CN116410377A - Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof - Google Patents

Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof Download PDF

Info

Publication number
CN116410377A
CN116410377A CN202111647902.0A CN202111647902A CN116410377A CN 116410377 A CN116410377 A CN 116410377A CN 202111647902 A CN202111647902 A CN 202111647902A CN 116410377 A CN116410377 A CN 116410377A
Authority
CN
China
Prior art keywords
titanium
molecular weight
high molecular
weight polyethylene
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.)
Pending
Application number
CN202111647902.0A
Other languages
Chinese (zh)
Inventor
王仪森
高克京
荔栓红
张丽洋
祝文亲
周京生
任晓兵
秦睿
何盛宝
胡杰
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 CN202111647902.0A priority Critical patent/CN116410377A/en
Publication of CN116410377A publication Critical patent/CN116410377A/en
Pending legal-status Critical Current

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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—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
    • 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
    • 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
    • C08F4/647—Catalysts containing a specific non-metal or metal-free compound
    • C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
    • C08F4/6494—Catalysts containing a specific non-metal or metal-free compound organic containing oxygen
    • 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
    • C08F4/651—Pretreating with non-metals or metal-free compounds
    • 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

Abstract

The invention relates to an ultra-high molecular weight polyethylene catalyst component, which comprises magnesium chloride, a titanium compound and C8-C25 fatty acid ester, and is prepared by a method comprising the following steps of: (1) Mixing magnesium chloride with fatty alcohol of C6-C12 and alkane of C8-C12 to form magnesium chloride solution; (2) Mixing the magnesium chloride solution with a titanium compound in the presence of a C8-C25 fatty acid ester, and precipitating to obtain solid catalyst particles containing magnesium chloride, the titanium compound and the C8-C25 fatty acid ester. The invention also relates to a preparation method of the ultra-high molecular weight polyethylene catalyst component and an ultra-high molecular weight polyethylene catalyst. The catalyst of the invention is particularly suitable for preparing ultra-high molecular weight polyethylene by slurry polymerization, and can be continuously carried out in a stirred reactor or a loop reactor.

