CN112646064A - Catalyst component for olefin polymerization, preparation method thereof, catalyst and application - Google Patents

Catalyst component for olefin polymerization, preparation method thereof, catalyst and application Download PDF

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CN112646064A
CN112646064A CN201910961043.9A CN201910961043A CN112646064A CN 112646064 A CN112646064 A CN 112646064A CN 201910961043 A CN201910961043 A CN 201910961043A CN 112646064 A CN112646064 A CN 112646064A
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compound
polymerization
catalyst component
titanium
alcohol
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CN112646064B (en
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王毅
马冬
郭子芳
苟清强
黄廷杰
徐世媛
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • 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 relates to a catalyst component for olefin polymerization, a preparation method thereof, a catalyst and application thereof, belonging to the field of olefin polymerization catalysts. The preparation raw materials of the catalyst component comprise the following components: (1) a magnesium compound; (2) a substance containing an aluminum element; (3) an organic epoxy compound; (4) an organic alcohol compound; (5) a titanium-containing compound. The catalyst prepared by the method has better activity and bulk density, the step of dissolution reaction of the precipitation aid is omitted, and the preparation period of the catalyst is shortened; meanwhile, the method avoids using phosphorus-containing compounds and phthalic anhydride with larger toxicity, and is more beneficial to environmental protection.

Description

Catalyst component for olefin polymerization, preparation method thereof, catalyst and application
Technical Field
The invention relates to the field of olefin polymerization catalysts, and in particular relates to a catalyst for ethylene polymerization reaction, a preparation method and application.
Background
Since the invention in the thirties of the twentieth century, polyethylene has been widely used in industry, agriculture, packaging and daily industry because of its abundant raw materials and excellent product performance.
The research of catalysts in the development of polyethylene has always been an important position in the synthesis and production of polyethylene. Among them, the titanium catalyst has been widely used and developed because of its high catalytic efficiency and low price.
Many studies and reports on the improvement of the catalyst performance are made, and the following aspects are mainly focused on: catalytic efficiency, particle morphology control, copolymerization ability, molecular weight distribution, and the like. For the production of general polyolefin resin, on the basis of further improving the catalyst performance, the catalyst preparation process is simplified, the catalyst cost is reduced, and an environment-friendly technology is developed to improve the benefit and enhance the competitiveness.
Chinese patent CN1282672C discloses a method for ethylene polymerization or copolymerization, the titanium-containing component of the catalyst is prepared by the following steps: (1) dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a uniform solution; (2) during or after the dissolution, simultaneously or respectively carrying out contact reaction with at least one organic alcohol and at least one compound selected from C3-C5 cyclic ethers; (3) and (3) carrying out contact reaction on the mixture obtained in the step (2) and at least one Ti-containing compound in the presence of at least one organic acid anhydride to obtain the titanium-containing solid catalyst component. When the catalyst system is used for ethylene polymerization, the defect of low apparent density of the obtained polymer is obvious.
Chinese patent CN1086191C proposes a catalyst for ethylene polymerization or copolymerization and its preparation method, wherein the catalyst is obtained by dissolving magnesium halide in organic epoxy compound, organic phosphorus compound, adding electron donor to form a uniform solution, reacting with at least one precipitation aid and halide of transition metal titanium or its derivative, and combining with organic aluminum compound during polymerization. The catalyst shows higher activity when used for ethylene polymerization, and the obtained polymer has higher apparent density.
In order to obtain catalyst solids in the preparation process of the two catalysts, both a dissolving system adopts an organic phosphorus compound and a method for adding a precipitation aid is adopted, particularly phthalic anhydride is adopted as the precipitation aid in the embodiment, and the phthalic anhydride is completely dissolved in a mixed solvent system and then cooled to be mixed with a titanium compound, so that the use of the precipitation aid correspondingly prolongs the preparation period of the catalyst. In addition, the auxiliary precipitating agent system has relatively high toxicity and high requirement on operation conditions.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for olefin polymerization, and particularly relates to a catalyst for ethylene polymerization, and a preparation method and application thereof. The improved titanium polyethylene catalyst is prepared under the condition of avoiding the adoption of the organic phosphorus-containing compound and the precipitation assistant, the catalyst prepared by the method has better performance than the catalyst disclosed in the patent, the step of dissolution reaction of the precipitation assistant is omitted, and the raw materials are more environment-friendly compared with the system containing the organic phosphorus-containing compound and phthalic anhydride while the preparation period of the catalyst is shortened.
