Method for producing solid catalyst component for olefin polymerization, method for producing catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

To provide a method of manufacturing a solid catalyst component for polymerizing olefins giving a catalyst capable of manufacturing olefin polymers that does not too lower catalyst activity and is excellent in stereoregularity, when polymerizing olefins by a catalyst using the solid catalyst component containing titanium, halogen, magnesium, an internal electron donating compound and an alkoxy group.SOLUTION: A manufacturing method of a solid catalyst component for polymerizing olefins characterized by comprising a first generation step for obtaining a contact product by mutually contacting titanium tetrachloride, a magnesium compound, an internal electron donating compound and an inert organic solvent, a cleaning step for cleaning the contact product obtained in the first generation step with an inactive organic solvent to obtain a cleaned product, and a second generation step for mutually contacting the cleaned product obtained in the cleaning step, silicon tetrachloride, organic acid chloride or metal chloride and the inactive organic solvent to obtain a solid catalyst component.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a solid catalyst component for olefin polymerization, a method for producing a catalyst for olefin polymerization, and a method for producing an olefin polymer. [Background technology]

[0002] A well-known method for producing polymers of olefins such as ethylene and propylene is the so-called Ziegler-Natta catalyst. In this production method, in addition to the stereoregular olefin polymers that are highly valuable industrially, amorphous polymers are by-produced, which deteriorate the mechanical properties of the polymers. The by-production of amorphous polymers also represents a loss of raw material monomers, and a process for removing them is required in the production equipment, resulting in a significant industrial disadvantage. Therefore, it is desirable to use a catalyst for olefin polymer polymerization that produces no or very little amorphous polymer by-production.

[0003] For example, Patent Document 1 describes a solid catalyst component for α-olefin polymerization, which contains magnesium, titanium, a halogen, an electron donor, and an alkoxysilane compound, wherein the electron donor is one or a mixture of two or more selected from the group consisting of organic acids, inorganic acids, and derivative compounds thereof, ether compounds, and ketone compounds, and the content of the electron donor is 5 to 40 μmol / g.

[0004] According to Patent Document 1, it is possible to provide an α-olefin polymerization catalyst that contains an alkoxysilane compound and contains an extremely small amount of electron donor, and that can produce an olefin polymer with a low soluble content and high stereoregularity in high yield.

[0005] For example, Patent Document 2 describes a solid catalyst component for olefin polymerization in which an oxide of a Group II to IV element (compound (a)) carrying an alkoxy group-containing magnesium compound or an alcohol complex of a halogen-containing magnesium compound is supported, and the oxide (a) is reacted with a halogen-containing silicon compound (compound (b-1)) having a halogen / magnesium molar ratio of 0.20 or more, and these are reacted with an electron donor compound (compound (c)) and a halogen-containing titanium compound (compound (d)) at a temperature of 120°C or higher and 150°C or lower, washed with an inert solvent, and then reacted again with compound (d) at a temperature of 120°C or higher and 150°C or lower, and washed with an inert solvent, resulting in a molar ratio of residual alkoxy group (RO) / supported titanium amount (Ti) of 0.70 or lower.

[0006] According to Patent Document 2, it is possible to provide a solid catalyst component for olefin polymerization that has high polymerization activity, little residual Cl, and can give an olefin polymer that is excellent in stereoregularity and powder form. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 2019-151680 [Patent Document 2] Japanese Patent Application Laid-Open No. 2003-137919 Summary of the Invention [Problem to be solved by the invention]

[0008] However, even with the production methods described in Patent Documents 1 and 2, in fields where olefin polymers are processed into injection-molded articles for use, there is a demand for molded articles with even higher rigidity, and there has been a demand for production methods that can produce olefin polymers with higher stereoregularity.

[0009] On the other hand, in the production of olefin polymers, even if the stereoregularity of the resulting olefin polymer is high, if the polymerization activity is too low, productivity is affected.

[0010] Therefore, an object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, which is a solid catalyst component containing titanium, halogen, magnesium, an internal electron donor compound, and an alkoxy group, and which provides a catalyst that does not exhibit excessively low catalytic activity during olefin polymerization using the solid catalyst component and is capable of producing an olefin polymer having excellent stereoregularity; and to provide a method for producing a catalyst for olefin polymerization using the solid catalyst component, and a method for producing an olefin polymer. [Means for solving the problem]

[0011] In order to solve the above technical problems, the present inventors have conducted extensive research and have found that the above technical problems can be solved by, in the production of a solid catalyst component for olefin polymerization, bringing titanium tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent into contact with each other to obtain a contact product, washing the product, and then contacting a chlorine-containing compound with the product. Based on this finding, the present invention has been completed.

[0012] That is, the present invention is (1) a first production step of contacting titanium tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent with each other to obtain a contact product; a washing step in which the contact product obtained in the first generation step is washed with an inert organic solvent to obtain a washed product; a second production step of contacting the washed product obtained in the washing step with a chlorine-containing compound and an inert organic solvent to obtain a solid catalyst component; and the chlorine-containing compound is silicon tetrachloride, an organic acid chloride, or a metal chloride; A method for producing a solid catalyst component for olefin polymerization, characterized by: (2) A method for producing a solid catalyst component for olefin polymerization according to (1), characterized in that in the first production step, titanium tetrachloride, silicon tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent are brought into contact with each other to obtain a contact product. (3) the chlorine-containing compound is silicon tetrachloride; the ratio (Si / Mg) of the number of moles of silicon, in atomic terms, in the silicon tetrachloride used in the second production step to the number of moles of magnesium, in atomic terms, in the magnesium compound used in the first production step is 1.5 to 30.0; (1) or (2) is a method for producing a solid catalyst component for olefin polymerization, (4) The method for producing a solid catalyst component for olefin polymerization according to (3), wherein in the second production step, the washed product obtained in the washing step, the silicon tetrachloride, and the inert organic solvent are brought into contact with each other at 95°C or higher. (5) The chlorine-containing compound is phthalic acid dichloride; a ratio (Cl / Mg) of the number of moles of chlorine atoms, in atomic terms, in the phthaloyl dichloride used in the second production step to the number of moles of magnesium, in atomic terms, in the magnesium compound used in the first production step is 0.1 to 5.0; (1) or (2) is a method for producing a solid catalyst component for olefin polymerization, (6) The chlorine-containing compound is a chloride of one or more metals selected from the group consisting of Li, Na, K, Ca, Zn, Bi, and Cu. (1) or (2) is a method for producing a solid catalyst component for olefin polymerization, (7) A method for producing a catalyst for olefin polymerization, comprising contacting a solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to any one of (1) to (6) with an organoaluminum compound to obtain a catalyst for olefin polymerization. (8) A method for producing a catalyst for olefin polymerization, comprising contacting a solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to any one of (1) to (6) with an organoaluminum compound and an external electron donor compound to obtain a catalyst for olefin polymerization. (9) A method for producing an olefin polymer, comprising polymerizing olefins using an olefin polymerization catalyst obtained by the method for producing an olefin polymerization catalyst according to (7) or (8). This provides: [Effects of the Invention]

[0013] According to the present invention, there are provided a method for producing a solid catalyst component for olefin polymerization, which is a solid catalyst component containing titanium, a halogen, magnesium, an internal electron donor compound, and an alkoxy group, and which provides a catalyst capable of producing an olefin polymer having excellent stereoregularity and does not exhibit excessively low catalytic activity during olefin polymerization using the solid catalyst component; and there are also provided a method for producing an olefin polymerization catalyst using the solid catalyst component, and a method for producing an olefin polymer. DETAILED DESCRIPTION OF THE INVENTION

[0014] <Method of producing a solid catalyst component for olefin polymerization> The method for producing a solid catalyst component for olefin polymerization according to the present invention comprises a first production step of contacting titanium tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent to obtain a contact product; a washing step in which the contact product obtained in the first generation step is washed with an inert organic solvent to obtain a washed product; a second production step of contacting the washed product obtained in the washing step with a chlorine-containing compound and an inert organic solvent to obtain a solid catalyst component; and the chlorine-containing compound is silicon tetrachloride, an organic acid chloride, or a metal chloride; It is characterized by the following.

