CN114539449A - Titanium catalyst component for ethylene polymerization and preparation method and application thereof - Google Patents
Titanium catalyst component for ethylene polymerization and preparation method and application thereof Download PDFInfo
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- CN114539449A CN114539449A CN202011333326.8A CN202011333326A CN114539449A CN 114539449 A CN114539449 A CN 114539449A CN 202011333326 A CN202011333326 A CN 202011333326A CN 114539449 A CN114539449 A CN 114539449A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a titanium catalyst component for ethylene polymerization, a preparation method and application thereof, wherein the preparation method comprises the following steps: step 1, mixing a magnesium compound with a solvent to form a microemulsion; step 2, carrying out contact reaction on the microemulsion of the step 1 and a titanium compound to form a titanium catalyst component; wherein, the preparation method also adds an organic boron compound, and the adding step is during or after the mixing of the magnesium compound and the solvent, or during the contact reaction process of the microemulsion of the step 1 and the titanium compound; the organoboron compound has no active hydrogen and contains a strong electron-withdrawing group. The titanium catalyst component of the invention has simple preparation process, spherical catalyst particles and narrow particle size distribution, is used for producing ethylene polymer, has the characteristics of high activity, good hydrogen regulation sensitivity, good polymer particle shape and less fine powder, is very suitable for ethylene slurry polymerization process, and is especially suitable for producing polyethylene resin with wide relative molecular mass distribution by adopting a double reactor.
Description
Technical Field
The invention relates to a solid titanium Ziegler-Natta catalyst component for ethylene homopolymerization or ethylene and other alpha-olefin copolymerization, a preparation method thereof, and application of an ethylene polymerization catalyst composed of the solid titanium Ziegler-Natta catalyst component and an organic metal compound in ethylene homopolymerization or ethylene and other alpha-olefin copolymerization.
Background
The preparation of high-efficiency Ziegler-Natta catalysts for ethylene polymerization is well known and consists essentially of MgCl2Or SiO2Supported titanium halide. The preparation method of the ethylene polymerization and copolymerization catalyst as disclosed in JP4951378 is: reacting the ground magnesium dichloride with ethanol to generate MgCl2·6C2H5OH alcohol compound slurry, esterification reaction with diethyl aluminum chloride, and final reaction with TiCl4Carrying out titanium carrying reaction to obtain MgCl2A titanium-based catalyst supported on a carrier. The catalyst has simple preparation method, mild reaction condition and high activity when catalyzing ethylene polymerization. However, the preparation method existsThe carrier magnesium chloride can not be dissolved in mineral oil, and the magnesium chloride has irregular flaky particles generated in the original grinding and crushing process in a slurry reaction system, so that the obtained solid catalyst has poor particle form and nonuniform thickness, and therefore, the polymer has poor form and more fine powder, static electricity is easily generated, and pipelines are easily blocked. Meanwhile, the catalyst causes great trouble in the post-treatment when the content of oligomer in the solvent is large during the polymerization.
Patent CN1229092A discloses a catalyst system for ethylene polymerization and copolymerization, which comprises: (1) a solid catalyst component comprising Ti; (2) an alkyl aluminum compound; the Ti-containing solid catalyst component is prepared through dissolving magnesium halide in organic epoxy compound and organic phosphorus compound to form homogeneous solution, adding alcohol to treat the dissolved magnesium halide, mixing the solution with titanium tetrahalide, and precipitating solid in the presence of precipitant such as organic acid anhydride, organic acid, ether, ketone and other compounds. When the catalyst system is used for ethylene polymerization, the obtained polymer has high fine powder content, low catalyst activity and poor hydrogen regulation performance, is not suitable for preparing bimodal polymers, and is difficult to replace the existing high-activity ethylene slurry polymerization Ziegler-Natta catalyst. At the same time, the bulk density of the polymer is slightly lower than that of the existing catalyst.
Patents CN101245115A, CN102272172A, CN1112373A, etc. disclose a solid titanium catalyst component and a preparation process thereof, which mainly adopt low carbon alcohol to dissolve magnesium halide, and add alkane diluent and silane electron donor compound or organic boron compound, then react with titanium halide to precipitate a solid catalyst. Although the catalysts show high catalytic activity when used for ethylene polymerization and produce ethylene polymers with excellent particle properties, the hydrogen control properties and oligomer content of such catalysts are still unsatisfactory. Patent CN1471541A discloses a method for preparing a solid titanium complex catalyst for ethylene polymerization, which comprises reacting a magnesium halide compound with an alcohol to prepare a magnesium solution, then reacting with an ester compound having at least one hydroxyl group and a boron compound having at least one alkoxy group, and reacting with a mixture of a titanium compound and a haloalkane compound to produce a solid catalyst by recrystallization. When the catalyst is used for ethylene polymerization, the advantages of high catalytic activity, high polymer bulk density, narrow particle size distribution and the like are shown, but the hydrogen regulation performance and the oligomer content of the catalyst are not satisfactory.
