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CN114573739B - solid titanium catalyst - Google Patents

solid titanium catalyst Download PDF

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CN114573739B
CN114573739B CN202011402074.XA CN202011402074A CN114573739B CN 114573739 B CN114573739 B CN 114573739B CN 202011402074 A CN202011402074 A CN 202011402074A CN 114573739 B CN114573739 B CN 114573739B
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magnesium
catalyst
component
alcohol
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CN114573739A (en
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王立娟
姜涛
王文燕
张瑞
孙彬彬
王�华
杨琦
牛娜
杨国兴
翟昌休
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Petrochina Co Ltd
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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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/65—Pretreating the metal or compound covered by group C08F4/64 before the final contacting with the metal or compound covered by group C08F4/44
    • C08F4/652—Pretreating with metals or metal-containing compounds
    • C08F4/657—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in groups C08F4/653 - C08F4/656
    • C08F4/6574—Pretreating with metals or metal-containing compounds with metals or metal-containing compounds, not provided for in groups C08F4/653 - C08F4/656 and magnesium or compounds thereof
    • 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
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/646—Catalysts comprising at least two different metals, in metallic form or as compounds thereof, in addition to the component covered by group C08F4/64
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention relates to a solid titanium catalyst which is prepared by adopting a microemulsion precipitation method, and is applied to ethylene polymerization. The diluent added in the dissolving process of the magnesium compound forms microemulsion of the magnesium compound with benign solvent, the microemulsion of the magnesium compound interacts with the organoboron compound without active hydrogen and then contacts with the liquid titanium compound to separate out solid catalyst components; the catalyst has the characteristics of simple preparation process, spherical catalyst particles and narrow particle size distribution, is used for producing ethylene polymers, has the characteristics of high activity, good hydrogen regulation sensitivity, good polymer particle morphology and less fine powder, is very suitable for ethylene slurry polymerization processes, and is especially suitable for producing polyethylene resins with wide relative molecular mass distribution by adopting double reactors.

Description

Solid titanium catalyst
Technical Field
The invention relates to a solid titanium catalyst, in particular to a preparation method of a solid titanium Ziegler-Natta catalyst component for ethylene homo-polymerization or ethylene and other alpha-olefin copolymerization, and an application of the solid catalyst component and an ethylene polymerization catalyst composed of an organic metal compound in ethylene homo-polymerization or ethylene and other alpha-olefin copolymerization.
Background
The preparation of high-efficiency Ziegler-Natta catalysts for the polymerization of ethylene is well known and consists essentially of MgCl 2 Or SiO 2 Titanium-loaded halide composition. The preparation method of the ethylene polymerization and copolymerization catalyst as disclosed in JP4951378 is: reacting ground magnesium dichloride with ethanol to generate MgCl 2 ·6C 2 H 5 The OH alcohol compound slurry is esterified with diethyl aluminum chloride and finally with TiCl 4 Carrying out titanium-carrying reaction to obtain MgCl 2 A titanium catalyst supported on a carrier. The catalyst has the advantages of simple preparation method, mild reaction conditions and high activity in catalyzing ethylene polymerization. However, the preparation method has the advantages that the carrier magnesium chloride is only swelled in mineral oil and can not be dissolved, and the magnesium chloride is in an irregular flaky particle generated during original grinding and crushing in a slurry reaction system, so that the obtained solid catalyst has poor particle form, lower bulk density and uneven thickness, and therefore, the polymer has poor form, more fine powder, is easy to generate static electricity and is easy to block a pipeline. Meanwhile, the catalyst brings great trouble in post-treatment because of more oligomer content in the solvent during polymerization.
Patent CN1229092 discloses a catalyst system for the polymerization and copolymerization of ethylene, comprising: (1) a Ti-containing solid catalyst component; (2) an alkylaluminum compound; wherein the Ti-containing solid catalyst component is prepared by dissolving magnesium halide in organic epoxy compound and organic phosphorus compound to form homogeneous solution, adding ethanol to treat the dissolved magnesium halide, mixing the solution with titanium tetrahalide, and precipitating solid in the presence of precipitant such as organic anhydride, organic acid, ether, ketone, etc. to obtain solid catalyst. When the catalyst system is used for ethylene polymerization, the obtained polymer has more fine powder content, lower 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.
