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

Abstract

A solid catalyst component for olefin polymerization, which is characterized in that: the total content of a 1, 3-diether compound that does not have a fluorene structure and a succinic acid diester compound is 13.0 mass% or more relative to the total amount of the contained components in terms of solid content; the molar ratio (S / T) represented by the molar content (S) of the succinic acid diester compound to the molar content (T) of the titanium is 0.71-1.30, the molar ratio (E / S) represented by the molar content (E) of the 1, 3-diether compound having no fluorene structure to the molar content (S) of the succinic acid diester compound is 0.10-0.70, the total pore volume having a diameter of 1 [mu] m or less is 0.3-1.0 cm3 / g, and the specific surface area is 200 m2 / g or more. According to the present invention, it is possible to provide a solid catalyst component for olefin polymerization, which contains an internal electron-donating compound other than a phthalate ester, and which is capable of producing an olefin polymer having excellent melt fluidity, high rigidity and few low-molecular-weight polymers.

Description

Technical Field

[0001] This invention relates to a solid catalyst composition for olefin polymerization, a method for manufacturing the solid catalyst composition for olefin polymerization, a catalyst for olefin polymerization, a method for manufacturing olefin polymers, and olefin polymers. Background Technology

[0002] In recent years, olefin polymers such as polypropylene (PP) have been used not only for molded products such as automotive parts or household appliances, but also for various other applications such as containers and films.

[0003] Polypropylene resin compositions are lightweight, have excellent formability, and the molded products exhibit excellent chemical stability, such as heat resistance and chemical resistance. They also offer excellent cost-effectiveness, making them one of the most important plastic materials used in many fields.

[0004] To further expand applications, it is desirable to use polypropylene with low molecular weight components, less amorphous polymer, high melt flow rate (MFR), excellent formability and high rigidity, which can replace polystyrene and ABS resin.

[0005] In the polymerization of olefins such as propylene, polymerization methods are known to use solid catalyst components containing magnesium atoms, titanium atoms, halogen atoms and internal electron-donating compounds as essential components. Many methods have been proposed to polymerize or copolymerize olefins in the presence of catalysts for olefin polymerization formed from the above-mentioned solid catalyst components, organoaluminum compounds and organosilicon compounds.

[0006] For example, Patent Document 1 discloses a method for polymerizing propylene using an olefin polymerization catalyst, wherein the olefin polymerization catalyst comprises a solid titanium catalyst component supported on an internal electron-donating compound such as phthalate, an organoaluminum compound as a co-catalyst component, and an organosilicon compound having at least one Si-OC bond. Many documents, including Patent Document 1, disclose methods for obtaining highly stereoregular polymers under high polymerization activity by using phthalate as an internal electron-donating compound.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 57-63310 Summary of the Invention

[0010] The problem the invention aims to solve

[0011] However, di-n-butyl phthalate and benzyl butyl phthalate, which are phthalate esters, have been identified as Substances of Very High Concern (SVHCs) under the European REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) regulation. From the perspective of reducing environmental impact, there is an increasing demand to switch to catalyst systems that do not use SVHCs.

[0012] Therefore, the inventors studied the composition of solid catalysts for olefin polymerization containing internal electron-donating compounds other than phthalates, and found that by using succinate diester compounds as internal electron-donating compounds, high-rigidity polypropylene with a flexural modulus (FM) of 1900 MPa or more can be obtained.

[0013] However, such polypropylene is known to have low hydrogen response. Therefore, it is difficult to manufacture polypropylene that combines high melt flowability (melt flow rate (MFR)) and high rigidity by using solid catalyst components containing internally electron-donating compounds other than phthalates as solid catalyst components for olefin polymerization.

[0014] Furthermore, when succinate diester compounds are used as solid catalyst components in olefin polymerization as internal electron-donating compounds, the molecular weight distribution becomes broader. Consequently, a large amount of low molecular weight polymers are present, which negatively impacts the polymer's physical properties and processability.

[0015] Under such circumstances, the object of the present invention is to provide a solid catalyst composition for olefin polymerization, which includes internally electron-donating compounds other than phthalates, and can produce olefin polymers with excellent melt flowability, high rigidity and low molecular weight polymers.

[0016] Solution for solving the problem

[0017] To address the aforementioned technical challenges, the inventors conducted repeated and in-depth research, and discovered that the total pore volume, measured by mercury porosimetry, for compounds containing magnesium, titanium, halogens, 1,3-diether compounds without a fluorene structure, and succinate diester compounds, is 0.3~1.0 cm³ with a diameter of less than 1 μm. 3 / g, specific surface area is 200m² 2When converting solid catalyst components for olefin polymerization at a concentration of / g or higher, the total content of 1,3-diether compounds without fluorene structures and succinate diester compounds in the total components is 13.0% by mass or higher. The molar ratio (S / T) of succinate diester compounds to titanium molar content (T) in the total components is 0.71 to 1.30, and the molar ratio (E / S) of 1,3-diether compounds without fluorene structures to succinate diester compounds (S) is 0.10 to 0.70. With such a solid catalyst component for olefin polymerization, the above-mentioned technical problems can be solved, and the present invention was completed based on this insight.

[0018] That is, the present invention provides the following solution.

[0019] (1) A solid catalyst composition for olefin polymerization, characterized in that it comprises magnesium, titanium, halogen, a 1,3-diether compound without a fluorene structure, and a succinic acid diester compound.

[0020] When converting the solid content, the sum of the contents of the 1,3-diether compound without the fluorene structure and the succinate diester compound in the total content of the components is 13.0% by mass or more.

[0021] The molar ratio (S / T), expressed as the molar content (S) of the succinate diester compound in the total amount of the ingredients relative to the molar content (T) of the titanium in the total amount of the ingredients, is 0.71 to 1.30.

[0022] The molar ratio (E / S), expressed as the molar content (E) of the 1,3-diether compound without the fluorene structure in the total amount of the contained components relative to the molar content (S) of the succinate diester compound in the total amount of the contained components, is 0.10 to 0.70.

[0023] The total pore volume, measured by mercury porosimetry, for diameters less than 1 μm, is 0.3–1.0 cm³. 3 / g, specific surface area is 200m² 2 / g or more.

[0024] (2) The solid catalyst composition for olefin polymerization according to (1) is characterized in that the 1,3-diether compound without a fluorene structure is selected from one or more of the 1,3-diether compounds represented by the following general formula (1).

[0025]

[0026] In equation (1), R 2 and R 3It represents hydrogen atoms, halogen atoms, alkyl groups with 1 to 12 carbon atoms, vinyl groups with 3 to 12 carbon atoms, alkenyl groups with 3 to 12 carbon atoms, cycloalkyl or cycloalkenyl groups with 3 to 12 carbon atoms, aromatic hydrocarbon groups or halogen-substituted aromatic hydrocarbon groups with 6 to 12 carbon atoms, aromatic hydrocarbon groups with 7 to 12 carbon atoms having substituents, alkylamino groups with 1 to 12 carbon atoms, or dialkylamino groups with 2 to 12 carbon atoms;

[0027] R 2 and R 3 Choose either the same or different from each other; R 2 and R 3 They can be arbitrarily bonded together to form a ring;

[0028] R 1 and R 4 Represents alkyl, vinyl, alkenyl, cycloalkyl, aromatic hydrocarbon group (6-12 carbons), or halogenated aromatic hydrocarbon group (7-12 carbons) with substituents; R 1 and R 4 Choose whether they are the same or different from each other.

[0029] (3) The solid catalyst composition for olefin polymerization according to (1) is characterized in that the succinate diester compound is selected from one or more compounds represented by the following general formula (2).

[0030]

[0031] In equation (2), R 6 and R 7 It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, optionally the same or different from each other; R 5 and R 8 It is a straight-chain alkyl or branched alkyl with 2 to 4 carbon atoms, which may be the same as or different from each other.

[0032] (4) A method for manufacturing a solid catalyst component for olefin polymerization, characterized in that it is a method for manufacturing the solid catalyst component for olefin polymerization of any one of (1) to (3) by contacting a magnesium dialkoxy compound, a titanium halide compound, a 1,3-diether compound without a fluorene structure and a succinate diester compound with each other.

[0033] The titanium halide compound is contacted with the dialkoxymagnesium multiple times.

[0034] When the titanium halide compound is first contacted with the dialkoxy magnesium, the contact amount of the titanium halide compound is 1.5 to 10.0 mol relative to 1.0 mol of the dialkoxy magnesium.

[0035] The total amount of the titanium halide compound used is 5.0 to 18.0 mol relative to 1.0 mol of the magnesium diekoxy.

[0036] The total molar amount of the 1,3-diether compound having no fluorene structure and the molar amount of the disuccinate compound is 0.10 to 0.20 mol relative to 1.0 mol of the dialkoxymagnesium.

[0037] The molar ratio (S / T) represented by the molar amount (S) of the disuccinate compound relative to the total molar amount (T) of the titanium halide compound is 0.020 to 0.040.

[0038] The molar ratio (E / S) represented by the molar amount (E) of the 1,3-diether compound having no fluorene structure relative to the molar amount (S) of the disuccinate compound is 0.50 or less.

[0039] The dialkoxymagnesium is composed of secondary particles that are aggregates of primary particles with an average particle diameter less than 2 μm, and has a specific surface area of 10 m 2 / g or more and less than 50 m 2 / g, and a particle size distribution index (SPAN) of 1.30 or less.

[0040] (5) An olefin polymerization catalyst, characterized in that it comprises:

[0041] (I) A solid catalyst component for olefin polymerization according to any one of (1) to (3); and

[0042] (II) An organoaluminum compound represented by the following general formula (3);

[0043]

[0044] In the formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, p is 0 < p ≤ 3, and when there are a plurality of R 9 , each R 9 is optionally the same or different from each other, and when there are a plurality of Q, each Q is optionally the same or different from each other.

[0045] (6) The olefin polymerization catalyst according to (5), characterized in that it comprises:

[0046] (I) A solid catalyst component for olefin polymerization according to any one of (1) to (3);

[0047] (II) An organoaluminum compound represented by the following general formula (3); and

[0048] (III) An external electron donor compound.

[0049]

[0050] In formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, 0 < p ≤ 3, and when there are multiple Rs 9 each R 9 is optionally the same as or different from each other, and when there are multiple Qs, each Q is optionally the same as or different from each other.

[0051] (7) A method for producing an olefin polymer, characterized in that an olefin is polymerized using the olefin polymerization catalyst of (5) or (6).

[0052] Effects of the Invention

[0053] According to the present invention, a solid catalyst component for olefin polymerization can be provided, which contains an internal electron donor compound other than phthalate, and can produce an olefin polymer having excellent melt fluidity, high rigidity, and a small amount of low molecular weight polymer. Brief Description of the Drawings

[0054] Figure 1 is a diagram for explaining a method for producing a measurement specimen for measuring the proportion of an oriented layer in a cross-section of an injection-molded plate of an olefin polymer.

[0055] Figure 2 is a diagram for explaining a method for producing a measurement specimen for measuring the proportion of an oriented layer in a cross-section of an injection-molded plate of an olefin polymer.