Patent CN1180712A discloses a catalyst for ethylene polymerization or copolymerization and a preparation method thereof, wherein at least one unsaturated fatty acid ester containing one or more ester groups and/or at least one water-in-oil type nonionic surfactant are added when magnesium compound and organic alcohol react to form alcohol compound slurry, so that magnesium halide and alcohol can form swollen alcohol compound slurry in diluent at lower temperature without dissolving magnesium halide to form solution at high temperature, the catalyst with particle morphology can be obtained, and the usage amount of alcohol is reduced when alcohol compound slurry is formed, so that the preparation process of the catalyst is simple, the operation is easy, and the cost is reduced. However, when the catalyst is used for ethylene polymerization, the disadvantages of insensitive hydrogen regulation, bad polymer particle morphology and much fines still exist, which is not favorable for producing polymers with wide molecular weight distribution by using one catalyst.
Patent CN1752116A discloses a catalyst for ethylene polymerization or copolymerization and a preparation method thereof, wherein at least one unsaturated fatty acid ester containing one or more ester groups and/or at least one water-in-oil type nonionic surfactant are added when magnesium compound and organic alcohol form alcohol mixture slurry, so as to solve the problem of hydrogen regulation sensitivity of the catalyst, but the particle morphology of the catalyst cannot be improved, thus when the catalyst is used in slurry polymerization process of ethylene, the disadvantages of uneven particle morphology and more fine powder of polymerization products still exist.
From the above analysis, in the preparation method of the Ziegler-Natta catalyst for ethylene polymerization, researchers can regulate the particle size, morphology and distribution of the catalyst by the emulsification technology, and regulate the activity of the catalyst by the components of the catalyst and the electron donor compound. However, the hydrogen response of the catalyst and the control of the amount of oligomer formed have been difficult problems, which are very important for the development of polyethylene products having a bimodal distribution.
Disclosure of Invention
The invention mainly aims to provide a titanium catalyst component for ethylene polymerization, and a preparation method and application thereof, so as to overcome the defects that the catalyst in the prior art is poor in hydrogen regulation sensitivity and high in oligomer content in a product obtained by using the catalyst in the prior art for ethylene polymerization.
In order to achieve the above objects, the present invention provides a method for preparing a titanium catalyst component for ethylene polymerization, comprising the steps of:
step 1, mixing a magnesium compound with a solvent to form a microemulsion;
step 2, carrying out contact reaction on the microemulsion of the step 1 and a titanium compound to form a titanium catalyst component;
wherein, the preparation method also adds an organic boron compound, and the adding step is during or after the mixing of the magnesium compound and the solvent, or during the contact reaction process of the microemulsion of the step 1 and the titanium compound; the organoboron compound has no active hydrogen and contains a strong electron-withdrawing group.
The preparation method of the titanium catalyst component for ethylene polymerization comprises the following steps of (1) calculating the magnesium compound by magnesium, calculating the titanium compound by titanium, wherein the molar ratio of the magnesium compound to the titanium compound is 1.0-15.0: 1.
the method for preparing the titanium catalyst component for ethylene polymerization according to the present invention, wherein the magnesium compound is XnMgR2-nWherein n is 0 or more and 2 or less; r is alkyl, aryl, cycloalkyl, alkoxy or aryloxy of 1-20 carbon atoms; when n is 0, the two R are the same or different; x is halogen.
The invention relates to a preparation method of a titanium catalyst component for ethylene polymerization, wherein a solvent in step 1 is alcohol, phenol, carboxylic acid, aldehyde, amine or ester; the alcohol is one or more of alkyl alcohol with 1-10 carbon atoms, cycloalkanol with 1-10 carbon atoms, aryl alcohol or aryl alkanol with 6-20 carbon atoms and halogenated substances of the alcohol; the magnesium compound is calculated by magnesium, and the molar ratio of the magnesium compound to the solvent is 1: 1 to 10.
