CN112759671B - Ti-containing solid catalyst component for olefin polymerization, preparation method thereof, catalyst containing Ti-containing solid catalyst component and application of Ti-containing solid catalyst component - Google Patents

Ti-containing solid catalyst component for olefin polymerization, preparation method thereof, catalyst containing Ti-containing solid catalyst component and application of Ti-containing solid catalyst component Download PDF

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CN112759671B
CN112759671B CN201910999607.8A CN201910999607A CN112759671B CN 112759671 B CN112759671 B CN 112759671B CN 201910999607 A CN201910999607 A CN 201910999607A CN 112759671 B CN112759671 B CN 112759671B
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compound
catalyst component
solid catalyst
magnesium
titanium
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CN112759671A (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
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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 a Ti-containing solid catalyst component for olefin polymerization, a preparation method thereof, a catalyst containing the Ti-containing solid catalyst component and application thereof, belonging to the field of olefin polymerization catalysts, wherein the Ti-containing solid catalyst component comprises the reaction product of the following components: (1) a magnesium compound; (2) an aluminum element-containing substance; (3) an organic alcohol compound; (4) an organic epoxy compound; (5) a titanium compound; (6) an acyl halide compound; (7) optionally an electron donor compound. The Ti-containing solid catalyst component is mixed with an aluminum-containing organic matter according to a certain proportion to obtain the catalyst for olefin polymerization, and the catalyst can be particularly used in ethylene homo-polymerization or copolymerization. The Ti-containing solid catalyst component and the preparation method thereof avoid using phosphorus-containing compounds and phthalic anhydride with larger toxicity, and are more beneficial to environmental protection; meanwhile, the preparation method reduces the use amount of titanium tetrachloride, and the obtained catalyst has good comprehensive performance.

Description

Ti-containing solid catalyst component for olefin polymerization, preparation method thereof, catalyst containing Ti-containing solid catalyst component and application of Ti-containing solid catalyst component
Technical Field
The invention belongs to the field of catalysts, in particular relates to a catalyst for olefin polymerization, and specifically relates to a Ti-containing solid catalyst component for olefin polymerization, a preparation method thereof, a catalyst containing the same and application of the catalyst, in particular to an ethylene polymerization catalyst.
Background
The Ti/Mg composite catalytic system is dominant in the polymerization industry of polyolefins, particularly polyethylene, and has been continuously developed.
Many studies and reports on catalyst performance improvement are currently focused on the following aspects: catalytic efficiency, particle morphology control, copolymerization capability, molecular weight distribution, and the like. For the production of general polyolefin resin, on the basis of further improving the catalyst performance, it is a development direction to simplify the catalyst preparation process, reduce the catalyst cost, develop an environmentally friendly technology to increase the benefit and enhance the competitiveness.
Chinese patent CN111516a discloses a process for the polymerization or copolymerization of ethylene, the titanium-containing component of the catalyst being prepared by the steps of: (1) Dissolving magnesium halide in an organic epoxy compound and an organic phosphorus compound to form a uniform solution; (2) Simultaneously or respectively carrying out contact reaction with at least one organic alcohol and at least one compound selected from C3-C5 cyclic ethers during or after complete dissolution; (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 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 obviously existed.
Chinese patent CN1229092a proposes a catalyst for polymerization or copolymerization of ethylene and a process for preparing the same, wherein the catalyst is obtained by dissolving magnesium halide in an organic epoxy compound, adding an organic phosphorus compound to an electron donor to form a homogeneous solution, reacting with at least one precipitation aid and a halide of transition metal titanium or a derivative thereof, and combining with an organic aluminum compound during polymerization. The catalyst shows higher activity when used for ethylene polymerization, and the apparent density of the obtained polymer is higher.
In the preparation process of the two catalysts, in order to obtain the catalyst solid, the organic phosphorus compound is adopted in the dissolution system, and meanwhile, the method of adding the precipitation aid is also adopted, especially in the embodiment, phthalic anhydride is adopted as the precipitation aid, and the phthalic anhydride is completely dissolved in the mixed solvent system, and then cooled and mixed with the titanium compound, so that the preparation period of the catalyst is correspondingly prolonged by using the precipitation aid. In addition, the precipitation aid system has relatively high toxicity and high requirements on operation conditions.
