Heterophagic propylene polymerization materials and olefin polymers

Abstract

To provide a heterophasic propylene polymerization material and an olefin polymer having a small high-boiling-point component amount index (FOG).SOLUTION: Disclosed is a heterophasic propylene polymerization material that satisfies a following formula (3): (X2×Y2) / Z2≤7.0 (3) wherein X2 represents a cold xylene soluble component amount (mass%) of the heterophasic propylene polymerization material; Y2 represents a percentage (%) of a component having molecular weight of 104.0 or less in terms of polystyrene and contained in a cold xylene soluble component of the heterophasic propylene polymerization material based on all components of the cold xylene soluble component of the heterophasic propylene polymerization material as measured by gel permeation chromatography; and Z2 represents a content (mass%) of a propylene-based copolymer contained in the heterophasic propylene polymerization material and containing a monomer unit derived from at least one compound selected from a group consisting of ethylene and C4-12 α-olefins and a propylene-derived monomer unit.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a heterophasic propylene polymerization material and an olefin polymer produced using a novel Ziegler-Natta catalyst composed of a combination of a solid catalyst component and an external electron donor.

Background Art

[0002] Conventionally, many catalysts for olefin polymerization have been proposed, and various olefin-based polymers have been produced.

[0003] For example, Patent Document 1 describes an olefin-based polymer produced by a specific catalyst.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] From the viewpoints of environment and health, it is preferable that the produced olefin-based polymer has a low resin odor. However, Patent Document 1 does not mention the resin odor of heterophasic propylene polymerization materials and olefin polymers.

[0006] Under such circumstances, the problem to be solved by the present invention is to provide a heterophasic propylene polymerization material and an olefin polymer having a small high-boiling component content index (FOG). Since high-boiling components are the basis of resin odor, the heterophasic propylene polymerization material and olefin polymer of the present invention have a low resin odor.

Means for Solving the Problems

[0007] In light of this background, the inventors conducted thorough research and have now completed the present invention. In other words, the present invention is as follows. [1] A heterophagic propylene polymerization material that satisfies the following formula (3). (X² × Y²) / Z² ≤ 7.0 (3) (In the formula, X2 represents the amount (mass%) of cold xylene-soluble portion of the heterophagic propylene polymerization material. Y2 is the polystyrene-equivalent molecular weight 10 contained in the cold xylene-soluble portion of the heterophagic propylene polymerization material relative to the total components of the cold xylene-soluble portion of the heterophagic propylene polymerization material as measured by gel permeation chromatography. 4.0 The percentages (%) of the following components are shown. Z2 represents the content (mass%) of a propylene copolymer contained in the heterophagic propylene polymerization material, which includes monomer units derived from ethylene and at least one selected from the group consisting of α-olefins having 4 to 12 carbon atoms, and monomer units derived from propylene. [2] A heterophagic propylene polymerization material as described in [1], satisfying the following formula (4). 0.3 < (X² × Y²) / Z² < 7.0 (4) (In the formula, X2, Y2, and Z2 have the same meanings as above.) [3] A propylene polymer (a) containing 80% by mass or more monomer units derived from propylene and having an intrinsic viscosity of 2.0 dL / g or less, A heterophagous propylene polymerization material according to [1] or [2], comprising a propylene copolymer (b) containing 30 to 55% by mass of monomer units derived from ethylene and at least one selected from the group consisting of α-olefins having 4 to 12 carbon atoms, monomer units derived from propylene, and having an intrinsic viscosity of 1.5 to 8.0 dL / g. [4] The heterophagic propylene polymerization material according to [3], wherein the content of the propylene polymer (a) is 50 to 90% by mass, and the content of the propylene copolymer (b) is 10 to 50% by mass. [5] The heterophagic propylene polymerization material according to [3] or [4], wherein the isotactic fraction of the propylene polymer (a) is greater than 0.975. [6] An olefin polymer that satisfies the following formula (1). Y1 / X1 ≤ 40 (1) (In the formula, X1 represents the amount (mass%) of the cold xylene-soluble portion of the olefin polymer. Y1 is the polystyrene-equivalent molecular weight 10 of the cold xylene-soluble portion of the olefin polymer relative to the total components of the cold xylene-soluble portion of the olefin polymer as measured by gel permeation chromatography. 3.5 The percentages (%) of the following components are shown. [7] An olefin polymer according to [6] that satisfies the following formula (2). 5.3 <Y1 / X1<40 (2) (In the formula, X1 and Y1 have the same meanings as described above.) [8] The olefin polymer according to [6] or [7], which is a propylene polymer. [9] The olefin polymer described in [8] is a propylene homopolymer. [Effects of the Invention]

[0008] According to the present invention, heterophagnum propylene polymerization materials and olefin polymers produced using a novel Ziegler-Natta catalyst, which combines a solid catalyst component with an external electron donor, are characterized by a low high-boiling-point component index (FOG). Since high-boiling-point components are the basis of resin odor, the heterophagnum propylene polymerization materials and olefin polymers of the present invention have a low resin odor. Furthermore, despite having a low high-boiling-point component index, the melting point of the olefin polymers of the present invention does not increase. There is a trade-off between a low high-boiling-point component index and a low melting point, but the olefin polymers of the present invention maintain, for example, low-temperature heat-sealability. [Modes for carrying out the invention]

[0009] [Definition] In this specification, the term "α-olefin" means an aliphatic unsaturated hydrocarbon having a carbon-carbon unsaturated double bond at the α-position. In this specification, the term "heterophasic propylene polymerization material" means a mixture having a structure in which a propylene copolymer containing monomer units derived from ethylene and at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms, and monomer units derived from propylene, is dispersed in a matrix of a propylene polymer (provided that the total mass of the propylene polymer is 100% by mass) containing 80% by mass or more monomer units derived from propylene.

[0010] Several embodiments of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments. In this specification, the description "lower limit to upper limit" representing a numerical range means "greater than or equal to the lower limit and less than or equal to the upper limit," and the description "upper limit to lower limit" means "less than or equal to the upper limit and greater than or equal to the lower limit." That is, these descriptions represent a numerical range that includes an upper limit and a lower limit.

[0011] [Heterophasic propylene polymerization material] The heterophagic propylene polymerization material of the present invention is a heterophagic propylene polymerization material that satisfies the following formula (3). (X² × Y²) / Z² ≤ 7.0 (3) (In the formula, X2 represents the amount (mass%) of cold xylene-soluble portion of the heterophagic propylene polymerization material. Y2 is the polystyrene-equivalent molecular weight 10 contained in the cold xylene-soluble portion of the heterophagic propylene polymerization material relative to the total components of the cold xylene-soluble portion of the heterophagic propylene polymerization material as measured by gel permeation chromatography. 4.0 The percentages (%) of the following components are shown. Z2 represents the content (mass%) of a propylene copolymer contained in the heterophagic propylene polymerization material, which includes monomer units derived from ethylene and at least one selected from the group consisting of α-olefins having 4 to 12 carbon atoms, and monomer units derived from propylene.

[0012] The heterophagic propylene polymerization material of the present invention is preferably a heterophagic propylene polymerization material that satisfies the following formula (4). 0.3 < (X² × Y²) / Z² < 7.0 (4) (In the formula, X2, Y2, and Z2 have the same meanings as above.)

[0013] The heterophagic propylene polymerization material of the present invention is more preferably, A propylene polymer (a) containing 80% by mass or more monomer units derived from propylene and having an intrinsic viscosity of 2.0 dL / g or less, The heterophagic propylene polymerization material comprises a propylene copolymer (b) containing 30 to 55% by mass of monomer units derived from ethylene and at least one selected from the group consisting of α-olefins having 4 to 12 carbon atoms, monomer units derived from propylene, and having an intrinsic viscosity of 1.5 to 8.0 dL / g.

[0014] The heterophagic propylene polymerization material of the present invention is more preferably, The heterophagic propylene polymerization material is characterized in that the content of the propylene polymer (a) is 50 to 90% by mass, and the content of the propylene copolymer (b) is 10 to 50% by mass.

[0015] In this specification, intrinsic viscosity ([η], unit: dL / g) is measured by the method described in the following examples.

[0016] The intrinsic viscosity of the propylene polymer (a) may be 0.3 to 1.2 dL / g, 0.4 to 1.0 dL / g, or 0.8 to 0.95 dL / g.

[0017] The propylene polymer (a) may be, for example, a propylene homopolymer, or it may contain monomer units derived from monomers other than propylene. If the propylene polymer (a) contains monomer units derived from monomers other than propylene, the amount may be, for example, 0.01% by mass or more and less than 20% by mass, based on the total mass of the propylene polymer (a).

[0018] Examples of monomers other than propylene include ethylene and α-olefins having 4 to 12 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.

[0019] Examples of propylene-based polymers containing monomer units derived from monomers other than propylene include propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer.

[0020] From the viewpoint of the rigidity of the molded article, the propylene-based polymer (a) is preferably a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, or a propylene-ethylene-1-butene copolymer, with a propylene homopolymer being more preferred.

[0021] The heterophagic propylene polymerization material of this embodiment may contain only one type of propylene polymer (a), or it may contain two or more types.

[0022] The intrinsic viscosity of the propylene copolymer (b) may be 2.0 to 10.0 dL / g, 3.0 to 9.0 dL / g, or 4.0 to 8.0 dL / g.

[0023] In the propylene copolymer (b), the content of monomer units derived from ethylene and at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms may be 20 to 50% by mass, 30 to 45% by mass, or 35 to 40% by mass.

[0024] In the propylene copolymer (b), the at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms is preferably at least one selected from the group consisting of ethylene and α-olefins having 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.

[0025] Examples of propylene copolymers (b) 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, or propylene-ethylene-1-butene copolymer are preferred as the above propylene copolymer (b), and propylene-ethylene copolymer is more preferred.

[0026] The heterophagic propylene polymerization material of this embodiment may contain only one type of propylene copolymer (b), or it may contain two or more types.

[0027] Examples of heterophagic propylene polymerization materials in this embodiment include (propylene)-(propylene-ethylene) polymerization materials, (propylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene)-(propylene-ethylene-1-hexene) polymerization materials, (propylene)-(propylene-ethylene-1-octene) polymerization materials, (propylene)-(propylene-1-butene) polymerization materials, (propylene)-(propylene-1-hexene) polymerization materials, (propylene)-(propylene-1-octene) polymerization materials, and (propylene)-(propylene-ethylene-1-octene) polymerization materials. (Pyrene-1-decene) polymerization material, (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) polymerization material, (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 (-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,Examples include (propylene-1-octene)-(propylene-1-octene) polymerization materials and (propylene-1-octene)-(propylene-1-decene) polymerization materials. Among these, (propylene)-(propylene-ethylene) polymerization materials, (propylene)-(propylene-ethylene-1-butene) polymerization materials, (propylene-ethylene)-(propylene-ethylene) polymerization materials, (propylene-ethylene)-(propylene-ethylene-1-butene) polymerization materials, or (propylene-1-butene)-(propylene-1-butene) polymerization materials are preferred, and (propylene)-(propylene-ethylene) polymerization materials are more preferred.

[0028] Here, the above description indicates "(type of propylene polymer containing 80% by mass or more monomer units derived from propylene)-(type of propylene copolymer (b))". In other words, the description "(propylene)-(propylene-ethylene) polymerization material" means "a heterophagous propylene polymerization material in which propylene polymer (a) and is a propylene homopolymer, and propylene copolymer (b) is a propylene-ethylene copolymer". The same applies to other similar expressions.

[0029] The content of propylene polymer (a) and propylene copolymer (b) may be 50-90% by mass and 10-50% by mass, respectively, with the total mass of the heterophagic propylene polymerization material being 100% by mass.

[0030] In this embodiment, the heterophagic propylene polymerization material has an intrinsic viscosity of 0.3 to 1.2 dL / g for the propylene polymer (a) and an intrinsic viscosity of 2.0 to 10.0 dL / g for the propylene copolymer (b). The propylene copolymer (b) contains 20 to 50% by mass of monomer units derived from at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms. From the viewpoint of dimensional stability, it is preferable that the content of the propylene polymer (a) and the propylene copolymer (b) is 50 to 90% by mass and 10 to 50% by mass, respectively, with the total mass of the heterophagic propylene polymerization material being 100% by mass.

[0031] The isotactic pentad fraction (also called the [mmmm] fraction) of the propylene polymer (a) contained in the heterophagic propylene polymerization material is preferably 0.950 or higher, more preferably 0.970 or higher, and even more preferably greater than 0.975, from the viewpoint of rigidity and dimensional stability of the molded article made of the resin composition. The isotactic pentad fraction of component (a) may be, for example, 1.000 or less. Polymers with an isotactic pentad fraction close to 1 are considered to have high stereoregularity of molecular structure and high crystallinity.

[0032] The isotactic pentad fraction refers to the isotactic fraction in pentad units. That is, the isotactic pentad fraction indicates the proportion of structures where five monomer units derived from propylene are consecutively linked by mesobonding, when viewed in pentad units. If the component in question is a copolymer, it refers to the value measured for the chain of monomer units derived from propylene.

[0033] In this specification, the isotactic pentad fraction is measured by the method described in the following examples.

