Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and method for producing olefin polymer

Abstract

The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer. Provided are 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, which have excellent polymerization activity and can produce a polymer with excellent stereospecificity. Provided is a method for producing a solid catalyst component for olefin polymerization, the method comprising contacting a magnesium compound and a specific styrene-based compound with each other to obtain a pre-contact product, and then contacting the pre-contact product, a titanium halide compound, and an internal electron donor compound with each other to obtain a solid catalyst component for olefin polymerization; and a method for producing a catalyst for olefin polymerization and a method for producing an olefin polymer using the solid catalyst component for olefin polymerization obtained by this production method.

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 Art

[0002] Conventionally, the polymerization of olefins such as propylene is carried out using a solid catalyst for olefin polymerization (also referred to as a "solid catalyst"), and the obtained olefin polymer has been used for various applications such as containers and films in addition to molded products for automotive parts and home appliance parts, etc., where the olefin polymer is melted and then formed by various molding machines and stretching machines, etc.

[0003] As such a solid catalyst, a solid catalyst obtained by bringing into contact with each other a solid catalyst component for olefin polymerization (also referred to as a "solid catalyst component") prepared from a magnesium compound, a titanium halide compound, and an electron donor compound, an organoaluminum compound, and an organosilicon compound is known, and a large number of production methods thereof have been proposed.

[0004] For example, Patent Document 1 describes a solid catalyst component including two internal electron donor compounds including a weakly soluble type and a strongly soluble type.

[0005] In addition, Patent Document 2 proposes a solid catalyst component in which a bifunctional electron donor compound ED selected from diesters, diketones, diamines, and diethers and a monofunctional electron donor MD selected from ethers, esters, amines, and ketones are contained in a quantitative ratio of ED / MD greater than 30 in magnesium dihalide, so that when the solid catalyst is used for the (co)polymerization of propylene or higher α-olefins, the solid catalyst is given high activity and stereospecificity.

[0006] [Citation List]

[0007] [Patent Document]

[0008] [Patent Document 1]

[0009] Japanese translation of PCT International Application Publication No. 2001 - 503079

[0010] [Patent Document 2]

[0011] Japanese Patent Laid - Open No. 2010 - 43267 Summary of the Invention

[0012] Problems to be Solved by the Invention

[0013] However, the present inventors have found through research that in the solid catalyst component described in Patent Document 1, since two internal electron donor compounds including a weakly soluble type and a strongly soluble type are brought into contact and reacted simultaneously, it is very likely that the weakly soluble internal electron donor compound is preferentially included, and it is difficult to exhibit the polymer properties derived from the strongly soluble internal electron donor compound, and the properties of the resulting polymer are difficult to control.

[0014] In addition, it has been found that in the solid catalyst component described in Patent Document 2, since the monofunctional electron donor as the internal electron donor compound reduces the stereospecificity of the solid catalyst component, the stereoregularity of the polymer obtained by using this solid catalyst component is also reduced.

[0015] Under such circumstances, an object of the present invention is to provide a method for producing a solid catalyst component for olefin polymerization, a method for producing a solid catalyst for olefin polymerization, and a method for producing an olefin polymer, which have excellent polymerization activity and can produce a polymer with excellent stereospecificity.

[0016] Solutions for Solving the Problems

[0017] The present inventors have conducted in-depth research on the production conditions of the solid catalyst component to solve the above technical problems, and as a result, have found that the above problems can be solved by previously bringing a specific compound into contact with a magnesium compound. Based on this finding, the present invention has been completed.

[0018] That is, the present invention provides the following (1) to (4).

[0019] (1) A method for producing a solid catalyst component for olefin polymerization, which includes: bringing a magnesium compound and a compound represented by the following general formula (I) into contact with each other to obtain a pre-contact product; and then bringing the pre-contact product, a titanium halide compound, and an internal electron donor compound into contact with each other to obtain a solid catalyst component for olefin polymerization,

[0020]

[0021] wherein, R 1 is any group selected from a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms, n and m are each an integer of 0 or more, n + m is 1 to 30,000, and X is a polymerization unit having the following structural unit (A) and the following structural unit (B) and having a total carbon atom number of 9 to 50,000.

[0022]

[0023]

[0024] (2) A method for manufacturing a catalyst for olefin polymerization, which includes: bringing the solid catalyst component for olefin polymerization obtained by the method described in the above (1) into contact with an organoaluminum compound represented by the following general formula (II):

[0025] R 2 p AlQ 3-p (II)

[0026] wherein, R 2 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number satisfying 0 < p ≤ 3, and when there are two or more Rs 2 , each R 2 may be the same as or different from each other, and when there are two or more Qs, each Q may be the same as or different from each other.

[0027] (3) The method for manufacturing a catalyst for olefin polymerization described in the above (2), which includes: bringing the solid catalyst component for olefin polymerization obtained by the method described in the above (1), an organoaluminum compound represented by the following general formula (II), and an external electron donor compound into contact with each other:

[0028] R 2 p AlQ 3-p (II)

[0029] wherein, R 2 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number satisfying 0 < p ≤ 3, and when there are two or more Rs 2 , each R 2 may be the same as or different from each other, and when there are two or more Qs, each Q may be the same as or different from each other.

[0030] (4) A method for manufacturing an olefin polymer, which includes: polymerizing an olefin using the catalyst for olefin polymerization obtained by the method described in the above (2) or (3).

[0031] Effects of the Invention

[0032] According to the present invention, a method for manufacturing a solid catalyst component for olefin polymerization, a method for manufacturing a catalyst for olefin polymerization, and a method for manufacturing an olefin polymer can be provided, which have excellent polymerization activity and can manufacture polymers with excellent stereospecificity. Detailed Embodiments

[0033] First, a method for manufacturing a solid catalyst component for olefin polymerization according to the present invention (hereinafter, appropriately referred to as "solid catalyst component") will be described.

[0034] The method for manufacturing a solid catalyst component for olefin polymerization according to the present invention includes: bringing a magnesium compound and a compound represented by the following general formula (I) into contact with each other to obtain a pre-contact product; and then bringing the pre-contact product, a titanium halide compound, and an internal electron donor compound into contact with each other to obtain a solid catalyst component for olefin polymerization,

[0035]

[0036] wherein, R 1 is any group selected from a linear alkyl group having 1 to 8 carbon atoms, a branched alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms, n and m are each an integer of 0 or more, n + m is 1 to 30,000, and X is a polymer unit having the following structural unit (A) and the following structural unit (B) and having a total carbon atom number of 9 to 50,000.

