CN117946298A - Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof - Google Patents

Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof Download PDF

Info

Publication number
CN117946298A
CN117946298A CN202211291169.8A CN202211291169A CN117946298A CN 117946298 A CN117946298 A CN 117946298A CN 202211291169 A CN202211291169 A CN 202211291169A CN 117946298 A CN117946298 A CN 117946298A
Authority
CN
China
Prior art keywords
compound
titanium
catalyst component
molecular weight
high molecular
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
CN202211291169.8A
Other languages
Chinese (zh)
Inventor
郭正阳
周俊领
刘萃莲
王迎
雷际平
唐璐
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.)
Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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 Sinopec Beijing Chemical Research Institute Co ltd, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Chemical Research Institute Co ltd
Priority to CN202211291169.8A priority Critical patent/CN117946298A/en
Publication of CN117946298A publication Critical patent/CN117946298A/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • 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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

The invention belongs to the technical field of olefin polymerization catalysts, and discloses a catalyst component for preparing ultra-high molecular weight polyethylene, which comprises, by weight, 1-10% of titanium, 10-20% of magnesium, 0.01-1% of phosphorus, 1-10% of alkoxy, 0.01-5% of an electron donor, 40-70% of halogen and 0.1-10% of an inert solvent. The catalyst component of the invention has higher activity, the prepared polymer has higher molecular weight and the bulk density of the polymer is obviously higher.

