[go: up one dir, main page]

CN114573739A - Solid titanium catalyst - Google Patents

Solid titanium catalyst Download PDF

Info

Publication number
CN114573739A
CN114573739A CN202011402074.XA CN202011402074A CN114573739A CN 114573739 A CN114573739 A CN 114573739A CN 202011402074 A CN202011402074 A CN 202011402074A CN 114573739 A CN114573739 A CN 114573739A
Authority
CN
China
Prior art keywords
compound
magnesium
alcohol
catalyst
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202011402074.XA
Other languages
Chinese (zh)
Other versions
CN114573739B (en
Inventor
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
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Petrochina Co Ltd
Original Assignee
Petrochina Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petrochina Co Ltd filed Critical Petrochina Co Ltd
Priority to CN202011402074.XA priority Critical patent/CN114573739B/en
Publication of CN114573739A publication Critical patent/CN114573739A/en
Application granted granted Critical
Publication of CN114573739B publication Critical patent/CN114573739B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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 reaction. The diluent added in the dissolving process of the magnesium compound and a benign solvent form a microemulsion of the magnesium compound, the microemulsion of the magnesium compound interacts with an organic boron compound without active hydrogen, and then contacts with a liquid titanium compound to separate out a solid catalyst component; the catalyst has the characteristics of simple preparation process, spherical catalyst particles, narrow particle size distribution, high activity, good hydrogen regulation sensitivity, good polymer particle shape and less fine powder when being used for producing ethylene polymers, is very suitable for an ethylene slurry polymerization process, and is particularly suitable for producing polyethylene resin with wide relative molecular mass distribution by adopting a double reactor.

