JP2010013588A - Method for producing propylene-based block copolymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a propylene-based block copolymer with excellent impact resistance while retaining rigidity. <P>SOLUTION: The method for producing a propylene-based block copolymer comprises a polymerization step (I) wherein propylene and so on are polymerized in the presence of a particular catalyst for polymerization, and a subsequent polymerization step (II) wherein propylene is further copolymerized with an olefin other than propylene. In the method, a compound (D) represented by general formula (d) and a linear hydrocarbon compound (E) containing an ether group are added in the reaction system during or prior to the polymerization step (II). M(OR<SP>1</SP>)<SB>p</SB>X<SB>q</SB>(d), wherein M represents a Zr or Hf atom, R<SP>1</SP>represents a hydrocarbon group, X represents a hydrogen atom and so on, p is a numerical value satisfying: 0≤p≤m, q is a numerical value satisfying: 0≤q≤m, while p+q=m, wherein m represents atomic valence of M. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a propylene-based block copolymer.

  Propylene-based block copolymers are widely used as molding materials such as automobile interior / exterior materials and electrical component boxes.

As a method for producing a propylene-based block copolymer having a good quality balance such as impact resistance, rigidity, and workability, for example, Patent Document 1 discloses a propylene homopolymer slurry obtained by polymerizing a specific amount of propylene or propylene and another olefin. A method is disclosed in which ethylene and propylene are further polymerized after transferring a copolymerization slurry obtained by copolymerizing a specific amount of to a reactor in which ether or ester and dialkylaluminum halide coexist.
Japanese Patent No. 3325419

  However, the propylene-based block copolymer obtained by the conventional method as described above does not always satisfy both rigidity and impact resistance.

  Then, an object of this invention is to provide the manufacturing method of the propylene-type block copolymer which is excellent in impact resistance, maintaining rigidity.

The present invention relates to a polymerization catalyst obtained by contacting a solid catalyst component (A) having a titanium atom, a magnesium atom and a halogen atom as essential components, an organoaluminum compound (B), and an electron donating compound (C). Polymerization in which propylene is homopolymerized or copolymerized with propylene and an olefin other than propylene to produce a polymer component (1) having a content of monomer units based on propylene of 90% by weight or more. After performing step (I), propylene and an olefin other than propylene are further copolymerized to produce a polymer component (2) having a content of monomer units based on propylene of 10 to 90% by weight. A method for producing a propylene-based block copolymer for performing a polymerization step (II), wherein the compound (D) represented by the following general formula (d) and an ether group-containing linear carbonization Containing compound (E), during the polymerization process (II), or is added to the reaction system prior to the polymerization step (II), to provide a method for manufacturing a propylene block copolymer.
M (OR ¹ ) _p X _q (d)

Here, in formula (d), M represents a Zr or Hf atom, R ¹ represents a hydrocarbon group, and X represents a hydrogen atom, a halogen atom or a hydrocarbon group. p represents a number satisfying 0 ≦ p ≦ m, q represents a number satisfying 0 ≦ q ≦ m, and p + q = m. Here, m represents the valence of M.

  According to such a method for producing a propylene-based block copolymer, a propylene-based block copolymer having excellent impact resistance while maintaining rigidity can be produced. The inventors presume this reason as follows. Generally, the rigidity of the propylene-based block copolymer is determined by the copolymerization ratio of propylene and an olefin other than propylene, the melting point of the polymer component (1), the polymer component (1) and the polymer component (2). It is generally determined by the ratio. And if these ratios are changed to increase the rigidity, the impact resistance usually decreases. On the other hand, in the present invention, the compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) are added after the polymerization step (I) is started. It is characterized by being added to the reaction system before the completion. Thus, by adding the compound (D) represented by the general formula (d) as a Lewis acid and the ether group-containing linear hydrocarbon compound (E) into the reaction system, electrons serving as donor components The donating compound (C) replaces the ether group-containing linear hydrocarbon compound (E). As a result, the polymer structure in the polymerization step (II) can be made suitable, and the particle diameter of the polymer component (2) formed when the propylene-based block copolymer is molded can be reduced. Therefore, the impact resistance of the propylene-based block copolymer is excellent. According to the production method of the present invention, the copolymerization ratio of propylene and an olefin other than propylene, the melting point of the polymer component (1), the ratio of the polymer component (1) to the polymer component (2), etc. are changed. Since the impact resistance can be improved, a propylene-based block copolymer having excellent impact resistance while maintaining rigidity can be produced.

  The compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) are obtained after the polymerization step (I) and before the polymerization step (II). The compound (D) represented by d) and the ether group-containing linear hydrocarbon compound (E) are preferably added to the reaction system in this order.

  By adding the compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) to the reaction system in this manner, the electron-donating compound (C) and the ether group-containing compound are contained. Since the linear hydrocarbon compound (E) is smoothly replaced, the impact resistance of the propylene-based block copolymer can be further improved.

The compound (D) represented by the general formula (d) preferably includes a compound represented by the following general formula (d-1) or a compound represented by the following general formula (d-2).
Zr (OR ¹ ) ₄ (d-1)
Hf (OR ¹ ) ₄ (d-2)

Here, in Formula (d-1) and Formula (d-2), R ¹ represents a hydrocarbon group.

  By using such a compound as the compound (D) represented by the general formula (d), the impact resistance of the propylene-based block copolymer can be further improved.

  In the presence of an organosilicon compound having a Si—O bond, the solid catalyst component (A) having a titanium atom, a magnesium atom, and a halogen atom as essential components is converted to a magnesium compound represented by the following general formula (i). A solid catalyst component obtained by bringing a solid catalyst component precursor (a) obtained by reduction with a compound, a halogen-containing compound (b), and an electron donor (c) into contact with each other is preferable.