Patent CN1112373 discloses a solid titanium catalyst component and a preparation process thereof, wherein low carbon alcohol is mainly used for dissolving magnesium halide, alkane diluent and silane electron donor compound are added, and then the mixture reacts with titanium halide to precipitate a solid catalyst. Although the catalyst can produce an ethylene polymer having excellent particle properties when used for ethylene polymerization, it has problems of long induction time, large fluctuation in catalytic activity and low oligomer content when used for ethylene polymerization.
In order to improve the problems of the above-mentioned technology, patent CN1180712 and CN1752116a disclose 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 an alcohol polymer slurry, so that magnesium halide and alcohol can form a swollen alcohol polymer slurry in a diluent at a lower temperature without dissolving magnesium halide at a high temperature to form a solution, a catalyst having a particle morphology can be obtained, and the amount of alcohol used is reduced when the alcohol polymer slurry is formed, so that the preparation process of the catalyst is simple, easy to operate, and the cost is reduced. However, when the catalyst is used for ethylene polymerization, the disadvantages of insensitive hydrogen regulation, poor polymer particle morphology and high amount of fine powder still exist, so that the catalyst is unfavorable for producing polymers with wide molecular weight distribution.
Patent CN101245115A, CN102272172A, CN1112373a and the like disclose a solid titanium catalyst component and a preparation process thereof, wherein a low carbon alcohol is mainly used for dissolving magnesium halide, an alkane diluent and a silane electron donor compound or an organoboron compound are added, and then the mixture reacts with titanium halide to precipitate a solid catalyst. Although the catalyst shows higher catalytic activity when used for ethylene polymerization and produces ethylene polymers with excellent particle properties, the hydrogen regulation performance and oligomer content of the catalyst are still not satisfactory. Patent CN1471541a discloses a process 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 then reacting with a mixture of a titanium compound and a haloalkane compound to produce a solid catalyst by recrystallization. The catalyst has the advantages of high catalytic activity, high polymer bulk density, narrow particle size distribution and the like, but the hydrogen regulation performance and the oligomer content of the catalyst are not satisfactory.
In the preparation method of the Ziegler-Natta catalyst for ethylene polymerization, researchers can regulate the particle size, morphology and distribution of the catalyst through an emulsification technology, and regulate the activity of the catalyst through the components of the catalyst and the electron donor compound. However, control of the hydrogen sensitivity of the catalyst and the amount of oligomer produced has been a problem, which is very important for the production of polyethylene products having a bimodal distribution.
Disclosure of Invention
The invention aims to add a multifunctional borate compound as a modifier in the dissolution process of magnesium chloride to enable the borate compound to interact with a diluent and a solvent to form a magnesium chloride microemulsion system, and then prepare a spheroidal ethylene polymerization solid titanium Ziegler-Natta catalyst by adopting a precipitation method, thereby overcoming the defects of the prior art and providing the Ziegler-Natta catalyst which is very suitable for ethylene slurry polymerization, in particular for producing polymers with wide relative molecular mass distribution. Compared with the existing catalyst, the catalyst has the advantages of spheroid catalyst particles, narrow particle size distribution, less fine powder, good hydrogen regulation sensitivity and good copolymerization performance, and can more effectively regulate the molecular weight and molecular weight distribution of the polymer. And the production process is simple and the production cost is low.
In order to achieve the above object, the present invention provides a solid titanium catalyst for ethylene polymerization or copolymerization, comprising the following components:
component A and component B; the component A is a titanium-containing solid catalyst component; component B is an organic aluminum compound with a general formula of AlR n X 3-n Wherein R is alkyl, X is halogen, n is more than or equal to 0 and less than or equal to 3, and is an integer; the proportion of the component B to the component A is 10-200 based on the molar ratio of aluminum to titanium; wherein the method comprises the steps ofThe component A is prepared by adopting a method of micro-emulsion precipitation, and comprises the following steps: and (3) the microemulsion of the magnesium compound is interacted with an organic boron compound without active hydrogen, and the interacted product is contacted with a liquid titanium compound to precipitate out to obtain the component A.
