CN108084305B - Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst - Google Patents
Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst Download PDFInfo
- Publication number
- CN108084305B CN108084305B CN201611053975.6A CN201611053975A CN108084305B CN 108084305 B CN108084305 B CN 108084305B CN 201611053975 A CN201611053975 A CN 201611053975A CN 108084305 B CN108084305 B CN 108084305B
- Authority
- CN
- China
- Prior art keywords
- compound
- ethylene polymerization
- catalyst component
- solid titanium
- titanium catalyst
- 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.)
- Active
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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solidThe preparation method of the titanium catalyst and the catalyst component comprises the following steps: (1) dissolving a magnesium compound in an alcohol solvent; (2) reacting the mixture obtained in the step (1), an organic silicon compound and a titanium compound at the temperature of 50-120 ℃, wherein the molar ratio of magnesium to silicon to titanium is 1: 0.2-0.4: 1.0-15.0; the magnesium compound has the general formula XnMgR2‑n(ii) a R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms; x is halogen; n is more than or equal to 0 and less than or equal to 2, and n is an integer, and when n is 0, two R are the same or different; the organic silicon compound is 3-glycidyl ether oxypropyl triethoxysilane; the titanium compound has the general formula of Ti (OR')aX＇b(ii) a R' is C1～C10X' is halogen, a is 0, 1, 2 or 3, 1 ≦ b ≦ 4, and b is an integer, a + b ≦ 3 or 4. The catalyst component is easy to separate out granular catalyst during preparation; the polyethylene powder is used for ethylene polymerization, has good hydrogen regulation sensitivity, and has low content of fine powder.
Description
Technical Field
The present invention relates to a preparation method of solid titanium catalyst component for ethylene homopolymerization or copolymerization of ethylene and other alpha-olefin, and an ethylene polymerization catalyst formed from said solid titanium catalyst component and organic metal compound.
Background
The preparation of high-efficiency Ziegler-Natta catalysts for ethylene polymerization is well known and consists essentially of MgCl2Or SiO2Supported titanium halide composition. The preparation of ethylene polymerization and copolymerization catalysts as disclosed in JP 4951378 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 and mild reaction conditions, and has high catalytic activity when being used for catalyzing ethylene polymerization. However, in the preparation method, the carrier magnesium chloride cannot be dissolved in mineral oil, and irregular flaky particles generated during grinding and crushing of magnesium chloride exist 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 CN1229092 discloses a catalyst system for ethylene polymerization and copolymerization, comprising: (1) a Ti-containing solid catalyst component, (2) an alkylaluminum compound, wherein the Ti-containing solid catalyst component is obtained by dissolving magnesium halide in an organic epoxy compound and an organophosphorus compound to form a homogeneous solution, adding ethanol to treat the dissolved magnesium halide, mixing the solution with titanium tetrahalide, and precipitating a solid in the presence of a precipitant such as an organic acid anhydride, an organic acid, an ether, a ketone and the like to obtain a solid catalyst. When the catalyst system is used for ethylene polymerization, the obtained polymer has high fine powder content, low catalyst activity and poor hydrogen regulation sensitivity, is not suitable for preparing bimodal polymers, and is difficult to replace the existing high-activity ethylene slurry polymerization 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 be used in ethylene polymerization to produce ethylene polymers having excellent particle properties, its catalytic activity and oligomer content are still not satisfactory.
Disclosure of Invention
The invention aims to provide an ethylene polymerization solid titanium catalyst component, a preparation method thereof and an ethylene polymerization solid titanium catalyst, so as to overcome the defects of poor catalytic activity, poor hydrogen regulation sensitivity and poor particle morphology of the obtained ethylene polymer in the prior art.
The object of the present invention is achieved by a method for preparing a solid titanium catalyst component for ethylene polymerization, which comprises:
(1) dissolving a magnesium compound in an alcohol solvent; and
(2) mixing and reacting the mixture obtained in the step (1), an organic silicon compound and a liquid titanium compound to separate out an ethylene polymerization solid titanium catalyst component, wherein the reaction temperature is 50-120 ℃, and the molar ratio of magnesium, silicon and titanium is 1: 0.2-0.4: 1.0-15.0;
wherein the magnesium compound has the general formula XnMgR2-n(ii) a R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms; x is halogen; n is more than or equal to 0 and less than or equal to 2, and n is an integer, and when n is 0, two R are the same or different;
wherein, the organic silicon compound is 3-glycidyl ether oxypropyl triethoxysilane, and the structure is as follows:
wherein the titanium compound has the general formula of Ti (OR')aX＇b(ii) a R' is C1～C10X' is halogen, a is 0, 1, 2 or 3, 1 ≦ b ≦ 4, and b is an integer, a + b ≦ 3 or 4.