The preparation method of the titanium catalyst component for ethylene polymerization according to the present invention, wherein the titanium compound is Ti (OR)aXbWherein R is an aliphatic hydrocarbon group having 1 to 10 carbons or an aryl group having 6 to 10 carbons, X is a halogen, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b is 3 or 4; the magnesium compound is magnesium, the titanium compound is titanium, and the molar ratio of the magnesium compound to the titanium compound is 1.0-15.0: 1.
the preparation method of the titanium catalyst component for ethylene polymerization, provided by the invention, comprises the following steps of (1) preparing an organoboron compound, wherein the organoboron compound is tris (hexafluoroisopropyl) borate and/or tris (2,2, 2-trifluoroethyl) borate; the magnesium compound is calculated by magnesium, the organoboron compound is calculated by boron, and the molar ratio of the organoboron compound to the magnesium compound is 0.20-0.25: 1.
the preparation method of the titanium catalyst component for ethylene polymerization, provided by the invention, comprises the following steps of (1) adding a diluent in the process of forming the microemulsion, wherein the diluent is a hydrocarbon solvent; the magnesium compound is calculated by magnesium, and the molar ratio of the diluent to the magnesium compound is 0.1-10.0: 1.
the preparation method of the titanium catalyst component for ethylene polymerization comprises the step of preparing a titanium catalyst component for ethylene polymerization, wherein the hydrocarbon solvent comprises one or more of aliphatic hydrocarbon, aromatic hydrocarbon and halogenated hydrocarbon.
The preparation method of the titanium catalyst component for ethylene polymerization, provided by the invention, comprises the following steps of mixing the magnesium compound and a solvent at a temperature of 50-150 ℃; the temperature of the contact reaction of the microemulsion and the titanium compound is 50-120 ℃.
In order to achieve the above objects, the present invention also provides a titanium catalyst component for ethylene polymerization, which is obtained by the above method for preparing a titanium catalyst component for ethylene polymerization.
In order to achieve the above objects, the present invention further provides a method for homopolymerizing or copolymerizing ethylene, comprising using the above titanium catalyst component for polymerizing ethylene.
The invention has the technical effects that:
the invention provides a titanium catalyst component for ethylene polymerization, which is added with an organic boron compound which has no active hydrogen and contains strong electron-withdrawing groups in the preparation process, plays the roles of a precipitator and a precipitation aid, improves the particle morphology of the catalyst, and further improves the particle morphology of a polymer prepared by the catalyst. In addition, the strong electron-withdrawing group in the boron compound influences the electron cloud density around the titanium active center, so that the titanium active center shows very good hydrogen regulation response capability. Therefore, when the titanium catalyst component obtained by the method is used for ethylene polymerization, the titanium catalyst component shows better hydrogen regulation sensitivity, and the by-product polyethylene wax obtained is further less.
The titanium catalyst component of the invention is very suitable for ethylene slurry polymerization process, especially for the process of producing polyethylene with wide relative molecular mass distribution by connecting two reactors in series. Since the magnesium compound is in a micro-emulsion state during the preparation of the catalyst component, spherical catalyst particles are easily precipitated during the preparation of the catalyst component. And in the process of carrying titanium, a large amount of titanium tetrachloride is not needed to promote the precipitation, and the precipitation is not needed to be treated by using the titanium tetrachloride for multiple times, so that the addition amount of the titanium tetrachloride is greatly reduced.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The invention provides a preparation method of a titanium catalyst component for ethylene polymerization, which comprises the following steps:
step 1, mixing a magnesium compound with a solvent to form a microemulsion;
step 2, carrying out contact reaction on the microemulsion of the step 1 and a titanium compound to form a titanium catalyst component;
wherein, the preparation method also adds an organic boron compound, and the adding step is during or after the mixing of the magnesium compound and the solvent, or during the contact reaction process of the microemulsion of the step 1 and the titanium compound; the organoboron compound is free of active hydrogen and contains a strong electron-withdrawing group.
In the preparation process of the titanium catalyst component, an organic boron compound which has no active hydrogen and contains strong electron-withdrawing groups is added, and the strong electron-withdrawing groups in the boron compound influence the electron cloud density around the titanium active center, so that the titanium active center shows very good hydrogen regulation response capability; in addition, the boron compound plays a role of a precipitator and a precipitation aid, improves the particle morphology of the catalyst, and further improves the particle morphology of the polymer prepared by the catalyst. Therefore, when the titanium catalyst component obtained by the method is used for ethylene polymerization, the titanium catalyst component shows better hydrogen regulation sensitivity, and the by-product polyethylene wax obtained is further less.