Description

Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts for preparing ultrahigh molecular weight polyethylene, in particular to an ultrahigh molecular weight polyethylene catalyst component, a preparation method thereof and an ultrahigh molecular weight polyethylene catalyst containing the same.
Background
Ultra High Molecular Weight Polyethylene (UHMWPE) generally refers to polyethylene with a viscosity average molecular weight of 150 ten thousand or more, and has a linear structure with the molecular formula- (CH) -CH 2 -CH 2 —) n And (3) preparing the preparation. The chain length of the ultra-high molecular weight polyethylene is 10 to 20 times that of the common HDPE, and the ultra-high molecular weight polyethylene has the performances of ultra-strong impact resistance, abrasion resistance, chemical corrosion resistance, low temperature resistance, stress cracking resistance, adhesion resistance, excellent insulativity, safety, sanitation, self lubrication (low friction coefficient) and the like. UHMWPE fibers spun by gel method have a strength coefficient up to four times that of carbon fibers, and thus UHMWPE is widely used in many important fields such as bulletproof vests, high voltage power cables, artificial joints, and the like.
Since the UHMWPE produced by the polymerization process is so high in molecular weight that processing and pelletization are a very difficult task, the UHMWPE raw materials are all sold as powder.
Currently, there are three main types of polymerization catalysts used industrially for the production of UHMWPE: (a) heterogeneous Mg-Ti catalyst, (b) homogeneous or supported metallocene complex, (c) homogeneous/heterogeneous phenoxy imine (FI) or other post-metallocene catalyst system. However, the UHMWPE sold on the market at present is still based on Mg-Ti based products based on cost and polymer properties and processing convenience. Chinese patent CN96106647.4 discloses a catalyst for preparing High Density Polyethylene (HDPE) by slurry polymerization of ethylene, which is a catalyst solid particle obtained by dropping an alcohol solution composed of anhydrous magnesium chloride, decane, isooctanol and tetraethoxysilane into cold titanium tetrachloride to precipitate out, when the catalyst is used for preparing HDPE or UHMWPE by slurry polymerization of ethylene, the polymerization activity is higher, the particle morphology is better, but the indexes such as bulk density and fine powder content of polymer powder still need to be improved.
In the preparation of UHMWPE by ethylene slurry polymerization, if the bulk density of the polymer powder is low, it will constitute a great obstacle to the powder separation process and will affect the space-time yield of the plant and thus limit the increase of the plant production load; when the polymer powder has more fine powder content, the scaling trend of the inner wall of the polymerization reactor is accelerated, thereby influencing the heat removal capacity of the reactor and the long-period operation of the device.
Disclosure of Invention
Based on the above, the present invention aims to provide an ultra-high molecular weight polyethylene catalyst component, wherein when the catalyst containing the component is used for preparing ultra-high molecular weight polyethylene (the viscosity average molecular weight is more than 150 ten thousand), the catalyst has high polymerization activity, and the prepared ultra-high molecular weight polyethylene powder has high bulk density and low fine powder content, and the fluctuation of the bulk density and the fine powder content of the powder is small along with the increase of the polymerization temperature.
In order to achieve the above object, the present invention provides an ultra-high molecular weight polyethylene catalyst component comprising magnesium chloride, a titanium compound and a C8-C25 fatty acid ester, which is prepared by a process comprising the steps of: (1) Mixing magnesium chloride with a C6-C12 fatty alcohol to form a magnesium chloride solution; (2) Mixing the magnesium chloride solution with a titanium compound in the presence of a C8-C25 fatty acid ester, and precipitating to obtain solid catalyst particles containing magnesium chloride, the titanium compound and the C8-C25 fatty acid ester.
The ultra-high molecular weight polyethylene catalyst component of the invention, wherein preferably, the C8-C25 fatty acid ester is selected from one or more of C1-C20 alkyl esters of aliphatic C8-C25 monocarboxylic acids, aliphatic C8-C20 monocarboxylic acids, C1-C4 alkyl monoesters of dicarboxylic acids and C1-C4 alkyl diesters of dicarboxylic acids; further preferred, the C8-C25 fatty acid ester is selected from one or more of isopropyl dodecanoate, isopropyl tetradecanoate, n-butyl tetradecanoate, di-n-butyl sebacate, (poly) (alkylene glycol) monoacetate or diacetate, (poly) (alkylene glycol) mono-or di-tetradecanoate, (poly) (alkylene glycol) mono-or di-dodecanoate and glyceryl tri (acetate).
The ultra-high molecular weight polyethylene catalyst component of the present invention, wherein preferably, the C8-C25 fatty acid ester is selected from one or more of isopropyl myristate, isopropyl laurate and di-n-butyl sebacate.
The ultra-high molecular weight polyethylene catalyst component of the present invention, wherein the C8-C25 fatty acid ester content is preferably more than 0 and 20% by weight or less, more preferably 2 to 10% by weight.
The ultra-high molecular weight polyethylene catalyst component of the invention, wherein preferably the titanium compound is selected from the group consisting of those having the general formula Ti (OR) 4-n Cl n Wherein R is alkyl with 2-6 carbon atoms, n is more than or equal to 0 and less than or equal to 4; further preferred, the titanium compound is selected from one or more of titanium tetrachloride, trichloro-mono-ethoxy titanium, trichloro-mono-propoxy titanium, trichloro-mono-butoxy titanium, trichloro-mono-pentoxy titanium, trichloro-mono-hexoxy titanium, dichloro-di-ethoxy titanium, dichloro-di-propoxy titanium, dichloro-di-butoxy titanium, dichloro-di-pentoxy titanium, dichloro-tri-ethoxy titanium, chloro-tri-propoxy titanium, chloro-tri-butoxy titanium, chloro-tri-pentoxy titanium, chloro-tri-hexoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tetrapentoxy titanium, tetrahexoxy titanium; titanium tetrachloride is more preferable.