The preparation method of the ethylene polymerization solid titanium catalyst component comprises the following steps of (2) preferably, uniformly mixing the mixture obtained in the step (1) and an organic silicon compound, cooling to room temperature, then dropwise adding the mixture into a liquid titanium compound at the temperature of-5 ℃, and heating to 50-120 ℃ for reaction.
The preparation method of the ethylene polymerization solid titanium catalyst component comprises the following steps of (2) preferably, cooling the mixture obtained in the step (1) to room temperature, then dropwise adding the mixture into a liquid titanium compound at the temperature of-5 ℃, adding an organic silicon compound in the dropwise adding process, uniformly mixing, and heating to 50-120 ℃ for reaction.
The preparation method of the ethylene polymerization solid titanium catalyst component, provided by the invention, is characterized in that the dissolving process in the step (1) is preferably carried out in the presence of a diluent, and the diluent is preferably aliphatic hydrocarbon.
The preparation method of the ethylene polymerization solid titanium catalyst component comprises the following steps of, preferably, selecting an alkyl alcohol with 1-10 carbon atoms, a cycloalkanol with 3-10 carbon atoms, a halogenated product of the alkyl alcohol, a halogenated product of the cycloalkanol, an aromatic alcohol with 6-20 carbon atoms, a halogenated product of the aromatic alcohol or a halogenated product of the aromatic alcohol as an alcohol solvent.
The preparation method of the ethylene polymerization solid titanium catalyst component is characterized in that the molar ratio of the alcohol solvent to the magnesium compound is preferably 0.1-10.0: 1.
The preparation method of the ethylene polymerization solid titanium catalyst component provided by the invention is characterized in that the dissolving temperature of the alcohol solvent and the magnesium compound is preferably 50-150 ℃.
The invention also provides the ethylene polymerization solid titanium catalyst component prepared by the preparation method of the ethylene polymerization solid titanium catalyst component.
The present invention also provides a solid titanium catalyst for ethylene polymerization, comprising:
the above ethylene polymerization solid titanium catalyst component; and
an organoaluminum compound;
wherein the organic aluminum compound has the general formula AlR ″mX〞3-mWherein R 'is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X' is halogen, 0<m≤3；
Wherein the molar ratio of the organic aluminum compound to the ethylene polymerization solid titanium catalyst component is 20-200: 1.
The invention has the beneficial effects that:
the catalyst of the invention adopts 3-glycidyl ether oxypropyl triethoxysilane as a separation aid, so that spheroidal catalyst particles are easy to separate out during the preparation of the catalyst. And in the process of carrying titanium, a large amount of titanium compound is not needed to promote the precipitation of the precipitate, and the precipitate is not needed to be treated by using the titanium compound for multiple times, so that the addition amount of the titanium compound is greatly reduced. Meanwhile, the addition of the organosilicon compound also contributes to the improvement of the activity of the catalyst and the particle morphology of the catalyst, thereby further improving the particle morphology of the polymer and ensuring that the content of the oligomer wax in the product polyethylene is lower. When the catalyst is used for ethylene polymerization, the catalyst shows better hydrogen regulation sensitivity.
Detailed Description
The solid titanium catalyst component for ethylene polymerization of the present invention comprises (a) a liquid magnesium compound, (b) 3-glycidoxypropyltriethoxysilane, and (c) a titanium compound. The solid titanium catalyst component contains magnesium, titanium, silicon and halogen. Each of the raw materials used for preparing the solid titanium catalyst component of the present invention is described below:
(a) liquid magnesium compound
The liquid magnesium compound is obtained by dissolving a magnesium compound in a solvent. Wherein the magnesium compound has the general formula XnMgR2-n(ii) a R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms; x is halogen; n is more than or equal to 0 and less than or equal to 2, and n is an integer, and when n is 0, two R are the same or different. The magnesium compound may specifically be an alkylmagnesium 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; 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, magnesium hydride and monobutyl 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.
The solvent for dissolving the magnesium compound includes alcohols, carboxylic acids, aldehydes, amines, metal acid esters, and the like. 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, hexadecanol, octadecanol, undecanol, oleyl alcohol and ethylene glycol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; aromatic alcohols such as benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, a-methylbenzyl alcohol, a' -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 aldehyde is preferably an aldehyde 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 an alcohol in a 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) Organosilicon compounds
The organic silicon compound without active hydrogen atoms is 3-glycidyl ether oxypropyl triethoxysilane, and the structure is as follows:
(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')aX＇b(ii) a R' is C1～C10X' is halogen, a is 0, 1, 2 or 3, 1 ≦ b ≦ 4, and b is an integer, a + b ≦ 3 or 4.