[0015] Hereinafter, in this application document, the "solid catalyst component for olefin polymerization" may be abbreviated to "solid catalyst component".

[0016] The method for producing a solid catalyst component for olefin polymerization according to the present invention comprises a first production step, a washing step, and a second production step.

[0017] The magnesium compound used in the method for producing a solid catalyst component for olefin polymerization according to the present invention is not particularly limited as long as it is a source of alkoxy groups and does not impair the effects of the present invention. Examples of such magnesium compounds include dialkoxymagnesium compounds such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium.

[0018] Among the above dialkoxymagnesium compounds, diethoxymagnesium is preferred in terms of polymerization activity and stereoregularity. In the present invention, these magnesium compounds may be used alone or in combination of two or more.

[0019] In the present invention, commercially available magnesium compounds may be used, or synthesized magnesium compounds may be used. For example, dialkoxymagnesium compounds obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound may be used.

[0020] The magnesium compound may be in the form of granules or powder, and may be amorphous or spherical. For example, when a spherical dialkoxymagnesium compound is used, a polymer powder having a better particle shape and a narrow particle size distribution is easily obtained, the handling of the polymer powder (produced polymer powder) produced by polymerization is improved, and problems such as clogging of the filter in the polymer separation device due to fine particles contained in the produced polymer powder are easily solved. The spherical dialkoxymagnesium compound does not necessarily have to be perfectly spherical, and may be ellipsoidal or potato-shaped.

[0021] The magnesium compound is not particularly limited in its average particle size (D50), but preferably 1 to 200 μm, more preferably 5 to 150 μm. Here, the average particle size refers to the particle size at 50% of the cumulative particle size in the volume cumulative particle size distribution measured using a laser light scattering diffraction particle size analyzer. For example, when a spherical dialkoxy magnesium compound is used, the average particle size is not particularly limited, but is preferably 1 to 100 μm, more preferably 5 to 80 μm, and most preferably 10 to 60 μm.

[0022] Furthermore, the magnesium compound preferably has a small amount of fine and coarse powder and a narrow particle size distribution. For example, when measured using a laser light scattering diffraction particle size analyzer, the proportion of particles (fine powder) with a particle size of 5 μm or less is preferably 20% or less, more preferably 10% or less, of the total amount of magnesium compound. Similarly, when measured using a laser light scattering diffraction particle size analyzer, the proportion of particles (coarse powder) with a particle size of 100 μm or more is preferably 10% or less, more preferably 5% or less, of the total amount of magnesium compound.

[0023] Furthermore, when the particle size distribution of the magnesium compound is expressed as D90 / D10, the D90 / D10 is preferably 3 or less, and more preferably 2 or less. Here, D90 refers to the particle size at 90% of the cumulative particle size in the volume cumulative particle size distribution when measured using a laser light scattering diffraction particle size analyzer. Furthermore, D10 refers to the particle size at 10% of the cumulative particle size in the volume cumulative particle size distribution when measured using a laser light scattering diffraction particle size analyzer.

[0024] In addition, as the spherical dialkoxymagnesium compound, for example, those produced by the methods exemplified in JP-A Nos. 58-4132, 62-51633, 3-74341, 4-368391, and 8-73388 may be used.

[0025] The internal electron donor compound used in the method for producing a solid catalyst component for olefin polymerization according to the present invention is not particularly limited as long as it is an organic compound capable of donating an electron pair during the formation of the solid catalyst component. The internal electron donor compound may be any organic compound in which the functional group donating the electron pair contains an oxygen atom or a nitrogen atom, such as alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si-O-C bond or a Si-N-C bond. In the present invention, the solid catalyst component may contain one or more of these internal electron donor compounds.

[0026] Among the above internal electron donor compounds, ethers such as monoethers, diethers, and ether carbonates, esters such as monocarboxylic acid esters and polycarboxylic acid esters are preferred; diethers, ether carbonates, aromatic polycarboxylic acid esters such as aromatic dicarboxylic acid diesters, aliphatic polycarboxylic acid esters, and alicyclic polycarboxylic acid esters are more preferred; diethers such as 2,2-dialkyl-1,3-dimethoxypropane and 9,9-bis(alkoxymethyl)fluorene, (2-alkoxyalkyl) alkyl carbonates, (2-alkoxyal

[0044] Most preferred are ether carbonates such as alkyl)phenyl carbonate, aromatic dicarboxylic acid diesters such as phthalic acid diesters, alkyl-substituted phthalic acid diesters, and halogen-substituted phthalic acid diesters, aliphatic dicarboxylic acid esters such as malonic acid diesters, alkyl-substituted malonic acid diesters, succinic acid diesters, alkyl-substituted succinic acid diesters, maleic acid diesters, and alkyl-substituted maleic acid diesters, and alicyclic dicarboxylic acid esters such as cycloalkane-1,2-dicarboxylic acid diesters, 1-cycloalkene-1,2-dicarboxylic acid diesters, and 4-cycloalkene-1,2-dicarboxylic acid diesters.

[0027] The inert organic solvent used in the method for producing a solid catalyst component for olefin polymerization according to the present invention is not particularly limited as long as it functions as a solvent or washing solvent in each of the above-mentioned production steps and does not impair the effects of the present invention. Examples of such inert organic solvents include linear aliphatic hydrocarbon compounds such as hexane, heptane, and decane, branched aliphatic hydrocarbon compounds such as methylheptane, alicyclic hydrocarbon compounds such as cyclohexane, methylcyclohexane, and ethylcyclohexane, and aromatic hydrocarbon compounds such as toluene, xylene, and ethylbenzene.

[0028] Among the above inert organic solvents, aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50 to 150° C. are preferred in terms of polymerization activity and stereoregularity. In the present invention, these inert organic solvents may be used alone or in combination of two or more.

[0029] The method for producing a solid catalyst component for olefin polymerization according to the present invention comprises a first production step, a washing step, and a second production step.

[0030] The first production step is a step of obtaining a contact product by contacting at least titanium tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent with each other.

[0031] The amount of titanium tetrachloride used in the first production step is expressed as a molar ratio (Ti moles / Mg moles) of preferably 1.0 to 30.0, more preferably 1.0 to 10.0, and even more preferably 1.0 to 3.0, in terms of titanium atoms, to the amount of magnesium compound used in terms of magnesium atoms.

[0032] The amount of the internal electron donor compound used in the first production step is preferably 0.05 to 0.25, more preferably 0.10 to 0.20, and even more preferably 0.12 to 0.18, in terms of molar ratio (number of moles of internal electron donor compound / number of moles of Mg) to the amount of the magnesium compound used in terms of magnesium atoms.

[0033] The amount of the inert organic solvent used in the first production step is not particularly limited and is appropriately selected depending on the amount of each raw material used.

[0034] In the first production step, silicon tetrachloride can be contacted in addition to titanium tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent. That is, in the first production step, titanium tetrachloride, silicon tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent are contacted with each other to obtain a contact product.

[0035] When silicon tetrachloride is used in the first production step, the molar ratio of the amount of silicon tetrachloride used in the first production step, calculated as silicon atoms, to the amount of magnesium compound used, calculated as magnesium atoms (Si moles / Mg moles), is preferably 0.1 to 5.0, more preferably 0.2 to 3.0, and even more preferably 0.3 to 2.0.