  Here, in formula (i), a represents the number of 1-20, R represents a C1-C20 hydrocarbon group. X represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all Xs may be the same or different.

  By using such a compound as the solid catalyst component (A), a highly rigid propylene-based block copolymer can be efficiently obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the propylene-type block copolymer excellent in impact resistance can be provided, maintaining rigidity.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The method for producing a propylene-based block copolymer of the present invention comprises a solid catalyst component (A) having a titanium atom, a magnesium atom and a halogen atom as essential components, an organoaluminum compound (B), and an electron donating compound (C). In the presence of a polymerization catalyst obtained by contacting with propylene, the content of monomer units based on propylene is 90% by weight or more by homopolymerizing propylene or copolymerizing propylene and an olefin other than propylene After carrying out the polymerization step (I) for producing the polymer component (1), propylene and an olefin other than propylene are further copolymerized, and the content of monomer units based on propylene is 10 to 90% by weight. A method for producing a propylene-based block copolymer which performs a polymerization step (II) for producing a polymer component (2), which is represented by the general formula (d) described later. That compound (D) and ether group-containing straight-chain hydrocarbon compound (E), during the polymerization process (II), or is intended to be added to the reaction system prior to the polymerization step (II).

  The solid catalyst component (A) is not particularly limited as long as it contains a titanium atom, a magnesium atom and a halogen atom, and a known catalyst can be used. Examples of such a solid catalyst component (A) include, for example, Japanese Patent Publication No. 46-34092, Japanese Patent Publication No. 47-41676, Japanese Patent Publication No. 55-23561, Japanese Patent Publication No. 57-24361, Japanese Patent Publication No. 52-. No. 39431, JP-B-52-36786, JP-B-1-28049, JP-B-3-43283, JP-A-4-80044, JP-A-55-52309, JP-A-58- 21405, JP 61-181807, JP 63-142008, JP 5-339319, JP 54-148093, JP 4-227604, JP 6 -2933, JP-A 64-6006, JP-A 6-179720, JP-B-7-116252, JP-A 8-134124 And solid catalyst components described in JP-A-9-31119, JP-A-11-228628, JP-A-11-80234, JP-A-11-322833, and JP-A-2004-182981. .

  The solid catalyst component (A) preferably further contains an electron donor in addition to the titanium atom, the magnesium atom and the halogen atom. The electron donor is preferably an organic acid ester or ether described below.

  The solid catalyst component (A) is produced, for example, by the following methods (1) to (5).

(1) A method of contacting a magnesium halide compound with a titanium compound.
(2) A method of contacting a magnesium halide compound, an electron donor, and a titanium compound.
(3) A method in which a magnesium halide compound and a titanium compound are dissolved in an electron donating solvent to obtain a solution, and then the carrier material is impregnated with the solution.
(4) A method of contacting a dialkoxymagnesium compound, a titanium halide compound, and an electron donor.
(5) A method of bringing a solid component containing a magnesium atom, a titanium atom and a hydrocarbon oxy group into contact with a halogenated compound, an electron donor and / or an organic acid halide.

  Among the methods (1) to (5), a solid component containing a magnesium atom, a titanium atom and a hydrocarbon oxy group, a halogenated compound, an electron donor and / or an organic acid halide (5) ) Is preferred.

  Specifically, the solid catalyst component (A) is obtained by reducing a titanium compound represented by the following general formula (i) with an organomagnesium compound in the presence of an organosilicon compound having a Si—O bond. A solid catalyst component obtained by bringing the solid catalyst component precursor (a), the halogen-containing compound (b), and the electron donor (c) into contact with each other is preferable.

  Here, in formula (i), a represents the number of 1-20, R represents a C1-C20 hydrocarbon group. X represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all Xs may be the same or different.

  Examples of the organosilicon compound having a Si—O bond include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, and diisopropoxy-diisopropyl. Silane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane, tetraphenoxysilane, triethoxyphenylsilane , Hexamethyldisilohexane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane, dimethyl Le polysiloxane, diphenyl polysiloxane, may be exemplified methylhydropolysiloxane, phenyl hydropolysiloxane like.

  Examples of the organic magnesium compound include methyl magnesium chloride, ethyl magnesium chloride, propyl magnesium chloride, isopropyl magnesium chloride, butyl magnesium chloride, sec-butyl magnesium chloride, tert-butyl magnesium chloride, isoamyl magnesium chloride, hexyl magnesium chloride, octyl magnesium. Examples include chloride, 2-ethylhexyl magnesium chloride, phenyl magnesium chloride, and benzyl magnesium chloride.

  The halogen-containing compound (b) is a compound containing halogen. Examples of the halogen-containing compound (b) include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide and other tetrahalogenated titanium, methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride. Dihalogenated dialkoxytitanium tetrachloromethane, trichloromethane, such as trihalogenated alkoxytitanium such as ethoxytitanium tribromide, dimethoxytitanium dichloride, diethoxytitanium dichloride, dibutoxytitanium dichloride, diphenoxytitanium dichloride, diethoxytitanium dibromide , Dichloromethane, monochloromethane, 1,1,1-trichloroethane, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane Tetrachlorosilane, trichlorosilane, methyltrichlorosilane, ethyltrichlorosilane, normal propyltrichlorosilane, normal butyltrichlorosilane, phenyltrichlorosilane, benzyltrichlorosilane, paratolyltrichlorosilane, cyclohexyltrichlorosilane, dichlorosilane, methyldichlorosilane, ethyldi Chlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, methylethyldichlorosilane, monochlorosilane, trimethylchlorosilane, triphenylchlorosilane, tetrachlorogermane, trichlorogermane, methyltrichlorogermane, ethyltrichlorogermane, phenyltrichlorogermane, dichlorogermane, dimethyldichlorogermane , Diethyldichlorogermane, di Phenyl dichlorogermane, monochlorogermane, trimethylchlorogermane, triethylchlorogermane, trinormalbutylchlorogermane, tetrachlorotin, methyltrichlorotin, normalbutyltrichlorotin, dimethyldichlorotin, dinormalbutyldichlorotin, diisobutyldichlorotin, diphenyldichloro Examples thereof include tin, divinyldichlorotin, methyltrichlorotin, phenyltrichlorotin, dichlorolead, methylchlorolead, and phenylchlorolead.