[0056] Figure 3 is a diagram for explaining a method for determining the proportion of an oriented layer. Detailed Description of the Invention

[0057] First, the solid catalyst component for olefin polymerization of the present invention will be described.

[0058] The solid catalyst component for olefin polymerization of the present invention is characterized in that it contains magnesium, titanium, halogen, a 1,3-diether compound not having a fluorene structure, and a succinic acid diester compound,

[0059] when converted to solid components, the total content of the components contained is such that the total content of the 1,3-diether compound not having a fluorene structure and the succinic acid diester compound is 13.0% by mass or more,

[0060] the molar ratio (S / T) represented by the molar content (S) of the succinic acid diester compound in the total content of the components contained relative to the molar content (T) of the titanium in the total content of the components contained is 0.71 to 1.30,

[0061] The molar ratio (E / S), expressed as the molar content (E) of the 1,3-diether compound without the fluorene structure in the total amount of the contained components relative to the molar content (S) of the succinate diester compound in the total amount of the contained components, is 0.10 to 0.70.

[0062] The total pore volume, measured by mercury porosimetry, for diameters less than 1 μm, is 0.3–1.0 cm³. 3 / g, specific surface area is 200m² 2 / g or more.

[0063] As a solid catalyst component for olefin polymerization of the present invention, examples include contact reactants formed by reacting raw material components that serve as a magnesium supply source, raw material components that serve as a titanium and halogen supply source, and 1,3-diether compounds and succinate diester compounds that are internal electron-donating compounds without a fluorene structure in an organic solvent. Specifically, examples include contact reactants formed by using dialkoxy magnesium as a magnesium supply source and tetravalent titanium halide compounds as a titanium and halogen supply source, and by contacting these raw materials with internal electron-donating compounds containing 1,3-diether compounds and succinate diester compounds without a fluorene structure.

[0064] In the solid catalyst composition for olefin polymerization of the present invention, the diekoxy magnesium, which serves as a raw material component for supplying magnesium, specifically includes dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium, ethoxymethoxy magnesium, ethoxypropoxy magnesium, butoxyethoxy magnesium, etc., with diethoxy magnesium being particularly preferred.

[0065] The aforementioned diekoxymagnesium can be obtained by reacting metallic magnesium with an alcohol in the presence of a halogen or a halogen-containing metal compound.

[0066] The aforementioned magnesium dialkoxy is preferably in granular or powder form, and its shape can be amorphous or spherical.

[0067] When using spherical dialkoxy magnesium as dialkoxy magnesium, polymer powder with better particle shape (more spherical) and narrower particle size distribution can be obtained. The processability of the polymer powder generated during polymerization is improved, and the occurrence of clogging and other issues caused by microparticles contained in the generated polymer powder can be suppressed.

[0068] The aforementioned spherical dialkoxy magnesium does not necessarily have to be spherical; oval or potato-shaped dialkoxy magnesium can also be used.

[0069] Furthermore, the average particle size (average particle size D50) of the aforementioned magnesium diethoxy group is preferably 1.0 to 200.0 μm, more preferably 5.0 to 150.0 μm. Here, the average particle size D50 refers to the particle size that accounts for 50% of the cumulative particle size in the volumetric cumulative particle size distribution when measured using a laser scattering diffraction particle size analyzer.

[0070] When the magnesium diekoxy is spherical, the average particle size D50 is preferably 1.0 to 100.0 μm, more preferably 5.0 to 80.0 μm, and even more preferably 10.0 to 70.0 μm.

[0071] In addition, for the particle size distribution of dialkoxy magnesium, dialkoxy magnesium with less fine powder and coarse powder and narrow particle size distribution is preferred.

[0072] Specifically, for magnesium dialkoxy, when measured using a laser scattering diffraction particle size analyzer, particles with a diameter of 5.0 μm or less preferably account for 20% or less, more preferably 10% or less. On the other hand, when measured using a laser scattering diffraction particle size analyzer, particles with a diameter of 100.0 μm or more preferably account for 20% or less, more preferably 10% or less.

[0073] Furthermore, when this particle size distribution is expressed as ln(D90 / D10), it is preferably 3 or less, more preferably 2 or less. Here, D90 refers to the particle size that accounts for 90% of the cumulative particle size in the volumetric cumulative particle size distribution when measured using a laser scattering diffraction particle size analyzer. D10 refers to the particle size that accounts for 10% of the cumulative particle size in the volumetric cumulative particle size distribution when measured using a laser scattering diffraction particle size analyzer. D50 refers to the particle size that accounts for 50% of the cumulative particle size in the volumetric cumulative particle size distribution when measured using a laser scattering diffraction particle size analyzer.

[0074] Examples of the above-mentioned methods for manufacturing spherical dialkoxy magnesium are, for example, Japanese Patent Application Publication No. 62-51633, Japanese Patent Application Publication No. 3-74341, Japanese Patent Application Publication No. 4-368391, and Japanese Patent Application Publication No. 8-73388.

[0075] In the solid catalyst composition for olefin polymerization of the present invention, magnesium dialkoxy is preferably composed of secondary particles that are aggregates of primary particles with an average particle size of less than 2 μm. By using the above-described substance as magnesium dialkoxy, a solid catalyst composition for olefin polymerization having a desired specific surface area and pore volume can be readily prepared.

[0076] In the solid catalyst component for olefin polymerization of the present invention, magnesium diekoxy preferably has a specific surface area of ​​10 m². 2 / g or more and less than 50m 2 / g, more preferably 10~50m2 / g, more preferably 10~40m 2 / g. By using magnesium dialkoxy with a specific surface area within the above range, it is possible to readily prepare solid catalyst components for olefin polymerization with a desired specific surface area.

[0077] In the solid catalyst component for olefin polymerization of the present invention, as dialkoxy magnesium, when measured using a laser scattering diffraction particle size analyzer, the particle size distribution index (SPAN = (D90-D10) / D50) is preferably 1.30 or less, more preferably 0.60 to 1.00, and even more preferably 0.70 to 0.90. By using dialkoxy magnesium with a particle size distribution index (SPAN) within the above-mentioned range, the processability of the polymer powder generated during polymerization is improved, and the occurrence of clogging and other problems caused by microparticles contained in the generated polymer powder can be suppressed.

[0078] In this invention, magnesium diethoxy is composed of secondary particles that are aggregates of primary particles with an average particle size of less than 2 μm. This is confirmed visually by taking negatives using a scanning electron microscope. The primary particle size is calculated by statistical analysis based on the longest diameter of more than 100 particles. The secondary particle size is confirmed by measuring using a laser scattering diffraction particle size analyzer.

[0079] It should be noted that in this application document, the specific surface area of ​​dialkoxy magnesium refers to the value determined by the BET method. Specifically, the specific surface area of ​​dialkoxy magnesium refers to the value determined by the BET method (automatic determination) after the test sample has been vacuum dried at 50°C for 2 hours, using an Automatic Surface Area Analyzer HM model-1230 manufactured by Mountech in the presence of a mixture of nitrogen and helium.

[0080] The aforementioned diethoxymagnesium is preferably in the form of a solution or suspension during the reaction, and by being in the form of a solution or suspension, the reaction can proceed appropriately.

[0081] When the aforementioned dialkoxy magnesium is a solid, it can be prepared as a solution by dissolving it in a solvent that has the solubilizing ability of dialkoxy magnesium, or as a suspension by suspending it in a solvent that does not have the solubilizing ability of dialkoxy magnesium.

[0082] It should be noted that when magnesium dialoxy is in liquid form, it can be used directly as a solution, or it can be further dissolved in a solvent with solubilizing properties to be used as a solution.

[0083] As compounds that can solubilize solids, magnesium dialkoxy compounds can be selected from at least one compound selected from the group consisting of alcohols, ethers and esters, with alcohols such as ethanol, propanol, butanol, and 2-ethylhexanol being preferred, and 2-ethylhexanol being particularly preferred.

[0084] On the other hand, as a medium that does not have the ability to solubilize solid dialoxy magnesium, one or more of the following can be listed: saturated hydrocarbon solvents or unsaturated hydrocarbon solvents that do not dissolve dialoxy magnesium.

[0085] In the solid catalyst composition for olefin polymerization of the present invention, there is no particular limitation on the tetravalent titanium halide compound that serves as a raw material component for supplying titanium and halogens, but it is preferred to select one or more compounds from the group consisting of titanium halide or alkoxy titanium halide as shown in the following general formula (4).

[0086]

[0087] In equation (4), R 10 It represents an alkyl group with 1 to 4 carbon atoms, X represents a halogen atom such as chlorine, bromine, or iodine, and r is 0 ≤ r ≤ 3.

[0088] In the above general formula (4), r is 0≤r≤3. Specifically, r can be 0, 1, 2 or 3.

[0089] As the titanium halide represented by the above general formula (4), one or more titanium halide selected from titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, etc. can be listed.

[0090] In addition, as the alkoxytitanium halide represented by the above general formula (4), one or more of the following can be selected: methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, n-butoxytitanium trichloride, dimethoxytitanium dichloride, diethoxytitanium dichloride, dipropoxytitanium dichloride, di-n-butoxytitanium dichloride, trimethoxytitanium chloride, triethoxytitanium chloride, tripropoxytitanium chloride, and tri-n-butoxytitanium chloride.

[0091] As a tetravalent titanium halide compound, titanium tetrahalide is preferred, and titanium tetrachloride is more preferred.

[0092] These titanium compounds can be used alone or in combination of two or more.

[0093] In the solid catalyst composition for olefin polymerization of the present invention, the 1,3-diether compound without a fluorene structure refers to a compound having a structure in which atoms are bonded in the order of carbon atom-oxygen atom-carbon atom-carbon atom-carbon atom-oxygen atom-carbon atom and without an intramolecular fluorene structure.

[0094] As a 1,3-diether compound that does not have a fluorene structure, one or more of the 1,3-diether compounds selected from the following general formula (1) can be listed;

[0095]

[0096] In equation (1), R 2 and R 3 Represents hydrogen atoms, halogen atoms, alkyl or vinyl groups having 1 to 12 carbon atoms, alkenyl groups having 3 to 12 carbon atoms, cycloalkyl or cycloalkenyl groups having 3 to 12 carbon atoms, aromatic hydrocarbon groups having 6 to 12 carbon atoms or halogen-substituted aromatic hydrocarbon groups, aromatic hydrocarbon groups having 7 to 12 carbon atoms with substituents, alkylamino groups having 1 to 12 carbon atoms, or dialkylamino groups having 2 to 12 carbon atoms; R 2 and R 3 Choose either the same or different from each other; R 2 and R 3 They can be arbitrarily bonded together to form a ring; R 1 and R 4 Represents alkyl, vinyl, alkenyl, cycloalkyl, aromatic hydrocarbon, halogenated aromatic hydrocarbon, or aromatic hydrocarbon with substituents having carbons of 7-12 (1-12 carbons); R 1 and R 4 Choose whether they are the same or different from each other.

[0097] In the 1,3-diether compound represented by general formula (1), R 1 and R 4 It is a straight-chain alkyl or branched alkyl with 1 to 4 carbon atoms, which may be the same as or different from each other.