[0036] In the first production step, the contact temperature when titanium tetrachloride, the magnesium compound, the internal electron donor compound, and the inert organic solvent are contacted is preferably 50 to 160° C., more preferably 80 to 130° C., and even more preferably 95 to 115° C. When the contact temperature in the first production step is within the above range, a solid catalyst component can be obtained that does not result in an excessively low polymerization activity and that is capable of producing an olefin polymer having high stereoregularity.

[0037] The washing step is a step in which the contact product obtained in the first production step is washed with an inert organic solvent to obtain a washed product.

[0038] In the washing step, the contact product is washed by contacting it with an inert organic solvent. The amount of the inert organic solvent used in the washing step is not particularly limited and is appropriately selected depending on the amount of each raw material used. In the washing step (1), the washing temperature when washing the contact product (1) is not particularly limited and is appropriately selected, for example, from 25 to 100°C.

[0039] The second production step is a step of obtaining a solid catalyst component by contacting the washed product obtained by the washing step with a chlorine-containing compound and an inert organic solvent.

[0040] The chlorine-containing compound in the second production step is silicon tetrachloride (first form), an organic acid chloride (second form), or a metal chloride (third form).

[0041] The first embodiment of the method for producing a solid catalyst component for olefin polymerization according to the present invention is an embodiment in which silicon tetrachloride is used as the chlorine-containing compound in the second production step.

[0042] That is, the second production step (hereinafter also referred to as the second production step (1)) in the method for producing a solid catalyst component for olefin polymerization according to the first embodiment of the present invention is a step of obtaining a solid catalyst component by contacting the washed product obtained by the washing step with silicon tetrachloride and an inert organic solvent.

[0043] The amount of silicon tetrachloride used in the second production step (1) is an amount such that the ratio of the number of moles of silicon, in atomic terms, in the silicon tetrachloride used in the second production step to the number of moles of magnesium, in atomic terms, in the magnesium compound used in the first production step (Si / Mg) is 1.5 to 30.0, more preferably 2.0 to 20.0, and even more preferably 2.0 to 11.0. When the amount of silicon tetrachloride used in the second production step is within the above range, it is possible to obtain a solid catalyst component that does not result in an excessively low polymerization activity and that is capable of producing an olefin polymer with high stereoregularity.

[0044] The amount of the inert organic solvent used in the second production step (1) is not particularly limited and is appropriately selected depending on the amount of each raw material used.

[0045] In the second production step (1), the contact temperature when the washed material, silicon tetrachloride, and the inert organic solvent are contacted is preferably 95° C. or higher, more preferably 95 to 135° C., and even more preferably 95 to 115° C. When the contact temperature in the second production step is within the above range, a solid catalyst component can be obtained that does not have an excessively low polymerization activity and that is capable of producing an olefin polymer having high stereoregularity.

[0046] The second embodiment of the method for producing a solid catalyst component for olefin polymerization according to the present invention is an embodiment in which an organic acid chloride is used as the chlorine-containing compound in the second production step.

[0047] That is, the second production step (hereinafter also referred to as the second production step (2)) in the method for producing a solid catalyst component for olefin polymerization according to the second embodiment of the present invention is a step of obtaining a solid catalyst component by bringing the washed product obtained by the washing step into contact with an organic acid chloride.

[0048] Examples of the organic acid chloride used in the second generation step (2) include phthalic acid dichloride, alkynyl halides, and monocarboxylic acid halides such as aliphatic monocarboxylic acid halides, aromatic monocarboxylic acid halides, aliphatic polycarboxylic acid halides, or aromatic polycarboxylic acid halides, specifically alkynyl halides such as ethyl chloride, propyl chloride, butyl chloride, pentyl chloride, and hexyl chloride, formic acid chloride, acetic acid chloride, propionic acid chloride, butyric acid chloride, benzoic acid chloride, p-toluic acid chloride, and p-toluic acid chloride. Examples of the organic acid chloride include monocarboxylic acid chlorides such as 2-methoxybenzoate chloride, anisic acid chloride, trimethylacetic acid chloride (pivalic acid chloride), triethylacetic acid chloride, tripropylacetic acid chloride, and triisopropylacetic acid chloride, and polycarboxylic acid chlorides such as maleic acid dichloride, malonic acid dichloride, diisopropylmalonic acid dichloride, diisobutylmalonic acid dichloride, adipic acid dichloride, phthalic acid dichloride, terephthalic acid dichloride, 1,2-cyclohexanedicarboxylic acid dichloride, and sebacic acid dichloride. Phthalic acid dichloride is preferred as the organic acid chloride.

[0049] When phthaloyl dichloride is used as the organic acid chloride in the second production step (2), the amount of phthaloyl dichloride used in the second production step (2) is an amount such that the ratio (Cl / Mg) of the number of moles of chlorine, in atomic terms, in the phthaloyl dichloride used in the second production step to the number of moles of magnesium, in atomic terms, in the dialkoxymagnesium compound used in the first production step is 0.1 to 5.0, more preferably 0.2 to 4.0, and even more preferably 0.3 to 3.0. When the amount of phthaloyl dichloride used in the second production step is within the above range, a solid catalyst component can be obtained that does not result in an excessively low polymerization activity and that is capable of producing an olefin polymer with high stereoregularity.

[0050] The amount of the inert organic solvent used in the second production step (2) is not particularly limited and is appropriately selected depending on the amount of each raw material used.

[0051] When phthaloyl dichloride is used in the second production step (2), the contact temperature when the washed material, phthaloyl dichloride, and the inert organic solvent are contacted in the second production step (2) is preferably 95° C. or higher, more preferably 95 to 135° C., and even more preferably 95 to 115° C. When the contact temperature in the second production step is within the above range, a solid catalyst component can be obtained that does not have an excessively low polymerization activity and that can produce an olefin polymer with high stereoregularity.

[0052] The method for producing a solid catalyst component for olefin polymerization according to the third embodiment of the present invention is an embodiment in which a metal chloride is used as the chlorine-containing compound in the second production step.

[0053] That is, the second production step (hereinafter also referred to as the second production step (3)) in the method for producing a solid catalyst component for olefin polymerization according to the third embodiment of the present invention is a step of obtaining a solid catalyst component by bringing the washed product obtained by the washing step into contact with a metal chloride.

[0054] Examples of the metal chloride used in the second production step (3) include chlorides of one or more metals selected from Li, Na, K, Ca, Zn, Bi, and Cu, such as LiCl, NaCl, KCl, CaCl2, ZnCl2, BiCl3, and CuCl2.

[0055] In the second production step (3), the amount of metal chloride used is an amount such that the ratio (M / Mg) of the number of moles of metal (M) in atomic terms in the metal chloride used in the second production step to the number of moles of magnesium (Mg) in atomic terms in the magnesium compound used in the first production step is 0.001 to 50.0. When the amount of metal chloride used in the second production step is within the above range, it is possible to obtain a solid catalyst component that does not result in an excessively low polymerization activity and that is capable of producing an olefin polymer with high stereoregularity.

[0056] In the second generation step (3), titanium tetrachloride (TiCl4) can be brought into contact with the washed product obtained by the washing step together with chlorides of one or more metals selected from Li, Na, K, Ca, Zn, Bi, and Cu. In this case, the ratio (X / Ti) of the number of moles of metal element (X) in atomic terms of chloride of one or more metals selected from Li, Na, K, Ca, Zn, Bi, and Cu to the number of moles of titanium element (Ti) in titanium tetrachloride (TiCl4) is preferably 0.002 to 0.050, more preferably 0.004 to 0.025.

