Heterophasic propylene polymer material, method for producing heterophasic propylene polymer material, and polypropylene composition

Abstract

Provided is a hydroxyl group-modified heterophasic propylene polymer material that achieves an excellent balance between good coatability and high impact strength. This heterophasic propylene polymer material has a propylene-based polymer moiety (A1) and a propylene-α-olefin copolymer moiety (A2). A part of component (A1) and / or component (A2) is modified by hydroxyl groups.

Description

Heterophasic propylene polymerisation material, method for producing the heterophasic propylene polymerisation material, and polypropylene composition

[0001] The present invention relates to a hydroxyl-modified heterophasic propylene polymer material, a method for producing the same, and a composition containing the same.

[0002] Polypropylene is a non-polar material. To improve the paintability of polypropylene, a polymer having a polar group, such as a polyolefin resin modified with an unsaturated carboxylic acid or an anhydride thereof, may be used in combination with polypropylene (see, for example, Patent Document 1).

[0003] Japanese Patent Application Publication No. 08-165403

[0004] As described in Patent Document 1, when polypropylene is combined with other polymers to form a composition, the impact strength may be insufficient. Under these circumstances, the problem to be solved by the present invention is to provide a hydroxyl group-modified heterophasic propylene polymer material that has an excellent balance between good coatability and high impact strength, a method for producing the same, a composition containing the same, and a resin in which the heterophasic propylene polymer material is covalently bonded to a polymer having a polar group.

[0005] The present inventors have conducted extensive research in light of the above background and have completed the present invention. Specifically, the present invention relates to the following items [1] to

[23] . [1] A heterophasic propylene polymer material having a propylene polymer portion (A1) and a propylene and α-olefin copolymer portion (A2), in which (A1) and / or (A2) are partially modified with a hydroxyl group. [2] The heterophasic propylene polymer material according to item [1], in which terminals of (A1) and / or (A2) are modified with a hydroxyl group. [3] The heterophasic propylene polymer material according to item [1] or [2], in which one terminal of (A1) and / or (A2) is modified with a hydroxyl group. [4] The amount of —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is 0.01×10 －３ wt% to 100 x 10 －３% by weight. [5] The heterophasic propylene polymerization material according to any one of [1] to [4], wherein the propylene polymer portion (A1) is a propylene homopolymer portion. [6] A method for producing a heterophasic propylene polymerization material according to any one of [1] to [5], in the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound, the method comprising the following steps (1) to (3) and satisfying condition (i): (1) a propylene polymerization step (A), (2) a propylene and α-olefin copolymerization step (B), (3) a reactive gas compound treatment step (C), (i) performing (A) and / or (B) in the presence of an organozinc compound. [7] A method for producing the heterophasic propylene polymerization material according to [6], further comprising a continuous supply step of continuously supplying propylene (and an α-olefin), an olefin polymerization solid catalyst component, an organoaluminum compound, and an organozinc compound to a reactor, and a continuous withdrawal step of continuously withdrawing a portion of the heterophasic propylene polymerization material obtained in the reactor from the reactor. [8] A method for producing the heterophasic propylene polymerization material according to [6] or [7], characterized in that the reactive gas compound treatment step (C) is a treatment step using oxygen gas, air, or water vapor containing oxygen gas or air.

[0006] [9] A polypropylene composition, graft-modified product, or block-modified product comprising the heterophasic propylene polymerization material according to any one of [1] to [5] and a polymer having a polar group.

[10] The polypropylene composition, graft-modified product, or block-modified product according to [9], wherein the polymer having a polar group is a polymer having a carboxylic acid anhydride residue and / or a carboxylic acid anhydride derivative residue.

[11] The polypropylene composition, graft-modified product, or block-modified product according to

[10] , wherein the polymer having a carboxylic acid anhydride residue and / or a carboxylic acid anhydride derivative residue is maleic anhydride-modified polypropylene.

[12] A molded article, film, or sheet comprising the polypropylene composition, graft-modified product, or block-modified product according to any one of [9] to

[11] .

[13] A polypropylene composition, graft-modified product, or block-modified product comprising the heterophasic propylene polymerization material according to any one of [1] to [5], a polymer having a polar group, and a crosslinking catalyst.

[14] The polypropylene composition, graft-modified product, or block-modified product according to

[13] , wherein the polymer having a polar group is a polymer having a carboxylic acid anhydride residue and / or a carboxylic acid anhydride derivative residue.

[15] The polypropylene composition, graft-modified product, or block-modified product according to

[14] , wherein the polymer having a carboxylic acid anhydride residue and / or a carboxylic acid anhydride derivative residue is maleic anhydride-modified polypropylene.

[16] The polypropylene composition, graft-modified product, or block-modified product according to any of

[13] to

[15] , wherein the crosslinking catalyst is a metal compound, a nitrogen-containing compound, or a Bronsted acid.

[17] The polypropylene composition, graft-modified product, or block-modified product according to any of

[13] to

[15] , wherein the crosslinking catalyst is a metal oxide, a metal hydroxide, a metal alkoxide, a metal carboxylate, a metal enolate, or a metal carbonate.

[18] The polypropylene composition, graft-modified product, or block-modified product according to any one of

[13] to

[15] , wherein the crosslinking catalyst is a transition metal oxide, transition metal hydroxide, transition metal alkoxide, transition metal carboxylate, transition metal enolate, or transition metal carbonate.

[19] A molded article, film, or sheet comprising the polypropylene composition, graft-modified product, or block-modified product according to any one of

[13] to

[18] .

[20] A graft-modified product in which the hydroxyl group of (A2) in the heterophasic propylene polymerization material according to any one of [9] to

[11] and

[13] to

[18] is bonded to the polymer having a polar group.

[21] A graft-modified product in which the hydroxyl group of (A2) in the heterophasic propylene polymerization material according to any one of [9] to

[11] and

[13] to

[18] is bonded to the polymer having a polar group by a covalent bond.

[22] A graft-modified product in which a hydroxyl group of (A2) in the heterophasic propylene polymer material according to any one of

[10] to

[11] and

[14] to

[18] is bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

[23] A graft-modified product in which a hydroxyl group of (A2) in the heterophasic propylene polymer material according to any one of

[10] to

[11] and

[14] to

[18] is bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group by a covalent bond.

[24] A block-modified product in which a hydroxyl group of (A2) in the heterophasic propylene polymer material according to any one of [9] to

[11] and

[13] to

[18] is bonded to a polymer having a polar group.

[25] A block modified material in which a hydroxyl group of (A2) in the heterophasic propylene polymer material according to any one of [9] to

[11] and

[13] to

[18] is covalently bonded to the polymer having a polar group.

[26] A block modified material in which a hydroxyl group of (A2) in the heterophasic propylene polymer material according to any one of

[10] to

[11] and

[14] to

[18] is covalently bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

[27] A block-modified product, in which a hydroxyl group of (A2) in the heterophasic propylene polymerization material according to any one of

[10] to

[11] and

[14] to

[18] is covalently bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

[28] A method for producing the polypropylene composition, graft-modified product, or block-modified product according to any one of [9] to

[11] and

[20] to

[23] , which comprises melt-kneading or heating in a solvent a material containing the heterophasic propylene polymerization material and the polymer having a polar group.

[29] A method for producing the polypropylene composition, graft-modified product, or block-modified product according to any one of

[13] to

[18] and

[24] to

[27] , which comprises melt-kneading or heating in a solvent a material containing the heterophasic propylene polymerization material, the polymer having a polar group, and the crosslinking catalyst.

[30] A polypropylene composition, a graft-modified product, or a block-modified product produced by the method according to

[28] .

[31] A polypropylene composition, a graft-modified product, or a block-modified product produced by the method according to

[29] .

[0007] According to the present invention, it is possible to obtain a hydroxyl group-modified heterophasic propylene polymer material that has an excellent balance between good paintability and high impact strength, a composition containing the same, and a resin in which the heterophasic propylene polymer material is covalently bonded to a polymer having a polar group.

[0008] Heterophagic Propylene Polymerization Material The heterophasic propylene polymerization material of the present invention having a propylene polymer portion (A1) and a propylene and α-olefin copolymer portion (A2) can be produced, for example, by a method including a first polymerization step in which propylene is polymerized in the presence of a polymerization catalyst to produce the propylene polymer portion (A1) (hereinafter also referred to as "polymer (I)"), and a second polymerization step in which propylene and an olefin are copolymerized to produce the propylene and α-olefin copolymer portion (A2) (hereinafter also referred to as "polymer (II)"). Examples of the polymerization catalyst, polymerization method, and polymerization system used in these polymerization steps are described below.

[0009] Preferably, the heterophasic propylene polymer material comprises: a polymer (I) containing 80% by mass or more of structural units derived from propylene and having an intrinsic viscosity of 2.0 dL / g or less; and a polymer (II) containing structural units derived from at least one selected from the group consisting of an α-olefin having 2 carbon atoms (ethylene) and an α-olefin having 4 to 12 carbon atoms and structural units derived from propylene and having an intrinsic viscosity of 1.5 to 8.0 dL / g. More preferably, the content of polymer (I) is 40 to 99% by mass, and the content of polymer (II) is 1 to 60% by mass.

[0010] The polymer (I) may be, for example, a propylene homopolymer, or may contain structural units derived from a monomer other than propylene. When the polymer (I) contains structural units derived from a monomer other than propylene, the content of such structural units may be, for example, 0.01% by mass or more and less than 10% by mass based on the total mass of the polymer (I).

[0011] Examples of the monomer other than propylene include ethylene and α-olefins having 4 or more carbon atoms. Among these, at least one selected from the group consisting of ethylene and α-olefins having 4 to 10 carbon atoms is preferred, at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, and 1-octene is more preferred, and at least one selected from the group consisting of ethylene and 1-butene is even more preferred.

[0012] Examples of polymers containing structural units derived from monomers other than propylene include propylene-ethylene copolymers, propylene-1-butene copolymers, propylene-1-hexene copolymers, propylene-1-octene copolymers, propylene-ethylene-1-butene copolymers, propylene-ethylene-1-hexene copolymers, and propylene-ethylene-1-octene copolymers.

[0013] From the viewpoint of dimensional stability of the molded article, the polymer (I) is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, and more preferably a propylene homopolymer.

[0014] The content of polymer (I) is preferably 40 to 99 mass%, more preferably 45 to 95 mass%, and even more preferably 50 to 92 mass%, based on the total mass of the heterophasic propylene polymerization material.

[0015] Polymer (II) preferably contains 10% by mass or more of structural units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms, and also contains structural units derived from propylene.

[0016] In polymer (II), the content of structural units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms may be 20 to 80 mass%, or may be 25 to 60 mass%.

[0017] In polymer (II), the at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms is preferably at least one selected from the group consisting of ethylene and α-olefins having from 4 to 10 carbon atoms, more preferably at least one selected from the group consisting of ethylene, 1-butene, 1-hexene, 1-octene, and 1-decene, and even more preferably at least one selected from the group consisting of ethylene and 1-butene.

[0018] Examples of polymer (II) include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, and propylene-1-decene copolymer. Among these, propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer are preferred, and propylene-ethylene copolymer is more preferred.

[0019] The content of polymer (II) is preferably 1 to 60 mass %, more preferably 5 to 55 mass %, and even more preferably 8 to 50 mass %, based on the total mass of the heterophasic propylene polymer material.

[0020] The content of xylene-insoluble (CXIS) components in the heterophasic propylene polymerization material is preferably 40 to 99 mass %, more preferably 45 to 95 mass %, based on the total mass of the heterophasic propylene polymerization material. The content of xylene-soluble (CXS components) components in the heterophasic propylene polymerization material is preferably 1 to 60 mass %, more preferably 5 to 55 mass %, based on the total mass of the heterophasic propylene polymerization material.

[0021] In this embodiment, it is considered that the CXIS component in the heterophasic propylene polymer material is mainly composed of polymer (I), and the CXS component in the heterophasic propylene polymer material is mainly composed of polymer (II).