One of the objects of the present invention is to provide a catalyst component for olefin polymerization, which is prepared from the following raw materials: (1) a magnesium compound; (2) a substance containing an aluminum element; (3) an organic epoxy compound; (4) an organic alcohol compound; (5) a titanium-containing compound.
Wherein the magnesium compound is one or more of magnesium dihalide, a complex of magnesium dihalide with water or alcohol, and a derivative of magnesium dihalide with one of its halogen atoms substituted by hydrocarbyl or hydrocarbyloxy groups. The magnesium compound is specifically: one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide, preferably magnesium dichloride. When said magnesium compound is dissolved, an inert diluent such as: benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbons or halogenated hydrocarbons, inert here means that the diluent should not take part in the reaction and should not adversely affect the dissolution of the magnesium compound.
The substance containing the aluminum element is selected from metallic aluminum and/or inorganic aluminum compounds.
Among them, in the case of metal aluminum, the smaller the size of the metal aluminum, the more advantageous the dispersion and the reduction of the reaction time, and the nano aluminum powder is preferable.
The inorganic aluminium compound is selected from aluminium chloride, preferably anhydrous aluminium chloride in the form of a fine powder.
In a preferred embodiment, the aluminum element-containing substance is used in an amount of 0.002 to 1mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the aluminum element-containing substance is used in an amount of 0.005 to 0.5mol based on 1mol of the magnesium compound.
Wherein the molar amount of the magnesium compound is based on the molar amount of the magnesium element therein, and the molar amount of the aluminum element-containing substance is based on the molar amount of the aluminum element therein.
After a great deal of experiments, the inventor finds that a catalyst system formed by adding a proper amount of a substance containing an aluminum element into a solid catalyst component containing Ti has higher catalytic activity, and the analysis reason may be that after the substance containing the aluminum element is added, a synergistic effect exists among the components, so that the invention emphasizes that the components in the solid catalyst component containing Ti are synergistic and are taken as a whole.
The organic alcohol compound comprises C1～C12Fatty alcohol or C7～C12Or substituted alcohols derived therefrom, such as: methanol, ethanol, propanol, and isopropanolOctanol, n-butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, phenethyl alcohol, or mixtures thereof. One or more of ethanol, isooctanol, n-butanol, 2-ethylhexanol, benzyl alcohol and phenethyl alcohol is preferably used; when two kinds of mixed alcohols are used, the molar ratio of the two kinds of mixed alcohols is 1 to 50:1, preferably 1 to 20: 1.
In the present application, the inventors avoided the use of organophosphorus compounds; the inventors have also surprisingly found that the dissolving effect of the magnesium-containing compound is better when two or more alcohol compounds are used. Meanwhile, different alcohols generate different titanium products when reacting with the titanium-containing compound at the later stage, so that more than two titanium products are obtained when more than two alcohol compounds are adopted, and a polymer with wider molecular weight distribution can be obtained when the alcohol compounds are applied to the preparation of polyolefin, thereby being beneficial to the processability of the polymer.
The organic epoxy compound is selected from one or more of compounds including aliphatic olefin oxide with 2-8 carbon atoms, aliphatic diene oxide, halogenated aliphatic olefin oxide, halogenated aliphatic diene oxide, glycidyl ether, internal ether and the like. The method specifically comprises the following steps: one or more of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, tetrahydrofuran, and the like. Among them, preferred is one or more of ethylene oxide, propylene oxide, epichlorohydrin and tetrahydrofuran, and most preferred is tetrahydrofuran and/or epichlorohydrin.
The general formula of the titanium-containing compound is TiXn(OR)4-nWherein: x is halogen and R is C1～C14Aliphatic hydrocarbon group of (C)6～C14An aromatic hydrocarbon group, n is an integer of 0 to 4, specifically, one or a mixture of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, tetrabutoxytitanium, tetraethoxytitanium, chlorotriethoxytitanium, dichlorodiethoxytitanium, and trichloromonoethoxytitanium, and titanium tetrachloride is preferable.
The molar ratio of the components is that the addition amount of the substance containing the aluminum element is 0.002-1 mol, preferably 0.005-0.5 mol per mol of the magnesium compound; the amount of the organic alcohol compound to be added is 0.1 to 10 moles, preferably 0.2 to 6 moles; the feeding amount of the organic epoxy compound is 0.01-5 mol, preferably 0.02-2 mol; the amount of the titanium-containing compound to be added is 0.2 to 100 mol, preferably 1.0 to 20 mol.