Disclosure of Invention
In order to develop an environment-friendly catalyst, avoiding the use of an organic phosphorus compound and a precipitation aid, the inventor has conducted intensive studies to prepare an improved titanium-containing polyolefin homo-or co-polymerization catalyst which has better performance than the existing catalyst, and omits the dissolution reaction step of the precipitation aid, while shortening the catalyst preparation period, the raw materials used are more environment-friendly than those containing the organic phosphorus compound and phthalic anhydride system.
It is an object of the present invention to provide a Ti-containing solid catalyst component for olefin polymerization comprising the reaction product of: (1) a magnesium compound; (2) an aluminum element-containing substance; (3) an organic alcohol compound; (4) an organic epoxy compound; (5) a titanium compound; (6) an acyl halide compound; (7) optionally an electron donor compound.
In a preferred embodiment, the organic epoxy compound is selected from at least one of an oxide, a glycidyl ether and a internal ether comprising an aliphatic olefin, an aliphatic diene, a halogenated aliphatic olefin or a halogenated aliphatic diene having 2 to 8 carbon atoms.
In a further preferred embodiment, the organic epoxy compound is selected from at least one of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether, and tetrahydrofuran.
In a still further preferred embodiment, the organic epoxy compound is selected from the group consisting of ethylene oxide, propylene oxide, epichlorohydrin, tetrahydrofuran, and at least one of tetrahydrofuran and epichlorohydrin.
The magnesium compound is dissolved by adopting organic alcohol and organic epoxy compound together.
In a preferred embodiment, the organic epoxy compound is used in an amount of 0.01 to 5mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the organic epoxy compound is used in an amount of 0.02 to 2mol based on 1mol of the magnesium compound.
In a preferred embodiment, the acyl halide compound has the formula R (COX) a Wherein R is H, C 1 ～C 8 Aliphatic radical, C 1 ～C 8 Halogenated aliphatic hydrocarbon radicals, C 6 ～C 10 Aromatic hydrocarbon or C of (2) 6 ～C 10 X is halogen and a is 1 or 2.
In a further preferred embodiment, the acid halide compound is an acid chloride compound, preferably at least one selected from benzoyl chloride, formyl chloride and dichloroacetyl chloride, for example benzoyl chloride.
In the invention, the acyl halide compound is adopted to prepare the Ti-containing solid catalyst component, wherein the acyl halide compound can be used as an electron donor to improve the hydrogen regulation sensitivity of the catalyst and can be used for providing chlorine for a reaction system, so that the use of titanium tetrachloride can be saved to a certain extent.
In a preferred embodiment, the acyl halide compound is used in an amount of 0.01 to 4.0mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the acyl halide compound is used in an amount of 0.02 to 2.0mol based on 1mol of the magnesium compound.
In a preferred embodiment, the magnesium compound is selected from one or more of magnesium dihalide, water complex of magnesium dihalide, alcohol complex of magnesium dihalide and magnesium dihalide derivative.
In a further preferred embodiment, the magnesium dihalide derivative is a derivative in which one of the halogen atoms in the magnesium dihalide molecule is replaced by a hydrocarbon or hydrocarbyloxy group.
In a still further preferred embodiment, the magnesium dihalide is selected from one or more of magnesium dichloride, magnesium dibromide, magnesium diiodide, preferably magnesium dichloride.
Wherein, inert diluents such as: benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbon or halogenated hydrocarbon compounds, by inert is meant that the diluent should not participate in the reaction and not adversely affect the dissolution of the magnesium dihalide.
In a preferred embodiment, the substance containing an aluminum element is selected from metallic aluminum and/or inorganic aluminum compounds.
Among them, in the case of metallic aluminum, the smaller the size of metallic aluminum is, the more advantageous to disperse and shorten the reaction time, and the nano aluminum powder is preferable.