Organoboron compounds
In one embodiment, the organoboron compounds of the invention have strong electron-withdrawing groups such as tertiary amine cations (-NR)3) Trihalomethyl (-CX)3) X ═ F, Cl, hydroxyl, ester, aminoacyl; in another embodiment, the organoboron compound of the present invention is tris (hexafluoroisopropyl) borate and/or tris (2,2, 2-trifluoroethyl) borate. In yet another embodiment, the magnesium compound is magnesium, the organoboron compound is boron, and the molar ratio of organoboron compound to magnesium compound is from 0.20 to 0.25: 1.
magnesium compound
In preparing the titanium catalyst component of the present invention, a microemulsion formed of a magnesium compound is used. If the magnesium compound is in the solid state, it should be converted to a microemulsion prior to use. The magnesium compound is an organomagnesium compound represented by the following formula: xnMgR2-n. Wherein n is a number of 0 or more and 2 or less; r is alkyl, aryl, cycloalkyl or alkoxy of 1-20 carbon atoms. When n is 0, the two R's may be the same or different, and are, for example, dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, octylbutylmagnesium and ethylbutylmagnesium. Alkyl magnesium halideCompounds such as monochloromoethylmagnesium, monochloropropylmethylmagnesium, monochlorobutylmethylmagnesium, monochloropentylmagnesium and monochlorohexylmagnesium; alkylmagnesium alkoxides such as butylethoxymagnesium, ethylbutoxymagnesium, and octylbutoxymagnesium; r may also be hydrogen, such as monobutyl magnesium hydride; magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxymagnesium halides such as chloromethoxymagnesium, monochlorooxymagnesium, monochloroisopropoxylmagnesium, chlorochlorochlorobutoxymagnesium and chlorooctyloxymagnesium; aryloxymagnesium halides, such as monochlorooxymagnesium, monochloromethylphenoxymagnesium; magnesium alkoxides such as magnesium ethoxide, magnesium isopropoxide, magnesium butoxide, magnesium n-octoxide and magnesium 2-ethylhexoxide; aryloxy magnesium such as phenoxymagnesium, bis (methylphenoxy) magnesium; magnesium carboxylates, such as magnesium laurate and magnesium stearate; magnesium metal and magnesium hydride. X is halogen, such as F, Cl, Br and I. Among the above compounds, preferred are halogen-containing magnesium compounds. Among them, magnesium chloride, monochloroalkoxymagnesium and monochloro aryloxymagnesium are preferable.
When the magnesium compound is in a solid state, the solid magnesium compound can be converted into a liquid state by using one or more solvents. The solvents include alcohols, phenols, carboxylic acids, aldehydes, amines, esters and metal acid esters. Examples of alcohols include: aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol, octadecanol, undecanol, oleyl alcohol and ethylene glycol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α -methylbenzyl alcohol, α' -dimethylbenzyl alcohol, phenethyl alcohol, cumyl alcohol, phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, and naphthol; alkoxy-containing alcohols such as ethylene glycol-n-butyl ether, ethylene glycol-ethyl ether, 1-butoxy-2-propanol; halogen-containing alcohols, such as trichloromethanol, trichloroethanol and trichlorohexanol. The carboxylic acid is preferably a carboxylic acid having seven or more carbon atoms, such as octanoic acid, 2-ethylhexanoic acid, nonanoic acid and undecylenic acid. The aldehydes are preferably those having seven or more carbon atoms, such as octanal, 2-ethylhexanal, undecanal, benzaldehyde, tolualdehyde and naphthaldehyde. The amine is preferably an amine having six or more carbon atoms, such as heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, and dodecylamine. Examples of the metal acid ester include: tetraethoxy titanium, tetra-n-propoxy titanium, tetra-isopropoxy titanium, tetrabutoxy titanium, tetrahexoxy titanium, tetrabutoxy zirconium and tetraethoxy zirconium. Among them, preferred are alcohols, and most preferred are alcohols having six or more carbon atoms. When an alcohol having six or more carbon atoms is used as a solvent for preparing the liquid magnesium compound, the alcohol/magnesium molar ratio (magnesium compound as magnesium) is usually not less than 1, preferably 1 to 40, more preferably 1.0 to 10. If an alcohol having five or less carbon atoms is used, the alcohol/magnesium molar ratio is usually not less than 1.