The raw materials for preparing the catalyst component also comprise an electron donor compound.
The electron donor compound is preferably 0 to 5mol, more preferably 0 to 1mol, per mol of the magnesium compound.
The electron donor is a compound known to those skilled in the art such as: an organic ether, a silicon-containing compound, a boron-containing compound, or a mixture of the foregoing. Wherein the organic ether is one of methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether and isoamyl ether, or a mixture thereof; wherein the silicon-containing compound is: as shown in the general formula R1 xR2 ySi(OR3)zSilicon compounds having no active hydrogen atom shown, wherein R1And R2Each is a C1-10 alkyl group or halogen, R3The carbon atom number of the alkyl is 1-10, wherein x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2, z is more than or equal to 0 and less than or equal to 4, and x + y + z is 4. Among them, silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and tetrakis (2-ethylhexyloxy) silane are preferable, and at least one of silicon tetrachloride and tetraethoxysilane is most preferable; wherein the boron-containing compound: as shown in the general formula R1 xR2 yB(OR3)zBoron compounds having no active hydrogen atom shown, wherein R1And R2Each is a C1-10 alkyl group or halogen, R3The carbon atom number is 1-10 alkyl, wherein x, y and z are positive integers, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 3, and x + y + z is 3. Among them, at least one of boron trichloride, trimethoxyborane, triethoxyborane, tripropoxyborane and tributoxyborane is preferable, and boron trichloride and/or triethoxyborane are most preferable.
The charging molar ratio among the components is 0.002-1 mol of the substance containing the aluminum element, preferably 0.005-0.5 mol, per mol of the magnesium compound; 0.1 to 10 moles, preferably 0.2 to 6 moles, of an organic alcohol compound; 0.01 to 5mol, preferably 0.02 to 2mol, of an organic epoxy compound; the electron donor compound is 0 to 5 moles, preferably 0 to 1 mole; the titanium-containing compound is preferably 0.2 to 100 mol, more preferably 1.0 to 20 mol.
It is another object of the present invention to provide a process for the preparation of a catalyst component for the polymerization of olefins. The preparation method comprises the following steps: reacting a magnesium compound and an aluminum-containing substance at the temperature of 0-170 ℃, preferably 40-140 ℃, with an organic alcohol compound and an organic epoxy compound under stirring in the presence of an inert diluent to form a magnesium-containing mixed solution, optionally adding an electron donor compound at the temperature of-35-60 ℃, preferably-30-20 ℃, dripping a titanium-containing compound into the mixed solution or dripping the mixed solution into the titanium-containing compound, maintaining for a period of time after dripping is finished, then heating, stirring the reaction mixture at the temperature of 10-150 ℃, preferably 20-130 ℃, stopping stirring, settling, filtering, removing a mother solution, washing a solid with a hydrocarbon solvent, and preparing the titanium-containing solid catalyst component. An electron donor compound may also be added during the above preparation. The titanium-containing solid catalyst component is powdery solid particles, the average particle size is about 2-50 microns, and the particle size can be controlled by changing preparation conditions.
The invention also aims to provide a catalyst for olefin polymerization or copolymerization, which comprises the following components:
A. catalyst components for the polymerization of olefins in accordance with one of the objects of the present invention: the preparation method comprises the steps of reacting a magnesium compound and a substance containing aluminum with an organic alcohol compound and an organic epoxy compound to form a magnesium-aluminum-containing solution, and then reacting the magnesium-aluminum-containing solution with a titanium-containing compound solution to obtain the compound, wherein an electron donor compound can be added in the preparation process;
B. the general formula is AlRnX3-nWherein R is a hydrocarbon group with 1-20 carbon atoms, X is halogen, and n is an integer more than 0 and less than or equal to 3;
wherein the molar ratio of aluminum in the component B to titanium in the component A is (5-1000): 1, preferably (20 to 800): 1.
the general formula is AlRnX3-nWherein R is a hydrocarbon group having 1 to 20 carbon atoms, particularly an alkyl group, an aralkyl group, an aryl group, etc.; x is halogen, in particular chlorine and bromine; n is an integer of more than 0 and less than or equal to 3. Specific compounds are as follows: at least one of trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, etc.; at least one of alkylaluminum chlorides such as diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride and ethylaluminum dichloride; among them, triethylaluminum and/or triisobutylaluminum are preferable.