[0098] As R 1 and R 4 Specifically, when it is a straight-chain alkyl or branched alkyl with 1 to 4 carbon atoms, examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0099] In the 1,3-diether compound represented by general formula (1), R 2 and R 3 It is a hydrogen atom or an alkyl group having 2 to 5 carbon atoms, which may be the same as or different from each other.

[0100] As R 2 and R 3 Specifically, when it is an alkyl group having 2 to 5 carbon atoms, examples include ethyl, n-propyl, isopropyl, n-butyl or isobutyl, n-pentyl, and isopentyl.

[0101] In the solid catalyst component for olefin polymerization of the present invention, there are no particular limitations on the 1,3-diether compound that does not have a fluorene structure. Examples of suitable compounds include, for instance, one or more selected from 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, and 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane. Preferably, one or more selected from 2-isopropyl-2-isobutyl-1,3-dimethoxypropane and 2-isopropyl-2-isopentyl-1,3-dimethoxypropane are used.

[0102] In the solid catalyst composition for olefin polymerization of the present invention, one or more compounds selected from those shown in the following general formula (2) may be listed as succinate diester compounds:

[0103]

[0104] In equation (2), R 6 and R 7 It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, optionally the same or different from each other; R 5 and R 8 It is a straight-chain alkyl or branched alkyl with 2 to 4 carbon atoms, which may be the same as or different from each other.

[0105] In the compound represented by general formula (2), R 5 and R 8 It is a straight-chain alkyl or branched alkyl with 2 to 4 carbon atoms, which may be the same as or different from each other.

[0106] R 5 and R 8 When it is a straight-chain alkyl or branched alkyl with 2 to 4 carbon atoms, specifically, ethyl, n-propyl, isopropyl, n-butyl or isobutyl can be listed.

[0107] In the compound represented by general formula (2), R 6 and R 7 It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same as or different from each other.

[0108] R 6 Or R 7 When the alkyl group has 1 to 4 carbon atoms, specifically, examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, or isobutyl.

[0109] In the solid catalyst composition for olefin polymerization of the present invention, there are no particular limitations on the succinate diester compound, and examples include one or more selected from the following substances:

[0110] Diethyl succinate, 2,3-dimethyldiethyl succinate, 2,3-diethyldiethyl succinate, 2,3-di-n-propyldiethyl succinate, 2,3-diisopropyldiethyl succinate, 2,3-di-n-butyldiethyl succinate, 2,3-diisobutyldiethyl succinate;

[0111] Dipropyl succinate, dipropyl 2,3-dimethylsuccinate, dipropyl 2,3-diethylsuccinate, dipropyl 2,3-dipropylsuccinate, dipropyl 2,3-diisopropylsuccinate, dipropyl 2,3-dibutylsuccinate, dipropyl 2,3-diisobutylsuccinate;

[0112] Diisopropyl succinate, 2,3-dimethyldiisopropyl succinate, 2,3-diethyldiisopropyl succinate, 2,3-di-n-propyldiisopropyl succinate, 2,3-diisopropyldiisopropyl succinate, 2,3-di-n-butyldiisopropyl succinate, 2,3-diisobutyldiisopropyl succinate;

[0113] Dibutyl succinate, dibutyl 2,3-dimethyl succinate, dibutyl 2,3-diethyl succinate, dibutyl 2,3-dipropyl succinate, dibutyl 2,3-diisopropyl succinate, dibutyl 2,3-dibutyl succinate, dibutyl 2,3-diisobutyl succinate;

[0114] Diisobutyl succinate, 2,3-dimethyldiisobutyl succinate, 2,3-diethyldiisobutyl succinate, 2,3-di-n-propyldiisobutyl succinate, 2,3-diisopropyldiisobutyl succinate, 2,3-di-n-butyldiisobutyl succinate, 2,3-diisobutyldiisobutyl succinate.

[0115] Among these dialkyl succinates, diethyl succinate, di-n-propyl succinate, di-n-butyl succinate, diisobutyl succinate, diethyl 2,3-di-n-propyl succinate, diethyl 2,3-diisopropyl succinate, di-n-propyl 2,3-diisopropyl succinate, di-n-propyl 2,3-diisopropyl succinate, diisopropyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, di-n-butyl 2,3-diisopropyl succinate, diisobutyl 2,3-diisopropyl succinate, and diisobutyl 2,3-diisopropyl succinate are preferred.

[0116] The solid catalyst composition for olefin polymerization of the present invention includes 1,3-diether compounds and succinate diester compounds without fluorene structures as essential components, but may also include other internal electron-donating compounds (hereinafter appropriately referred to as "other internal electron-donating compounds") as internal electron-donating compounds other than 1,3-diether compounds and succinate diester compounds without fluorene structures.

[0117] Other internally electron-donating compounds include one or more selected from carbonates, acyl halides, amides, nitriles, acid anhydrides, diethers, and carboxylic acid esters.

[0118] As other internally electron-donating compounds, specifically, one or more selected from ether carbonate compounds, cycloalkane dicarboxylic acid diesters, cycloalkene dicarboxylic acid diesters, malonate diesters, alkyl-substituted malonate diesters, maleic acid diesters, and other carboxylic acid diesters, diether compounds, etc.

[0119] More specifically, it is more preferably selected from one or more ether carbonate compounds such as (2-ethoxyethyl)methyl carbonate, (2-ethoxyethyl)ethyl carbonate, and (2-ethoxyethyl)phenyl carbonate, dialkyl malonate such as diisobutylmalonate and diethyl diisobutylmalonate, and cycloalkanes such as dimethyl cyclohexane-1,2-dicarboxylic acid ester.

[0120] On the other hand, in the solid catalyst composition for olefin polymerization of the present invention, the phthalate content is preferably 0.2% by mass or less (0.0 to 0.2% by mass), more preferably 0.1% by mass or less (0.0 to 0.1% by mass), and even more preferably 0.0% by mass (substantially free of phthalates (below the detection limit)).

[0121] In the solid catalyst composition for olefin polymerization of the present invention, when converting the solid component content, the sum of the content of 1,3-diether compounds without fluorene structures and the content of succinate diester compounds in the total amount of components contained is 13.0% by mass or more, preferably 14.0% by mass or more, and more preferably 15.0% by mass or more. Furthermore, in the solid catalyst composition for olefin polymerization of the present invention, when converting the solid component content, there is no particular upper limit to the sum of the content of 1,3-diether compounds without fluorene structures and the content of succinate diester compounds in the total amount of components contained, but the sum of the content of 1,3-diether compounds without fluorene structures and the content of succinate diester compounds in the total amount of components contained is preferably 25.0% by mass or less, and more preferably 21.0% by mass or less. By ensuring that the sum of the contents of 1,3-diether compounds without fluorene structures and succinate diester compounds in the total amount of components when performing solid component conversion is within the above-mentioned range, olefin polymers with excellent flowability and high rigidity can be easily manufactured when used for olefin polymerization.

[0122] In the solid catalyst composition for olefin polymerization of the present invention, when the solid component is converted, the content of titanium atoms in the total amount of the components is 2.0 to 6.0% by mass, preferably 2.5 to 5.0% by mass, more preferably 2.5 to 4.0% by mass. By ensuring that the content of titanium atoms in the total amount of the components when the solid component is converted is within the above range, it is possible to easily produce olefin polymers with excellent flowability and high rigidity when used for olefin polymerization.

[0123] In the solid catalyst composition for olefin polymerization of the present invention, the molar ratio (S / T), expressed as the molar content (S) of the succinate diester compound in the total amount of the contained components to the molar content (T) of titanium in the total amount of the contained components, is 0.71 to 1.30, preferably 0.71 to 1.10, and more preferably 0.80 to 1.10. By keeping the above molar ratio (S / T) within the above range, when supplied for olefin polymerization, it is possible to easily produce olefin polymers with excellent flowability and high rigidity.

[0124] In the solid catalyst composition for olefin polymerization of the present invention, the molar ratio (E / S), expressed as the molar content (E) of the 1,3-diether compound without a fluorene structure in the total amount of the contained components to the molar content (S) of the succinate diester compound in the total amount of the contained components, is 0.10 to 0.70, preferably 0.10 to 0.50, and more preferably 0.10 to 0.40. By keeping the above molar ratio (E / S) within the above range, when supplied for olefin polymerization, it is possible to easily produce olefin polymers with excellent flowability and high rigidity.

[0125] The total pore volume of the solid catalyst for olefin polymerization of the present invention, measured by mercury porosimetry, is 0.3~1.0 cm³ with a diameter of less than 1 μm. 3 / g, preferably 0.3~0.8cm 3 / g, more preferably 0.3~0.6cm 3 / g. The total pore volume of the solid catalyst component for olefin polymerization of the present invention, with a diameter of less than 1 μm as determined by mercury porosimetry, is within the above-mentioned range. Therefore, when used for block polymerization of olefins, it can adequately retain the rubber component within the particles, and can easily produce block copolymers with excellent flowability.

[0126] The solid catalyst for olefin polymerization of the present invention has a specific surface area of ​​200 m², as determined by mercury porosimetry. 2 / g or more, preferably 300~500m 2 / g, more preferably 350~500m 2 / g. When the specific surface area of ​​the solid catalyst component for olefin polymerization of the present invention, as determined by mercury porosimetry, is within the above-mentioned range, when supplied for olefin polymerization, particularly for olefin copolymerization, the olefins enter the pores formed on the surface of the solid catalyst component, and the polymerization reaction is carried out within these pores. Therefore, olefin polymers can be prepared under high polymerization activity, and the stickiness of the solid catalyst component surface accompanying copolymer formation can be suppressed, and the polymerization reaction can be carried out easily under high operability.

[0127] The total pore volume and specific surface area of ​​the solid catalyst component for olefin polymerization of the present invention, measured by mercury porosimetry, with a diameter of less than 1 μm, are within the above-mentioned range. Furthermore, the total content of 1,3-diether compounds without fluorene structures and the total content of succinate diester compounds in the total amount of the components, the molar ratio (S / T) of the molar content (S) of succinate diester compounds to the molar content (T) of titanium, and the molar ratio (E / S) of the molar content (E) of 1,3-diether compounds without fluorene structures to the molar content (S) of succinate diester compounds are the values ​​specified above. This enables the olefin polymer obtained using this solid catalyst component to maintain high rigidity, increase melt flow rate, and reduce the amount of low molecular weight polymers generated.

[0128] The solid catalyst component for olefin polymerization in this invention may include polysiloxane.

[0129] The solid catalyst for olefin polymerization in this invention is composed of a substance containing polysiloxane, which makes it easy to improve the stereoregularity or crystallinity of the resulting polymer during olefin polymerization, and further makes it easy to reduce the amount of polymer powder generated.

[0130] Polysiloxanes are polymers with siloxane bonds (-Si-O- bonds) in their main chain, also known as silicone oils, and have a viscosity of 0.02~100.00 cm⁻¹ at 25°C. 2 / s (2~10000 centiliters), more preferably 0.03~5.00cm 2 Chains, partially hydrogenated, cyclic, or modified polysiloxanes, in a liquid or viscous state at room temperature, with a concentration of 3~500 centiliters per second.