  The electron donor (c) is a compound that exhibits an electron donating property. Examples of the electron donor (c) include phthalic acid, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-normal phthalate, diisopropyl phthalate, di-butyl phthalate, diisobutyl phthalate, phthalate Dipentyl acid, di-normal hexyl phthalate, di-normal heptyl phthalate, diisoheptyl phthalate, di-normal octyl phthalate, di (2-ethylhexyl) phthalate, di-normal phthalate, diisodecyl phthalate, dicyclohexyl phthalate, phthalic acid Phthalic acid derivatives such as diphenyl and phthalic dichloride, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1 , -Dimethoxypropane, 2-isopropyl-2-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2 , 2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-diisopropyl-1, 3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane, 2, 2-dicyclopentyl-1,3-dimethyl Xipropane, 2-normalheptyl-2-isopentyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2, 1,3-diether compounds such as 2-diisobutyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane and 2,2-dicyclohexyl-1,3-dimethoxypropane, dimethyl ether, diethyl ether, Dialkyl ethers such as di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, di-n-amyl ether, diisoamyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, etc. Ether compounds.

  By using such a compound as the solid catalyst component (A), a highly rigid propylene-based block copolymer can be efficiently obtained.

  The organoaluminum compound (B) is a compound having at least one Al-carbon bond in the molecule. Examples of the organoaluminum compound (B) include compounds represented by the following general formula (b-1) and the following formula (b-2).

R ² _w AlY _3-w (b-1)
R ³ R ⁴ Al—O—AlR ⁵ R ⁶ (b-2)

In formula (b-1), R ^{2 to} R ⁶ represent a hydrocarbon group having 1 to 20 carbon atoms, Y represents a halogen atom, a hydrogen atom or an alkoxy group, and w represents 2 ≦ w ≦ 3. It is a satisfactory number.

  Examples of the compound represented by the following general formula (b-1) or the following formula (b-2) include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, and the like. Dialkylaluminum hydrides, dialkylaluminum halides such as diethylaluminum chloride, mixtures of trialkylaluminum and dialkylaluminum halides such as mixtures of triethylaluminum and diethylaluminum chloride, alkyls such as tetraethyldialumoxane, tetrabutyldialumoxane Alumoxane.

  From the viewpoint of polymerization activity and stereoregularity of the polymer component (1), the organoaluminum compound (B) is preferably a trialkylaluminum, a mixture of a trialkylaluminum and a dialkylaluminum halide, or an alkylalumoxane. Triethylaluminum, triisobutylaluminum, a mixture of triethylaluminum and diethylaluminum chloride or tetraethyldialumoxane is preferred.

  The electron donating compound (C) is a compound containing an electron donating element. Examples of the electron donating compound (C) include an oxygen-containing compound, a nitrogen-containing compound, a phosphorus-containing compound, and a sulfur-containing compound. Among them, an oxygen-containing compound or a nitrogen-containing compound is preferable, and an oxygen-containing compound is particularly preferable. By using such a compound, it becomes possible to efficiently obtain a propylene-based block copolymer containing the polymer component (1) having high stereoregularity.

  Examples of the oxygen-containing compound include alkoxy silicons, ethers, esters, and ketones. From the viewpoint of polymerization activity and stereoregularity of the polymer component (1), alkoxysilicones or ethers are preferred.

  Examples of the alkoxysilicones include compounds represented by the following general formula (c-1).

R ⁷ _r Si (OR ⁸ ) _4-r (c-1)

In formula (c-1), R ⁷ represents a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a heteroatom-containing substituent, R ⁸ represents a hydrocarbon group having 1 to 20 carbon atoms, and r Represents a number satisfying 0 ≦ r <4. All R ⁷ and all R ⁸ may be the same or different.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include linear alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group, isopropyl group, sec-butyl group, tert-butyl group, Examples thereof include a branched alkyl group such as a tert-amyl group, a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a cycloalkenyl group such as a cyclopentenyl group, and an aryl group such as a phenyl group and a tolyl group. When a hydrocarbon group having 1 to 20 carbon atoms is used as R ⁷ , in the alkoxysilicon compound represented by the general formula (c-1), the carbon atom directly bonded to the silicon atom is a secondary or tertiary carbon. It is preferable to have at least one R ⁷ .

Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom. Specific examples of the hetero atom-containing substituent include a dimethylamino group, a methylethylamino group, a diethylamino group, an ethyl n-propylamino group, a di-n-propylamino group, a pyrrolyl group, a pyridyl group, a pyrrolidinyl group, and a piperidyl group. Perhydroindolyl group, perhydroisoindolyl group, perhydroquinolyl group, perhydroisoquinolyl group, perhydrocarbazolyl group, perhydroacridinyl group, furyl group, pyranyl group, perhydrofuryl group And thienyl group. When a hetero atom-containing substituent is used as R ⁷ , the alkoxysilicon compound represented by the general formula (c-1) is preferably a silicon compound represented by the following general formula (c-2).

(R ⁹ R ¹⁰ N) Si (OR ¹¹ ) ₃ (c-2)

Here, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ¹⁰ represents a hydrocarbon group having 1 to 12 carbon atoms or hydrogen, and R ¹¹ represents a hydrocarbon group having 1 to 6 carbon atoms.