[0034] To the heterophagic propylene polymerization material, additives such as heat stabilizers, UV stabilizers, antioxidants, nucleating agents, lubricants, colorants, antiblocking agents, antistatic agents, antifogging agents, flame retardants, petroleum resins, foaming agents, foaming aids, and organic or inorganic fillers may be added as needed. The amount of additive added is preferably 0.01% by mass or more, and preferably 30% by mass or less, relative to the total heterophagic propylene polymerization material. Additives may be used individually, or two or more may be used in combination in any proportion.

[0035] <Olefin polymer> The olefin polymer of the present invention is an olefin polymer that satisfies the following formula (1). Y1 / X1 ≤ 40 (1) (In the formula, X1 represents the amount (mass%) of the cold xylene-soluble portion of the olefin polymer. Y1 is the polystyrene-equivalent molecular weight 10 of the cold xylene-soluble portion of the olefin polymer relative to the total components of the cold xylene-soluble portion of the olefin polymer as measured by gel permeation chromatography. 3.5 The percentages (%) of the following components are shown.

[0036] The olefin polymer of the present invention is preferably an olefin polymer that satisfies the following formula (2). 5.3 <Y1 / X1<40 (2) (In the formula, X1 and Y1 have the same meanings as described above.)

[0037] Examples of olefins include ethylene and α-olefins having 3 or more carbon atoms. Examples of α-olefins include linear monoolefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 1-decene; branched monoolefins such as 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl-1-pentene; cyclic monoolefins such as vinylcyclohexane; and combinations of two or more of these. Preferably, these are homopolymers of ethylene or propylene, or copolymers of multiple olefins mainly composed of ethylene or propylene. The above combinations of multiple olefins may include combinations of two or more types of olefins, and may include combinations of olefins with compounds having polyunsaturated bonds, such as conjugated dienes and unconjugated dienes.

[0038] The olefin polymer of the present invention is preferably an ethylene homopolymer, a propylene homopolymer, a 1-butene homopolymer, a 1-pentene homopolymer, a 1-hexene homopolymer, an ethylene-propylene copolymer, an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, an propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, an ethylene-propylene-1-butene copolymer, an ethylene-propylene-1-hexene copolymer, or a polymer obtained by multi-stage polymerization of these. The olefin polymer of the present invention is more preferably a propylene polymer, and even more preferably a propylene homopolymer. The intrinsic viscosity of the olefin polymer may be 0.3 to 8.0 dL / g, 0.5 to 5.0 dL / g, or 0.7 to 3.0 dL / g. Additives such as heat stabilizers, UV stabilizers, antioxidants, nucleating agents, lubricants, colorants, antiblocking agents, antistatic agents, antifogging agents, flame retardants, petroleum resins, foaming agents, foaming aids, and organic or inorganic fillers may be added to the olefin polymer as needed. The amount of additive added is preferably 0.01% by mass or more, and preferably 30% by mass or less, relative to the total amount of the olefin polymer. Additives may be used individually, or two or more may be used in combination in any proportion.

[0039] <Solid catalyst components for olefin polymerization> The heterophagic propylene polymerization material and olefin polymer of the present invention can preferably be produced by the following manufacturing method: A step of obtaining a catalyst for olefin polymerization by contacting component (A), component (B), and component (C), A method for producing an olefin, comprising the step of polymerizing an olefin in the presence of an olefin polymerization catalyst to obtain a heterophagic propylene polymerization material or an olefin polymer. Component (A): Solid catalyst component for olefin polymerization containing titanium atoms, magnesium atoms, halogen atoms, and internal electron donors. Component (B): Organoaluminum compound Component (C): A silicon compound represented by the following formula (i) or (ii) R 1 Si(OR 2 )3(i) (R 1 : A hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom, R 2 : A hydrocarbyl group having 1 to 20 carbon atoms) R 3 2Si(NR 4 R 5 )2(ii) (R 3 : A hydrocarbyl group having 1 to 20 carbon atoms or a hydrogen atom, R 4 and R 5 : A hydrocarbyl group having 1 to 12 carbon atoms or a hydrogen atom)

[0040] In this specification, the "solid catalyst component for olefin polymerization" means a component that exists as a solid content at least in toluene and becomes a catalyst for olefin polymerization when combined with a cocatalyst for olefin polymerization such as an organoaluminum compound.

[0041] Part or all of the titanium atoms in the solid catalyst component for olefin polymerization are derived from a titanium halide compound. Part or all of the halogen atoms in the solid catalyst component for olefin polymerization are derived from a titanium halide compound.

[0042] Part or all of the magnesium atoms in the solid catalyst component for olefin polymerization are derived from a magnesium compound. The magnesium compound may be any compound containing a magnesium atom, and specific examples include compounds represented by the following formulas (i) to (iii). MgR 1 k X 2-k ···(i) Mg(OR 1 ) m X 2-m ···(ii) MgX2·nR 1 OH···(iii) (where k is a number satisfying 0 ≦ k ≦ 2; m is a number satisfying 0 < m ≦ 2; n is a number satisfying 0 ≦ n ≦ 3; R 1 is a hydrocarbyl group having 1 to 20 carbon atoms; X is a halogen atom.)

[0043] Examples of X in the above formulas (i) to (iii) include a chlorine atom, a bromine atom, an iodine atom, and a fluorine atom, preferably a chlorine atom. A plurality of X's may be the same or different.

[0044] Specific examples of the magnesium compounds of formulas (i) to (iii) include magnesium dialkoxides and magnesium halides.

[0045] The magnesium halide may be used as it is a commercially available product, or a precipitate formed by dropping a solution of a commercially available product dissolved in alcohol into a hydrocarbon liquid may be separated from the liquid and used, or those produced based on the methods described in U.S. Patent No. 6,825,146, International Publication No. 1998 / 044009 pamphlet, International Publication No. 2003 / 000754 pamphlet, International Publication No. 2003 / 000757 pamphlet, or International Publication No. 2003 / 085006 pamphlet may also be used.

[0046] Examples of the method for producing magnesium dialkoxide include, for example, a method of contacting metallic magnesium and alcohol in the presence of a catalyst (for example, JP-A-4-368391, JP-A-3-74341, JP-A-8-73388, and International Publication No. 2013 / 058193 pamphlet). Examples of the alcohol include methanol, ethanol, propanol, butanol, and octanol. Examples of the catalyst include halogens such as iodine, chlorine, and bromine; magnesium halides such as magnesium iodide and magnesium chloride, and preferably iodine.

[0047] The magnesium compound may be supported on a carrier material. Examples of carrier materials include porous inorganic oxides such as SiO2, Al2O3, MgO, TiO2, and ZrO2; and organic porous polymers such as polystyrene, styrene-divinylbenzene copolymer, styrene-ethylene glycol dimethacrylate copolymer, methyl polyacrylate, ethyl polyacrylate, methyl acrylate-divinylbenzene copolymer, polymethyl methacrylate, methyl methacrylate-divinylbenzene copolymer, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyethylene, and polypropylene. Of these, porous inorganic oxides are preferred, and SiO2 is preferred.

[0048] Preferably, the carrier material is porous, and the total volume of pores with a pore radius of 10 to 780 nm, as determined by the mercury intrusion method according to standard ISO 15901-1:2005, is 0.3 cm³. 3 A porous carrier material with a density of 0.4 cm or more is more preferable. 3 A porous carrier material with a density of 1 / g or more is even more preferred. Furthermore, a porous carrier material in which the total volume of pores with a pore radius of 10 to 780 nm is 25% or more of the total volume of pores with a pore radius of 2 to 100 μm is preferred, and a porous carrier material in which it is 30% or more is more preferred.

[0049] Magnesium compounds may be used individually or in combination of two or more. The magnesium compounds may be contacted with the titanium halide compound solution in the form of a magnesium compound slurry containing the magnesium compound and a solvent, or in a solvent-free form, within the range in which the effects of the present invention can be obtained.

[0050] Some or all of the magnesium atoms in the solid catalyst component for olefin polymerization originate from magnesium compounds. Furthermore, some of the halogen atoms in the solid catalyst component for olefin polymerization may originate from magnesium compounds.

[0051] The internal electron donor refers to an organic compound capable of donating an electron pair to one or more metal atoms contained in the solid catalyst component for olefin polymerization. Specifically, examples include monoester compounds, dicarboxylic acid ester compounds, diol diester compounds, β-alkoxy ester compounds, and diether compounds.

[0052] Furthermore, the internal electron donor described in Japanese Patent Publication No. 2011-246699 can also be cited as an example.

[0053] In particular, dicarboxylic acid ester compounds, diol diester compounds, and β-alkoxy ester compounds are preferred. The internal electron donors may be used individually or in combination of two or more types.

[0054] Solid catalyst components for olefin polymerization can be produced by the following manufacturing method: A method for producing a solid catalyst component for olefin polymerization, comprising the step (I) of contacting a titanium halide compound with a magnesium compound to obtain a slurry containing a solid product.

[0055] Preferably, the above-described method for producing a solid catalyst component for olefin polymerization further comprises step (I), in which a magnesium compound is added to a titanium halide compound solution, the internal electron donor being at least one compound selected from the group consisting of monoester compounds, dicarboxylic acid ester compounds, diol diester compounds, β-alkoxyester compounds, and diether compounds, and the magnesium compound being a magnesium dialkoxide, and further step (II) in which the internal electron donor is added to a slurry containing a solid product.

[0056] <Catalyst for olefin polymerization> In one embodiment, an olefin polymerization catalyst can be produced by contacting the above-mentioned solid catalyst component for olefin polymerization with an organoaluminum compound, for example, by a known method. In another embodiment, an olefin polymerization catalyst can be produced by contacting the above-mentioned solid catalyst component for olefin polymerization with an organoaluminum compound and an external electron donor.

[0057] Therefore, in one embodiment, the catalyst for olefin polymerization includes the above-mentioned solid catalyst component for olefin polymerization and an organoaluminum compound. In another embodiment, the catalyst for olefin polymerization includes the above-mentioned solid catalyst component for olefin polymerization, an organoaluminum compound, and an external electron donor.

[0058] Organoaluminum compounds are compounds having one or more carbon-aluminum bonds, and specific examples include the compounds described in Japanese Patent Publication No. 10-212319. Preferably, these are trialkylaluminum, a mixture of trialkylaluminum and dialkylaluminum halide, or alkylaluminoxane, and more preferably, triethylaluminum, triiso-butylaluminum, a mixture of triethylaluminum and diethylaluminum chloride, or tetraethyldiarmoxane.

[0059] Examples of external electron donors include compounds described in Japanese Patent Publication No. 2950168, Japanese Unexamined Patent Publication No. 2006-96936, Japanese Unexamined Patent Publication No. 2009-173870, and Japanese Unexamined Patent Publication No. 2010-168545. Among these, oxygen-containing compounds or nitrogen-containing compounds are preferred. Examples of oxygen-containing compounds include alkoxysilicon, ethers, esters, and ketones. Among these, alkoxysilicon or ethers are preferred. Examples of nitrogen-containing compounds include aminosilicon, amines, imines, amides, imides, and cyanides. Among these, aminosilicon is preferred.

[0060] As an external electron donor, alkoxysilicon or aminosilicon is preferably a silicon compound of the following formula. Component (C): Silicon compound represented by the following formula (i) or (ii) R 1 Si(OR 2 )3(i) (R 1 : Hydrocarbyl group with 1 to 20 carbon atoms or hydrogen atom, R 2 (Hydrocarbyl groups with 1 to 20 carbon atoms) R 3 2Si(NR 4 R 5 )2(ii) (R 3 : Hydrocarbyl group with 1 to 20 carbon atoms or hydrogen atom, R 4 and R 5 : A hydrocarbyl group or hydrogen atom with 1 to 12 carbon atoms.

[0061] R in equation (i) above 1 and R 2 Examples of hydrocarbyl groups include alkyl groups, aralkyl groups, aryl groups, alkenyl groups, etc. 1 and R 2 Examples of alkyl groups include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl groups; branched alkyl groups such as iso-propyl, iso-butyl, tert-butyl, iso-pentyl, neopentyl, and 2-ethylhexyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups, preferably linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms. 1 and R 2 Examples of aralkyl groups include benzyl groups and phenethyl groups, preferably aralkyl groups having 7 to 20 carbon atoms. 1 and R 2Examples of aryl groups include phenyl groups, tolyl groups, and xylyl groups, and preferably aryl groups having 6 to 20 carbon atoms. 1 and R 2 Examples of alkenyl groups include linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl groups; branched alkenyl groups such as iso-butenyl and 5-methyl-3-pentenyl groups; and cyclic alkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl groups, preferably alkenyl groups having 2 to 10 carbon atoms.

[0062] Specific examples of alkoxysilicon represented by formula (i) above include phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, iso-butyltriethoxysilane, vinyltriethoxysilane, sec-butyltriethoxysilane, cyclohexyltriethoxysilane, cyclopentyltriethoxysilane, and benzyltriethoxysilane. Preferably, cyclohexyltriethoxysilane and triethoxyphenylsilane are included.

[0063] R in equation (ii) above 3 The hydrocarbyl group is the one shown in the above formula R 1 Examples include the same things as above.