In a further preferred embodiment, the inorganic aluminium compound is selected from aluminium chloride, preferably finely divided anhydrous aluminium chloride.
In a preferred embodiment, the aluminum-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-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 calculated based on the molar amount of the magnesium element therein, and the molar amount of the substance containing the aluminum element is calculated based on the molar amount of the aluminum element therein.
The inventors have found through a great deal of experiments that the catalyst system formed by adding a proper amount of substances containing aluminum elements into the Ti-containing solid catalyst component has higher catalytic activity, and the analysis reasons are probably that after the substances containing aluminum elements are added, the synergistic effect exists among the components, so that it is emphasized that the synergistic effect exists among the components in the Ti-containing solid catalyst component, which are acted as a whole and cannot be split and analyzed.
In a preferred embodiment, the organic alcohol compound is selected from C 1 ～C 12 Fatty alcohol, C 7 ～C 12 One or more of the aromatic alcohol and the substituted alcohol, wherein the extractingThe substituted alcohol is C 1 ～C 12 Fatty alcohol or C of (C) 7 ～C 12 Substituted alcohols derived from aromatic alcohols of (a).
In a further preferred embodiment, the organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol and phenethyl alcohol.
In a still further preferred embodiment, the organic alcohol compound is selected from one or more of ethanol, isooctanol, butanol, 2-ethylhexanol, benzyl alcohol, and phenethyl alcohol. When two mixed alcohols are adopted, the molar ratio of the two is 1 to 50:1, 1 to 20:1 is preferred.
Among them, the organic alcohol compound has a main function of dissolving the magnesium compound and forming an alkoxide with the magnesium compound.
In a preferred embodiment, the organic alcohol compound is used in an amount of 0.01 to 10mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the organic alcohol compound is used in an amount of 0.02 to 6mol 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.
In the application, the use of an organic phosphorus compound is avoided, and good dissolution of the magnesium compound is successfully realized by adopting a proper amount of an organic alcohol compound and an organic epoxy compound; further, it was found that the dissolution effect of the magnesium compound is better when two or more organic alcohol compounds are used. Meanwhile, when the titanium compound is reacted with the titanium compound in the later period, different alcohols generate different titanium products, when the invention adopts more than two organic alcohol compounds, different titanium products are obtained, and when the invention is applied to the preparation of polyolefin, a polymer with wider molecular weight distribution can be obtained, thus being beneficial to the processability of the polymer.
In a preferred embodiment, the titanium compound has the formula TiX n (OR) 4-n Wherein: x represents halogen, R represents C 1 ～C 14 Aliphatic hydrocarbon radicals or C 6 ～C 14 An aromatic hydrocarbon group, n is an integer of 0 to 4.
In a further preferred embodiment, the titanium compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, titanium monochlorotriethoxide, titanium dichlorodiethoxide, titanium trichloromonoethoxide, for example titanium tetrachloride.
In a preferred embodiment, the titanium compound is used in an amount of 0.2 to 100mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the titanium compound is used in an amount of 1.0 to 20mol based on 1mol of the magnesium compound.
Wherein the molar amount of the magnesium compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the titanium compound is calculated based on the molar amount of the titanium element therein.
In a preferred embodiment, the electron donor is selected from one or more of an organic ether, a silicon-containing compound and a boron-containing compound.
Wherein: (1) The organic ether is selected from one or more of methyl ether, diethyl ether, propyl ether, butyl ether, amyl ether and isoamyl ether; (2) the silicon-containing compound is: the general formula is R 1 x R 2 y Si(OR 3 ) z The silicon compounds having no active hydrogen atoms, wherein R 1 And R is 2 R is a hydrocarbon group having 1 to 10 carbon atoms or halogen 3 Is a hydrocarbon group having 1 to 10 carbon atoms, wherein x, y and z are positive integers, x is 0.ltoreq.2, y is 0.ltoreq.2 and z is 0.ltoreq.4, and x+y+z=4. Wherein the boron compound: the general formula is R 1 x R 2 y B(OR 3 ) z Boron compounds without active hydrogen atoms, where R 1 And R is 2 R is a hydrocarbon group having 1 to 10 carbon atoms or halogen 3 Is hydrocarbon group with 1-10 carbon atoms, 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=3.