  Examples of the alkoxysilicon compound represented by the general formula (c-1) include diisopropyldimethoxysilane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, and tert-butyl. N-propyldimethoxysilane, tert-butyl-n-butyldimethoxysilane, tert-amylmethyldimethoxysilane, tert-amylethyldimethoxysilane, tert-amylnpropyldimethoxysilane, tert-amyl-n-butyldimethoxysilane, isobutyl Isopropyldimethoxysilane, tert-butylisopropyldimethoxysilane, dicyclobutyldimethoxysilane, cyclobutylisopropyldimethoxysilane, Butylisobutyldimethoxysilane, cyclobutyl-tert-butyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylisobutyldimethoxysilane, cyclopentyl-tert-butyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, Cyclohexylisopropyldimethoxysilane, cyclohexylisobutyldimethoxysilane, cyclohexyl-tert-butyldimethoxysilane, cyclohexylcyclopentyldimethoxysilane, cyclohexylphenyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, phenylisopropyl Methoxysilane, phenylisobutyldimethoxysilane, phenyl-tert-butyldimethoxysilane, phenylcyclopentyldimethoxysilane, diisopropyldiethoxysilane, diisobutyldiethoxysilane, di-tert-butyldiethoxysilane, tert-butylmethyldiethoxysilane, tert- Butylethyldiethoxysilane, tert-butyl-n-propyldiethoxysilane, tert-butyl-n-butyldiethoxysilane, tert-amylmethyldiethoxysilane, tert-amylethyldiethoxysilane, tert-amyl-n- Propyldiethoxysilane, tert-amyl-n-butyldiethoxysilane, dicyclopentyldiethoxysilane, dicyclohexyldiethoxysilane, cyclohexyl Methyldiethoxysilane, cyclohexylethyldiethoxysilane, diphenyldiethoxysilane, phenylmethyldiethoxysilane, 2-norbornanemethyldimethoxysilane, bis (perhydroquinolino) dimethoxysilane, bis (perhydroisoquinolino) dimethoxysilane, ( Perhydroquinolino) (perhydroisoquinolino) dimethoxysilane, (perhydroquinolino) methyldimethoxysilane, (perhydroisoquinolino) methyldimethoxysilane, (perhydroquinolino) ethyldimethoxysilane, (perhydroisoquinolino) Ethyldimethoxysilane, (perhydroquinolino) (n-propyl) dimethoxysilane, (perhydroisoquinolino) (n-propyl) dimethoxysilane, ((perhydroquinolino) (tert-butyl L) Dimethoxysilane, (perhydroisoquinolino) (tert-butyl) dimethoxysilane, dimethylaminotriethoxysilane, diethylaminotriethoxysilane, diethylaminotrimethoxysilane, diethylaminotri-n-propoxysilane, di-n-propylaminotriethoxy Examples include silane, methyl n-propylaminotriethoxysilane, t-butylaminotriethoxysilane, ethyl n-propylaminotriethoxysilane, ethylisopropylaminotriethoxysilane, and methylethylaminotriethoxysilane.

  Examples of the ethers include dialkyl ethers and diether compounds and cyclic ether compounds represented by the following general formula (c-3). In addition, ethers may be used individually by 1 type, and 2 or more types may be mixed and used for them.

In General Formula (c-3), R ¹² and R ¹⁵ each independently represent a linear, branched or alicyclic alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms. R ¹³ and R ¹⁴ each independently represent a linear, branched or alicyclic alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group or a hydrogen atom.

  Specific examples of the ethers described above include dimethyl ether, diethyl ether, di-n-butyl ether, methyl ethyl ether, methyl-n-butyl ether, methyl cyclohexyl ether, 2,2-diisobutyl-1,3-dimethoxypropane, 2- Isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane, 2-isopropyl-2-3,7-dimethyloctyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-isobutyl- 1,3-dimethoxypropa 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl- Examples thereof include 1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2-heptyl-2-pentyl-1,3-dimethoxypropane and the like.

  The cyclic ether compound is a heterocyclic compound having at least one —C—O—C— bond in the ring system. Specific examples thereof include ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, and 2,5. -Dimethoxytetrahydrofuran, tetrahydropyran, hexamethylene oxide, 1,3-dioxepane, 1,3-dioxane, 1,4-dioxane, 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl -1,3-dioxolane, 4-methyl-1,3-dioxolane, 2,4-dimethyl-1,3-dioxolane, furan, 2,5-dimethylfuran and s-trioxane.

  Examples of the nitrogen-containing compound include 2,6-substituted piperidines such as 2,6-dimethylpiperidine and 2,2,6,6-tetramethylpiperidine, 2,5-substituted piperidines, N, N, N ′. , N′-tetramethylmethylenediamine, substituted methylenediamines such as N, N, N ′, N′-tetraethylmethylenediamine, and substituted imidazolidines such as 1,3-dibenzylimidazolidine.

  Examples of the phosphorus-containing compound include phosphonic acid esters such as dimethyl phenylphosphonate and diethyl phenylphosphonate, and phosphinic acid esters such as dimethoxyphenylphosphine, methoxydiphenylphosphine, diethoxyphenylphosphine, and ethoxyphenylphosphine. .

  Examples of the sulfur-containing compound include thiophenes such as thiophene, 2,5-dimethylthiophene, 2,5-diethylthiophene, tetrahydrothiophene, 2,5-dimethyltetrahydrothiophene, and 2,5-diethyltetrahydrothiophene.

The method for contacting the solid catalyst component (A), the organoaluminum compound (B), and the electron donating compound (C) when obtaining the polymerization catalyst is not particularly limited. For example, the following (6) to ( The method of 8) is mentioned.
(6) A method in which the above components are mixed and contacted before being supplied to the polymerization tank.
(7) A method in which the above components are separately supplied to the polymerization tank and contacted in the polymerization tank.
(8) A method in which a part of each of the above components is mixed and brought into contact before being supplied to the polymerization tank, and the remaining components are separately supplied to and contacted in the polymerization tank.