[0064] R in equation (ii) above 4 and R 5 Examples of hydrocarbyl groups include alkyl groups and alkenyl groups, and R 4 and R 5 Examples of alkyl groups include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl groups; branched alkyl groups such as iso-propyl, iso-butyl, tert-butyl, iso-pentyl, and neopentyl groups; and cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups, preferably linear alkyl groups having 1 to 6 carbon atoms. 4and R 5 Examples of alkenyl groups include linear alkenyl groups such as vinyl, allyl, 3-butenyl, and 5-hexenyl groups; branched alkenyl groups such as iso-butenyl and 5-methyl-3-pentenyl groups; and cyclic alkenyl groups such as 2-cyclohexenyl and 3-cyclohexenyl groups. Linear alkenyl groups having 2 to 6 carbon atoms are preferred, and methyl and ethyl groups are particularly preferred.

[0065] Specific examples of aminosilicon represented by formula (ii) above include bis(ethylamino)dicyclopentylsilane, bis(ethylamino)diisopropylsilane, and bis(methylamino)di-t-butylsilane. Bis(ethylamino)dicyclopentylsilane is preferred. Furthermore, aminosilicon, as described in WO2006 / 129773, can also be given as an example.

[0066] The external electron donor ether is preferably a cyclic ether compound. A cyclic ether compound is a heterocyclic compound having at least one -COC- bond in its ring structure, more preferably a cyclic ether compound having at least one -COCOC- bond in its ring structure, and particularly preferably 1,3-dioxolane or 1,3-dioxane.

[0067] External electron donors may be used individually or in combination of two or more types.

[0068] The method of contacting the solid catalyst component for olefin polymerization, the organoaluminum compound, and the external electron donor is not particularly limited, as long as a catalyst for olefin polymerization is produced. The contact may or may not be carried out in the presence of a solvent. These contact mixtures may be supplied to a polymerization tank, or each component may be supplied to the polymerization tank separately and contacted in the polymerization tank, or any two-component contact mixture and the remaining component may be supplied to the polymerization tank separately and contacted in the polymerization tank.

[0069] The amount of organoaluminum compound used is typically 0.01 to 1000 μmol, preferably 0.1 to 500 μmol, per 1 mg of solid catalyst component for olefin polymerization.

[0070] The amount of external electron donor used is typically 0.0001 to 1000 μmol per 1 mg of solid catalyst component for olefin polymerization, preferably 0.001 to 500 μmol, and more preferably 0.01 to 150 μmol.

[0071] As described below, the above-mentioned catalyst for olefin polymerization can yield polymers with a low high-boiling-point component index when used to polymerize olefins.

[0072] <Method for producing olefin polymers> The present invention provides a method for producing an olefin polymer, which involves polymerizing an olefin in the presence of the above-mentioned olefin polymerization catalyst.

[0073] In one embodiment, a method for forming a catalyst for olefin polymerization may be preferred, consisting of the following steps: (i) A step of polymerizing a small amount of olefin (identical or different from the olefin used in the actual polymerization (usually called the main polymerization)) in the presence of a solid catalyst component for olefin polymerization and an organoaluminum compound (a chain transfer agent such as hydrogen or an external electron donor may be used to adjust the molecular weight of the resulting olefin polymer) to produce a catalyst component whose surface is covered with the olefin polymer (this polymerization is usually called prepolymerization, and therefore the catalyst component is usually called a prepolymerization catalyst component). (ii) A step of bringing a prepolymerization catalyst component into contact with an organoaluminum compound and an external electron donor.

[0074] Prepolymerization is preferably slurry polymerization using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene, and toluene as the solvent.

[0075] The amount of organoaluminum compound used in step (i) above is typically 0.5 mol to 700 mol, preferably 0.8 mol to 500 mol, and particularly preferably 1 mol to 200 mol per mol of titanium atoms in the solid catalyst component used in step (i).

[0076] The amount of olefin to be prepolymerized is typically 0.01g to 1000g, preferably 0.05g to 500g, and particularly preferably 0.1g to 200g, per gram of solid catalyst component for olefin polymerization used in step (i).

[0077] The slurry concentration of the solid catalyst component for olefin polymerization in step (i) above is preferably 1 to 500 g-solid catalyst component for olefin polymerization / liter-solvent, and particularly preferably 3 to 300 g-solid catalyst component for olefin polymerization / liter-solvent.

[0078] The prepolymerization temperature is preferably -20°C to 100°C, and particularly preferably 0°C to 80°C. The partial pressure of the olefin in the gas phase during prepolymerization is preferably 0.01 MPa to 2 MPa, and particularly preferably 0.1 MPa to 1 MPa, however, this does not apply to olefins that are liquid at the pressure and temperature of prepolymerization. The prepolymerization time is preferably 2 minutes to 15 hours.

[0079] The following methods (1) and (2) can be used as examples of methods for supplying solid catalyst components for olefin polymerization, organoaluminum compounds, and olefins to the polymerization tank during prepolymerization: (1) A method of supplying olefins after supplying a solid catalyst component for olefin polymerization and an organoaluminum compound. (2) A method for supplying an organoaluminum compound after supplying a solid catalyst component for olefin polymerization and an olefin.

[0080] The following methods (1) and (2) can be used as examples of methods for supplying olefins to the polymerization tank during prepolymerization: (1) A method of sequentially supplying olefins to a polymerization tank so as to maintain the pressure inside the polymerization tank at a predetermined pressure. (2) A method of supplying the entire predetermined amount of olefin to the polymerization tank in one go.

[0081] The amount of external electron donor used in prepolymerization is typically 0.01 mol to 400 mol, preferably 0.02 mol to 200 mol, and particularly preferably 0.03 mol to 100 mol, per 1 mol of titanium atoms contained in the solid catalyst component for olefin polymerization, and typically 0.003 mol to 50 mol, preferably 0.005 mol to 30 mol, and particularly preferably 0.01 mol to 10 mol, per 1 mol of organoaluminum compound.

[0082] The following methods (1) and (2) can be exemplified as methods for supplying an external electron donor to the polymerization tank during prepolymerization: (1) Method of supplying an external electron donor to a polymerization tank by itself (2) A method for supplying a contact product of an external electron donor and an organoaluminum compound to a polymerization tank.

[0083] The amount of organoaluminum compound used during this polymerization is typically 1 to 1000 moles, and particularly preferably 5 to 600 moles, per mole of titanium atoms in the solid catalyst component for olefin polymerization.

[0084] When an external electron donor is used in this polymerization, the amount of external electron donor used is typically 0.1 mol to 2000 mol, preferably 0.3 mol to 1000 mol, and particularly preferably 0.5 mol to 800 mol per mol of titanium atoms contained in the solid catalyst component for olefin polymerization, and typically 0.001 mol to 5 mol, preferably 0.005 mol to 3 mol, and particularly preferably 0.01 mol to 1 mol per mol of organoaluminum compound.

[0085] The polymerization temperature is typically -30°C to 300°C, preferably 20°C to 180°C. The polymerization pressure is not particularly limited, but is generally atmospheric pressure to 10 MPa, preferably 200 kPa to 5 MPa, for industrial and economic reasons. Polymerization can be carried out in batch or continuous order, and examples of polymerization methods include slurry polymerization or solution polymerization using inert hydrocarbons such as propane, butane, isobutane, pentane, hexane, heptane, and octane as solvents, bulk polymerization using olefins that are liquid at the polymerization temperature as a medium, and gas-phase polymerization.

[0086] To adjust the molecular weight of the polymer obtained by this polymerization, a chain transfer agent (for example, hydrogen or alkyl zinc such as dimethylzinc and diethylzinc) may be used.

[0087] <Method for producing heterophagic propylene polymerization material> The present invention provides a method for producing a heterophagic propylene polymerization material, which involves polymerizing propylene or the like in the presence of the above-mentioned olefin polymerization catalyst. An example of a method for producing the above-mentioned heterophagic propylene polymerization material is described below. This method includes steps 1 and 2.

[0088] Step 1: Polymerize a monomer containing propylene in the liquid phase under conditions where the hydrogen / propylene ratio is appropriate to obtain at least a portion of the propylene-based polymer (a); and, Step 1-b involves polymerizing a monomer containing propylene in the gas phase under conditions where the hydrogen / propylene ratio is appropriate, to obtain at least a portion of the propylene-based polymer (a). at least one process selected from the group consisting of Step 2: A process to polymerize a monomer containing ethylene and at least one α-olefin selected from the group consisting of α-olefins having 4 to 12 carbon atoms, and propylene, under conditions where the hydrogen / propylene ratio is appropriate, in order to obtain a propylene copolymer (b).

[0089] However, in this specification, the hydrogen / propylene ratio is defined as follows: In liquid-phase polymerization, the hydrogen / propylene ratio refers to the ratio of the amounts of gaseous hydrogen to liquid propylene in the reactor supply section. In vapor polymerization, the hydrogen / propylene ratio refers to the ratio of the amounts of gaseous hydrogen to gaseous propylene at the outlet of the reaction apparatus. In this specification, for example, the statement "the hydrogen / propylene ratio is 1 mol ppm" means "the hydrogen / propylene ratio is 1 × 10⁻¹⁰ -6 This is synonymous with "mol / mol," meaning that for every 1 mole of propylene, there are 1 × 10¹⁶ hydrogen atoms. -6 It means it is in moles. The hydrogen / propylene ratio is typically 0.00001 to 10 mol / mol, preferably 0.0001 to 1 mol / mol, and more preferably 0.001 to 0.5 mol / mol.

[0090] [Step 1-a] In step 1-a, for example, a monomer containing propylene is polymerized in the presence of a polymerization catalyst and hydrogen using a liquid-phase polymerization reactor. The composition of the monomers used for polymerization can be appropriately adjusted based on the type and content of monomer units constituting the propylene polymer (a). The propylene content in the monomer may be, for example, 80% by mass or more, 90% by mass or more, or 100% by mass, relative to the total mass of the monomer.

[0091] Examples of liquid-phase polymerization reactors include loop-type liquid-phase reactors and vessel-type liquid-phase reactors.

[0092] Examples of polymerization catalysts include Ziegler-Natta type catalysts and metallocene-based catalysts, with Ziegler-Natta type catalysts being preferred. Examples of Ziegler-Natta type catalysts include catalysts containing the above-mentioned olefin polymerization and solid catalyst components, organoaluminum compounds, and electron-donating compounds. A catalyst pre-activated by contacting it with a small amount of olefin can also be used as a polymerization catalyst.

[0093] As a polymerization catalyst, a prepolymerization catalyst component obtained by prepolymerizing an olefin in the presence of the above-mentioned solid catalyst component for olefin polymerization, n-hexane, triethylaluminum, bis(ethylamino)dicyclopentylsilane, etc., can also be used. The olefin used for prepolymerization is preferably one of the olefins that constitute the heterophagic propylene polymerization material.

[0094] The polymerization temperature can be, for example, 0 to 120°C. The polymerization pressure can be, for example, atmospheric pressure to 10 MPaG.

[0095] Step 1-a may be carried out continuously in multiple stages using multiple reactors in series.

[0096] [Step 1-b] In step 1-b, for example, a monomer containing propylene is polymerized in the presence of a polymerization catalyst and hydrogen using a gas-phase polymerization reactor. The composition of the monomers used for polymerization can be appropriately adjusted based on the type and content of monomer units constituting the propylene polymer (a). The propylene content in the monomer may be, for example, 80% by mass or more, 90% by mass or more, or 100% by mass, relative to the total mass of the monomer.

[0097] Examples of gas-phase polymerization reactors include fluidized bed reactors and jet bed reactors.

[0098] The gas-phase polymerization reactor may be a multi-stage gas-phase polymerization reactor having multiple reaction regions connected in series. The multi-stage gas-phase polymerization reactor may be a multi-stage gas-phase polymerization reactor having multiple polymerization tanks connected in series. With such a device, it is considered easier to adjust the intrinsic viscosity of the propylene-based polymer (a) to the above range.

[0099] A multi-stage gas-phase polymerization reactor can include, for example, a cylindrical section extending vertically, a reduced-diameter section formed in the cylindrical section whose inner diameter decreases towards the bottom and which has a gas introduction opening at the lower end, a jet-bed type olefin polymerization reaction region surrounded by the inner surface of the reduced-diameter section and the inner surface of the cylindrical section above the reduced-diameter section, with a jet layer formed inside, and a fluid-bed type olefin polymerization reaction region.

[0100] A multi-stage gas-phase polymerization reactor preferably has multiple reaction regions in the vertical direction. From the viewpoint of the intrinsic viscosity of the propylene polymer (a), it is preferable that the multi-stage gas-phase polymerization reactor has multiple reaction regions in the vertical direction, with the uppermost stage being a fluidized bed type olefin polymerization reaction region and the remaining stages being multiple jet-bed type olefin polymerization reaction regions. In such a device, for example, a fluidized bed or jet bed is formed in the reaction region by supplying solid components from the top of the device and gaseous components from the bottom of the device. The gaseous components may include monomers containing propylene and hydrogen, as well as inert gases such as nitrogen. In the device, it is preferable that there are three or more jet-bed type olefin polymerization reaction regions.

[0101] When multiple reaction regions are arranged vertically, the lower reaction region may be positioned diagonally below the upper reaction region. In such an apparatus, for example, the solid components obtained in the upper reaction region are discharged diagonally downward, and the discharged solid components are supplied to the lower reaction region from diagonally above. In this case, the gaseous components are supplied, for example, from the lower part of the upper reaction region, with the gaseous components discharged from the upper part of the lower reaction region.