The microemulsion of the magnesium compound of the present invention is a microemulsion formed by a magnesium halide-organic alcohol compound-diluent dissolution system.
The method of the present invention uses 0.1 to 10.0 mol of the organic alcohol compound, 0.20 to 0.25 mol of the organic boron compound, and 0.1 to 10.0 mol of the diluent per mol of the magnesium halide in the magnesium compound.
The titanium compound of the invention has the general formula of Ti (OR) a X b Wherein R is C 1 ～C 10 X is halogen, a is an integer from 1 to 3, b is an integer from 1 to 4, a+b=3 or 4.
The molar ratio of the magnesium compound to the titanium compound is 1.0-15.0.
The organic boron compound without active hydrogen is triethylene glycol methyl ether boric acid triester.
The magnesium compound of the present invention is at least one of magnesium dihalide and a derivative in which one halogen atom of magnesium dihalide is substituted with a hydrocarbon group or a hydrocarbon oxy group.
The organic alcohol compound of the present invention is a linear or branched alkyl alcohol having 1 to 10 carbon atoms, a cycloalkanol, an aralkyl alcohol having 6 to 20 carbon atoms or an aralkanol, or a halogenated product of the above organic alcohol; the alcohol is at least one of methanol, ethanol, propanol, isopropanol, butanol, amyl alcohol, hexanol, 2-methyl amyl alcohol, 2-ethyl butanol, heptanol, 2-ethyl hexanol, octanol and decanol.
The molar ratio of the organic alcohol compound to the magnesium compound of the present invention is 1 to 10, preferably 3 to 4.
The organoaluminum compound of the present invention is at least one of triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and ethylaluminum sesquioxide.
The invention can be further described as follows: the solid titanium Ziegler-Natta catalyst component for ethylene polymerization or copolymerization consists of:
A. a titanium-containing solid catalyst component prepared by the reaction of:
(a) A microemulsion of a magnesium compound;
(b) An organoboron compound free of active hydrogen;
(c) A titanium compound;
the component A of the invention is prepared by adopting a method of micro-emulsion precipitation, and specifically comprises the following steps:
(1) The titanium-containing solid catalyst component is formed by the interaction of a magnesium compound microemulsion and an organic boron compound without active hydrogen, and the products of the magnesium compound microemulsion and the organic boron compound are contacted with a liquid titanium compound to separate out the solid catalyst component;
wherein the microemulsion of the magnesium compound is formed by a magnesium halide-organic alcohol-dispersing agent dissolution system;
the ratio between the reactants is calculated by each mole of magnesium halide in the magnesium compound, and the organic alcohol compound is as follows: 0.1 to 10.0 mol, 0.20 to 0.25 mol of organoboron compound and 0.1 to 10.0 mol of diluent.
(2) The general formula of the titanium compound is Ti (OR) a X b Wherein R is a C1 to C10 aliphatic or aryl group, X is halogen, a is 0, 1, 2 or 3, b is an integer from 1 to 4, a+b=3 or 4;
wherein the molar ratio of the magnesium compound to the titanium compound is 1.0-15.0.