The ultra-high molecular weight polyethylene catalyst component is characterized in that preferably, the fatty alcohol of C6-C12 is selected from one or more of the group consisting of hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol and octadecanol; further preferably one or more of the group consisting of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol; still more preferably 2-ethylhexanol.
The ultra-high molecular weight polyethylene catalyst component of the invention, wherein preferably, the magnesium chloride solution also contains C8-C12 alkane, further preferably, the C8-C12 alkane is selected from one or more of n-octane and isomer, n-nonane and isomer, n-decane and isomer, n-undecane and isomer and n-dodecane and isomer; decane is more preferable.
Therefore, the invention also provides a preparation method of the ultra-high molecular weight polyethylene catalyst component, which comprises the following steps:
(1) Mixing magnesium chloride with a C6-C12 fatty alcohol to form a magnesium chloride solution;
(2) At C 8 -C 25 Mixing the above magnesium chloride solution with titanium compound at a temperature below 40deg.C, heating, mixing at 80-150deg.C for more than 0.5 hr, and precipitating to obtain a solution containing magnesium chloride, titanium compound and C 8 -C 25 Catalyst solid particles of fatty acid esters in an amount of 0 to 0.5 mole of C per mole of magnesium chloride 8 -C 25 Fatty acid esters of (a).
The preparation method of the ultra-high molecular weight polyethylene catalyst component, disclosed by the invention, is characterized in that the C8-C25 fatty acid ester is preferably selected from one or more of C1-C20 alkyl esters of aliphatic C8-C25 monocarboxylic acids, aliphatic C8-C20 monocarboxylic acids, C1-C4 alkyl monoesters of dicarboxylic acids and C1-C4 alkyl diesters of dicarboxylic acids; further preferred, the fatty acid ester is selected from one or more of isopropyl dodecanoate, isopropyl tetradecanoate, n-butyl tetradecanoate, di-n-butyl sebacate, (poly) (alkylene glycol) monoacetate or diacetate, (poly) (alkylene glycol) mono-or di-tetradecanoate, (poly) (alkylene glycol) mono-or di-dodecanoate and glyceryl tri (acetate).
The preparation method of the ultra-high molecular weight polyethylene catalyst component, disclosed by the invention, is characterized in that the fatty acid ester is preferably one or more selected from isopropyl myristate, isopropyl laurate and di-n-butyl sebacate.
The preparation method of the ultra-high molecular weight polyethylene catalyst component is characterized in that preferably, the fatty alcohol of C6-C12 is selected from one or more of the group consisting of hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol and octadecanol; further preferably one or more of the group consisting of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol; still more preferably 2-ethylhexanol.
The preparation method of the ultra-high molecular weight polyethylene catalyst component of the invention is characterized in that in the step (1), preferably, the magnesium chloride solution also contains C8-C12 alkane, and more preferably, the C8-C12 alkane is selected from one or more of n-octane and isomer, n-nonane and isomer, n-decane and isomer, n-undecane and isomer, n-dodecane and isomer; decane is more preferable.
In order to obtain catalyst solid particles with higher fluidity, the preparation method of the ultra-high molecular weight polyethylene catalyst component of the invention preferably further comprises the following step (3): washing the solid catalyst component obtained in step (2) with an inert solvent to elute and remove by-products generated during the preparation of the catalyst component from the catalyst component particles, and further preferably, the inert solvent is selected from alkanes or aromatic hydrocarbons of C5 to C12. Typical inert solvents of this type are isopentane, hexane, heptane, silane, toluene, etc.
The preparation method of the ultra-high molecular weight polyethylene catalyst component, disclosed by the invention, is characterized in that in the step (1), preferably, the molar ratio of the fatty alcohol to the magnesium chloride is 1-10; in the step (2), the molar ratio of the titanium compound to the magnesium chloride is 1-100, the initial mixing temperature is-25-30 ℃, the mixing temperature after heating is 90-130 ℃, and the mixing time after heating is 0.5-10 hours.
The preparation method of the ultra-high molecular weight polyethylene catalyst component, disclosed by the invention, is characterized in that in the step (1), the molar ratio of the fatty alcohol to the magnesium chloride is preferably 2-6; in the step (2), the molar ratio of the titanium compound to the magnesium chloride is 20-50, the initial mixing temperature is-25-30 ℃, and the mixing time is 1-5 hours after the temperature is raised.
For this purpose, the invention also provides an ultra-high molecular weight polyethylene catalyst comprising the following components:
(I) The above ultra-high molecular weight polyethylene catalyst component;
(II) an organoaluminum compound of the formula AlR1 n X 3-n Wherein R1 is an alkyl group having 2 to 8 carbon atoms, X is a halogen, and n is 1, 2 or 3;
wherein the proportion of the component (II) to the component (I) is 5 to 500, preferably 20 to 200, of aluminum to titanium in terms of aluminum-titanium molar ratio.
The ultra-high molecular weight polyethylene catalyst according to the present invention, wherein the organoaluminum compound is preferably selected from one or more of the group consisting of triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum dichloride and ethylaluminum sesquichloride, and further preferably, the organoaluminum compound is selected from at least one of triethylaluminum, diethylaluminum monochloride and triisobutylaluminum.
The invention has the following beneficial effects:
(1) The Ti-Mg series ultra-high molecular weight polyethylene catalyst containing the aliphatic acid ester of C8-C25 has the characteristics of high polymer powder bulk density and low fine powder content, and the polymer powder bulk density and the fine powder content are less sensitive to the change of the polymerization temperature. After the catalyst is applied to the production of ultra-high molecular weight polyethylene, the polymerization reaction is smoother, the polymer performance is more stable, and the risks of lower bulk density and higher content of fine powder of polymer powder caused by rapid release of the catalyst activity are reduced. Therefore, when the catalyst component is used for preparing the ultra-high molecular weight polyethylene, the bulk density of polymer powder is obviously improved, particularly when the polymerization temperature is increased, the polymerization activity of the catalyst is relatively stable, the fluctuation of the bulk density and the fine powder content of the polymer is small, and the viscosity average molecular weight of the polymer is reduced slightly.