The component A in the catalyst system can be used in the form of solid or suspension, and the A, B component in the catalyst system can be directly applied to a polymerization system or can be pre-complexed and then applied to the polymerization system.
The catalyst of the present invention may be used in homopolymerization of ethylene and copolymerization of ethylene and alpha-olefin, and the comonomer may be propylene, butene, pentene, hexene, octene or 4-methyl-1-pentene.
The polymerization may be carried out by liquid phase polymerization or gas phase polymerization. In the liquid phase polymerization, an inert solvent such as a saturated aliphatic hydrocarbon or an aromatic hydrocarbon such as propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc. may be used as a reaction medium, and a prepolymerization may be carried out before the polymerization. The polymerization may be carried out in a batch, semi-continuous or continuous manner.
The polymerization temperature is preferably from room temperature to 150 ℃ and more preferably from 50 ℃ to 100 ℃. In order to regulate the molecular weight of the polymer, hydrogen is used as a molecular weight regulator.
Compared with the prior art, the invention has the following obvious advantages: the catalyst prepared by the method has better activity and bulk density, the step of dissolution reaction of the precipitation aid is omitted, and the preparation period of the catalyst is shortened; meanwhile, the method avoids using phosphorus-containing compounds and phthalic anhydride with larger toxicity, and is more beneficial to environmental protection.
Detailed Description
The present invention will be further described with reference to the following examples. However, the present invention is not limited to these examples.
Example 1
(1) Preparation of solid catalyst component A
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0015mol of aluminum powder and 0.4mol of n-decane, 0.13mol of isooctanol and 0.02mol of n-butanol, heating to 130 ℃, maintaining for 1 hour, cooling to 70 ℃, adding 0.03mol of epichlorohydrin, cooling to-5 ℃, dripping 0.3mol of titanium tetrachloride into the solution, maintaining for half an hour, adding 0.015mol of tetraethoxysilane, maintaining for 1 hour, heating to 110 ℃, maintaining for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid catalyst component A.
(2) Homopolymerization reaction
A stainless steel reaction kettle with the volume of 2L is fully replaced by high-purity hydrogen, 1L of hexane and 1.0mL of triethylaluminum hexane solution with the concentration of 1M are added, 9-12 mg of the solid catalyst component prepared by the method is added, the temperature is raised to 70 ℃, hydrogen is introduced to enable the pressure in the kettle to reach 0.26MPa (gauge pressure), ethylene is introduced to enable the total pressure in the kettle to reach 0.72MPa (gauge pressure), and polymerization is carried out for 2 hours at the temperature of 80 ℃, wherein the polymerization result is shown in Table 1.
Example 2
(1) Preparation of solid catalyst component A
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.006mol of aluminum powder and 0.4mol of n-decane, 0.009mol of silicon tetrachloride is added, the mixture is maintained for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃, the mixture is maintained for half an hour, 0.04mol of benzyl alcohol is added, the mixture is maintained for half an hour, the temperature is lowered to 70 ℃, 0.03mol of epichlorohydrin is added, the temperature is lowered to-10 ℃, 0.5mol of titanium tetrachloride is dripped into the mixture, the mixture is maintained for half an hour, 0.015mol of tetraethoxysilane is added, the mixture is maintained for 1 hour, the temperature is raised to 110 ℃, the mixture is maintained for 1 hour, the mixture is filtered, washed for 4 times by hexane.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 3
(1) Preparation of solid catalyst component A
In the presence of high purity N2In the fully displaced reactor, 0.03mol of anhydrous MgCl was added in succession20.012mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride is added, the mixture is maintained for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃, the mixture is maintained for half an hour, 0.04mol of n-butanol is added, the mixture is maintained for half an hour, the temperature is lowered to 70 ℃, 0.03mol of epichlorohydrin is added, the temperature is lowered to-15 ℃, 0.6mol of titanium tetrachloride is dripped into the mixture, the mixture is maintained for half an hour, 0.015mol of tetraethoxysilane is added, the mixture is maintained for 1 hour, the mixture is heated to 110 ℃, the mixture is maintained for 1 hour, the mixture is filtered, washed for 4 times by hexane.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 4
(1) Preparation of solid catalyst component A