Preparation of solid titanium catalyst component for ethylene polymerization
1. The catalyst component of the present invention can be prepared by the following method:
(1) dissolving a magnesium compound in an alcohol solvent, adding an inert diluent to form a uniform solution, wherein the dissolving temperature is preferably 50-130 ℃; 3-glycidoxypropyltriethoxysilane was added during the formation of the solution.
(2) And (2) carrying out contact reaction on the solution and a titanium compound, slowly heating the mixture to 50-120 ℃, gradually precipitating solids to form particles, reacting for a certain time, removing unreacted substances and a solvent, and washing by adopting an inert diluent to obtain the catalyst component.
2. The catalyst component of the invention can also be prepared by the following method:
(1) dissolving a magnesium compound in an alcohol solvent, adding an inert diluent to form a uniform solution, wherein the dissolving temperature is preferably 50-130 ℃;
(2) and (2) carrying out contact reaction on the solution and a titanium compound, simultaneously adding 3-glycidyl ether oxypropyl triethoxysilane, slowly heating the mixture to 50-120 ℃, gradually separating out solids to form particles, reacting for a certain time, removing unreacted substances and the solvent, and washing by adopting an inert diluent to obtain the catalyst component.
The invention also provides a catalyst for homopolymerization of ethylene or copolymerization of ethylene and other alpha-olefins, wherein the alpha-olefins comprise propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, styrene, methyl styrene and the like; the catalyst comprises the solid titanium catalyst component for ethylene polymerization and the general formula of AlRmX〞3-mWherein R' is hydrogen or 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; 0<m is less than or equal to 3. Specific compounds are as follows: and alkylaluminum halides such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, 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: 1, preferably 20-200: 1.
When the solid titanium catalyst is used for ethylene polymerization, liquid phase polymerization or gas phase polymerization may be employed. The liquid phase polymerization medium comprises: and inert solvents such as saturated aliphatic hydrocarbons and aromatic hydrocarbons, such as 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.
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 isooctanol were heated to 130 ℃ and reacted with stirring for 3 hours to obtain a homogeneous solution. To the solution was added 12.5mmol of 3-glycidyloxypropyltriethoxysilane and stirred at 50 ℃ for 2 hours to dissolve it in the solution. All the homogeneous solutions obtained above were cooled to room temperature and then added dropwise to 150mL of titanium tetrachloride maintained at 0 ℃ over 1 hour with stirring. After the addition was complete, the mixture was kept at 0 ℃ for 1 hour, then the temperature was raised to 120 ℃ over 2 hours with stirring and kept 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 decane and hexane respectively until no precipitated titanium compound is detected in the cleaning solution, and drying to obtain the solid titanium catalyst component.
(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 is added 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 polymerization is carried out for 2 hours at the temperature of 80 ℃, and the evaluation result of the polymer is shown in Table 1.
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 isooctanol were heated to 130 ℃ and allowed to react for 3 hours to obtain a homogeneous solution. The homogeneous solution 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 12.5mmol of 3-glycidyloxypropyltriethoxysilane was added to the solution and kept for 1 hour to dissolve 3-glycidyloxypropyltriethoxysilane 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 decane and hexane respectively until no precipitated titanium compound is detected in the cleaning solution, and drying to obtain the solid titanium catalyst component.
(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 1.0mol/L are added, accurately weighed catalyst is added 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 polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the evaluation result of the polymer is shown in Table 1.
Example 3
The same as in example 1 except that the amount of 3-glycidoxypropyltriethoxysilane added was 20 mmol. The polymerization results are shown in Table 1.
Example 4
The same as in example 2 except that the amount of 3-glycidoxypropyltriethoxysilane added was 10 mmol. The polymerization results are shown in Table 1.
Example 5
The same as example 1 except that decane was added in an amount of 50 mL. The polymerization results are shown in Table 1.
Example 6
The same as example 1 except that 100mL of decane was added. The polymerization results are shown in Table 1.
Comparative example 1
The same as in example 1. Except that 3-glycidoxypropyltriethoxysilane was not added. The catalyst is difficult to separate out and form, the separated particles are extremely fine and difficult to settle, and the catalyst is not formed because all the particles are pumped away during suction filtration.
Comparative example 2
The same as in example 1. Except that the precipitant aid was changed to tetraethoxysilane, and the ethylene polymerization results were shown in table 1.
Comparative example 3
The catalyst was prepared as described in example 1 of CN 1229092.