[0037]

[0038]

[0039] In the method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, the magnesium compound is not particularly limited as long as it is a conventionally known magnesium compound.

[0040] Examples of the magnesium compound may include one or more selected from magnesium dihalides, dialkylmagnesiums, alkylmagnesium halides, dialkoxymagnesiums, diaryloxymagnesiums, alkoxymagnesium halides, and magnesium fatty acids, etc.

[0041] Among these magnesium compounds, magnesium dihalides, a mixture of magnesium dihalides and dialkoxymagnesiums, and dialkoxymagnesiums are preferred, and dialkoxymagnesiums are particularly preferred.

[0042] Specifically, dialkoxymagnesiums include one or more selected from dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, ethoxymethoxymagnesium, ethoxypropoxymagnesium, and butoxyethoxymagnesium, and among these, diethoxymagnesium is particularly preferred.

[0043] Examples of the method for manufacturing dialkoxymagnesiums may include the methods exemplified in Japanese Patent Laid-Open No. 58-4132, Japanese Patent Laid-Open No. 62-51633, Japanese Patent Laid-Open No. 3-74341, Japanese Patent Laid-Open No. 4-368391, and Japanese Patent Laid-Open No. 8-73388, etc.

[0044] In the method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, a magnesium compound and a compound represented by the following general formula (I) are brought into contact with each other to obtain a pre-contact product.

[0045]

[0046] In the compound represented by the general formula (I), the above-mentioned R 1 is any group selected from a straight-chain alkyl group having 1 to 8 carbon atoms, a branched-chain alkyl group having 3 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic group having 6 to 12 carbon atoms.

[0047] When R 1 is a straight-chain alkyl group having 1 to 8 carbon atoms, examples of R 1 may include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.

[0048] When R 1 is a branched-chain alkyl group having 3 to 8 carbon atoms, examples of R 1 may include isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, 3-methylhexyl, 2-ethylhexyl, and the like.

[0049] When R 1 is a cycloalkyl group having 3 to 8 carbon atoms, examples of R 1 may include cyclopropyl, methylcyclopropyl, ethylcyclopropyl, cyclobutyl, methylcyclobutyl, ethylcyclobutyl, cyclopentyl, methylcyclopentyl, ethylcyclopentyl, cyclohexyl, methylcyclohexyl, ethylcyclohexyl, cycloheptyl, methylcycloheptyl, cyclooctyl, and the like.

[0050] When R 1 is an aromatic group having 6 to 12 carbon atoms, R 1 may include phenyl, methylphenyl, ethylphenyl, benzyl, naphthyl, biphenyl, and the like.

[0051] R 1 is preferably an aromatic group having 6 to 12 carbon atoms, and more preferably phenyl.

[0052] In the compound represented by the general formula (I), n and m are each an integer of 0 or more. Further, n + m is 1 to 30,000, preferably 2 to 20,000, more preferably 2 to 10,000, still more preferably 10 to 5,000, further preferably 50 to 1,000, and still further preferably 100 to 500.

[0053] In the compound represented by the general formula (I), X is a polymer unit having the following structural unit (A) and the following structural unit (B) and having a total carbon atom number of 9 to 50,000.

[0054]

[0055]

[0056] In the compound represented by the general formula (I), the total number of carbon atoms in X is from 9 to 50,000, preferably from 9 to 25,000, more preferably from 9 to 10,000, and still more preferably from 9 to 5,000.

[0057] In the method for producing the solid catalyst component for olefin polymerization according to the present invention, the structure of the compound represented by the general formula (I) can be determined by analysis using gel permeation chromatography (GPC), a nuclear magnetic resonance apparatus ( 1 1H-NMR, 13 13C-NMR) and Fourier transform infrared spectroscopy (FT-IR).

[0058] That is, the number average molecular weight (Mn) of the compound represented by the general formula (I) is determined by gel permeation chromatography (GPC).

[0059] In addition, partial structures such as various substituents or structural units are measured and the overall structure is evaluated based on the positions of the respective peaks detected by 1 1H-NMR spectroscopy, the spectral intensities at these positions, and the peaks appearing in certain wavelength regions in the FT-IR spectrum.

[0060] Then, the polymerization numbers of the respective structural units constituting the compound represented by the general formula (I) are determined based on the peak positions detected by 13 13C-NMR spectroscopy and the spectral intensities at these positions (based on the peak intensity ratios of the respective peaks).

[0061] Then, considering these results together (note that when the types of substituents can be determined by the above 1 1H-NMR spectroscopy, FT-IR spectral measurement is not always required), the molecular structure of the compound represented by the general formula (I) is determined.

[0062] In this application document, the respective analysis conditions for performing the above GPC analysis, 1 1H-NMR analysis, FT-IR analysis, and 13 13C-NMR analysis are as follows.

[0063] [GPC analysis]

[0064] The number average molecular weight (Mn) is obtained from the results measured using a gel permeation chromatography (GPC) (HLC-8321 (GPC / HT)) manufactured by Tosoh Corporation under the following conditions.

[0065] Solvent: o-dichlorobenzene (ODCB)

[0066] Temperature: 140 °C

[0067] Column: GMHHR-H(20)HT×1, GMHHR-H(S)HT2×1

[0068] Sample concentration: 0.5 mg / mL (4 mL / 8 mL - ODCB)

[0069] Injection volume: 0.5 mL

[0070] Flow rate: 1.0 mL / min

[0071] The number-average molecular weight (Mn) is calculated from the retention time obtained by GPC measurement through a calibration curve based on the correlation between the retention time and the number-average molecular weight (Mn) obtained using standard polystyrene.

[0072] 1 [H-NMR analysis]

[0073] Measuring device: ECA400( 1 H resonance frequency 400 MHz), manufactured by JEOL Ltd. (JEOL) Measuring solvent: CDCl3

[0074] Number of scans: 20 times

[0075] Measuring temperature: 20 °C

[0076] Internal standard: Tetramethylsilane (TMS)

[0077] [FT-IR analysis]

[0078] Measuring device: Avatar, manufactured by Thermo Fisher Scientific K.K.

[0079] Measuring method: Transmission method after film formation

[0080] Measuring temperature: Room temperature (20 °C)

[0081] 13 [C-NMR analysis]

[0082] Measuring device: ECA400( 13 C resonance frequency 100 MHz), manufactured by JEOL Ltd. (JEOL)

[0083] Measuring solvent: CDCl3

[0084] Number of scans: 5,000 times

[0085] Measuring temperature: 20 °C

[0086] Internal standard: Tetramethylsilane (TMS) ​​

[0087] It is considered that in the method for producing a solid catalyst component for olefin polymerization according to the present invention, the excessive adsorption of the internal electron donor compound can be suppressed by previously contacting a specific compound represented by the general formula (I) with a magnesium compound as a carrier.