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0003mol of anhydrous aluminum chloride, 0.6mol of toluene, 0.07mol of n-butyl alcohol, 0.07mol of ethanol and 0.04mol of epoxy chloropropane, raising the temperature to 80 ℃, maintaining for 1 hour, reducing the temperature to-20 ℃, then dripping 0.6mol of titanium tetrachloride into the solution, maintaining for half an hour, raising the temperature to 85 ℃, maintaining for 1 hour, filtering, washing with hexane for 4 times, and drying in vacuum to obtain the solid catalyst component A.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 5
(1) Preparation of solid catalyst component A
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.0003mol of anhydrous aluminum chloride, 0.6mol of toluene, 0.16mol of n-butyl alcohol, 0.08mol of phenethyl alcohol and 0.004mol of epoxy chloropropane, raising the temperature to 80 ℃, maintaining for 1 hour, reducing the temperature to 0 DEG CThen 0.6mol of titanium tetrachloride is dropped into the solution for half an hour, then the temperature is raised to 85 ℃ for 1 hour, and the solution is filtered, washed with hexane for 4 times and dried in vacuum to obtain a solid catalyst component A.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Example 6
(1) Preparation of solid catalyst component A
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.003mol of anhydrous aluminum chloride, 0.6mol of toluene and 0.14mol of isooctanol, heating to 130 ℃, maintaining for 1 hour, cooling to 70 ℃, adding 0.012mol of epoxy chloropropane, maintaining for half an hour, cooling to-20 ℃, then dripping 0.8mol of titanium tetrachloride into the solution, maintaining for half an hour, heating to 60 ℃, maintaining for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid catalyst component A.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 1
(1) Preparation of solid catalyst component
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.6mol of toluene, 0.03mol of epichlorohydrin, 0.02mol of tributyl phosphate and 0.06mol of ethanol are added under stirring, the temperature is raised to 60 ℃ and maintained for 1 hour, 0.0074mol of phthalic anhydride is added and maintained for half an hour, the solution is cooled to-15 ℃, 0.60mol of titanium tetrachloride is dripped into the solution and maintained for 1 hour, then the temperature is raised to 60 ℃ and maintained for 1 hour, and after filtration, the solution is washed for 4 times by hexane and dried in vacuum, thus obtaining the solid catalyst component A.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 2
(1) Preparation of solid catalyst component: as in comparative example 1, only phthalic anhydride was changed to 0.011 mol.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 3
(1) Preparation of solid catalyst component
In the presence of high purity N2To the fully displaced reactor, 0.04mol of anhydrous MgCl was added in sequence20.30mol of n-decane, 0.15mol of 2-ethylhexanol is added under stirring, the temperature is raised to 115 ℃, the temperature is maintained for 1 hour, the temperature is lowered to 50 ℃, 0.026mol of silicon tetrachloride is added, the solution is cooled to-10 ℃, 0.45mol of titanium tetrachloride is dripped into the solution, the temperature is maintained for 1 hour, then the temperature is raised to 120 ℃, the solution is maintained for 1 hour, the solution is washed by hexane for 4 times after being filtered, and the solid catalyst component A is obtained after vacuum drying.
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
Comparative example 4
(1) Preparation of solid catalyst component
The procedure of example 4 was repeated except for replacing "0.07 mol of n-butanol, 0.07mol of ethanol, 0.04mol of epichlorohydrin" with "0.09 mol of n-butanol, 0.08mol of ethanol".
(2) Homopolymerization reaction
The polymerization results are shown in Table 1, as in example 1.
TABLE 1
Figure BDA0002228910370000101
As can be seen from the data in table 1, the catalyst of the present invention has better activity and bulk density under the same polymerization conditions than the comparative example.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not 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 described embodiments.

Claims (14)

1. A catalyst component for the polymerization of olefins, characterized in that it is prepared from a starting material comprising the following components: (1) a magnesium compound; (2) a substance containing an aluminum element; (3) an organic epoxy compound; (4) an organic alcohol compound; (5) a titanium-containing compound.
2. The catalyst component for the polymerization of olefins according to claim 1 characterized in that:
the aluminum-containing substance is at least one selected from metallic aluminum and inorganic aluminum compounds.
3. Catalyst component for the polymerization of ethylene according to claim 2, characterized in that: the inorganic aluminum compound is selected from anhydrous aluminum chloride.
4. The catalyst component for the polymerization of olefins according to claim 2 characterized in that:
the metal aluminum is nano aluminum powder.