[0022] Examples of heterophasic propylene polymer materials include (propylene)-(propylene-ethylene) polymer materials, (propylene)-(propylene-ethylene-1-butene) polymer materials, (propylene)-(propylene-ethylene-1-hexene) polymer materials, (propylene)-(propylene-ethylene-1-octene) polymer materials, (propylene)-(propylene-1-butene) polymer materials, (propylene)-(propylene-1-hexene) polymer materials, (propylene)-(propylene-1-octene) polymer materials, and (propylene)-(propylene- (propylene-ethylene)-(propylene-ethylene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-ethylene-1-decene) polymerization material, (propylene-ethylene)-(propylene-1-butene) polymerization material, (propylene-ethylene)-(propylene-1-hexene) (propylene-ethylene)-(propylene-1-octene) polymerization material, (propylene-ethylene)-(propylene-1-decene) polymerization material, (propylene-1-butene)-(propylene-ethylene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-butene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-hexene) polymerization material, (propylene-1-butene)-(propylene-ethylene-1-octene) polymerization material, (propylene-1-butene)-(propylene-ethylene- (propylene-1-decene) polymerization material, (propylene-1-butene)-(propylene-1-butene) polymerization material, (propylene-1-butene)-(propylene-1-hexene) polymerization material, (propylene-1-butene)-(propylene-1-octene) polymerization material, (propylene-1-butene)-(propylene-1-decene) polymerization material, (propylene-1-hexene)-(propylene-1-hexene) polymerization material, (propylene-1-hexene)-(propylene-1-octene) polymerization material, (propylene-1-hexene)-(propylene-1-decene) polymerization material,(propylene-1-octene)-(propylene-1-octene) polymeric materials, and (propylene-1-octene)-(propylene-1-decene) polymeric materials.

[0023] Here, the expression "(propylene)-(propylene-ethylene) polymer material" means "a heterophasic propylene polymer material in which polymer (I) is a propylene homopolymer and polymer (II) is a propylene-ethylene copolymer." The same applies to other similar expressions.

[0024] As the heterophasic propylene polymer material, a (propylene)-(propylene-ethylene) polymer material, a (propylene)-(propylene-ethylene-1-butene) polymer material, a (propylene-ethylene)-(propylene-ethylene) polymer material, a (propylene-ethylene)-(propylene-ethylene-1-butene) polymer material, or a (propylene-1-butene)-(propylene-1-butene) polymer material is preferred, and a (propylene)-(propylene-ethylene) polymer material is more preferred.

[0025] The intrinsic viscosity number ([η]I) of the polymer (I) is preferably 0.10 to 3.00 dL / g, more preferably 0.50 to 2.0 dL / g, and even more preferably 0.70 to 1.50 dL / g.

[0026] The intrinsic viscosity ([η]II) of the polymer (II) is preferably from 1.50 to 8.00 dL / g, more preferably from 2.00 to 8.00 dL / g, and even more preferably from 2.50 to 8.00 dL / g.

[0027] The ratio ([η]II / [η]I) of the intrinsic viscosity number ([η]II) of polymer (II) to the intrinsic viscosity number ([η]I) of polymer (I) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 9.

[0028] The intrinsic viscosity number ([η]I) of the polymer (I) can be measured, for example, by forming the polymer (I) and then measuring the intrinsic viscosity number of the polymer.

[0029] The intrinsic viscosity number ([η]II) of polymer (II) can be calculated, for example, by the following formula (6) using the intrinsic viscosity number ([η]whole) of the heterophasic propylene polymerization material, the intrinsic viscosity number ([η]I) of polymer (I), and the contents of polymer (II) and polymer (I).

[0030] [η]II=([η]whole-[η]I×XI) / XII (6) [η]whole: intrinsic viscosity number (dL / g) of the heterophasic propylene polymerization material [η]I: intrinsic viscosity number (dL / g) of polymer (I) XI: ratio of the mass of polymer (I) to the total mass of the heterophasic propylene polymerization material (mass of polymer (I) / mass of heterophasic propylene polymerization material) XII: ratio of the mass of polymer (II) to the total mass of the heterophasic propylene polymerization material (mass of polymer (II) / mass of heterophasic propylene polymerization material)

[0031] Here, XII was calculated using the following formula by measuring the heat of fusion of the heterophasic propylene polymer material. A sample (approximately 5 mg) of the heterophasic propylene polymer material was placed in an aluminum pan and placed in a differential scanning calorimeter DSC8500 (manufactured by PerkinElmer). The sample was heated to 230°C, held at 230°C for 5 minutes, cooled to 0°C at a rate of 5°C / min, held at 0°C for 5 minutes, and then heated to 200°C at a rate of 5°C / min to measure a melting curve. The temperature was corrected using the melting point of indium as 156.6°C. The heat of fusion (unit: J / g) was calculated from the melting peak area in the melting curve, and then XII was determined using the following formula: XII = (1 - (heat of fusion of heterophasic propylene polymer material) / 105) x 100

[0032] XI and XII may be calculated from the material balance during polymerization.

[0033] The intrinsic viscosity number ([η]CXIS) of the CXIS component is preferably 0.10 to 3.00 dL / g, more preferably 0.50 to 2.00 dL / g, and even more preferably 0.70 to 1.50 dL / g.

[0034] The intrinsic viscosity number ([η]CXS) of the CXS component is preferably 1.50 to 8.00 dL / g, more preferably 2.00 to 8.00 dL / g, and even more preferably 2.50 to 8.00 dL / g.

[0035] The ratio ([η]CXS / [η]CXIS) of the intrinsic viscosity number of the CXS component ([η]CXS) to the intrinsic viscosity number of the CXIS component ([η]CXIS) is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 9.

[0036] The isotactic pentad fraction (also referred to as the [mmmm] fraction) of the polymer (I) is preferably 0.950 or more, more preferably 0.970 or more, from the viewpoint of rigidity and dimensional stability of a molded article made from the resin composition. The isotactic pentad fraction of the polymer (I) may be, for example, less than 1.000.

[0037] The isotactic pentad fraction means the isotactic fraction in pentad units. That is, the isotactic pentad fraction indicates the content of a structure in which five consecutive propylene-derived structural units are meso-bonded when viewed in pentad units. When the target component is a copolymer, the isotactic pentad fraction refers to a value measured for a chain of propylene-derived structural units.

[0038] In this specification, the isotactic pentad fraction is １３ It refers to the value measured by C-NMR spectrum. １３ The ratio of the area of ​​the mmmm peak to the area of ​​all absorption peaks in the methyl carbon region obtained by C-NMR spectrum is defined as the isotactic pentad fraction. １３ The method for measuring the isotactic pentad fraction by C-NMR spectroscopy is described, for example, in A. Zambelli et al., Macromolecules, 6, 925 (1973). １３ The assignment of absorption peaks obtained by C-spectrometry is based on the description in Macromolecules, 8, 687 (1975).

[0039] In this specification, the melt flow rate of polymer (I) at a temperature of 230°C and a load of 2.16 kgf refers to a value measured at 230°C under a load of 2.16 kgf in accordance with JIS K6758. The melt flow rate may also be referred to as MFR hereinafter. From the viewpoint of the molding processability of the resin composition, the melt flow rate of polymer (I) is preferably 3 g / 10 min or more, and more preferably 10 g / 10 min to 500 g / 10 min.

[0040] The melt flow rate of polymer (II) at a temperature of 230°C and a load of 2.16 kgf refers to a value measured at 230°C and under a load of 2.16 kgf in accordance with JIS K 6758. From the viewpoint of moldability of the resin composition, the melt flow rate of polymer (II) is preferably 0.01 g / 10 min or more, and more preferably 0.02 g / 10 min to 20 g / 10 min.

[0041] In producing the polymer (I) and the polymer (II), fossil resource-derived monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), plant-derived monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), chemically recycled monomers (ethylene, propylene, 1-butene, 1-hexene, etc.), etc. can be used, and two or more of these may be used in combination. Specific monomer combinations include, for example, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene / fossil resource-derived 1-butene / plant-derived 1-butene / chemically recycled 1-butene, fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene / fossil resource-derived 1-hexene / plant-derived 1-hexene / chemically recycled 1-hexene, fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene, fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene / fossil resource-derived ethylene / plant-derived ethylene / chemically recycled ethylene, and fossil resource-derived propylene / plant-derived propylene / chemically recycled propylene / fossil resource-derived 1-butene / plant-derived 1-butene / chemically recycled 1-butene.

[0042] Fossil resource-derived monomers are derived from carbon found in underground resources such as petroleum, coal, and natural gas, and generally contain almost no carbon-14 (C). Methods for producing fossil resource-derived monomers include known methods, such as cracking petroleum-derived naphtha, ethane, etc., and producing olefins by dehydrogenation of ethane, propane, etc.

[0043] Plant-derived monomers are derived from carbon circulating on the earth's surface as plants and animals, and generally contain a certain proportion of carbon-14 (14C). Examples of methods for producing plant-derived monomers include known methods, such as cracking bionaphtha, vegetable oil, animal oil, etc., dehydrogenation of biopropane, methods of separating alcohol from fermented products such as sugars extracted from plant materials such as sugarcane and corn, and subjecting the alcohol to a dehydration reaction (JP Patent Publication Nos. 2010-511634, 2011-506628, 2013-503647, etc.), and methods of subjecting ethylene obtained from plant-derived ethanol to a metathesis reaction with n-butene (WO 2007 / 055361, etc.).

[0044] Chemically recycled monomers are derived from carbon generated by the decomposition or combustion of waste, and their carbon-14 (14C) content varies depending on the waste. Methods for producing chemically recycled monomers include known methods, such as a method of thermally decomposing waste plastics (JP Patent Publication No. 2017-512246, etc.), a method of cracking waste vegetable oil, waste animal oil, etc. (JP Patent Publication No. 2018-522087, etc.), and a method of gasifying, converting to alcohol, and dehydrating waste such as food waste, biomass waste, food waste, waste oil, waste wood, waste paper, and waste plastic (JP Patent Publication No. 2019-167424, WO2021 / 006245, etc.).

[0045] When two or more of fossil resource-derived olefins, plant-derived olefins, and chemically recycled olefins are used, olefins produced individually may be mixed and used in combinations such as fossil resource-derived olefins / plant-derived olefins, fossil resource-derived olefins / chemically recycled olefins, plant-derived olefins / chemically recycled olefins, or fossil resource-derived olefins / plant-derived olefins / chemically recycled olefins. Furthermore, a mixture of the above olefin combinations may be produced by using a mixture of combinations such as fossil resource-derived compound / plant-derived compound, fossil resource-derived compound / chemically recycled compound, plant-derived compound / chemically recycled compound, or fossil resource-derived compound / plant-derived compound / chemically recycled compound as a raw material or production intermediate in the olefin production process.

[0046] From the viewpoint of reducing the environmental load, the carbon-14 (C) concentration of polymer (I) and polymer (II) is preferably 0.2 pMC(%) or more, more preferably 0.5 pMC(%) or more, even more preferably 1 pMC(%) or more, still more preferably 5 pMC(%) or more, and particularly preferably 10 pMC(%) or more. From the viewpoint of cost, the carbon-14 (C) concentration is preferably 99 pMC(%) or less, more preferably 95 pMC(%) or less, even more preferably 90 pMC(%) or less, still more preferably 70 pMC(%) or less, and particularly preferably 50 pMC(%) or less.

[0047] The carbon-14 (14C) concentration of polymer (I) and polymer (II) can be adjusted by changing the ratio of fossil resource-derived olefin, plant-derived olefin, and chemically recycled olefin used in the production of the polyolefin resin.

[0048] <Solid catalyst component for olefin polymerization> The solid catalyst component for olefin polymerization used in the production method of the present invention preferably contains titanium and magnesium atoms. Examples of methods for preparing the solid catalyst component for olefin polymerization used in the production method of the present invention include the following methods (1) to (5): (1) a method of contacting a magnesium halide compound with a titanium compound; (2) a method of contacting a magnesium halide compound with an internal electron donor and a titanium compound; (3) a method of dissolving a magnesium halide compound and a titanium compound in an electron-donating solvent to obtain a solution, and then impregnating a support material with the solution; (4) a method of contacting a dialkoxymagnesium compound, a titanium halide compound and an internal electron donor; (5) a method of contacting a solid component containing magnesium atoms, titanium atoms and hydrocarbonoxy groups with a halide compound, an internal electron donor and / or an organic acid halide.

[0049] Among these, a solid catalyst component obtained by the method (4) or (5) is preferred, and a solid catalyst component containing at least one compound selected from the group consisting of a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, or a β-alkoxy ester compound as an internal electron donor is more preferred. Examples of the monoester compound, dicarboxylic acid ester compound, diol diester compound, diether compound, and β-alkoxy ester compound include compounds described in Patent Document (Japanese Patent Application No. 2018-531923) and combinations of two or more thereof. Examples of the solid catalyst component for olefin polymerization include those described in JP-A-63-142008, JP-A-4-227604, JP-A-5-339319, JP-A-6-179720, JP-B-7-116252, JP-A-8-134124, JP-A-9-31119, JP-A-11-228628, JP-A-11-80234, JP-A-11-322833, Japanese Patent Application No. 2018-531923, JP-A-2021-161216, JP-A-2022-31142, etc. When using this solid catalyst component for olefin polymerization, it is preferable to use an organoaluminum compound in combination, and if necessary, an external electron donor compound is used in combination.