[0088] That is, although the internal electron donor compound has a higher adsorptivity to the magnesium compound than the specific compound represented by the general formula (I), by previously contacting the specific compound represented by the general formula (I) with the magnesium compound, when the magnesium compound and the internal electron donor compound are brought into contact with each other, the specific compound represented by the general formula (I) serves as a protective agent to suppress the excessive adsorption of the internal electron donor compound to the magnesium carrier, and the polymerization properties derived from the internal electron donor compound are effectively maintained.

[0089] It is considered that in the method for producing a solid catalyst component for olefin polymerization according to the present invention, by previously contacting a specific compound represented by the general formula (I) with a magnesium compound, especially when using two or more internal electron donor compounds having different adsorptivities to the magnesium compound as a carrier, the excessive adsorption of the internal electron donor compound having poor solubility (strong adsorptivity) can be prevented.

[0090] That is, it is considered that by previously contacting the magnesium compound as a carrier and the compound represented by the general formula (I) with each other during the production of the solid catalyst component, the compound represented by the general formula (I) serves as a protective agent for the adsorption sites of the internal electron donor compound in the carrier to suppress the excessive adsorption of the internal electron donor compound having poor solubility (strong adsorptivity) to the carrier, and especially when using two or more internal electron donor compounds, the adsorption amount of the internal electron donor compound to the carrier can be adjusted thereby.

[0091] It is considered that the compound represented by the general formula (I) has a faster adsorption rate to the carrier than each electron donor compound, can block the adsorption of the internal electron donor compound having poor solubility (strong adsorptivity) for a certain period of time and has the property of separating from the carrier after a certain period of time so as not to block the adsorption of the internal electron donor compound having strong solubility (weak adsorptivity), and is preferably used as the above protective agent.

[0092] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, when the magnesium compound and the compound represented by the general formula (I) are previously contacted, the mass-based contact amount of the compound represented by the general formula (I) relative to the magnesium compound (the amount of the compound represented by the general formula (I) / the amount of the magnesium compound) is preferably 0.001 to 0.500, more preferably 0.005 to 0.350, and still more preferably 0.050 to 0.200.

[0093] When the contact amount of the compound represented by the general formula (I) falls within the above range, the content ratio of the internal electron donor compound having strong solubility (weak adsorption property) in the solid catalyst component can be easily controlled within a desired range.

[0094] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, when the magnesium compound and the compound represented by the general formula (I) are pre-contacted, the contact temperature is preferably -20°C to 50°C, more preferably -10°C to 40°C, and still more preferably 0°C to 30°C.

[0095] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, when the magnesium compound and the compound represented by the general formula (I) are pre-contacted, the contact time is preferably 3 to 360 minutes, more preferably 5 to 240 minutes, and still more preferably 5 to 120 minutes.

[0096] The method for pre-contacting the magnesium compound and the compound represented by the general formula (I) may include a method in which the magnesium compound and the compound represented by the general formula (I) are mixed and stirred in the presence of an organic solvent inert to these two compounds.

[0097] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, the pre-contact product of the magnesium compound and the compound represented by the general formula (I), the titanium halide compound, and the internal electron donor compound are contacted with each other.

[0098] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, the titanium halide compound is not particularly limited as long as it is a tetrahalide compound and is conventionally known.

[0099] Examples of the titanium halide compound may include one or more selected from titanium tetrahalide and alkoxy titanium halide, etc.

[0100] Such titanium halide compounds include titanium tetrahalide or alkoxy titanium halide represented by the following general formula (III):

[0101] Ti(OR 3 ) i Y 4-i (III)

[0102] Wherein, R 3 represents a hydrocarbon group having 1 to 10 carbon atoms, Y is a halogen atom, when there are two or more Ys, each Y may be the same or different from each other, and i is an integer of 0 to 3.

[0103] As the titanium halide compound, titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide, and titanium tetraiodide are preferred, and titanium tetrachloride is more preferred.

[0104] In the method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, the internal electron donor compound is not particularly limited as long as it is an organic compound that can provide an electron pair during the preparation of the solid catalyst component and has a functional group containing an oxygen atom or a nitrogen atom for providing the electron pair.

[0105] In addition, one kind of internal electron donor compound can be used alone, or two or more kinds thereof can be used in combination. When two or more kinds of internal electron donor compounds are used in combination, examples thereof can include two or more kinds of internal electron donor compounds having different adsorption properties for the magnesium compound.

[0106] The strength and weakness of the adsorption of the internal electron donor compound to the magnesium compound can be determined based on the amount (the amount of the internal electron donor compound in the solid catalyst component) of the internal electron donor compound remaining in each solid catalyst component when preparing solid catalyst components using a stirrer in which 20 g of the magnesium compound used for preparing the solid catalyst component is stirred in 60 mL of toluene and each internal donor compound stirred at a temperature of -6°C under the same conditions (only changing the internal electron donor compound used) in the same molar amount.

[0107] That is, in each solid catalyst component, it can be defined as follows: the larger the residual amount of the internal electron donor compound, the stronger its adsorption property, and the smaller the residual amount of the internal electron donor compound, the weaker its adsorption property.

[0108] The amount of the internal electron donor compound in the above solid catalyst component can be determined by hydrolyzing the solid catalyst, then extracting the internal electron donor compound using an aromatic solvent, and measuring the solution using the gas chromatography flame ionization detector (FID, hydrogen flame ionization type detector) method described below.

[0109] In the method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, the internal electron donor compound can be a phthalate compound or can be a compound other than the phthalate compound (non-phthalate compound).

[0110] The above phthalate compound is a compound having the following phthalate structure.

[0111]

[0112] Such phthalate compounds are compounds represented by the following general formula (IV):

[0113]

[0114] Wherein, R 4 、R5 and R 6 is an organic group, and o is an integer from 0 to 4. When there are two or more Rs 4 , each R 4 may be the same as or different from each other, and R 4 , R 5 and R 6 may be the same as or different from each other.

[0115] Specifically, phthalate compounds include di-n-propyl phthalate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, etc.

[0116] A non-phthalate compound is a compound that does not have the above phthalate structure in the molecule and does not fall into phthalate compounds such as the compounds represented by the general formula (IV).

[0117] Examples of non-phthalate compounds may include one or more selected from diether compounds, ether carbonate compounds, aliphatic dicarboxylate compounds, ether-carboxylate compounds, and dicarbonate compounds, etc.