[0057] The amount of the inert organic solvent used in the second production step (3) is not particularly limited and is appropriately selected depending on the amount of each raw material used.

[0058] In the second production step (3), the contact temperature when the washed material, metal chloride, and inert organic solvent are contacted is preferably 95° C. or higher, more preferably 95 to 135° C., and even more preferably 95 to 115° C. When the contact temperature in the second production step is within the above range, a solid catalyst component can be obtained that does not have an excessively low polymerization activity and that can produce an olefin polymer with high stereoregularity.

[0059] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, after the second production step (second production step (1), (2) or (3)), the solid catalyst component obtained by carrying out the second production step can be washed, if necessary, with an inert organic solvent.

[0060] <Solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to the present invention> The solid catalyst component for olefin polymerization (hereinafter also referred to as the solid catalyst component for olefin polymerization according to the present invention) obtained by carrying out the method for producing a solid catalyst component for olefin polymerization according to the present invention contains titanium, a halogen, magnesium, an internal electron donor compound, and an alkoxy group, The titanium content relative to the total amount of the solid catalyst component for olefin polymerization is 0.10 to 1.00 mass% in terms of titanium atom, and The solid catalyst component for olefin polymerization is characterized in that the content of alkoxy groups relative to the total amount of the solid catalyst component for olefin polymerization is 0.150 mass % or less.

[0061] The internal electron donor compound in the solid catalyst component for olefin polymerization according to the present invention is not particularly limited as long as it is an organic compound capable of donating an electron pair during the formation of the solid catalyst component. The internal electron donor compound may be any organic compound in which the functional group donating the electron pair contains an oxygen atom or a nitrogen atom, such as alcohols, phenols, ethers, esters, ketones, acid halides, aldehydes, amines, amides, nitriles, isocyanates, and organosilicon compounds containing a Si-O-C bond or a Si-N-C bond. In the present invention, the solid catalyst component may contain one or more of these internal electron donor compounds.

[0062] Among the above internal electron donor compounds, ethers such as monoethers, diethers, and ether carbonates, esters such as monocarboxylic acid esters and polycarboxylic acid esters are preferred; diethers, ether carbonates, aromatic polycarboxylic acid esters such as aromatic dicarboxylic acid diesters, aliphatic polycarboxylic acid esters, and alicyclic polycarboxylic acid esters are more preferred; diethers such as 2,2-dialkyl-1,3-dimethoxypropane and 9,9-bis(alkoxymethyl)fluorene, (2-alkoxyalkyl) alkyl carbonates, (2-alkoxyal

[0044] Most preferred are ether carbonates such as alkyl)phenyl carbonate, aromatic dicarboxylic acid diesters such as phthalic acid diesters, alkyl-substituted phthalic acid diesters, and halogen-substituted phthalic acid diesters, aliphatic dicarboxylic acid esters such as malonic acid diesters, alkyl-substituted malonic acid diesters, succinic acid diesters, alkyl-substituted succinic acid diesters, maleic acid diesters, and alkyl-substituted maleic acid diesters, and alicyclic dicarboxylic acid esters such as cycloalkane-1,2-dicarboxylic acid diesters, 1-cycloalkene-1,2-dicarboxylic acid diesters, and 4-cycloalkene-1,2-dicarboxylic acid diesters.

[0063] The alkoxy group in the solid catalyst component for olefin polymerization according to the present invention is not particularly limited in structure, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, an isooctoxy group, etc. In the present invention, the solid catalyst component may contain one or more of these alkoxy groups.

[0064] The solid catalyst component for olefin polymerization according to the present invention has a titanium content, calculated as titanium atoms, of 0.10 to 1.00 mass%, preferably 0.20 to 1.00 mass%, more preferably 0.40 to 1.00 mass%, and most preferably 0.50 to 1.00 mass%, relative to the total amount of the solid catalyst component. By ensuring that the titanium content is within the above range relative to the total amount of the solid catalyst component, it is possible to reduce the production of olefin polymers with low stereoregularity.

[0065] In the solid catalyst component for olefin polymerization according to the present invention, the contents of magnesium, halogen and electron donor compound constituting the solid catalyst component are not particularly limited as long as the effects of the present invention can be exhibited.

[0066] The solid catalyst component for olefin polymerization according to the present invention has a halogen content, calculated as halogen atoms, of 20.0 to 85.0 mass%, preferably 30.0 to 80.0 mass%, more preferably 40.0 to 75.0 mass%, and most preferably 45.0 to 70.0 mass%, relative to the total amount of the solid catalyst component.

[0067] The solid catalyst component for olefin polymerization according to the present invention has a magnesium content, calculated as magnesium atoms, of 10.0 to 70.0 mass%, preferably 10.0 to 50.0 mass%, more preferably 15.0 to 40.0 mass%, and most preferably 15.0 to 25.0 mass%, relative to the total amount of the solid catalyst component.

[0068] The solid catalyst component for olefin polymerization according to the present invention has an internal electron donor compound content of 1.0 to 25.0 mass%, preferably 5.0 to 25.0 mass%, more preferably 10.0 to 25.0 mass%, and most preferably 10.0 to 20.0 mass%, relative to the total mass of the solid catalyst component.

[0069] The solid catalyst component for olefin polymerization according to the present invention has an alkoxy group content of 0.150% by mass or less, preferably 0.001 to 0.150% by mass, more preferably 0.001 to 0.100% by mass, and most preferably 0.001 to 0.050% by mass, based on the total amount of the solid catalyst component. By ensuring that the alkoxy group content is within the above range based on the total amount of the solid catalyst component, it is possible to reduce the production of olefin polymers with low stereoregularity.

[0070] In order to achieve a well-balanced overall performance, the solid catalyst component for olefin polymerization according to the present invention preferably has a titanium content of 0.50 to 1.00 mass% calculated as titanium atoms, a halogen content of 45.0 to 70.0 mass% calculated as halogen atoms, a magnesium content of 15.0 to 25.0 mass% calculated as magnesium atoms, an internal electron donor compound content of 10.0 to 20.0 mass%, and an alkoxy group content of 0.001 to 0.050 mass%.

[0071] In order to ensure that the solid catalyst component for olefin polymerization according to the present invention exhibits a well-balanced overall performance, the content of the internal electron donor compound relative to the content of titanium atoms in atomic terms is preferably in a molar ratio (number of moles of internal electron donor compound / number of moles of titanium atoms in atomic terms) of 3.0 or more, more preferably 3.0 to 20.0, even more preferably 3.0 to 10.0, and most preferably 3.0 to 6.0.

[0072] In the production method of the solid catalyst component for olefin polymerization according to the present invention, when silicon tetrachloride is used in the second generation step, Si may not be detected in the solid catalyst component for olefin polymerization, even though silicon tetrachloride is used in the second generation step. That is, although the details are not necessarily clear, silicon tetrachloride has a low boiling point, and therefore, when the inert organic solvent is removed from the solid catalyst component by drying after the second generation step, silicon tetrachloride evaporates together with the inert organic solvent. As a result, the amount of Si in the solid catalyst component for olefin polymerization obtained by the production method of the solid catalyst component for olefin polymerization according to the present invention becomes below the detection limit, and Si may not be detected.

[0073] In the present application, the titanium content in the solid catalyst component refers to a value measured in accordance with the method (oxidation-reduction titration) described in Japanese Industrial Standards (JIS) "JIS 8311-1997" (Method for determining titanium in titanium ore).

[0074] In the present application, the magnesium content in the solid catalyst component refers to a value measured by an EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

[0075] In addition, in the present application, the halogen content in the solid catalyst component refers to a value measured by a silver nitrate titration method in which the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to prepare an aqueous solution, and then titrated with a silver nitrate standard solution.