[0131] Examples of chain-like polysiloxanes include dimethyl polysiloxane and methylphenyl polysiloxane; examples of partially hydrogenated polysiloxanes include methylhydrogen polysiloxanes with a hydrogenation rate of 10-80%; and examples of cyclic polysiloxanes include one or more selected from hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 2,4,6-trimethylcyclotrisiloxane, and 2,4,6,8-tetramethylcyclotetrasiloxane.

[0132] The solid catalyst component for olefin polymerization of the present invention is preferably a solid catalyst component prepared by contacting the above-mentioned dialkoxy magnesium, titanium halide compound and succinate diester compound in the presence of an inactive organic solvent.

[0133] In this invention, the preferred non-reactive organic solvent is one that dissolves the titanium halide compound without dissolving magnesium dialkoxy. Specifically, it can be selected from one or more saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,2-diethylcyclohexane, methylcyclohexene, decahydronaphthalene, and mineral oil; aromatic hydrocarbon compounds such as benzene, toluene, xylene, and ethylbenzene; and halogenated hydrocarbon compounds such as o-dichlorobenzene, dichloromethane, 1,2-dichlorobenzene, carbon tetrachloride, and dichloroethane.

[0134] As the aforementioned inactive organic solvent, a saturated hydrocarbon compound or aromatic hydrocarbon compound with a boiling point of about 50 to 200°C and which is liquid at room temperature is preferably used. Among them, one or more of hexane, heptane, octane, ethylcyclohexane, mineral oil, toluene, xylene, and ethylbenzene are preferred, and any one or more of hexane, heptane, ethylcyclohexane, and toluene are particularly preferred.

[0135] In the solid catalyst composition for olefin polymerization of the present invention, magnesium, titanium, halogen, 1,3-diether compounds without fluorene structures, and succinate diester compounds may be contained in desired amounts as long as the total content of the aforementioned 1,3-diether compounds without fluorene structures and succinate diester compounds, the molar ratio expressed as the content (molar amount) of the aforementioned succinate diester compounds / the content (molar amount) of titanium, and the molar ratio expressed as the content (molar amount) of 1,3-diether compounds without fluorene structures / succinate diester compounds satisfy the above-mentioned requirements.

[0136] The solid catalyst for olefin polymerization of the present invention preferably contains 3.0 to 6.0% by mass of titanium, more preferably 3.5 to 6.0% by mass, and even more preferably 4.0 to 6.0% by mass.

[0137] The solid catalyst for olefin polymerization of the present invention preferably contains 15.0 to 25.0% by mass of magnesium, more preferably 16.0 to 23.0% by mass, even more preferably 17.0 to 22.0% by mass, and even more preferably 18.0 to 21.0% by mass.

[0138] The solid catalyst for olefin polymerization of the present invention preferably contains 50.0 to 70.0% by mass of halogen, more preferably 55.0 to 68.0% by mass, even more preferably 58.0 to 67.0% by mass, and even more preferably 60.0 to 66.0% by mass.

[0139] In this application, the titanium content in the solid catalyst for olefin polymerization refers to the value measured according to the method (redox titration) described in JIS 8311-1997 "Method for quantifying titanium in titanium ore".

[0140] In addition, in this application, the magnesium content in the solid catalyst component for olefin polymerization refers to the value determined by EDTA titration method, which involves dissolving the solid catalyst component for olefin polymerization in hydrochloric acid solution and titrating it with EDTA solution.

[0141] In addition, in this application, the halogen content in the solid catalyst component for olefin polymerization refers to the value obtained as follows: after the solid catalyst component is treated with a mixed solution of sulfuric acid and pure water to prepare an aqueous solution, a specified amount is taken and the halogen is determined by silver nitrate titration using a standard silver nitrate solution.

[0142] Furthermore, in this application, the percentages of 1,3-diether compounds and succinate diester compounds without fluorene structures, as well as other internal electron-donating compounds added as needed, contained in the solid catalyst components for olefin polymerization refer to the values ​​obtained by hydrolyzing the solid catalyst components for olefin polymerization, extracting the 1,3-diether compounds and succinate diester compounds without fluorene structures using aromatic solvents, and then measuring the solution using gas chromatography-FID (Flame Ionization Detector).

[0143] The solid catalyst component for olefin polymerization of the present invention can be suitably manufactured by the manufacturing method of the solid catalyst component for olefin polymerization of the present invention described below.

[0144] Next, the method for manufacturing the solid catalyst component for olefin polymerization of the present invention will be described.

[0145] The method for manufacturing the solid catalyst component for olefin polymerization of the present invention is characterized in that,

[0146] A method for producing solid catalyst components for olefin polymerization by contacting magnesium dialkoxy, titanium halide compounds, 1,3-diether compounds without fluorene structures, and succinate diester compounds together.

[0147] The titanium halide compound is contacted with the dialkoxymagnesium multiple times.

[0148] When the titanium halide compound is first contacted with the dialkoxy magnesium, the contact amount of the titanium halide compound is 1.5 to 10.0 mol relative to 1.0 mol of the dialkoxy magnesium.

[0149] The total amount of the titanium halide compound used is 5.0 to 18.0 mol relative to 1.0 mol of the magnesium diekoxy.

[0150] The total molar amount of the 1,3-diether compound without the fluorene structure and the molar amount of the succinate diester compound is 0.10 to 0.20 moles relative to 1.0 mole of the magnesium dialkoxy.

[0151] The molar ratio (S / T) of the succinate diester compound relative to the total molar amount (T) of the titanium halide compound is 0.020 to 0.040.

[0152] The molar ratio (E / S) of the 1,3-diether compound without the fluorene structure relative to the molar amount (S) of the succinate diester compound is 0.50 or less.

[0153] The dialkoxy magnesium is composed of secondary particles, which are aggregates of primary particles with an average particle size of less than 2 μm, and has a specific surface area of ​​10 m². 2 / g or more and less than 50m 2 / g, with a particle size distribution index (SPAN) of less than 1.30.

[0154] The dialkoxy magnesium used in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention is the same as the dialkoxy magnesium described above in the solid catalyst component for olefin polymerization of the present invention.

[0155] The dialkoxy magnesium used in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention is composed of secondary particles, which are aggregates of primary particles with an average particle size of less than 2 μm. Furthermore, the dialkoxy magnesium used in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention has a specific surface area of ​​10 m². 2 / g or more and less than 50m 2 / g, more preferably 10~50m 2 / g, more preferably 10~40m 2 / g. Furthermore, the particle size distribution index (SPAN) of the magnesium dialkoxy used in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention is 1.30 or less, preferably 0.60 to 1.00, and more preferably 0.70 to 0.90.

[0156] The 1,3-diether compound and succinate diester compound without fluorene structure used in the manufacturing method of the solid catalyst component for olefin polymerization of the present invention are the same as the 1,3-diether compound and succinate diester compound without fluorene structure mentioned above in the solid catalyst component for olefin polymerization of the present invention.

[0157] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, a titanium halide compound is contacted with magnesium dialkoxy multiple times. During the first contact between the titanium halide compound and magnesium dialkoxy, 1.5 to 10.0 moles of titanium halide compound, preferably 2.0 to 8.0 moles, are used relative to 1.0 mole of magnesium dialkoxy. Furthermore, 5.0 to 18.0 moles of titanium halide compound are used relative to 1.0 mole of magnesium dialkoxy, and 5.0 to 15.0 moles of titanium halide compound are used relative to 1.0 mole of magnesium dialkoxy. More preferably, 5.0 to 12.0 moles of titanium halide compound are used relative to 1.0 mole of magnesium dialkoxy.

[0158] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, when the titanium halide compound is first contacted with dialkoxymagnesium, by controlling the amount of titanium halide compound relative to dialkoxymagnesium within the above-mentioned range, a highly active solid catalyst component for olefin polymerization can be prepared with a small amount of titanium halide compound.

[0159] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, by controlling the total amount of titanium compound relative to 1.0 moles of dialkoxy magnesium within the above-mentioned range, a highly active solid catalyst component for olefin polymerization can be prepared with a small amount of titanium halide compound.

[0160] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the succinate diester compound is preferably 0.08 to 0.16 mol relative to 1.0 mol of dialkoxy magnesium, more preferably 0.09 to 0.15 mol relative to 1.0 mol of dialkoxy magnesium, and more preferably 0.10 to 0.14 mol relative to 1.0 mol of dialkoxy magnesium.

[0161] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, by controlling the amount of succinate diester compound relative to 1.0 moles of dialkoxy magnesium within the above-mentioned range, it is possible to suppress the excessive loading of titanium halide compound on the support and to fully load the succinate diester compound.

[0162] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the total molar amount of the 1,3-diether compound without fluorene structure and the succinate diester compound relative to 1.0 mole of dialkoxy magnesium is 0.10 to 0.20 moles, and the total molar amount of the 1,3-diether compound without fluorene structure and the succinate diester compound relative to 1.0 mole of dialkoxy magnesium is 0.12 to 0.18 moles.

[0163] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, by controlling the total amount of the molar amount of the 1,3-diether compound without the fluorene structure relative to 1.0 mole of dialkoxy magnesium and the molar amount of the succinate diester compound relative to 1.0 mole of dialkoxy magnesium within the above-mentioned range, it is possible to suppress the excessive loading of the titanium halide compound on the support and to fully load the 1,3-diether compound and the succinate diester compound.

[0164] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the molar ratio (S / T) expressed as the molar amount (S) of the succinate diester compound to the total molar amount (T) of the titanium halide compound is 0.020 to 0.040, preferably 0.022 to 0.030, and more preferably 0.024 to 0.030.

[0165] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, by controlling the molar ratio (S / T) of the succinate diester compound to the total molar amount (T) of the titanium halide compound within the above-mentioned range, the excessive loading of the titanium halide compound on the support can be suppressed, and the 1,3-diether compound and the succinate diester compound can be sufficiently loaded.

[0166] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the molar ratio (E / S) of the molar amount (E) of the 1,3-diether compound without fluorene structure to the molar amount (S) of the succinate diester compound is 0.50 or less, preferably 0.10 to 0.40, and more preferably 0.20 to 0.40.

[0167] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, by controlling the molar ratio (E / S) of the 1,3-diether compound without a fluorene structure to the molar amount (S) of the succinate diester compound within the above-mentioned range, the excessive loading of the titanium halide compound on the support can be suppressed, and the 1,3-diether compound and the succinate diester compound can be sufficiently loaded.

[0168] More specifically, as a method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the following method can be cited as an example: magnesium dialkoxy, a titanium halide compound, a 1,3-diether compound without a fluorene structure, and a succinate diester compound are suspended in an inactive hydrocarbon solvent, and after being heated and contacted for a specified time, a titanium halide compound is further added to the obtained suspension, and the mixture is heated and contacted to obtain a solid product. The solid product is then washed with a hydrocarbon solvent to obtain the target solid catalyst component for olefin polymerization.

[0169] As the aforementioned inactive organic solvent, it is preferred to be an inactive organic solvent that is liquid at room temperature (20°C) and has a boiling point of 50 to 150°C, and more preferably an aromatic hydrocarbon compound or a saturated hydrocarbon compound that is liquid at room temperature and has a boiling point of 50 to 150°C.