[0118] Specifically, these non-phthalate compounds include one or more selected from diethyl maleate, diethyl benzylidenemalonate, diethyl 2,3-diisopropyl succinate, diethyl cyclohexane-1,2-dicarboxylate, di-n-propyl cyclohexane-1,2-dicarboxylate, di-n-butyl cyclohexane-1,2-dicarboxylate, diethyl cyclohexene-1,2-dicarboxylate, di-n-propyl cyclohexene-1,2-dicarboxylate, di-n-butyl cyclohexene-1,2-dicarboxylate, ethyl 3-ethoxy-2-isopropylpropionate, ethyl 3-ethoxy-2-tert-butylpropionate, ethyl 3-ethoxy-2-tert-amylpropionate, dibenzoate of 2,4-pentanediol, dibenzoate of 3-methyl-2,4-pentanediol, dibenzoate of 3-methyl-5-tert-butyl-1,2-phenylene, dibenzoate of 3,5-diisopropyl-1,2-phenylene, 2-ethoxyethyl methyl carbonate, 2-ethoxyethyl ethyl carbonate, 2-propoxyethyl methyl carbonate, 2-benzyloxyethyl phenyl carbonate, 5-tert-butyl-1,2-phenylene diphenyl dicarbonate; 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene, etc.

[0119] In the method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, when using a plurality of internal electron donor compounds, the combination of the internal electron donor compounds can be a combination of different phthalate compounds, can be a combination of different non-phthalate compounds, or can be a combination of a phthalate compound and a non-phthalate compound.

[0120] When using a plurality of internal electron donor compounds, preferred combinations of internal electron donor compounds may include combinations selected from ethyl 2-ethoxyethyl carbonate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, diethyl benzylidenemalonate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, di-n-butyl cyclohexane-1,2-dicarboxylate and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, ethyl 2-ethoxyethyl carbonate and diethyl benzylidenemalonate, ethyl 2-ethoxyethyl carbonate and di-n-butyl cyclohexane-1,2-dicarboxylate, and diethyl benzylidenemalonate and di-n-butyl cyclohexane-1,2-dicarboxylate.

[0121] When using, as the internal electron donor compound, a combination of two internal electron donor compounds having different adsorbabilities for the magnesium compound, the amounts used are as follows: the ratio of the amount used of the internal electron donor compound having poor solubility (strong adsorbability) to the amount used of the internal electron donor compound having good solubility (weak adsorbability) (the internal electron donor compound having poor solubility (strong adsorbability) / the internal electron donor compound having good solubility (weak adsorbability)) is preferably from 1 / 6 to 6 / 1, more preferably from 1 / 5 to 5 / 1, and still more preferably from 1 / 4 to 4 / 1 by volume ratio.

[0122] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, a titanium halide compound and an internal electron donor compound are brought into contact with a pre-contact product obtained after previously contacting the polymer represented by the above general formula (I) with a magnesium compound.

[0123] There is no particular limitation on the order of contacting the titanium halide compound and the internal electron donor compound with the above pre-contact product. The titanium halide compound and the internal electron donor compound may be brought into contact with the above pre-contact product separately or may be brought into contact with the above pre-contact product simultaneously. Further, the titanium halide compound and the internal electron donor compound may each be added in one portion in their entirety or may be added in divided doses to contact the above pre-contact product, and the divided doses may be added continuously or intermittently. When the titanium halide compound or the internal electron donor compound is added intermittently in divided doses, the addition intervals may be constant or may not be constant. The addition interval is preferably from 1 minute to 60 minutes, more preferably from 3 minutes to 30 minutes, and still more preferably from 5 minutes to 15 minutes.

[0124] In the method for producing a solid catalyst component for olefin polymerization according to the present invention, it is preferred to bring the pre-contact product, the titanium halide compound, and the internal electron donor compound into contact with each other in an inert gas atmosphere to prepare the solid catalyst component.

[0125] Specifically, a solid catalyst component can be obtained by bringing a pre-contact product, a titanium halide compound, and an internal electron donor compound into contact with each other while stirring in a container equipped with a stirrer under an inert gas atmosphere and in the absence of water or the like, and then reacting them at a predetermined temperature.

[0126] When only bringing the respective components into contact with each other, stirring (mixing) the mixture, or dispersing or suspending the respective components for effective modification, the temperature at which the pre-contact product, the titanium halide compound, and the internal electron donor compound are brought into contact with each other can be in a relatively low temperature range near room temperature.

[0127] When obtaining a product by reaction after bringing the pre-contact product, the titanium halide compound, and the internal electron donor compound into contact with each other, a temperature range of 40°C to 130°C is preferred. In this case, it is preferred to carry out the reaction after bringing the respective components into contact while maintaining the temperature.

[0128] When the temperature when obtaining the above product is lower than 40°C, the reaction cannot proceed sufficiently, and the resulting solid catalyst component is difficult to exhibit sufficient performance. In addition, when the above temperature exceeds 130°C, the reaction is likely to be difficult to control due to significant evaporation of the solvent used, etc.

[0129] The reaction time for obtaining the above product is preferably 1 minute or more, more preferably 10 minutes or more, and still more preferably 30 minutes or more.

[0130] The ratio of the amounts used of the respective components for preparing the solid catalyst component varies depending on the preparation method, and thus can be appropriately determined.

[0131] In the method for manufacturing a solid catalyst component for olefin polymerization according to the present invention, the contents of titanium atoms, magnesium atoms, halogen atoms, and the internal electron donor compound constituting the obtained solid catalyst component are not particularly limited as long as the effects of the present invention can be exhibited.

[0132] The obtained solid catalyst component contains titanium atoms in a proportion of preferably 1.0% to 10.0% by mass, more preferably 1.5% to 8.0% by mass, and still more preferably 1.5% to 5.0% by mass.

[0133] The obtained solid catalyst component contains magnesium atoms in a proportion of preferably 10.0% to 70.0% by mass, more preferably 10.0% to 50.0% by mass, still more preferably 15.0% to 40.0% by mass, and further preferably 15.0% to 25.0% by mass.

[0134] The obtained solid catalyst component contains halogen atoms in a proportion of preferably 20.0% to 90.0% by mass, more preferably 30.0% to 85.0% by mass, still more preferably 40.0% to 80.0% by mass, and further preferably 45.0% to 80.0% by mass.

[0135] The obtained solid catalyst component contains an internal electron donor compound in a proportion of preferably 0.5% to 30.0% by mass in total, more preferably 1.0% to 25.0% by mass in total, and still more preferably 2.0% to 20.0% by mass in total.