Description

Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof
Technical Field
The invention belongs to the technical field of olefin polymerization catalysts, and particularly relates to a catalyst component for preparing ultrahigh molecular weight polyethylene and a preparation method thereof.
Background
Ultra-high molecular weight polyethylene is generally prepared by using a granular Z-N catalyst to facilitate the particle size control of the product. One of the preparation methods of the particulate Z-N catalyst is to dissolve a magnesium compound into a uniform solution, and then react with a titanium compound to precipitate magnesium chloride particles while supporting titanium chloride, as disclosed in patent documents CN85100997, CN1112373C, CN1229092A, CN1958620, and the like. In such a method, a magnesium compound is generally dissolved in a polar solvent, and the dissolution liquid is contacted with titanium tetrachloride to react, thereby precipitating titanium-magnesium-containing catalyst component particles.
In the prior art, the main solvent for dissolving magnesium chloride is an alcohol compound or forms a mixed solvent together with other solvents. Different magnesium chloride dissolution systems form different catalyst systems, and these catalyst components have respective characteristics.
Generally, the fewer the number of carbon atoms in an alcohol compound used for dissolving magnesium chloride, the higher the polarity of the alcohol compound is, so that the dissolution of magnesium chloride is facilitated, and the smaller the steric hindrance around an active center atom in a prepared catalyst component is, the higher the activity is when the catalyst component is used for ethylene polymerization; meanwhile, the fewer the number of carbon atoms in the alcohol compound adopted for dissolving magnesium chloride, the faster the precipitation reaction of the dissolution liquid and the titanium compound, the poorer the controllability of the precipitated particle morphology, and the harder the prepared catalyst component particle morphology is controlled.
For the preparation of ultra-high molecular weight polyethylene, it is desirable that the particle morphology of the catalyst is as spherical as possible and the particle size distribution is as concentrated as possible while the catalyst component has a certain activity. The prior art has not fully met the requirements.
For example, in patent document CN85100997, magnesium halide is dissolved in an organic epoxy compound and an organic phosphorus compound to form a homogeneous solution, and then reacted with at least one precipitation aid, a halide of transition metal titanium, and a derivative thereof. Because the organic epoxy compound and the organic phosphorus compound which do not contain active hydrogen are adopted as solvents, the magnesium chloride is slowly dissolved, the reaction of the organic epoxy compound and the titanium tetrachloride is convenient to control, the precipitated particles are better in particle shape, are similar to spheres, the prepared polymer is better in particle shape and higher in bulk density, but because the magnesium chloride is dissolved without adopting low-carbon alcohol compounds, the activity is very low when the organic epoxy compound and the organic phosphorus compound are used for ethylene polymerization, and the ash content in the prepared ultra-high molecular weight polyethylene is high.
For example, in patent document CN1112373C, magnesium chloride is dissolved in isooctanol using decane as a dispersant, and silane is added as a precipitating agent, and the catalyst component particles are precipitated by reaction with titanium tetrachloride. The solvent used in the system is isooctyl alcohol, the raw material is simple, the catalyst component has higher activity and better hydrogen regulation performance in ethylene polymerization, but the preparation method of the catalyst component uses more titanium tetrachloride, the activity of the catalyst component is not too high, and the particle shape is not too regular.
For example, patent document CN1229092a discloses a catalyst for ethylene polymerization or copolymerization, which is prepared by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound, adding a low carbon alcohol as an electron donor activator to form a homogeneous solution, and reacting with at least one acid anhydride-based co-precipitation agent, and a halide of transition metal titanium and its derivatives. The catalyst shows high activity when used in slurry polymerization of ethylene, but the morphology and particle size distribution of the catalyst component prepared by the method still need to be improved.
For example, in patent document CN1958620, a magnesium halide is dissolved in an organic epoxy compound, an organic phosphorus compound and a low-carbon alcohol to form a homogeneous solution, and then reacted with at least one silane compound and a halide of transition metal titanium and its derivative. The catalyst has higher activity when used for slurry polymerization of ethylene, but the particle morphology and particle size distribution of the catalyst component prepared by the method still need to be improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst component for preparing ultra-high molecular weight polyethylene, which has high activity and high molecular weight and bulk density.