[0050] <Organoaluminum Compound> Examples of the organoaluminum compound used in the production method of the present invention include trialkylaluminums such as trimethylaluminum, triethylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, and tridecylaluminum; alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride; alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride; aluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide; alumoxanes such as methylalumoxane, ethylalumoxane, isobutylalumoxane, and methylisobutylalumoxane; and combinations of two or more thereof. Among these, trialkylaluminums are preferred, and triethylaluminum is more preferred.

[0051] <External Electron Donor Compound> In the production method of the present invention, an external electron donor compound (external electron donor) can also be continuously supplied to the reactor as an optional component. The external electron donor compound is a monoester compound, a dicarboxylic acid ester compound, a diol diester compound, a diether compound, a β-alkoxy ester compound, or a silicon compound represented by the following formula [7], preferably a silicon compound represented by the following formula [7]: R ７ ｒ Si(OR ８ ) ４－ｒ [7] In the formula, R ７ represents a hydrogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, or a group containing a heteroatom; R ７ When there are multiple, they may be the same or different; R ８ represents a hydrocarbyl group having 1 to 20 carbon atoms, R ８When there are a plurality of , they may be the same or different; and r represents an integer of 0 to 3. r is preferably 1 or 2, and more preferably 2.

[0052] R ７ and R ８ Examples of hydrocarbyl groups having 1 to 20 carbon atoms include linear alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, and pentyl groups; branched alkyl groups having 3 to 20 carbon atoms such as isopropyl, sec-butyl, tert-butyl, and tert-amyl groups; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopentyl and cyclohexyl groups; cycloalkenyl groups having 3 to 20 carbon atoms such as cyclopentenyl groups; and aryl groups having 6 to 20 carbon atoms such as phenyl and tolyl groups. ７ R is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a tert-butyl group, a tert-amyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, or a diethylamino group, and more preferably a methyl group, an ethyl group, an n-propyl group, a tert-butyl group, a cyclohexyl group, or a diethylamino group. ８ is preferably a methyl group or an ethyl group, and more preferably a methyl group.

[0053] R ７Examples of heteroatom-containing groups include oxygen atom-containing groups such as furyl, pyranyl, and perhydrofuryl groups; nitrogen atom-containing groups such as dimethylamino, methylethylamino, diethylamino, ethyl-n-propylamino, di-n-propylamino, pyrrolyl, pyridyl, pyrrolidinyl, piperidyl, perhydroindolyl, perhydroisoindolyl, perhydroquinolyl, perhydroisoquinolyl, perhydrocarbazolyl, and perhydroacridinyl groups; sulfur atom-containing groups such as thienyl; and phosphorus atom-containing groups. Among these, preferred are groups in which the heteroatom can be directly chemically bonded to the silicon atom of the silicon compound, and more preferred are dimethylamino, methylethylamino, diethylamino, ethyl-n-propylamino, and di-n-propylamino groups.

[0054] Examples of external electron donor compounds include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butyl-n-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amyl-n-propyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, and isobutylisopropyl Dimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, cyclobutylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane Silane, cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyldimethoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxy Silane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert-butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n-propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexylmethyldiethoxysilane,Cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis(perhydroquinolino)dimethoxysilane, bis(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)(perhydroisoquinolino)dimethoxysilane, (perhydroquinolino)methyldimethoxysilane, (perhydroisoquinolino)methyldimethoxysilane, (perhydroquinolino) Examples of the silane include (perhydroquinolino)(n-propyl)dimethoxysilane, (perhydroisoquinolino)(n-propyl)dimethoxysilane, (perhydroquinolino)(tert-butyl)dimethoxysilane, (perhydroisoquinolino)(tert-butyl)dimethoxysilane, and diethylaminotriethoxysilane, as well as combinations of two or more thereof.

[0055] <Organic Zinc Compound> Examples of the organic zinc compound used in the production method of the present invention include dialkyl zincs such as dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisobutyl zinc, and di-n-hexyl zinc; diaryl zincs such as diphenyl zinc and dinaphthyl zinc; bis(cyclopentadienyl) zinc; and dialkenyl zincs such as diallyl zinc. Among these, dialkyl zincs are preferred, more preferably dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-n-butyl zinc, diisobutyl zinc, or di-n-hexyl zinc, even more preferably dimethyl zinc or diethyl zinc, and particularly preferably diethyl zinc.

[0056] The number of polymerization steps in the production method of the present invention is one or more. The type and amount of monomer polymerized in each step and the polymerization conditions in each step may be different from each other, but propylene is polymerized in at least one step. The olefin polymer discharged from the final step is essentially a mixture of polymers produced in each step.

[0057] The contact of the organozinc compound, the solid catalyst component, the organoaluminum compound, and the external electron donor compound is carried out in a reactor or outside the reactor, with or without diluting these compounds or components with a solvent. The order of contacting these compounds and components is not particularly limited, but an example method is to supply the organoaluminum compound and the external electron donor compound to a reactor, and then supply the contact product of the organozinc compound and the solid catalyst component to the reactor. The supply to the reactor is preferably carried out in an inert gas such as nitrogen or argon in a moisture-free state.

[0058] In the polymerization step (hereinafter referred to as "main polymerization") in the production method of the present invention, the amount of the organoaluminum compound used is usually 1 to 1,000 mol, preferably 5 to 600 mol, per mol of titanium atom in the solid catalyst component. The amount of the external electron donor compound used in the main polymerization is usually 0.1 to 2,000 mol, preferably 0.3 to 1,000 mol, more preferably 0.5 to 800 mol, per mol of titanium atom contained in the solid catalyst component, and usually 0.001 to 5 mol, preferably 0.005 to 3 mol, more preferably 0.01 to 1 mol, per mol of the organoaluminum compound.

[0059] The polymerization temperature for this polymerization is usually -30 to 300°C, preferably 20 to 180°C, and more preferably 40 to 100°C. The polymerization pressure is usually atmospheric pressure to 10 MPa, and preferably 200 kPa to 5 MPa. The polymerization time is usually 0.2 to 10 hours, and preferably 0.5 to 6 hours. When multiple reactors are used, the average residence time in each reactor is 0.05 to 5 hours, and preferably 0.1 to 3 hours. Examples of polymerization reactors include loop reactors, continuous stirred tank reactors, fluidized bed reactors, and spouted bed reactors.

[0060] The polymerization may be carried out by a slurry polymerization method or a solution polymerization method using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, or octane; a bulk polymerization method using an olefin that is liquid at the polymerization temperature; a gas-phase polymerization method; or a combination of two or more of these methods. Among these, at least bulk polymerization is preferred. The polymerization may also be carried out in a batch mode, at least a continuous mode, or a combination of these. The polymerization may also be carried out using multiple polymerization reactors arranged in series and having different polymerization conditions. The polymerization conditions may also be continuously changed within a single reactor. A chain transfer agent such as hydrogen may be used to adjust the molecular weight of the propylene polymer material obtained by the polymerization.

[0061] In this polymerization, a prepolymerized solid catalyst component described below may be used instead of the solid catalyst component in order to improve the particle properties of the resulting propylene polymer material powder. When a prepolymerized solid catalyst component is used in this polymerization, the use of an organoaluminum compound in this polymerization is not essential.

[0062] In the production of propylene polymer materials, prepolymerization may be performed by a known method before the main polymerization. Known prepolymerization methods include, for example, a method in which a small amount of olefin (the same or different from the olefin used in the main polymerization) is supplied to a solid catalyst component and an organoaluminum compound, and the resulting mixture is polymerized in a slurry state using a solvent. Examples of the solvent used for the slurrying include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene, and toluene. A liquid olefin may be used in place of a part or all of the solvent. Alternatively, prepolymerization may be performed in the presence of a viscous substance such as an olefin wax to obtain a prepolymerized catalyst that is stable during storage and handling. The prepolymerization method is not particularly limited, and may be performed in a batch, semi-batch, or continuous manner.

[0063] The amount of the organoaluminum compound used in the prepolymerization is usually 0.5 to 700 mol, preferably 0.8 to 500 mol, more preferably 1 to 200 mol per mol of titanium atom in the solid catalyst component.

[0064] The amount of the olefin to be prepolymerized is usually 0.01 to 1000 g, preferably 0.05 to 500 g, more preferably 0.1 to 200 g, per gram of the solid catalyst component.

[0065] The slurry concentration in the prepolymerization is preferably 1 to 500 g of solid catalyst component / liter of solvent, more preferably 3 to 300 g of solid catalyst component / liter of solvent. The temperature in the prepolymerization is preferably −20 to 100° C., more preferably 0 to 80° C. The polymerization time in the prepolymerization is usually 30 seconds to 15 hours. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 1 kPa to 2 MPa, more preferably 10 kPa to 1 MPa, although this does not apply to olefins that are liquid at the pressure and temperature of the prepolymerization.

[0066] In the prepolymerization, examples of methods for feeding a solid catalyst component, an organoaluminum compound, and an olefin to a prepolymerization vessel include (1) a method in which the solid catalyst component is contacted with an organoaluminum compound and then the contact product and the olefin are fed, and (2) a method in which the solid catalyst component is contacted with an olefin and then the contact product and the organoaluminum compound are fed. Examples of methods for feeding the olefin include (1) a method in which the olefin is fed sequentially so as to maintain a predetermined pressure inside the prepolymerization vessel, and (2) a method in which the entire predetermined amount of olefin is fed initially. A chain transfer agent such as hydrogen may be added to adjust the molecular weight of the prepolymerized olefin polymer. In addition to the solid catalyst component and the organoaluminum compound, the prepolymerization may also use an organozinc compound or an external electron donor compound. The amount of the external electron donor compound used is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, and more preferably 0.03 to 100 mol, relative to 1 mol of titanium atoms contained in the solid catalyst component, and usually 0.003 to 5 mol, preferably 0.005 to 3 mol, and more preferably 0.01 to 2 mol, relative to 1 mol of the organoaluminum compound.

[0067] In prepolymerization, examples of methods for supplying an external electron donor compound to a prepolymerization reactor include (1) a method of supplying it separately from the organoaluminum compound, and (2) a method of supplying a contact product of the external electron donor compound and the organoaluminum compound. In the production of propylene polymer materials, preactivation may be performed by a known method. Preactivation can be performed instead of or before prepolymerization. Known preactivation methods include, for example, contacting a solid catalyst component with an organoaluminum in a solvent in the absence of an olefin. Examples of the solvent include inert hydrocarbon solvents such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, 2,2,4-trimethylpentane, cyclohexane, benzene, xylene, and toluene. Preactivation may also be performed using an organozinc compound or an external electron donor compound in addition to the solid catalyst component and the organoaluminum compound. The preactivated catalyst exhibits a significantly lower tendency to deposit, and the degree of preactivation allows for a stable storage time and for reproducible production conditions to be established over a long period of time. The resulting preactivated catalyst can be metered into a continuously operated stirred reactor. Preactivation can also be carried out in the presence of a viscous substance such as an olefin wax to obtain a preactivated catalyst that is stable during storage and handling. The preactivation method is not particularly limited and can be carried out in a batch, semi-batch, or continuous manner.

[0068] The heterophasic propylene polymer material obtained in the polymerization process of the present invention has organometallic end groups containing organozinc at at least a portion of its polymer chain ends. In the case of linear polymer chains, the organometallic end group is usually present at only one end. The organometallic end groups are generally highly reactive and can be modified with hydroxyl groups in any non-polymerization reaction process with reactive gas compounds, such as oxygen gas, air, water vapor containing oxygen gas or air, or alcohol containing oxygen gas or air. The heterophasic propylene polymer material of the present invention may be a heterophasic propylene polymer material having organometallic end groups or a heterophasic propylene polymer material modified with hydroxyl groups. It may also be a polymer material containing the polymer produced by combining the polymerization process of the present invention with another polymerization process.

[0069] 3. Method for Producing Heterophagic Propylene Polymerization Material The method for producing a heterophasic propylene polymerization material of the present invention is, for example, as follows: A method for producing a heterophasic propylene polymerization material, comprising: a first polymerization step of polymerizing propylene in the presence of an olefin polymerization catalyst obtained by contacting an aluminum compound with a solid olefin polymerization catalyst component containing a titanium atom, a magnesium atom, a halogen atom, and an internal electron donor; and a second polymerization step of copolymerizing propylene with at least one selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms in the presence of the polymer (I) and the contact product described below to form a polymer (II).

[0070] In the method for producing a heterophasic propylene polymerization material of the present invention, propylene or the like is polymerized in the presence of the above-mentioned olefin polymerization catalyst.

[0071] An example of a method for producing the heterophasic propylene polymer material will now be described. This method includes: (Step 1) a propylene polymerization step; (Step 2) a propylene and α-olefin copolymerization step; and (Step 3) a reactive gas compound treatment step.