The solid titanium catalyst component contains magnesium, titanium, boron and halogen. Each of the ingredients used to prepare the solid titanium catalyst component of the present invention is described below:
(a) Microemulsion of magnesium compound
In preparing the solid titanium catalyst component of the present invention, a microemulsion of a magnesium compound is used. If the magnesium compound is solid, it should be converted to a microemulsion prior to use. The magnesium compound is an organomagnesium compound represented by the following formula: x is X n MgR 2-n . Wherein n is a number of 0 or more and 2 or less; r is an alkyl group of 1 to 20 carbon atoms, an aryl group orCycloalkyl; when n is 0, two R's may be the same or different, such as dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, dipentyl magnesium, dihexyl magnesium, didecyl magnesium, octyl butyl magnesium and ethyl butyl magnesium; alkyl magnesium halides such as ethyl magnesium monochloride, propyl magnesium monochloride, butyl magnesium monochloride, amyl magnesium monochloride, and hexyl magnesium monochloride; alkyl magnesium alkoxides such as butyl ethoxy magnesium, ethyl butoxy magnesium, and octyl butoxy magnesium; and other compounds such as monobutyl magnesium; magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; alkoxy magnesium halides such as methoxy magnesium monochloride, ethoxy magnesium monochloride, isopropoxy magnesium monochloride, butoxy magnesium monochloride and octoxy magnesium monochloride; aryloxy magnesium halides such as magnesium chlorophenoxide and magnesium chloromethylphenoxy; alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexyl magnesium; aryloxy magnesium such as phenoxy magnesium, di (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, magnesium monochloroalkoxide and magnesium monochloroaryloxide are preferable.
When the magnesium compound is in a solid state, the solid magnesium compound may be converted to 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: fatty 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-diethyl 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 metal acid esters include: tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, tetrahexyloxytitanium, tetrabutoxyzirconium and tetraethoxyzirconium. Among them, preferred are alcohols, and most preferred are alcohols having six or more carbon atoms. If an alcohol having six or more carbon atoms is used as the solvent for the liquid magnesium compound, the alcohol/magnesium molar ratio 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 amount thereof is usually not less than 1.
When the solid magnesium compound is contacted with an alcohol, a hydrocarbon solvent may be used. 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 aromatic hydrocarbon is used in these solvents, the amount of alcohol is the same as in the case of using alcohol of six or more carbon atoms as described above, and the magnesium compound is soluble regardless of the number of carbon atoms of the alcohol used. When aliphatic hydrocarbon and/or alicyclic hydrocarbon are used, the amount of alcohol used varies depending on the number of carbon atoms as mentioned above. In the present invention, it is preferable to contact the solid magnesium compound with the alcohol in the hydrocarbon solvent. In order to dissolve the solid magnesium compound in the alcohol, it is generally employed to react the solid magnesium compound with the alcohol under heating and stirring, and the reaction is preferably carried out in the presence of a hydrocarbon solvent, and if necessary, heated. The temperature of such contact is generally from 0 to 300 ℃, preferably from 20 to 180 ℃, more preferably from 50 to 150 ℃, for a period of about 15 minutes to 5 hours, more preferably from about 30 minutes to 3 hours.
(b) Organoboron compounds without active hydrogen
The organoboron compound free of active hydrogen in the catalyst component of the present invention is selected from triethylene glycol methyl ether borate triester.
(c) Liquid titanium compound
The liquid 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) n X 4-n . Wherein R is C 1 ～C 10 X is halogen, n is more than or equal to 0 and less than or equal to 4. Typical titanium compounds include: titanium tetrahalides, e.g. TiCl 4 、TiBr 4 、TiI 4 ；
Preparation of solid titanium catalyst
The catalyst component of the invention can be prepared by the following method:
(1) Preparation of magnesium Compound microemulsion
Dissolving magnesium halide in an alcohol solvent system, adding an inert diluent into a preferable solvent system to form uniform microemulsion, wherein the dissolving temperature is preferably 50-150 ℃; the organoboron compound having no active hydrogen atoms is added during or after the formation of the solution.
(2) Preparation of solid titanium catalyst
The solution and the titanium compound are subjected to contact reaction, and the organoboron compound without active hydrogen atoms can be added when the solution in the step (1) and the titanium compound are subjected to contact reaction, the mixture is slowly heated to 50-120 ℃, solid matters are gradually separated out and form particles, unreacted matters and solvents are removed after a certain period of reaction, and an inert diluent is adopted for washing, so that the catalyst component is obtained.