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 epichlorohydrin, 0.022mol of tributyl phosphate and 0.017mol of ethanol, the temperature is raised to 80 ℃ under stirring, the solid is maintained for 15 minutes to be completely dissolved to form a uniform solution, then 0.0074mol of phthalic anhydride is added, the solution is maintained for 1 hour, and the solution is preparedCooling to-25 deg.C, dripping 0.5mol titanium tetrachloride (about 55ml) into it, slowly heating to 80 deg.C, reacting for 3 hr, filtering, washing with toluene and hexane for 3 times, and vacuum drying to obtain solid catalyst.
The ethylene polymerization conditions were the same as in example 1, and the evaluation results of the polymer are shown in Table 1.
TABLE 1 evaluation results of polymers
As can be seen from Table 1, the particle size distribution of the polymer prepared in the example is more concentrated, mainly concentrated on 100-140 mesh, and the second is 80-100 mesh, while in the case of comparative example 1 without adding 3-glycidoxypropyltriethoxysilane, the catalyst is difficult to be precipitated and formed, and no catalyst can be obtained at all, while in comparative examples 2 and 3, although the catalyst can be obtained, the particle size of the obtained polymer is not uniform, and a considerable proportion of the polymer is distributed in each particle size interval of 20-200 mesh, and the proportion of the polymer with smaller particle size is significantly larger than that of the polymer in the example.
The invention has the beneficial effects that:
the catalyst of the invention adopts 3-glycidyl ether oxypropyl triethoxysilane as a separation aid, so that spheroidal catalyst particles are easy to separate out during the preparation of the catalyst. And in the process of carrying titanium, a large amount of titanium compound is not needed to promote the precipitation of the precipitate, and the precipitate is not needed to be treated by using the titanium compound for multiple times, so that the addition amount of the titanium compound is greatly reduced. Meanwhile, the addition of the organosilicon compound also contributes to the improvement of the activity of the catalyst and the particle morphology of the catalyst, thereby further improving the particle morphology of the polymer and ensuring that the content of the oligomer wax in the product polyethylene is lower. When the catalyst is used for ethylene polymerization, the catalyst shows better hydrogen regulation sensitivity.
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 (9)
1. A preparation method of a solid titanium catalyst component for ethylene polymerization is characterized by comprising the following steps:
(1) dissolving a magnesium compound in an alcohol solvent; and
(2) mixing and reacting the mixture obtained in the step (1), an organic silicon compound and a liquid titanium compound to separate out an ethylene polymerization solid titanium catalyst component, wherein the reaction temperature is 50-120 ℃, and the molar ratio of magnesium, silicon and titanium is 1: 0.2-0.4: 1.0-15.0;
wherein the magnesium compound has a general formula XnMgR2-n(ii) a R is hydrogen or a hydrocarbon group of 1 to 20 carbon atoms; x is halogen; n is more than or equal to 0 and less than or equal to 2, and n is an integer, and when n is 0, two R are the same or different;
wherein the organic silicon compound is 3-glycidyl ether oxypropyl triethoxysilane, and has the following structure:
wherein the titanium compound has a general formula of Ti (OR')aX＇b(ii) a R' is C1～C10X' is halogen, a is 0, 1, 2 or 3, 1 ≦ b ≦ 4, and b is an integer, a + b ≦ 3 or 4.
2. The method for preparing the solid titanium catalyst component for ethylene polymerization according to claim 1, wherein the step (2) comprises mixing the mixture obtained in the step (1) with the organosilicon compound uniformly, cooling to room temperature, adding dropwise the mixture into a liquid titanium compound at a temperature of-5 to 5 ℃, and heating to 50 to 120 ℃ for reaction.
3. The method for preparing the solid titanium catalyst component for ethylene polymerization according to claim 1, wherein the step (2) comprises cooling the mixture obtained in the step (1) to room temperature, then dropwise adding the mixture into a liquid titanium compound at a temperature of-5 to 5 ℃, adding an organosilicon compound during dropwise adding, uniformly mixing, and heating to 50 to 120 ℃ for reaction.
4. The method for preparing a solid titanium catalyst component for ethylene polymerization according to any one of claims 1 to 3, wherein the dissolving process of step (1) is carried out in the presence of a diluent which is an aliphatic hydrocarbon.
5. The method for preparing a solid titanium catalyst component for ethylene polymerization according to claim 4, wherein the alcohol solvent is an alkyl alcohol having 1 to 10 carbon atoms, a cycloalkanol having 3 to 10 carbon atoms, a halogenated product of the alkyl alcohol, a halogenated product of the cycloalkanol, an aromatic alcohol having 6 to 20 carbon atoms, a halogenated product of the aromatic alcohol, or a halogenated product of the aromatic alcohol.