[0072] (Step 1) Propylene polymerization step: Step 1-a, in which a monomer containing propylene is polymerized in a liquid phase in the presence of a specified amount of diethyl zinc under conditions where the hydrogen / propylene ratio is appropriate to obtain at least a portion of a propylene-based polymer (a); and Step 1-b, in which a monomer containing propylene is polymerized in a gas phase in the presence of a specified amount of diethyl zinc under conditions where the hydrogen / propylene ratio is appropriate to obtain at least a portion of a propylene-based polymer (a). (Step 2) Propylene and α-olefin copolymerization step: Step 1-a, in which a monomer containing propylene and at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms is polymerized in the presence of a specified amount of diethyl zinc under conditions where the hydrogen / propylene ratio is appropriate to obtain a propylene-based copolymer (b). (Step 3) Reactive gas compound treatment step: A step of treating the propylene polymer (b) obtained through (Step 1) and (Step 2) with a reactive gas compound to obtain a heterophasic propylene polymer modified with hydroxyl groups.

[0073] In this specification, the hydrogen / propylene ratio is defined as follows: In the case of polymerization in a liquid phase, the hydrogen / propylene ratio refers to the ratio of the amounts of hydrogen in a gaseous state to propylene in a liquid state at the reactor supply section. In the case of polymerization in a gaseous phase, the hydrogen / propylene ratio refers to the ratio of the amounts of hydrogen in a gaseous state to propylene in a gaseous state at the reactor outlet. In this specification, for example, the expression "the hydrogen / propylene ratio is 1 mol ppm" means "the hydrogen / propylene ratio is 1 x 10 －６ mol / mol" and hydrogen is 1 x 10 －６ The hydrogen / propylene ratio is usually 0.00001 to 10 mol / mol, preferably 0.0001 to 1 mol / mol, and more preferably 0.001 to 0.5 mol / mol.

[0074] [Step 1-a] In step 1-a, for example, a liquid-phase polymerization reactor is used to polymerize a monomer containing propylene in the presence of a polymerization catalyst, hydrogen, and diethylzinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the type and content of the structural units constituting the propylene polymer (a). The content of propylene in the monomers may be, for example, 80% by mass or more, 90% by mass or more, or even 100% by mass, based on the total mass of the monomers.

[0075] Examples of the liquid phase polymerization reactor include a loop type liquid phase reactor and a vessel type liquid phase reactor.

[0076] Examples of the polymerization catalyst include Ziegler-Natta catalysts and metallocene catalysts, with Ziegler-Natta catalysts being preferred. Examples of Ziegler-Natta catalysts include catalysts containing the above-mentioned solid catalyst component for olefin polymerization, an aluminum compound, and an electron donor compound. A catalyst pre-activated by contacting with a small amount of olefin can also be used as the polymerization catalyst.

[0077] As the polymerization catalyst, a prepolymerization catalyst component obtained by prepolymerizing an olefin in the presence of the above-mentioned solid catalyst component for olefin polymerization, normal hexane, triethylaluminum, diethylzinc, cyclohexylethyldimethoxysilane, etc. The olefin used for prepolymerization is preferably any one of the olefins constituting the heterophasic propylene polymerization material.

[0078] The polymerization temperature can be, for example, 0 to 120° C. The polymerization pressure can be, for example, normal pressure to 10 MPaG.

[0079] Step 1-a may be carried out continuously in multiple stages using a plurality of reactors in series.

[0080] [Step 1-b] In step 1-b, for example, a gas-phase polymerization reactor is used to polymerize a monomer containing propylene in the presence of a polymerization catalyst, hydrogen, and diethyl zinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the type and content of the structural units constituting the propylene polymer (a). The content of propylene in the monomers may be, for example, 80% by mass or more, 90% by mass or more, or even 100% by mass, based on the total mass of the monomers.

[0081] Examples of gas phase polymerization reactors include vessel type reactors, fluidized bed type reactors, and spouted bed type reactors.

[0082] The gas-phase polymerization reactor may be a multistage gas-phase polymerization reactor having a plurality of reaction zones connected in series. The multistage gas-phase polymerization reactor may be a multistage gas-phase polymerization reactor having a plurality of polymerization vessels connected in series. It is considered that such an apparatus makes it easy to adjust the intrinsic viscosity of the propylene polymer (a) to fall within the above range.

[0083] The multistage gas phase polymerization reactor may comprise, for example, a cylindrical section extending in the vertical direction, and a tapered section formed in the cylindrical section, the inner diameter of which decreases downward and which has a gas inlet opening at its lower end, and may comprise a spouted bed type olefin polymerization reaction region surrounded by the inner surface of the tapered section and the inner surface of the cylindrical section above the tapered section, within which a spouted bed is formed, and a fluidized bed type olefin polymerization reaction region.

[0084] The multistage gas-phase polymerization reactor preferably has multiple reaction zones in the vertical direction. From the viewpoint of the intrinsic viscosity of the propylene polymer (a), the multistage gas-phase polymerization reactor preferably has multiple reaction zones in the vertical direction, of which the uppermost one is a fluidized-bed olefin polymerization reaction zone and the remaining ones are multiple spouted-bed olefin polymerization reaction zones. In such an apparatus, for example, a fluidized bed or spouted bed is formed in the reaction zone by supplying a solid component from the top of the apparatus and a gas component from the bottom of the apparatus. The gas component may contain an inert gas such as nitrogen in addition to a monomer containing propylene and hydrogen. In such an apparatus, the number of spouted-bed olefin polymerization reaction zones is preferably 3 or more.

[0085] When multiple reaction zones are arranged vertically, the lower reaction zone may be disposed diagonally below the upper reaction zone. In such an apparatus, for example, the solid component obtained in the upper reaction zone is discharged diagonally downward, and the discharged solid component is supplied to the lower reaction zone from diagonally above. In this case, the gas component is, for example, discharged from the top of the lower reaction zone and supplied from the bottom of the upper reaction zone.

[0086] Specific examples of the polymerization catalyst are the same as those mentioned above.

[0087] The polymerization temperature may be, for example, 0 to 120° C., 20 to 100° C., or 40 to 100° C. The polymerization pressure may be, for example, atmospheric pressure to 10 MPaG, or 1 to 5 MPaG.

[0088] [Second Polymerization Step] The second polymerization step may be carried out in a liquid phase or a gas phase, for example, in a gas phase. When carried out in a liquid phase, for example, a liquid phase reactor such as a loop type or a vessel type can be used. When carried out in a gas phase, for example, a gas phase reactor such as a vessel type reactor, a fluidized bed type reactor, or a spouted bed type reactor can be used.

[0089] In the second polymerization step, for example, a monomer containing propylene and at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms is polymerized in the presence of a polymerization catalyst, hydrogen, and diethyl zinc. The composition of the monomers used in the polymerization can be appropriately adjusted based on the type and content of the structural units constituting the propylene-based copolymer (b). The content of at least one α-olefin selected from the group consisting of ethylene and α-olefins having from 4 to 12 carbon atoms in the monomers used in the polymerization may be, for example, 30 to 55% by mass, or 35 to 50% by mass, based on the total mass of the monomers.

[0090] Specific examples of the polymerization catalyst are the same as those mentioned above.

[0091] In the case of polymerization in a liquid phase, the polymerization temperature is, for example, 40 to 100° C., and the polymerization pressure is, for example, normal pressure to 5 MPaG. In the case of polymerization in a gas phase, the polymerization temperature is, for example, 40 to 100° C., and the polymerization pressure is, for example, 0.5 to 5 MPaG.

[0092] The propylene polymer (a) and the propylene copolymer (b) may be produced in separate steps, and the polymerization catalysts may be deactivated before they are mixed in a solution state, a melt state, or the like. Alternatively, the polymer may be continuously produced by supplying the resulting polymer to the next step without deactivating the catalyst. When continuous polymerization is carried out without deactivating the catalyst, the polymerization catalyst in the previous step also acts as a polymerization catalyst in the subsequent step.

[0093] The order of the first polymerization step and the second polymerization step is not particularly limited. The first polymerization step can include step 1-a and step 1-b.

[0094] The production method according to this embodiment may include, for example, step 1-a, step 1-b, and the second polymerization step in this order, or may not include step 1-b.

[0095] The order of steps 1 and 2 and step 3 can be selected as follows: (a) Step 3 is carried out after steps 1 and 2 are completed; (b) Step 3 is carried out simultaneously with step 1; (c) Step 3 is carried out simultaneously with step 2; (d) Step 3 is carried out simultaneously with step 1 and step 2. (a) can be achieved by carrying out step 3 before carrying out a deactivation treatment after the polymerization step or simultaneously with the deactivation treatment. (b), (c), and (d) can be achieved by causing an organozinc compound such as diethylzinc and a reactive gas such as oxygen gas to coexist during the polymerization step of step 1 or step 2.

[0096] The hydroxyl-modified heterophasic propylene polymer material of the present invention is as follows: A heterophasic propylene polymer material having a propylene polymer portion (A1) and a propylene-α-olefin copolymer portion (A2), in which (A1) and / or (A2) are partially modified with hydroxyl groups. The amount of —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is preferably 0.01×10 －３ wt% to 100 x 10 －３ wt%, more preferably 0.03 × 10 －３ wt% to 50 x 10 －３ wt%, more preferably 0.05 × 10 －３ wt% to 10 x 10 －３ The amount of —OH (hydroxyl group) is 0.01×10 －３ When the amount of -OH (hydroxyl group) is less than 100×10 wt %, the coating property of the resulting heterophasic propylene polymer material modified with hydroxyl groups may be insufficient. －３ If the content exceeds 100% by weight, the impact strength of the resulting heterophasic propylene polymer material modified with hydroxyl groups may be insufficient. Preferably, the propylene polymer portion (A1) is a propylene homopolymer portion.

[0097] The site of modification with a hydroxyl group may be (A1) only, (A2) only, or both (A1) and (A2). However, (A2) only or both (A1) and (A2) are preferred, and (A2) only is most preferred.

[0098] The bonding site in the polymer chain of the —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is preferably a terminal of the polymer chain, and particularly preferably only one terminal (one end). Because polymer chain terminals have higher mobility than the polymer chain itself, the hydroxyl groups bonded to the polymer chain terminals can effectively contribute to reactions and interactions with polar resins, inorganic fillers, and other fillers. Furthermore, by limiting the site of modification by hydroxyl groups to one terminal of the polymer chain, the number of hydroxyl groups per polymer chain is one or less. Therefore, when reacting with or interacting with polar resins, inorganic fillers, and the like, gelation due to a crosslinking reaction does not occur in principle, and deterioration of the appearance or mechanical properties does not occur. Furthermore, because the hydroxyl group is bonded to only one terminal of the polymer chain, the movement and crystallization of the polymer chain are not hindered, and the inherent physical properties of the polymer chain are not impaired, allowing the effects of the hydroxyl group to be utilized.

[0099] The ratio (A) of the number of hydroxyl group terminals to the number of initiation terminals of the propylene polymer material having a hydroxyl group is preferably 0.01 to 0.90, more preferably 0.02 to 0.70, even more preferably 0.03 to 0.50, particularly preferably 0.04 to 0.30, and most preferably 0.05 to 0.25.

[0100] 2. Method for producing a heterophasic propylene polymerization material modified with hydroxyl groups The method for producing a heterophasic propylene polymerization material modified with hydroxyl groups of the present invention is as follows: A method for producing a heterophasic propylene polymerization material in the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound, the method comprising the following steps (1) to (3) and satisfying condition (i): (1) a propylene polymerization step (A), (2) a propylene and α-olefin copolymerization step (B), (3) a reactive gas compound treatment step (C), (i) carrying out (A) and / or (B) in the presence of an organozinc compound.

[0101] The propylene polymer material obtained in the polymerization process of the present invention has organometallic end groups containing organozinc at at least a portion of its polymer chain ends. In the case of linear polymer chains, the organometallic end group is usually present at only one end. The organometallic end groups are generally highly reactive and can be stabilized in any non-polymerization reaction process, for example, with active proton compounds such as water, alcohols, and carboxylic acids, or reactive gas compounds such as oxygen and carbon dioxide. Examples of the stabilized end groups include hydroxyl groups and carboxyl groups. The propylene polymer material of the present invention may be a polymer material having organometallic end groups, or a terminally stabilized polymer material that has undergone any non-polymerization reaction process. It may also be a polymer material containing the polymer produced by combining the polymerization process of the present invention with another polymerization process.