[0136] In this application document, the content ratio of titanium atoms contained in the solid catalyst component refers to the value measured according to the method (oxidation-reduction titration method) described in JIS 8311-1997 "Method for determination of titanium in titanium ores".

[0137] In this application document, the content ratio of magnesium atoms contained in the solid catalyst component refers to the value determined by the EDTA titration method in which the solid catalyst component is dissolved in a hydrochloric acid solution and titrated with an EDTA solution.

[0138] In this application document, the content of halogen atoms contained in the solid catalyst component refers to the value measured by the 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, then a predetermined amount thereof is collected, and the halogen atoms are titrated with a silver nitrate standard solution.

[0139] In addition, in this application document, the content of the internal electron donor compound refers to the value obtained by hydrolyzing the solid catalyst, then extracting the internal electron donor compound using an aromatic solvent, and measuring the solution using the gas chromatography flame ionization detector (FID, hydrogen flame ionization type detector) method.

[0140] According to the method for manufacturing a solid catalyst component for olefin polymerization of the present invention, by pre-contacting a magnesium compound and the compound represented by the above general formula (I) with each other, and then contacting the obtained pre-contact product, a titanium halide compound, and an internal electron donor compound with each other, the content of the internal electron donor compound in the solid catalyst component can be easily controlled to fall within an appropriate range.

[0141] That is, in the method for producing a solid catalyst component for olefin polymerization according to the present invention, when using a single internal electron donor compound, by pre-contacting the magnesium compound and the compound represented by the above general formula (I) with each other, excessive adsorption of the internal electron donor compound to the magnesium compound is appropriately suppressed, and it is thus considered that the proportion of active sites with high stereospecificity in the solid catalyst component is increased.

[0142] In addition, in the method for producing a solid catalyst component for olefin polymerization according to the present invention, when using two or more internal electron donor compounds, by pre-contacting the magnesium compound and the compound represented by the above general formula (I) with each other, excessive adsorption of the internal electron donor compound having strong adsorptivity to the magnesium compound is appropriately suppressed, and adsorption of the internal electron donor compound having weak adsorptivity to the magnesium compound is promoted, and it is thus considered that the proportion of active sites with high stereospecificity in the solid catalyst component is increased.

[0143] As a result, in the method for producing a solid catalyst component for olefin polymerization according to the present invention, a solid catalyst component that can produce an olefin polymer with high stereoregularity in high yield when the solid catalyst component is used for olefin polymerization can be easily produced, and at the same time, the content of the internal electron donor compound can be easily controlled to fall within an appropriate range.

[0144] Next, the method for producing a catalyst for olefin polymerization according to the present invention will be described.

[0145] The method for producing a catalyst for olefin polymerization according to the present invention includes contacting the solid catalyst component for olefin polymerization obtained by the production method according to the present invention with an organoaluminum compound represented by the following general formula (II):

[0146] R 2 p AlQ 3-p (II)

[0147] Wherein, R 2 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number satisfying 0 < p ≤ 3, and when there are two or more Rs 2 , each R 2 can be the same or different from each other, and when there are two or more Qs, each Q can be the same or different from each other.

[0148] In the method for producing a catalyst for olefin polymerization according to the present invention, the details of the solid catalyst component for olefin polymerization obtained by the production method according to the present invention are as described above.

[0149] In the method for producing a catalyst for olefin polymerization according to the present invention, the organoaluminum compound represented by the general formula (II) includes one or more selected from trialkylaluminums such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and triisobutylaluminum; and alkylhaloaluminums such as diethylaluminum chloride and diethylaluminum bromide.

[0150] Among these organoaluminum compounds, one or more selected from alkylhaloaluminums such as diethylaluminum chloride; and trialkylaluminums such as triethylaluminum, tri-n-butylaluminum, and triisobutylaluminum are preferred, and one or more selected from triethylaluminum and triisobutylaluminum are more preferred.

[0151] In the method for producing a catalyst for olefin polymerization according to the present invention, it is preferred that an external electron donor compound further contacts the solid catalyst component for olefin polymerization obtained by the production method according to the present invention and the organoaluminum compound represented by the general formula (II).

[0152] In the method for producing a catalyst for olefin polymerization according to the present invention, examples of the external electron donor compound may include one or more organosilicon compounds selected from phenylalkoxysilanes, alkylalkoxysilanes, phenylalkylalkoxysilanes, cycloalkylalkoxysilanes, cycloalkylalkylalkoxysilanes, (alkylamino)alkoxysilanes, alkyl(alkylamino)alkoxysilanes, alkyl(alkylamino)silanes, and alkylaminosilanes.

[0153] Among them, one or more selected from cyclohexylmethyldimethoxysilane, dicyclopentyldimethoxysilane, ethyltriethoxysilane, dicyclopentylbis(ethylamino)silane, cyclopentylcyclohexylbis(ethylamino)silane, bis(perhydroisoquinoline)dimethoxysilane, diethylaminotrimethoxysilane, or diethylaminotriethoxysilane are more preferred.

[0154] In the method for producing a catalyst for olefin polymerization according to the present invention, the catalyst for olefin polymerization can be prepared by contacting the solid catalyst component for olefin polymerization obtained by the production method according to the present invention, the organoaluminum compound represented by the general formula (II), and, if necessary, the external electron donor compound in the absence of olefins, or the catalyst for olefin polymerization can be prepared by contacting them in the presence of olefins (in the polymerization system) as described below.

[0155] Although the components constituting the above-mentioned catalyst for olefin polymerization are contacted in any order, it is desirable that, for example, first, the organoaluminum compound represented by the above general formula (II) is charged into the polymerization system, then the above external electron donor compound is charged therein and contacted, and then the above solid catalyst component for olefin polymerization is charged therein and contacted.

[0156] In the method for producing a catalyst for olefin polymerization according to the present invention, the respective components are brought into contact in any proportion and there is no limitation thereon, as long as the effects of the present invention are not impaired thereby.

[0157] Generally, with respect to 1 mol of titanium atoms in the above solid catalyst component for olefin polymerization, the contact amount of the organoaluminum compound represented by the general formula (II) is preferably from 1 to 2000 mol, and more preferably from 50 to 1000 mol.

[0158] Further, in the catalyst for olefin polymerization obtained by the production method according to the present invention, with respect to 1 mol of the above organoaluminum compound, the contact amount of the external electron donor compound is preferably from 0.002 to 10 mol, more preferably from 0.01 to 2 mol, and still more preferably from 0.01 to 0.5 mol.