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 homopolymerization or copolymerization of ethylene and other alpha-olefins, and an application of an ethylene polymerization catalyst consisting of the solid catalyst component and an organic metal compound in ethylene homopolymerization or copolymerization of ethylene and other alpha-olefins.
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 of ethylene polymerization and copolymerization catalysts 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, in the preparation method, the magnesium chloride as a carrier only swells in mineral oil and cannot be dissolved, and irregular flaky particles generated in the original grinding and crushing process exist in a slurry reaction system of the magnesium chloride, so that the obtained solid catalyst has poor particle shape, low bulk density and nonuniform thickness, and therefore, the polymer has poor shape and more fine powder, is easy to generate static electricity, and is easy to produce static electricityIt is easy to block the pipeline. Meanwhile, the catalyst causes great trouble in the post-treatment when the content of oligomer in the solvent is large during the polymerization.
Patent CN1229092 discloses a catalyst system for ethylene polymerization and copolymerization, comprising: (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.
Patent CN1112373 discloses a solid titanium catalyst component and a preparation process thereof, which mainly adopts low carbon alcohol to dissolve magnesium halide, and adds alkane diluent and silane electron donor compound, and then 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 technologies, patents 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 is added when a magnesium compound and an organic alcohol react to form an alcohol slurry, so that a magnesium halide and an alcohol can form a swollen alcohol slurry in a diluent at a lower temperature without dissolving the magnesium halide into a solution at a high temperature, a catalyst having a particle form can be obtained, and the amount of the alcohol used when the alcohol slurry is formed is reduced, 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.
Patents CN101245115A, CN102272172A, CN1112373A and the like disclose a solid titanium catalyst component and a preparation process thereof, wherein low carbon alcohol is mainly used to dissolve magnesium halide, and alkane diluent and silane electron donor compound or organic boron compound are added, and then the mixture reacts 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. 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.
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 an 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 aims to add a multifunctional boric acid ester compound as a modifier in the dissolving process of magnesium chloride, so that the boric acid ester compound interacts with a diluent and a solvent to form a micro-emulsion system of the magnesium chloride, and then a precipitation method is adopted to prepare a sphere-like ethylene polymerization solid titanium Ziegler-Natta catalyst, thereby overcoming the defects of the prior art and providing the Ziegler-Natta catalyst which is very suitable for slurry polymerization of ethylene and is particularly suitable for producing polymers with wide relative molecular mass distribution. 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 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:
a component A and a component B; the component A is a titanium-containing solid catalyst component; the component B is an organic aluminum compound with the general formula of AlRnX3-nWherein 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 ratio 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 microemulsion precipitation method, and comprises the following steps: and (3) interacting the microemulsion of the magnesium compound with an organic boron compound without active hydrogen, and contacting an interacted product with a liquid titanium compound to precipitate the component A.
The microemulsion of the magnesium compound of the present invention is a microemulsion formed from a magnesium halide-organic alcohol compound-diluent dissolving system.
The method comprises the steps of using 0.1-10.0 mol of organic alcohol compound, 0.20-0.25 mol of organic boron compound and 0.1-10.0 mol of diluent in each mol of magnesium halide in the magnesium compound.
The titanium compound of the present invention has the general formula of Ti (OR)aXbWherein R is C1～C10X is halogen, a is an integer from 1 to 3, b is an integer from 1 to 4, and a + b is 3 or 4.
The molar ratio of the magnesium compound to the titanium compound is 1.0 to 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 in magnesium dihalide is substituted with a hydrocarbon group or a hydrocarbon oxy group.
The organic alcohol compound is C1-10 straight chain or branched chain alkyl alcohol, naphthenic alcohol and C6-20 aromatic alcohol or aromatic alcohol, and the halogenated product of the organic alcohol; the alcohol is at least one of methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, and decanol.
The molar ratio of the organic alcohol compound to the magnesium compound is 1 to 10, preferably 3 to 4.
The organic aluminum compound of the present invention is at least one of triethyl aluminum, triisobutyl aluminum, diethyl aluminum monochloride, ethyl aluminum dichloride and ethyl aluminum sesqui.
The invention can also be detailed as follows: the solid titanium Ziegler-Natta catalyst component for ethylene polymerization or copolymerization of the present invention is prepared from:
A. a titanium-containing solid catalyst component prepared by reacting:
(a) a microemulsion of a magnesium compound;
(b) an active hydrogen-free organoboron compound;
(c) a titanium compound;
the component A is prepared by adopting a microemulsion precipitation method, and specifically comprises the following steps:
(1) the titanium-containing solid catalyst component is prepared by the interaction of a microemulsion of a magnesium compound and an organic boron compound without active hydrogen, and the product of the microemulsion of the magnesium compound and the organic boron compound is contacted with a liquid titanium compound to separate out the solid catalyst component;
wherein the microemulsion of the magnesium compound is a microemulsion formed by a magnesium halide-organic alcohol-dispersant dissolving system;
the ratio between the reactants, per mole of magnesium halide in the magnesium compound, is: 0.1 to 10.0 mol, 0.20 to 0.25 mol of an organoboron compound, and 0.1 to 10.0 mol of a diluent.
(2) What is needed isThe titanium compound has a general formula of Ti (OR)aXbWherein R is C1-C10 aliphatic or aryl, X is halogen, a is 0, 1, 2 or 3, b is an integer from 1 to 4, and a + b is 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 components 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 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 or cycloalkyl of 1-20 carbon atoms; when n is 0, both R's may be the same or different, such as dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, octylbutylmagnesium and ethylbutylmagnesium; alkyl magnesium halides such as monochloro magnesium, chlorobutyl magnesium, monochloropentyl magnesium and monochlorohexyl magnesium; alkylmagnesium alkoxides such as butylethoxymagnesium, ethylbutoxymagnesium, and octylbutoxymagnesium; and other compounds 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 monochloraryloxymagnesium 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 producing 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 an aromatic hydrocarbon is used in these solvents, the 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 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, heating is carried out. 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.