[0102] Examples of active proton compounds that can be used in any non-polymerization reaction step include water (including, for example, atmospheric moisture, hydrated nitrogen gas, boiled water, etc.), alcohols (ethanol, boiled ethanol, methanol, boiled methanol, isopropyl alcohol, boiled isopropyl alcohol, etc.), hydrocarbons having active protons (toluene, etc.), carboxylic acids (acetic acid, etc.), inorganic acids (concentrated hydrochloric acid, carbonic acid, etc.), etc. Preferred active proton compounds are water, methyl alcohol, ethyl alcohol, isopropyl alcohol, and n-butyl alcohol, more preferably water, methyl alcohol, and ethyl alcohol, and even more preferably water.

[0103] The solid catalyst component for olefin polymerization and the organoaluminum compound used in the production method of the present invention may be the same as the solid catalyst component for olefin polymerization and the aluminum compound described above. The polymerization step 1) (propylene polymerization step) in the production method of the present invention may be the same as the first polymerization step described above. The polymerization step 2) (propylene and α-olefin copolymerization step) in the production method of the present invention may be the same as the second polymerization step described above.

[0104] The production method of the present invention can also employ a continuous supply step and a continuous withdrawal step. The reactor used in these steps is a reactor in which internal homogeneity is maintained by stirring or the like in the liquid phase and by gas flow or the like in the gas phase. The reactor may have a fractional structure in the polymerization region therein, but it is preferable that each fractional structure is as homogeneous as possible. The reactor may be constructed as a single unit, or it can be constructed by connecting multiple reactors. When multiple reactors are connected, they are preferably connected in series. When multiple reactors are connected in series, at least propylene, the solid catalyst component for olefin polymerization, and the organoaluminum compound are supplied to the most upstream reactor, and the reactor to which the organozinc compound is supplied may be continuously supplied as a polymer-containing material from the previous reactor. Furthermore, the organozinc compound is supplied to at least one reactor, but may also be supplied to multiple reactors. In the production method of the present invention, for example, in the continuous supply step, it is preferable to continuously supply the organoaluminum compound and the organozinc compound to the reactor using separate lines. That is, ３ Impurities (e.g., AlHEt ２When the organozinc compound reacts with the aluminum compound, the organozinc compound is reduced to zinc. Because zinc is gray, the resulting propylene polymer material is discolored. This discoloration can be avoided by supplying the organoaluminum compound and the organozinc compound to the reactor through separate lines. In the production method of the present invention, for example, a propylene polymer material is obtained through a polymerization step (a continuous supply step) in which propylene continuously supplied in a continuous supply step is polymerized in the reactor, and the propylene polymer material obtained in the reactor is then continuously removed from the reactor. In this continuous removal step, the propylene supplied in the continuous supply step, the solid catalyst component for olefin polymerization, the organoaluminum compound, and a portion of the organozinc compound are also removed, and their concentrations in the reactor are maintained within a certain range. Maintaining the concentration of the organozinc compound consumed during the polymerization reaction within a certain range is particularly important in maintaining a constant structure of the hydroxyl-modified heterophasic propylene polymer material. In batch polymerization, the organozinc compound is consumed as the polymerization reaction progresses, and the concentration of the organozinc compound in the polymerization system decreases. Therefore, the structure (molecular weight and amount of hydroxyl group modification) of the resulting hydroxyl-modified heterophasic propylene polymer material will differ between the initial stage and the final stage of polymerization. The supply rate of each component supplied in the continuous supply step and the withdrawal rate in the continuous withdrawal step can be changed within a range that maintains a constant concentration of each component in the reactor. The concentration of each component in the reactor is preferably maintained within ±30% of the target concentration, more preferably within ±10%. It is preferable that at least a portion of the continuous supply step and at least a portion of the continuous withdrawal step are carried out simultaneously.

[0105] The feed rate of the organozinc compound in the continuous feed step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 20 to 1,000 (mmol-Zn / kg-PP), more preferably 20 to 500 (mmol-Zn / kg-PP).

[0106] In the continuous supply step, the ratio of the supply rate of the organozinc compound to the supply rate of the organoaluminum compound is preferably 1.1 to 15 (mol Zn / mol Al), more preferably 1.2 to 10 (mol Zn / mol Al).

[0107] The feed rate of the organoaluminum compound in the continuous feed step relative to the production rate of the propylene polymer material in the continuous removal step is preferably 1 to 30 (mmol-Al / kg-PP), more preferably 2 to 30 (mmol-Al / kg-PP).

[0108] In the continuous supply step, it is preferable to further continuously supply hydrogen gas to the reactor.

[0109] The number of polymerization steps in the production method of the present invention is one or two or more. When the number of steps is two or more, the type and amount of monomer polymerized in each step and the polymerization conditions in each step may be different from each other, but propylene is polymerized in at least one step. The olefin polymer discharged from the final step is essentially a mixture of polymers produced in each step.

[0110] The contact of the organozinc compound, the solid catalyst component, the organoaluminum compound, and the external electron donor compound is carried out in a reactor or outside the reactor, with or without diluting these compounds or components with a solvent. The order of contacting these compounds and components is not particularly limited, but an example method is to supply the organoaluminum compound and the external electron donor compound to a reactor, and then supply the contact product of the organozinc compound and the solid catalyst component to the reactor. The supply to the reactor is preferably carried out in an inert gas such as nitrogen or argon in a moisture-free state.

[0111] Reactive Gas Compound Examples of reactive gas compounds used in the production method of the present invention include oxygen gas, air, water vapor containing oxygen gas or air, ozone gas, ethylene oxide gas, propylene oxide gas, and formaldehyde gas. For example, the reactive gas compound is preferably at least one gas selected from the group consisting of oxygen gas, air, and ozone gas. The reactive gas compound can also be diluted with nitrogen gas or the like before use. When diluted, the volume fraction of the reactive gas compound after dilution is preferably 0.05 to 15 vol%, more preferably 1 to 10 vol%, even more preferably 1 to 5 vol%, and most preferably 1 to 3 vol%. When the reactive gas compound is oxygen gas, an inert gas containing a lower concentration of oxygen gas than air is preferred.

[0112] Reactive Gas Compound Treatment Step The reactive gas compound treatment step can be carried out, for example, under conditions of a total pressure of 3 MPa or less. Carrying out a reaction under high-pressure conditions requires an expensive reaction vessel capable of withstanding high pressures, which is undesirable from an economic standpoint. It is preferable to carry out the reaction under conditions of a total pressure of 0.1 MPa or more. More preferably, the total pressure is 0.1 to 1 MPa, and most preferably, 0.1 to 0.2 MPa. When the molar amount of the reactive gas compound used is A and the molar amount of the organozinc compound used is B, the value of A / B is preferably 1 to 100,000. The value of A / B is more preferably 1 to 10,000, even more preferably 1 to 1,000, particularly preferably 1 to 100, and most preferably 1 to 50. The duration of the reactive gas compound treatment step is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes.

[0113] When a polymeric material having organometallic end groups is treated with a reactive gas compound in any non-polymerization reaction step, it is preferable to further treat it with an active proton compound. The treatment time with the active proton compound is preferably 1 to 120 minutes, more preferably 1 to 90 minutes, and even more preferably 1 to 60 minutes. In any non-polymerization reaction step of a polymeric material having organometallic end groups, the treatment with the reactive gas compound and the treatment with the active proton compound may be carried out simultaneously. That is, the polymeric material having organometallic end groups may be treated with a mixture of the reactive gas compound and the active proton compound. In this case, the number of treatments can be reduced, which is preferable in terms of efficiency and economy.

[0114] The terminal-stabilized polymer material that has undergone any non-polymerization reaction step is preferably further treated in a step of removing volatile compounds. Specific examples of the step of removing volatile compounds include a method of reducing pressure while heating, a method of passing nitrogen gas while heating, and a method of continuously extracting and removing volatile compounds with heated water or heated alcohol, followed by a method of reducing pressure or passing nitrogen gas. Possible volatile compounds include (a) dilution solvents such as propylene, hydrogen gas, hexane, and heptane; (b) ethanol and low-molecular-weight (oligomeric) alcohols (e.g., 2-methyl-1-butanol and 2-methyl-1-pentanol) produced from unreacted diethylzinc compounds or triethylaluminum and oxygen gas; and (c) active proton compounds such as water and ethanol that were added in the non-polymerization reaction step. If (b) remains in the propylene polymer material, it may interfere with the functional expression of the propylene polymer material or may cause the propylene polymer material to have an odor. The time required for the step of removing volatile compounds is preferably 1 to 120 minutes. It is more preferably 1 to 90 minutes. It is more preferable that the time is 1 to 60 minutes.

[0115] The melting point (Tm) of the propylene polymer material of the present invention is preferably 150 to 170°C, more preferably 158 to 170°C, even more preferably 160 to 168°C, and most preferably 161 to 168°C.

[0116] The heat of fusion (ΔH) of the propylene polymer material of the present invention is preferably 80 to 150 (kJ / mol), more preferably 100 to 135 (kJ / mol).

[0117] Polypropylene composition, graft modified product, or block modified product The polypropylene composition, graft modified product, or block modified product of the present invention is as follows: A polypropylene composition, graft modified product, or block modified product comprising the heterophasic propylene polymer material and a polymer having a polar group.

[0118] Polymers Having Polar Groups The polar groups of polymers having polar groups are functional groups that can react with or interact with hydroxyl groups. Specific functional groups may be carboxyl groups, carbonyl groups, isocyanate groups, epoxy groups, carbodiimide groups, oxazoline groups, or amino groups. Polymers containing carboxyl groups may also be polymers having unsaturated carboxylic acids or derivatives of unsaturated carboxylic acids. Examples of unsaturated carboxylic acids include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid. In addition, examples of derivatives of unsaturated carboxylic acids include acid anhydrides, ester compounds, amide compounds, imide compounds, metal salts, and the like derived from the unsaturated carboxylic acids. Specific examples include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, glycidyl methacrylate, monoethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, acrylamide, methacrylamide, monoamide maleate, diamide maleate, monoamide fumarate, maleimide, N-butylmaleimide, and sodium methacrylate. Compounds that dehydrate to produce unsaturated carboxylic acids during graft polymerization onto polypropylene, such as citric acid and malic acid, may also be used. The polymer used in the polymer having a polar group is not particularly limited. Examples include homopolymers, copolymers, and terpolymers of olefins, etc.

[0119] Examples of polymers having a polar group include maleic anhydride-modified polypropylene, polyamide, nylon 4, nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon 610, polymethyl methacrylate, polymethyl acrylate, polyacrylic acid, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polybutylene succinate polylactic acid, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyethylene glycol, polyethylene oxide, polypropylene glycol, polypropylene oxide, polyurethane, polycarbodiimide, and polyimide.

[0120] When maleic anhydride-modified polypropylene is used as the polymer having a polar group, the intrinsic viscosity ([η]II) of the polymer (II) in the heterophasic propylene polymerization material is preferably 1.50 to 8.00 dL / g, more preferably 2.00 to 8.00 dL / g, and even more preferably 2.50 to 8.00 dL / g.

[0121] When nylon is used as the polymer having a polar group, the intrinsic viscosity ([η]II) of the polymer (II) in the heterophasic propylene polymerization material is preferably 1.50 to 8.00 dL / g, more preferably 2.00 to 8.00 dL / g, and even more preferably 2.50 to 8.00 dL / g.

[0122] <<Coupling Compound>> In the heterophasic propylene polymer material of the present invention, the heterophasic propylene polymer material and a polymer having a polar group may be bonded, preferably by a covalent bond. A hydroxyl group of the heterophasic propylene polymer material may be bonded, preferably by a covalent bond, to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group. The covalent bond is preferably an ester bond.

[0123] <<Method for Producing a Coupling Product>> A coupling product can be produced by melt-kneading a heterophasic propylene polymerization material and a polymer having a polar group in an extruder, or by heating a heterophasic propylene polymerization material and a polymer having a polar group in a solvent. The coupling product may be in the form of either a graft-modified product or a block-modified product. The coupling product is a graft-modified product and / or a block-modified product comprising the following segment (I) and segment (II): Segment (I): A propylene polymerization segment containing 90% by weight or more of structural units derived from propylene, relative to 100% by weight of the total weight of the propylene polymerization segment. Segment (II): At least one segment selected from the group consisting of an ethylene-α-olefin copolymer segment and a hydrogenated conjugated diene copolymer segment, wherein the ethylene-α-olefin copolymer segment contains structural units derived from ethylene and structural units derived from an α-olefin having 3 to 10 carbon atoms, and the structural units derived from ethylene are more than 10 wt% and not more than 99 wt% relative to 100 wt% of the total weight of the ethylene-α-olefin copolymer segment. A coupling catalyst (crosslinking catalyst) can also be added during production of the coupled product.