The catalyst composed of the catalyst component A and the catalyst component B is suitable for homo-polymerization of ethylene and copolymerization of ethylene and other alpha-olefins, and the polymerization mode can adopt a slurry method, a gas phase method, a solution method and the like, 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 catalyst comprises the aboveThe catalyst component of the invention has a general formula of AlR n X 3-n Wherein R may be a hydrocarbon group having from l to 20 carbon atoms, particularly an alkyl group, an aralkyl group, an aryl group; x is halogen, especially chlorine and bromine; n is a number of 0.ltoreq.n.ltoreq.3. Specific compounds are as follows: alkyl aluminum halides such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, diisobutylaluminum chloride, sesquiethylaluminum chloride and ethylaluminum dichloride are preferable, and trialkylaluminum compounds are particularly preferable. Wherein the molar ratio of the component aluminum to the component titanium is 5 to 500, preferably 20 to 200.
The polymerization may be carried out by solution polymerization or slurry polymerization or by gas phase polymerization. The slurry polymerization medium comprises: saturated aliphatic or aromatic hydrocarbon inert solvents such as propane, isobutane, hexane, heptane, cyclohexane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc.
The polymerization may be carried out batchwise, semi-continuously or continuously. The polymerization temperature is 0 to 150℃and preferably 40 to 100 ℃. In order to adjust the molecular weight of the final polymer, hydrogen was used as a molecular weight regulator.
Compared with the prior art, the invention has the following advantages:
the present invention provides a catalyst which is very suitable for ethylene slurry polymerization processes, in particular for the production of polyethylene having a broad relative molecular mass distribution. Since the magnesium compound is brought into a microemulsion state during the catalyst preparation process, spherical catalyst particles are easily precipitated during the catalyst preparation. In addition, a large amount of titanium tetrachloride is not needed to promote the precipitation of the precipitate in the titanium carrying process, and the titanium tetrachloride is not needed to be used for multiple times to treat the precipitate, so that the adding amount of the titanium tetrachloride is greatly reduced. The organoboron compound without active hydrogen not only plays roles of a precipitant and a precipitation aid, but also improves the particle morphology of the catalyst and further improves the particle morphology of the polymer. In addition, the triethylene glycol methyl ether boric acid triester participates in coordination of an active center, so that the chemical environment of the active center titanium is influenced, and the catalyst has better hydrogen regulation sensitivity performance and copolymerization performance.
Detailed Description
The present invention is further described below with reference to examples, to which the scope of the present invention is not limited. The scope of the invention is set forth in the claims.
Example 1
(1) Preparation of the catalyst component: 4.76 g (50 mmol) of anhydrous magnesium chloride, 75 ml of decane and 16.3 g (125 mmol) of isooctanol were heated to 130℃under nitrogen atmosphere and allowed to react with stirring for 3 hours to give a microemulsion of a homogeneous magnesium compound. To the microemulsion was added 2.5mmol of triethylene glycol methyl ether borate triester and stirred at 50℃for 2 hours to dissolve in the solution. The microemulsion obtained above was cooled to room temperature, and then added dropwise to 150mL of titanium tetrachloride maintained at a temperature of 0 ℃ with stirring over 1 hour. After the completion of the dropping, the temperature of the mixture was kept at 0℃for 1 hour, and then the temperature was raised to 120℃for 2 hours under stirring, and this temperature was kept for 2 hours. After completion of the 2-hour reaction, the resulting solid was separated by hot filtration. And (3) fully washing the solid catalyst by decane and hexane respectively until no precipitated titanium compound is detected in the cleaning liquid, and drying to obtain the solid titanium catalyst component. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1.
(2) Ethylene polymerization
After the 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 accurately weighed catalyst is added by a syringe, the temperature is raised to 70 ℃, hydrogen is introduced to enable the pressure in the kettle to reach 0.28MPa, ethylene is introduced to enable the total pressure in the kettle to reach 0.73MPa (gauge pressure), and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2 under the condition of 80 ℃ for polymerization for 2 hours.
