.
The alkyl esters of aliphatic or aromatic monocarboxylic acids, and the alkyl esters of aliphatic or aromatic polycarboxylic acids may be any of those conventionally used in the art, and may be, for example, alkyl esters of saturated aliphatic carboxylic acids having C1-C4, and alkyl esters of aromatic carboxylic acids having C7-C8.
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 methyl formate, ethyl acetate, butyl acetate, diisobutyl phthalate, di-n-butyl phthalate, diisooctyl phthalate, diethyl ether, hexyl ether, Tetrahydrofuran (THF), acetone, methyl isobutyl ketone, etc., preferably diisobutyl phthalate, di-n-butyl phthalate, which may be used alone or in combination of several.
The inert solvent is various solvents commonly used in the art and capable of dissolving the magnesium compound, the cyclic ether compound, the alcohol compound, the titanium compound and the internal electron donor compound, and specifically, may be one or more of an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent. The aliphatic hydrocarbon solvent may be, for example, one or more of pentane, hexane, heptane, octane, and decane, the alicyclic hydrocarbon solvent may be cyclohexane and/or methylcyclohexane, and the aromatic hydrocarbon solvent may be one or more of toluene, ethylbenzene, benzene, xylene, and chlorobenzene. Of these, toluene and chlorobenzene are most preferred.
According to a specific embodiment of the present invention, the method for preparing the spherical catalyst component for olefin polymerization comprises: (1) mixing a magnesium compound, a cyclic ether compound, an alcohol compound and an inert solvent at 50-110 ℃ for 0.5-4 hours under stirring to obtain a uniform solution; (2) cooling the homogeneous solution to-30 ℃ to 60 ℃, preferably 0-30 ℃, at a cooling rate of 0.5-8 ℃/min, more preferably 1-4 ℃/min, then dropping a titanium compound into the homogeneous solution or into the titanium compound, then heating the obtained mixture to 85-100 ℃ at a heating rate of 0.1-1 ℃/min, more preferably 0.3-0.8 ℃/min, and contacting for 0.5-2 hours to precipitate solid particles; (3) contacting the solid particles with a titanium compound and an inert solvent at the temperature of 120-150 ℃ for 0.5-1.5 hours; then contacting with titanium compound, inert solvent and internal electron donor at the temperature of 120-150 ℃ for 1-3 hours to obtain the suspension containing the catalyst component.
The preparation method according to the present invention further comprises subjecting the obtained suspension containing the catalyst component to solid-liquid separation, washing the obtained solid with the inert solvent to further purify the catalyst component, and then drying the washed solid product to obtain the solid catalyst component of the present invention. Among them, the drying is preferably vacuum drying. The solid-liquid separation and washing with an inert solvent are conventional in the art and are not described in detail herein.
In a second aspect, the present invention also provides a spherical catalyst component for olefin polymerization prepared by the method as described above.
In a third aspect, the present invention provides a catalyst for the polymerization of olefins, the catalyst comprising:
(i) a catalyst component which is the spherical catalyst component for olefin polymerization according to the present invention;
(ii) at least one alkyl aluminum compound; and
(iii) optionally, at least one external electron donor.
According to the invention, the aluminum alkyl may be conventionally selected in the art, for example, the aluminum alkyl may have the general formula AlR16R16′R16", wherein R16、R16′、R16Each independently is C1-8And wherein one or both groups may be halogen; said C is1-8Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, propyl, n-butyl, isobutyl, pentyl, hexyl, n-heptyl, n-octyl and the halogen may be fluorine, chlorine, bromine, iodine. Specifically, the alkyl aluminum may be selected from, for example, triethyl aluminum, tripropyl aluminum, triisobutylAluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum monohydrogen, diisobutylaluminum monohydrogen, diethylaluminum monochloride, diisobutylaluminum monochloride, di-n-butylaluminum monochloride, di-n-hexylaluminum monochloride, ethylaluminum dichloride, isobutylaluminum dichloride, n-butylaluminum dichloride, n-hexylaluminum dichloride, Al (n-C)6H13)3、Al(n-C8H17)3、AlEt2One or more of Cl, preferably triethylaluminum and/or triisobutylaluminum.