In a further preferred embodiment, the silicon-containing compound is selected from one or more of silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and tetrakis (2-ethylhexyloxy) silane, preferably silicon tetrachloride, tetraethoxysilane; the boron-containing compound is selected from one or more of boron trichloride, trimethoxyborane, triethoxy borane, tripropoxy borane and tributoxy borane, preferably boron trichloride, triethoxy borane.
Wherein the electron donor acts as a lewis base in the Ti-containing solid catalyst component, providing the electron pair to the metal in the catalyst.
In a preferred embodiment, the electron donor is used in an amount of 0 to 5mol based on 1mol of the magnesium compound.
In a further preferred embodiment, the electron donor is used in an amount of 0 to 1mol 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.
In the present invention, most preferably, in the Ti-containing solid catalyst component, the aluminum-containing substance is 0.02 to 0.5mol, the organic alcohol compound is 3.0 to 6.0mol, the organic epoxy compound is 0.75 to 2mol, the acyl halide compound is 0.05 to 1.25mol, the electron donor compound is 0 to 0.5mol, and the titanium compound is 6.0 to 20mol, per mol of the magnesium compound.
Another object of the present invention is to provide a process for producing a Ti-containing solid catalyst component for olefin polymerization according to one of the objects of the present invention, comprising the steps of: (1) Mixing a magnesium compound, a substance containing aluminum element, an organic alcohol compound and an organic epoxy compound in the presence of an inert diluent, and then adding an acyl halide compound to obtain a mixed solution; (2) Cooling, then dripping the titanium compound into the mixed solution, or dripping the mixed solution into the titanium compound for reaction; (3) And heating, stirring and post-treating after the reaction to obtain the Ti-containing solid catalyst component.
In a preferred embodiment, in step (1), the mixing is performed at a temperature of 0 to 170 ℃, preferably 40 to 140 ℃, more preferably the mixing is performed with stirring.
In a further preferred embodiment, in step (1), the inert diluent may be selected from one or more of benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene and other hydrocarbon or halogenated hydrocarbon compounds.
The term inert means that the diluent should not participate in the reaction and should not adversely affect the dissolution of the magnesium compound.
In a preferred embodiment, in step (2), the temperature is reduced to-35 to 60 ℃, preferably to-30 to 20 ℃.
In a preferred embodiment, in step (3), the temperature is raised to 10 to 150 ℃, preferably to 20 to 130 ℃.
In a further preferred embodiment, in step (3), the post-treatment comprises sedimentation, filtration, washing of the solids and drying.
Wherein the mother liquor is filtered off and the solids are preferably washed with a hydrocarbon solvent.
In a preferred embodiment, an electron donor is optionally added in step (1) or step (2).
In the present invention, the Ti-containing solid catalyst component obtained is in the form of powdery solid particles having an average particle diameter of about 2 to 50 μm, and the particle size can be controlled by changing the preparation conditions.
It is still another object of the present invention to provide a catalyst for olefin polymerization, comprising:
A. the Ti-containing solid catalyst component for olefin polymerization according to one of the objects of the present invention or the Ti-containing solid catalyst component for olefin polymerization obtained by the two of the preparation methods according to the second object of the present invention;
B. the general formula is AlR n X 3-n Wherein R is a hydrocarbon group having 1 to 20 carbon atoms, X is a halogen, and n is an integer of 0 < n.ltoreq.3.
In a preferred embodiment, the organoaluminum compound is selected from one or more of trialkylaluminum, alkylaluminum hydride and alkylaluminum chloride.
Wherein the trialkylaluminum comprises trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, and the like; the alkylaluminum hydride includes diethylaluminum monohydride, diisobutylaluminum monohydride and the like; the alkyl aluminum chloride comprises diethyl aluminum chloride, diisobutyl aluminum chloride, sesquiethyl aluminum chloride, ethyl aluminum dichloride and the like.
In a further preferred embodiment, the organoaluminum compound is selected from triethylaluminum and/or triisobutylaluminum.