(b) Organic boron compounds without active hydrogen
The active hydrogen-free organoboron compound described in the catalyst component of the present invention is selected from the group consisting of triethylene glycol methyl ether borate triesters.
(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)nX4-n. Wherein R is C1～C10The aliphatic hydrocarbon group, alicyclic hydrocarbon group or aryl group, X is halogen, and n is more than or equal to 0 and less than or equal to 4. Typical titanium compounds include: titanium tetrahalides, e.g. TiCl4、TiBr4、TiI4；
Preparation of solid titanium catalyst
The catalyst component of the present invention can be prepared by the following method:
(1) preparation of a microemulsion of a magnesium Compound
Dissolving magnesium halide in an alcohol solvent system, adding an inert diluent in a preferable solvent system to form uniform microemulsion, wherein the preferable dissolving temperature is 50-150 ℃; the organoboron compound having no active hydrogen atom is added during or after the formation of the solution.
(2) Preparation of solid titanium catalyst
And (2) carrying out contact reaction on the solution and a titanium compound, adding an organic boron compound without active hydrogen atoms during the contact reaction of the solution and the titanium compound in the step (1), slowly heating the mixture to 50-120 ℃, gradually precipitating solids and forming particles, reacting for a certain time, removing unreacted substances and a solvent, and washing by adopting an inert diluent to obtain the catalyst component.
The catalyst formed by the component A and the component B is suitable for homopolymerization 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 method. As the above-mentioned alpha-olefin, propylene, butene, pentene, hexene, octene, 4-methylpentene-1 and the like can be used. The catalyst comprises the catalyst component of the invention and AlR with a general formulanX3-nWherein R may be a hydrocarbon group having l to 20 carbon atoms, particularly an alkyl group, an aralkyl group, an aryl group; x is halogen, in particular chlorine and bromine; n is a number of 0-3. Specific compounds are as follows: and alkylaluminum halides such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride and ethylaluminum dichlorochloride, and among them, trialkylaluminum compounds are preferable, and triethylaluminum and triisobutylaluminum are more preferable. Wherein the molar ratio of the component aluminum to the component titanium is 5-500, preferably 20-200.
Solution polymerization, slurry polymerization, or gas phase polymerization may be employed for the polymerization. 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.
Compared with the prior art, the invention has the following advantages:
the present invention provides a catalyst which is well suited for slurry polymerization of ethylene, particularly for the production of polyethylene having a broad relative molecular mass distribution. Since the magnesium compound is in a micro-emulsion state during the catalyst preparation, spherical catalyst particles are easily precipitated during the catalyst preparation. 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. The organic boron compound without active hydrogen not only plays the role of a precipitator and a precipitation assistant, but also improves the particle shape of the catalyst and further improves the particle shape of the polymer. In addition, the triethylene glycol methyl ether boric acid triester participates in the coordination of the active center, influences the chemical environment of the active center titanium, and enables the catalyst to show better hydrogen regulation sensitivity performance and copolymerization performance.
Detailed Description
The present invention is further described below with reference to examples, but the scope of the present invention is not limited by these examples. The scope of the invention is set forth in the claims.
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 2.5mmol of triethylene glycol methyl ether borate and stirred at 50 ℃ for 2 hours to dissolve it in the solution. 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 triethyl aluminum with the concentration of 1mol/L are added, accurately weighed catalyst is 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), and the mixture is polymerized for 2 hours at the temperature of 80 ℃, wherein the polymerization activity, the polymer stacking density and the particle size distribution result are shown in Table 2.
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 2.5mmol of triethylene glycol methyl ether borate was added to the solution and kept 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 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 is 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), and the mixture is polymerized for 2 hours at the temperature of 80 ℃, wherein the polymerization activity, the polymer bulk density and the particle size distribution result are shown in Table 2.
Example 3
The same as in example 1 except that 5.0mmol of triethylene glycol methyl ether borate triester was added. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, and the results of the polymerization activity, the bulk density of the polymer and the particle size distribution are shown in Table 2.
Example 4
The same as in example 2, except that the active hydrogen-free organoboron compound was triethylene glycol methyl ether borate triester and the amount added was 5.0 mmol. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, and the results of the polymerization activity, the bulk density of the polymer and the particle size distribution are shown in Table 2.
Example 5
The same as in example 1 except that 10.0mmol of triethylene glycol methyl ether borate triester was added. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, and the results of the polymerization activity, the bulk density of the polymer and the particle size distribution are shown in Table 2.
Example 6
The same as example 1, except that ethylene was changed to a mixed gas of ethylene and butene-1 in the polymerization of ethylene, and the butene-1 was contained in an amount of 3 mol%. The results of the particle size distribution and the radial distance analysis of the catalyst are shown in Table 1, and the results of the polymerization activity, the bulk density of the polymer and the particle size distribution are shown in Table 2.
Example 7
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, and the results of the polymerization activity, the bulk density of the polymer and the particle size distribution are shown in Table 2.
Comparative example 1
The same as in example 1. Except that no active hydrogen-free 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 as in example 1, and the polymerization activity, the bulk density of the polymer and the results of the particle size distribution are shown in Table 2.
Comparative example 2
The catalyst was synthesized as described in example 1 of CN 1229092.
In the reaction fully replaced by high-purity nitrogen0.042mol of anhydrous MgCl is added into the reactor 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, and the results of the polymerization activity, the polymer bulk density and the particle size distribution are shown in Table 2.
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 bulk density of the polymer and the particle size distribution were as shown in Table 2.
TABLE 1 particle size distribution and radial distances of the catalysts
Figure BDA0002812818350000101
Figure BDA0002812818350000111
TABLE 2 polymerization Activity, Polymer bulk Density and particle size distribution results
Figure BDA0002812818350000112