5. The catalyst component for the polymerization of olefins according to claim 1 characterized in that:
the magnesium compound is selected from one or more of magnesium dihalide, water or alcohol complex of magnesium dihalide, and derivatives of magnesium dihalide in which one halogen atom is substituted by a hydrocarbyl or hydrocarbyloxy group, preferably one or more of magnesium dichloride, magnesium dibromide, and magnesium diiodide, and more preferably magnesium dichloride.
6. The catalyst component for the polymerization of olefins according to claim 1 characterized in that:
the organic alcohol compound is selected from C1～C12Fatty alcohol of (2), C7～C12Wherein the substituted alcohol is selected from one or more of aromatic alcohol and substituted alcohol of (1), wherein the substituted alcohol is selected from C1～C12Fatty alcohol or C7～C12Substituted alcohols derived from aromatic alcohols of (a); preferably, the organic alcohol compound is selected from methanol, ethanol, propanol, isopropanol, butanolOne or more selected from the group consisting of isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol and phenethyl alcohol, and more preferably one or more selected from the group consisting of ethanol, isooctanol, butanol, 2-ethylhexanol, benzyl alcohol and phenethyl alcohol.
7. The catalyst component for the polymerization of olefins according to claim 1 characterized in that:
the organic epoxy compound comprises at least one compound of an oxide of aliphatic olefin with 2-8 carbon atoms, an oxide of aliphatic diene, an oxide of halogenated aliphatic olefin, an oxide of halogenated aliphatic diene, glycidyl ether and internal ether; the organic epoxy compound is preferably selected from one or more of ethylene oxide, propylene oxide, epichlorohydrin and tetrahydrofuran; the organic epoxy compound is more preferably tetrahydrofuran and/or epichlorohydrin.
8. The catalyst component for the polymerization of olefins according to claim 1 characterized in that:
the general formula of the titanium-containing compound is TiXn(OR)4-nWherein: x is a halogen atom, R is C1～C14Aliphatic hydrocarbon group of (C)6～C14An aromatic hydrocarbon group, n is an integer of 0 to 4, preferably at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxyate, titanium dichlorodiethoxytitanium, and titanium trichloromonoethoxylate, and more preferably titanium tetrachloride.
9. The catalyst component for the polymerization of olefins according to claim 1 characterized in that: the addition amount of the material containing the aluminum element is 0.002 to 1mol, preferably 0.005 to 0.5mol per mol of the magnesium compound; the amount of the organic alcohol compound to be added is 0.1 to 10 moles, preferably 0.2 to 6 moles; the feeding amount of the organic epoxy compound is 0.01-5 mol, preferably 0.02-2 mol; the amount of the titanium-containing compound to be added is 0.2 to 100 mol, preferably 1.0 to 20 mol.
10. The catalyst component for the polymerization of olefins according to one of claims 1 to 9, characterized in that:
the preparation raw material of the catalyst component also comprises an electron donor compound, and preferably, the electron donor compound is at least one selected from organic ether, silicon compound and boron compound.
11. The catalyst component for the polymerization of olefins according to claim 10 characterized in that: the amount of the electron donor compound to be added is 0 to 5mol, preferably 0 to 1 mol.
12. The process for preparing a catalyst component for olefin polymerization according to any one of claims 1 to 11, characterized by comprising the steps of:
reacting a magnesium compound and a substance containing aluminum elements at a temperature of 0-170 ℃, preferably 40-140 ℃, with an organic alcohol compound and an organic epoxy compound in the presence of an inert diluent to form a magnesium-containing mixed solution, and optionally adding an electron donor compound; then, mixing a titanium-containing compound and the mixed solution at the temperature of-35-60 ℃, preferably-30-20 ℃ to form a reaction mixture; then stirring the reaction mixture at the temperature of 10-150 ℃, preferably 20-130 ℃; stopping stirring, separating out solids, filtering, removing mother liquor, and washing the solids to obtain the catalyst component.
13. A catalyst for the polymerization of olefins, the catalyst comprising:
A. the catalyst component for the polymerization of olefins according to anyone of claims 1 to 11 or prepared according to the process of claim 12;
B. the general formula is AlRnX3-nWherein R is a hydrocarbon group with 1-20 carbon atoms, X is halogen, and n is an integer more than 0 and less than or equal to 3;
wherein the molar ratio of aluminum in the component B to titanium in the component A is (5-1000): 1, preferably (20 to 800): 1.
14. use of the catalyst for olefin polymerization according to claim 13 in homopolymerization or copolymerization of olefins.
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