[0076] In addition, in the present application, the content ratio of the internal electron donor compound in the solid catalyst component means a value determined by using a calibration curve measured in advance based on known concentrations when measured using gas chromatography (GC-14B, manufactured by Shimadzu Corporation) under the following conditions:

[0077] <Measurement conditions> Column: Packed column (φ2.6 × 2.1 m, Silicone SE-30 10%, Chromosorb WAWDMCS 80 / 100, GL Sciences Inc.) Detector: Hydrogen flame ionization detector (FID: Flame Ionization Detector) Carrier gas: Helium (flow rate 40 mL / min) Measurement temperature: Vaporizer 280°C, column 225°C, detector 280°C, or vaporizer 265°C, column 180°C, detector 265°C

[0078] In addition, in the present application, the content of alkoxy groups in the solid catalyst component is measured using an NMR measurement device (Avance III 400, 1 The value is determined by measuring the following sample with a 1H resonance frequency of 400 MHz and an accumulation count of 64, using the signal intensity of tetrachloroethane (TCE) used as a reference substance.

[0079] <Sample preparation method> Approximately 20 mg of the catalyst was placed in a weighed NMR tube under a nitrogen atmosphere, sealed, and then weighed. Next, 800 microliters of deuterated dimethyl sulfoxide (d-DMSO) was poured into the tube under a nitrogen atmosphere, sealed, and then weighed. The catalyst was dissolved in deuterated DMSO, and then 30 microliters of TCE was poured into the tube under a nitrogen atmosphere. After sealing, the entire amount was weighed, and the NMR tube was inverted upside down to homogenize the contents.

[0080] <Method of manufacturing an olefin polymerization catalyst> The method for producing a catalyst for olefin polymerization according to the present invention is characterized in that the solid catalyst component for olefin polymerization obtained by the above-mentioned method for producing a solid catalyst component for olefin polymerization is brought into contact with an organoaluminum compound and, if necessary, an external electron donor compound to obtain a catalyst for olefin polymerization.

[0081] As the solid catalyst component for olefin polymerization, the same solid catalyst component as the above-mentioned solid catalyst component for olefin polymerization can be applied, and therefore the explanation thereof will be omitted.

[0082] In the method for producing a catalyst for olefin polymerization according to the present invention, the organoaluminum compound applied is not particularly limited as long as it does not inhibit the effects of the present invention. Such organoaluminum compounds include the following general formula (I) R 1 p AlQ 3-p (I) (In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, and p is a real number of 0 < p ≦ 3.) Compounds represented by are exemplified. In the present invention, these organoaluminum compounds may be applied alone or in combination of two or more.

[0083] In the organoaluminum compound represented by the above general formula (I), R 1 is an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, etc. Among these R 1 , an ethyl group or an isobutyl group is preferable.

[0084] Also, in the organoaluminum compound represented by the above general formula (I), Q is a hydrogen atom or a halogen atom, and among these Q, a hydrogen atom, a chlorine atom or a bromine atom is preferable.

[0085] Also, in the organoaluminum compound represented by the above general formula (I), p is a real number of 0 < p ≦ 3, and among these p, a real number of 2 to 3 is preferable, and 2, 2.5 or 3 is more preferable.

[0086] Examples of such organoaluminum compounds include triethylaluminum, diethylaluminum chloride, triisobutylaluminum, diethylaluminum bromide, diethylaluminum hydride, etc. Among these organoaluminum compounds, triethylaluminum or triisobutylaluminum is preferable.

[0087] The external electron donor compound used in the method for producing a catalyst for olefin polymerization according to the present invention is not particularly limited as long as it does not impair the effects of the present invention. Examples of such external electron donor compounds include the same internal electron donor compounds as those in the solid catalyst component for olefin polymerization described above, and among them, carbonates, ethers, esters, or organosilicon compounds are preferred. In the present invention, these external electron donor compounds may be used alone or in combination of two or more.

[0088] In the present invention, when the external electron donor compound is a carbonate, 2-ethoxyethyl phenyl carbonate, 2-benzyloxyethyl phenyl carbonate, or 2-ethoxyethyl-1-methyl carbonate is preferred. When the external electron donor compound is an ether, 1,3-diethers are preferred, and among them, 9,9-bis(methoxymethyl)fluorene or 2-isopropyl-2-isopentyl-1,3-dimethoxypropane is more preferred. When the external electron donor compound is an ester, methyl benzoate or ethyl benzoate is preferred.

[0089] In the present invention, when the external electron donor compound is an organosilicon compound, examples thereof include organosilicon compounds containing an Si-OC bond and organosilicon compounds containing an Si-NC bond.

[0090] Such organosilicon compounds include those represented by the following general formula (II): R 3 r Si(NR 4 R 5 ) s (OR 6 ) 4-(r+s) (II) (Wherein, r is an integer of 0≦r≦4, s is an integer of 0≦s≦4, and r+s is an integer of 0≦r+s≦4. R 3 , R 4 and R 5R is one selected from a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a vinyl group, an allyl group, a substituted or unsubstituted cycloalkyl group, a phenyl group, and an aralkyl group. 3 , R 4 and R 5 R may contain heteroatoms. 3 , R 4 and R 5 R may be the same or different. 4 and R 5 may be bonded to form a ring. 6 R is one selected from an alkyl group having 1 to 4 carbon atoms, a vinyl group, an allyl group, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group having 6 to 12 carbon atoms, and an aralkyl group. 6 may contain a hetero atom.

[0091] In the organosilicon compound represented by the general formula (II), R 3 is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, and these R 3 Among these, a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms is preferred.

[0092] In addition, in the organosilicon compound represented by the general formula (II), R 4 and R 5 is a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms, and these R 4 and R 5 Among these, a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, or a cycloalkyl group having 5 to 7 carbon atoms is preferred. 4 and R 5 may be linked to form a ring, in which case the ring is formed by (NR 4 R 5) groups include a perhydroquinolino group and a perhydroisoquinolino group.

[0093] In addition, in the organosilicon compound represented by the general formula (II), R 6 is an alkyl group, a cycloalkyl group, a phenyl group, a vinyl group, an allyl group, or an aralkyl group having 1 to 4 carbon atoms, and these R 6 Among these, a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms is preferred, and a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms is more preferred.

[0094] Examples of such external electron donating compounds include phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkyl(alkyl)alkoxysilanes, (alkylamino)alkoxysilanes, alkyl(alkylamino)alkoxysilanes, alkyl(alkylamino)silanes, and alkylaminosilanes. Among these external electron donating compounds, phenyltrimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, diisopropyldimethoxysilane, and methyltrimethoxysilane are particularly preferred. Preferred are methoxysilane, isopropylisobutyldimethoxysilane, diisopentyldimethoxysilane, diphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, tetramethoxysilane, tetraethoxysilane, t-butylmethylbis(ethylamino)silane, bis(ethylamino)dicyclohexylsilane, dicyclopentylbis(ethylamino)silane, bis(perhydroquinolino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, and diethylaminotriethoxysilane.

[0095] In the method for producing a catalyst for olefin polymerization according to the present invention, the solid catalyst component for olefin polymerization and the organoaluminum compound may be brought into contact with each other either in the presence of an external electron-donor compound or in the absence of an external electron-donor compound. In the present invention, when the solid catalyst component and the organoaluminum compound are brought into contact with each other in the absence of an external electron-donor compound, it is preferred that after the solid catalyst component and the organoaluminum compound are brought into contact with each other, the contact-treated product thus obtained is further brought into contact with the external electron-donor compound.

[0096] <Method of producing olefin polymer> The method for producing an olefin polymer according to the present invention is characterized in that olefins are polymerized using the olefin polymerization catalyst obtained by the above-mentioned method for producing an olefin polymerization catalyst.