[0102] Specific examples of polymerization catalysts are the same as described above.

[0103] 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.

[0104] [Process 2] Step 2 may be carried out in either the liquid or gas phase, but for example, it is carried out in the gas phase. If carried out in the liquid phase, for example, a liquid-phase reactor such as a loop type or vessel type can be used. If carried out in the gas phase, for example, a gas-phase reactor such as a fluidized bed reactor or a jet bed reactor can be used.

[0105] In step 2, for example, a monomer containing ethylene and at least one α-olefin selected from the group consisting of α-olefins having 4 to 12 carbon atoms, and propylene is polymerized in the presence of a polymerization catalyst and hydrogen. The composition of the monomers used for polymerization can be appropriately adjusted based on the type and content of monomer units constituting the propylene copolymer (b). The content of at least one α-olefin selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms in the monomers used for polymerization may be, for example, 30 to 55% by mass or 35 to 50% by mass, relative to the total mass of the monomer.

[0106] Specific examples of polymerization catalysts are the same as described above.

[0107] When polymerization occurs in the liquid phase, the polymerization temperature is, for example, 40 to 100°C, and the polymerization pressure is, for example, atmospheric pressure to 5 MPaG. When polymerization occurs in the gas phase, the polymerization temperature is, for example, 40 to 100°C, and the polymerization pressure is, for example, 0.5 to 5 MPaG.

[0108] A propylene polymer (a) and a propylene copolymer (b) may be prepared in separate steps, the polymerization catalyst may be deactivated, and then they may be mixed in a solution or molten state. Alternatively, the polymer may be continuously produced by supplying the resulting polymer to the next step without deactivating the catalyst. When polymerization is carried out continuously without deactivating the catalyst, the polymerization catalyst from the previous step also acts as the polymerization catalyst for the subsequent step.

[0109] There are no particular restrictions on the order of steps 1 and 2. Step 1 preferably includes steps 1-a and 1-b.

[0110] The manufacturing method according to this embodiment may include, for example, steps 1-a, 1-b, and 2 in this order. [Examples]

[0111] The present invention will be described in more detail below using examples and comparative examples, but the present invention is not limited to the following examples.

[0112] Table 1 shows the silicon compounds (external donors) that are brought into contact with the solid catalyst components for olefin polymerization, along with their structures.

[0113] [Table 1]

[0114] <Measurement of soluble portion of cold xylene (CXS), unit: mass%> The sample (olefin polymer or heterophagic propylene polymerization material) was dissolved in boiling xylene, and the resulting xylene solution was cooled to precipitate the cold xylene-insoluble portion. The resulting mixture was filtered, and the olefin polymer or heterophagic propylene polymerization material (cold xylene-soluble portion) dissolved in the filtrate was quantified using liquid chromatography (LC).

[0115] (Pretreatment conditions) • Sample quantity: 1g for olefin polymer, 0.1g for heterophagic propylene polymerization material • Solvent: 100 mL of xylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) with dibutylhydroxytoluene (BHT) added at a concentration of 2 mg / 100 mL. • Dissolution conditions: Reflux for 30 minutes after boiling. • Temperature conditions: Cool in ice water for 20 minutes, then raise to 20°C and stir for 1 hour. • Filtration conditions: Filtered using filter paper (No. 50) and measured using LC.

[0116] (LC measurement conditions) • Liquid transfer pump: LC-20AD (manufactured by Shimadzu Corporation) • Degasser: DGU-20A3 (manufactured by Shimadzu Corporation) • Autosampler: SIL-20A HT (manufactured by Shimadzu Corporation) • Column oven: CTO-20A (manufactured by Shimadzu Corporation) • Differential refractive index detector: RID-10A (manufactured by Shimadzu Corporation) • System controller: CBM-20A (manufactured by Shimadzu Corporation) • Measurement and analysis software: LC solution ver. 1.24 SP1 • Column: SHODEX GPC KF-801 (Upper exclusion limit molecular weight 1500) • Eluent: Tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd., special grade, stabilizer-free) • Column oven temperature: 40°C • Sample injection volume: 130 μL ·Flow rate: 1mL / min • Detector: Differential refractometer

[0117] <The polystyrene-equivalent molecular weight contained in the cold xylene-soluble portion of the olefin polymer is 10 3.5 The following components' proportions should be measured, or the polystyrene-equivalent molecular weight contained in the cold xylene-soluble portion of the heterophagic propylene polymerization material should be 10 4.0 Measurement of the percentage of the following components, in units: %> The polystyrene-equivalent molecular weight contained in the cold xylene-soluble portion of the olefin polymer relative to the total components of the cold xylene-soluble portion of the olefin polymer is 10 3.5 The proportions of the following components, and the polystyrene-equivalent molecular weight contained in the cold xylene-soluble portion of the heterophagic propylene polymerization material relative to the total components of the cold xylene-soluble portion of the heterophagic propylene polymerization material, are 10 4.0 The proportions of the following components were measured by gel permeation chromatography (GPC) under the following conditions.

[0118] (Measurement sample) In the CXS measurement described above, the filtrate (i.e., a xylene solution in which the olefin polymer or heterophagic propylene polymerization material (cold xylene soluble portion) is dissolved) was used as the measurement sample.

[0119] (GPC measurement conditions) • Liquid transfer pump: LC-20AD (manufactured by Shimadzu Corporation) • Degasser: DGU-20A3 (manufactured by Shimadzu Corporation) • Autosampler: SIL-20A HT (manufactured by Shimadzu Corporation) • Column oven: CTO-20A (manufactured by Shimadzu Corporation) • Differential refractive index detector: RID-10A (manufactured by Shimadzu Corporation) • System controller: CBM-20A (manufactured by Shimadzu Corporation) • Measurement and analysis software: LC solution ver. 1.24 SP1 (manufactured by Shimadzu Corporation) • GPC Columns: Plus Pore Series Poly Pore 7.5mm ID x 300mm (Agilent Technologies) 2 tubes Mobile phase: Tetrahydrofuran (Kanto Chemical, special grade, stabilizer-free) ·Flow rate: 1mL / min • Column oven temperature: 35℃ • Detection: Differential refractive index detector Differential refractive index detector cell temperature: 35℃ • Sample solution injection volume: 300 μL for olefin polymers, 100 μL for heterophagic propylene polymerization materials. • GPC column calibration standard: PStQuick Kit-H (manufactured by Tosoh Corporation)

[0120] (Analysis method) Calibration curve samples were prepared by adding 1 mL of tetrahydrofuran (Kanto Chemical Co., Ltd., special grade, stabilizer-free) to each vial of the Tosoh Corporation's standard polystyrene kit PStQuick Kit-H (PStQuickA: polystyrene mixture with weight-average molecular weights of 1,090,000, 1,900,000, 18,100, 2,420; PStQuickB: polystyrene mixture with weight-average molecular weights of 706,000, 96,400, 10,200, 1,010; PStQuickC: polystyrene mixture with weight-average molecular weights of 427,000, 37,900, 5,970, 500) and dissolving the mixture. Calibration curves were created using LC analysis software (Shimadzu Corporation, LC solution) based on the elution time and molecular weight of the peak top in the chromatogram obtained from GPC measurement of the calibration curve samples. The calibration curve was an octagonal approximation equation. Based on the calibration curve, the polystyrene-equivalent molecular weight was 10 3.5 or 10 4.0 The elution time of the components was calculated.

[0121] In the GPC chromatogram, the peak area for all components of the cold xylene soluble part was calculated by considering the period from the rise of the cold xylene soluble part's peak to just before the rise of the BHT peak as a single peak. The polystyrene-equivalent molecular weight was 10 3.5 or 10 4.0 From the chromatogram obtained by vertical partitioning based on the elution time of the component (i.e., from the chromatogram from the point of vertical partitioning up to just before the rise of the BHT peak), the polystyrene-equivalent molecular weight is 10 3.5 or 10 4.0 The peak areas of the following components were calculated. For the total peak area of ​​all components in the cold xylene soluble portion, the polystyrene-equivalent molecular weight was 100%. 3.5 or 10 4.0 The percentage of peak area for the following components was calculated.

[0122] <Ethylene monomer unit content in propylene copolymer, unit: mass%> The content of ethylene monomer units in the heterophasic propylene polymerization material obtained by IR spectroscopy was determined in accordance with the IR spectral measurement described on page 619 of the Polymer Analysis Handbook (1995, Kinokuniya Shoten). The content of ethylene monomer units in the propylene copolymer was determined by dividing the content of ethylene monomer units in the heterophasic propylene polymerization material by the content of propylene copolymer in the heterophasic propylene polymerization material. The ethylene-propylene copolymer ratio (Z2) in the heterophasic propylene polymerization material was determined by the method described later.

[0123] <Measurement of intrinsic viscosity [η], unit: dL / g> Tetralin solutions (concentrations: 0.1 g / dL, 0.2 g / dL, and 0.5 g / dL) of olefin polymers, propylene polymers, or heterophagic propylene polymer materials were prepared. The reduced viscosity of the tetralin solutions was then measured at 135°C using an Ubbelohde viscometer. The intrinsic viscosities were then determined by the calculation method described on page 491 of "Polymer Solutions, Polymer Experiments 11" (Kyoritsu Shuppan Co., Ltd., 1982), specifically by plotting the reduced viscosity against concentration and extrapolating the concentration to zero.

[0124] <Measuring the melting point (Tm), unit: °C> The Tm of the olefin polymer was measured using a differential scanning calorimeter (DSC). A sample of the olefin polymer (approximately 5 mg) was placed in an aluminum pan and placed inside a PerkinElmer DSC8500 differential scanning calorimeter. The temperature was raised to 230°C, held at 230°C for 5 minutes, then cooled to 0°C at a rate of 5°C / min, held at 0°C for 5 minutes, and finally raised to 200°C at a rate of 5°C / min to measure the melting curve. The temperature was corrected using the melting point of indium (156.6°C). The temperature at the melting peak top in the melting curve was defined as the Tm of the olefin polymer.

[0125] <Iso-tactic pentad fraction [mmmm]> The isotactic pentad fraction of propylene polymers was measured according to the method using 13C-NMR spectra described by A. Zambelli et al. in Macromolecules, 6, 925 (1973). The assignment of absorption peaks obtained from 13C-NMR spectra was based on Macromolecules, 8, 687 (1975). Specifically, the ratio of the area of ​​mmmm peaks to the area of ​​all absorption peaks in the methyl carbon region obtained from 13C-NMR spectra was determined as the isotactic pentad fraction. The isotactic pentad fraction of the NPL standard material CRM No. M19-14 Polypropylene PP / MWD / 2 from the National Physical Laboratory, UK, obtained by this method, was 94.4. The 13C-NMR measurements were performed under the following conditions.

[0126] (Measurement conditions) • Model: Bruker AVANCE600 • Probe: 10mm cryoprepole ·Measurement temperature: 135℃ • Pulse repetition time: 4 seconds • Pulse width: 45° • Total number of times: 256 ·Magnetic field strength: 600MHz

[0127] <Measurement of high-boiling point component content index of olefin polymers, unit: mass ppm> The olefin polymer granules were heated at 105°C for 6 hours to remove the light-boiling components. The obtained olefin polymer granules were measured using a Seiko Instruments TG-TDA-6200 thermomass-differential thermal analyzer. The measurement was performed under a nitrogen atmosphere, starting at 30°C with a heating rate of 50°C / min, and then raised to 125°C, where it was maintained. The high-boiling point component content index (mass ppm) of the olefin polymer was then calculated according to the following formula. (Mass at 3 minutes after measurement (g) - Mass at 60 minutes after measurement (g)) / (Mass at 3 minutes after measurement (g)) × 1,000,000

[0128] <Measurement of high-boiling point component content index for heterophagic propylene polymerization materials, unit: mass ppm> The obtained heterophagic propylene polymerization material, propylene resin composition pellets, or molded articles were measured using a Seiko Instruments TG-TDA-6200 thermomass-differential thermal analyzer. The measurements were performed under a nitrogen atmosphere, starting at 30°C with a heating rate of 50°C / min, and then maintained at 125°C. The high-boiling point component content index (mass ppm) of the heterophagic propylene polymerization material, propylene resin composition pellets, or molded articles was then calculated according to the following formula. (Mass at 3 minutes after measurement (g) - Mass at 60 minutes after measurement (g)) / (Mass at 3 minutes after measurement (g)) × 1,000,000

[0129] <Example 1> (1) Synthesis of Solid Catalyst Component A for Olefin Polymerization After replacing the gas in a 200 LSUS reaction vessel equipped with a stirrer with nitrogen gas, toluene (52.8 L) and titanium tetrachloride (33.3 L) were added and stirred to obtain a toluene solution of titanium tetrachloride. After lowering the temperature of the obtained toluene solution of titanium tetrachloride to below 0°C, magnesium diethoxide (11 kg) was added in six portions at 72-minute intervals while stirring. The resulting mixture was maintained at a temperature not exceeding 2°C for 150 minutes. Ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.76 kg) was added to the resulting mixture, and the temperature was raised to 10°C and maintained for 120 minutes. Toluene (14.3 L) was added to the resulting mixture, and the temperature was raised to 60°C. At the same temperature, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (4.0 kg) was added. The resulting mixture was raised to 110°C and stirred at the same temperature for 180 minutes. The obtained mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed three times with toluene (83 L) at 95°C. Toluene (44 L) was added to the resulting mixture, and then titanium tetrachloride (22 L) and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.95 kg) were added at 60°C. The temperature of the resulting mixture was raised to 110°C and stirred at the same temperature for 30 minutes. The resulting mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed three times with toluene (83 L) at 60°C. The resulting mixture was washed three times with hexane (83 L) and then dried to obtain solid catalyst component A for olefin polymerization (10.2 kg).