In a preferred embodiment, in the catalyst, the molar amount ratio of the organoaluminum compound to the Ti-containing solid catalyst component is (5 to 1000): 1, preferably (20 to 800): 1.
wherein the molar amount of the Ti-containing solid catalyst component is calculated based on the molar amount of the titanium element therein, and the molar amount of the organoaluminum compound is calculated based on the molar amount of the aluminum element therein.
In the present invention, the Ti-containing solid catalyst component may be used in the form of a solid or a suspension, and the Ti-containing solid catalyst component and the organoaluminum compound may be directly applied to the polymerization system or may be pre-complexed and then applied to the polymerization system.
It is a fourth object of the present invention to provide the use of the catalyst for olefin polymerization of the third object of the present invention in olefin polymerization, for olefin homo-and co-polymerization, preferably for ethylene homo-or for co-polymerization of ethylene with alpha-olefins selected from one or more of propylene, butene, pentene, hexene, octene and 4-methyl 1-pentene.
Wherein, liquid phase polymerization or gas phase polymerization can be used in the polymerization. In the case of the liquid phase polymerization, an inert solvent such as saturated aliphatic hydrocarbon or aromatic hydrocarbon, e.g., propane, hexane, heptane, cyclohexane, isobutane, isopentane, naphtha, raffinate oil, hydrogenated gasoline, kerosene, benzene, toluene, xylene, etc., may be used as the reaction medium, and the polymerization may be performed before the polymerization. The polymerization may be carried out batchwise, semi-continuously or continuously.
In the polymerization, the polymerization temperature is preferably from 50℃to 100℃and is from room temperature to 150 ℃. 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 good activity and bulk density, correspondingly reduces the use amount of titanium tetrachloride, omits the dissolution reaction step of the precipitation aid, and shortens the preparation period of the catalyst; 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 is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Example 1
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.0015mol of aluminum powder and 0.4mol of n-decane, adding 0.13mol of isooctanol and 0.02mol of n-butanol, heating to 130 ℃, maintaining for 1 hour, cooling to 70 ℃, adding 0.04mol of epichlorohydrin, maintaining for half an hour, adding 0.002mol of benzoyl chloride, cooling to-5 ℃, dripping 0.6mol of titanium tetrachloride into the mixture, 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.
Example 2
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.006mol of aluminum powder and 0.4mol of n-decane, 0.009mol of silicon tetrachloride is added for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃, the temperature is maintained for half an hour, 0.04mol of n-butanol is added, the temperature is lowered to 70 ℃, 0.03mol of epichlorohydrin is added, the temperature is maintained for half an hour, 0.010mol of benzoyl chloride is added, the temperature is lowered to-10 ℃, then 0.5mol of titanium tetrachloride is dripped into the reactor, the temperature is raised to 110 ℃ for 1 hour, the filtration is carried out, the reactor is washed with hexane for 4 times, and the reactor is dried in vacuum, thus obtaining the solid catalyst.
Example 3
In the warp of high purity N 2 Fully is provided withInto the replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.012mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride is added for 5 minutes, 0.13mol of isooctanol is added, the temperature is raised to 130 ℃, the temperature is maintained for half an hour, 0.05mol of n-butanol is added, the temperature is lowered to 70 ℃ for half an hour, 0.06mol of epichlorohydrin is added, the temperature is maintained for half an hour, 0.020mol of benzoyl chloride is added, the temperature is lowered to-15 ℃, then 0.3mol of titanium tetrachloride is dripped into the catalyst, the temperature is raised to 110 ℃ for 1 hour, the filtration is carried out, the hexane is used for washing for 4 times, and the vacuum drying is carried out, so that the solid catalyst is obtained.
Example 4
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.0008mol of anhydrous aluminum chloride, 0.6mol of toluene, 0.05mol of n-butanol, 0.07mol of ethanol and 0.08mol of epichlorohydrin, heating to 80 ℃, maintaining for 1 hour, adding 0.050mol of benzoyl chloride, cooling to 20 ℃, dripping 0.25mol of titanium tetrachloride into the mixture for half an hour, then heating to 85 ℃ for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid catalyst.