According to the present invention, the external electron donor may be various external electron donors commonly used in the art, for example, the external electron donor may be one or more of carboxylic acid, acid anhydride, ester, ketone, ether, alcohol, organic phosphorus compound, and organic silicon compound; preferably, the external electron donor is a compound containing at least one Si-OR bond and having the general formula (R)17)a(R18)bSi(OR19)cWherein R is17、R18And R19Is C1-C18A and b are each independently an integer from 0 to 2, c is an integer from 1 to 3, and the sum of a, b and c is 4. Preferably, R17、R18Is C3-C10Alkyl, cycloalkyl, optionally containing heteroatoms; r19Is C1-C10Optionally containing heteroatoms. Specifically, the external electron donor may be, for example, one or more selected from the group consisting of cyclohexylmethyldimethoxysilane, diisopropyldimethoxysilane, di-n-butyldimethoxysilane, diisobutyldimethoxysilane, diphenyldimethoxysilane, methyl-t-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexyltrimethoxysilane, t-butyltrimethoxysilane, t-hexyltrimethoxysilane, 2-ethylpiperidinyl-2-t-butyldimethoxysilane, (1,1, 1-trifluoro-2-propyl) -2-ethylpiperidinyl-dimethoxysilane and (1,1,1-, trifluoro-2-propyl) -methyldimethoxysilane.
Further, in general, in the catalyst for olefin polymerization, the molar ratio of the catalyst component for olefin polymerization in terms of titanium element to the amount of aluminum alkyl in terms of aluminum element may be 1: (1-1000), preferably 1: (10-300), more preferably 1: (20-200); the molar ratio of the external electron donor to the aluminum alkyl in terms of aluminum element may be 1: (2-500), preferably 1: (5-200).
According to the present invention, in the preparation process of the catalyst for olefin polymerization, the alkylaluminum and the optional external electron donor compound may be respectively mixed with the catalyst component for olefin polymerization and then reacted, or the alkylaluminum and the optional external electron donor compound may be mixed in advance and then mixed with the catalyst component for olefin polymerization and reacted.
According to the present invention, when the catalyst for olefin polymerization is used for olefin polymerization, the catalyst component for olefin polymerization, the aluminum alkyl, and the optional external electron donor may be added into the polymerization reactor separately, or may be added into the polymerization reactor after mixing, or may be added into the polymerization reactor after olefin prepolymerization by a prepolymerization method known in the art.
In a fourth aspect, the present invention provides the use of the spherical catalyst component for olefin polymerization according to the present invention or the catalyst for olefin polymerization according to the present invention in olefin polymerization reactions.
In a fifth aspect, the present invention provides an olefin polymerisation process comprising contacting one or more olefins with a catalyst as described above under olefin polymerisation conditions.
The improvement of the present invention is that the catalyst component prepared by the specific method of the present invention is adopted, and the specific kinds of olefin, the polymerization reaction method and conditions of olefin can be the same as those of the prior art.
According to the invention, the above-mentioned catalysts are particularly suitable for use with catalysts of the formula CH2CHR (wherein R is hydrogen, C)1-C6Alkyl or C6-C12Aryl) olefins, such as, in particular, ethylene, propylene, 1-n-butene, 1-n-pentene, 1-n-hexene, 1-n-octene and 4-methyl-1-pentene. Preferably, the general formula CH2The olefins represented by CHR areOne or more of ethylene, propylene, 1-n-butene, 1-n-hexene and 4-methyl-1-pentene. More preferably, the general formula CH2The olefin represented by ═ CHR is propylene.