According to a first aspect of the present invention, there is provided a catalyst component for the preparation of ultra-high molecular weight polyethylene, the catalyst component comprising titanium, magnesium, alkoxy groups, phosphorus, an electron donor, halogen and an inert solvent, wherein the titanium content is 1 to 10%, the magnesium content is 10 to 20%, the phosphorus content is 0.01 to 1%, the alkoxy groups content is 1 to 10%, the electron donor content is 0.01 to 5%, the halogen content is 40to 70%, and the inert solvent content is 0.1 to 10% by weight.
The second aspect of the present invention provides a method for preparing the catalyst component for preparing polyethylene, wherein the preparation method is a first method or a second method:
A method one, comprising the steps of:
a. mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and an optional diluent, and stirring for reaction to obtain a uniform solution;
b. Adding an electron donor and an optional precipitation aid into the uniform solution for reaction;
c. Cooling the material obtained in the step b to-30 ℃ to 5 ℃, dropwise adding a titanium compound for reaction, heating to separate out solid particles, washing with an inert solvent, and drying to obtain the catalyst component;
the second method comprises the following steps:
(1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and an optional diluent, and stirring for reaction to obtain a uniform solution;
(2) Optionally adding a precipitation aid to the homogeneous solution for reaction;
(3) And (3) cooling the material obtained in the step (2) to-30 ℃ to 5 ℃, dropwise adding a titanium compound for reaction, then dropwise adding an organic alcohol compound and an electron donor, heating to separate out solid particles, washing with an inert solvent, and drying to obtain the catalyst component.
The catalyst component of the invention has high activity when being used for ethylene polymerization, and the prepared polyethylene has high molecular weight and high bulk density.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
According to a first aspect of the present invention, there is provided a catalyst component for the preparation of ultra-high molecular weight polyethylene, the catalyst component comprising titanium, magnesium, alkoxy groups, phosphorus, an electron donor, halogen and an inert solvent, wherein the titanium content is 1 to 10% by weight, the magnesium content is 10 to 20% by weight, the phosphorus content is 0.01 to 1% by weight, the alkoxy group content is 1 to 10% by weight, the electron donor content is 0.01 to 5% by weight, the halogen content is 40 to 70% by weight, and the inert solvent content is 0.1 to 10% by weight.
Preferably, in the catalyst component, the titanium content is 2-7% by weight, the magnesium content is 12-20% by weight, the phosphorus content is 0.1-0.8% by weight, the alkoxy content is 2-8% by weight, the electron donor content is 0.1-4.8% by weight, the halogen content is 45-60% by weight, and the inert solvent content is 0.5-8% by weight.
According to a second aspect of the present invention, there is provided a process for preparing the above catalyst component for the preparation of ultra-high molecular weight polyethylene, the process being either process one or process two:
A method one, comprising the steps of:
a. mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and an optional diluent, and stirring for reaction to obtain a uniform solution;
b. Adding an electron donor and an optional precipitation aid into the uniform solution for reaction;
c. Cooling the material obtained in the step b to-30 ℃ to 5 ℃, dropwise adding a titanium compound for reaction, heating to separate out solid particles, washing with an inert solvent, and drying to obtain the catalyst component;
the second method comprises the following steps:
(1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and an optional diluent, and stirring for reaction to obtain a uniform solution;
(2) Optionally adding a precipitation aid to the homogeneous solution for reaction;
(3) And (3) cooling the material obtained in the step (2) to-30 ℃ to 5 ℃, dropwise adding a titanium compound for reaction, then dropwise adding an organic alcohol compound and an electron donor, heating to separate out solid particles, washing with an inert solvent, and drying to obtain the catalyst component.
In the present invention, the magnesium compound may be any of various existing magnesium compounds which can be used for olefin polymerization catalysts, for example, the magnesium compound may be magnesium dihalide or a derivative in which one halogen atom in the formula of magnesium dihalide is substituted with a hydrocarbon group or a halogen hydrocarbyloxy group.
According to the present invention, the organic epoxy compound may be selected from aliphatic olefins having 2 to 8 carbon atoms, diolefins, halogenated aliphatic olefins, oxides of diolefins, glycidyl ethers or internal ethers. Specifically, at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether may be used.