(2) The catalyst of the invention is particularly suitable for preparing ultra-high molecular weight polyethylene by slurry polymerization, can be continuously carried out in a stirred reactor or a loop reactor, and is more convenient for industrialization.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The ultra-high molecular weight polyethylene catalyst component provided by the invention comprises magnesium chloride, a titanium compound and C8-C25 fatty acid ester, and is prepared by a method comprising the following steps of: (1) Mixing magnesium chloride with a C6-C12 fatty alcohol to form a magnesium chloride solution; (2) Mixing the magnesium chloride solution with a titanium compound in the presence of a C8-C25 fatty acid ester, and precipitating to obtain solid catalyst particles containing magnesium chloride, the titanium compound and the C8-C25 fatty acid ester.
In some embodiments it is preferred that the C8-C25 fatty acid ester is selected from one or more of a C1-C20 alkyl ester of an aliphatic C8-C25 monocarboxylic acid, an aliphatic C8-C20 monocarboxylic acid, a C1-C4 alkyl monoester of a dicarboxylic acid, a C1-C4 alkyl diester of a dicarboxylic acid; further preferred, the C8-C25 fatty acid ester is selected from one or more of isopropyl dodecanoate, isopropyl tetradecanoate, n-butyl tetradecanoate, di-n-butyl sebacate, (poly) (alkylene glycol) monoacetate or diacetate, (poly) (alkylene glycol) mono-or di-tetradecanoate, (poly) (alkylene glycol) mono-or di-dodecanoate and glyceryl tri (acetate).
In some embodiments it is preferred that the C8-C25 fatty acid ester is selected from one or more of isopropyl myristate, isopropyl dodecanoate and di-n-butyl sebacate.
In some embodiments, it is preferable that the C8-C25 fatty acid ester content is more than 0 and 20% by weight or less, and more preferably 2-10% by weight.
In some embodiments it is preferred that the titanium compound is selected from the group consisting of titanium of the general formula Ti (OR) 4-n Cl n Wherein R is alkyl with 2-6 carbon atoms, n is more than or equal to 0 and less than or equal to 4; further preferred, the titanium compound is selected from one or more of titanium tetrachloride, trichloro-mono-ethoxy titanium, trichloro-mono-propoxy titanium, trichloro-mono-butoxy titanium, trichloro-mono-pentoxy titanium, trichloro-mono-hexoxy titanium, dichloro-di-ethoxy titanium, dichloro-di-propoxy titanium, dichloro-di-butoxy titanium, dichloro-di-pentoxy titanium, dichloro-tri-ethoxy titanium, chloro-tri-propoxy titanium, chloro-tri-butoxy titanium, chloro-tri-pentoxy titanium, chloro-tri-hexoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tetrapentoxy titanium, tetrahexoxy titanium; titanium tetrachloride is more preferable.
In some embodiments, it is preferred that the C6-C12 fatty alcohol is selected from one or more of the group consisting of hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol, and octadecanol; further preferably one or more of the group consisting of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol; still more preferably 2-ethylhexanol.
In some embodiments, it is preferable that the magnesium chloride solution further contains C8-C12 alkane, and it is further preferable that the C8-C12 alkane is selected from one or more of n-octane and isomer, n-nonane and isomer, n-decane and isomer, n-undecane and isomer, and n-dodecane and isomer; decane is more preferable.
The preparation method of the ultra-high molecular weight polyethylene catalyst component provided by the invention comprises the following steps:
(1) Mixing magnesium chloride with a C6-C12 fatty alcohol to form a magnesium chloride solution;
(2) At C 8 -C 25 Mixing the above magnesium chloride solution with titanium compound at a temperature below 40deg.C, heating, mixing at 80-150deg.C for more than 0.5 hr, and precipitating to obtain a solution containing magnesium chloride, titanium compound and C 8 -C 25 Catalyst solid particles of fatty acid esters in an amount of 0 to 0.5 mole of C per mole of magnesium chloride 8 -C 25 Fatty acid esters of (a).
In some embodiments it is preferred that the C8-C25 fatty acid ester is selected from one or more of a C1-C20 alkyl ester of an aliphatic C8-C25 monocarboxylic acid, an aliphatic C8-C20 monocarboxylic acid, a C1-C4 alkyl monoester of a dicarboxylic acid, a C1-C4 alkyl diester of a dicarboxylic acid; further preferred, the fatty acid ester is selected from one or more of isopropyl dodecanoate, isopropyl tetradecanoate, n-butyl tetradecanoate, di-n-butyl sebacate, (poly) (alkylene glycol) monoacetate or diacetate, (poly) (alkylene glycol) mono-or di-tetradecanoate, (poly) (alkylene glycol) mono-or di-dodecanoate and glyceryl tri (acetate).
In some embodiments it is preferred that the fatty acid ester is selected from one or more of isopropyl myristate, isopropyl laurate and di-n-butyl sebacate.
In some embodiments, it is preferred that the C6-C12 fatty alcohol is selected from one or more of the group consisting of hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol, and octadecanol; further preferably one or more of the group consisting of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol; still more preferably 2-ethylhexanol.
In some embodiments, it is preferable that in step (1), the magnesium chloride solution further contains C8-C12 alkane, and it is further preferable that the C8-C12 alkane is selected from one or more of n-octane and isomer, n-nonane and isomer, n-decane and isomer, n-undecane and isomer, and n-dodecane and isomer; decane is more preferable.
In some embodiments, to obtain a more fluid catalyst solid particle, it is preferable to further include step (3) after step (2): washing the solid catalyst component obtained in step (2) with an inert solvent to elute and remove by-products generated during the preparation of the catalyst component from the catalyst component particles, and further preferably, the inert solvent is selected from alkanes or aromatic hydrocarbons of C5 to C12. Typical inert solvents of this type are isopentane, hexane, heptane, silane, toluene, etc.