[0130] (2) Synthesis of olefin polymer (1) A 3 L autoclave with a stirrer was thoroughly dried and then evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), bis(ethylamino)dicyclopentylsilane (silicon compound P) (0.26 mmol), and solid catalyst component A for olefin polymerization (5.84 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.2 MPa). The autoclave temperature was raised to 80 °C, and propylene was polymerized at this temperature for 1 hour. Unreacted monomers were then purged to obtain olefin polymer (1). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 69 kg (olefin polymer (1)) / g (solid catalyst component A for olefin polymerization). The CXS of olefin polymer (1) was 1.52 mass%, [η] was 0.90 dL / g, Tm was 161.1 °C, and the high boiling point component index was 204 mass ppm. The olefin polymer (1) has a polystyrene-equivalent molecular weight of 10, as measured by gel permeation chromatography. 3.5 The following components accounted for 38.95% of the total. The results are shown in Table 2.

[0131] <Example 2> Synthesis of Olefin Polymer (2) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), bis(ethylamino)dicyclopentylsilane (silicon compound P) (0.26 mmol), and solid catalyst component A for olefin polymerization (6.29 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.08 MPa). The autoclave temperature was raised to 80 °C, and propylene was polymerized at the same temperature for 1 hour. After that, unreacted monomers were purged to obtain olefin polymer (2). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 45 kg (olefin polymer (2)) / g (solid catalyst component A for olefin polymerization). The CXS of olefin polymer (2) was 1.27% by mass, [η] was 1.32 dL / g, Tm was 161.3°C, and the high-boiling point component index was 246 ppm by mass. The polystyrene-equivalent molecular weight of olefin polymer (2) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 18.28% of the total. The results are shown in Table 2.

[0132] <Example 3> Synthesis of Olefin Polymer (3) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), bis(ethylamino)dicyclopentylsilane (silicon compound P) (0.26 mmol), and solid catalyst component A for olefin polymerization (8.23 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.01 MPa). The autoclave temperature was raised to 80°C, and propylene was polymerized at the same temperature for 1 hour. After that, unreacted monomers were purged to obtain olefin polymer (3). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 19 kg (olefin polymer (3)) / g (solid catalyst component A for olefin polymerization). The CXS of olefin polymer (3) was 3.00% by mass, [η] was 2.64 dL / g, Tm was 160.5°C, and the high-boiling point component index was 434 ppm by mass. The polystyrene-equivalent molecular weight of olefin polymer (3) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 3.16% of the total. The results are shown in Table 2.

[0133] <Example 4> Synthesis of Olefin Polymer (4) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), cyclohexyltriethoxysilane (silicon compound Q) (0.26 mmol), and solid catalyst component A for olefin polymerization (7.20 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.11 MPa). The autoclave temperature was raised to 80 °C, and propylene was polymerized at this temperature for 1 hour. After that, unreacted monomers were purged to obtain propylene polymer alone (4). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 42 kg (olefin polymer (4)) / g (solid catalyst component A for olefin polymerization). The CXS of olefin polymer (4) was 1.19% by mass, [η] was 1.19 dL / g, Tm was 161.6°C, and the high-boiling point component index was 273 ppm by mass. The polystyrene-equivalent molecular weight of olefin polymer (4) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 20.11% of the total. The results are shown in Table 2.

[0134] <Example 5> (1) Synthesis of Solid Catalyst Component B for Olefin Polymerization After replacing the gas in a 200 LSUS reaction vessel equipped with a stirrer with nitrogen gas, toluene (60.1 L) and titanium tetrachloride (22.3 L) were added and stirred to obtain a toluene solution of titanium tetrachloride. After lowering the temperature of the obtained toluene solution of titanium tetrachloride to below 0°C, magnesium diethoxide (11 kg) was added in six portions at 72-minute intervals while stirring. The resulting mixture was maintained at a temperature not exceeding 2°C for 90 minutes. The resulting mixture was then heated to 10°C and maintained for 90 minutes. Toluene (14.3 L) was added to the resulting mixture, and the temperature was raised to 60°C. At the same temperature, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (4.0 kg) was added. The resulting mixture was heated to 110°C and stirred at the same temperature for 180 minutes. After solid-liquid separation of the resulting mixture at 110°C, the obtained solid was washed three times with toluene (83 L) at 95°C. Toluene (43 L) was added to the resulting mixture, and then titanium tetrachloride (22 L) was added at 60°C. The resulting mixture was heated to 105°C and stirred at the same temperature for 60 minutes. The resulting mixture was separated into solid and liquid at 105°C, and the resulting solid was washed three times with toluene (83 L) at 60°C. The resulting mixture was washed three times with hexane (83 L) and then dried to obtain solid catalyst component B for olefin polymerization (8.4 kg). (2) Synthesis of olefin polymer (5) A 3L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), bis(ethylamino)dicyclopentylsilane (silicon compound P) (0.26 mmol), and solid catalyst component B for olefin polymerization (8.96 mg) were added to the autoclave, followed by the addition of propylene (780 g) and hydrogen (0.08 MPa). The autoclave temperature was raised to 80°C, and the propylene was polymerized at this temperature for 1 hour. Unreacted monomers were then purged to obtain olefin polymer (5). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 53 kg (olefin polymer (5)) / g (solid catalyst component B for olefin polymerization). The CXS of olefin polymer (5) was 2.06% by mass, [η] was 1.18 dL / g, Tm was 161.0°C, and the high-boiling point component index was 303 ppm by mass. The polystyrene-equivalent molecular weight of olefin polymer (5) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 17.92% of the total. The results are shown in Table 2.

[0135] <Example 6> Synthesis of Olefin Polymer (6) A 3 L autoclave with a stirrer was thoroughly dried and then evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), triethoxyphenylsilane (silicon compound R) (0.26 mmol), and solid catalyst component B for olefin polymerization (8.14 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.08 MPa). The autoclave temperature was raised to 80 °C, and propylene was polymerized at this temperature for 1 hour. Unreacted monomers were then purged to obtain olefin polymer (6). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 43 kg (olefin polymer (6)) / g (solid catalyst component B for olefin polymerization). The CXS of propylene polymer alone (6) was 1.17 mass%, [η] was 1.32 dL / g, Tm was 161.9 °C, and the high boiling point component index was 478 mass ppm. The olefin polymer (6) has a polystyrene-equivalent molecular weight of 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 12.50% of the total. The results are shown in Table 2.

[0136] <Comparative Example 1> Synthesis of Olefin Polymer (C1) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), cyclohexylethyldimethoxysilane (silicon compound S) (0.26 mmol), and solid catalyst component A for olefin polymerization (6.10 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.15 MPa). The autoclave temperature was raised to 80°C, and the propylene was polymerized at that temperature for 1 hour. After that, the unreacted monomer was purged to obtain the olefin polymer (C1). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 51 kg (olefin polymer (C1) / g (solid catalyst component A for olefin polymerization)). The CXS of olefin polymer (C1) was 0.66 mass%, [η] was 1.32 dL / g, Tm was 162.2°C, and the high boiling point component index was 983 mass ppm. The polystyrene-equivalent molecular weight of olefin polymer (C1), as measured by gel permeation chromatography, was 10 3.5 The following components accounted for 38.28% of the total. The results are shown in Table 2.

[0137] <Comparative Example 2> Synthesis of Olefin Polymer (C2) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), tert-butyl-n-propyl-dimethoxysilane (silicon compound T) (0.26 mmol), and solid catalyst component A for olefin polymerization (4.73 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.43 MPa). The autoclave temperature was raised to 80°C, and propylene was polymerized at this temperature for 1 hour. After that, unreacted monomers were purged to obtain olefin polymer (C2). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 80 kg (olefin polymer (C2)) / g (solid catalyst component A for olefin polymerization). The CXS of the olefin polymer (C2) was 1.04% by mass, [η] was 0.89 dL / g, Tm was 161.6°C, and the high-boiling point component index was 860 ppm by mass. The polystyrene-equivalent molecular weight of the olefin polymer (C2) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 64.08% of the total. The results are shown in Table 2.

[0138] <Comparative Example 3> Synthesis of Olefin Polymer (C3) A 3L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), tert-butyl-n-propyl-dimethoxysilane (silicon compound T) (0.26 mmol), and solid catalyst component A for olefin polymerization (4.55 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.30 MPa). The autoclave temperature was raised to 80°C, and propylene was polymerized at this temperature for 1 hour. Unreacted monomers were then purged to obtain olefin polymer (C3). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 104 kg (olefin polymer (C3)) / g (solid catalyst component A for olefin polymerization). The CXS of the olefin polymer (C3) was 0.46% by mass, [η] was 1.27 dL / g, Tm was 162.3°C, and the high-boiling point component index was 821 ppm by mass. The polystyrene-equivalent molecular weight of the olefin polymer (C3), measured by gel permeation chromatography, was 10. 3.5 The following components accounted for 56.32% of the total. The results are shown in Table 2.

[0139] <Comparative Example 4> Synthesis of Olefin Polymer (C4) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), tert-butyl-n-propyl-dimethoxysilane (silicon compound T) (0.26 mmol), and solid catalyst component B for olefin polymerization (5.15 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.25 MPa). The autoclave temperature was raised to 80°C, and propylene was polymerized at this temperature for 1 hour. After that, unreacted monomers were purged to obtain olefin polymer (C4). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 79 kg (olefin polymer (C4)) / g (solid catalyst component B for olefin polymerization). The CXS of the olefin polymer (C4) was 1.24% by mass, [η] was 1.29 dL / g, Tm was 162.0°C, and the high-boiling point component index was 820 ppm by mass. The polystyrene-equivalent molecular weight of the olefin polymer (C4) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 54.83% of the total. The results are shown in Table 2.

[0140] <Comparative Example 5> Synthesis of Olefin Polymer (C5) A 3 L autoclave with a stirrer was thoroughly dried, and then the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), dicyclopentyl dimethoxysilane (silicon compound U) (0.26 mmol), and solid catalyst component A for olefin polymerization (5.14 mg) were added to the autoclave, followed by propylene (780 g) and hydrogen (0.40 MPa). The autoclave temperature was raised to 80°C, and propylene was polymerized at this temperature for 1 hour. Unreacted monomers were then purged to obtain olefin polymer (C5). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 134 kg (olefin polymer (C5)) / g (solid catalyst component A for olefin polymerization). The CXS of the olefin polymer (C5) was 0.60 mass%, [η] was 1.17 dL / g, Tm was 163.2°C, and the high-boiling point component index was 1269 mass ppm. The polystyrene-equivalent molecular weight of the olefin polymer (C5) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 70.17% of the total. The results are shown in Table 2.

[0141] <Comparative Example 6> Synthesis of Olefin Polymer (C6) After thoroughly drying a 3 L autoclave equipped with a stirrer, the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), cyclohexylethyldimethoxysilane (silicon compound S) (0.26 mmol), and solid catalyst component C (6.22 mg) described in Example 1(2) of Japanese Patent Application Publication No. 2004-182981 were added to the autoclave, followed by the addition of propylene (780 g) and hydrogen (0.27 MPa). The autoclave temperature was raised to 80°C, and the propylene was polymerized at this temperature for 1 hour. After that, the unreacted monomer was purged to obtain olefin polymer (C6). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 42 kg (olefin polymer (C6)) / g (solid catalyst component C for olefin polymerization). The CXS of the olefin polymer (C6) was 0.97% by mass, [η] was 1.16 dL / g, Tm was 161.8°C, and the high-boiling point component index was 1135 ppm by mass. The polystyrene-equivalent molecular weight of the olefin polymer (C6) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 62.87% of the total. The results are shown in Table 2.

[0142] <Comparative Example 7> Synthesis of Olefin Polymer (C7) After thoroughly drying a 3 L autoclave equipped with a stirrer, the inside was evacuated. Triethylaluminum (organoaluminum compound) (2.63 mmol), tert-butyl-n-propyl-dimethoxysilane (silicon compound T) (0.26 mmol), and solid catalyst component C (4.73 mg) described in Example 1(2) of Japanese Patent Application Publication No. 2004-182981 were added to the autoclave, followed by the addition of propylene (780 g) and hydrogen (0.37 MPa). The autoclave temperature was raised to 80°C, and the propylene was polymerized at the same temperature for 1 hour. After that, unreacted monomers were purged to obtain olefin polymer (C7). The amount of polymer produced per unit amount of catalyst (polymerization activity) was 61 kg (olefin polymer (C7)) / g (solid catalyst component C for olefin polymerization). The CXS of the olefin polymer (C7) was 0.75% by mass, [η] was 1.17 dL / g, Tm was 162.7°C, and the high-boiling point component index was 889 ppm by mass. The polystyrene-equivalent molecular weight of the olefin polymer (C7) was 10 as measured by gel permeation chromatography. 3.5 The following components accounted for 72.55% of the total. The results are shown in Table 2.