According to the present invention, the polymerization of the olefin can be carried out according to the existing methods, specifically, under the protection of inert gas, in a liquid phase monomer or an inert solvent containing a polymeric monomer, or in a gas phase, or by a combined polymerization process in a gas-liquid phase. The polymerization temperature may be generally 0 to 150 ℃ and preferably 60 to 100 ℃. The pressure of the polymerization reaction may be normal pressure or higher; for example, it may be in the range of 0.01 to 10MPa, preferably 0.5 to 5 MPa. The polymerization time is from 0.1 to 5 hours, preferably from 0.5 to 3 hours. The pressure in the present invention is a gauge pressure. During the polymerization, hydrogen may be added to the reaction system as a polymer molecular weight regulator to regulate the molecular weight and melt index of the polymer. In addition, the kinds and amounts of the inert gas and the solvent are well known to those skilled in the art during the polymerization of olefins, and will not be described herein.
The present invention will be described in detail below by way of specific examples, which are not intended to limit the scope of the present invention. In the following examples, the following examples are given,
1. shape of the catalyst: observing by using an optical microscope and a scanning electron microscope;
2. catalyst activity-weight of polymer obtained using catalyst/weight of catalyst;
3. 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 extracted polymer/2 × 100;
4. the bulk density of the polymer is determined by reference to ASTM D1895-96.
Preparation example 1
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
4.8 g of anhydrous magnesium chloride, 176 ml of toluene, 9.6 ml of tetrahydrofuran and 9.2 ml of butanol are sequentially added into a reaction kettle repeatedly replaced by high-purity nitrogen, the reaction is carried out for 2 hours at the temperature of 103 ℃, the temperature is reduced to 10 ℃ at the speed of 2 ℃/min, 5 ml of titanium tetrachloride is dropwise added, the temperature is increased to 93 ℃ at the speed of 0.5 ℃/min, the temperature is kept for one hour, mother liquor is filtered out, the reaction kettle is washed by toluene for 2 times, 48 ml of titanium tetrachloride and 72 ml of chlorobenzene are added, the temperature is kept at 130 ℃ for 1 hour, the temperature is kept at 1 hour after filtration, 48 ml of titanium tetrachloride, 72 ml of chlorobenzene and 2.1 ml of di-n-butyl phthalate (DNBP) are added after filtration, the temperature is kept at 130 ℃ for 1.5 hours, the filtration is washed by hexane for 5 times, and the residual solid product is. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 2
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
4.8 g of anhydrous magnesium chloride, 176 ml of toluene, 9.6 ml of tetrahydrofuran and 9.2 ml of amyl alcohol are sequentially added into a reaction kettle repeatedly replaced by high-purity nitrogen, the reaction is carried out for 2 hours at the temperature of 90 ℃, the temperature is reduced to 20 ℃ at the speed of 1 ℃/min, 5 ml of titanium tetrachloride is dropwise added, then the temperature is increased to 85 ℃ at the speed of 0.3 ℃/min, the temperature is kept for one hour, 48 ml of titanium tetrachloride and 72 ml of chlorobenzene are added, the temperature is kept for 1 hour at the temperature of 140 ℃, 48 ml of titanium tetrachloride, 72 ml of chlorobenzene and 2.1 ml of di-n-butyl phthalate (DNBP) are added after filtration, the temperature is kept for 1.5 hours at the temperature of 120 ℃, the filtrate is washed for 5 times by hexane, and the residual solid product is dried in vacuum to obtain the solid titanium catalyst component. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 3
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
4.8 g of anhydrous magnesium chloride, 176 ml of toluene, 9.6 ml of tetrahydrofuran and 9.2 ml of butanol are sequentially added into a reaction kettle repeatedly replaced by high-purity nitrogen, the reaction is carried out for 1.5 hours at the temperature of 100 ℃, the temperature is reduced to 0 ℃ at the speed of 3 ℃/min, 5 ml of titanium tetrachloride is dropwise added, the temperature is increased to 100 ℃ at the speed of 0.7 ℃/min, the temperature is kept constant for one hour, 48 ml of titanium tetrachloride and 72 ml of chlorobenzene are added, the temperature is kept constant for 0.5 hour at the temperature of 150 ℃, 48 ml of titanium tetrachloride, 72 ml of chlorobenzene and 2.1 ml of di-n-butyl phthalate (DNBP) are added after filtration, the temperature is kept constant for 1 hour at the temperature of 130 ℃, toluene is used for washing for 2 times after filtration, hexane is used for washing for 3 times, and the residual solid product is dried in vacuum to obtain the. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 4
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
The catalyst component was prepared according to the method of example 1, except that the toluene-washed precipitate was directly reacted with 96 ml of titanium tetrachloride, 144 ml of chlorobenzene and 2.1 ml of DNBP at 130 ℃ for 2.5 hours. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 5
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
The preparation of the catalyst component was carried out in the same manner as in example 1, except that the step of cooling to 10 ℃ was not included, but titanium tetrachloride was added dropwise by directly cooling to 93 ℃. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 6
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
The preparation of the catalyst component was carried out as in example 1, except that the rate of temperature decrease was 0.5 ℃/min and the rate of temperature increase was 1 ℃/min. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 7
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
The preparation of the catalyst component was carried out in the same manner as in example 1 except that tetrahydrofuran was used in an amount of 3.5 ml. The particle shape of the obtained catalyst component is shown in Table 1.