In some embodiments it is preferred that in step (1) the molar ratio of the fatty alcohol to the magnesium chloride is from 1 to 10; in the step (2), the molar ratio of the titanium compound to the magnesium chloride is 1-100, the initial mixing temperature is-25-30 ℃, the mixing temperature after heating is 90-130 ℃, and the mixing time after heating is 0.5-10 hours.
In some embodiments it is preferred that in step (1) the molar ratio of the fatty alcohol to the magnesium chloride is from 2 to 6; in the step (2), the molar ratio of the titanium compound to the magnesium chloride is 20-50, the initial mixing temperature is-25-30 ℃, and the mixing time is 1-5 hours after the temperature is raised.
The ultra-high molecular weight polyethylene catalyst provided by the invention comprises the following components:
(I) The above ultra-high molecular weight polyethylene catalyst component;
(II) an organoaluminum compound of the formula AlR1 n X 3-n Wherein R1 is an alkyl group having 2 to 8 carbon atoms, X is a halogen, and n is 1, 2 or 3;
wherein the proportion of the component (II) to the component (I) is 5 to 500, preferably 20 to 200, of aluminum to titanium in terms of aluminum-titanium molar ratio.
In some embodiments, it is preferable that the organoaluminum compound is selected from one or more of the group consisting of triethylaluminum, triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride and ethylaluminum sesquichloride, and it is further preferable that the organoaluminum compound is selected from at least one of triethylaluminum, diethylaluminum chloride and triisobutylaluminum.
Test method
(1) Mg, ti content:
determined by ICP analysis.
(2) Catalyst solid particle size:
using Malvern Mastersizer TM 2000 determining the particle size of the solid catalyst component; average particle size (D50): corresponding to a particle size of 50% cumulative weight.
(3) Polymer powder bulk density:
a quantity of ultra high molecular weight polymer powder was loosely added to a fixed vessel, the vessel was tared on a balance to give the weight of the polymer powder (in grams, two positions after decimal point).
Value of bulk density = measured weight/measured volume. The units are g/cm 3 The arithmetic average of the values obtained in the two determinations was recorded as the measurement result.
(4) Particle size distribution of polymer powder:
measured by a mechanical vibrating screen.
(5) Polymer viscosity average molecular weight
Determination of the viscosity average molecular weight the intrinsic viscosity, [ eta ] of the polymer was first determined in accordance with GB1841-1980]And viscosity average molecular weight M η Is [ eta ]]＝KM η α, K and α are constants, k=6.67×10 2 Alpha=0.67, from which the viscosity average molecular weight M can be calculated η 。
Example 1
(1) Preparation of the catalyst component
To the reactor fully replaced with nitrogen gas, 4.76g of magnesium dichloride, 25mL of n-decane, 23mL of isooctanol and 2.8mL of isopropyl dodecanoate (molar ratio of ester to magnesium: 0.2) were added, and the mixture was stirred and heated to 130℃and reacted at this temperature for 3 hours to form a uniform solution, cooled to room temperature, and then added dropwise to 200mL of titanium tetrachloride maintained at-10℃over 1 hour. After the dripping is finished, the temperature of the mixture is kept at-10 ℃ for 0.5 hour, then the system is heated to 100 ℃ within 1 hour and 50 minutes, the temperature is kept for 2 hours, and after the reaction is finished, the generated solid components are subjected to hot filtration separation, and the solid components are collected; then 200ml of titanium tetrachloride was added to the solid component, and the reaction was carried out by heating at 105℃for 2 hours, and the obtained solid component was subjected to thermal filtration, and then the solid catalyst component was sufficiently washed with purified hexane until no precipitated free titanium compound was detected in the washing liquid, and dried to obtain a spherical-like solid catalyst component (A). The composition and average particle diameter of the solid catalyst component (A) are shown in Table 1.
(2) Slurry polymerization of ethylene
1L of hexane, 2mmol of triisobutylaluminum and 7mg of the solid catalyst component (A) obtained in the step (1) were added to a 2L stainless steel high-pressure stirring reaction kettle, then the temperature was raised, and when the kettle temperature was raised to 60 ℃, ethylene addition was started, and the kettle temperature was maintained at 65℃and the ethylene partial pressure was 0.3MPa, for 4 hours. After the polymerization was completed, the addition of ethylene was stopped, the temperature was lowered and the pressure was released to obtain 156g of a polymer material, and the properties of the polymer were shown in Table 2.
Example 2
(1) Preparation of the catalyst component
As in example 1.
(2) Slurry polymerization of ethylene
1L of hexane, 2mmol of triisobutylaluminum and 7mg of the solid catalyst component (A) obtained in the step (1) were added into a 2L stainless steel high-pressure stirring reaction kettle, then the temperature was raised, and when the kettle temperature was raised to 70 ℃, ethylene addition was started, and the kettle temperature was maintained at 75 ℃ and the ethylene partial pressure was 0.3MPa for 4 hours. After the polymerization was completed, the addition of ethylene was stopped, and the temperature was lowered and the pressure was released to obtain 162g of a polymer material, the polymer properties of which are shown in Table 2.
Example 3
(1) Preparation of the catalyst component
To the reactor fully replaced with nitrogen gas, 4.76g of magnesium dichloride, 20mL of n-decane, 30mL of isooctanol and 1.5mL of isopropyl myristate (ester/magnesium: 0.1) were added, and the mixture was stirred and heated to 130℃and reacted at this temperature for 3 hours to form a uniform solution, cooled to room temperature, and then added dropwise to 200mL of titanium tetrachloride maintained at-15℃over 1 hour. After the dripping is finished, the temperature of the mixture is kept at-15 ℃ for 0.5 hour, then the system is heated to 90 ℃ within 1 hour and 40 minutes, the temperature is kept for 2 hours, and after the reaction is finished, the generated solid components are subjected to hot filtration separation, and the solid components are collected; then 200ml of titanium tetrachloride was added to the solid component, and the reaction was carried out by heating at 110℃for 2 hours, and the obtained solid component was subjected to thermal filtration, and then the solid catalyst component was sufficiently washed with purified hexane until no precipitated free titanium compound was detected in the washing liquid, and dried to obtain a spherical-like solid catalyst component (A). The composition and average particle diameter of the solid catalyst component (A) are shown in Table 1.