When the solid magnesium compound is contacted with an alcohol, a diluent may be used, and in one embodiment, the diluent is a hydrocarbon solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and cyclooctane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and cymene; halogenated hydrocarbons such as carbon tetrachloride, dichloroethane, dichloropropane, trichloroethylene, chlorobenzene and the like. If an aromatic hydrocarbon is used in these solvents, the solvent alcohol is used in the same amount as in the case of using the alcohol having six or more carbon atoms as described above, and the magnesium compound is soluble regardless of the alcohol having any carbon atom. When an aliphatic hydrocarbon and/or alicyclic hydrocarbon is used, the amount of the alcohol to be used is different depending on the number of carbon atoms as mentioned above. In the present invention, it is preferable to contact the solid magnesium compound with an alcohol in a hydrocarbon solvent. In order to dissolve the solid magnesium compound in the alcohol, the solid magnesium compound is generally reacted with the alcohol under heating and stirring, and the reaction is preferably carried out in the presence of a hydrocarbon solvent. Typically, the contacting is carried out at a temperature of from 0 to 300 deg.C, preferably from 20 to 180 deg.C, more preferably from 50 to 150 deg.C, for a period of time of from about 15 minutes to about 5 hours, more preferably from about 30 minutes to about 3 hours.
In one embodiment, the magnesium compound is magnesium, and the molar ratio of the diluent to the magnesium compound is 0.1-10.0: 1.
titanium compound
The titanium compound in the present invention is preferably a tetravalent titanium compound. The tetravalent titanium compound can be represented by the following general formula: ti (OR)aXb. Wherein R is C1～C10X is halogen, a is an integer from 0 to 3, b is an integer from 1 to 4, and a + b is 3 or 4. Typical titanium compounds include: titanium tetrahalides, e.g. TiCl4、TiBr4、TiI4；
In one embodiment, the magnesium compound is magnesium, the titanium compound is titanium, and the molar ratio of the magnesium compound to the titanium compound is 1.0-15.0: 1.
preparation of the titanium catalyst component
The titanium catalyst component of the present invention can be prepared by the following method:
(1) preparation of a microemulsion of a magnesium Compound
Dissolving a magnesium compound in a solvent system, preferably adding an inert diluent into the solvent system to form uniform microemulsion, wherein the dissolving temperature is preferably 50-150 ℃; adding an organoboron compound which has no active hydrogen and contains strong electron-withdrawing groups during or after the formation of the microemulsion.
(2) Preparation of the titanium catalyst component
And (2) carrying out contact reaction on the microemulsion and a titanium compound, adding an organic boron compound which has no active hydrogen and contains a strong electron-withdrawing group during the contact reaction of the microemulsion and the titanium compound in the step (1), slowly heating the mixture to 50-120 ℃, gradually separating out a solid and forming particles, removing unreacted substances and a solvent after reacting for a certain time, and washing by adopting an inert diluent to obtain the titanium catalyst component.
The titanium catalyst component of the present invention is generally associated with the general formula AlRnX3-nThe organic aluminum compound is combined into a catalyst for ethylene polymerization, wherein R can be a hydrocarbon group with the carbon number of l-20, in particular alkyl, aralkyl and aryl; x is halogen, in particular chlorine and bromine; n is more than or equal to 0 and less than or equal to 3. Specific compounds are as follows: trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, monochlorodiethylAlkylaluminum halides such as alkylaluminum, chlorodiisobutylaluminum, ethylaluminum sesquichloride and ethylaluminum dichloride, among which trialkylaluminum compounds are preferred, and triethylaluminum and triisobutylaluminum are particularly preferred. Wherein the molar ratio of the component aluminum to the component titanium is 5-500, preferably 20-200.
The catalyst of the present invention is suitable for homopolymerization of ethylene and copolymerization of ethylene and other alpha-olefin, and the polymerization mode can adopt a slurry method, a gas phase method, a solution method, etc., wherein the slurry method is the best. As the above-mentioned alpha-olefin, propylene, butene, pentene, hexene, octene, 4-methylpentene-1 and the like can be used. The slurry polymerization medium comprises: and inert solvents such as saturated aliphatic hydrocarbons and aromatic hydrocarbons such as propane, isobutane, hexane, heptane, cyclohexane, naphtha, raffinate, hydrogenated gasoline, kerosene, benzene, toluene, and xylene.
The polymerization may be carried out in a batch, semi-continuous or continuous manner. The polymerization temperature is preferably from 0 to 150 ℃ and more preferably from 40 to 100 ℃. In order to adjust the molecular weight of the final polymer, hydrogen was used as a molecular weight regulator.