[0124] <<Coupling Catalyst (Crosslinking Catalyst)>> By adding a coupling catalyst, hydroxyl groups and polar groups in the heterophasic propylene polymer material are covalently bonded to form a coupling product in which the heterophasic propylene polymer material and a polymer having a polar group are covalently bonded. The coupling product can be either a graft type or a block type. Adding a coupling catalyst to form a coupling product can impart toughness, such as impact resistance and tensile elongation. Examples of coupling catalysts include metal compounds, nitrogen-containing compounds, and Bronsted acids. Preferred are inorganic metal compounds such as metal oxides, metal hydroxides, metal alkoxides, metal carboxylates, metal enolates, and metal carbonates. More preferred are inorganic transition metal compounds such as transition metal oxides, transition metal hydroxides, transition metal alkoxides, transition metal carboxylates, transition metal enolates, and transition metal carbonates. Specific examples of metal oxides include lithium oxide, sodium oxide, potassium oxide, magnesium oxide, calcium oxide, titanium oxide, zirconium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zinc oxide, aluminum oxide, and tin oxide. Specific examples of metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, titanium hydroxide, zirconium hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, zinc hydroxide, aluminum hydroxide, and tin hydroxide. Specific examples of metal alkoxides include lithium alkoxide, sodium alkoxide, potassium alkoxide, magnesium alkoxide, calcium alkoxide, titanium alkoxide, zirconium alkoxide, iron alkoxide, cobalt alkoxide, nickel alkoxide, copper alkoxide, zinc alkoxide, aluminum alkoxide, and tin alkoxide.Specific examples of metal carboxylates include lithium carboxylate, sodium carboxylate, potassium carboxylate, magnesium carboxylate, calcium carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, copper carboxylate, zinc carboxylate, aluminum carboxylate, tin carboxylate, etc. Specific examples of metal enolates include lithium enolate, sodium enolate, potassium enolate, magnesium enolate, calcium enolate, titanium enolate, zirconium enolate, iron enolate, cobalt enolate, nickel enolate, copper enolate, zinc enolate, aluminum enolate, tin enolate, etc. Specific examples of metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, titanium carbonate, zirconium carbonate, iron carbonate, cobalt carbonate, nickel carbonate, copper carbonate, zinc carbonate, aluminum carbonate, and tin carbonate. The inorganic metal compound is preferably an inorganic transition metal compound. Specific examples of transition metal oxides include titanium oxide, zirconium oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide. Specific examples of transition metal hydroxides include titanium hydroxide, zirconium hydroxide, iron hydroxide, cobalt hydroxide, nickel hydroxide, copper hydroxide, and zinc hydroxide. Specific examples of transition metal alkoxides include titanium alkoxides, zirconium alkoxides, iron alkoxides, cobalt alkoxides, nickel alkoxides, copper alkoxides, and zinc alkoxides.Preferred examples of the transition metal alkoxide include tetraalkyl titanates such as tetrastearyl titanate, tetraisopropyl titanate, and tetranormalbutyl titanate, and tetraalkyl zirconates such as tetrastearyl zirconate, tetraisopropyl zirconate, and tetranormalbutyl zirconate. Specific examples of the transition metal carboxylate include titanium carboxylate, zirconium carboxylate, iron carboxylate, cobalt carboxylate, nickel carboxylate, copper carboxylate, and zinc carboxylate. Preferred examples of the transition metal carboxylate include titanium carboxylates such as titanium stearate and titanium octanoate, and zirconium carboxylates such as zirconium stearate and zirconium octanoate. Specific examples of transition metal enolates include titanium enolate, zirconium enolate, iron enolate, cobalt enolate, nickel enolate, copper enolate, and zinc enolate. Preferable transition metal enolates include titanium enolates derived from 1,3-diketones, such as titanium tetraacetylacetonate, and zirconium enolates derived from 1,3-diketones, such as zirconium tetraacetylacetonate. Specific examples of transition metal carbonates include titanium carbonate, zirconium carbonate, iron carbonate, cobalt carbonate, nickel carbonate, copper carbonate, and zinc carbonate. Preferred inorganic transition metal compounds are transition metal oxides, transition metal hydroxides, transition metal alkoxides, and transition metal enolates.

[0125] Method for Producing Polypropylene Composition, Graft Modified Product, or Block Modified Product The method for producing the polypropylene composition, graft modified product, or block modified product of the present invention may include, for example, melt-kneading a material containing the heterophasic propylene polymerization material and the polymer having a polar group, or a material containing the heterophasic propylene polymerization material, the polymer having a polar group, and the crosslinking catalyst, in an extruder or heating in a solvent.

[0126] The polypropylene composition, graft modified product, or block modified product of the present invention can be produced, for example, by the above-mentioned method for producing the polypropylene composition, graft modified product, or block modified product.

[0127] The heterophasic propylene polymer material and polypropylene composition, graft-modified product, or block-modified product of the present invention can be mixed with known thermoplastic elastomers in a powder state or a hot-molten state. Specific examples of thermoplastic elastomers include styrene-based thermoplastic elastomers (TPS) such as styrene-ethylene-butene-styrene (SEBS), olefin-based thermoplastic elastomers (TPO) such as ethylene-propylene copolymers (EPR), ethylene-butene copolymers (EBR), and ethylene-octene copolymers (EOR), vinyl chloride-based thermoplastic elastomers, urethane-based thermoplastic elastomers (TPU), ester-based thermoplastic elastomers (TPC), amide-based thermoplastic elastomers (TPA), and butadiene-based thermoplastic elastomers.

[0128] Fillers: The heterophasic propylene polymer material and polypropylene composition, graft-modified product, or block-modified product of the present invention can be mixed with known fillers in a powder or molten state. Specific examples of fillers include glass fiber, carbon fiber, mica, talc, clay, alumina, silica, wolsenite, kaolin, bentonite, calcium silicate, aluminum silicate, sand, diatomaceous earth, titanium oxide, iron oxide, aluminum oxide, magnesium oxide, antimony oxide, barium ferrite, strontium ferrite, beryllium oxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, dolomite, dawsonite, calcium sulfate, magnesium sulfate, calcium sulfite, carbon black, molybdenum sulfide, magnet powder, cadmium sulfide, whiskers, wood flour, wood fiber, bamboo powder, melamine, and cellulose. Fillers may be used alone or in combination of at least two or more.

[0129] Other Components The heterophasic propylene polymer material and polypropylene composition, graft-modified product, or block-modified product of the present invention can be mixed with known additives in a powder or molten state. Examples of such additives include neutralizers, antioxidants, UV absorbers, light stabilizers, antistatic agents, antiblocking agents, processing aids, organic peroxides, colorants (inorganic pigments, organic pigments, pigment dispersants, etc.), foaming agents, foam nucleating agents, plasticizers, flame retardants, crosslinking aids, brightness enhancers, antibacterial agents, light diffusing agents, and scratch resistance inhibitors. These additives may be mixed alone or in combination of two or more.

[0130] Molded Articles The polypropylene composition, graft modified product, or block modified product of the present invention is used to produce molded articles by, for example, injection molding, press molding, extrusion molding, sheet molding, blow molding, vacuum molding, inflation molding, etc.

[0131] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0132] <Synthesis of Hydroxyl Group-Modified Heterophagic Propylene Polymerization Material-1> [Preparation of Solid Catalyst Component] A solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP-A-2009-173870.

[0133] [Prepolymerization] 1.5 L of n-hexane, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution), which had been thoroughly dehydrated and degassed, were charged into a 2 L internal volume SUS autoclave equipped with a stirrer. 13 g of the solid catalyst component for olefin polymerization prepared above was added thereto, and while maintaining the temperature inside the autoclave at about 3 to 10°C, 46 g of propylene was continuously fed over about 30 minutes to carry out prepolymerization. Thereafter, the prepolymerized slurry was transferred to a 160 L internal volume SUS autoclave equipped with a stirrer, and 130 L of fully purified liquid butane was added to form a slurry of the prepolymerized catalyst component, which was then stored at a temperature of 10°C or below.

[0134] Propylene homopolymerization was carried out using a 42 L vessel-type slurry polymerization reactor equipped with a stirrer. The liquid level in the slurry polymerization reactor was adjusted to 18 L, and propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the slurry of prepolymerized catalyst component prepared above were continuously fed into the reactor to polymerize. The reaction conditions were: polymerization temperature: 70°C, pressure: 4.23 MPaG, propylene feed rate: 23 kg / h, hydrogen feed rate: 179.3 NL / h, triethylaluminum feed rate: 28.1 mmol / h (hexane solution), cyclohexylethyldimethoxysilane feed rate: 4.2 mmol / h (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.51 g / h. The amount of propylene polymer component (A) continuously discharged from the reactor was 3.0 kg / h. The resulting slurry containing the propylene polymer component (A) was continuously transferred to the reactor for the second step without being deactivated.

[0135] [Second Step: Propylene Polymerization (Gas-Phase Polymerization)] Propylene homopolymerization was carried out using a 1.4 m3 gas-phase fluidized-bed reactor equipped with an agitator. Propylene, hydrogen, and nitrogen were supplied to the reactor so that the fluidized-bed propylene polymer material load was 49.5 kg, the polymerization temperature was 83°C, the polymerization pressure was 1.94 MPaG, the reactor gas superficial velocity was 0.144 m / s, the hydrogen concentration in the gas phase was 6.87 mol%, and the propylene concentration was 80.4 mol%. The slurry containing the propylene polymer component (A) continuously discharged from the reactor was continuously polymerized. The amount of propylene polymer material (B) continuously discharged from the reactor was 13.4 kg / h. The resulting propylene polymer material (B) was continuously transferred to the reactor for the third step without deactivation.

[0136] Third-stage propylene-ethylene copolymerization (gas-phase polymerization reaction) Propylene and ethylene were copolymerized using a 0.98 m3 gas-phase fluidized-bed reactor equipped with an agitator. Propylene, hydrogen, ethylene, and nitrogen were supplied to the reactor under the following conditions: fluidized bed propylene polymer material load: 27.9 kg; polymerization temperature: 70°C; polymerization pressure: 1.25 MPaG; superficial gas velocity inside the reactor: 0.103 m / s; hydrogen concentration in the gas phase: 0.96 mol%; propylene concentration: 80.0 mol%; and ethylene concentration: 17.6 mol%. Diethylzinc: 20.2 mmol / h (hexane solution) was also supplied. The propylene polymer material (B) continuously discharged from the reactor was continuously polymerized under these conditions. Diethylzinc was supplied to the reactor via a separate feed line. The propylene polymer material continuously discharged from the reactor was 16.7 kg / h and continuously transferred to a post-treatment process. While continuously receiving the obtained propylene polymer material 7, nitrogen at 60°C was passed through for 1 hour at a flow rate of 20 Nm3 / h, and then nitrogen at 60°C was passed through for another 1 hour at a flow rate of 20 Nm3 / h to dry, thereby obtaining a heterophasic propylene polymer material-1 having a zinc atom bonded to one end. Thereafter, the heterophasic propylene polymer material-1 having a zinc atom bonded to one end was contacted with dry air for 1 hour, and then with air containing water for 1 hour to obtain a hydroxyl group-modified heterophasic propylene polymer material-1.

[0137] <Composition of Hydroxyl Group-Modified Heterophagic Propylene Polymer Material-1> (1) Content of Ethylene-Propylene Copolymer Component (B-1) (X Ｂ－１ The heat of crystal fusion of the propylene homopolymer component (AI) and the hydroxyl group-modified heterophasic propylene polymer material-1 as a whole was measured, and the content (X Ａ－１ ) and the content of ethylene-propylene copolymer component (B-1) (X Ｂ－１ The heat of fusion of crystals was measured by differential scanning calorimetry (DSC).

[0138] The conditions for differential scanning calorimetry (DSC) were as follows: first, in the first run (first scan), the temperature was increased from 50°C to 220°C at 200°C / min and held at 220°C for 5 minutes; then, the temperature was decreased from 220°C to 180°C at 70°C / min and held at 180°C for 1 minute; then, the temperature was decreased from 180°C to 50°C at 150°C / min and held at 50°C for 2 minutes (temperature decrease process); then, in the second run (second scan), the temperature was increased from 50°C to 185°C at 16°C / min. The endothermic peak of the heterophasic propylene polymer material or the propylene homopolymer component during the second run was measured, and the (ΔHf) shown below was calculated from the obtained peak area. Ｔ and (ΔHf) Ａ－Ｉ The amount of sample used for each differential scanning calorimetry (DSC) was about 5 mg.