6. The method for preparing a solid titanium catalyst component for ethylene polymerization according to claim 4, wherein the molar ratio of the alcohol solvent to the magnesium compound is 0.1 to 10.0: 1.
7. The method for preparing a solid titanium catalyst component for ethylene polymerization according to claim 4, wherein the dissolution temperature of the alcohol solvent and the magnesium compound is 50 to 150 ℃.
8. The solid titanium catalyst component for ethylene polymerization prepared by the process for preparing a solid titanium catalyst component for ethylene polymerization according to any one of claims 1 to 7.
9. A solid titanium catalyst for ethylene polymerization, comprising:
the ethylene polymerizing solid titanium catalyst component of claim 8; and
an organoaluminum compound;
wherein the organic aluminum compoundThe general formula of the compound is AlRmX〞3-mWherein R 'is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, X' is halogen, 0<m≤3；
Wherein the molar ratio of the organoaluminum compound to the ethylene polymerization solid titanium catalyst component according to claim 8 is 20 to 200: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611053975.6A CN108084305B (en) | 2016-11-22 | 2016-11-22 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611053975.6A CN108084305B (en) | 2016-11-22 | 2016-11-22 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108084305A CN108084305A (en) | 2018-05-29 |
| CN108084305B true CN108084305B (en) | 2020-12-01 |
Family
ID=62171811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611053975.6A Active CN108084305B (en) | 2016-11-22 | 2016-11-22 | Ethylene polymerization solid titanium catalyst component, preparation method thereof and ethylene polymerization solid titanium catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108084305B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115975080A (en) * | 2021-10-14 | 2023-04-18 | 中国石油化工股份有限公司 | Magnesium-titanium-containing catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method |
| CN115043961A (en) * | 2022-07-25 | 2022-09-13 | 吉化集团吉林市天龙催化剂有限公司 | Ziegler-Natta catalyst, preparation method and catalyst component for ethylene polymerization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102060945B (en) * | 2009-11-17 | 2012-07-18 | 中国石油天然气股份有限公司 | Preparation and application of solid titanium catalyst component for vinyl polymerization |
-
2016
- 2016-11-22 CN CN201611053975.6A patent/CN108084305B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108084305A (en) | 2018-05-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0245854B1 (en) | Process for producing olefin polymer | |
| EP0032294B1 (en) | Solid catalyst component for olefin polymerization | |
| EP0055589B1 (en) | Catalyst for polymerization of olefins and polymerization process using the catalyst | |
| JP2004527635A (en) | Improved olefin polymerization catalyst composition and method of manufacture | |
| JPH04306203A (en) | Improved drying catalyst for olefin polymerization | |
| KR101571054B1 (en) | A Catalyst Component for Ethylene Polymerization, Preparation thereof and a Catalyst Comprising the Catalyst Component | |
| 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 | |
| CN103130931B (en) | A kind of Ball shape ethylene polymerization solid titanium catalytic and Synthesis and applications thereof | |
| CN111072803A (en) | Olefin polymerization catalyst carrier, preparation method and application thereof | |
| US5225502A (en) | Method of producing polyolefin | |
| CN102060945B (en) | Preparation and application of solid titanium catalyst component for vinyl polymerization | |
| CN104710549A (en) | Spherical ethylene polymerization solid titanium catalyst prepared through emulsion method, and application thereof | |
| CA2536804A1 (en) | Ziegler-natta catalyst for polyolefins | |
| CN114539449A (en) | Titanium catalyst component for ethylene polymerization and preparation method and application thereof | |
| CN107915793B (en) | Olefin polymerization catalyst component and olefin polymerization catalyst, application thereof and olefin polymerization method | |
| CN114573739B (en) | solid titanium catalyst | |
| CN101519463A (en) | Preparation method of catalyst for ethylene polymerization and copolymerization | |
| JPH0822890B2 (en) | Method for producing propylene polymer | |
| CN115806637B (en) | Catalyst system for olefin polymerization and olefin polymerization method | |
| CN112625154A (en) | Titanium catalyst component for olefin polymerization, preparation method thereof, catalyst containing titanium catalyst component and application of catalyst | |
| CN115746177B (en) | Catalyst for olefin polymerization and olefin polymerization method | |
| CN115746182B (en) | Catalyst for olefin polymerization and olefin polymerization method | |
| JPH06172432A (en) | Catalyst for olefin polymerization | |
| EP0108489B1 (en) | Method for preparing an improved catalyst support |
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 |