(2) Slurry polymerization of ethylene
As in example 1. 152g of a polymer mass was obtained, the polymer properties being given in Table 2.
Example 4
(1) Preparation of the catalyst component
As in example 3.
(2) Slurry polymerization of ethylene
As in example 2. 160g of a polymer material was obtained, and the polymer properties are shown in Table 2.
Example 5
To the reactor fully replaced with nitrogen gas, 4.76g of magnesium dichloride, 35mL of n-decane, 34mL of isooctanol and 1.7mL of di-n-butyl sebacate (ester/magnesium: 0.1) were added, and the mixture was stirred and heated to 130℃and reacted at this temperature for 3 hours to form a uniform solution, cooled to room temperature, and then added dropwise to 200mL of titanium tetrachloride maintained at-5℃over 1 hour. After the dripping is finished, the temperature of the mixture is kept at-5 ℃ for 0.5 hour, then the system is heated to 110 ℃ within 1 hour and 55 minutes, the temperature is kept for 2 hours, and after the reaction is finished, the generated solid components are subjected to hot filtration separation, and the solid components are collected; then 200ml of titanium tetrachloride was added to the solid component, and the reaction was carried out by heating at 110℃for 2 hours, and the obtained solid component was subjected to thermal filtration, and then the solid catalyst component was sufficiently washed with purified hexane until no precipitated free titanium compound was detected in the washing liquid, and dried to obtain a spherical-like solid catalyst component (A). The composition and average particle diameter of the solid catalyst component (A) are shown in Table 1.
(2) Slurry polymerization of ethylene
1L of hexane, 2mmol of triisobutylaluminum and 7mg of the solid catalyst component (A) obtained in the step (1) were added to a 2L stainless steel high-pressure stirring reaction vessel, and then the temperature was raised, and ethylene was started to be added when the temperature of the vessel was raised to 60℃and the reaction was carried out for 6 hours while maintaining the vessel temperature at 65℃and the ethylene partial pressure at 0.4 MPa. After the polymerization was completed, the addition of ethylene was stopped, the temperature was lowered and the pressure was released to obtain 190g of a polymer material, and the properties of the polymer were shown in Table 2.
Comparative example 1
(1) Preparation of the catalyst component
The procedure is as in example 1, except that no fatty acid ester is added.
(2) Slurry polymerization of ethylene
As in example 1, 166g of a polymer material was obtained, and the polymer properties are shown in Table 2.
Comparative example 2
(1) Preparation of the catalyst component
As in comparative example 1.
(2) Slurry polymerization of ethylene
As in example 2. 178g of a polymer were obtained, the polymer properties being given in Table 2.
Comparative example 3
(1) Preparation of the catalyst component
To the reactor fully replaced with nitrogen gas, 4.76g of magnesium dichloride, 28mL of n-decane and 20mL of isooctanol were added, stirred and heated to 130℃and reacted at this temperature for 3 hours to form a uniform solution, 3.1 g (15 mmol) of tetraethoxysilane was added to the solution, cooled to 50℃and stirred and dispersed at 50℃for 2 hours, and then the above solution was cooled to room temperature and added dropwise to 200mL of titanium tetrachloride maintained at-10℃over 1 hour. After the dripping is finished, the temperature of the mixture is kept at-10 ℃ for 0.5 hour, then the system is heated to 100 ℃ within 1 hour and 50 minutes, the temperature is kept for 2 hours, and after the reaction is finished, the generated solid components are subjected to hot filtration separation, and the solid components are collected; then 200ml of titanium tetrachloride was added to the solid component, and the reaction was carried out by heating at 110℃for 2 hours, and the obtained solid component was subjected to thermal filtration, and then the solid catalyst component was sufficiently washed with purified hexane until no precipitated free titanium compound was detected in the washing liquid, and dried to obtain a spherical-like solid catalyst component (A). The composition and average particle diameter of the solid catalyst component (A) are shown in Table 1.
(2) Slurry polymerization of ethylene
As in example 2, 195g of a polymer material was obtained, and the polymer properties are shown in Table 2.
Comparative example 4
(1) Preparation of the catalyst component
1.7ml of isopropyl isovalerate (molar ester/magnesium 0.2) was added as in example 1.
(2) Slurry polymerization of ethylene
As in example 2, 138g of a polymer material was obtained, and the polymer properties are shown in Table 2.
TABLE 1
Figure BDA0003443293740000141
Figure BDA0003443293740000151
TABLE 2
Figure BDA0003443293740000152
From the above examples, it is apparent that the catalyst according to the present invention has a remarkable improvement in bulk density of polymer powder when used for preparing ultra-high molecular weight polyethylene, and particularly has relatively stable polymerization activity, little fluctuation in bulk density and fine powder content of polymer, and small decrease in viscosity average molecular weight of polymer when polymerization temperature is raised. The performance shows that the catalyst can be used for preparing the ultra-high molecular weight polyethylene at a higher temperature, so that the heat removal bottleneck in the production process of the ultra-high molecular weight polyethylene is improved, and the production capacity of a single device is improved; secondly, as the ultra-high molecular weight polyethylene powder prepared by the catalyst has higher bulk density, the powder separation is smoother; meanwhile, the scaling trend of the inner wall of the polymerization reactor is greatly improved due to the low content of the fine powder generated in the polymerization process, and the long-period operation capability of the device is enhanced. Therefore, the solid catalyst component and the catalyst for the ultra-high molecular weight polyethylene have good industrial application prospects.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.