The invention provides a preparation method of a titanium catalyst component, wherein a microemulsion system of magnesium chloride is formed through the interaction of a diluent and a solvent in the dissolving process of the magnesium chloride, an organic boron compound which has no active hydrogen and contains a strong electron-withdrawing group is added in the preparation process, and then a precipitation method is adopted to prepare the sphere-like ethylene polymerization solid titanium Ziegler-Natta catalyst, so that the defects of the prior art are overcome, and the Ziegler-Natta catalyst which has good hydrogen regulation sensitivity and is very suitable for ethylene slurry polymerization and especially suitable for producing a polymer with bimodal relative molecular mass distribution by a double-reactor series process is provided. Compared with the existing catalyst, the catalyst has the advantages of spherical catalyst particles, narrow particle size distribution, less fine powder, good hydrogen regulation sensitivity, capability of more effectively regulating the molecular weight and molecular weight distribution of the polymer and low wax content of the byproduct in the obtained polyethylene product. And the production process is simple and the production cost is low.
The present invention is further described below with reference to examples, but the scope of the present invention is not limited by these examples.
Example 1
(1) Preparation of catalyst component: 4.76 g (50mmol) of anhydrous magnesium chloride, 75 ml of decane and 16.3 g (125mmol) of isooctyl alcohol are heated to 130 ℃ under the protection of nitrogen, and stirred for reaction for 3 hours to obtain a microemulsion of a homogeneous magnesium compound. To the microemulsion was added 12.5mmol of tris (hexafluoroisopropyl) borate and stirred at 50 ℃ for 2 hours to dissolve it in the microemulsion. The microemulsion obtained above was cooled to room temperature, and then added dropwise to 150mL of titanium tetrachloride maintained at 0 ℃ over 1 hour with stirring. After the completion of the dropping, the temperature of the mixture was maintained at 0 ℃ for 1 hour, and then the temperature was raised to 120 ℃ over 2 hours under stirring, and the temperature was maintained for 2 hours. After the reaction was completed for 2 hours, the resultant solid was separated by hot filtration. And fully washing the solid catalyst with decane and hexane respectively until no precipitated titanium compound is detected in the cleaning solution, and drying to obtain the solid titanium catalyst component. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1.
(2) Ethylene polymerization
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of triethylaluminum with the concentration of 1mol/L are added, accurately weighed catalyst components are added by an injector, the temperature is raised to 70 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure), the mixture is polymerized for 2 hours at the temperature of 80 ℃, the polymerization activity, the polymer bulk density and the particle size distribution result are shown in a table 2, and the catalyst hydrogen regulation performance is shown in a table 3.
Example 2
(1) Preparation of catalyst component: 4.76 g (50mmol) of anhydrous magnesium chloride, 75 ml of decane and 16.3 g (125mmol) of isooctyl alcohol were heated to 130 ℃ and reacted for 3 hours to obtain a microemulsion of a magnesium compound. The microemulsion of the magnesium compound obtained above was cooled to room temperature, and then added dropwise to 150mL of titanium tetrachloride maintained at 0 ℃ over 1 hour with stirring. After completion of the dropping, the mixture was kept at 0 ℃ for 1 hour, and then 12.5mmol of tris (hexafluoroisopropyl) borate was added to the solution and kept for 1 hour to dissolve the tris (hexafluoroisopropyl) borate in the system. The temperature was then raised to 120 ℃ over 2 hours with stirring and maintained at this temperature for 2 hours. After the reaction was completed for 2 hours, the resultant solid was separated by hot filtration. And (3) fully washing the solid catalyst with hexane and decane respectively until no precipitated titanium compound is detected in the cleaning solution, and drying to obtain the solid titanium catalyst component. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1.
(2) Ethylene polymerization
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity nitrogen, 1L of hexane and 1.0mL of triethylaluminum with the concentration of 1mol/L are added, the prepared catalyst components are accurately weighed by an injector, the temperature is raised to 75 ℃, hydrogen is introduced to ensure that the pressure in the kettle reaches 0.28MPa, ethylene is introduced to ensure that the total pressure in the kettle reaches 0.73MPa (gauge pressure), the polymerization is carried out for 2 hours at the temperature of 80 ℃, the polymerization activity, the polymer bulk density and the particle size distribution result are shown in a table 2, and the catalyst hydrogen regulation performance is shown in a table 3.