Example 2
(1) Preparation of the catalyst component: 4.76 g (50 mmol) of anhydrous magnesium chloride, 75 ml of decane and 16.3 g (125 mmol) of isooctanol 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 a temperature of 0 ℃ with stirring over 1 hour. After the completion of the dropping, the temperature of the mixture was kept at 0℃for 1 hour, and then 2.5mmol of triethylene glycol methyl ether boric acid triester was added to the solution for 1 hour to dissolve tetraethoxysilane in the solution system. The temperature was then raised to 120℃over 2 hours with stirring and maintained at this temperature for 2 hours. After completion of the 2-hour reaction, the resulting solid was separated by hot filtration. And (3) fully washing the solid catalyst by hexane and decane respectively until no precipitated titanium compound is detected in the cleaning liquid, and drying to obtain the solid titanium catalyst component. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1.
(2) Ethylene polymerization
After the 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 is accurately weighed by a syringe, the temperature is raised to 75 ℃, hydrogen is introduced to enable the pressure in the kettle to reach 0.28MPa, ethylene is introduced to enable the total pressure in the kettle to reach 0.73MPa (gauge pressure), and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2 under the condition of 80 ℃ for polymerization for 2 hours.
Example 3
The procedure is as in example 1, except that 5.0mmol of triethylene glycol monomethyl ether borate triester is added. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1, and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2.
Example 4
The same as in example 2 was conducted except that the organoboron compound having no active hydrogen was added in an amount of 5.0mmol as triethylene glycol methyl ether borate triester. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1, and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2.
Example 5
The procedure is as in example 1, except that 10.0mmol of triethylene glycol monomethyl ether borate are added. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1, and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2.
Example 6
The same as in example 1 was found to be different in that ethylene was changed to a mixture of ethylene and butene-1 at the time of ethylene polymerization, and the butene-1 was contained in 3 mol%. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1, and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2.
Example 7
The procedure of example 1 is followed, except that 20ml of hexene are added during the polymerization of ethylene. The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1, and the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2.
Comparative example 1
As in example 1. Except that no organoboron compound having no active hydrogen was added, the particle size distribution and the diameter-distance analysis results of the catalyst were shown in Table 1, and the polymerization activity and the polymer bulk density and the particle size distribution results were shown in Table 2, as in example 1.
Comparative example 2
The catalyst synthesis was prepared as described in example 1 of CN 1229092.
In a reactor fully replaced by high-purity nitrogen, 0.042mol of anhydrous MgCl is added in sequence 2 (about 4 g), 60mL of toluene, 0.032mol of epichlorohydrin, 0.022mol of tributyl phosphate and 0.017mol of ethanol, heating to 80 ℃ with stirring, maintaining the solid to be completely dissolved for 15 minutes to form a uniform solution, then adding 0.0074mol of phthalic anhydride, maintaining the solution for 1 hour, cooling the solution to-25 ℃, adding 0.5mol of titanium tetrachloride (about 55 mL) dropwise into the solution, slowly heating to 80 ℃ for reaction for 3 hours, filtering, washing with toluene and hexane for 3 times respectively, and drying in vacuum to obtain a solid catalyst.
The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1, and the polymerization activity, the polymer bulk density and the particle size distribution result of the ethylene polymerization are shown in Table 2.
Comparative example 3
The synthesis of the catalyst was prepared as described in the examples of JP 4951378.
Filling high-purity nitrogen gasAdding commercial anhydrous MgCl into a reactor with partial replacement 2 10 mol, suspended in 10L of hexane, 60mol of ethanol was added dropwise at room temperature, and stirred for 30 minutes. Dropping 31mol of diethyl aluminum chloride at the temperature of not more than 40 ℃, stirring for 30 minutes, and adding 5mol of TiCl 4 The system was maintained at 60℃and stirred for 6 hours. Filtering and washing with hexane to obtain the solid catalyst.
The particle size distribution and the diameter-distance analysis result of the catalyst are shown in Table 1. The polymerization activity and polymer bulk density and particle size distribution were evaluated as in example 1 and the results are shown in Table 2.