[0139] X Ａ－１ = (ΔHf) Ｔ / (ΔHf) Ａ－１ X Ｂ－１ = 1 - (ΔHf) Ｔ / (ΔHf) Ａ－１ (ΔHf) Ｔ ΔHf: heat of fusion (J / g) of the propylene homopolymer component (A-1) contained in the entire hydroxyl group-modified heterophasic propylene polymer material-1 Ａ－Ｉ: Heat of fusion (J / g) of propylene homopolymer component (A-1) In differential scanning calorimetry (DSC) under the above conditions, ethylene-propylene copolymer component (B-1) does not substantially exhibit an endothermic peak. Ｔ The peak area for determining (ΔHf) corresponds to the peak area derived from the propylene homopolymer component (A-1) contained in the entire hydroxyl group-modified heterophasic propylene polymer material-1. Ｔ corresponds to the heat of fusion of the propylene homopolymer component (A-1) contained in the entire hydroxyl-modified heterophasic propylene polymer material-1, which is determined by measuring the heat of fusion of the entire hydroxyl-modified heterophasic propylene polymer material-1.

[0140] (X Ａ－１ ) and (X Ｂ－１ ), the content of the propylene homopolymer component (A-1) and the content of the ethylene-propylene copolymer component (B-1) were 78% by mass and 22% by mass, respectively, relative to 100% by mass of the total amount of the propylene homopolymer component (A-1) and the ethylene-propylene copolymer component (B-1).

[0141] (2) Ethylene-Derived Monomer in Ethylene-Propylene Copolymer Component (B-1) The infrared absorption spectrum of the hydroxyl-modified heterophasic propylene polymer material-1 was measured using an FT-IR5200 model (manufactured by JASCO Corporation). From the obtained infrared absorption spectrum, the content of the ethylene-derived monomer unit in the hydroxyl-modified heterophasic propylene polymer material-1 was calculated using the following formula:

[0142] Y Ｂ－１ = (T - C2') / X Ｂ－１ (mass %) T-C2': content of monomer units derived from ethylene in hydroxyl group-modified heterophasic propylene polymer material. T-C2' was quantified in accordance with the method described in the Polymer Analysis Handbook (author: Polymer Analysis Research Forum, Japan Society for Analytical Chemistry, published by Kinokuniya Shoten). 1) Density of infrared absorption spectrum measurement sample: ρ (g / cm ３ ) and thickness: t (cm), and wave number 736 cm －１ Absorbance A' at７３６ and wave number 722 cm －１ Absorbance A' at ７２２ Therefore, the wave number is 736 cm according to the following formula: －１ The apparent extinction coefficient (K' ７３６ ) ａ and wave number 722 cm －１ The apparent extinction coefficient (K' ７２２ ) ａ The density of the sample used for measuring the infrared absorption spectrum was 0.9 g / cm ３ The thickness of the sample used for measuring the infrared absorption spectrum was measured using a commercially available digital thickness gauge (contact type thickness gauge, product name: Ultra High Precision Decimicrohead MH-15M, manufactured by Nippon Kogaku Co., Ltd.) and was found to be 0.02 cm. (K' ７３６ ) ａ = A' ７３６ / (ρt) (K' ７２２ ) ａ = A' ７２２ / (ρt) 2) Wave number 736 cm according to the following formula －１ The corrected extinction coefficient (K' ７３６ ) ｃ and wave number 722 cm －１ The corrected extinction coefficient (K' ７２２ ) ｃ (K') was calculated. ７３６ ) ｃ =1 / 0.96 {(K' ７３６ ) ａ -0.268 (K' ７２２ ) ａ (K' ７２２ ) ｃ =1 / 0.96 {(K' ７２２ ) ａ -0.150 (K' ７３６ ) ａ 3) T-C2' (mass%) was calculated using the following formula: T-C2' = 0.575 {(K' ７２２ ) ｃ +(K' ７３６ ) ｃ X B－Ｉ Y: Content (mass%) of ethylene-propylene copolymer component (B-1) in the entire hydroxyl group-modified heterophasic propylene polymer material Ｂ－ＩY: Content (mass%) of monomer units derived from ethylene in the ethylene-propylene copolymer component (B-I) The content (mass%) of monomer units derived from ethylene relative to 100% by mass of the total amount of monomer units derived from propylene and monomer units derived from ethylene Ｂ－１ ) was 24% by mass.

[0143] (3) Measurement of OH group content in ethylene-propylene copolymer component (B-1) Model: Bruker AVANCE600 Probe: 10 mm Cryoprobe Measurement solvent: 1,1,2,2-tetrachloroethane-d2 Measurement temperature: 135°C Pulse repetition time: 3.8 seconds 90° pulse width: 15.10 usec Measurement: 30° pulse Number of accumulations: 2048 BHT concentration: 0.5 mg / mL Magnetic field strength: 600 MHz (1H) Measurement standard: tetramethylsilane 1H NMR measurement was performed under the above conditions, and the integral values ​​of the following peaks (a1 to a3) were calculated when the integral value of all peaks present between 2 and 0 ppm was set to 1,000,000. The OH group content in (B-1) was calculated by substituting these values ​​into the following formula: a1 (3.721 to 3.650 ppm): CH2CH2OH a2 (3.632 to 3.534 ppm): CH (CH3) CH2OH a3 (3.515 to 3.406 ppm): CH (CH3) CH2OH OH group content = ((a1+a2+a3) / 1000,000)×(17 / 14)×100(%)

[0144] (4) Intrinsic viscosity of propylene homopolymer component (A-1) The intrinsic viscosity ([η Ａ－１ ]) is the intrinsic viscosity measured in tetralin at a temperature of 135°C, and was determined by the calculation method described on page 491 of "Polymer Solutions, Polymer Experiments 22" (published by Kyoritsu Shuppan Co., Ltd. in 1982). That is, the reduced viscosity was plotted against the concentration, and the viscosity was determined by an extrapolation method in which the concentration was extrapolated to zero. The reduced viscosity was measured at three concentrations of 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL using an Ubbelohde viscometer under the conditions of a temperature of 135°C and a tetralin solvent. The intrinsic viscosity of the propylene homopolymer component (A-1) was 1.0 g / dL.

[0145] (5) Intrinsic viscosity of ethylene-propylene copolymer component (B-1) Intrinsic viscosity of hydroxyl group-modified heterophasic propylene polymer material-1 ([η １ ]) was measured by the intrinsic viscosity ([η Ａ－Ｉ The intrinsic viscosity ([η Ｂ－１ ]) was sought.

[0146] [η Ｂ－１ ]=([η １ ]-[η Ｂ－１ ]×[X Ｂ－１ ]) / X Ｂ－１

[0147] The intrinsic viscosity of the ethylene-propylene copolymer component (B-1) was 2.8 g / dL.

[0148] <Synthesis of Hydroxyl Group-Modified Heterophagic Propylene Polymerization Material-2> [Preparation of Solid Catalyst Component] A solid catalyst component for olefin polymerization was obtained according to the method described in Example 1 of JP-A-2009-173870.

[0149] [Prepolymerization] 1.5 L of n-hexane, 30.7 mmol of triethylaluminum (hexane solution), and 4.0 mmol of cyclohexylethyldimethoxysilane (hexane solution), which had been thoroughly dehydrated and degassed, were charged into a 2 L internal volume SUS autoclave equipped with a stirrer. 13 g of the solid catalyst component for olefin polymerization prepared above was added thereto, and while maintaining the temperature inside the autoclave at about 3 to 10°C, 46 g of propylene was continuously fed over about 30 minutes to carry out prepolymerization. Thereafter, the prepolymerized slurry was transferred to a 160 L internal volume SUS autoclave equipped with a stirrer, and 130 L of fully purified liquid butane was added to form a slurry of the prepolymerized catalyst component, which was then stored at a temperature of 10°C or below.

[0150] [First-Stage Propylene Polymerization (Liquid-Phase Polymerization)] Propylene homopolymerization was carried out using a 42 L vessel-type slurry polymerization reactor equipped with an agitator. The liquid level in the slurry polymerization reactor was adjusted to 18 L, and polymerization was carried out by continuously feeding propylene, hydrogen, triethylaluminum, cyclohexylethyldimethoxysilane, and the prepolymerized catalyst component slurry prepared above into the reactor. The reaction conditions were: polymerization temperature: 70°C, pressure: 4.21 MPaG, propylene feed rate: 23 kg / h, hydrogen feed rate: 179.7 NL / h, triethylaluminum feed rate: 29.3 mmol / h (hexane solution), cyclohexylethyldimethoxysilane feed rate: 4.3 mmol / h (hexane solution), and prepolymerized catalyst component slurry feed rate (solid catalyst component equivalent): 0.52 g / h. The amount of propylene polymer component (A) continuously discharged from the reactor was 3.3 kg / hour. The resulting slurry containing propylene polymer component (A) was continuously transferred to the reactor for the second step without being deactivated.

[0151] [Second-Stage Propylene Polymerization (Gas-Phase Polymerization)] Propylene homopolymerization was carried out using a 1.4 m3 gas-phase fluidized-bed reactor equipped with a stirrer. Propylene, hydrogen, and nitrogen were supplied to the reactor so that the fluidized-bed propylene polymer material load was 49.6 kg, the polymerization temperature was 83°C, the polymerization pressure was 1.94 MPaG, the reactor gas superficial velocity was 0.141 m / s, the hydrogen concentration in the gas phase was 6.95 mol%, and the propylene concentration was 80.0 mol%. The slurry containing the propylene polymer component (A) continuously discharged from the reactor was continuously polymerized. The amount of propylene polymer material (B) continuously discharged from the reactor was 13.9 kg / h. The resulting propylene polymer material (B) was continuously transferred to the reactor for the third step without deactivation.

[0152] Third-stage propylene-ethylene copolymerization (gas-phase polymerization reaction) Propylene and ethylene copolymerization was carried out using a 0.98 m3 gas-phase fluidized-bed reactor equipped with an agitator. Propylene, hydrogen, ethylene, and nitrogen were supplied to the reactor under the following conditions: fluidized bed propylene polymer material load: 27.9 kg; polymerization temperature: 70°C; polymerization pressure: 1.24 MPaG; superficial gas velocity inside the reactor: 0.105 m / s; hydrogen concentration in the gas phase: 0.12 mol%; propylene concentration: 75.5 mol%; and ethylene concentration: 23.6 mol%. Diethylzinc: 21.0 mmol / h (hexane solution) was also supplied. The propylene polymer material (B) continuously discharged from the reactor was continuously polymerized under these conditions. Diethylzinc was supplied to the reactor via a separate feed line. The propylene polymer material continuously discharged from the reactor was 17.4 kg / h and continuously transferred to a post-treatment process. While continuously receiving the obtained propylene polymer material 7, nitrogen at 60°C was passed through for 1 hour at a flow rate of 20 Nm / h, and then nitrogen at 60°C was passed through for another 1 hour at a flow rate of 20 Nm / h to dry the propylene polymer material 7. Thereafter, the propylene polymer material was brought into contact with dry air for 1 hour, and then with air containing water for 1 hour.

[0153] <Hydroxyl-modified heterophasic propylene polymerization material-3> Under nitrogen, degassed ethanol (100 mL) was added to heterophasic propylene polymerization material-1 (4 kg) having a zinc atom bonded to one end, and the mixture was allowed to stand at room temperature for 16 hours. After that, the mixture was brought into contact with water-containing air at room temperature. The mixture was dried in a vacuum dryer at 80°C for 1 hour to obtain hydroxyl-modified heterophasic propylene polymerization material-3.

[0154] Heterophagic propylene polymer material-4 (Noblen AZ640G manufactured by Sumitomo Chemical Co., Ltd.) The content of ethylene-propylene copolymer component (B-4), the content of monomer units derived from ethylene in ethylene-propylene copolymer component (B-4), the OH group content in ethylene-propylene copolymer component (B-4), the intrinsic viscosity of propylene homopolymer component (A-4), and the intrinsic viscosity of ethylene-propylene copolymer component (B-4) were measured in the same manner as in the case of hydroxyl group-modified heterophasic propylene polymer material-1. Content of ethylene-propylene copolymer component (B-4): 20% by mass Content of monomer units derived from ethylene in ethylene-propylene copolymer component (B-4): 40% by mass OH group content in ethylene-propylene copolymer component (B-4): 0% by mass Intrinsic viscosity of propylene homopolymer component (A-4): 1.1 dl / g Intrinsic viscosity of ethylene-propylene copolymer component (B-1): 3.0 dl / g

[0155] Hydroxyl-modified heterophasic propylene polymer material-2, hydroxyl-modified heterophasic propylene polymer material-3, and heterophasic propylene polymer material-4 were analyzed using DSC, IR, and NMR in the same manner as hydroxyl-modified heterophasic propylene polymer material-1. The analytical results are summarized in Table 1.

[0156]

[0157] Maleic anhydride-modified polypropylene-1: Synthesis Example 2 described in WO2020 / 009090 was used.