Example 3
The same as in example 1 except that 25.0mmol of tris (hexafluoroisopropyl) borate was added. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 4
The same as in example 1, except that the organoboron compound was tris (2,2, 2-trifluoroethyl) borate, and the amount added was 12.5 mmol. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 5
The same as in example 2, except that the organoboron compound was tris (2,2, 2-trifluoroethyl) borate, and the amount added was 12.5 mmol. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the bulk density of the polymer and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 6
The same as in example 1 except that the magnesium compound added was monochloroalkoxymagnesium. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 7
The same as in example 1 except that the magnesium compound added was a monochloro aryloxymagnesium. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 8
The same as in example 1 except that the isooctanol added was changed to octanoic acid. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 9
The same as in example 1 except that the isooctanol added was changed to benzaldehyde. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance is shown in Table 3.
Example 10
The same as in example 1 except that the isooctyl alcohol added was changed to 2-ethylhexylamine. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 11
The same as example 4, except that ethylene was changed to a mixed gas of ethylene and butene-1 in the polymerization of ethylene, the butene-1 content by mole was 3%. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Example 12
The same as example 1 except that 20ml of hexene was added at the time of ethylene polymerization. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance is shown in Table 3.
Comparative example 1
The same as in example 1. Except that no organoboron compound was added, the particle size distribution and the results of the radial distance analysis of the catalyst are shown in Table 1, the ethylene polymerization was evaluated by the same methods as in example 1, the polymerization activity, the bulk density of the polymer and the results of the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Comparative example 2
The catalyst synthesis was carried out as described in example 1 of CN 1229092A.
0.042mol of anhydrous MgCl is added into a reactor fully replaced by high-purity nitrogen in sequence2(about 4g), 60mL of toluene, 0.032mol of epoxy chloropropane, 0.022mol of tributyl phosphate and 0.017mol of ethanol are stirred and heated to 80 ℃ for 15 minutes to completely dissolve the solid to form a uniform solution, 0.0074mol of phthalic anhydride is added to the uniform solution for 1 hour, the solution is cooled to-25 ℃, 0.5mol of titanium tetrachloride (about 55mL) is dripped into the solution, the temperature is slowly raised to 80 ℃, the reaction is carried out for 3 hours, the solution is filtered and washed with toluene and hexane for 3 times respectively, and the solid catalyst is obtained after vacuum drying.
The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, the ethylene polymerization evaluation is as in example 1, the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
Comparative example 3
The catalyst synthesis was carried out as described in the example of JP 4951378.
Commercial anhydrous MgCl was added to a reactor fully purged with high purity nitrogen210 mol of the suspension was suspended in 10L of hexane, and 60mol of ethanol was added dropwise thereto at room temperature, followed by stirring for 30 minutes. Dropping 31mol of diethyl aluminum chloride while maintaining the temperature of the system not to exceed 40 ℃, stirring for 30 minutes, and adding 5mol of TiCl4The reaction was stirred at 60 ℃ for 6 hours. Filtering and washing with hexane to obtain the solid catalyst.
The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1. The ethylene polymerization was evaluated as in example 1, and the polymerization activity, the polymer bulk density and the particle size distribution were as shown in Table 2, and the hydrogen control performance of the catalyst was as shown in Table 3.
Comparative example 4
The same as in example 1. Except that the organoboron compound was boron trifluoride, the results of particle size distribution and diameter distance analysis of the catalyst are shown in Table 1, the evaluation methods of ethylene polymerization are as in example 1, the results of polymerization activity, bulk density of the polymer and particle size distribution are shown in Table 2, and the hydrogen control performance of the catalyst is shown in Table 3.
TABLE 1 particle size distribution and radial distances of the catalysts
TABLE 2 polymerization Activity, Polymer bulk Density and particle size distribution results
TABLE 3 comparison of catalyst Hydrogen Condition Performance
*Data representing a melt flow rate of 2.16kg there.
As shown in tables 2 and 3, when the catalyst component obtained in the embodiment of the present invention is used for ethylene polymerization, the catalyst component has good hydrogen regulation performance, and the obtained polymer has low wax content and high melt flow index.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (11)
1. A method for preparing a titanium catalyst component for ethylene polymerization, comprising the steps of:
step 1, mixing a magnesium compound with a solvent to form a microemulsion;
step 2, carrying out contact reaction on the microemulsion of the step 1 and a titanium compound to form a titanium catalyst component;
wherein, the preparation method also adds an organic boron compound, and the adding step is during or after the mixing of the magnesium compound and the solvent, or during the contact reaction process of the microemulsion of the step 1 and the titanium compound; the organoboron compound has no active hydrogen and contains a strong electron-withdrawing group.