Example 5
In the warp of high purity N 2 In the fully replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.012mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride is added for 5 minutes, 0.13mol of isooctanol and 0.05mol of benzyl alcohol are added, the temperature is raised to 130 ℃ for 1 hour, the temperature is reduced to 70 ℃, 0.03mol of epoxy chloropropane is added, the temperature is maintained for half an hour, 0.020mol of benzoyl chloride is added, the temperature is reduced to-15 ℃, then 0.3mol of titanium tetrachloride is dripped into the reactor, the temperature is maintained for 1 hour, the temperature is raised to 110 ℃ for 1 hour, the reactor is filtered, washed 4 times by hexane, and the reactor is dried in vacuum, thus obtaining the solid catalyst.
Example 6
In the warp of high purity N 2 In the fully replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.003mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride and 0.15mol of isooctanol and 0.03mol of phenethyl alcohol are added for 5 minutes, the temperature is raised to 130 ℃ and maintained for 1 hour, the temperature is lowered to 70 ℃, and 0.05 is addedmaintaining the epoxy chloropropane at a temperature of minus 15 ℃ for half an hour, adding 0.020mol of benzoyl chloride, dropping 0.6mol of titanium tetrachloride into the epoxy chloropropane, maintaining the temperature for 1 hour, heating to 110 ℃ for 1 hour, filtering, washing with hexane for 4 times, and drying in vacuum to obtain the solid catalyst.
Example 7
In the warp of high purity N 2 In the fully replaced reactor, 0.03mol of anhydrous MgCl is added in sequence 2 0.003mol of anhydrous aluminum chloride and 0.4mol of n-decane, adding 0.01mol of silicon tetrachloride, maintaining for 5 minutes, adding 0.15mol of n-butanol, heating to 110 ℃, maintaining for 1 hour, cooling to 70 ℃, adding 0.05mol of epichlorohydrin, maintaining for half an hour, adding 0.015mol of benzoyl chloride, cooling to-15 ℃, dripping 0.45mol of titanium tetrachloride into the mixture, 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.
Comparative example 1
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.6mol 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 ℃, the temperature is maintained for 1 hour, 0.0074mol of phthalic anhydride is added for half an hour, the solution is cooled to-15 ℃, 0.60mol of titanium tetrachloride is dripped into the solution for 1 hour, the temperature is raised to 60 ℃ for 1 hour, the filtration is carried out, the washing is carried out for 4 times by hexane, and the solid catalyst component containing Ti is obtained by vacuum drying.
Comparative example 2
Example 1 was repeated with the difference that: the phthalic anhydride was changed to 0.011mol only.
Comparative example 3
In the warp of high purity N 2 In a fully replaced reactor, 0.04mol of anhydrous MgCl is added in sequence 2 0.30mol of n-decane, adding 0.15mol of 2-ethylhexanol under stirring, heating to 115 ℃ for 1 hour, cooling to 50 ℃, adding 0.026mol of silicon tetrachloride, cooling the solution to-10 ℃, then dripping 1.20mol of titanium tetrachloride into the solution for 1 hour, heating to 120 ℃ for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the productA solid Ti-containing solid catalyst component.
Comparative example 4
The difference from example 3 is that only benzoyl chloride is not used.
Experimental example ethylene polymerization
Stainless steel kettle with volume of 2 liters is subjected to H 2 After sufficient displacement, 1000mL of hexane, 1.0mL of triethylaluminum hexane solution having a concentration of 1mol/L, and metered (9 to 12 mg) amounts of the Ti-containing solid catalyst components prepared in examples 1 to 6 and comparative examples 1 to 4 were added thereto, the temperature was raised to 70℃and hydrogenated to 0.26MPa (gauge pressure), and then ethylene was introduced into the autoclave to 0.72MPa (gauge pressure) and polymerized at 80℃for 2 hours. The results are shown in Table 1.
Table 1:
Figure BDA0002240875040000111
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Figure BDA0002240875040000121
as can be seen from the data in Table 1, the catalysts of the present invention have better activity and bulk density and higher MI under the same polymerization conditions than those of comparative examples 1 to 4 2.16 。

Claims (18)

1. A Ti-containing solid catalyst component for olefin polymerization, characterized in that the Ti-containing solid catalyst component comprises the reaction product of: (1) a magnesium compound; (2) an aluminum element-containing substance; (3) an organic alcohol compound; (4) an organic epoxy compound; (5) a titanium compound; (6) an acyl halide compound; (7) optionally an electron donor compound; wherein the substance containing aluminum element is selected from at least one of metallic aluminum and/or inorganic aluminum compound; the amount of the aluminum-containing substance is 0.002 to 1mol, the amount of the organic alcohol compound is 0.1 to 10mol, the amount of the organic epoxy compound is 0.01 to 5mol, the amount of the titanium compound is 0.2 to 100mol, the amount of the acyl halide compound is 0.01 to 4.0mol, and the amount of the electron donor is 0 to 5mol, per mol of the magnesium compound, wherein the molar amount of the magnesium compound is based on the molar amount of the magnesium element, the molar amount of the aluminum-containing substance is based on the molar amount of the aluminum element, and the molar amount of the titanium compound is based on the molar amount of the titanium element.
2. A Ti-containing solid catalyst component for olefin polymerization according to claim 1,
the magnesium compound is selected from one or more of magnesium dihalide, water complex of magnesium dihalide, alcohol complex of magnesium dihalide and magnesium dihalide derivative, wherein the magnesium dihalide derivative is a derivative in which one halogen atom in a magnesium dihalide molecule is replaced by a hydrocarbon group or a hydrocarbyloxy group; and/or
The metal aluminum is nano aluminum powder; the inorganic aluminum compound is aluminum chloride; and/or
The organic alcohol compound is selected from C 1 ～C 12 Fatty alcohol, C 7 ～C 12 One or more of the aromatic alcohols and substituted alcohols, wherein the substituted alcohol is a compound selected from the group consisting of C 1 ～C 12 Fatty alcohol or C of (C) 7 ～C 12 Substituted alcohols derived from aromatic alcohols; and/or
The general formula of the titanium compound is TiX n (OR) 4-n Wherein: x represents halogen, R represents C 1 ～C 14 Aliphatic hydrocarbon radicals or C 6 ～C 14 An aromatic hydrocarbon group, n is an integer of 0 to 4.
3. A Ti-containing solid catalyst component for olefin polymerization according to claim 2,
the magnesium dihalide is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide; and/or
The inorganic aluminum compound is fine powder anhydrous aluminum chloride; and/or
The organic alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol and phenethyl alcohol; and/or
The titanium compound is one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy and titanium trichloromonoethoxy.
4. A Ti-containing solid catalyst component for olefin polymerization according to claim 1,
the organic epoxy compound is at least one selected from the group consisting of aliphatic olefins, aliphatic diolefins, halogenated aliphatic olefins or oxides and glycidyl ethers of halogenated aliphatic diolefins with the carbon number of 2-8; and/or
The organic epoxy compound is used in an amount of 0.02 to 2mol based on 1mol of the magnesium compound.
5. A Ti-containing solid catalyst component for olefin polymerization according to claim 4,
the organic epoxy compound is at least one selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, butadiene double oxide, epichlorohydrin, methyl glycidyl ether, diglycidyl ether and tetrahydrofuran.
6. A Ti-containing solid catalyst component for olefin polymerization according to claim 1,
the acyl halide compound has the general formula of R (COX) a Wherein R is H, C 1 ～C 8 Aliphatic radical, C 1 ～C 8 Halogenated aliphatic hydrocarbon radicals, C 6 ～C 10 Aromatic hydrocarbon or C of (2) 6 ～C 10 X is halogen and a is 1 or 2.
7. A Ti-containing solid catalyst component for olefin polymerization according to claim 6,
the acyl halide compound is acyl chloride compound; and/or
The acyl halide compound is used in an amount of 0.02 to 2.0mol based on 1mol of the magnesium compound.
8. The Ti-containing solid catalyst component for olefin polymerization according to claim 7, wherein the acid halide compound is at least one selected from the group consisting of benzoyl chloride, formyl chloride and dichloroacetyl chloride.
9. A Ti-containing solid catalyst component for olefin polymerization according to claim 2, wherein the catalyst component is prepared by reacting, based on 1mol of the magnesium compound,
the dosage of the substance containing aluminum element is 0.005-0.5 mol; and/or
The dosage of the organic alcohol compound is 0.2-6 mol; and/or
The dosage of the titanium compound is 1.0-20 mol;
wherein the molar amount of the magnesium compound is calculated based on the molar amount of the magnesium element, the molar amount of the aluminum-containing substance is calculated based on the molar amount of the aluminum element, and the molar amount of the titanium compound is calculated based on the molar amount of the titanium element.
10. A Ti-containing solid catalyst component for olefin polymerization according to any one of claims 1 to 9,
the electron donor is selected from one or more of organic ether, silicon-containing compound and boron-containing compound; and/or
The electron donor is used in an amount of 0 to 1mol based on 1mol of the magnesium compound, wherein the molar amount of the magnesium compound is calculated on the molar amount of magnesium element therein.
11. Process for the preparation of a Ti-containing solid catalyst component for the polymerization of olefins according to one of claims 1 to 10, characterized in that it comprises the following steps:
step 1, mixing a magnesium compound, a substance containing aluminum element, an organic alcohol compound and an organic epoxy compound in the presence of an inert diluent, and then adding an acyl halide compound to obtain a mixed solution;
step 2, cooling, then dripping the titanium compound into the mixed solution, or dripping the mixed solution into the titanium compound for reaction;
and step 3, heating, stirring and carrying out aftertreatment after the reaction to obtain the Ti-containing solid catalyst component.
12. The method according to claim 11, wherein,
in the step 1, the mixing is carried out at a temperature of 0-170 ℃; and/or
In step 1, the inert diluent is selected from one or more of benzene, toluene, xylene, 1, 2-dichloroethane, chlorobenzene, and other hydrocarbons or halogenated hydrocarbons; and/or
In the step 2, the temperature is reduced to minus 35 to 60 ℃; and/or
In the step 3, the temperature is raised to 10-150 ℃; and/or
In step 3, the post-treatment includes sedimentation, filtration, washing of solids and drying; and/or
Optionally, the electron donor is added in step 1 or step 2.
13. The method according to claim 12, wherein,
in the step 1, the mixture is mixed at 40-140 ℃; and/or
In the step 2, the temperature is reduced to minus 30 to 20 ℃; and/or
In step 3, the temperature is raised to 20-130 ℃.
14. A catalyst for olefin polymerization comprising the Ti-containing solid catalyst component for olefin polymerization according to any one of claims 1 to 9 or the Ti-containing solid catalyst component obtained by the production process according to any one of claims 11 to 13, wherein an organoaluminum compound is further contained.
15. The catalyst for olefin polymerization according to claim 14, wherein,
the general formula of the organic aluminum compound is AlR n X 3-n Wherein: r is C 1 ～C 20 Is a hydrocarbon group of (2)The method comprises the steps of carrying out a first treatment on the surface of the X is halogen; n is an integer of 0 < n.ltoreq.3; and/or
In the catalyst, the molar ratio of the organoaluminum compound to the Ti-containing solid catalyst component is (20 to 800): 1, a step of; wherein the molar amount of the Ti-containing solid catalyst component is calculated based on the molar amount of the titanium element therein, and the molar amount of the organoaluminum compound is calculated based on the molar amount of the aluminum element therein.
16. The catalyst for olefin polymerization according to claim 15, wherein the organoaluminum compound has the general formula AlR n X 3-n Wherein: r is selected from alkyl, aralkyl or aryl; x is chlorine and/or bromine; n is an integer of 0 < n.ltoreq.3.
17. Use of the catalyst for olefin polymerization according to any one of claims 14 to 16 in olefin polymerization.
18. Use according to claim 17, in ethylene homo-or copolymerization.
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