  In addition, after each component of (A)-(C) is diluted with a solvent, you may make it contact and may make it contact without diluting.

  Further, the supply of the catalyst to the polymerization tank in the method (6) and the supply of the components to the polymerization tank in the methods (7) and (8) are usually performed under an inert gas atmosphere such as nitrogen or argon. And it implements in the state without moisture.

  The polymerization catalyst may be prepared by a method in which the components (A) to (C) are contacted as they are as described above. For example, in the presence of the solid catalyst component (A) and the organoaluminum compound (B). Alternatively, after a small amount of olefin is prepolymerized to obtain a prepolymerization catalyst, it may be prepared by a method in which a necessary amount of components (A) to (C) and the prepolymerization catalyst are brought into contact with each other.

  The prepolymerization method is not particularly limited, but it is preferable to use a slurry polymerization method using an inert hydrocarbon such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, cyclohexane, benzene and toluene as a solvent. . A part or all of the solvent may be changed to a liquid olefin.

  The amount of the organoaluminum compound (B) used in the prepolymerization is usually 0.5 to 700 moles, preferably 0.8 to 500 moles, particularly preferably 1 to 1 mole per mole of titanium atoms in the solid catalyst component (A). 200 moles.

  The amount of the prepolymerized olefin is usually 0.01 to 1000 g, preferably 0.05 to 500 g, particularly preferably 0.1 to 200 g, per 1 g of the solid catalyst component (A).

  The slurry concentration in the slurry polymerization method is preferably 1 to 500 g-solid catalyst component (A) / liter-solvent, particularly preferably 3 to 300 g-solid catalyst component (A) / liter-solvent. The prepolymerization temperature is preferably -20 to 100 ° C, particularly preferably 0 to 80 ° C. The partial pressure of the olefin in the gas phase in the prepolymerization is preferably 0.01 to 2 MPa, particularly preferably 0.1 to 1 MPa. However, for olefins that are liquid at the prepolymerization pressure and temperature, Absent. The prepolymerization time is not particularly limited, and is preferably usually 2 minutes to 15 hours.

  In the prepolymerization, as a method of supplying the solid catalyst component (A), the organoaluminum compound (B) and the olefin to the polymerization tank, after supplying the solid catalyst component (A) and the organoaluminum compound (B), the olefin is added. Examples thereof include a method of supplying and a method of supplying an organoaluminum compound after supplying the solid catalyst component (A) and the olefin. Examples of the method for supplying olefin to the polymerization tank include a method for sequentially supplying the olefin so that the pressure in the polymerization tank is maintained at a predetermined pressure, and a method for supplying all the predetermined amount of olefin at once. Can do. In addition, in order to adjust the molecular weight of the olefin polymer obtained by preliminary polymerization, a chain transfer agent such as hydrogen may be used.

  Moreover, you may add an electron-donating compound (C) to a reaction system at the time of prepolymerization as needed. The amount of the electron donating compound (C) used in the prepolymerization is usually 0.01 to 400 mol, preferably 0.02 to 200 mol, per 1 mol of the titanium atom contained in the solid catalyst component (A). In particular, it is 0.03 to 100 mol, and is usually 0.003 to 5 mol, preferably 0.005 to 3 mol, particularly preferably 0.01 to 2 mol, relative to 1 mol of the organoaluminum compound. is there.

  In the preliminary polymerization, the method for supplying the electron donating compound (C) to the polymerization tank is not particularly limited. Examples of such methods include a method of supplying only the electron donating compound (C) and a method of supplying a contact product between the electron donating compound (C) and the organoaluminum compound (B). Can do. The olefin used in the prepolymerization may be the same as or different from the olefin used in the polymerization steps (I) and (II).

  The polymerization step (I) is a step of producing a polymer component (1) by homopolymerizing propylene or copolymerizing propylene and an olefin other than propylene in the presence of the polymerization catalyst prepared as described above. . Here, the content of the monomer unit based on propylene in the polymer component (1) is 90% by weight or more, preferably 95% by weight or less based on the total weight of the polymer component (1). Prepared. The polymer component (1) is particularly preferably a propylene homopolymer. By setting the content of the monomer unit based on propylene within such a range, the physical properties of the propylene-based block copolymer such as rigidity can be brought close to desired ones. In addition, as olefins other than propylene used for superposition | polymerization process (I) and the below-mentioned superposition | polymerization process (II), ethylene and a C4-C10 alpha olefin are mentioned, for example. Moreover, it is preferable that melting | fusing point (Tm) measured by the differential scanning calorimeter (DSC) of a polymer component (1) is 160 degreeC or more. The propylene-based block copolymer formed from the polymer component (1) having such a melting point (Tm) has a desired rigidity when used as a molding material.

  The polymerization step (II) is a step in which the polymer component (1) obtained by the polymerization step (I) is further copolymerized with propylene and an olefin other than propylene to produce the polymer component (2). By this step, a propylene-based block copolymer containing the polymer components (1) and (2) can be produced. Here, the content of the monomer unit based on propylene in the polymer component (2) is 10 to 90% by weight, preferably 30 to 70% by weight, based on the total weight of the polymer component (2). To be adjusted. Further, the content of the polymer component (2) with respect to the total weight of the propylene-based block copolymer is preferably 10 to 50% by weight, and more preferably 15 to 40% by weight. By setting the content of the monomer unit based on propylene in the polymer component (2) and the content of the polymer component (2) in the propylene-based block copolymer within such ranges, propylene such as rigidity can be obtained. The physical properties of the system block copolymer can be brought close to desired ones.

  The intrinsic viscosity ([η]) of the polymer component (2) is 0.1 to 10 dl / g, preferably 1 to 8 dl / g, and more preferably 2 to 6 dl / g. Here, the intrinsic viscosity ([η]) is measured in 135 ° C. tetralin.