2. The method of preparing the titanium catalyst component for ethylene polymerization according to claim 1, wherein the magnesium compound is magnesium, the titanium compound is titanium, and the molar ratio of the magnesium compound to the titanium compound is 1.0 to 15.0: 1.
3. the method for preparing the titanium catalyst component for ethylene polymerization according to claim 1, wherein the magnesium compound is XnMgR2-nWherein n is 0 or more and 2 or less; r is alkyl, aryl, cycloalkyl, alkoxy or aryloxy of 1-20 carbon atoms; when n is 0, the two R are the same or different; x is halogen.
4. The method for preparing a titanium catalyst component for ethylene polymerization according to claim 1, wherein the solvent in the step 1 is alcohol, phenol, carboxylic acid, aldehyde, amine or ester; the alcohol is one or more of alkyl alcohol with 1-10 carbon atoms, cycloalkanol with 1-10 carbon atoms, aryl alcohol or aryl alkanol with 6-20 carbon atoms and halogenated substances of the alcohol; the magnesium compound is calculated by magnesium, and the molar ratio of the magnesium compound to the solvent is 1: 1 to 10.
5. The method of preparing the titanium catalyst component for ethylene polymerization according to claim 1, wherein the titanium compoundIs Ti (OR)aXbWherein R is an aliphatic hydrocarbon group having 1 to 10 carbons or an aryl group having 6 to 10 carbons, X is a halogen, a is an integer of 0 to 3, b is an integer of 1 to 4, and a + b is 3 or 4; the magnesium compound is magnesium, the titanium compound is titanium, and the molar ratio of the magnesium compound to the titanium compound is 1.0-15.0: 1.
6. the method for preparing a titanium catalyst component for ethylene polymerization according to claim 1, wherein the organoboron compound is tris (hexafluoroisopropyl) borate and/or tris (2,2, 2-trifluoroethyl) borate; the magnesium compound is calculated by magnesium, the organoboron compound is calculated by boron, and the molar ratio of the organoboron compound to the magnesium compound is 0.20-0.25: 1.
7. the method for preparing a titanium catalyst component for ethylene polymerization according to claim 1, wherein a diluent is further added during the formation of the micro-emulsion in the step 1, wherein the diluent is a hydrocarbon solvent; the magnesium compound is calculated by magnesium, and the molar ratio of the diluent to the magnesium compound is 0.1-10.0: 1.
8. the method for preparing titanium catalyst component for ethylene polymerization according to claim 7, wherein the hydrocarbon solvent comprises one or more of aliphatic hydrocarbon, aromatic hydrocarbon, and halogenated hydrocarbon.
9. The method for preparing a titanium catalyst component for ethylene polymerization according to claim 1, wherein the mixing temperature of the magnesium compound and the solvent is 50 to 150 ℃; the temperature of the contact reaction of the microemulsion and the titanium compound is 50-120 ℃.
10. A titanium catalyst component for ethylene polymerization, characterized in that it is obtained by the process for preparing a titanium catalyst component for ethylene polymerization according to any one of claims 1 to 9.
11. A process for homo-or co-polymerization of ethylene, comprising using the titanium catalyst component for ethylene polymerization according to claim 10.
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| CN114573739A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Solid titanium catalyst |
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| US5141910A (en) * | 1990-10-18 | 1992-08-25 | Shell Oil Company | Olefin polymerization catalyst |
| CN101245115A (en) * | 2008-04-07 | 2008-08-20 | 郭琦 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
| CN102272172A (en) * | 2008-04-07 | 2011-12-07 | 南方化学股份公司 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141910A (en) * | 1990-10-18 | 1992-08-25 | Shell Oil Company | Olefin polymerization catalyst |
| CN101245115A (en) * | 2008-04-07 | 2008-08-20 | 郭琦 | Homopolymerization and combined polymerization catalyst of ethylene and preparation method thereof |
| CN102272172A (en) * | 2008-04-07 | 2011-12-07 | 南方化学股份公司 | Method for preparing a titanium catalyst component, titanium catalyst component, method for preparing a titanium catalyst and titanium catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573739A (en) * | 2020-12-02 | 2022-06-03 | 中国石油天然气股份有限公司 | Solid titanium catalyst |
| CN114573739B (en) * | 2020-12-02 | 2023-12-22 | 中国石油天然气股份有限公司 | solid titanium catalyst |
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