[0097] The solid catalyst component for olefin polymerization and the catalyst for olefin polymerization may be the same as the solid catalyst component for olefin polymerization and the catalyst for olefin polymerization described above, and therefore further explanation will be omitted.

[0098] When olefins are polymerized using the olefin polymerization catalyst obtained by the above-mentioned method for producing an olefin polymerization catalyst, the polymerization catalyst can be isolated after the above-mentioned contact treatment and contacted with olefins, or can be directly contacted with olefins after the above-mentioned contact treatment and subjected to polymerization treatment. The polymerization of olefins may be homopolymerization of olefins or copolymerization. When olefins are copolymerized, it may be random copolymerization or block copolymerization.

[0099] In the method for producing an olefin polymer according to the present invention, examples of the olefin to be polymerized include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, 1-hexene, and 1,5-hexadiene. Among these olefins, ethylene, propylene, 4-methyl-1-pentene, 1-hexene, and 1,5-hexadiene are preferred, and ethylene or propylene is more preferred.

[0100] In the present invention, when olefins are copolymerized, for example, when propylene is copolymerized with an olefin other than propylene, examples of the olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, and vinylcyclohexane. Among these olefins, ethylene or 1-butene is preferred.

[0101] For example, when propylene and ethylene are copolymerized, examples include random copolymerization in which propylene and a small amount of ethylene are polymerized as comonomers in one stage, and so-called propylene-ethylene block copolymerization in which propylene is homopolymerized in a first stage (first polymerization tank) and propylene and ethylene are copolymerized in a second stage (second polymerization tank) or multiple stages (multistage polymerization tanks) greater than this stage.

[0102] The polymerization temperature of the olefins is preferably from room temperature to 200° C., more preferably from room temperature to 100° C. Here, room temperature means 20° C.

[0103] The polymerization pressure of the olefins is preferably 10 MPa or less, more preferably 6 MPa or less.

[0104] The polymerization of olefins may be carried out by a continuous polymerization method or a batch polymerization method. Furthermore, the polymerization reaction may be carried out in one stage or in two or more stages.

[0105] The polymerization of olefins may be carried out in an inert gas atmosphere, or in a gas atmosphere of the olefin to be polymerized, such as propylene. [Example]

[0106] Example 1 <Preparation of solid catalyst component> 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium, 287 mL of toluene, and 12 mL (45 mmol) of dibutyl phthalate (DBP) were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 65 mL of titanium tetrachloride was placed in the round-bottom flask, the temperature was raised from 5° C. to 110° C., and the suspension was reacted at 110° C. for 2 hours while being stirred.

[0107] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate, which was washed four times with 200 mL of toluene at room temperature (25° C.) (post-reaction washing) to obtain a toluene slurry of solid component A.

[0108] 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 89 mL of toluene and 61 mL of a toluene slurry containing 4.8 g of solid component A were charged into the round-bottom flask. After stirring, the mixture was allowed to stand for 5 minutes. The supernatant was then removed, and the mixture was washed four times with 100 mL of toluene at 100°C (pre-reaction washing). After washing, the liquid toluene was replaced with p-xylene to prepare 150 mL of p-xylene slurry. Next, 10 mL of silicon tetrachloride was added, the temperature was raised from room temperature to 110°C, and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization).

[0109] The titanium element and ethoxy group contents in the obtained solid catalyst component were measured to be 0.74 mass % and 0.017 mass %, respectively.

[0110] <Formation of polymerization catalyst and olefin polymerization> A 1.0 L autoclave equipped with a stirrer and completely purged with nitrogen gas was charged with 400 mL of n-heptane, 2.0 mmol of triethylaluminum, 0.2 mmol of cyclohexyldimethoxysilane, and 0.005 mmol of the solid catalyst component (titanium atom equivalent) to form a polymerization catalyst. Hydrogen gas was then added to the autoclave until the pressure reached 0.25 atm, and the temperature was raised to 70°C while stirring and propylene was added until the total pressure reached 6.0 atm. The polymerization reaction was carried out at 70°C for 30 minutes, after which the pressure was quickly released while cooling. The contents were then transferred to a stainless steel tray, air-dried overnight, and then vacuum-dried at 60°C for 8 hours. The catalytic activity, boiling heptane extractable fraction (HS), and boiling heptane extractable residue (HI) of the resulting polymer were measured using the following methods. The results are shown in Table 1.

[0111] <Polymerization activity> The polymerization activity (g-PP / g-cat), which indicates the amount of polymer (F) produced per 1 g of solid catalyst component and per 30 minutes of polymerization time, was calculated by the following formula. Polymerization activity (g-PP / (g-cat)) = (amount of polymer produced (g) / (solid catalyst component (g)))

[0112] <Measurement of boiling heptane extractables (HS) and boiling heptane extractable residue (HI)> 6.0 g of polymer was placed in a thimble and extracted with boiling heptane for 6 hours using a Soxhlet extractor. After the extraction was complete, the thimble containing the residue was removed, air-dried, and then vacuum-dried at 60°C for 8 hours. The weight of the resulting polymer (boiling heptane extraction residue) relative to the weight of the polymer charged was expressed as the boiling heptane extraction residue (HI, wt%). The value obtained by subtracting HI from 100 was expressed as the boiling heptane extraction amount (HS, wt%).

[0113] Example 2 The same procedure as in Example 1 was carried out to prepare a solid catalyst component, except that the reaction temperature after adding silicon tetrachloride was changed from 110°C to 120°C. Table 1 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0114] Example 3 The solid catalyst component was prepared in the same manner as in Example 1, except that the amount of silicon tetrachloride added was changed from 10 mL to 15 mL. Table 1 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0115] Example 4 The same procedure as in Example 1 was carried out to prepare solid component A in Example 1, except that after adding 65 mL of titanium tetrachloride, stirring was carried out at 5°C for 1 hour before increasing the temperature from 5°C to 110°C. Table 1 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0116] Example 5 1) Preparation of solid component A The same procedure as in Example 1 was carried out to obtain a toluene slurry of solid component A. 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 89 mL of toluene and 61 mL of a toluene slurry containing 4.8 g of solid component A were charged into the round-bottom flask, stirred, and then allowed to stand for 5 minutes. Next, the liquid toluene was substituted with p-xylene to prepare 150 mL of a p-xylene slurry. Next, 10 mL of silicon tetrachloride was added, the temperature was raised from room temperature to 110°C, and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization). Table 1 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0117] Example 6 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium, 287 mL of toluene, and 12 mL (45 mmol) of dibutyl phthalate (DBP) were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 65 mL of titanium tetrachloride was placed in the round-bottom flask, the temperature was raised from 5° C. to 110° C., and the suspension was reacted at 110° C. for 2 hours while being stirred.

[0118] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate, which was washed four times with 200 mL of toluene at 100° C. (washing after the reaction) to obtain a toluene slurry of solid component A.

[0119] 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 89 mL of toluene and 61 mL of a toluene slurry containing 4.8 g of solid component A were charged into the round-bottom flask, stirred, and then allowed to stand for 5 minutes. Next, the liquid toluene was substituted with p-xylene to prepare 150 mL of a p-xylene slurry. Next, 10 mL of silicon tetrachloride was added, the temperature was raised from room temperature to 110°C, and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization). Table 2 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0120] Example 7 The same procedure as in Example 1 was carried out to prepare solid component A, except that the reaction temperature was changed from 110°C to 85°C. Table 2 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0121] Example 8 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium, 287 mL of toluene, and 12 mL (45 mmol) of dibutyl phthalate (DBP) were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 65 mL of titanium tetrachloride was placed in the round-bottom flask, the temperature was raised from 5° C. to 85° C., and the suspension was reacted at 85° C. for 2 hours while being stirred.