  The amount of the organoaluminum compound (B) used in the polymerization steps (I) and (II) is usually 1 to 1000 mol, preferably 5 to 600 mol, per 1 mol of titanium atom in the solid catalyst component (A). is there.

  The amount of the electron donating compound (C) used in the polymerization steps (I) and (II) is usually 0.1 to 2000 mol, preferably 1 mol per 1 mol of titanium atoms contained in the solid catalyst component (A). Is from 0.3 to 1000 mol, particularly preferably from 0.5 to 800 mol, and is usually from 0.001 to 5 mol, preferably from 0.005 to 3 mol, particularly from 1 mol of the organoaluminum compound (B). Preferably it is 0.01-1 mol.

  The polymerization temperature in the polymerization steps (I) and (II) is usually −30 to 300 ° C., preferably 20 to 180 ° C., more preferably 50 to 95 ° C. The polymerization pressure is not particularly limited, and is generally a normal pressure to 10 MPa, preferably about 0.2 to 5 MPa from the viewpoint of being industrial and economical. The polymerization format may be batch or continuous. As a polymerization method, a slurry polymerization method using an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane and octane, a solution polymerization method using the solvent, and an olefin which is liquid at the polymerization temperature as a medium. Examples thereof include a bulk polymerization method and a gas phase polymerization method. From the viewpoint of obtaining good powder properties, the polymerization step (II) is preferably a gas phase polymerization method.

  In the polymerization steps (I) and (II), the molecular weight of the resulting olefin polymer may be adjusted by using a chain transfer agent such as hydrogen.

  And in the manufacturing method of the propylene-type block copolymer of this invention, the compound (D) represented by the following general formula (d) and the ether group containing linear hydrocarbon compound (E) are superposed | polymerized (II). ) Or before the polymerization step (II). By performing such an operation, it is possible to produce a propylene-based block copolymer having excellent impact resistance while maintaining rigidity.

M (OR ¹ ) _p X _q (d)

Here, in formula (d), M represents a Zr or Hf atom, R ¹ represents a hydrocarbon group, and X represents a hydrogen atom, a halogen atom or a hydrocarbon group. p represents a number satisfying 0 ≦ p ≦ m, q represents a number satisfying 0 ≦ q ≦ m, and p + q = m. Here, m represents the valence of M.

The number of carbon atoms in the hydrocarbon group used as R ¹ is preferably from 1 to 20, 3 to 6 is more preferable. Examples of the hydrocarbon group used as R ¹ include a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Branched alkyl groups such as tert-amyl group, cycloalkyl groups such as cyclopentyl group and cyclohexyl group, cycloalkenyl groups such as cyclopentenyl group, and aryl groups such as phenyl group and tolyl group. From the viewpoint of polymerization activity, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group are preferable.

1-20 are preferable and, as for the carbon atom number of the hydrocarbon group used as X, 3-6 are more preferable. Examples and preferred examples of the hydrocarbon group used as X are the same as those for R ¹ .

Moreover, it is preferable that the compound (D) represented by general formula (d) contains the compound represented by the following general formula (d-1) or the compound represented by the following general formula (d-2). By using such a compound as the compound (D) represented by the general formula (d), the impact resistance of the propylene-based block copolymer can be further improved.
Zr (OR ¹ ) ₄ (d-1)
Hf (OR ¹ ) ₄ (d-2)

Here, ^{R 1} in the formula (d-1) and Formula (d-2) is the same meaning as ^{R 1} in the formula (d).

  The ether group-containing linear hydrocarbon compound (E) is a linear hydrocarbon compound containing an ether group. Examples of the ether group-containing linear hydrocarbon compound (E) include 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxypropane, 1,1,2-trimethoxyethane, 2 -Methoxyethoxymethyl chloride, 1,2-bis (2-chloroethoxy) ethane, dibutyl ether, butyl ethyl ether, dipropyl ether, 2-amino-1-methoxybutane, 3-methoxypropylamine, N- (2- Methoxyethyl) methylamine and N- (2-methoxyethyl) ethylamine may be mentioned. From the viewpoint of physical properties of the propylene-based block copolymer such as impact strength, 1,2-dimethoxyethane, 1,2-diethoxy Ethane, 2-methoxyethoxymethyl chloride, 1,2-bis (2-chloroethoxy) ethane, 2-amino 1-methoxy-butane, 3-methoxypropylamine, N-(2-methoxyethyl) methylamine, N-(2-methoxyethyl) ethylamine is preferred.

  The order of addition of the compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) is the same as that of the compound (D) represented by the general formula (d) and the ether group-containing linear chain. It is preferable to add the linear hydrocarbon compound (E) at the same time or add the ether group-containing linear hydrocarbon compound (E) after adding the compound (D) represented by the general formula (d).

  The addition method may be a batch method or a continuous method. The compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) may be used as they are, or may be diluted with an inert hydrocarbon solvent or the like.

  The timing of adding the compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) may be at the start of the polymerization step (II), It may be just before the end of the polymerization step (I). From the viewpoint of further improving the impact resistance of the propylene-based block copolymer, the compound (D) represented by the general formula (d) after the polymerization step (I) and before the polymerization step (II). The ether group-containing linear hydrocarbon compound (E) is preferably added to the reaction system in this order.

  The amount of the compound (D) represented by the general formula (d) is usually 0.001 to 10 moles, preferably 0.01 to 1 mole, per mole of titanium atoms in the solid catalyst component (A). . By making the usage-amount of (D) component into such a range, the impact resistance of a propylene-type block copolymer can further be improved.