[0170] Specifically, one or more of the following can be listed as non-reactive organic solvents: straight-chain aliphatic hydrocarbons such as hexane, heptane, and decane; branched-chain aliphatic hydrocarbons such as methylheptane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane; and aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

[0171] Among the aforementioned inactive organic solvents, aromatic hydrocarbon compounds that are liquid at room temperature and have a boiling point of 50-150℃ are suitable because they can improve the activity of the obtained solid catalyst components and improve the stereoregularity of the obtained polymer.

[0172] The heating temperature is preferably 70~150℃, more preferably 80~120℃, and even more preferably 90~115℃.

[0173] The heating time is preferably 30 to 240 minutes, more preferably 60 to 180 minutes, and even more preferably 60 to 120 minutes.

[0174] There is no particular limitation on the number of times titanium halide compounds can be added relative to the above suspension.

[0175] When adding titanium halide compounds to the above suspension multiple times, the heating temperature and the heating time for each addition should be within the above range.

[0176] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the timing for contacting the succinate diester compound with dialkoxymagnesium can be listed as follows: before the first contact of the titanium halide compound with dialkoxymagnesium, after the first contact of the titanium halide compound with dialkoxymagnesium, before and after multiple contactes of the titanium halide compound, and before washing the solid product with a hydrocarbon solvent. Furthermore, in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the timing for contacting the succinate diester compound with dialkoxymagnesium is preferably after the first contact of the titanium halide compound with dialkoxymagnesium, from the viewpoint of suppressing particle aggregation of the support and fully loading the succinate diester compound.

[0177] In the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the timing for contacting the 1,3-diether compound without a fluorene structure with magnesium dialoxy can be exemplified as follows: before the first contact of the titanium halide compound with magnesium dialoxy, after the first contact of the titanium halide compound with magnesium dialoxy, before and after multiple contactes of the titanium halide compound, and before washing the solid product with a hydrocarbon solvent. Furthermore, in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the timing for contacting the 1,3-diether compound without a fluorene structure with magnesium dialoxy is preferably after the first contact of the titanium halide compound with magnesium dialoxy, from the perspective of suppressing particle aggregation of the support and fully loading the 1,3-diether compound.

[0178] Furthermore, in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, the 1,3-diether compound without a fluorene structure can be contacted together with the succinate diester compound, or the succinate diester compound can be contacted with the succinate diester compound first, followed by contact with the 1,3-diether compound without a fluorene structure. Moreover, in the method for manufacturing the solid catalyst component for olefin polymerization of the present invention, by contacting the succinate diester compound with the succinate diester compound first, and then contacting the 1,3-diether compound without a fluorene structure with the succinate diester compound, excessive loading of the 1,3-diether on the support is suppressed, and sufficient loading of the succinate diester compound is achieved. From this perspective, it is preferable.

[0179] It should be noted that in the above preparation method, in addition to the diester compound of succinic acid, other internal electron donor compounds can be used in combination. Further, the above contact can be carried out in the coexistence of other reaction reagents such as silicon, phosphorus, and aluminum, and surfactants.

[0180] In the method for producing a solid catalyst component for olefin polymerization of the present invention, the preferred mode of the obtained solid catalyst component for olefin polymerization is as described in the description of the solid catalyst component for olefin polymerization of the present invention.

[0181] Next, the catalyst for olefin polymerization of the present invention will be described.

[0182] The catalyst for olefin polymerization of the present invention is characterized in that it contains:

[0183] (I) The solid catalyst component for olefin polymerization of the present invention; and

[0184] (II) An organoaluminum compound represented by the following general formula (3).

[0185]

[0186] In formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, p is 0 < p ≤ 3, and when there are multiple Rs 9 , each R 5 is optionally the same as or different from each other, and when there are multiple Qs, each Q is optionally the same as or different from each other.

[0187] As the catalyst for olefin polymerization of the present invention, it preferably contains:

[0188] (I) The solid catalyst component for olefin polymerization of the present invention;

[0189] (II) An organoaluminum compound represented by the following general formula (3); and

[0190] (III) An external electron donor compound.

[0191]

[0192] In formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and when there are multiple Rs 9 , each R 5 is optionally the same as or different from each other, and when there are multiple Qs, each Q is optionally the same as or different from each other.

[0193] The details of the solid catalyst component for olefin polymerization of the present invention, which constitutes the catalyst for olefin polymerization of the present invention, are as described above.

[0194] In the olefin polymerization catalyst of the present invention, (II) the organoaluminum compound is represented by the following general formula (3):

[0195]

[0196] In formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen atom, p is 0 < p ≤ 3, and when there are multiple Rs 9 , each R 5 is optionally the same as or different from each other. When there are multiple Qs, each Q is optionally the same as or different from each other.

[0197] In the compound represented by the general formula (3), p is 0 < p ≤ 3. Specifically, examples of p include 1, 2, or 3.

[0198] Specific examples of such (II) organoaluminum compounds include one or more selected from trialkylaluminums such as triethylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, triisobutylaluminum, etc., haloalkylaluminums such as diethylaluminum chloride, diethylaluminum bromide, etc., and diethylaluminum hydride, etc. Preferably, one or more selected from haloalkylaluminums such as diethylaluminum chloride, trialkylaluminums such as triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, etc. are used, and more preferably, one or more selected from triethylaluminum and triisobutylaluminum are used.

[0199] As the (III) external electron donor compound constituting the olefin polymerization catalyst of the present invention, compounds represented by the following general formula (5) can be cited.

[0200]

[0201] In formula (5), r is 0 or 1 to 2, s is 0 or 1 to 2, r + s is 0 or 1 to 4, R 11 , R 12 or R 13 is a hydrogen atom or any group selected from linear or branched alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl groups, phenyl groups, allyl groups, and aralkyl groups, optionally containing heteroatoms, and optionally the same as or different from each other. R 12 and R 13 are optionally bonded to form a cyclic shape, and R 11 , R 12 or R 13 are optionally the same or different. In addition, R 14 is any group selected from alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups, phenyl groups, vinyl groups, allyl groups, and aralkyl groups, optionally containing heteroatoms.

[0202] In the compound represented by the above general formula (5), R 11It is a hydrogen atom or any group selected from straight-chain or branched alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl groups, phenyl groups, allyl groups, and aralkyl groups, optionally containing heteroatoms.

[0203] As R 11 Preferably, it is a straight-chain or branched alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, and particularly preferably a straight-chain or branched alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms.

[0204] In the compounds represented by the above general formula (5), R 12 Or R 13 It is a hydrogen atom or any group selected from straight-chain or branched alkyl groups having 1 to 12 carbon atoms, substituted or unsubstituted cycloalkyl groups, phenyl groups, allyl groups, and aralkyl groups, optionally containing heteroatoms.

[0205] As R 12 Or R 13 Preferably, straight-chain or branched alkyl groups having 1 to 10 carbon atoms, or cycloalkyl groups having 5 to 8 carbon atoms, and particularly preferably straight-chain or branched alkyl groups having 1 to 8 carbon atoms, or cycloalkyl groups having 5 to 8 carbon atoms.

[0206] Additionally, R 12 Or R 13 Optional bonding forms a ring shape, at which point the ring shape (NR) is formed. 12 Or R 13 Preferred are perhydroquinoline and perhydroisoquinoline.

[0207] In the compounds represented by the above general formula (5), R 11 R 12 and R 13 Choose either the same or different.

[0208] In the compounds represented by the above general formula (5), R 14 It is any group selected from alkyl, cycloalkyl, phenyl, allyl and aralkyl groups having 1 to 4 carbon atoms, optionally containing heteroatoms.

[0209] As R 14 Preferably, it is a straight-chain or branched alkyl group with 1 to 4 carbon atoms.

[0210] In the compounds shown in the above general formula (5), r is 0 or 1~2. Specifically, r can be 0, 1 or 2.

[0211] In the compounds represented by the general formula (5) above, s is 0 or 1 to 2. Specifically, 0, 1 or 2 can be listed as s.

[0212] In the compounds shown in the general formula (5) above, r+s is 0 or 1~4. Specifically, r+s can be 0, 1, 2, 3 or 4.

[0213] Specifically, as a compound represented by the above general formula (5), one or more organosilicon compounds selected from phenylalkoxysilane, alkylalkoxysilane, phenylalkylalkoxysilane, cycloalkylalkoxysilane, cycloalkylalkylalkoxysilane, (alkylamino)alkoxysilane, alkyl(alkylamino)alkoxysilane, alkyl(alkylamino)silane, alkylaminosilane, alkylaminosilane, etc. can be listed.

[0214] As compounds in the above general formula (5) where s is 0, those selected from di-n-propyl dimethoxysilane, diisopropyl dimethoxysilane, di-n-butyl dimethoxysilane, diisobutyl dimethoxysilane, di-tert-butyl dimethoxysilane, tert-butylmethyl dimethoxysilane, tert-butylethyl dimethoxysilane, di-n-butyl diethoxysilane, tert-butyltrimethoxysilane, tert-butyltriethoxysilane, dicyclohexyl dimethoxysilane, dicyclohexyl diethoxysilane, cyclohexylmethyl dimethoxysilane, and cyclohexylmethyl diethoxysilane are particularly preferred. One or more organosilicon compounds selected from oxysilane, cyclohexylethyldimethoxysilane, cyclohexylethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, cyclopentylmethyldimethoxysilane, cyclopentylmethyldiethoxysilane, cyclopentylethyldiethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylcyclopentyldiethoxysilane, 3-methylcyclohexylcyclopentyldimethoxysilane, 4-methylcyclohexylcyclopentyldimethoxysilane, and 3,5-dimethylcyclohexylcyclopentyldimethoxysilane.

[0215] As compounds in the above general formula (5) where s is 1 or 2, examples include one or more organosilicon compounds selected from di(alkylamino)dialkoxysilane, (alkylamino)(cycloalkylamino)dialkoxysilane, (alkylamino)(alkyl)dialkoxysilane, di(cycloalkylamino)dialkoxysilane, vinyl(alkylamino)dialkoxysilane, allyl(alkylamino)dialkoxysilane, (alkoxyamino)trialkoxysilane, (alkylamino)trialkoxysilane, (cycloalkylamino)trialkoxysilane, etc., with particular preference being ethyl( The following are organosilicon compounds selected from tert-butylamino)dimethoxysilane, cyclohexyl(cyclohexylamino)dimethoxysilane, ethyl(tert-butylamino)dimethoxysilane, bis(cyclohexylamino)dimethoxysilane, bis(perhydroisoquinolinyl)dimethoxysilane, bis(perhydroquinolinyl)dimethoxysilane, ethyl(isoquinolinyl)dimethoxysilane, diethylaminotrimethoxysilane, diethylaminotriethoxysilane, etc., wherein one or more organosilicon compounds are selected from bis(perhydroisoquinolinyl)dimethoxysilane, diethylaminotrimethoxysilane, or diethylaminotriethoxysilane.

[0216] It should be noted that the compounds shown in the above general formula (5) can be used in combination of two or more.