Preparation example 8
The preparation examples are provided to illustrate the catalyst component and the preparation method thereof
The preparation of the catalyst component was carried out in the same manner as in example 1 except that tetrahydrofuran was used in an amount of 80 ml. The particle shape of the obtained catalyst component is shown in Table 1.
Comparative preparation example 1
This comparative preparation is illustrative of a reference catalyst component and method of making
The preparation of the catalyst component was carried out in accordance with the procedure of example 1, except that 130 ℃ was changed to 110 ℃. The particle shape of the obtained catalyst component is shown in Table 1.
Comparative preparation example 2
This comparative preparation is illustrative of a reference catalyst component and method of making
The catalyst component was prepared in accordance with the method of comparative preparation example 1, except that 48 ml of titanium tetrachloride and 72 ml of chlorobenzene were again added after the second constant temperature, and the constant temperature was maintained at 110 ℃ for 1 hour. The particle shape of the obtained catalyst component is shown in Table 1.
Comparative preparation example 3
The comparative preparation example is used for the catalyst component provided by the prior art and the preparation method thereof
The preparation of the catalyst component was carried out with reference to the method of Chinese patent Z L99816964.1 the particle shape of the obtained catalyst component is shown in Table 1.
Comparative preparation example 4
The comparative preparation example is used for the catalyst component provided by the prior art and the preparation method thereof
The preparation of the catalyst component is carried out with reference to the method of chinese patent 200780052352X. The particle shape of the obtained catalyst component is shown in Table 1.
Test examples 1 to 8
After a 5-liter stainless steel reaction vessel was sufficiently purged with nitrogen, 5 ml of a triethylaluminum hexane solution having a concentration of 0.5 mol/liter and 1 ml of a methylcyclohexyldimethoxysilane (CMMS) hexane solution having a concentration of 1 mol/liter and 10 mg of the catalyst prepared in preparation examples 1 to 8 were added, and then 10 ml of hexane was added to flush the feed line, 1 liter (under a standard condition) of hydrogen and 2 liters of purified propylene were added, and the temperature was raised to 70 ℃ to make the hydrogen partial pressure 0.2MPa, at which temperature polymerization was carried out for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging a reaction product, and drying to obtain a white polymer. The activity of the catalyst, the bulk density of the resulting polymer and the isotacticity are shown in Table 1.
Comparative test examples 1 to 4
After a 5-liter stainless steel reaction vessel was sufficiently purged with nitrogen, 5 ml of a triethylaluminum hexane solution having a concentration of 0.5 mol/liter and 1 ml of a methylcyclohexyldimethoxysilane (CMMS) hexane solution having a concentration of 1 mol/liter and 10 mg of the catalyst prepared in comparative preparation examples 1 to 4 were added, and then 10 ml of hexane was added to flush the feed line, 1 liter (under a standard condition) of hydrogen and 2 liters of purified propylene were added, and the temperature was raised to 70 ℃ so that the hydrogen partial pressure was 0.2MPa, at which temperature polymerization was carried out for 1 hour. After the reaction is finished, cooling the reaction kettle, stopping stirring, discharging a reaction product, and drying to obtain a white polymer. The activity of the catalyst, the bulk density of the resulting polymer and the isotacticity are shown in Table 1.