[0122] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate, which was washed four times with 200 mL of toluene at room temperature (25° C.) (post-reaction washing) to obtain a toluene slurry of solid component A.

[0123] 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 89 mL of toluene and 61 mL of a toluene slurry containing 4.8 g of solid component A were charged into the round-bottom flask, stirred, and then allowed to stand for 5 minutes. Next, the liquid toluene was substituted with p-xylene to prepare 150 mL of a p-xylene slurry. Next, 10 mL of silicon tetrachloride was added, the temperature was raised from room temperature to 110°C, and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization). Table 2 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0124] Example 9 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium and 287 mL of toluene were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 45 mL of titanium tetrachloride was placed in the round-bottom flask, and the temperature was raised from 5°C. When the temperature reached 90°C, 12 mL (45 mmol) of dibutyl phthalate (DBP) was added, and the temperature was further raised to 110°C. The suspension was reacted at 110°C for 2 hours while stirring.

[0125] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate, which was washed four times with 200 mL of toluene at room temperature (25° C.) (post-reaction washing) to obtain a toluene slurry of solid component A.

[0126] 2) Preparation of solid catalyst component The same procedure as in Example 1 was carried out. Table 2 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0127] Example 10 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium and 287 mL of toluene were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 45 mL of titanium tetrachloride was added to the round-bottom flask, followed by 21 mL of silicon tetrachloride. The temperature was raised from 5°C until it reached 90°C, at which point 12 mL (45 mmol) of dibutyl phthalate (DBP) was added. The temperature was then raised to 110°C, and the suspension was reacted at 110°C for 2 hours while being stirred.

[0128] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate, which was washed four times with 200 mL of toluene at room temperature (25° C.) (post-reaction washing) to obtain a toluene slurry of solid component A.

[0129] 2) Preparation of solid catalyst component The same procedure as in Example 1 was carried out. Table 2 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0130] Example 11 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium and 287 mL of toluene were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 45 mL of titanium tetrachloride was added to the round-bottom flask, followed by 21 mL of silicon tetrachloride. The temperature was raised from 5°C until it reached 90°C, at which point 12 mL (45 mmol) of dibutyl phthalate (DBP) was added. The temperature was then raised to 110°C, and the suspension was reacted at 110°C for 2 hours while being stirred.

[0131] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate, which was washed four times with 200 mL of toluene at room temperature (25° C.) (post-reaction washing) to obtain a toluene slurry of solid component A.

[0132] 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 89 mL of toluene and 61 mL of a toluene slurry containing 4.8 g of solid component A were charged into the round-bottom flask. After stirring, the mixture was allowed to stand for 5 minutes. The supernatant was then removed, and the mixture was washed four times with 100 mL of toluene at 100°C (pre-reaction washing). After washing, the liquid toluene was replaced with p-xylene to prepare 150 mL of p-xylene slurry. Next, 36 mL of silicon tetrachloride was added, the temperature was raised from room temperature to 100° C., and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization). Table 3 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0133] Example 12 1) Preparation of solid component A The same procedure as in Example 1 was carried out to obtain a toluene slurry of solid component A.

[0134] 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 53 mL of toluene and 100 mL of a toluene slurry containing 15.0 g of solid component A were charged into the round-bottom flask, stirred, and then allowed to stand for 5 minutes. Next, 7 mL of phthaloyl dichloride was added, and the temperature was raised from room temperature to 110°C, and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization). Table 3 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0135] (Comparative Example 1) 1) Preparation of solid component A The inside of a 500 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 33.5 g of diethoxymagnesium, 287 mL of toluene, and 12 mL (45 mmol) of dibutyl phthalate (DBP) were placed in the round-bottom flask to obtain a diethoxymagnesium-containing suspension. The temperature of this diethoxymagnesium-containing liquid was maintained at 5°C. Next, 65 mL of titanium tetrachloride was placed in the round-bottom flask, and the temperature was raised from 5° C. to 110° C. The suspension was reacted at 110° C. for 2 hours with stirring to obtain a toluene slurry of solid component A.

[0136] 2) Preparation of solid catalyst component The inside of a 300 mL round-bottom flask equipped with a stirrer was purged with nitrogen gas, and 89 mL of toluene and 61 mL of a toluene slurry containing 4.8 g of solid component A were charged into the round-bottom flask, stirred, and then allowed to stand for 5 minutes. Next, the liquid toluene was substituted with p-xylene to prepare 150 mL of a p-xylene slurry. Next, 10 mL of titanium tetrachloride was added, the temperature was raised from room temperature to 110°C, and the reaction was carried out for 2 hours to obtain a reaction product. The obtained reaction product was washed eight times with 150 mL of n-heptane at room temperature (washing after the reaction) and subjected to solid-liquid separation to obtain a solid catalyst component (solid catalyst component for olefin polymerization). Table 3 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0137] (Comparative Example 2) The solid catalyst component of Example 1 was prepared in the same manner as in Example 1, except that 34 mL of titanium tetrachloride was used instead of 10 mL of silicon tetrachloride. Table 3 shows the titanium element and ethoxy group contents in the obtained solid catalyst component, the catalytic activity determined from the obtained polymer, the boiling heptane extractable fraction (HS), and the boiling heptane extractable residue (HI).

[0138] In Tables 1 to 3, "Si / Mg" in the preparation of the solid catalyst component indicates the ratio of the number of moles of silicon, in atomic terms, in the silicon tetrachloride used in the preparation of the solid catalyst component to the number of moles of magnesium, in atomic terms, in the magnesium compound used in the preparation of solid component A. In addition, "Cl / Mg" in the preparation of the solid catalyst component indicates the ratio of the number of moles of chlorine atoms, in atomic terms, in the silicon tetrachloride or phthaloyl dichloride used in the preparation of the solid catalyst component to the number of moles of magnesium, in atomic terms, in the magnesium compound used in the preparation of solid component A.

[0139] [Table 1]

[0140] [Table 2]

[0141] [Table 3]

[0142] The olefin polymerization catalysts obtained in Examples 1 to 12 in Tables 1 to 3 have a low titanium content and a high ratio of the number of moles of the internal electron donor compound to the number of moles of titanium atoms in atomic terms. Furthermore, the olefin polymerization catalysts are characterized by low titanium and alkoxy group contents. The active sites of olefin polymerization catalysts are formed by titanium. However, if the titanium content is high, the titanium disperses poorly in the support, titanium aggregates tend to form, and stereoregularity is reduced. If the alkoxy group content is high, aggregates also tend to form, and furthermore, electron donor compounds are less likely to adsorb to the support, adversely affecting stereoregularity. Therefore, it is preferable that the titanium and alkoxy group contents in olefin polymerization catalysts are low. It is also believed that the internal electron donor compound present on magnesium chloride is abstracted by the organoaluminum compound, and the external electron donor compound is adsorbed to the abstracted site, forming an active site from the titanium present nearby, thereby obtaining an olefin polymerization catalyst having high stereoregularity. In other words, the content of the internal electron donor compound is significantly reduced by contact with the organoaluminum compound, which allows the subsequent formation of active sites to proceed smoothly, and high stereoregularity can be obtained in the olefin polymerization product. The solid catalyst component for olefin polymerization of the present invention has a low content of alkoxy groups and titanium, which have adverse effects on stereoregularity, and further has a high content of internal electron-donor compounds. Therefore, after contact with an organoaluminum compound, many active sites are formed that can be replaced with many external electron-donor compounds to obtain high stereoregularity, thereby enabling the production of olefin polymers with excellent stereoregularity.