[0143] [Table 2]

[0144] As can be seen from the results shown in Table 2, the olefin polymers of Examples 1-6 have a lower high-boiling-point component content index than Comparative Examples 1-7, and therefore have less resin odor. Despite having a lower high-boiling-point component content index, the olefin polymers of Examples 1-6 do not have a high melting point, but rather maintain a stable melting point; in fact, their melting points are lower than those of Comparative Examples 1-7, thus maintaining properties such as low-temperature heat sealability. Comparative Example 1 corresponds to a follow-up experiment of an example in the publicly available document (WO2018 / 025862).

[0145] <Example 11> (1) Synthesis of Solid Catalyst Component D for Olefin Polymerization After replacing the gas in a 200 LSUS reaction vessel equipped with a stirrer with nitrogen gas, toluene (52.8 L) was added and stirred, and then magnesium diethoxide (11 kg) was added to obtain a slurry. After lowering the temperature of the obtained slurry to below 0°C, titanium tetrachloride (33.3 L) was added in three parts while stirring. The temperature of the resulting mixture was maintained at no more than 2°C for 150 minutes. Ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.76 kg) was added to the resulting mixture, and the temperature was raised to 10°C and maintained for 120 minutes. Toluene (14.3 L) was added to the resulting mixture, and the temperature was raised to 60°C. At the same temperature, ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (4.0 kg) was added, and the resulting mixture was raised to 110°C and stirred at the same temperature for 180 minutes. The obtained mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed three times with toluene (83 L) at 95°C. Toluene (33 L) was added to the resulting mixture, and then titanium tetrachloride (33 L) and ethyl 2-ethoxymethyl-3,3-dimethylbutanoate (0.95 g) were added at 60°C. The resulting mixture was heated to 110°C and stirred at the same temperature for 30 minutes. The resulting mixture was subjected to solid-liquid separation at 110°C, and the resulting solid was washed three times with toluene (83 L) at 95°C. The resulting mixture was washed three times with hexane (83 L) and then dried to obtain solid catalyst component D for olefin polymerization (10.6 kg).

[0146] (2) Synthesis of heterophagic propylene polymerization material (11) [Prepolymerization] A 2L stainless steel (SUS) autoclave with a stirrer contained 1.7L of thoroughly dehydrated and degassed n-hexane, 59 mmol of triethylaluminum (organoaluminum compound), and 43 mmol of bis(ethylamino)dicyclopentylsilane (silicon compound P). 22 g of solid catalyst component D for olefin polymerization was added to the autoclave, and then 77 g of propylene was continuously supplied over approximately 30 minutes while maintaining the autoclave temperature at approximately 10°C to perform prepolymerization. The resulting slurry was then transferred to a 160L SUS316L autoclave with a stirrer, and 131 L of liquid butane was added to obtain a slurry.

[0147] [This polymerization] This polymerization process was carried out using an apparatus consisting of three slurry polymerization reactors and two gas-phase polymerization reactors arranged in series and connected, in polymerization steps 1-a1, 1-a2, 1-a3, 1-b, and 2. Specifically, a propylene-based polymer (a), which is an olefin polymer, was produced in polymerization steps 1-a1, 1-a2, and 1-a3 (all in slurry polymerization reactors) and polymerization step 1-b (gas-phase polymerization reactor). The generated propylene-based polymer (a) was then transferred to the next polymerization reactor without deactivating the olefin polymerization catalyst, and the propylene-based copolymer (b), which is an ethylene-propylene copolymer, was polymerized in polymerization step 2 (gas-phase polymerization reactor). However, polymerization step 1-a3 was omitted in Examples 11 and 12. Polymerization steps 1-a1, 1-a2, 1-a3, 1-b, and 2 will be described in detail below.

[0148] [Polymerization process 1-a1] (Homopolymerization of propylene using a slurry polymerization reactor) The homopolymerization of propylene was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, a slurry of propylene, hydrogen, triethylaluminum (organoaluminum compound), bis(ethylamino)dicyclopentylsilane (silicon compound P), and the aforementioned prepolymerization catalyst components obtained in the prepolymerization step was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 78℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 18L • Propylene supply: 28 kg / hour • Hydrogen supply: 84.1 NL / hour • Supply rate of triethylaluminum (organoaluminum compound): 23.5 mmol / hour • Supply rate of bis(ethylamino)dicyclopentylsilane (silicon compound P): 18.2 mmol / hour • Slurry supply rate (calculated as solid catalyst component): 1.03 g / hour • Polymerization pressure: 4.32 MPa (gauge pressure)

[0149] [Polymerization process 1-a2] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a1 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 78℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 15 kg / hour • Hydrogen supply: 44.3 NL / hour • Polymerization pressure: 3.87 MPa (gauge pressure)

[0150] [Polymerization Process 1-b] (Homopolymerization of propylene using a gas-phase polymerization reactor (gas-phase polymerization)) The slurry obtained in polymerization step 1-a2 was continuously supplied to the subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 1-b was a reactor equipped with a gas dispersion plate. Propylene and hydrogen were continuously supplied from the bottom of the gas-phase polymerization reactor. This formed a fluidized bed in each of the multi-stage reaction regions, and the supply amounts of propylene and hydrogen were controlled to maintain a constant gas composition and pressure, while further homopolymerization of propylene was carried out while purging excess gas. The reaction conditions were as follows. ·Polymerization temperature: 80℃ • Polymerization pressure: 1.74 MPa (gauge pressure) • Gas concentration ratio (hydrogen / (hydrogen + propylene)): 5.0 mol% The intrinsic viscosity [η]PP of the product (propylene polymer (a)) sampled from the outlet of the gas-phase polymerization reactor was 0.92 dL / g.

[0151] [Polymerization Process 2] (Propylene-ethylene copolymerization using a gas-phase polymerization reactor (gas-phase polymerization)) The propylene polymer (a) discharged from the gas-phase polymerization reactor used in polymerization step 1-b was continuously supplied to a subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 2 was a reactor equipped with a gas dispersion plate. Propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerization reactor with the above configuration, and the gas supply amount was adjusted to maintain a constant gas composition and pressure, while purging excess gas. In the presence of the propylene polymer (a) (particles), copolymerization of propylene and ethylene was carried out to produce an ethylene-propylene copolymer, which is a propylene copolymer (b), and a heterophagous propylene polymerization material, which is a mixture of the propylene polymer (a) and the propylene copolymer (b), was obtained. The reaction conditions were as follows. ·Polymerization temperature: 70℃ • Polymerization pressure: 1.25 MPa (gauge pressure) • Gas concentration ratio (ethylene / (propylene + ethylene)): 18.8 mol% (Hydrogen / (Hydrogen + Propylene + Ethylene)): 0.26 mol% The intrinsic viscosity [η]whole of the product (heterophasic propylene polymerization material) sampled from the outlet of the gas-phase polymerization reactor was 1.54 dL / g.

[0152] To the obtained heterophagic propylene polymerization material, water was added at a rate of approximately 100 g / h while the mixture was incubated under nitrogen at 60°C for 2 hours at a flow rate of 20 Nm. 3 After deactivating the catalyst components at / h, the treatment is further carried out at 60°C under nitrogen for 1 hour at a flow rate of 20 Nm. 3 The material was flow-dried at a rate of / h. The content of propylene copolymer (b) (Z2) in the dried heterophagic propylene polymerization material was calculated using the following formula, after measuring the heat of fusion of the propylene polymer (a) and the entire heterophagic propylene polymerization material. Here, the heat of fusion was measured by differential scanning thermal analysis (DSC). X = 1 - (ΔHf)T / (ΔHf)P (ΔHf)T: Total heat of fusion of the heterophagic propylene polymerization material (J / g) (ΔHf)P: Heat of fusion of propylene polymer (a) (J / g)

[0153] The product obtained from the outlet of the gas-phase polymerization reactor is a mixture of a propylene polymer (a) and a propylene copolymer (b). The intrinsic viscosity [η]EP of the propylene copolymer (b) was calculated using the following formula. [η]EP=([η]PP-[η]whole×(1-Z2)) / Z2

[0154] The obtained heterophagic propylene polymerization material (11) had a cold xylene-soluble portion CXS of 8.29 mass%, and a high-boiling point component index of 1347 mass ppm. Furthermore, the polystyrene-equivalent molecular weight of the heterophagic propylene polymerization material (11), measured by gel permeation chromatography, was 10 4.0The following components accounted for 7.89% of the total. The heterophagic propylene polymerization material (11) contained 4.3% by mass of ethylene monomer units and 95.7% by mass of propylene monomer units. The content of propylene copolymer (b) (Z2) was 11.2% by mass. The ethylene monomer unit content in propylene copolymer (b) was 38.3% by mass, and the intrinsic viscosity [η]EP of propylene copolymer (b) was 6.44 dL / g. The isotactic pentad fraction of propylene polymer (a) was 0.985.

[0155] [Manufacturing of propylene resin composition pellets] After uniformly pre-mixing 100 parts by mass of heterophagic propylene polymerization material (11), 0.05 parts by mass of "Calcium Stearate (CAS No. 1592-23-0)" manufactured by Sakai Chemical Industry Co., Ltd., 0.075 parts by mass of "Sumilyzer GA80 (CAS No. 90498-90-1)" manufactured by Sumitomo Chemical Co., Ltd., and "SONGNOX6260 (CAS No. 26741-53-7)" manufactured by Songwon Co., Ltd., the mixture was melt-kneaded in a nitrogen atmosphere under the conditions of an extrusion rate of 85 kg / hr, 180°C, and a screw rotation speed of 280 rpm using a twin-screw kneading extruder to produce propylene resin composition pellets (11). The high-boiling point component content index of the propylene resin composition pellet (11) was 901 ppm by mass. Furthermore, the polystyrene-equivalent molecular weight of the propylene resin composition pellet (11), as measured by gel permeation chromatography, was 10 4.0 The following components accounted for 8.82% of the total.

[0156] [Molding] A propylene resin composition pellet (11) was supplied to a Sumitomo Heavy Industries "SE130 type molding machine," and a flat plate with a length of 150 mm, a width of 90 mm, and a thickness of 3.0 mm was molded at a molding temperature of 220°C, a mold cooling temperature of 50°C, and a pressure of 50 MPa. The obtained flat plate was cut into pellets to obtain molded bodies (11). The high-boiling point component content index of the molded body (11) was 862 mass ppm. Furthermore, the polystyrene-equivalent molecular weight of the molded body (11), measured by gel permeation chromatography, was 10 4.0 The following components accounted for 9.31% of the total.

[0157] These results are shown in Tables 3 and 4.

[0158] <Example 12> Synthesis of heterophagic propylene polymerization material (12) [Prepolymerization] In a 2L stainless steel (SUS) autoclave equipped with a stirrer, 1.7L of thoroughly dehydrated and degassed n-hexane, 60 mmol of triethylaluminum (organoaluminum compound), and 43 mmol of bis(ethylamino)dicyclopentylsilane (silicon compound P) were placed. After adding 22 g of solid catalyst component D for olefin polymerization to the autoclave, prepolymerization was carried out by continuously supplying 77 g of propylene over approximately 30 minutes while maintaining the autoclave temperature at approximately 10°C. Subsequently, the resulting slurry was transferred to a 160L SUS316L autoclave equipped with a stirrer, and 131 L of liquid butane was added to obtain a slurry.

[0159] [This polymerization] <Polymerization process 1-a1> (Homopolymerization of propylene using a slurry polymerization reactor) The homopolymerization of propylene was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, a slurry of propylene, hydrogen, triethylaluminum (organoaluminum compound), bis(ethylamino)dicyclopentylsilane (silicon compound P), and the aforementioned prepolymerization catalyst components obtained in the prepolymerization step was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 78℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 18L • Propylene supply: 28 kg / hour • Hydrogen supply: 84.2 NL / hour • Supply rate of triethylaluminum (organoaluminum compound): 23.9 mmol / hour • Supply rate of bis(ethylamino)dicyclopentylsilane (silicon compound P): 17.9 mmol / hour • Slurry supply rate (calculated as solid catalyst component): 1.00 g / hour • Polymerization pressure: 4.29 MPa (gauge pressure)

[0160] [Polymerization process 1-a2] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a1 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 78℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 15 kg / hour • Hydrogen supply: 44.5 NL / hour • Polymerization pressure: 3.85 MPa (gauge pressure)

[0161] [Polymerization Process 1-b] (Homopolymerization of propylene using a gas-phase polymerization reactor (gas-phase polymerization)) The slurry obtained in polymerization step 1-a2 was continuously supplied to the subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 1-b was a reactor equipped with a gas dispersion plate. Propylene and hydrogen were continuously supplied from the bottom of the gas-phase polymerization reactor. This formed a fluidized bed in each of the multi-stage reaction regions, and the supply amounts of propylene and hydrogen were controlled to maintain a constant gas composition and pressure, while further homopolymerization of propylene was carried out while purging excess gas. The reaction conditions were as follows. ·Polymerization temperature: 80℃ • Polymerization pressure: 1.75 MPa (gauge pressure) • Gas concentration ratio (hydrogen / (hydrogen + propylene)): 5.6 mol% The intrinsic viscosity [η]PP of the product (propylene polymer (a)) sampled from the outlet of the gas-phase polymerization reactor was 0.87 dL / g.