In the present invention, the organophosphorus compound may be selected from hydrocarbyl or halocarbyl esters of orthophosphoric acid, hydrocarbyl or halocarbyl esters of phosphorous acid. Specifically, the organic acid is selected from trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite and benzyl phosphite.
According to the present invention, the organic alcohol compound may be selected from linear alcohols having 1 to 8 carbon atoms or isomeric alcohols. For example, at least one selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol and isooctanol may be used.
In the present invention, the electron donor may be selected from an oxygen-containing ester compound or an acid anhydride compound having 6 or more carbon atoms, and preferably at least one selected from a benzoate compound, a phthalate compound and a phthalic anhydride compound.
According to the invention, the precipitation aid can be at least one selected from organic acid anhydride, organic acid, ether and ketone; preferably at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether and pentyl ether.
In the present invention, the diluent may be benzene, toluene, xylene, chlorobenzene or derivatives thereof, optionally added or not added when preparing a homogeneous solution.
According to the invention, the inert solvent may be selected from C 5-C15 alkanes or C 6-C8 aromatics, preferably at least one of hexane, heptane, toluene. The washing can be carried out by selecting toluene for washing and then hexane for washing.
In the present invention, the titanium compound may be selected conventionally in the art, for example, the titanium compound has the general formula Ti (OR ') aX'b in which R ' is an aliphatic hydrocarbon group OR an aromatic hydrocarbon group of C 1-C14, X ' is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, and a+b=3 OR 4.
Specifically, the titanium compound may be at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxide and titanium trichloride, preferably titanium tetrachloride, titanium trichloromonoethoxide or titanium trichloride.
According to the invention, in the first and second methods, the conditions for stirring reaction and the conditions for heating to precipitate solid particles are the same. Specifically, the conditions for the stirring reaction include: stirring speed is 350-500rpm, reaction temperature is 50-60 ℃, and reaction time is 0.5-1.5h. The conditions for heating to precipitate solid particles include: the temperature is raised to 60-110 ℃ and the constant temperature is maintained for 0.5-2h.
In the first and second methods of the present invention, the organic epoxy compound is used in an amount of 0.01 to 10 moles, preferably 0.02 to 4 moles, per mole of the magnesium compound; 0.01 to 10 moles, preferably 0.02 to 4 moles of the organic phosphorus compound; the organic alcohol compound is used in an amount of 0.01 to 15 moles, preferably 0.05 to 10 moles; the dosage of the diluent is 0.2-5L; the electron donor is used in an amount of 0.001 to 0.5 mol, preferably 0.01 to 0.2 mol; the amount of the precipitation aid is 0 to 0.1 mole, preferably 0 to 0.05 mole; the titanium compound is used in an amount of 0.2 to 30 moles, preferably 1 to 20 moles.
The catalyst component of the present invention can be used in combination with an organoaluminum co-catalyst when used for ethylene polymerization, and the organoaluminum co-catalyst can be conventionally selected according to the prior art, for example, aluminum alkyl compound or aluminum alkoxy compound, specifically triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane.
According to the present invention, the polymerization of ethylene may be carried out under the protection of an inert gas in an inert solvent containing the polymerized monomer or in the liquid phase of the monomer or in the gas phase. The polymerization conditions include: the reaction temperature is 50-90 ℃, preferably 50-75 ℃; the reaction pressure is 0.01-5MPa, preferably 0.02-2MPa; the reaction time is 0.5 to 4 hours, preferably 1 to 3 hours. In addition, the kind and amount of the inert gas and the solvent are well known to those skilled in the art during the polymerization reaction, and will not be described herein.
The substances and parameters not defined in the present invention can be selected according to the prior art, and are conventional in the art.
The invention will be further illustrated with reference to the following examples. But are not limited by these examples.
Determination of data in the following examples and comparative examples:
the apparent Bulk Density (BD) of the polymer was measured with reference to ASTM D1895-96.
The contents of elements titanium, magnesium and halogen in the catalyst are determined by adopting a chemical analysis method, the contents of alkoxy, electron donor and inert solvent are determined by adopting gas chromatography, and the content of phosphorus is determined by adopting X-ray energy spectrum analysis.
The polymer molecular weight (Mv) was determined by the viscosity method.
Example 1
Preparing a catalyst component: adding 4.8 g of magnesium chloride, 76 ml of toluene, 4.0 ml of epichlorohydrin, 12.5 ml of tributyl phosphate and 4.0 ml of butanol into a reaction kettle, reacting for 1 hour at the stirring speed of 450rpm and the temperature of 60 ℃, adding 1.0 g of phthalic anhydride and 0.4 ml of ethyl benzoate, reacting for 1 hour, cooling to-28 ℃, dropwise adding 56 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene at the temperature of 60 ℃, washing for 4 times with hexane as an organic solvent, and drying to obtain the catalyst component. The composition of the catalyst components is shown in Table 1.