Claims (10)

1. A solid titanium catalyst for ethylene polymerization or copolymerization, which is characterized by comprising the following components:
a component A and a 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 AlRnX3-nWherein 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 microemulsion precipitation method, and comprises the following steps: and (3) interacting the microemulsion of the magnesium compound with an organic boron compound without active hydrogen, and contacting an interacted product with a liquid titanium compound to precipitate the component A.
2. The solid titanium catalyst according to claim 1, wherein the microemulsion of the magnesium compound is a microemulsion formed by a magnesium halide-organic alcohol compound-diluent dissolving system.
3. The solid titanium catalyst according to claim 2, wherein the organic alcohol compound is used in an amount of 0.1 to 10.0 mol, the organic boron compound is used in an amount of 0.20 to 0.25 mol, and the diluent is used in an amount of 0.1 to 10.0 mol, per mol of the magnesium halide in the magnesium compound.
4. The solid titanium catalyst according to claim 1, wherein said titanium compound has the general formula ti (or)aXbWherein R is C1～C10X is halogen, a is an integer from 1 to 3, b is an integer from 1 to 4, and a + b is 3 or 4.
5. The solid titanium catalyst according to claim 1, wherein the molar ratio of the magnesium compound to the titanium compound is 1.0 to 15.0.
6. The solid titanium catalyst according to claim 1, wherein the organoboron compound having no active hydrogen is triethylene glycol methyl ether borate.
7. The solid titanium catalyst according to claim 1, wherein the magnesium compound is at least one of a magnesium dihalide and a derivative in which one halogen atom in the magnesium dihalide is substituted with a hydrocarbon group or a hydrocarbon oxy group.
8. The solid titanium catalyst according to claim 2, wherein the organic alcohol compound is a linear or branched alkyl alcohol having 1 to 10 carbon atoms, a cycloalkyl alcohol, an aryl alcohol having 6 to 20 carbon atoms, or an aryl alcohol, or a halogenated product of the organic alcohol; the alcohol is at least one of methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, and decanol.
9. The solid titanium catalyst according to claim 2, wherein the molar ratio of the organic alcohol compound to the magnesium compound is 1 to 10, preferably 3 to 4.
10. The solid titanium catalyst according to claim 1, wherein the organoaluminum compound is at least one of triethylaluminum, triisobutylaluminum, diethylaluminum monochloride, ethylaluminum dichloride and ethylaluminum sesquichloride.
CN202011402074.XA 2020-12-02 2020-12-02 solid titanium catalyst Active CN114573739B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011402074.XA CN114573739B (en) 2020-12-02 2020-12-02 solid titanium catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011402074.XA CN114573739B (en) 2020-12-02 2020-12-02 solid titanium catalyst

Publications (2)

Publication Number Publication Date
CN114573739A true CN114573739A (en) 2022-06-03
CN114573739B CN114573739B (en) 2023-12-22

Family

ID=81769616

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011402074.XA Active CN114573739B (en) 2020-12-02 2020-12-02 solid titanium catalyst

Country Status (1)

Country Link
CN (1) CN114573739B (en)

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
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

Also Published As

Publication number Publication date
CN114573739B (en) 2023-12-22

Similar Documents

Publication Publication Date Title
AU683403B2 (en) Supported olefin polymerization catalyst
EP0055589B1 (en) Catalyst for polymerization of olefins and polymerization process using the catalyst
US6511935B2 (en) Methods of making magnesium/transition metal alkoxide complexes and polymerization catalysts made therefrom
JP2004527635A (en) Improved olefin polymerization catalyst composition and method of manufacture
CN103130931B (en) Spherical ethylene polymerization solid titanium catalyst, preparation and application thereof
US4822763A (en) Catalyst component for polymerization of olefin
CN108084305B (en) Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst
JP4917533B2 (en) Catalyst component for ethylene polymerization, preparation method thereof, catalyst and polymerization method
CN102060945B (en) Preparation and application of ethylene polymerization solid titanium catalyst component
CN114539449A (en) Titanium catalyst component for ethylene polymerization and preparation method and application thereof
WO2004072122A2 (en) The preparation of a magnesium halide support for olefin polymerization and a catalyst composition using the same
CN114573739B (en) solid titanium catalyst
US5286694A (en) Lanthanide halide catalyst, method of producing the catalyst, and polymerization process employing the catalyst
US5322911A (en) Polymerization process employing metal halide catalyst and polymer produced
JPH0822890B2 (en) Method for producing propylene polymer
CN115746177B (en) Catalyst for olefin polymerization and olefin polymerization method
CN115746182B (en) Catalyst for olefin polymerization and olefin polymerization method
EP0132288B1 (en) A method of polymerizing an olefin
JPH0397706A (en) Production of olefinic polymer
CN115806637B (en) Catalyst system for olefin polymerization and olefin polymerization method
RU2356911C1 (en) Method of obtaining polyethylene and copolymers of ethylene with alpha-olefins with wide molecular mass distribution
JPH0725806B2 (en) Olefin polymerization catalyst component
KR100377288B1 (en) A method for propylene polymerization or copolymerization
KR100546500B1 (en) Process for preparing ethylene polymer and copolymer having polymer tail in molecular weight distribution
JP2005524742A (en) Mixed catalyst composition for producing polyolefins

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant