CN112625154B - Titanium catalyst component for olefin polymerization, preparation method thereof, catalyst containing titanium catalyst component and application of titanium catalyst component - Google Patents
Titanium catalyst component for olefin polymerization, preparation method thereof, catalyst containing titanium catalyst component and application of titanium catalyst component Download PDFInfo
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- CN112625154B CN112625154B CN201910953736.3A CN201910953736A CN112625154B CN 112625154 B CN112625154 B CN 112625154B CN 201910953736 A CN201910953736 A CN 201910953736A CN 112625154 B CN112625154 B CN 112625154B
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- 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
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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Abstract
The invention relates to a titanium catalyst component for olefin polymerization, a preparation method thereof, a catalyst containing the titanium catalyst component and application thereof. In the preparation process, a magnesium-containing compound, an aluminum-containing substance and an alcohol compound are mixed in the presence of an inert diluent, then mixed with a titanium-containing compound for reaction, and then post-treated to obtain the titanium catalyst component. The titanium 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 titanium 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 omits the dissolution reaction step of the precipitation aid, and shortens the preparation period of the titanium catalyst component.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst for olefin polymerization, in particular to a titanium catalyst component for olefin polymerization, a catalyst containing the titanium catalyst component, and a preparation method and application of the titanium catalyst component.
Background
Currently, polyolefin has been involved in various industries, especially polyethylene has been widely used in industry, agriculture, packaging and daily industries since the thirty-year invention of the twentieth century due to the abundant raw materials and excellent product properties.
The catalyst plays an important role in the synthesis and production of polyolefin, wherein titanium-based catalysts are widely applied and continuously developed due to high catalytic efficiency and low price.
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.
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 polyolefin catalyst, the catalyst prepared by the method has better performance than the existing catalyst, and the dissolution reaction step of the precipitation aid is omitted, so that the preparation period of the catalyst is shortened, and the raw materials are more environment-friendly than the organic phosphorus compound and phthalic anhydride system.
It is an object of the present invention to provide a titanium-based catalyst component for olefin polymerization, which is prepared from a raw material comprising a magnesium-containing compound, an aluminum-containing substance, an alcohol-containing compound and a titanium-containing compound.
According to a preferred embodiment of the present invention, the magnesium-containing 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.
According to a preferred embodiment of the invention, the substance containing aluminium is selected from metallic aluminium and/or inorganic aluminium 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.
According to a preferred embodiment of the present invention, the aluminum-containing substance is used in an amount of 0.002 to 1mol based on 1mol of the magnesium-containing 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-containing compound.
Wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the aluminum-containing substance is calculated based on the molar amount of the aluminum element therein.
The inventor finds that the catalyst system formed by adding a proper amount of aluminum-containing substances into the catalyst component has higher catalytic activity after a large number of experiments, and the analysis reasons probably lie in that after the aluminum-containing substances are added, synergistic effects exist among the components, so that the fact that the components in the catalyst component are synergistic and act as a whole can not be split and analyzed is emphasized.
According to a preferred embodiment of the invention, the 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 of (a).
In a further preferred embodiment, the alcohol compound is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, 2-ethylhexanol, n-octanol, dodecanol, benzyl alcohol, phenethyl alcohol.
In a still further preferred embodiment, the alcohol compound is selected from one or more of ethanol, isooctanol, butanol and 2-ethylhexanol, benzyl alcohol, 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.
Wherein, the main function of the alcohol compound is to dissolve the magnesium-containing compound and form an alcohol compound with the magnesium-containing compound.
According to a preferred embodiment of the present invention, the alcohol compound is used in an amount of 0.1 to 10mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the alcohol compound is used in an amount of 0.2 to 6mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
In the prior art, for example, chinese patent CN1229092a proposes a catalyst for ethylene polymerization or copolymerization and a process for preparing the same, wherein the catalyst is obtained by dissolving magnesium halide in an organic epoxy compound, an organic phosphorus compound and then adding an electron donor compound to form a homogeneous solution, and then reacting with at least one precipitation aid and a halide of transition metal titanium or its derivative. For another example, 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.
In the preparation process of the catalyst disclosed in the prior art, in order to obtain a catalyst solid, an organic phosphorus compound is adopted in a dissolution system, and meanwhile, a method of adding an auxiliary precipitation agent is also adopted, especially phthalic anhydride is adopted as the auxiliary precipitation agent in the embodiment, and the phthalic anhydride is completely dissolved in a mixed solvent system, and then cooled and mixed with a titanium compound, so that the use of the auxiliary precipitation agent correspondingly prolongs the preparation period of the catalyst. In addition, the precipitation aid system has relatively high toxicity and high requirements on operation conditions.
In the present application, the use of an organic phosphorus compound is avoided, and complete dissolution of the magnesium-containing compound is successfully achieved; further, it was found that the dissolution effect of the magnesium-containing compound is better when two or more alcohol compounds are used. Meanwhile, when the titanium-containing compound reacts with the titanium-containing compound in the later stage, different alcohols generate different titanium products, when the invention adopts more than two 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.
According to a preferred embodiment of the invention, the titanium-containing compound has the general 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-containing compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy, titanium trichloromonoethoxy, for example titanium tetrachloride.
According to a preferred embodiment of the present invention, the titanium-containing compound is used in an amount of 0.2 to 100mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the titanium-containing compound is used in an amount of 1.0 to 20mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the titanium-containing compound is calculated based on the molar amount of the titanium element therein.
According to a preferred embodiment of the invention, the starting materials for the preparation of the catalyst component optionally further comprise an electron donor compound.
In a further preferred embodiment, the electron donor compound 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 still 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 compound acts as a lewis base in the catalyst component, providing the electron pair to the metal in the catalyst.
According to a preferred embodiment of the present invention, the electron donor compound is used in an amount of 0 to 5mol based on 1mol of the magnesium-containing compound.
In a further preferred embodiment, the electron donor compound is used in an amount of 0 to 1mol based on 1mol of the magnesium-containing compound.
Wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
In the present invention, in the titanium-based catalyst component, the aluminum-containing substance is 0.0075 to 0.4mol, the alcohol compound is 4.0 to 6.0mol, the electron donor compound is 0 to 0.9mol, and the titanium-containing compound is 7.5 to 20mol, per mol of the magnesium-containing compound.
The second object of the present invention is to provide a method for preparing the titanium-based catalyst component according to one of the objects of the present invention, comprising the steps of:
step 1, mixing a magnesium-containing compound, an aluminum-containing substance and an alcohol compound in the presence of an inert diluent to obtain a mixed solution containing magnesium;
step 2, cooling, then dripping the titanium-containing compound into the magnesium-containing mixed solution, or dripping the magnesium-containing mixed solution into the titanium-containing compound for reaction;
and step 3, heating, stirring and post-treating after the reaction to obtain the titanium catalyst component.
According to a preferred embodiment of the invention, 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 take part in the reaction and should not adversely affect the dissolution of the magnesium-containing compound.
According to a preferred embodiment of the invention, in step 2, the temperature is reduced to-35 to 60 ℃, preferably-30 to 20 ℃.
According to a preferred embodiment of the invention, 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.
According to a preferred embodiment of the invention, optionally, an electron donor compound is added in step 1 or step 2.
In the present invention, the titanium-based catalyst component obtained is a powdery solid fine particle having an average particle diameter of about 2 to 50 μm, and the particle size can be controlled by changing the production conditions.
The third object of the present invention is to provide a catalyst for olefin polymerization comprising the titanium-based catalyst component according to one of the objects of the present invention or the titanium-based catalyst component obtained by the production method according to the second object of the present invention, and further comprising an organoaluminum compound.
According to a preferred embodiment of the invention, the organoaluminium compound has the general formula AlR n X 3-n Wherein: r is C 1 ～C 20 Preferably R is selected from alkyl, aralkyl or aryl; x is halogen, preferably chlorine and/or bromine; n is an integer of 0 < n.ltoreq.3.
In a further 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 still further preferred embodiment, the organoaluminum compound is selected from triethylaluminum and/or triisobutylaluminum.
According to a preferred embodiment of the present invention, the molar ratio of the organoaluminum compound to the titanium-based catalyst component in the catalyst is (5 to 1000): 1, preferably (20 to 800): 1.
Wherein the molar amount of the titanium-based 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 titanium-based catalyst component may be used in the form of a solid or a suspension, and the titanium-based 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 beneficial effects:
(1) The titanium 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;
(2) The preparation method omits the dissolution reaction step of the precipitation aid, and shortens the preparation period of the titanium catalyst component;
(3) The catalyst of the invention has better activity and bulk density.
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 0.035mol of n-butanol, heating to 130 ℃, maintaining for 1 hour, cooling to-5 ℃, dripping 0.3mol of titanium tetrachloride into the mixture for half an hour, adding 0.015mol of tetraethoxysilane, maintaining for 1 hour, heating to 110 ℃ and maintaining for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid titanium catalyst component.
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, 0.06mol of n-butanol is added, the temperature is lowered to-10 ℃ for half an hour, then 0.5mol of titanium tetrachloride is dripped into the catalyst, the temperature is maintained for half an hour, 0.015mol of tetraethoxysilane is added, the temperature is raised to 110 ℃ for 1 hour, the catalyst is filtered, washed with hexane for 4 times, and vacuum drying is carried out, so that the solid titanium catalyst component is obtained.
Example 3
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, adding 0.01mol of silicon tetrachloride for 5 minutes, adding 0.13mol of isooctanol, heating to 130 ℃ for half an hour, adding 0.05mol of n-butanol for half an hour, cooling to-15 ℃, dripping 0.6mol of titanium tetrachloride into the mixture for half an hour, and adding 0.015mol of the mixturel tetraethoxysilane, maintaining for 1 hour, then heating to 110 ℃ for 1 hour, filtering, washing with hexane for 4 times, and drying in vacuum to obtain the solid titanium catalyst component.
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 0.0003mol of anhydrous aluminum chloride, 0.6mol of toluene, 0.09mol of n-butanol and 0.08mol of ethanol, heating to 80 ℃, maintaining for 1 hour, cooling to 20 ℃, dripping 0.6mol of titanium tetrachloride into the mixture, maintaining for half an hour, heating to 85 ℃, maintaining for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid titanium catalyst component.
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 is added, the temperature is raised to 130 ℃ for half an hour, 0.05mol of phenethyl alcohol is added, the temperature is lowered to-20 ℃ for half an hour, then 0.6mol of titanium tetrachloride is dripped into the catalyst, the temperature is maintained for half an hour, 0.015mol of tetraethoxysilane is added, the temperature is raised to 110 ℃ for 1 hour, the catalyst is filtered, washed with hexane for 4 times, and vacuum drying is carried out, so that the solid titanium catalyst component is obtained.
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 0.006mol of anhydrous aluminum chloride and 0.4mol of n-decane, 0.01mol of silicon tetrachloride is added for 5 minutes, 0.18mol of n-butanol is added, the temperature is raised to 110 ℃, the temperature is maintained for 1 hour, the temperature is reduced to-20 ℃, then 0.6mol of titanium tetrachloride is dripped into the reactor for 1 hour, 0.015mol of tetraethoxysilane is added, the temperature is maintained for 1 hour, then the temperature is raised to 110 ℃, the temperature is maintained for 1 hour, the filtration is carried out, the hexane is used for washing 4 times, and the vacuum drying is carried out, so that the solid titanium catalyst component is obtained.
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 was added thereto with stirring.03mol of epichlorohydrin, 0.02mol of tributyl phosphate and 0.06mol of ethanol, heating to 60 ℃ for 1 hour, adding 0.0074mol of phthalic anhydride for half an hour, cooling the solution to-15 ℃, then dripping 0.60mol of titanium tetrachloride into the solution for 1 hour, heating to 60 ℃ for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid titanium catalyst component.
Comparative 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 0.30mol of n-decane, adding 0.15mol of 2-ethylhexanol under stirring, heating to 115 ℃, maintaining the temperature for 1 hour, cooling to 50 ℃, adding 0.026mol of silicon tetrachloride, cooling the solution to-10 ℃, dripping 0.45mol of titanium tetrachloride into the solution, maintaining the temperature for 1 hour, heating to 120 ℃, maintaining the temperature for 1 hour, filtering, washing with hexane for 4 times, and vacuum drying to obtain the solid titanium catalyst component.
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 the measured (9 to 12 mg) titanium-based catalyst components prepared in examples 1 to 5 and comparative examples 1 to 2 were added thereto, the temperature was raised to 70℃and hydrogenated to 0.26MPa (gauge pressure), and ethylene was introduced into the autoclave to 0.72MPa (gauge pressure), and polymerization was carried out at 80℃for 2 hours. The results are shown in Table 1.
Table 1:
as can be seen from the data of table 1, the catalyst of the present invention has better activity and bulk density under the same polymerization conditions than the comparative example.
Claims (17)
1. The titanium catalyst component for olefin polymerization is characterized in that the preparation raw materials of the titanium catalyst component comprise magnesium-containing compounds, aluminum-containing substances, alcohol compounds and titanium-containing compounds; the aluminum-containing substance is selected from goldThe aluminum-containing substance is used in an amount of 0.0375 to 1mol based on 1mol of the magnesium-containing compound, wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the aluminum-containing substance is calculated based on the molar amount of the aluminum element therein; the preparation raw materials of the titanium catalyst component further comprise electron donor compounds, wherein the electron donor compounds are selected from one or more of silicon-containing compounds, and the silicon-containing compounds are as follows: the general formula is R 1 xR 2 ySi(OR 3 ) z is a silicon compound having no active hydrogen atom, 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 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 2, z is more than or equal to 0 and less than or equal to 4, and x+y+z=4; the electron donor compound is used in an amount of 0.375 to 5mol based on 1mol of the magnesium-containing compound;
the preparation method of the titanium catalyst component for olefin polymerization comprises the following steps: step 1, mixing a magnesium-containing compound, an aluminum-containing substance and an alcohol compound in the presence of an inert diluent to obtain a mixed solution containing magnesium; step 2, cooling, then dripping the titanium-containing compound into the magnesium-containing mixed solution, or dripping the magnesium-containing mixed solution into the titanium-containing compound for reaction; adding the silicon-containing compound in step 1 or step 2; and step 3, heating, stirring and then post-treating after the reaction, wherein the post-treating comprises sedimentation, filtering, washing solid matters and drying treatment to obtain the titanium catalyst component.