TABLE 1 particle size distribution and diameter spacing of catalysts
TABLE 2 polymerization Activity, polymer bulk Density and particle size distribution results

Claims (7)

1. A solid titanium catalyst for ethylene polymerization or copolymerization, characterized by comprising the following components:
component A and component B; the component A is a titanium-containing solid catalyst component; the component B is an organic aluminum compound with a general formula of AlR n X 3-n Wherein R is alkyl, X is halogen, n is more than or equal to 0 and less than or equal to 3, and is an integer; the proportion of the component B to the component A is 10-200 in terms of aluminum-titanium molar ratio;
the component A is prepared by adopting a method of micro-emulsion precipitation, and comprises the following steps: the microemulsion of the magnesium compound is interacted with an organic boron compound without active hydrogen, and the interacted product is contacted with a liquid titanium compound to be separated out to obtain the component A;
wherein the organic boron compound without active hydrogen is triethylene glycol methyl ether boric acid triester;
the microemulsion of the magnesium compound is formed by a magnesium halide-organic alcohol compound-diluent dissolution system;
the method comprises the steps of using 0.1-10.0 mol of organic alcohol compound, 0.05, 0.10 or 0.20 mol of organic boron compound and 0.1-10.0 mol of diluent per mol of magnesium halide in the magnesium compound.
2. The solid titanium catalyst according to claim 1, wherein the titanium compound has the general formula Ti (OR) a X b Wherein R is C 1 ～C 10 X is halogen, a is an integer from 0 to 3, b is an integer from 1 to 4, a+b=3 or 4.
3. The solid titanium catalyst according to claim 1, wherein the magnesium compound is at least one of magnesium dihalide and a derivative in which one halogen atom of magnesium dihalide is substituted with a hydrocarbon group or a hydrocarbon oxy group.
4. The solid titanium catalyst according to claim 1, wherein the organic alcohol compound is a linear or branched alkyl alcohol having 1 to 10 carbon atoms, a cycloalkanol, an aralkyl alcohol having 6 to 20 carbon atoms or an aralkanol, or a halide of the above organic alcohol.
5. The solid titanium catalyst of claim 4, wherein the alkyl alcohol is at least one of methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, and decanol.
6. The solid titanium catalyst according to claim 1, wherein the molar ratio of the organic alcohol compound to the magnesium compound is 1 to 10.
7. The solid titanium catalyst according to claim 1, wherein the organoaluminum compound is at least one of triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquioxide.
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Citations (6)

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CN1471541A (en) * 2001-06-21 2004-01-28 ������ѧ��ʽ���� Catalysts for polymerization and copolymerization of ethylene
CN101633704A (en) * 2008-07-24 2010-01-27 中国石油化工股份有限公司 Catalyst component used for ethylene polymerization reaction and catalyst 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
CN103130931A (en) * 2011-11-30 2013-06-05 中国石油天然气股份有限公司 Spherical ethylene polymerization solid titanium catalyst, preparation and application thereof
CN104829758A (en) * 2015-05-17 2015-08-12 北京化工大学 Alkene polymerization catalyst as well as preparation method and application thereof
CN114539449A (en) * 2020-11-24 2022-05-27 中国石油天然气股份有限公司 Titanium catalyst component for ethylene polymerization and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1471541A (en) * 2001-06-21 2004-01-28 ������ѧ��ʽ���� Catalysts for polymerization and copolymerization of ethylene
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
CN101633704A (en) * 2008-07-24 2010-01-27 中国石油化工股份有限公司 Catalyst component used for ethylene polymerization reaction and catalyst thereof
CN103130931A (en) * 2011-11-30 2013-06-05 中国石油天然气股份有限公司 Spherical ethylene polymerization solid titanium catalyst, preparation and application thereof
CN104829758A (en) * 2015-05-17 2015-08-12 北京化工大学 Alkene polymerization catalyst as well as preparation method and application thereof
CN114539449A (en) * 2020-11-24 2022-05-27 中国石油天然气股份有限公司 Titanium catalyst component for ethylene polymerization and preparation method and application thereof

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