[0159] In the catalyst for olefin polymerization obtained by the production method according to the present invention, the contents of the solid catalyst component for olefin polymerization, the organoaluminum compound represented by the general formula (II), and the external electron donor compound preferably correspond to the contact amounts of the respective components.

[0160] According to the present invention, there can be provided a method for producing a catalyst for olefin polymerization which has excellent polymerization activity and can produce a polymer having excellent stereospecificity.

[0161] Next, the method for producing an olefin polymer according to the present invention will be described.

[0162] The method for producing an olefin polymer according to the present invention includes polymerizing an olefin using the catalyst for olefin polymerization obtained by the production method according to the present invention.

[0163] In the method for producing an olefin polymer according to the present invention, the polymerization of the olefin may be homopolymerization or may be copolymerization with other α-olefins.

[0164] In the method for producing an olefin polymer according to the present invention, the olefin to be polymerized may include one or more selected from ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like. Among these olefins, one or more selected from ethylene, propylene, and 1-butene are preferred, and propylene is more preferred.

[0165] When the above olefin is propylene, propylene can be homopolymerized, but it can also be copolymerized with other α-olefins.

[0166] The olefins copolymerized with propylene may include one or more selected from ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, and the like.

[0167] When the catalyst for olefin polymerization is prepared by the above-described method for producing a catalyst for olefin polymerization in the presence of an olefin (in a polymerization system), the solid catalyst component for olefin polymerization, the organoaluminum compound represented by the general formula (II), and the optionally used external electron donor compound are preferably brought into contact in the above-described quantitative ratio.

[0168] The method for producing an olefin polymer according to the present invention can be carried out in the presence or absence of an organic solvent.

[0169] In addition, an olefin monomer such as propylene can be used in either a gaseous state or a liquid state. The polymerization temperature is preferably 200°C or lower, more preferably 100°C or lower, and the polymerization pressure is preferably 10 MPa or lower, more preferably 5 MPa or lower. In addition, the olefin can be polymerized by either a continuous polymerization method or a batch polymerization method. Furthermore, the polymerization reaction can be carried out in one stage or in two or more stages.

[0170] In addition, when an olefin is polymerized (also referred to as main polymerization) using the catalyst for olefin polymerization obtained by the production method according to the present invention, it is preferable to perform prepolymerization before the main polymerization in order to further improve catalytic activity, stereoregularity, and the particle properties of the produced polymer, etc. The same olefin as in the main polymerization or a monomer such as styrene can be used for prepolymerization.

[0171] Although the respective components and monomers (olefins) constituting the above-described catalyst for olefin polymerization are brought into contact in any order during prepolymerization, it is preferable that, first, the organoaluminum compound is charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the solid catalyst component for olefin polymerization obtained by the production method according to the present invention is charged therein and brought into contact, and then an olefin such as propylene is contacted alone, or a mixture of an olefin such as propylene and one or more other olefins is contacted.

[0172] When an external electron donor compound is further charged into the prepolymerization system during the above prepolymerization, it is preferable that, first, the organoaluminum compound is charged into a prepolymerization system set to an inert gas atmosphere or an olefin gas atmosphere, and then the external electron donor compound is charged therein and brought into contact, and the solid catalyst component for olefin polymerization obtained by the production method according to the present invention is further brought into contact therewith, and then an olefin such as propylene is contacted alone, or a mixture of an olefin such as propylene and one or more other olefins is contacted.

[0173] In the method for producing an olefin polymer according to the present invention, as the polymerization method, a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane; a bulk polymerization method using a solvent such as liquefied propylene; and a gas phase polymerization method substantially free of a solvent can be exemplified, and the bulk polymerization method or the gas phase polymerization method is preferable.

[0174] When copolymerizing monomers of propylene and other α-olefins, random copolymerization in which propylene and a small amount of ethylene as a comonomer are polymerized in one stage, and so-called propylene-ethylene block copolymerization in which propylene is homopolymerized in the first stage (first polymerization vessel) and propylene and other α-olefins such as ethylene are copolymerized in the second stage (second polymerization vessel) or more stages (multi-stage polymerization vessel) are representative, and block copolymerization of propylene and other α-olefins is preferred.

[0175] The block copolymer obtained by block copolymerization is a polymer in the form of including segments having two or more continuously varying monomer compositions and having polymer chains (segments) in which two or more primary structures such as monomer type, comonomer type, comonomer composition, comonomer content, comonomer sequence, and stereoregularity are connected in one molecular chain.

[0176] In the method for producing an olefin polymer according to the present invention, the block copolymerization reaction between propylene and other α-olefins can generally be carried out by contacting propylene alone or contacting propylene and a small amount of other α-olefins (such as ethylene) in the previous stage in the presence of a catalyst for olefin polymerization obtained by the production method according to the present invention, and then contacting propylene and other α-olefins (such as ethylene) in the subsequent stage. The polymerization reaction in the previous stage can be repeated two or more times, or the polymerization reaction in the subsequent stage can be repeated two or more times by multi-stage reaction.

[0177] Specifically, in the block polymerization reaction between propylene and other α-olefins, preferably, in the previous stage, polymerization is carried out at a controlled polymerization temperature and time so that the proportion of the polypropylene part (in the finally obtained copolymer) becomes 20% to 90% by mass, and then in the subsequent stage, propylene and ethylene or other α-olefins are introduced for polymerization so that the proportion of the rubber part such as ethylene-propylene rubber (EPR) (in the finally obtained copolymer) becomes 10% to 80% by mass.

[0178] The polymerization temperature in both the previous stage and the subsequent stage is preferably 200 °C or lower, more preferably 100 °C or lower, and still more preferably 75 °C to 80 °C, and the polymerization pressure is preferably 10 MPa or lower, more preferably 6 MPa or lower, and still more preferably 5 MPa or lower.

[0179] Either a continuous polymerization method or a batch polymerization method can be adopted, and in the above copolymerization reaction, the polymerization reaction can be carried out in one stage, or can also be carried out in two or more stages.

[0180] In addition, in each polymerization stage in the previous stage or the subsequent stage or in the case of continuous polymerization, the polymerization time (residence time in the reactor) is preferably 1 minute to 5 hours.

[0181] As the polymerization method, a slurry polymerization method using a solvent of an inert hydrocarbon compound such as cyclohexane and heptane; a bulk polymerization method using a solvent such as liquefied propylene; and a gas phase polymerization method substantially free of solvent are exemplified, and the bulk polymerization method or the gas phase polymerization method is preferred. Generally, for the purpose of suppressing the elution of EPR from PP particles, the reaction in the latter stage is preferably a gas phase polymerization reaction.