Claims (17)

1. An ultra high molecular weight polyethylene catalyst component comprising magnesium chloride, a titanium compound and a C8-C25 fatty acid ester, prepared by a process comprising the steps of: (1) Mixing magnesium chloride with a C6-C12 fatty alcohol to form a magnesium chloride solution; (2) Mixing the magnesium chloride solution with a titanium compound in the presence of a C8-C25 fatty acid ester, and precipitating to obtain solid catalyst particles containing magnesium chloride, the titanium compound and the C8-C25 fatty acid ester.
2. The ultra-high molecular weight polyethylene catalyst component according to claim 1, wherein the C8-C25 fatty acid ester is selected from one or more of C1-C20 alkyl esters of aliphatic C8-C25 monocarboxylic acids, aliphatic C8-C20 monocarboxylic acids, C1-C4 alkyl monoesters of dicarboxylic acids, C1-C4 alkyl diesters of dicarboxylic acids; preferably, the C8-C25 fatty acid ester is selected from one or more of isopropyl dodecanoate, isopropyl tetradecanoate, n-butyl tetradecanoate, di-n-butyl sebacate, (poly) (alkylene glycol) monoacetate or diacetate, (poly) (alkylene glycol) mono-or di-tetradecanoate, (poly) (alkylene glycol) mono-or di-dodecanoate and glyceryl tri (acetate).
3. The ultra high molecular weight polyethylene catalyst component according to claim 2, wherein the C8-C25 fatty acid ester is selected from one or more of isopropyl myristate, isopropyl laurate and di-n-butyl sebacate.
4. An ultra high molecular weight polyethylene catalyst component according to any one of claims 1 to 3, wherein the C8-C25 fatty acid ester content is greater than 0 and less than or equal to 20% by weight, preferably 2 to 10% by weight.
5. The ultra-high molecular weight polyethylene catalyst component according to claim 4, wherein the titanium compound is selected from the group consisting of titanium having the general formula Ti (OR) 4-n Cl n Wherein R is alkyl with 2-6 carbon atoms, n is more than or equal to 0 and less than or equal to 4; preferably, the titanium compound is selected from one or more of titanium tetrachloride, trichloro-mono-ethoxy titanium, trichloro-mono-propoxy titanium, trichloro-mono-butoxy titanium, trichloro-mono-pentoxy titanium, trichloro-mono-hexoxy titanium, dichloro-di-ethoxy titanium, dichloro-di-propoxy titanium, dichloro-di-pentoxy titanium, dichloro-di-hexoxy titanium, mono-chloro-triethoxy titanium, mono-chloro-tripropoxy titanium, mono-chloro-tri-pentoxy titanium, mono-chloro-tri-hexoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium, tetrapropoxy titanium, tetrahexoxy titanium; titanium tetrachloride is more preferred.
6. The ultra-high molecular weight polyethylene catalyst component according to claim 1, wherein the C6-C12 fatty alcohol is selected from one or more of the group consisting of hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol and octadecanol; preferably one or more of the group consisting of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol; more preferably 2-ethylhexanol.
7. The ultra-high molecular weight polyethylene catalyst component according to claim 1, wherein the magnesium chloride solution further comprises C8-C12 alkane, preferably, the C8-C12 alkane is selected from one or more of n-octane and isomer, n-nonane and isomer, n-decane and isomer, n-undecane and isomer and n-dodecane and isomer; more preferably decane.
8. A process for preparing the ultra high molecular weight polyethylene catalyst component of claim 1, comprising the steps of:
(1) Mixing magnesium chloride with a C6-C12 fatty alcohol to form a magnesium chloride solution;
(2) At C 8 -C 25 Mixing the above magnesium chloride solution with titanium compound at a temperature below 40deg.C, heating, mixing at 80-150deg.C for more than 0.5 hr, and precipitating to obtain a solution containing magnesium chloride, titanium compound and C 8 -C 25 Catalyst solid particles of fatty acid esters in an amount of 0 to 0.5 mole of C per mole of magnesium chloride 8 -C 25 Fatty acid esters of (a).
9. The method of preparing an ultra high molecular weight polyethylene catalyst component according to claim 8, wherein said C8-C25 fatty acid ester is selected from one or more of C1-C20 alkyl esters of aliphatic C8-C25 monocarboxylic acids, aliphatic C8-C20 monocarboxylic acids, C1-C4 alkyl monoesters of dicarboxylic acids, C1-C4 alkyl diesters of dicarboxylic acids; preferably, the fatty acid ester is selected from one or more of isopropyl dodecanoate, isopropyl tetradecanoate, n-butyl tetradecanoate, di-n-butyl sebacate, (poly) (alkylene glycol) monoacetate or diacetate, (poly) (alkylene glycol) mono-or di-tetradecanoate, (poly) (alkylene glycol) mono-or di-dodecanoate and glyceryl tri (acetate).
10. The method of preparing an ultra high molecular weight polyethylene catalyst component according to claim 9, wherein the fatty acid ester is selected from one or more of isopropyl myristate, isopropyl laurate and di-n-butyl sebacate.
11. The method for preparing an ultra-high molecular weight polyethylene catalyst component according to claim 8, wherein the C6-C12 fatty alcohol is one or more selected from the group consisting of hexanol, 2-methylpentanol, 2-ethylbutanol, heptanol, 2-ethylhexanol, octanol, decanol, dodecanol, tetradecanol and octadecanol; preferably one or more of the group consisting of 2-ethylhexanol, 2-methylpentanol and 2-ethylbutanol; more preferably 2-ethylhexanol.
12. The method for preparing an ultra-high molecular weight polyethylene catalyst component according to claim 8, wherein in the step (1), the magnesium chloride solution further comprises C8-C12 alkane, preferably, the C8-C12 alkane is selected from one or more of n-octane and isomer, n-nonane and isomer, n-decane and isomer, n-undecane and isomer, and n-dodecane and isomer; more preferably decane.
13. The method for preparing an ultra high molecular weight polyethylene catalyst component according to claim 8, further comprising step (3) after step (2): washing the solid catalyst component obtained in step (2) with an inert solvent, preferably selected from the group consisting of C5-C12 alkanes and aromatic hydrocarbons.
14. The method for preparing an ultra high molecular weight polyethylene catalyst component according to claim 8, wherein in the step (1), the molar ratio of the fatty alcohol to the magnesium chloride is 1 to 10; in the step (2), the molar ratio of the titanium compound to the magnesium chloride is 1-100, the initial mixing temperature is-25-30 ℃, the mixing temperature after heating is 90-130 ℃, and the mixing time after heating is 0.5-10 hours.
15. The method for preparing an ultra high molecular weight polyethylene catalyst component according to claim 14, wherein in the step (1), the molar ratio of the fatty alcohol to the magnesium chloride is 2 to 6; in the step (2), the molar ratio of the titanium compound to the magnesium chloride is 20-50, the initial mixing temperature is-25-30 ℃, and the mixing time is 1-5 hours after the temperature is raised.
16. An ultra-high molecular weight polyethylene catalyst characterized by comprising the following components:
(I) An ultra high molecular weight polyethylene catalyst component according to claims 1-7;
(II) an organoaluminum compound of the formula AlR1 n X 3-n Wherein R1 is an alkyl group having 2 to 8 carbon atoms, X is a halogen, and n is 1, 2 or 3;
wherein the proportion of the component (II) to the component (I) is 5 to 500, preferably 20 to 200, of aluminum to titanium in terms of aluminum-titanium molar ratio.
17. The ultra-high molecular weight polyethylene catalyst according to claim 16, wherein the organoaluminum compound is selected from one or more of the group consisting of triethylaluminum, triisobutylaluminum, diethylaluminum chloride, diethylaluminum dichloride and ethylaluminum sesquichloride, preferably the organoaluminum compound is selected from at least one of triethylaluminum, diethylaluminum monochloride and triisobutylaluminum.
CN202111647902.0A 2021-12-29 2021-12-29 Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof Pending CN116410377A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111647902.0A CN116410377A (en) 2021-12-29 2021-12-29 Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111647902.0A CN116410377A (en) 2021-12-29 2021-12-29 Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116410377A true CN116410377A (en) 2023-07-11