[0158] Other materials Antioxidant 1: Irganox 1010 manufactured by BASF Japan Ltd. Antioxidant 2: Irgafos 168 manufactured by BASF Japan Ltd. Neutralizer: calcium stearate manufactured by Sun-Ace Co., Ltd. Crosslinking catalyst 1: Orgatix ZC-150 (tetrastearyl titanate (Ti catalyst)) manufactured by Matsumoto Fine Chemical Co., Ltd. Crosslinking catalyst 2: Orgatix TA-90 (zirconium tetraacetylacetonate (Zr catalyst)) manufactured by Matsumoto Fine Chemical Co., Ltd.

[0159] Example 1 Melt-Kneading and Production of Injection-Molded Articles 100 parts by mass of the heterophasic propylene polymerization material-1, 0.2 parts by mass of antioxidant 1, 0.2 parts by mass of antioxidant 2, and 0.05 parts by mass of neutralizer were mixed to obtain a mixture. The mixture was melt-kneaded in a 40 mm single-screw extruder (VS40-28 vented extruder, manufactured by Tanabe Plastics Co., Ltd.) at a cylinder temperature of 200°C and a screw rotation speed of 100 rpm, and pelletized. 95 parts by mass of the resulting pellets were mixed with 5 parts by mass of maleic anhydride-modified polypropylene-1 and melt-kneaded in a twin-screw kneader (manufactured by Technovel Co., Ltd., KZW12TW-60 / 75mg-NH, screw diameter 12 mm, L / D = 75, cylinder temperature 200°C, rotation speed 300 rpm, and discharge rate 2 kg / hr) to obtain pellets of a polypropylene composition. The obtained pellets of the polypropylene composition were injection molded using an injection molding machine (M-70CSJ manufactured by Meiki Seisakusho Co., Ltd.) under conditions of a cylinder temperature of 197°C and a mold temperature of 40°C, to obtain an injection-molded article of JIS K7139 A-type multipurpose test piece (ISO3167 A-type multipurpose test piece).

[0160] Examples 2 to 5 and Comparative Example 1 Polypropylene compositions of Examples 2 to 5 and Comparative Example 1 were produced in the same manner as in Example 1, except that the materials shown in Table 1 were used.

[0161] 1. Flexural modulus (unit: MPa) Using test pieces having a thickness of 4 mm molded by the molding method described in the above "Melt kneading and production of injection molded articles," the flexural modulus (FM) was measured at a loading rate of 2.0 mm / min according to the method specified in ISO 178.

[0162] 2. Notched Charpy impact strength (unit: kJ / m ２ ) Molded articles molded by the molding method described above in "Melt kneading and production of injection molded articles" were cut into pieces measuring 80 mm x 10 mm x 4 mm, and notched to serve as test pieces. The notched Charpy impact strength was measured by edgewise impact according to the method specified in ISO 179-1. The notch shape was Shape A described in ISO 179-1.

[0163]

[0164] The results in Table 2 indicate that the polypropylene compositions of Examples 1 to 5, which used a hydroxyl-modified heterophasic propylene polymer material, exhibited a high flexural modulus and a high notched Charpy impact strength (Charpy 23°C), whereas the polypropylene composition of Comparative Example 1, which used a non-hydroxyl-modified heterophasic propylene polymer material, exhibited a poorly low notched Charpy impact strength (Charpy 23°C). Furthermore, the polypropylene compositions of Examples 4 and 5, which used a crosslinking catalyst, exhibited higher notched Charpy impact strength (Charpy 23°C) than the polypropylene compositions of Examples 1 to 3, which did not use a crosslinking catalyst. This is presumably due to the presence of more covalent bonds between the hydroxyl groups in the heterophasic propylene polymer material and the polymer (maleic anhydride-modified polypropylene) having the polar group, resulting from the use of a crosslinking catalyst. The basis for this is shown in the NMR measurement results below.

[0165] ​<Analysis of Graft-Modified Products in Which the Hydroxyl Group of (A2) in the Heterophagic Propylene Polymerization Material and the Carboxylic Acid Anhydride Residue or Carboxylic Acid Anhydride Derivative Residue of the Polymer Having a Polar Group are Covalently Bonded> The polypropylene compositions of Examples 4 and 5 were analyzed using two-dimensional NMR to analyze graft-modified products in Which the hydroxyl group of (A2) in the heterophasic propylene polymerization material and the carboxylic acid anhydride residue or the carboxylic acid anhydride derivative residue of the polymer having a polar group are covalently bonded. 1H-13C HSQC [Measurement conditions] Model: Bruker AVANCE600 Probe: 10mm Cryoprobe Measurement solvent: 1,1,2,2-tetrachloroethane-d2 (2,6-bis(1,1-dimethylethyl)-4-methylphenol added: 50mg / 100ml) Measurement concentration: 300mg / 2.5ml Measurement temperature: 135°C Number of accumulations: 128 Magnetic field strength: 600MHz Chemical shift reference: tetramethylsilane (0ppm) 1H-13C HMBC [Measurement conditions] Model: Bruker AVANCE600 Probe: 10mm Cryoprobe Measurement solvent: 1,1,2,2-tetrachloroethane-d2 (2,6-bis(1,1-dimethylethyl)-4-methylphenol added: 50mg / 100ml) Measurement concentration: 300 mg / 2.5 ml Measurement temperature: 135°C Number of accumulations: 256 Magnetic field strength: 600 MHz Chemical shift reference: tetramethylsilane (0 ppm) 1H NMR of hydroxyl-modified heterophasic propylene polymer material-2 confirmed the presence of a multiplet (A) at 4.15-4.12 ppm. 1H-13C HSQC analysis showed a correlation between (A) and the 13C signal appearing at 64.5 ppm, supporting the -CH2-O- structure. 1H-13C HMBC analysis showed a correlation between (A) and the 13C signals appearing at 172.0 ppm and / or 173.2 ppm, supporting the -CH2-OC(=O)- structure.In other words, this supports the formation of a covalent bond between the OH group bonded to the propylene-ethylene copolymer portion (A2) in the hydroxyl group-modified heterophasic propylene polymer material-2 and the maleic anhydride residue in the maleic anhydride-modified polypropylene-1.

[0166] The modified heterophasic propylene polymer material of the present invention can be used as a filler or a compatibilizer for other resins (e.g., to improve strength, heat resistance, paintability, adhesion, printability, etc.), as a raw material for synthesizing graft polymers or block polymers with other resins (e.g., after grafting or blocking, used as a compatibilizer to improve strength, heat resistance, paintability, adhesion, printability, etc.). The modified heterophasic propylene polymer material of the present invention can also be molded into parts for products such as electrical appliances and automobiles by molding methods such as injection molding, injection compression molding, gas-assisted molding, and extrusion molding. Particularly preferred applications include automobile parts such as door trims, pillars, instrument panels, and bumpers. The modified heterophasic propylene polymerization material of the present invention is suitable for use in a variety of automobile interior and exterior parts, including injection molding materials, such as instrument panels, glove boxes, trims, housings, pillars, bumpers, fenders, and back doors, as well as various parts for home appliances, various housing equipment parts, various industrial parts, and various building material parts, and is highly applicable in various industrial fields, such as the transportation machinery industry, the electrical and electronics industry, and the building and construction industry.

Claims

1. A heterophasic propylene polymerization material having a propylene-based polymer portion (A1) and a propylene and α-olefin copolymer portion (A2), in which a portion of (A1) and / or (A2) is modified with a hydroxyl group.

2. The heterophasic propylene polymer material according to claim 1, wherein the terminals of (A1) and / or (A2) in the heterophasic propylene polymer material are modified with a hydroxyl group.

3. The heterophasic propylene polymer material according to claim 1 or 2, wherein one end of (A1) and / or (A2) in the heterophasic propylene polymer material is modified with a hydroxyl group.

4. The amount of —OH (hydroxyl group) contained in the hydroxyl-modified (A1) and / or (A2) is 0.01×10 －３ wt% to 100 x 10 －３ 3. The heterophasic propylene polymerization material of claim 1 or claim 2, wherein the heterophasic propylene polymerization material is in the range of 1:1 wt.

5. The heterophasic propylene polymer material according to claim 1 or 2, wherein the propylene-based polymer portion (A1) is a propylene homopolymer portion.

6. A method for producing a heterophasic propylene polymerization material according to claim 1 or 2 in the presence of an olefin polymerization solid catalyst component and an organoaluminum compound, comprising the following steps (1) to (3) and satisfying condition (i): (1) a propylene polymerization step (A); (2) a propylene and α-olefin copolymerization step (B); (3) a reactive gas compound treatment step (C); (i) carrying out steps (A) and / or (B) in the presence of an organozinc compound.

7. A method for producing the heterophasic propylene polymerization material according to claim 6, further comprising the steps of: continuously feeding propylene (and α-olefins), a solid catalyst component for olefin polymerization, an organoaluminum compound, and an organozinc compound to a reactor; and continuously removing a portion of the heterophasic propylene polymerization material obtained in the reactor from the reactor.

8. A method for producing a heterophasic propylene polymerization material according to claim 6, characterized in that the reactive gas compound treatment step (C) is a treatment step using any one of oxygen gas, air, oxygen gas or water vapor containing air.

9. A polypropylene composition, graft modified product, or block modified product, comprising the heterophasic propylene polymerization material according to claim 1 or 2 and a polymer having a polar group.

10. The polypropylene composition, graft modified product, or block modified product according to claim 9, wherein the polymer having a polar group is a polymer having a carboxylic acid anhydride residue and / or a residue of a carboxylic acid anhydride derivative.

11. The polypropylene composition, graft modified product, or block modified product according to claim 10, wherein the polymer having a carboxylic acid anhydride residue and / or a carboxylic acid anhydride derivative residue is a maleic anhydride modified polypropylene.

12. A molded article, film or sheet comprising the polypropylene composition, graft modified product or block modified product according to claim 9.

13. A polypropylene composition, graft modified product, or block modified product, comprising the heterophasic propylene polymerization material according to claim 1 or 2, a polymer having a polar group, and a crosslinking catalyst.

14. The polypropylene composition, graft modified product, or block modified product according to claim 13, wherein the polymer having a polar group is a polymer having a carboxylic acid anhydride residue and / or a residue of a carboxylic acid anhydride derivative.

15. The polypropylene composition, graft modified product, or block modified product according to claim 13, wherein the polymer having a carboxylic acid anhydride residue and / or a carboxylic acid anhydride derivative residue is a maleic anhydride modified polypropylene.

16. The polypropylene composition, graft modified product, or block modified product according to claim 13, wherein the crosslinking catalyst is a metal compound, a nitrogen-containing compound, or a Bronsted acid.

17. The polypropylene composition, graft modified product, or block modified product according to claim 13, wherein the crosslinking catalyst is a metal oxide, metal hydroxide, metal alkoxide, metal carboxylate, metal enolate, or metal carbonate.

18. The polypropylene composition, graft modified product, or block modified product according to claim 13, wherein the crosslinking catalyst is a transition metal oxide, transition metal hydroxide, transition metal alkoxide, transition metal carboxylate, transition metal enolate, or transition metal carbonate.

19. A molded article, film, or sheet comprising the polypropylene composition, graft modified product, or block modified product according to claim 13.

20. A graft modified material in which the hydroxyl group of (A2) in the heterophasic propylene polymer material according to claim 9 is bonded to the polymer having a polar group.

21. A graft modified material in which the hydroxyl group of (A2) in the heterophasic propylene polymer material according to claim 9 is covalently bonded to the polymer having a polar group.

22. A graft modified material in which the hydroxyl group of (A2) in the heterophasic propylene polymer material described in claim 10 is bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

23. A graft modified material in which the hydroxyl group of (A2) in the heterophasic propylene polymer material described in claim 10 is covalently bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

24. A block modified product in which the hydroxyl group of (A2) in the heterophasic propylene polymer material according to claim 9 is bonded to the polymer having a polar group.

25. A block modified product in which the hydroxyl group of (A2) in the heterophasic propylene polymer material according to claim 9 is covalently bonded to the polymer having a polar group.

26. A block modified product in which a hydroxyl group of (A2) in the heterophasic propylene polymer material according to claim 10 is bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

27. A block modified material in which the hydroxyl group of (A2) in the heterophasic propylene polymer material described in claim 10 is covalently bonded to a carboxylic acid anhydride residue or a residue of a carboxylic acid anhydride derivative of the polymer having a polar group.

28. A method for producing the polypropylene composition, graft modified product, or block modified product according to claim 9, comprising melt-kneading or heating in a solvent a material comprising the heterophasic propylene polymerization material and the polymer having a polar group.

29. A method for producing the polypropylene composition, graft modified product, or block modified product according to claim 13, comprising melt-kneading or heating in a solvent a material comprising the heterophasic propylene polymerization material, the polymer having a polar group, and the crosslinking catalyst.

30. A polypropylene composition, graft modified product, or block modified product produced by the method according to claim 28.

31. A polypropylene composition, graft modified product, or block modified product produced by the method according to claim 29.

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