[0143] In contrast, the olefin polymerization catalysts obtained in Comparative Examples 1 and 2 in Table 3 have a high titanium content, a low ratio of the number of moles of internal electron donor compound to the number of moles of titanium atom converted into atoms, and a high alkoxy group content. Therefore, the olefin polymerization catalysts obtained in the comparative examples have a high content of alkoxy groups and titanium, which have a negative effect on stereoregularity, and a low content of internal electron donor compound, which reduces the replacement of external electron donor compound upon contact with organoaluminum compounds. As a result, it can be seen that the olefin polymers obtained with the olefin polymerization catalysts shown in Comparative Examples 1 and 2 have high HS and poor stereoregularity.

[0144] Example 13 <Preparation of solid catalyst component> A 500 mL round-bottom flask equipped with a stirrer and thoroughly purged with nitrogen gas was charged with 20 g of diethoxymagnesium and 100 mL of toluene to form a turbid solution. Next, a mixed solution of 60 mL of titanium tetrachloride and 40 mL of toluene was added to the turbid solution, which was maintained at a temperature of 5°C. After maintaining this temperature for 1 hour, 4 mL (15.0 mmol) of dibutyl phthalate (DBP) was added and the temperature was raised. During the temperature increase, 2 mL (7.5 mmol) of dibutyl phthalate (DBP) was added at 60°C, and the temperature was further raised to 90°C. The reaction was carried out at 90°C with stirring for 1 hour.

[0145] After the reaction was completed, the supernatant was removed from the suspension to obtain a precipitate (solid component A). Next, the precipitate (solid component A) was washed four times with 200 mL of toluene at 90° C. (washing after the reaction) to obtain a toluene slurry of solid component A.

[0146] 2) Preparation of solid catalyst component Next, 60 mL of room temperature toluene, 60 mL of titanium tetrachloride, and 1.4 g (4.4 mmol) of bismuth chloride (BiCl) were added to the solid component A, and the mixture was heated to 115°C and reacted with stirring for 1 hour. After the reaction was completed, the supernatant was removed. The mixture was then washed seven times with 150 mL of n-heptane at 40°C (washing after the reaction), and after the supernatant was removed, the mixture was dried to obtain a particulate solid catalyst component (solid catalyst component for olefin polymerization).

[0147] The content of titanium element in the obtained solid catalyst component was 2.8 mass %.

[0148] <Formation of polymerization catalyst and olefin polymerization> Into a 2.0 L autoclave equipped with a stirrer and whose internal volume had been completely replaced with nitrogen gas, 1.3 mmol of triethylaluminum, 0.13 mmol of cyclohexylmethyldimethoxysilane (CMDMS), and 0.0026 mmol (in terms of titanium atom) of the above solid catalyst component were charged to prepare a catalyst for olefin polymerization. Thereafter, 1.5 liters of hydrogen gas and 1.4 liters of liquefied propylene were charged, and prepolymerization was carried out at 20°C for 5 minutes, followed by heating and polymerization reaction at 70°C for 1 hour to obtain a propylene homopolymer. The polymerization activity and the proportion of p-xylene soluble matter (XS) of the obtained polymer were measured by the following methods. The results are shown in Table 4.

[0149] <Polymerization activity> The polymerization activity per 1 g of the solid catalyst component was calculated by the following formula. Polymerization activity (g-pp / g-catalyst) = mass of polymer (g) / mass of solid catalyst component (g)

[0150] <Proportion of p-xylene solubles in polymer (XS)> A flask equipped with a stirrer was charged with 4.0 g of polymer (polypropylene) and 200 mL of p-xylene. The external temperature was raised above the boiling point of xylene (approximately 150°C), and the temperature of the p-xylene inside the flask was maintained below the boiling point (137-138°C) while the polymer was dissolved over 2 hours. The liquid temperature was then cooled to 23°C over 1 hour, and the insoluble and soluble components were separated by filtration. The solution of the soluble components was collected and dried under reduced pressure to remove the p-xylene. The weight of the resulting residue was determined, and the relative proportion (mass%) to the produced polymer (polypropylene) was calculated to determine the xylene-soluble fraction (XS).

[0151] Example 14 <Preparation of solid catalyst component> A solid catalyst component was obtained in the same manner as in Example 13, except that 1.4 g (4.4 mmol) of bismuth chloride (BiCl) was replaced with 0.6 g (4.4 mmol) of zinc chloride (ZnCl). The solid catalyst component thus obtained was subjected to component analysis, the results of which are shown in Table 4.

[0152] <Formation of polymerization catalyst and olefin polymerization> The obtained propylene homopolymer was subjected to polymerization evaluation, and the results are shown in Table 4.

[0153] (Comparative Example 3) <Preparation of solid catalyst component> A solid catalyst component was obtained in the same manner as in Example 13, except that 1.4 g (4.4 mmol) of bismuth chloride (BiCl3) was not used in the preparation of the solid catalyst component of Example 13. The solid catalyst component thus obtained was subjected to component analysis, the results of which are shown in Table 4.

[0154] <Formation of polymerization catalyst and olefin polymerization> The obtained propylene homopolymer was subjected to polymerization evaluation, and the results are shown in Table 4.

[0155] [Table 4] [Industrial Applicability]

[0156] According to the present invention, it is possible to provide a method for producing an olefin polymerization catalyst that can suppress a decrease in polymerization activity due to early deactivation of active sites after catalyst formation, thereby preventing an excessive decrease in catalytic activity during olefin polymerization, even when the content of titanium atoms in the solid catalyst component is low, and can produce olefin polymers with excellent stereoregularity.

Claims

1. a first production step of contacting titanium tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent with each other to obtain a contact product; a washing step in which the contact product obtained in the first production step is washed with an inert organic solvent to obtain a washed product; a second production step of contacting the washed product obtained in the washing step with a chlorine-containing compound and an inert organic solvent to obtain a solid catalyst component; and the chlorine-containing compound is silicon tetrachloride; In the first production step, the molar ratio (Ti moles / Mg moles) of the amount of the titanium tetrachloride used in terms of titanium atoms to the amount of the magnesium compound used in terms of magnesium atoms is 1.0 to 3.0, In the first production step, a molar ratio of the amount of the internal electron donor compound used to the amount of the magnesium compound used in terms of magnesium atoms (moles of internal electron donor compound / moles of Mg) is 0.05 to 0.25; the ratio (Si / Mg) of the number of moles of silicon, in atomic terms, in the silicon tetrachloride used in the second production step to the number of moles of magnesium, in atomic terms, in the magnesium compound used in the first production step is 1.5 to 30.0; A method for producing a solid catalyst component for olefin polymerization, characterized by:

2. 2. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein in the first production step, titanium tetrachloride, silicon tetrachloride, a magnesium compound, an internal electron donor compound, and an inert organic solvent are brought into contact with each other to obtain a contact product.

3. 3. The method for producing a solid catalyst component for olefin polymerization according to claim 1, wherein in the second production step, the washed product obtained in the washing step, the silicon tetrachloride, and the inert organic solvent are brought into contact with each other at a temperature of 95°C or higher.

4. A method for producing a catalyst for olefin polymerization, comprising contacting a solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 3 with an organoaluminum compound to obtain a catalyst for olefin polymerization.

5. A method for producing a catalyst for olefin polymerization, comprising contacting a solid catalyst component for olefin polymerization obtained by the method for producing a solid catalyst component for olefin polymerization according to any one of claims 1 to 3 with an organoaluminum compound and an external electron donor compound to obtain a catalyst for olefin polymerization.

6. A method for producing an olefin polymer, comprising polymerizing olefins using the olefin polymerization catalyst obtained by the method for producing an olefin polymerization catalyst according to claim 4 or 5.

Images