2. The titanium-based catalyst component for olefin polymerization according to claim 1, wherein,
the magnesium-containing 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.
3. The titanium-based catalyst component for olefin polymerization according to claim 2, wherein,
the magnesium dihalide is selected from one or more of magnesium dichloride, magnesium dibromide and magnesium diiodide; and/or
The metal aluminum is nano aluminum powder; the inorganic aluminum compound is aluminum chloride.
4. The titanium-based catalyst component for olefin polymerization according to claim 3, wherein the aluminum-containing substance is used in an amount of 0.005 to 0.5mol based on 1mol of the magnesium-containing compound;
wherein the molar amount of the magnesium-containing compound is calculated based on the molar amount of the magnesium element therein, and the molar amount of the aluminum-containing substance is calculated based on the molar amount of the aluminum element therein.
5. The titanium-based catalyst component for olefin polymerization according to claim 1, wherein,
the 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 alcohol compound is used in an amount of 0.1 to 10mol based on 1mol of the magnesium-containing compound, wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
6. The titanium-based catalyst component for olefin polymerization according to claim 5, wherein,
the 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 alcohol compound is used in an amount of 0.2 to 6mol based on 1mol of the magnesium-containing compound, wherein the molar amount of the magnesium-containing compound is based on the molar amount of magnesium element therein.
7. The titanium-based catalyst component for olefin polymerization according to claim 1, wherein,
the general formula of the titanium-containing 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; and/or
The titanium-containing compound is used in an amount of 0.2 to 100mol based on 1mol of the magnesium-containing compound, wherein the molar amount of the magnesium-containing compound is based on the molar amount of the magnesium element therein, and the molar amount of the titanium-containing compound is based on the molar amount of the titanium element therein.
8. The titanium-based catalyst component for olefin polymerization according to claim 7, wherein,
the titanium-containing compound is selected from one or more of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxy, titanium monochlorotriethoxy, titanium dichlorodiethoxy and titanium trichloromonoethoxy; and/or
The titanium-containing compound is used in an amount of 1.0 to 20mol based on 1mol of the magnesium-containing compound, wherein the molar amount of the magnesium-containing compound is based on the molar amount of the magnesium element therein, and the molar amount of the titanium-containing compound is based on the molar amount of the titanium element therein.
9. The titanium-based catalyst component for olefin polymerization according to any one of claims 1 to 8, wherein the silicon-containing compound is selected from one or more of silicon tetrachloride, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane and tetrakis (2-ethylhexyloxy) silane.
10. The method for producing a titanium-based catalyst component for olefin polymerization according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
step 1, mixing a magnesium-containing compound, an aluminum-containing substance and an alcohol compound in the presence of an inert diluent to obtain a mixed solution containing magnesium;
step 2, cooling, then dripping the titanium-containing compound into the magnesium-containing mixed solution, or dripping the magnesium-containing mixed solution into the titanium-containing compound for reaction; adding the electron donor compound in step 1 or step 2;
and step 3, heating, stirring and post-treating after the reaction to obtain the titanium catalyst component.
11. The method according to claim 10, 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 n-decane; and/or
In the step 2, the temperature is reduced to minus 35 to 60 ℃; and/or
In step 3, the temperature is raised to 10-150 ℃.
12. The method according to claim 11, wherein,
in the step 1, the mixing is carried out at a temperature of 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 ℃.
13. A catalyst for olefin polymerization comprising the titanium-based catalyst component for olefin polymerization according to any one of claims 1 to 9 or the titanium-based catalyst component obtained by the production method according to any one of claims 10 to 12, wherein an organoaluminum compound is further contained.
14. The catalyst for olefin polymerization according to claim 13, 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); 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 titanium-based catalyst component is (5 to 1000): 1, a step of; wherein the molar amount of the titanium-based 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.
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 selected from alkyl, aralkyl or aryl; x is chlorine and/or bromine; n is an integer of 0 < n.ltoreq.3; and/or
In the catalyst, the molar ratio of the organoaluminum compound to the titanium-based catalyst component is (20 to 800): 1, a step of; wherein the molar amount of the titanium-based 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 use of the catalyst for olefin polymerization according to any one of claims 13 to 15 in olefin polymerization.
17. Use according to claim 16, of the catalyst for olefin polymerization in ethylene homo-or copolymerization.
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