[0162] [Polymerization Process 2] (Propylene-ethylene copolymerization using a gas-phase polymerization reactor (gas-phase polymerization)) The propylene polymer (a) discharged from the gas-phase polymerization reactor used in polymerization step 1-b was continuously supplied to a subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 2 was a reactor equipped with a gas dispersion plate. Propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerization reactor with the above configuration, and the gas supply amount was adjusted to maintain a constant gas composition and pressure, while purging excess gas. In the presence of the propylene polymer (a) (particles), copolymerization of propylene and ethylene was carried out to produce an ethylene-propylene copolymer, which is a propylene copolymer (b), and a heterophagous propylene polymerization material, which is a mixture of the propylene polymer (a) and the propylene copolymer (b), was obtained. The reaction conditions were as follows. ·Polymerization temperature: 70℃ • Polymerization pressure: 1.25 MPa (gauge pressure) • Gas concentration ratio (ethylene / (propylene + ethylene)): 18.6 mol% (Hydrogen / (Hydrogen + Propylene + Ethylene)): 0.20 mol% The intrinsic viscosity [η]whole of the product (heterophasic propylene polymerization material) sampled from the outlet of the gas-phase polymerization reactor was 1.62 dL / g.

[0163] To the obtained heterophagic propylene polymerization material, water was added at a rate of approximately 100 g / h while the mixture was incubated under nitrogen at 60°C for 2 hours at a flow rate of 20 Nm. 3 After deactivating the catalyst components at / h, the treatment is further carried out at 60°C under nitrogen for 1 hour at a flow rate of 20 Nm. 3The material was flow-dried at a rate of / h. The content of propylene copolymer (b) (Z2) in the dried heterophagic propylene polymerization material and the intrinsic viscosity [η]EP of propylene copolymer (b) were calculated in the same manner as in Example 11.

[0164] The obtained heterophagic propylene polymerization material (12) had a cold xylene-soluble portion CXS of 10.26 mass%, and a high-boiling point component index of 1342 mass ppm. Furthermore, the polystyrene-equivalent molecular weight of the heterophagic propylene polymerization material (12), measured by gel permeation chromatography, was 10 4.0 The following components accounted for 0.46% of the total. The heterophagic propylene polymerization material (12) contained 4.7% by mass of ethylene monomer units and 95.3% by mass of propylene monomer units. The content of propylene copolymer (b) (Z2) was 13.3% by mass. The ethylene monomer unit content in propylene copolymer (b) was 35.4% by mass, and the intrinsic viscosity [η]EP of propylene copolymer (b) was 6.52 dL / g. The isotactic pentad fraction of propylene polymer (a) was 0.983.

[0165] The propylene resin composition pellets (12) and molded articles (12) were prepared in the same manner as in Example 11. The high boiling point component content index of the propylene resin composition pellets (12) was 840 ppm by mass, and the high boiling point component content index of the molded articles (12) was 814 ppm by mass.

[0166] These results are shown in Tables 3 and 4.

[0167] <Example 13> Synthesis of heterophagic propylene polymerization material (13) [Prepolymerization] A stainless steel (SUS) autoclave with a stirrer and an internal volume of 2 L was charged with 1.9 L of n - hexane that had been thoroughly dehydrated and degassed, 52 mmol of triethylaluminum (an organoaluminum compound), and 6.8 mmol of triethoxyphenylsilane (silicon compound R). After adding 19 g of a solid catalyst component D for olefin polymerization into the autoclave, prepolymerization was carried out by continuously supplying 68 g of propylene over about 30 minutes while maintaining the temperature inside the autoclave at about 10°C. Then, the resulting slurry was transferred to a SUS316L autoclave with a stirrer and an internal volume of 160 L, and further made into a slurry by adding 130 L of liquid butane.

[0168] [Main Polymerization] <Polymerization Step 1 - a1> (Homopolymerization of Propylene Using a Slurry Polymerization Reactor) Homopolymerization of propylene was carried out using a vessel - type slurry polymerization reactor made of SUS304 with a stirrer. Specifically, a slurry of propylene, hydrogen, triethylaluminum (an organoaluminum compound), triethoxyphenylsilane (silicon compound R), and the above - mentioned prepolymerization catalyst component obtained in the prepolymerization step was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. · Polymerization temperature: 66°C · Stirring speed: 150 rpm · Liquid level in the slurry polymerization reactor: 18 L · Supply rate of propylene: 40 kg / hour · Supply rate of hydrogen: 88.2 NL / hour · Supply rate of triethylaluminum (an organoaluminum compound): 30.8 mmol / hour · Supply rate of triethoxyphenylsilane (silicon compound R): 16.6 mmol / hour · Supply rate of the slurry (in terms of solid catalyst component): 0.73 g / hour · Polymerization pressure: 4.17 MPa (gauge pressure)

[0169] [Polymerization Step 1 - a2] (Homopolymerization of Propylene Using a Slurry Polymerization Reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a1 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 74℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 25 kg / hour • Hydrogen supply: 55.9 NL / hour • Polymerization pressure: 3.83 MPa (gauge pressure)

[0170] [Polymerization process 1-a3] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a2 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 65℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 0 kg / hour • Polymerization pressure: 3.44 MPa (gauge pressure)

[0171] [Polymerization Process 1-b] (Homopolymerization of propylene using a gas-phase polymerization reactor (gas-phase polymerization)) The slurry obtained in polymerization step 1-a3 was continuously supplied to the subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 1-b was a reactor equipped with a gas dispersion plate. Propylene and hydrogen were continuously supplied from the bottom of the gas-phase polymerization reactor. This formed a fluidized bed in each of the multi-stage reaction regions, and the supply amounts of propylene and hydrogen were controlled to maintain a constant gas composition and pressure, while further homopolymerization of propylene was carried out while purging excess gas. The reaction conditions were as follows. ·Polymerization temperature: 80℃ • Polymerization pressure: 1.75 MPa (gauge pressure) • Gas concentration ratio (hydrogen / (hydrogen + propylene)): 4.4 mol% The intrinsic viscosity [η]PP of the product (propylene polymer (a)) sampled from the outlet of the gas-phase polymerization reactor was 0.92 dL / g.

[0172] [Polymerization Process 2] (Propylene-ethylene copolymerization using a gas-phase polymerization reactor (gas-phase polymerization)) The propylene polymer (a) discharged from the gas-phase polymerization reactor used in polymerization step 1-b was continuously supplied to a subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 2 was a reactor equipped with a gas dispersion plate. Propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerization reactor with the above configuration, and the gas supply amount was adjusted to maintain a constant gas composition and pressure, while purging excess gas. In the presence of the propylene polymer (a) (particles), copolymerization of propylene and ethylene was carried out to produce an ethylene-propylene copolymer, which is a propylene copolymer (b), and a heterophagous propylene polymerization material, which is a mixture of the propylene polymer (a) and the propylene copolymer (b), was obtained. The reaction conditions were as follows. ·Polymerization temperature: 70℃ • Polymerization pressure: 1.25 MPa (gauge pressure) • Gas concentration ratio (ethylene / (propylene + ethylene)): 15.7 mol% (Hydrogen / (Hydrogen + Propylene + Ethylene)): 0.20 mol% The intrinsic viscosity [η]whole of the product (heterophasic propylene polymerization material) sampled from the outlet of the gas-phase polymerization reactor was 1.57 dL / g.

[0173] To the obtained heterophagic propylene polymerization material, water was added at a rate of approximately 100 g / h while the mixture was incubated under nitrogen at 60°C for 2 hours at a flow rate of 20 Nm. 3 After deactivating the catalyst components at / h, the treatment is further carried out at 60°C under nitrogen for 1 hour at a flow rate of 20 Nm. 3It was dried by flow drying at / h. The ratio (Z2) of the propylene-based copolymer (b) in the heterophagic propylene polymerization material obtained by drying and the intrinsic viscosity [η]EP of the propylene-based copolymer (b) were calculated in the same manner as in Example 11.

[0174] The amount of cold xylene-soluble part CXS of the obtained heterophagic propylene polymerization material (13) was 12.45% by mass, and the high-boiling component amount index was 1193 ppm by mass. Furthermore, the polystyrene-converted molecular weight 10 measured by gel permeation chromatography of the heterophagic propylene polymerization material (13) 4.0 The proportion occupied by the following components in the whole was 8.24%. The content of ethylene monomer units in the heterophagic propylene polymerization material (13) was 5.0% by mass, and the content of propylene monomer units was 95.0% by mass. Also, the content (Z2) of the propylene-based copolymer (b) was 15.6% by mass. The content of ethylene monomer units in the propylene-based copolymer (b) was 32.1% by mass, and the intrinsic viscosity [η]EP of the propylene-based copolymer (b) was 5.09 dL / g. The isotactic pentad fraction of the propylene-based polymer (a) was 0.976.

[0175] The propylene resin composition pellets (13) and the molded body (13) were produced in the same manner as in Example 11. The high-boiling component amount index of the propylene resin composition pellets (13) was 924 ppm by mass, and the high-boiling component amount index of the molded body (13) was 781 ppm by mass.

[0176] These results are shown in Tables 3 and 4.

[0177] <Comparative Example 11> Synthesis of Heterophagic Propylene Polymerization Material (C11) [Prepolymerization] A 2L stainless steel (SUS) autoclave with a stirrer contained 1.6L of thoroughly dehydrated and degassed n-hexane, 40 mmol of triethylaluminum (organoaluminum compound), and 1 mmol of tert-butyl-n-propyl-dimethoxysilane (silicon compound T). After adding 14 g of solid catalyst component B for olefin polymerization to the autoclave, prepolymerization was carried out by continuously supplying 49 g of propylene over approximately 30 minutes while maintaining the autoclave temperature at approximately 10°C. Subsequently, the resulting slurry was transferred to a 160L SUS316L autoclave with a stirrer, and 130 L of liquid butane was added to obtain a slurry.

[0178] [This polymerization] <Polymerization process 1-a1> (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, a slurry of propylene, hydrogen, triethylaluminum (organoaluminum compound), tert-butyl-n-propyl-dimethoxysilane (silicon compound T), and the aforementioned prepolymerization catalyst components obtained in the prepolymerization step was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 66℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 18L • Propylene supply: 23 kg / hour • Hydrogen supply: 126.5 NL / hour • Supply rate of triethylaluminum (organoaluminum compound): 28.5 mmol / hour • Supply rate of tert-butyl-n-propyl-dimethoxysilane (silicon compound T): 8.5 mmol / hour • Slurry supply rate (calculated as solid catalyst component): 0.53 g / hour • Polymerization pressure: 4.30 MPa (gauge pressure)

[0179] [Polymerization process 1-a2] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a1 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 73℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 15 kg / hour • Hydrogen supply: 86.1 NL / hour • Polymerization pressure: 3.94 MPa (gauge pressure)

[0180] [Polymerization process 1-a3] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a2 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 65℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 4 kg / hour • Polymerization pressure: 3.60 MPa (gauge pressure)

[0181] [Polymerization Process 1-b] (Homopolymerization of propylene using a gas-phase polymerization reactor (gas-phase polymerization)) The slurry obtained in polymerization step 1-a3 was continuously supplied to the subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 1-b was a reactor equipped with a gas dispersion plate. Propylene and hydrogen were continuously supplied from the bottom of the gas-phase polymerization reactor. This formed a fluidized bed in each of the multi-stage reaction regions, and the supply amounts of propylene and hydrogen were controlled to maintain a constant gas composition and pressure, while further homopolymerization of propylene was carried out while purging excess gas. The reaction conditions were as follows. ·Polymerization temperature: 80℃ • Polymerization pressure: 1.74 MPa (gauge pressure) • Gas concentration ratio (hydrogen / (hydrogen + propylene)): 7.8 mol% The intrinsic viscosity [η]PP of the product (propylene polymer (a)) sampled from the outlet of the gas-phase polymerization reactor was 0.90 dL / g.

[0182] [Polymerization Process 2] (Propylene-ethylene copolymerization using a gas-phase polymerization reactor (gas-phase polymerization)) The propylene polymer (a) discharged from the gas-phase polymerization reactor used in polymerization step 1-b was continuously supplied to a subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 2 was a reactor equipped with a gas dispersion plate. Propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerization reactor with the above configuration, and the gas supply amount was adjusted to maintain a constant gas composition and pressure, while purging excess gas. In the presence of the propylene polymer (a) (particles), copolymerization of propylene and ethylene was carried out to produce an ethylene-propylene copolymer, which is a propylene copolymer (b), and a heterophagous propylene polymerization material, which is a mixture of the propylene polymer (a) and the propylene copolymer (b), was obtained. The reaction conditions were as follows. ·Polymerization temperature: 70℃ • Polymerization pressure: 1.25 MPa (gauge pressure) • Gas concentration ratio (ethylene / (propylene + ethylene)): 25.9 mol% (Hydrogen / (Hydrogen + Propylene + Ethylene)): 0.27 mol% The intrinsic viscosity [η]whole of the product (heterophasic propylene polymerization material) sampled from the outlet of the gas-phase polymerization reactor was 1.71 dL / g.

[0183] To the obtained heterophagic propylene polymerization material, water was added at a rate of approximately 100 g / h while the mixture was incubated under nitrogen at 60°C for 2 hours at a flow rate of 20 Nm. 3 After deactivating the catalyst components at / h, the treatment is further carried out at 60°C under nitrogen for 1 hour at a flow rate of 20 Nm. 3 The material was flow-dried at a rate of / h. The content of propylene copolymer (b) (Z2) in the dried heterophagic propylene polymerization material and the intrinsic viscosity [η]EP of propylene copolymer (b) were calculated in the same manner as in Example 11.