[0182] According to the present invention, a method for producing an olefin polymer capable of producing a polymer having excellent polymerization activity and excellent stereospecificity can be provided.

[0183] Next, the present invention will be described more specifically by way of the given examples, but these examples are given for illustrative purposes only and do not limit the present invention.

[0184] [Examples]

[0185] (Example 1)

[0186] Into a 500 mL round bottom flask internally purged with nitrogen (inert gas) and equipped with a stirrer, 20 g of diethoxymagnesium and 60 mL of toluene were charged to form a toluene suspension of diethoxymagnesium. Then, while stirring at 20 °C for 5 minutes, 2.0 g of a styrene copolymer having a styrene content ratio of 28% by mass (a compound A in which one end of SEPTON HG-252(R) manufactured by Kuraray Co., Ltd. is substituted with benzoyloxy (C6H5C(=O)O-)) was added and contacted to obtain a pre-contact product. 1 wherein R is phenyl (C6H5-), X is a polymer unit having a block structural unit (A) and a block structural unit (B) and a total carbon atom number of 2000, and n + m = 200).

[0187] The contact amount of compound A with the above diethoxymagnesium (the amount of compound A / the amount of diethoxymagnesium) is 1 / 10 by mass ratio.

[0188] Then, the entire amount of the above pre-contact product (the liquid containing diethoxymagnesium) was added to a mixed solution of 50 mL of toluene and 40 mL of titanium tetrachloride that had been previously charged into a 500 mL round bottom flask that had been purged with nitrogen and equipped with a stirrer, thereby preparing a suspension.

[0189] The temperature of the resulting suspension was raised to 100 °C, and 8 mL of di-n-propyl phthalate was added thereto midway, and then stirred at 100 °C for 2 hours.

[0190] Then, the supernatant was taken out and washed three times with 150 mL of toluene at 90 °C. 20 mL of titanium tetrachloride and 100 mL of toluene were added to the obtained reaction product, and the temperature was raised to 100 °C for reaction for 15 minutes twice. Subsequently, it was washed six times with 150 mL of n-heptane at 40 °C to obtain a solid catalyst component.

[0191] The content of titanium atoms and the content of di-n-propyl phthalate in the obtained solid catalyst component were 2.1% by mass and 13.5% by mass, respectively, and did not contain the terminal substituents of the above styrene copolymer.

[0192] <Content of halogen atoms and internal electron donor compound in the solid catalyst component>

[0193] The content of halogen atoms in the solid catalyst component was measured by a silver nitrate titration method in which the solid catalyst component obtained by treating with a mixed solution of sulfuric acid and pure water was used to prepare an aqueous solution, and then a predetermined amount thereof was collected and titrated with a silver nitrate standard solution for halogen atoms.

[0194] In addition, the content of the internal electron donor compound (di-n-propyl phthalate in Example 1) in the solid catalyst component was obtained by using a calibration curve previously determined based on known concentrations when measured under the following conditions using a gas chromatograph (GC-14B, manufactured by SHIMADZU CORPORATION).

[0195] In the following Examples and Comparative Examples, the respective contents were also obtained by the same method.

[0196] [Measurement conditions]

[0197] Column: Capillary column (I.D. 0.32 mm × length 30 m df 1.00 μm IntertCap1, manufactured by GL Sciences Inc.)

[0198] Detector: Flame ionization detector (FID, hydrogen flame ionization type detector)

[0199] Carrier gas: Helium, flow rate 7 mL / min

[0200] Measurement temperature: Injection port 280 °C, column 225 °C, detector 280 °C

[0201] <Preparation of catalyst for olefin polymerization and olefin polymer>

[0202] After the internal atmosphere of an autoclave with an internal volume of 2.0 L equipped with a stirrer was replaced with nitrogen, first, 1.32 mmol of triethylaluminum was charged into the autoclave, and then 0.13 mmol of cyclohexylmethyltrimethoxysilane was charged therein and brought into contact. Thereafter, a solid catalyst component for olefin polymerization obtained by the above method was charged in an amount of 0.00264 mmol in terms of titanium atoms, and the interior of the autoclave was maintained at 20 °C for 5 minutes to prepare a catalyst for olefin polymerization.

[0203] Then, 1.4 L of liquefied propylene and 67 mmol of hydrogen were charged into an autoclave equipped with a stirrer and containing the above catalyst for olefin polymerization. After pre-polymerization was carried out at 20 °C for 5 minutes, the temperature was raised, and a polymerization reaction was carried out at 70 °C for 60 minutes to obtain a propylene homopolymer (PP).

[0204] The polymerization activity (g-PP / (g-catalyst·hour)) in the formation of the obtained propylene homopolymer was calculated according to the following equation. The results are shown in Table 1.

[0205] Polymerization activity of propylene homopolymerization (g-PP / (g-catalyst·hour)) = amount of obtained PP (g) / (mass (g) of the solid catalyst component contained in the catalyst for olefin polymerization · 1 hour)

[0206] In addition, the percentage of the p-xylene soluble part (XS) in the obtained propylene homopolymer was measured.

[0207] <Percentage of p-xylene soluble part (XS) in the polymer>

[0208] 4.0 g of a polymer (PP) and 200 mL of p-xylene were charged into a flask equipped with a stirring device, and by setting the external temperature above the boiling point of p-xylene (150 °C), while maintaining the temperature of p-xylene in the flask below its boiling temperature (137 °C to 138 °C), the polymer was dissolved within 2 hours. Then, the liquid temperature was cooled to 23 °C within 1 hour, and the insoluble components were separated from the soluble components by filtration. The solution of the above soluble components was collected, p-xylene was distilled off by heating and drying under reduced pressure, the weight of the obtained residue was measured, and the relative ratio (mass%) based on the produced polymer (PP) was calculated to determine the p-xylene soluble part (XS).

[0209] (Comparative Example 1)

[0210] A solid catalyst component was obtained in the same manner as in Example 1 except that the above styrene-based copolymer with a substituted end was not added.

[0211] The contents of titanium atoms and di-n-propyl phthalate in the obtained solid catalyst component are 2.0% by mass and 13.8% by mass, respectively.

[0212] Except for using the obtained solid catalyst component and then carrying out homopolymerization of propylene, an olefin polymerization catalyst was prepared in the same manner as in Example 1.

[0213] The polymerization activity during homopolymerization of propylene and the percentage of the p-xylene soluble part (XS) in the polymer were obtained in the same method as in Example 1. The results are shown in Table 1.