[0217] The catalyst for olefin polymerization of the present invention is a catalyst comprising (I) the solid catalyst component for olefin polymerization of the present invention and (II) the organoaluminum compound represented by general formula (3); or a catalyst comprising (I) the solid catalyst component for olefin polymerization of the present invention, (II) the organoaluminum compound represented by general formula (3) and (III) an externally electron-donating compound; i.e., contact materials of these, etc.

[0218] The catalyst for olefin polymerization of the present invention can be a substance prepared by contacting (I) the solid catalyst component for olefin polymerization of the present invention and (II) the organoaluminum compound of general formula (3), or (III) the externally electron-donating compound, in the absence of olefins, as described below, or it can be a substance obtained by contacting in the presence of olefins (within the polymerization system).

[0219] In the catalyst for olefin polymerization of the present invention, the content ratio of each component is arbitrary and not particularly limited, as long as it does not affect the effect of the present invention. Generally, relative to 1 mole of titanium atoms in the solid catalyst component for olefin polymerization described in (I) above, it is preferable to contain 1 to 2000 moles of the organoaluminum compound described in (II), more preferably 50 to 1000 moles. In addition, relative to 1 mole of the organoaluminum compound described in (II) above, the catalyst for olefin polymerization of the present invention preferably contains 0.002 to 10.000 moles of the externally electron-donating compound described in (III) above, more preferably 0.010 to 2.000 moles, and even more preferably 0.010 to 0.500 moles.

[0220] According to the present invention, a catalyst for olefin polymerization can be provided that enables the easy manufacture of olefin polymers containing internally electron-donating compounds other than phthalates, exhibiting excellent melt flowability and high rigidity. Furthermore, according to the present invention, a solid catalyst for olefin polymerization can be provided that, in addition to possessing the aforementioned excellent melt flowability and high rigidity, also improves the particle size and copolymerization properties of the catalyst.

[0221] Next, the method for manufacturing the olefin polymer of the present invention will be described.

[0222] The method for manufacturing olefin polymers of the present invention is characterized in that the polymerization of olefins is carried out in the presence of the catalyst for olefin polymerization of the present invention.

[0223] In the method for manufacturing olefin polymers of the present invention, the polymerization of olefins can be either homopolymerization or copolymerization.

[0224] In the method for manufacturing olefin polymers of the present invention, the olefin to be polymerized may be selected from one or more of ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc., wherein it is suitable to select one or more of ethylene, propylene and 1-butene, and propylene is more suitable.

[0225] When the olefin mentioned above is propylene, it can be a homopolymer of propylene or a copolymer of propylene with other α-olefins.

[0226] As olefins copolymerized with propylene, one or more of the following can be listed: ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, vinylcyclohexane, etc.

[0227] The catalyst for olefin polymerization of the present invention is prepared in the presence of olefins (within the polymerization system). The ratio of each component is arbitrary and not particularly limited, as long as it does not affect the effect of the present invention. Generally, the organoaluminum compound (II) is preferably in contact with 1 mole of titanium atoms in the solid catalyst component (I) for olefin polymerization at a ratio of 1 to 2000 moles, more preferably 50 to 1000 moles. Furthermore, the externally electron-donating compound (III) is preferably in contact with 0.002 to 10.000 moles, more preferably 0.010 to 2.000 moles, and even more preferably 0.010 to 0.500 moles, of 1 mole of the organoaluminum compound (II).

[0228] The contact order of the components constituting the catalyst for olefin polymerization is arbitrary, but ideally, the above-mentioned organoaluminum compound (II) is first loaded into the polymerization system, and when using the external electron-donating compound (III), the above-mentioned external electron-donating compound (III) is then loaded and contacted, and then the above-mentioned solid catalyst component (I) for olefin polymerization is loaded and contacted.

[0229] The method for manufacturing the olefin polymer of the present invention can be carried out in the presence of an organic solvent or in the absence of an organic solvent.

[0230] Furthermore, olefin monomers such as propylene can be used in either gaseous or liquid states. The polymerization temperature is preferably below 200°C, more preferably below 100°C, and the polymerization pressure is preferably below 10 MPa, more preferably below 5 MPa. Additionally, the polymerization of olefins can be either continuous polymerization or batch polymerization. Moreover, the polymerization reaction can be carried out in one stage or in two or more stages.

[0231] Furthermore, when using the catalyst for olefin polymerization of the present invention to polymerize olefins (also known as formal polymerization), in order to further improve the catalytic activity, stereoregularity and particulate properties of the resulting polymer, it is preferable to perform prepolymerization before formal polymerization. During prepolymerization, the same olefins or monomers such as styrene as those used in formal polymerization can be used.

[0232] During prepolymerization, the contact order of the components constituting the catalyst for olefin polymerization and the monomers (olefins) is arbitrary, but it is preferred that (II) organoaluminum compound is first loaded into the prepolymerization system set in an inactive gas atmosphere or an olefin gas atmosphere, and then (I) solid catalyst component for olefin polymerization of the present invention is loaded and brought into contact, so that olefins such as propylene are contacted individually, or a mixture of one or more olefins such as propylene and other olefins are contacted.

[0233] In the above-mentioned prepolymerization, it is preferable that when (III) external electron-donating compound is further added to the prepolymerization system, (II) organoaluminum compound is first added to the prepolymerization system in an inactive gas atmosphere or an olefin gas atmosphere, and then (III) external electron-donating compound is added to make them contact, and then (I) solid catalyst component for olefin polymerization of the present invention is further contacted, and olefins such as propylene are contacted individually or mixed with one or more olefins such as propylene and other olefins.

[0234] In the method for manufacturing olefin polymers of the present invention, the polymerization methods include slurry polymerization using solvents such as cyclohexane and heptane, bulk polymerization using solvents such as liquefied propylene, and gas-phase polymerization that does not substantially use solvents, with bulk polymerization or gas-phase polymerization being preferred.

[0235] In the case of copolymerizing propylene with other α-olefin monomers, a typical example is random copolymerization in which propylene is prepared as a comonomer with a small amount of ethylene and polymerized in one stage; and so-called propylene-ethylene block copolymerization, in which propylene is homopolymerized in a first stage (first polymerization tank) and copolymerized with other α-olefins such as ethylene in a second stage (second polymerization tank) or more, preferably block copolymerization of propylene with other α-olefins.

[0236] Block copolymers obtained through block copolymerization refer to polymers containing segments with continuously varying compositions of two or more monomers. They are polymer chains (segments) with different primary structures, such as monomer types, comonomer types, comonomer composition, comonomer content, comonomer arrangement, and stereoregularity, connected in a single molecular chain.

[0237] In the method for manufacturing olefin polymers of the present invention, the block copolymerization reaction of propylene with other α-olefins can generally be carried out as follows: in the presence of the catalyst for olefin polymerization of the present invention, propylene is contacted alone or with a small amount of α-olefin (ethylene, etc.) in the front stage, and then propylene is contacted with α-olefin (ethylene, etc.) in the rear stage. It should be noted that the above-described front-stage polymerization reaction can be repeated multiple times, and the above-described rear-stage polymerization reaction can also be repeated multiple times through multi-stage reactions.

[0238] Specifically, the block copolymerization reaction of propylene with other α-olefins is preferably carried out as follows: polymerization is carried out with the polymerization temperature and time adjusted so that the ratio of the polypropylene portion (in the final copolymer) is 20 to 90% by mass in the first stage, and then propylene and ethylene or other α-olefins are introduced in the second stage and polymerization is carried out with the ratio of the rubber portion (such as ethylene-propylene rubber (EPR) in the final copolymer) being 10 to 80% by mass.

[0239] The polymerization temperature in both the front and rear stages is preferably below 200°C, more preferably below 100°C, even more preferably 65°C to 80°C, and even more preferably 75°C to 80°C. The polymerization pressure is preferably below 10 MPa, more preferably below 6 MPa, and even more preferably below 5 MPa.

[0240] In the above copolymerization reaction, any polymerization method, such as continuous polymerization or batch polymerization, can be used. The polymerization reaction can be carried out in one stage or in two or more stages.

[0241] In addition, the polymerization time (residence time in the reactor) is preferably 1 minute to 5 hours in each polymerization stage in the front or back section, or in continuous polymerization.

[0242] Examples of polymerization methods include slurry polymerization using solvents such as cyclohexane and heptane, bulk polymerization using solvents such as liquefied propylene, and gas-phase polymerization that does not use solvents in essence. Bulk polymerization or gas-phase polymerization is the most suitable method.

[0243] In particular, ethylene-propylene block copolymers contain EPR (a copolymer of ethylene and propylene). If EPR seeps onto the surface of polymer particles, it causes the particles to become sticky (adhesive) and their flowability to deteriorate. In polymer manufacturing equipment, the deterioration of particle flowability is a major cause of reduced equipment operability. Therefore, it is desirable to select a manufacturing method that can inhibit the seepage of EPR onto the particle surface.

[0244] According to the present invention, a method for easily manufacturing olefin polymers with excellent melt flowability and high rigidity can be provided.

[0245] Next, the olefin polymers of the present invention will be described.

[0246] The olefin polymers of the present invention are characterized in that (a) the melt flow rate is 0.5 to 200 g / 10 min, (b) the flexural modulus is 1900 MPa or higher, and (c) the molecular weight distribution is Mw / Mn ≥ 6.0 and Mz / Mw ≥ 4.0.

[0247] In the olefin polymers of the present invention, the melt flow rate (MFR), which represents the melt flowability of the olefin polymer, is 0.5 to 200 g / 10 min, preferably 10 to 160 g / 10 min.

[0248] In the olefin polymers of the present invention, sufficient formability can be easily achieved in practical applications by ensuring that the melt flow rate (MFR) is within the above-mentioned range.

[0249] It should be noted that in this application document, melt flow rate (MFR) refers to the value measured based on ASTM D 1238 and JIS K7210.

[0250] The flexural modulus (FM) of the olefin polymer of the present invention is 1900 MPa or more, preferably 2000 to 2300 MPa, and more preferably 2000 to 2200 MPa.

[0251] The olefin polymers of the present invention exhibit excellent formability and can easily achieve high rigidity by having a flexural modulus (FM) within the above-mentioned range.

[0252] It should be noted that, in this application document, the flexural modulus (FM) of olefin polymers refers to the value (in MPa) measured using NEX30III3EG manufactured by Nissei Resin Kogyo Co., Ltd., with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 80.0 mm, produced under conditions of a molding temperature of 200°C and a mold temperature of 40°C.

[0253] The olefin polymers of the present invention, by satisfying the above-mentioned limitations on melt flow rate and flexural modulus, have sufficient fluidity in practical applications, and therefore have excellent formability and can easily exhibit excellent rigidity.

[0254] The xylene-soluble component (c-XS) of the olefin polymer of the present invention is 3.0% or less, preferably 2.5% or less, and more preferably 2.0% or less.

[0255] In the olefin polymers of the present invention, since the xylene-soluble component (c-XS) is within the above-mentioned range, the low molecular weight polymer is reduced. Therefore, the low molecular weight polymer will not adversely affect the physical properties and molding processability of the polymer, and polypropylene that balances high melt flowability and high rigidity can be manufactured.