Polymerization of ethylene: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5mg of a catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and molecular weight were measured as shown in table 2.
Example 2
Preparing a catalyst component: adding 4.8 g of magnesium chloride, 76 ml of toluene, 2.0 ml of epoxy chloropropane, 6.0 ml of tributyl phosphate, 3.0 ml of ethanol and 6.0 ml of isooctanol into a reaction kettle, reacting for 1 hour at the stirring speed of 450rpm and the temperature of 60 ℃, adding 1.0 ml of isobutyl phthalate, reacting for 1 hour, cooling to-20 ℃, dropwise adding 56 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene at the temperature of 60 ℃, washing for 4 times with hexane as an organic solvent, and drying to obtain the catalyst component. The composition of the catalyst components is shown in Table 1.
Polymerization of ethylene: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5mg of a catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and molecular weight were measured as shown in table 2.
Example 3
Preparing a catalyst component: adding 4.8 g of magnesium chloride, 76 ml of toluene, 4.0 ml of epichlorohydrin, 12.5 ml of tributyl phosphate and 2.0 ml of butanol into a reaction kettle, reacting for 1 hour at the stirring speed of 450rpm and the temperature of 60 ℃, adding 0.4 g of phthalic anhydride and 1.0 ml of ethyl benzoate, reacting for 1 hour, cooling to-28 ℃, dropwise adding 56 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene and 60 ℃, washing for 4 times with hexane as an organic solvent, and drying to obtain the catalyst component. The composition of the catalyst components is shown in Table 1.
Polymerization of ethylene: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5mg of a catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and molecular weight were measured as shown in table 2.
Example 4
Preparing a catalyst component: adding 4.8 g of magnesium chloride, 76 ml of toluene, 4.0 ml of epichlorohydrin and 12.5 ml of tributyl phosphate into a reaction kettle, reacting for 1 hour at the stirring rotation speed of 450rpm and the temperature of 60 ℃, adding 1.4 g of phthalic anhydride, reacting for 1 hour, cooling to-28 ℃, dropwise adding 56 ml of titanium tetrachloride, dropwise adding 6.0 ml of butanol, dropwise adding 1.0ml of isobutyl phthalate, heating to 80 ℃ within 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing for 4 times with organic solvent hexane, and drying to obtain the catalyst component. The composition of the catalyst components is shown in Table 1.
Polymerization of ethylene: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5mg of a catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and molecular weight were measured as shown in table 2.
Comparative example 1
Preparing a catalyst component: adding 4.8 g of magnesium chloride, 76 ml of toluene, 4.0 ml of epichlorohydrin, 12.5 ml of tributyl phosphate and 4.0 ml of butanol into a reaction kettle, reacting for 1 hour at the stirring speed of 450rpm and the temperature of 60 ℃, adding 1.4 g of phthalic anhydride, reacting for 1 hour, cooling to-28 ℃, dropwise adding 56 ml of titanium tetrachloride, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene at the temperature of 60 ℃, washing for 4 times with hexane as an organic solvent, and drying to obtain the catalyst component. The composition of the catalyst components is shown in Table 1.
Polymerization of ethylene: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5mg of a catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and molecular weight were measured as shown in table 2.
Comparative example 2
Preparing a catalyst component: adding 4.8 g of magnesium chloride, 76 ml of toluene, 4.0 ml of epichlorohydrin and 12.5 ml of tributyl phosphate into a reaction kettle, reacting for 1 hour at the stirring rotation speed of 450rpm and the temperature of 60 ℃, adding 1.4 g of phthalic anhydride, reacting for 1 hour, cooling to-28 ℃, dropwise adding 56 ml of titanium tetrachloride, dropwise adding 1.0ml of isobutyl phthalate, heating to 80 ℃ in 4 hours, washing twice with 120 ml of toluene at 60 ℃, washing for 4 times with hexane as an organic solvent, and drying to obtain a catalyst component. The composition of the catalyst components is shown in Table 1.
Polymerization of ethylene: a2-liter polymerization reactor was alternately purged with nitrogen and evacuated three times, 1 liter of n-hexane, 2mmol of triethylaluminum and 5mg of a catalyst component were added, the temperature was raised to 60℃and ethylene was further added to maintain the reactor pressure at 0.7MPa, and the reaction was carried out at 60℃for 2 hours. The catalyst activity was calculated and the polymer bulk density and molecular weight were measured as shown in table 2.
TABLE 1
TABLE 2
As can be seen from Table 1, the catalyst component of the present invention has higher activity, the molecular weight of the polymer prepared is higher, and the bulk density of the polymer is significantly higher.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.