[0214] (Example 2)

[0215] Except for adding a mixture of 4 mL of di-n-propyl phthalate and 4 mL of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane instead of 8 mL of di-n-propyl phthalate, a solid catalyst component was obtained in the same manner as in Example 1.

[0216] The contents of titanium atoms, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and di-n-propyl phthalate in the obtained solid catalyst component are 1.5% by mass, 6.7% by mass, and 7.6% by mass, respectively, and do not contain the end substituents of the above styrene copolymer.

[0217] Except for using the obtained solid catalyst component and then carrying out homopolymerization of propylene, an olefin polymerization catalyst was prepared in the same manner as in Example 1.

[0218] The polymerization activity during homopolymerization of propylene and the percentage of the p-xylene soluble part (XS) in the polymer were obtained in the same method as in Example 1. The results are shown in Table 1.

[0219] (Comparative Example 2)

[0220] Except for not adding the above styrene copolymer with its end substituted, a solid catalyst component was obtained in the same manner as in Example 2.

[0221] The contents of titanium atoms, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, and di-n-propyl phthalate in the obtained solid catalyst component are 1.4% by mass, 7.6% by mass, and 8.7% by mass, respectively.

[0222] Except for using the obtained solid catalyst component and then carrying out homopolymerization of propylene, an olefin polymerization catalyst was prepared in the same manner as in Example 1.

[0223] The polymerization activity during homopolymerization of propylene and the percentage of the p-xylene soluble part (XS) in the polymer were obtained in the same method as in Example 1. The results are shown in Table 1.

[0224] (Comparative Example 3)

[0225] Except for adding 2.0 g of Compound B (SEPTON HG-252(R), manufactured by Kuraray Co., Ltd.) composed of a styrene copolymer in which one end is not substituted with a functional group and the styrene content ratio is 28% by mass instead of the above-mentioned styrene copolymer with a substituted end, a solid catalyst component was obtained in the same manner as in Example 1.

[0226] The contents of titanium atoms and di-n-propyl phthalate in the obtained solid catalyst component were 1.4% by mass and 7.3% by mass, respectively.

[0227] Except for using the obtained solid catalyst component and then carrying out homopolymerization of propylene, an olefin polymerization catalyst was prepared in the same manner as in Example 1.

[0228] The polymerization activity during homopolymerization of propylene and the percentage of the p-xylene soluble part (XS) in the polymer were obtained in the same manner as in Example 1. The results are shown in Table 1.

[0229] (Comparative Example 4)

[0230] Except for adding 0.2 mL of ethyl benzoate instead of the above-mentioned styrene copolymer with a substituted end, a solid catalyst component was obtained in the same manner as in Example 2.

[0231] The contents of titanium atoms, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, di-n-propyl phthalate, and ethyl benzoate in the obtained solid catalyst component were 1.5% by mass, 6.9% by mass, 8.0% by mass, and 0.1% by mass, respectively.

[0232] Except for using the obtained solid catalyst component and then carrying out homopolymerization of propylene, an olefin polymerization catalyst was prepared in the same manner as in Example 1.

[0233] The polymerization activity during homopolymerization of propylene and the percentage of the p-xylene soluble part (XS) in the polymer were obtained in the same manner as in Example 1. The results are shown in Table 1.

[0234] [Table 1]

[0235]

[0236] Compound A: SEPTON HG-252(R), one end of which is substituted with benzoyloxy (C6H5C(=O)O-)

[0237] Compound B: SEPTON HG-252(R)

[0238] Compound C: Ethyl benzoate

[0239] Donor A: Di-n-propyl phthalate

[0240] Donor B: 2-Isopropyl-2-isopentyl-1,3-dimethoxypropane

[0241] As shown in Table 1, in Example 1 and Example 2, since a solid catalyst component prepared by contacting one or more internal electron donor compounds and a titanium halide compound after previously contacting a magnesium compound and a specific compound with each other was used, when the obtained solid catalyst component was used for olefin polymerization, excellent polymerization activity was exhibited, and the stereoregularity of the obtained polymer remained high.

[0242] From the above results, it is speculated that by the pre-adsorption of the compound represented by the above general formula (I) on the surface of the magnesium compound, the adsorption amount of one or more internal electron donor compounds subsequently contacted on the surface of the solid catalyst is moderately controlled, and the proportion of active sites excellent in stereospecificity and activity in the solid catalyst component is increased.

[0243] On the other hand, in Comparative Examples 1 to 4, it was found that since a specific compound was not previously contacted with the magnesium compound or the compound to be pre-contacted was different from the compound defined in the present invention, the polymerization activity when the obtained solid catalyst component was used for polymerization was low or the stereoregularity of the obtained polymer was low.

[0244] Industrial Applicability

[0245] According to the present invention, a method for producing a solid catalyst component for olefin polymerization, a method for producing a solid catalyst for olefin polymerization, and a method for producing an olefin polymer, which have excellent polymerization activity and can produce a polymer excellent in stereospecificity, can be provided.

Claims

1. A method for preparing a solid catalyst component for olefin polymerization, comprising: Bring a magnesium compound and a compound represented by the following general formula (I) into contact with each other to obtain a pre-contact product; Subsequently, bring the pre-contact product, a titanium halide compound, and an internal electron donor compound into contact with each other to obtain a solid catalyst component for olefin polymerization, wherein, R 1 is an aromatic group having 6 to 12 carbon atoms, n and m are each an integer of 0 or more, n + m is from 1 to 30,000, and X is a polymer unit having the following structural unit (A) and the following structural unit (B) and having a total carbon atom number of 9 to 50,000 2. A method for manufacturing a catalyst for olefin polymerization, which comprises: Bring the solid catalyst component for olefin polymerization obtained by the method according to claim 1 and an organoaluminum compound represented by the following general formula (II) into contact with each other: R 2 p AlQ 3-p (II) Wherein, R 2 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number satisfying 0 < p ≤ 3, and when there are two or more R 2 , each R 2 is the same as or different from each other, and when there are two or more Q, each Q is the same as or different from each other.

3. The method for manufacturing a catalyst for olefin polymerization according to claim 2, which comprises: Bring the solid catalyst component for olefin polymerization obtained by the method according to claim 1, an organoaluminum compound represented by the following general formula (II), and an external electron donor compound into contact with each other: R 2 p AlQ 3-p (II) Wherein, R 2 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is a real number satisfying 0 < p ≤ 3, and when there are two or more R 2 , each R 2 is the same as or different from each other, and when there are two or more Q, each Q is the same as or different from each other.

4. A method for manufacturing an olefin polymer, comprising: Polymerize an olefin using the catalyst for olefin polymerization obtained by the method according to claim 2 or 3.

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