  The amount of the ether group-containing linear hydrocarbon compound (E) used is usually 0.001 to 10 mol, preferably 0.01 to 5 mol, per 1 mol of titanium atoms contained in the solid catalyst component (A). Especially preferably, it is 0.01-1 mol, and is 0.1-50 mol normally with respect to 1 mol of compounds (D) represented by General formula (d), Preferably it is 0.5-20 mol. By making the usage-amount of (E) component into such a range, the impact resistance of a propylene-type block copolymer can further be improved.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.

  First, the measuring method of each physical property value in Examples and Comparative Examples is shown below.

[Measurement method of physical properties]
(1) Intrinsic viscosity ([η], unit: dl / g);
Using a Ubbelohde viscometer, reduced viscosities were measured at three concentrations of 0.1, 0.2 and 0.5 g / dl. The intrinsic viscosity is calculated by the calculation method described in “Polymer Solution, Polymer Experiments 11” (published by Kyoritsu Shuppan Co., Ltd.), page 491. That is, the reduced viscosity is plotted against the concentration and the concentration is extrapolated to zero It was estimated by extrapolation. Tetralin was used as the solvent, and the temperature was measured at 135 ° C.

(1-1) Intrinsic viscosity of propylene-based block copolymer;
(1-1a) Intrinsic viscosity of polymer component (1) ([η] P);
The intrinsic viscosity ([η] P) of the polymer component (1) is obtained by taking out the polymer powder from the polymerization tank after the polymerization step (I), and measuring the intrinsic viscosity of the removed polymer powder by the method (1) above. Was determined by

(1-1b) Intrinsic viscosity of polymer component (2) ([η] EP);
The intrinsic viscosity ([η] EP) of the polymer component (2) is the intrinsic viscosity ([η] P) of the polymer component (1) and the intrinsic viscosity ([η] T) of the entire propylene-based block copolymer. Each was measured by the method of (1) above, and calculated from the following formula using the weight ratio (X) of the polymer component (2) to the entire propylene block copolymer. The weight ratio (X) was determined by the measurement method (2) described later.
[Η] EP = [η] T / X− (1 / X−1) [η] P;

(2) The weight ratio of the polymer component (2) to the entire propylene block copolymer (X, unit: wt%) and the ethylene content in the polymer component (2): (C2 ′, unit: wt%);
A sample was prepared by uniformly dissolving about 200 mg of a propylene block copolymer in 3 ml of orthodichlorobenzene in a 10 mmφ test tube, and the sample was measured by ¹³ C-NMR spectrum. The measurement conditions in the ¹³ C-NMR spectrum are shown below.
Measurement temperature: 135 ° C;
Pulse repetition time: 10 seconds;
Pulse width: 45 °;
Integration count: 2500 times;

Using the results of ¹³ C-NMR spectrum of the propylene-based block copolymer measured as described above, in accordance with the method described in Kakugo et al. (Macromolecules 1982, No. 15, pages 1150 to 1152), The weight ratio (X, unit: wt%) of the combined component (2) to the entire propylene block copolymer and the ethylene content in the polymer component (2): (C2 ′, unit: wt%) were determined.

(3) Glass transition temperature (Tg, unit: ° C.) of polymer component (2);
Using a differential scanning calorimeter (DS Instruments Q100, manufactured by TA Instruments), about 10 mg of a propylene-based block copolymer was melted at 200 ° C. in a nitrogen atmosphere, and then held at 200 ° C. for 5 minutes, and then 10 ° C. After the temperature was lowered to −90 ° C. at a rate of temperature fall / min, the temperature was measured by the method defined in JIS K7121 from the endothermic curve when the temperature was raised at 10 ° C./min.

(4) Melting point (Tm, unit: ° C) of polymer component (1);
Among the endothermic peaks measured in (3) above, the peak appearing in the range of 150 ° C. to 170 ° C. was defined as Tm.

(5) 20 ° C. xylene-soluble part amount of polymer component (1) (CXS, unit: wt%);
After the polymerization step (I), the polymer component (1) was taken out from the polymerization vessel as a polymer powder, and the amount soluble in cold xylene at 20 ° C. was expressed as a percentage (% by weight).

(6) Melt flow rate of propylene-based block copolymer (MFR, unit: g / 10 minutes);
The polymer obtained by the method of Example 1 described later and the polymer whose EP part content was prepared by the method described in Comparative Examples 1 and 2 described below were evaluated. 0.05 weight part of calcium stearate (manufactured by Kyodo Yakuhin Co., Ltd.), 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5) as an antioxidant was added to the prepared polymer. -Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer GA80: manufactured by Sumitomo Chemical Co., Ltd.) 2 parts by weight, 0.2 parts by weight of bis (2,4-di-t-butyl-phenyl) pentaerythritol diphosphite (trade name: Ultranox 626: manufactured by GE Specialty Chemicals) was added, and a twin-screw kneader with an inner diameter of 15 mm. Granulation at a set temperature: 190 ° C. and screw rotation speed: 300 rpm (Technobel KZW15-45MG, inner diameter: 15 mm, L / D = 45) The formation of the granulated pellets.

  The granulated pellets formed as described above were injection-molded at a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C. using a Toyo Machine Metal Co., Ltd. Si-30III type injection molding machine. Got.