Family

ID=87054872

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111647902.0A Pending CN116410377A (en) 2021-12-29 2021-12-29 Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116410377A (en)

Similar Documents

Publication Publication Date Title
CA1302640C (en) Process for producing stereoregular polymers having a narrow molecular weight distribution
US5459116A (en) Highly active catalyst for the polymerization of olefins and method for the preparation of the same
FI71325C (en) FOERFARANDE FOER PRODUKTION AV ALFA-OLEFINPOLYMERER ELLER -COPOLYMERER OCH DAERI ANVAEND FAST TITANKATALYSATORKONPONENT
CA2510679A1 (en) Polymerization catalysts comprising titanium and magnesium
EP2701843A1 (en) Emulsion process for improved large spherical polypropylene catalysts
JPS61123607A (en) Polymerization of copolymerization of alpha-olefin in gas phase
KR20160073986A (en) Spherical carriers for olefin polymerization catalyst, catalyst components, catalyst, and preparation methods therefor
JPH0725819B2 (en) Process for polymerizing olefins using improved Ziegler-Natsuta catalyst
CA2060053A1 (en) Process for producing ethylene polymers
TW201522400A (en) Catalyst composition for olefin polymerization and application of same
CN109526217B (en) Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and derivatives thereof
CN101165073B (en) Catalyst component used for olefin polymerization reaction and catalyst thereof
WO2018114453A1 (en) Catalyst components for the polymerization of olefins and catalysts therefrom obtained
JPH0819184B2 (en) Liquid monomer polymerization method
CN110734510B (en) Olefin polymerization catalyst containing cyclotri veratrum hydrocarbon and its derivatives
CA2058215A1 (en) High activity vanadium-based catalyst
EP2462168A2 (en) Mixed donor system for high melt flow and high activity
CN116410377A (en) Ultra-high molecular weight polyethylene catalyst component and preparation method and application thereof
IE74880B1 (en) Catalytic solid usable for the stereospecific polymerisation of alpha-olefins process for preparing it and process for polymerising alpha-olefins in its presence
WO2004065431A1 (en) Method of polymerization and copolymerization of ethylene
WO2001004166A1 (en) Process for producing polypropylene
JPS6026407B2 (en) Method for producing ethylene copolymer
CN102432709B (en) Titaniferous spherical catalyst component used for vinyl polymerization and catalyst
US5071928A (en) Process for polymerizing ethylene and copolymerizing ethylene with alpha-olefins and relevant catalyst
JPS61151207A (en) Production of poly(1-butene)

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