[0256] It should be noted that in this application, the xylene-soluble component (c-XS) of the olefin polymer is a value determined by the following procedure: 4.0 g of polymer (polypropylene) and 200 ml of p-xylene are placed in a flask equipped with a stirrer. The external temperature is raised to the same level as the boiling point of xylene (approximately 150°C), and the p-xylene in the flask is kept at the boiling point temperature (137-138°C) while the polymer is dissolved over 2 hours. The solution is cooled to 23°C over 1 hour, and the insoluble and dissolved components are separated by filtration. The solution containing the dissolved component is collected and heated (dried) under reduced pressure to evaporate the p-xylene. The weight of the residue is calculated, and the relative proportion (mass %) to the polymer (polypropylene) is calculated to determine the xylene-soluble component (XS).

[0257] The molecular weight distribution (Mw / Mn) of the olefin polymer of the present invention is 6.0 or more, preferably 6.5 to 15.0, and more preferably 7.0 to 10.0.

[0258] Furthermore, the molecular weight distribution of the olefin polymer of the present invention, which is the ratio of Z-average molecular weight Mz to mass-average molecular weight Mw, as shown by Mz / Mw, is 4.0 or more, preferably 4.0 to 8.0, and more preferably 4.5 to 6.0.

[0259] In the olefin polymers of the present invention, the molecular weight distributions Mw / Mn and Mz / Mw are within the above-mentioned range, thereby becoming olefin polymers with excellent rigidity that contain a large amount of polymers with very high molecular weight.

[0260] It should be noted that in this application, the molecular weight of olefin polymers is a value converted from styrene determined by gel permeation chromatography (GPC).

[0261] When the olefin polymer of the present invention is formed into an injection molded plate, the proportion of the orientation layer in the cross section of the injection molded plate is preferably 20% or more, more preferably 20-50%, and even more preferably 25-40%.

[0262] When the olefin polymer of the present invention is formed into an injection molded sheet, since the proportion of the orientation layer in the cross section of the injection molded sheet meets the above-mentioned limitation, the thickness of the orientation layer becomes thicker, and it is easy to provide an injection molded sheet with excellent flexural modulus.

[0263] It should be noted that, in this application document, the proportion of the orientation layer in the cross-section of the injection-molded plate of the olefin polymer refers to the value determined by the following method.

[0264] 1. Formation of molded articles

[0265] According to JIS K 7152-1 and JIS K 6921-2, olefin polymers are injection molded under the following conditions to obtain [the desired product / product]. Figure 1 The molded product with the appearance shape shown.

[0266] Device: NEX-III-3EG, manufactured by Nissei Resin Kogyo Co., Ltd.

[0267] Types of test specimens: Multi-purpose test specimen type A1 as described in JIS K 7139

[0268] Resin melting temperature: 200℃

[0269] Mold temperature: 40℃

[0270] Injection speed: 180 mm / s

[0271] Pressure holding time: 50MPa - 40 seconds

[0272] 2. Preparation of the test sample (thin section for polarization microscope observation)

[0273] (1) As Figure 1 As shown, at a position c1 approximately 2 cm from the resin travel direction MD of the obtained molded article's gate G, a cut is made in a direction perpendicular to the resin travel direction MD, thereby obtaining... Figure 2 The cut-off piece S1 shown in (a)

[0274] (2) Figure 2 As shown in (a), the cut sample S1 obtained in (1) is cut at the center (position c2) parallel to the resin travel direction MD to obtain the sample. Figure 2 The cut-off piece S2 shown in (b)

[0275] (3) Figure 2 As shown in (b), using a rotary slicing apparatus (RX-860 manufactured by Yamato Koki Industries, Ltd.), the cut sample S2 was sliced ​​at position c3 in a manner parallel to the resin travel direction MD and with a thickness of 30 μm, resulting in... Figure 2 The sheet-like test sample S3 is shown in (c).

[0276] (4) Figure 2 (d) is a schematic diagram showing the obtained sheet-like test sample S3. Figure 2 The diagram on the left of (d) shows the relationship with Figure 2(c) is the side view of the sheet-like test sample S3. Figure 2 The diagram on the right of (d) shows a front view of the sheet-like test sample S4.

[0277] 3. Observation using a polarization microscope

[0278] Figure 3 yes Figure 2 The right side of (d) shows an enlarged view of the front view of the sheet-like test sample S3. The test sample S3 was observed using a polarizing microscope (NIKON Corporation EPCLIPSE LV-100NDA) to determine the core layer c and the orientation layers h1 and h2. The thickness of the core layer was set as Tc, and the thicknesses of the orientation layers were set as Th1 and Th2. The ratio F (%) of the thickness of the orientation layer to the thickness of the forming layer was calculated using the following formula (6).

[0279]

[0280] It should be noted that the core layer thickness Tc and the orientation layer thicknesses Th1 and Th2 are the arithmetic averages of the thicknesses of the core layer c and the orientation layers h1 and h2 measured at any 10 locations.

[0281] When the olefin polymer of the present invention is a crystalline polymer, when the molten polymer flows into the mold for injection molding, orientation crystallization occurs near the surface of the resulting injection-molded article because the polymer flows into the mold under high shear stress and cools. If the injection-molded article is cut into a thin section using a slicing machine or the like and the cross-section is observed under a polarizing microscope, it can be confirmed that the orientation layer with high birefringence formed near the surface is clearly separated from the inner core layer. Therefore, the thickness Tc of the core layer and the thicknesses Th1 and Th2 of the orientation layer can be easily determined.

[0282] When the olefin polymers of the present invention are measured by cross-fractional chromatography at a measurement temperature of 40 to 140°C, the total amount of olefin polymers dissolved at a measurement temperature of 120°C or higher is preferably 10% by mass or more, more preferably 20% by mass or more, relative to the total amount of olefin polymers being measured. Furthermore, the proportion of olefin polymers with a molecular weight of 1 million or more in the total amount of olefin polymers dissolved at a measurement temperature of 120°C or higher is preferably 2% by mass or more, more preferably 3% by mass or more.

[0283] The olefin polymers of the present invention can be easily manufactured by the method for manufacturing olefin polymers of the present invention.

[0284] According to the present invention, olefin polymers with excellent melt flowability, high rigidity, and low molecular weight polymers can be provided.

[0285] Example

[0286] Next, examples will be given to further illustrate the present invention, but these are merely examples and are not intended to limit the present invention.

[0287] (Example 1)

[0288] 1. Synthesis of solid catalyst components

[0289] As an internal electron-donating compound, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, a 1,3-diether compound without a fluorene structure, and diisopropylsuccinate, a diethyl succinate compound, were used to prepare a solid catalyst component for olefin polymerization by the following method.

[0290] (i) In a 500 mL flask equipped with a stirrer and purged with nitrogen, 20 g (174.8 mmol) of magnesium diethoxy and 110.0 mL of toluene were added to form a suspension.

[0291] (ii) Then, 40.0 mL (365 mmol) of titanium tetrachloride was added to obtain a liquid containing the initial contact.

[0292] (iii) To the above-mentioned liquid containing the initial contact material, add 6.0 mL (22.4 mmol) of diisopropyl succinate, and further increase the temperature. React for 90 minutes at the same temperature as 100°C. After the reaction is complete, remove the supernatant and wash the first contact product, which is the reaction product, four times with 105 mL of toluene at 90°C.

[0293] (iv) Next, 60 mL (547 mmol) of titanium tetrachloride was added to the first contact product, and 1.4 mL (5.6 mmol) of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was added while heating. The temperature was further increased to 115 °C and the reaction was allowed to proceed for 60 minutes. After the reaction was completed, the supernatant was removed. The second contact product, which was the reaction product, was washed twice with 105 mL of toluene at 90 °C to obtain the final contact product.

[0294] Next, the final contact product was washed six times with 100 mL of n-heptane at 40 °C to separate the solid and liquid phases, thereby obtaining the solid catalyst component (solid catalyst component for olefin polymerization).

[0295] The obtained solid catalyst components were subjected to solid-liquid separation, and the contents of titanium, 1,3-diether, and succinate diester compound in the solid components were determined to be 3.2% by mass, 3.3% by mass, and 15.8% by mass, respectively. The total content of 1,3-diether and succinate diester compound was 19.1% by mass. The molar ratio of succinate diester compound content to titanium content was 0.92. The molar ratio of 1,3-diether content to succinate diester compound content was 0.25. The total pore volume of the solid catalyst components with a diameter of less than 1 μm, determined by mercury porosimetry, was 0.4 cm³. 3 / g, specific surface area is 330m² 2 / g.

[0296] The characteristics of the obtained solid catalyst components are shown in Tables 1 to 3.

[0297] It should be noted that the content of titanium in the solid catalyst, the content of 2-isopropyl-2-isopentyl-1,3-dimethoxypropane (equivalent to a 1,3-diether compound without fluorene structure) as an internal electron-donating compound, and the content and physical properties of diisopropyl succinate (equivalent to a succinate diester compound) were determined by the following methods.

[0298] <Titanium content in solid catalyst>

[0299] The titanium content in the solid catalyst was determined according to the method in JIS 8311-1997.

[0300] <Content of internal electron-donating compounds>

[0301] The content of the internal electron-donating compound was determined using a gas chromatograph (Shimadzu Corporation, GC-14B) under the following conditions. Furthermore, the molar number of the internal electron-donating compound was determined using a standard curve measured at a previously known concentration, based on the gas chromatograph results.

[0302] (Measurement conditions)

[0303] • Column: Packed column (φ2.6×2.1m, Silicon SE-30 10%, Chromosorb WAW DMCS 80 / 100, manufactured by GL Sciences Co., Ltd.)

[0304] • Detector: FID (Flame Ionization Detector)

[0305] • Carrier gas: Helium, flow rate 40 mL / min

[0306] • Measurement temperatures: vaporization chamber 280℃, column 225℃, detector 280℃

[0307] 2. Formation of polymerization catalysts and polymerization reaction

[0308] In a 2.0-liter autoclave equipped with a stirrer and purged with nitrogen, 1.32 mmol of triethylaluminum, 0.131 mmol of diisopropyldimethoxysilane (DIPDMSi), and 0.00264 mmol of the aforementioned solid catalyst (equivalent to titanium atoms) were added to form a polymerization catalyst. Then, 6.0 liters of hydrogen and 1.4 liters of liquefied propylene were added, and the mixture was prepolymerized at 20°C for 5 minutes, followed by a further heating to 70°C for 1 hour of polymerization.

[0309] The polymerization activity, melt flow rate (MFR), xylene-soluble content (XS), flexural modulus (FM), proportion of oriented layers in the cross-section of the injection-molded plate made from the resulting polymer, and molecular weight distribution (Mw / Mn and Mz / Mw) per 1g of solid catalyst were determined using the following methods. The results are shown in Table 2.

[0310] <Polymerization activity per 1g solid catalyst component>

[0311] The polymerization activity of each 1g solid catalyst component is determined by the following formula (7).

[0312]

[0313] <Polymer Melt Flow Rate (MFR)>

[0314] Melt flow rate (MFR) (g / 10 min), which indicates the melt flowability of polymers, was determined according to ASTM D 1238 and JIS K 7210.