TABLE 1
As can be seen from the above Table 1, the preparation method of the present invention has the advantages of simple process, no need of complicated equipment, high activity of the prepared catalyst component, and high isotacticity and bulk density of the olefin polymerization obtained by catalysis.
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 (12)
1. A method for preparing a spherical catalyst component for olefin polymerization, the method comprising:
(1) in the presence of an inert solvent, carrying out first contact on a magnesium compound, a cyclic ether compound and an alcohol compound at 50-110 ℃ for 0.5-4 hours to obtain a uniform solution;
(2) firstly, mixing the uniform solution obtained in the step (1) with a titanium compound at a temperature of between 30 ℃ below zero and 60 ℃, then heating to 85 ℃ to 100 ℃ at a heating rate of 0.1 to 1 ℃/min, and contacting for 0.5 to 2 hours to precipitate a solid;
wherein the temperature of the first contacting is 50-100 ℃ higher than the temperature of the mixing, and the rate of lowering the temperature of the first contacting to the temperature of the mixing is 0.5-8 ℃/min;
(31) contacting the mixture containing the precipitate obtained in the step (2) with a titanium compound at a temperature of 120-150 ℃ for 0.5-1.5 hours in the presence of an inert solvent, followed by filtration to obtain a solid precipitate;
(32) in the presence of an inert solvent, contacting the solid precipitate obtained in the step (31) with a titanium compound and an internal electron donor at the temperature of 120-150 ℃ for 1-3 hours again to obtain a suspension containing the catalyst component;
wherein, the dosage of the cyclic ether compound is 1 to 20 moles, the dosage of the alcohol compound is 0.5 to 20 moles, the dosage of the titanium compound is 0.5 to 20 moles, and the dosage of the internal electron donor is 0.06 to 10 moles per mole of the magnesium compound.
2. The production method according to claim 1, wherein at least one of the magnesium compound and the titanium compound is a halogen-containing compound.
3. The production method according to claim 2, wherein 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),
MgXR1(Ⅰ)
in the formula (I), R1Is one of halogen and C1-C5 straight chain or branched chain alkyl, and X is halogen.
4. The production method according to claim 2, wherein the titanium compound is a compound represented by the formula (II),
TiXm(OR2)4-mformula (II)
In the formula (II), X is halogen, R2Is a C1-C20 hydrocarbon group, and m is an integer of 1-4.
5. The production method according to claim 1, wherein the alcohol compound is one or more of an aliphatic alcohol, an alicyclic alcohol and an aromatic alcohol.
6. The production method according to claim 5, wherein the alcohol compound is a C1-C12 alcohol.
7. The production method according to claim 1, wherein the cyclic ether compound is C3-C6Cyclic ethers of (a).
8. The production method according to claim 7, wherein the cyclic ether compound is tetrahydrofuran and/or 2-methyltetrahydrofuran.
9. Spherical catalyst component for the polymerization of olefins prepared by the process according to any of claims 1 to 8.
10. A catalyst for the polymerization of olefins, the catalyst comprising:
(i) a catalyst component for olefin polymerization according to claim 9;
(ii) at least one alkyl aluminum compound; and
(iii) optionally, at least one external electron donor.
11. Use of the spherical catalyst component for olefin polymerization according to claim 9 or the catalyst for olefin polymerization according to claim 10 in olefin polymerization reactions.
12. A process for the polymerization of olefins comprising contacting one or more olefins with the catalyst of claim 10 under olefin polymerization conditions.
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| CN101421316A (en) * | 2006-04-19 | 2009-04-29 | 三星Total株式会社 | Olefin polymerization and copolymerization method |
| CN104558275A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, and preparation method and application thereof |
| CN104558276A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, and preparation method and application thereof |
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| CN101421316A (en) * | 2006-04-19 | 2009-04-29 | 三星Total株式会社 | Olefin polymerization and copolymerization method |
| CN104558275A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, and preparation method and application thereof |
| CN104558276A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Olefin polymerization catalyst, and preparation method and application thereof |
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