[0184] The obtained heterophagic propylene polymerization material (C11) had a cold xylene-soluble portion (CXS) of 12.25% by mass, and a high-boiling point component index of 2009 ppm by mass. Furthermore, the polystyrene-equivalent molecular weight of the heterophagic propylene polymerization material (C11), measured by gel permeation chromatography, was 10. 4.0 The following components accounted for 12.55% of the total. The heterophagic propylene polymerization material (C11) contained 5.5% by mass of ethylene monomer units and 94.5% by mass of propylene monomer units. The content of propylene copolymer (b) (Z2) was 14.7% by mass. The ethylene monomer unit content in propylene copolymer (b) was 37.4% by mass, and the intrinsic viscosity [η]EP of propylene copolymer (b) was 6.41 dL / g. The isotactic pentad fraction of propylene polymer (a) was 0.977.

[0185] The propylene resin composition pellets (C11) and molded articles (C11) were prepared in the same manner as in Example 11. The high-boiling point component index of the propylene resin composition pellets (C11) was 1700 ppm by mass, and the high-boiling point component index of the molded articles (C11) was 1405 ppm by mass.

[0186] These results are shown in Tables 3 and 4.

[0187] <Comparative Example 12> Synthesis of Heterophagic Propylene Polymerization Material (C12)

[0188] [Prepolymerization] A 2 L stainless steel (SUS) autoclave with a stirrer contained 1.7 L of thoroughly dehydrated and degassed n-hexane, 35 mmol of triethylaluminum (organoaluminum compound), and 4 mmol of tert-butyl-n-propyl-dimethoxysilane (silicon compound T). After adding 14 g of solid catalyst component D for olefin polymerization to the autoclave, prepolymerization was carried out by continuously supplying 49 g of propylene over approximately 30 minutes while maintaining the autoclave temperature at approximately 10°C. Subsequently, the resulting slurry was transferred to a 160 L SUS316L autoclave with a stirrer, and 131 L of liquid butane was added to obtain a slurry.

[0189] [This polymerization] <Polymerization process 1-a1> (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, a slurry of propylene, hydrogen, triethylaluminum (organoaluminum compound), tert-butyl-n-propyl-dimethoxysilane (silicon compound T), and the aforementioned prepolymerization catalyst components obtained in the prepolymerization step was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 57℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 18L • Propylene supply: 23 kg / hour • Hydrogen supply: 126.8 NL / hour • Supply rate of triethylaluminum (organoaluminum compound): 27.2 mmol / hour • Supply rate of tert-butyl-n-propyl-dimethoxysilane (silicon compound T): 7.6 mmol / hour • Slurry supply rate (calculated as solid catalyst component): 0.60 g / hour • Polymerization pressure: 4.08 MPa (gauge pressure)

[0190] [Polymerization process 1-a2] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a1 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 57℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 15 kg / hour • Hydrogen supply: 82.5 NL / hour • Polymerization pressure: 3.39 MPa (gauge pressure)

[0191] [Polymerization process 1-a3] (Homopolymerization of propylene using a slurry polymerization reactor) Propylene homopolymerization was carried out using a SUS304 vessel-type slurry polymerization reactor equipped with a stirrer. Specifically, the slurry obtained in polymerization step 1-a2 was continuously supplied to the slurry polymerization reactor to carry out the polymerization reaction. The reaction conditions were as follows. ·Polymerization temperature: 50℃ ·Stirring speed: 150rpm • Liquid level in slurry polymerization reactor: 44L • Propylene supply: 0 kg / hour • Polymerization pressure: 3.16 MPa (gauge pressure)

[0192] [Polymerization Process 1-b] (Homopolymerization of propylene using a gas-phase polymerization reactor (gas-phase polymerization)) The slurry obtained in polymerization step 1-a3 was continuously supplied to the subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 1-b was a reactor equipped with a gas dispersion plate. Propylene and hydrogen were continuously supplied from the bottom of the gas-phase polymerization reactor. This formed a fluidized bed in each of the multi-stage reaction regions, and the supply amounts of propylene and hydrogen were controlled to maintain a constant gas composition and pressure, while further homopolymerization of propylene was carried out while purging excess gas. The reaction conditions were as follows. ·Polymerization temperature: 80℃ • Polymerization pressure: 1.75 MPa (gauge pressure) • Gas concentration ratio (hydrogen / (hydrogen + propylene)): 10.9 mol% The intrinsic viscosity [η]PP of the product (propylene polymer (a)) sampled from the outlet of the gas-phase polymerization reactor was 0.86 dL / g.

[0193] [Polymerization Process 2] (Propylene-ethylene copolymerization using a gas-phase polymerization reactor (gas-phase polymerization)) The propylene polymer (a) discharged from the gas-phase polymerization reactor used in polymerization step 1-b was continuously supplied to a subsequent gas-phase polymerization reactor. The gas-phase polymerization reactor used in polymerization step 2 was a reactor equipped with a gas dispersion plate. Propylene, ethylene, and hydrogen were continuously supplied to the gas-phase polymerization reactor with the above configuration, and the gas supply amount was adjusted to maintain a constant gas composition and pressure, while purging excess gas. In the presence of the propylene polymer (a) (particles), copolymerization of propylene and ethylene was carried out to produce an ethylene-propylene copolymer, which is a propylene copolymer (b), and a heterophagous propylene polymerization material, which is a mixture of the propylene polymer (a) and the propylene copolymer (b), was obtained. The reaction conditions were as follows. ·Polymerization temperature: 70℃ • Polymerization pressure: 1.250 MPa (gauge pressure) • Gas concentration ratio (ethylene / (propylene + ethylene)): 22.9 mol% (Hydrogen / (Hydrogen + Propylene + Ethylene)): 0.11 mol% The intrinsic viscosity [η]whole of the product (heterophasic propylene polymerization material) sampled from the outlet of the gas-phase polymerization reactor was 1.77 dL / g.

[0194] To the obtained heterophagic propylene polymerization material, water was added at a rate of approximately 100 g / h while the mixture was incubated under nitrogen at 60°C for 2 hours at a flow rate of 20 Nm. 3 After deactivating the catalyst components at / h, the treatment is further carried out at 60°C under nitrogen for 1 hour at a flow rate of 20 Nm. 3 The material was flow-dried at a rate of / h. The content of propylene copolymer (b) (Z2) in the dried heterophagic propylene polymerization material and the intrinsic viscosity [η]EP of propylene copolymer (b) were calculated in the same manner as in Example 11.

[0195] The obtained heterophagic propylene polymerization material (C12) had a cold xylene-soluble portion (CXS) of 12.66 mass%, and a high-boiling point component index of 1852 mass ppm. Furthermore, the polystyrene-equivalent molecular weight of the heterophagic propylene polymerization material (C12), measured by gel permeation chromatography, was 10 4.0 The following components accounted for 7.53% of the total. The heterophagic propylene polymerization material (C12) contained 4.9% by mass of ethylene monomer units and 95.1% by mass of propylene monomer units. The content of propylene copolymer (b) (Z2) was 13.4% by mass. The ethylene monomer unit content in propylene copolymer (b) was 36.6% by mass, and the intrinsic viscosity [η]EP of propylene copolymer (b) was 7.66 dL / g. The isotactic pentad fraction of propylene polymer (a) was 0.980.

[0196] The propylene resin composition pellet (C12) was prepared in the same manner as in Example 11, and the high-boiling point component content index of the propylene resin composition pellet (C12) was 1774 ppm by mass.

[0197] These results are shown in Tables 3 and 4.

[0198] [Table 3]

[0199] [Table 4]

[0200] As can be seen from the results shown in Table 3, the heterophagic propylene polymerization materials of Examples 11-13 have a lower high-boiling point component content index than Comparative Examples 11-12, and therefore have less resin odor.

[0201] When comparing the high-boiling-point component content index of heterophagic propylene polymerization materials (Examples 11-13) with that of olefin polymers (Comparative Examples 1-7), some examples show that "Examples (heterophagic propylene polymerization materials) > Comparative Examples (olefin polymers)." This is because heterophagic propylene polymerization materials have a higher amorphous component content, making them more susceptible to leakage of volatile components from the sample, thus resulting in a higher high-boiling-point component content index compared to olefin polymers. [Industrial applicability]

[0202] The olefin polymer of the present invention has excellent properties, such as low resin odor and a low high-boiling point component index, yet its melting point does not increase. Therefore, it is suitable for use in various automotive interior and exterior parts, including 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. It has high applicability in various fields of industry, such as the transportation machinery industry, the electrical and electronics industry, and the building and construction industry.

Claims

1. A heterophagic propylene polymerization material that satisfies the following formula (3), (X² × Y²) / Z² ≤ 7.0 (3) (In the formula, X2 represents the amount (mass%) of cold xylene-soluble portion of the heterophagic propylene polymerization material. Y2 is the polystyrene-equivalent molecular weight 10 contained in the cold xylene-soluble portion of the heterophagic propylene polymerization material, relative to the total components of the cold xylene-soluble portion of the heterophagic propylene polymerization material as measured by gel permeation chromatography. ４．０ The percentages (%) of the following components are shown. Z2 represents the content (mass%) of a propylene-based copolymer contained in the heterophagic propylene polymerization material, which includes monomer units derived from at least one selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms, and monomer units derived from propylene. X2 is 8.29–12.45 mass%, Y2 is 0.46–8.24%, and Z2 is 11.2–15.6 mass%, Propylene copolymers are propylene-ethylene copolymers. A heterophagic propylene polymerization material having a high-boiling point component content index of 1347 ppm by mass or less, The high-boiling-point component content index is measured according to the following method for heterophagic propylene polymerization materials. <Method for measuring the high-boiling point component content index> The heterophagic propylene polymerization material is measured using simultaneous thermomass-differential thermal analysis. The measurement is performed under a nitrogen atmosphere, starting at 30°C, with a heating rate of 50°C / min, and then raised to 125°C, where it is maintained. The high-boiling point component index (mass ppm) of the heterophagic propylene polymerization material is then calculated according to the following formula. (Mass at 3 minutes after measurement starts (g) - Mass at 60 minutes after measurement starts (g)) / (Mass at 3 minutes after measurement starts (g)) × 1,000,000.

2. A heterophagic propylene polymerization material according to claim 1, satisfying the following formula (4). 0.3<(X2×Y2) / Z2<7.0 (4) (In the formula, X2, Y2, and Z2 have the same meanings as above.)

3. A propylene polymer (a) containing 80% by mass or more monomer units derived from propylene and having an intrinsic viscosity of 2.0 dL / g or less, A heterophagous propylene polymerization material according to claim 1 or 2, comprising a propylene copolymer (b) containing 30 to 55% by mass of monomer units derived from at least one selected from the group consisting of ethylene and α-olefins having 4 to 12 carbon atoms, and monomer units derived from propylene, and having an intrinsic viscosity of 1.5 to 8.0 dL / g.

4. The heterophagic propylene polymerization material according to claim 3, wherein the content of the propylene polymer (a) is 50 to 90% by mass, and the content of the propylene copolymer (b) is 10 to 50% by mass.

5. The heterophagic propylene polymerization material according to claim 3 or 4, wherein the isotactic fraction of the propylene polymer (a) is greater than 0.

975.

6. The heterophagic propylene polymerization material according to claim 1, wherein the high-boiling point component content index of the heterophagic propylene polymerization material is 1193 ppm by mass to 1347 ppm by mass.

7. An olefin polymer that satisfies the following formula (1), Y1 / X1≦40 (1) (In the formula, X1 represents the amount (mass%) of the cold xylene-soluble portion of the olefin polymer. Y1 is the polystyrene-equivalent molecular weight 10 contained in the cold xylene-soluble portion of the olefin polymer, relative to the total components of the cold xylene-soluble portion of the olefin polymer as measured by gel permeation chromatography. ３．５ The percentages (%) of the following components are shown. X1 is 1.17–3.00 mass%, and Y1 is 3.16–38.95%. Olefin polymers are propylene homopolymers, An olefin polymer having a high-boiling point component content index of 478 ppm by mass or less, The high-boiling point component content index is measured according to the following method for olefin polymers. <Method for measuring the high-boiling point component content index> The olefin polymer granules are heated at 105°C for 6 hours to remove the light-boiling components. The obtained olefin polymer granules are measured using simultaneous thermomass-differential thermal analysis. The measurement is performed under a nitrogen atmosphere, starting at 30°C, with a heating rate of 50°C / min, and then raised to 125°C, where it is maintained. The high-boiling point component content index (mass ppm) of the olefin polymer is then calculated according to the following formula. (Mass at 3 minutes after measurement starts (g) - Mass at 60 minutes after measurement starts (g)) / (Mass at 3 minutes after measurement starts (g)) × 1,000,000.

8. The olefin polymer according to claim 7, satisfying the following formula (2). 5.3<Y1 / X1<40 (2) (In the formula, X1 and Y1 have the same meanings as described above.)

9. The olefin polymer according to claim 7, wherein the index of the high boiling point component of the olefin polymer is 204 ppm by mass to 478 ppm by mass.

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