Claims (11)

1. The catalyst component for preparing the ultra-high molecular weight polyethylene is characterized by comprising, by weight, 1-10% of titanium, 10-20% of magnesium, 0.01-1% of phosphorus, 1-10% of alkoxy, 0.01-5% of an electron donor, 40-70% of halogen and 0.1-10% of an inert solvent.
2. The catalyst component for the preparation of ultra-high molecular weight polyethylene according to claim 1, wherein the titanium is contained in an amount of 2 to 7% by weight, the magnesium is contained in an amount of 12 to 20% by weight, the phosphorus is contained in an amount of 0.1 to 0.8% by weight, the alkoxy is contained in an amount of 2 to 8% by weight, the electron donor is contained in an amount of 0.1 to 4.8% by weight, the halogen is contained in an amount of 45 to 60% by weight, and the inert solvent is contained in an amount of 0.5 to 8% by weight.
3. The method for preparing a catalyst component for the preparation of ultra-high molecular weight polyethylene according to claim 1 or 2, characterized in that the preparation method is a method one or a method two:
A method one, comprising the steps of:
a. mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound, an organic alcohol compound and an optional diluent, and stirring for reaction to obtain a uniform solution;
b. Adding an electron donor and an optional precipitation aid into the uniform solution for reaction;
c. Cooling the material obtained in the step b to-30 ℃ to 5 ℃, dropwise adding a titanium compound for reaction, heating to separate out solid particles, washing with an inert solvent, and drying to obtain the catalyst component;
the second method comprises the following steps:
(1) Mixing a magnesium compound, an organic epoxy compound, an organic phosphorus compound and an optional diluent, and stirring for reaction to obtain a uniform solution;
(2) Optionally adding a precipitation aid to the homogeneous solution for reaction;
(3) And (3) cooling the material obtained in the step (2) to-30 ℃ to 5 ℃, dropwise adding a titanium compound for reaction, then dropwise adding an organic alcohol compound and an electron donor, heating to separate out solid particles, washing with an inert solvent, and drying to obtain the catalyst component.
4. The method for preparing a catalyst component for the preparation of ultra-high molecular weight polyethylene according to claim 3, wherein the magnesium compound is magnesium dihalide or a derivative in which one halogen atom in the formula of magnesium dihalide is replaced with a hydrocarbon group or a halogen hydrocarbyloxy group;
the organic epoxy compound is selected from aliphatic olefin, diene, halogenated aliphatic olefin, oxide of diene, glycidyl ether or internal ether with 2-8 carbon atoms; preferably at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether and diglycidyl ether.
5. The method for preparing a catalyst component for ultra-high molecular weight polyethylene production according to claim 3, wherein the organic phosphorus compound is selected from hydrocarbyl or halogenated hydrocarbyl esters of orthophosphoric acid, hydrocarbyl or halogenated hydrocarbyl esters of phosphorous acid; preferably trimethyl orthophosphate, triethyl orthophosphate, tributyl orthophosphate, triphenyl orthophosphate, trimethyl phosphite, triethyl phosphite, tributyl phosphite, benzyl phosphite;
The organic alcohol compound is selected from straight-chain alcohol or isomeric alcohol with carbon number of 1-8; preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-octanol and isooctanol.
6. The method for producing a catalyst component for the production of ultra-high molecular weight polyethylene according to claim 3, wherein the electron donor is selected from an oxygen-containing ester compound or an acid anhydride compound having 6 or more carbon atoms, preferably at least one selected from a benzoate compound, a phthalate compound and a phthalic anhydride compound.
7. The method for preparing a catalyst component for ultra-high molecular weight polyethylene production according to claim 3, wherein the precipitation aid is at least one selected from the group consisting of organic acid anhydride, organic acid, ether, ketone; preferably at least one of acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, pyromellitic dianhydride, acetic acid, propionic acid, butyric acid, acrylic acid, methacrylic acid, acetone, methyl ethyl ketone, benzophenone, methyl ether, diethyl ether, propyl ether, butyl ether and pentyl ether.
8. The method for preparing a catalyst component for ultra-high molecular weight polyethylene production according to claim 3, wherein the diluent is benzene, toluene, xylene, chlorobenzene or a derivative thereof; the inert solvent is selected from C 5-C15 alkane or C 6-C8 arene, preferably at least one of hexane, heptane and toluene.
9. The method for producing a catalyst component for the production of ultra-high molecular weight polyethylene according to claim 3, wherein the titanium compound has the general formula Ti (OR ') aX'b, wherein R ' is an aliphatic hydrocarbon group OR an aromatic hydrocarbon group of C 1-C14, X ' is a halogen atom, a is an integer of 0 to 2, b is an integer of 0 to 4, a+b=3 OR 4; the titanium compound is preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium monochloroethoxide and titanium trichloride, more preferably titanium tetrachloride, titanium monochloroethoxide or titanium trichloride.
10. The method for preparing a catalyst component for the preparation of ultra-high molecular weight polyethylene according to claim 3, wherein in the first and second methods, the condition of stirring reaction comprises: stirring speed is 350-500rpm, reaction temperature is 50-60 ℃, and reaction time is 0.5-1.5h; the temperature of the heating is 60-11O ℃.
11. The method for producing a catalyst component for the production of ultra-high molecular weight polyethylene according to claim 3, wherein in the first and second methods, the organic epoxy compound is used in an amount of 0.01 to 10 moles, preferably 0.02 to 4 moles, per mole of the magnesium compound; 0.01 to 10 moles, preferably 0.02 to 4 moles of the organic phosphorus compound; the organic alcohol compound is used in an amount of 0.01 to 15 moles, preferably 0.05 to 10 moles; the dosage of the diluent is 0.2-5L; the electron donor is used in an amount of 0.001 to O.5 mol, preferably 0.01 to 0.2 mol; the amount of the precipitation aid is 0 to 0.1 mole, preferably 0 to 0.05 mole; the titanium compound is used in an amount of 0.2 to 30 moles, preferably 1 to 20 moles.
CN202211291169.8A 2022-10-20 2022-10-20 Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof Pending CN117946298A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211291169.8A CN117946298A (en) 2022-10-20 2022-10-20 Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211291169.8A CN117946298A (en) 2022-10-20 2022-10-20 Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof

Publications (1)

Publication Number Publication Date
CN117946298A true CN117946298A (en) 2024-04-30

Family

ID=90803644

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211291169.8A Pending CN117946298A (en) 2022-10-20 2022-10-20 Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof

Country Status (1)

Country Link
CN (1) CN117946298A (en)

Similar Documents

Publication Publication Date Title
CN1359395A (en) Catalyst for ethylene homo-and co-polymerization
EP0219998A1 (en) Polymerisation of olefins using modified ziegler-natta catalyst
KR101010668B1 (en) A solid catalyst component for polymerization of ethylene, preparation thereof and a catalyst containing the same
US7153804B2 (en) Catalyst component for ethylene polymerization, the preparation thereof and catalyst comprising the same
CN103772537B (en) A kind of preparation method of ultrahigh molecular weight polyethylene(UHMWPE)
KR20160149265A (en) Method for preparation of a catalyst component used for olefin polymerization
CN102040693A (en) Gas-phase polymerization method and polymer of polybutene-1
CN104974283A (en) Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN105622798A (en) Catalyst component for olefin polymerization, preparation method and applications thereof
US4259461A (en) Process for producing propylene-ethylene block copolymers
CN102040692A (en) High-isotacticity polybutylene-1 polymer and preparation method thereof
CN117946298A (en) Catalyst component for preparing ultra-high molecular weight polyethylene and preparation method thereof
CN104974279A (en) Catalyst component used in ethylene polymerization reaction, catalyst and preparation method thereof
CN112661885B (en) Titanium magnesium-based catalyst component for olefin polymerization, preparation method, catalyst and application
CN112724284B (en) Solid catalyst component, preparation method, olefin polymerization catalyst and application
CN115490789B (en) Micron-sized catalyst component for olefin polymerization, preparation method thereof and olefin polymerization method
CN114426605A (en) Catalyst component for olefin polymerization and preparation method and application thereof
CN109705241B (en) Spherical catalyst and spherical catalyst component, preparation method and application thereof, and olefin polymerization method
CN103087227B (en) Catalyst component used in ethylene polymerization, and preparation method and application thereof
CN108341902B (en) Catalyst component for ethylene polymerization, preparation method thereof and catalyst for ethylene polymerization
CN115975083A (en) Catalyst component for ethylene polymerization, catalyst and ethylene polymerization reaction method
CN112707981A (en) Catalyst component for ethylene polymerization, catalyst and application
CN117946299A (en) Catalyst component for preparing polyethylene, and preparation method and application thereof
CN115960281B (en) Catalyst component for olefin polymerization, catalyst, method for preparing ultrahigh molecular weight polyolefin and application
CN118359748A (en) Catalyst component for olefin polymerization, preparation method thereof, catalyst and application

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