[0315] <Proportion of p-xylene-soluble substances in the polymer (XS)>

[0316] In a flask equipped with a stirrer, 4.0 g of polymer (polypropylene) and 200 ml of p-xylene were added. The external temperature was then set to approximately 150°C, and the mixture was stirred for 2 hours while maintaining reflux of the p-xylene (boiling point 137-138°C) to dissolve the polymer. The solution was then cooled to 23°C over 1 hour, and the insoluble and soluble components were separated by filtration. The solution containing the dissolved components was collected and distilled to remove the p-xylene by heating under reduced pressure. The weight of the residue was calculated, and its relative proportion (mass %) to the generated polymer (polypropylene) was determined as the xylene-soluble substance (XS).

[0317] <Polymer Flexural Modulus (FM)>

[0318] Using NEX30III3EG manufactured by Nissei Resin Kogyo Co., Ltd., an injection molded test piece with a thickness of 4.0 mm, a width of 10.0 mm, and a length of 80 mm was prepared under the conditions of a molding temperature of 200°C and a mold temperature of 40°C. The test was conducted based on JIS K7171, with a measurement atmosphere temperature of 23°C.

[0319] <Proportion of orientation layers in the cross-section of an injection-molded plate made of polymer>

[0320] 1. Formation of molded articles

[0321] According to JIS K 7152-1 and JIS K 6921-2, olefin polymers are injection molded under the following conditions to obtain [the desired product / product]. Figure 1 The molded product with the appearance shape shown.

[0322] Device: NEX-III-3EG, manufactured by Nissei Resin Kogyo Co., Ltd.

[0323] Types of test specimens: Multi-purpose test specimen type A1 as described in JIS K 7139

[0324] Resin melting temperature: 200℃

[0325] Mold temperature: 40℃

[0326] Injection speed: 180 mm / s

[0327] Pressure holding time: 50MPa - 40 seconds

[0328] 2. Preparation of the test sample (thin section for polarization microscope observation)

[0329] (1) As Figure 1 As shown, at a position c1 approximately 2 cm from the resin travel direction MD of the obtained molded article's gate G, a cut is made in a direction perpendicular to the resin travel direction MD, thereby obtaining... Figure 2 The cut-off piece S1 shown in (a)

[0330] (2) Figure 2 As shown in (a), the cut sample S1 obtained in (1) is cut at the center (position c2) parallel to the resin travel direction MD to obtain the sample. Figure 2 The cut-off piece S2 shown in (b)

[0331] (3) Figure 2As shown in (b), using a rotary slicing apparatus (RX-860 manufactured by Yamato Koki Industries, Ltd.), the cut sample S2 was sliced ​​at position c3 in a manner parallel to the resin travel direction MD and with a thickness of 30 μm, resulting in... Figure 2 The sheet-like test sample S3 is shown in (c).

[0332] (4) Figure 2 (d) is a schematic diagram showing the obtained sheet-like test sample S3. Figure 2 The diagram on the left of (d) shows the relationship with Figure 2 (c) is the side view of the sheet-like test sample S3. Figure 2 The diagram on the right of (d) shows a front view of the sheet-like test sample S4.

[0333] 3. Observation using a polarization microscope

[0334] Figure 3 yes Figure 2 The right side of (d) shows an enlarged view of the front view of the sheet-like test sample S3. The test sample S3 was observed using a polarizing microscope (NIKON Corporation EPCLIPSE LV-100NDA) to determine the core layer c and the orientation layers h1 and h2. The thickness of the core layer was set as Tc, and the thicknesses of the orientation layers were set as Th1 and Th2. The ratio F (%) of the thickness of the orientation layer to the thickness of the forming layer was calculated using the following formula (6).

[0335]

[0336] It should be noted that the thickness of the core layer Tc and the thicknesses of the orientation layers Th1 and Th2 are the arithmetic averages of the thicknesses of the core layer c and the orientation layers h1 and h2 at any 10 points of the test sample S3.

[0337] <Polymer leaching ratio (CFC) at high temperatures>

[0338] The amount of polymer dissolved per unit molecular weight at high temperatures was determined using cross-fractional chromatography (CFC) (manufactured by PolymerChar) under the following conditions. The proportion of the total amount of olefin polymers dissolved above 120°C to the total amount of olefin polymers (the proportion of o-dichlorobenzene insoluble components at the measurement temperature above 120°C to the total amount of polymers) was determined. Furthermore, the proportion of olefin polymers with a molecular weight of 1 million or more in the total amount of olefin polymers dissolved above 120°C was determined.

[0339] Solvent: o-Dichlorobenzene (ODCB)

[0340] Column: Shodex GPC UT-806M

[0341] Sample concentration: 5 g / L - ODCB

[0342] Sample volume: 0.5 mL

[0343] Pump flow rate: 1.0 mL / min

[0344] Crystallization rate: 1.0℃ (SEC) / min

[0345] Measurement temperature range: 40~140℃ (SEC)

[0346] Flow rate: 1.0 mL / min

[0347] Measurement range: 40℃~140℃

[0348] <Polymer Molecular Weight Distribution>

[0349] The molecular weight distribution of the polymer was evaluated based on the ratio of mass-average molecular weight Mw to number-average molecular weight Mn (Mw / Mn) and the ratio of Z-average molecular weight Mz to mass-average molecular weight Mw (Mz / Mw), determined by gel permeation chromatography (GPC) (Waters GPCV2000) under the following conditions.

[0350] Solvent: o-Dichlorobenzene (ODCB)

[0351] Temperature: 140℃ (SEC)

[0352] Column: Shodex GPC UT-806M

[0353] Sample concentration: 1 g / liter-ODCB (50 mg / 50 mL-ODCB)

[0354] Injection volume: 0.5 mL

[0355] Flow rate: 1.0 mL / min

[0356] (Examples 2-4 and Comparative Examples 1-6)

[0357] The conditions shown in Table 1 were applied, and the procedure was performed in the same manner as in Example 1. The results are shown in Tables 1 through 3.

[0358] [Table 1]

[0359]

[0360] [Table 2]

[0361]

[0362] [Table 3]

[0363]

[0364] Industrial availability

[0365] According to the present invention, a solid catalyst composition for olefin polymerization can be provided, which includes an internally electron-donating compound other than phthalates, and can produce a polymer with excellent melt flowability, high rigidity and low molecular weight polymer.

Claims

1. A solid catalyst composition for olefin polymerization, characterized in that, It contains magnesium, titanium, halogens, 1,3-diether compounds without a fluorene structure, and succinate diester compounds. When converting the solid content, the sum of the contents of the 1,3-diether compound without the fluorene structure and the succinate diester compound in the total content of the components is 13.0% by mass or more. The molar ratio (S / T), expressed as the molar content (S) of the succinate diester compound in the total amount of the ingredients relative to the molar content (T) of the titanium in the total amount of the ingredients, is 0.71 to 1.

30. The molar ratio (E / S), expressed as the molar content (E) of the 1,3-diether compound without the fluorene structure in the total amount of the components relative to the molar content (S) of the succinate diester compound in the total amount of the components, is 0.10 to 0.

70. The total pore volume, measured by mercury porosimetry, for diameters less than 1 μm, is 0.3–1.0 cm³. 3 / g, specific surface area is 200m² 2 / g or more.

2. The solid catalyst composition for olefin polymerization according to claim 1, characterized in that, The 1,3-diether compound that does not have a fluorene structure is selected from one or more of the 1,3-diether compounds shown in general formula (1) below. In equation (1), R 2 and R 3 It represents hydrogen atoms, halogen atoms, alkyl groups with 1 to 12 carbon atoms, vinyl groups with 3 to 12 carbon atoms, alkenyl groups with 3 to 12 carbon atoms, cycloalkyl or cycloalkenyl groups with 3 to 12 carbon atoms, aromatic hydrocarbon groups or halogen-substituted aromatic hydrocarbon groups with 6 to 12 carbon atoms, aromatic hydrocarbon groups with 7 to 12 carbon atoms having substituents, alkylamino groups with 1 to 12 carbon atoms, or dialkylamino groups with 2 to 12 carbon atoms; R 2 and R 3 Choose either the same or different from each other; R 2 and R 3 They can be arbitrarily bonded together to form a ring; R 1 and R 4 Represents alkyl, vinyl, alkenyl, cycloalkyl, aromatic hydrocarbon group (6-12 carbons), or halogenated aromatic hydrocarbon group (7-12 carbons) with substituents; R 1 and R 4 Choose whether they are the same or different from each other.

3. The solid catalyst composition for olefin polymerization according to claim 1, characterized in that, The succinate diester compound is selected from one or more compounds represented by the following general formula (2). In equation (2), R 6 and R 7 It is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, optionally the same or different from each other; R 5 and R 8 It is a straight-chain alkyl or branched alkyl with 2 to 4 carbon atoms, which may be the same as or different from each other.

4. A method for manufacturing a solid catalyst component for olefin polymerization, characterized in that, This method involves contacting magnesium diethoxylate, a titanium halide compound, a 1,3-diether compound without a fluorene structure, and a succinate diester compound to produce the solid catalyst composition for olefin polymerization as described in any one of claims 1 to 3. The titanium halide compound is contacted with the dialkoxymagnesium multiple times. When the titanium halide compound is first contacted with the dialkoxy magnesium, the contact amount of the titanium halide compound is 1.5 to 10.0 mol relative to 1.0 mol of the dialkoxy magnesium. The total amount of the titanium halide compound used is 5.0 to 18.0 mol relative to 1.0 mol of the magnesium diekoxy. The total molar amount of the 1,3-diether compound without the fluorene structure and the molar amount of the succinate diester compound is 0.10 to 0.20 moles relative to 1.0 mole of the magnesium dialkoxy. The molar ratio (S / T) of the succinate diester compound relative to the total molar amount (T) of the titanium halide compound is 0.020 to 0.

040. The molar ratio (E / S) of the 1,3-diether compound without the fluorene structure relative to the molar amount (S) of the succinate diester compound is 0.50 or less. The dialkoxy magnesium is composed of secondary particles, which are aggregates of primary particles with an average particle size of less than 2 μm, and has a specific surface area of ​​10 m². 2 / g or more and less than 50m 2 / g, with a particle size distribution index (SPAN) of less than 1.

30.

5. A catalyst for olefin polymerization, characterized in that, It includes: (I) the solid catalyst composition for olefin polymerization according to any one of claims 1 to 3; and (II) Organoaluminum compounds represented by the following general formula (3), In formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, p is 0 < p ≤ 3, and when there are multiple R 9 s, each R 9 is optionally the same as or different from each other, and when there are multiple Qs, each Q is optionally the same as or different from each other.

6. The catalyst for olefin polymerization according to claim 5, characterized in that, It includes: (I) The solid catalyst composition for olefin polymerization according to any one of claims 1 to 3; (II) Organoaluminum compounds represented by the following general formula (3); as well as (III) Externally electron-donating compounds In formula (3), R 9 is an alkyl group having 1 to 6 carbon atoms, Q is a hydrogen atom or a halogen, p is 0 < p ≤ 3, and when there are multiple R 9 , each R 9 is optionally the same as or different from each other, and when there are multiple Q, each Q is optionally the same as or different from each other.

7. A method for manufacturing an olefin polymer, characterized in that, The polymerization of olefins is carried out using the catalyst for olefin polymerization as described in claim 5 or 6.

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