Using the test piece obtained as described above, the melt flow rate was measured according to the method defined in JIS-K-6758. The measurement temperature and load at the time of measurement are shown below.
Measurement temperature: 230 ° C .;
Load: 2.16 kg;

(7) Tensile strength (unit: MPa) of the propylene-based block copolymer;
Using the test piece obtained by the same method as in (6), the tensile strength of the propylene-based block copolymer was measured. The measurement conditions are shown below.
Measurement temperature: 23 ° C;
Sample shape: JIS No. 1 small dumbbell (2 mm thick);
Tensile speed: 10 mm / min;

(8) Bending strength of propylene-based block copolymer (unit: MPa);
Using the test piece obtained by the same method as in (6), the bending strength of the propylene-based block copolymer was measured. The measurement conditions are shown below.
Measurement temperature: 23 ° C;
Sample shape: 12.7 × 80 mm (4 mm thickness);
Span: 64 mm;
Tensile speed: 50 mm / min;

(9) IZOD impact strength of propylene-based block copolymer (unit: kJ / m ² )
Using the test piece obtained by the same method as in (6), the IZOD impact strength of the propylene-based block copolymer was measured. The measurement conditions are shown below.
Measurement temperature: 23 ° C. or −30 ° C .;
Sample shape: 12.7 × 65 mm (4 mm thickness) [with V notch];

(10) Volume average equivalent-circle particle diameter (Dv) (unit: μm) of dispersed particles corresponding to the polymer component (2) formed when a propylene-based block copolymer is molded;
A cross section of a test piece (thickness 2 mm) molded for measuring the tensile strength of (7) above was cut out at −80 ° C. using a microtome, dyed with ruthenic acid vapor at 60 ° C. for 90 minutes, and then at −50 ° C. An ultrathin section having a thickness of about 800 angstroms was prepared using a diamond cutter. The ultrathin slice was observed at an observation magnification of 6000 times using a transmission electron microscope (H-8000 transmission electron microscope manufactured by Hitachi, Ltd.). The part dyed black corresponds to the polymer component (2) part (hereinafter referred to as the EP part in some cases). Using the high-accuracy image analysis software “A Image-kun” manufactured by Asahi Engineering Co., Ltd., from the photographs taken from three different fields of view, the following image analysis processing is performed, and the volume average circle equivalent of the dispersed particles corresponding to the EP part The particle diameter (Dv) was determined.

(Image analysis processing) A photograph obtained from a transmission electron microscope with a scanner GT-9600 manufactured by EPSON Corporation is taken into a computer (100 dpi, 8 bits), 2 using high-accuracy image analysis software “A Image-kun” manufactured by Asahi Engineering Co., Ltd. Priced. The analysis area was 1116 μm ² . Since the shape of the dispersed particles corresponding to the EP part is indefinite, the diameter of the circle having the same area as the EP part (circle equivalent particle diameter: Di, unit: μm) is obtained, and the volume average equivalent circle particle diameter is obtained from the following formula. (Dv) was determined.

  In the formula (α), i is an integer of 1 to n, and Di is the circle equivalent particle diameter of each particle.

[Production Example 1]
A stainless steel autoclave with a stirrer with an internal volume of 3 liters was dried under reduced pressure, and then purged with argon and cooled. Thereafter, the autoclave was evacuated.

(B) Triethylaluminum 4.4 mmol, (C) tert-butyl-n-propyldimethoxysilane 0.44 mmol, and (A) component described in Example 1 (2) of JP-A-2004-182981 11.5 milligrams of the catalyst component was prepared, and the prepared components (A) to (C) were contacted in heptane in a glass charger.

  The components (A) to (C) that were brought into contact were charged all at once into the autoclave. Next, 780 g of liquefied propylene was supplied into the autoclave, and further 1 MPa of hydrogen was supplied. Thereafter, the temperature of the autoclave was raised to 80 ° C. to initiate polymerization.

  Ten minutes after the start of polymerization, unreacted propylene was purged out of the polymerization system. Thereafter, the inside of the autoclave was replaced with argon, and a small amount of the produced polymer component (1) (hereinafter sometimes referred to as part P) was sampled. The intrinsic viscosity [η] P of the sampled polymer was 0.94 dl / g.

Next, the 3 liter autoclave is decompressed, and 0.15 mmol of zirconium (IV) isopropoxide (Zr (O-iPr) ₄ ) and 20 ml of heptane are mixed in the autoclave as component (D). The mixture was added and stirred for 30 minutes. Thereafter, 0.22 mmol of 1,2-dimethoxyethane and 20 ml of heptane as components (E) were mixed in a glass charger, charged into the autoclave, and stirred for 30 minutes.

  Further, the inside of a cylinder having a volume of 24 liters connected to the 3 liter autoclave was evacuated, 380 g of propylene and 110 g of ethylene were added (quantity ratio of ethylene to propylene = 0.43 mol / mol), and then the temperature was raised to 80 ° C. The mixed gas thus prepared was continuously fed to the 3 liter autoclave, and polymerization was carried out at a polymerization pressure of 0.8 MPa for 4 hours. After 4 hours, the gas in the autoclave was purged to complete the polymerization, and the produced polymer was dried under reduced pressure at 60 ° C. for 5 hours to obtain 242 g of polymer powder. The intrinsic viscosity [η] T of the obtained polymer was 1.91 dl / g, and as a result of analysis, the content of the polymer component (2), that is, the EP part was 16.6% by weight. Thereby, the intrinsic viscosity [η] EP of the polymer produced in the latter part (EP part) is estimated to be 5.77 dl / g. Moreover, Tm of P part was 161.2 degreeC, and ethylene content in EP part was 46 weight%. Table 1 shows the structure of the obtained propylene-based block copolymer.

[Production Example 2]
The amount of component (A) used was 11.6 milligrams, zirconium (IV) isopropoxide (Zr (O-iPr) ₄ ) as component (D) and 1,2-dimethoxy as component (E) Polymerization was carried out in the same manner as in Production Example 1 except that ethane was not added and the polymerization step (II), that is, the polymerization time for generating the EP part was 1 hour. Table 1 shows the structure of the obtained propylene-based block copolymer.

[Example 1]
Polymers obtained by performing the polymerization operation described in Production Example 1 twice were evaluated according to the physical property measurement methods described in (6) to (10) above. Table 2 shows the evaluation results for (6) to (9), and Table 3 shows the evaluation results for (10).

[Comparative Example 1]
The polymerization operation described in Production Example 2 was performed twice, and these were mixed with homopolypropylene ([η] = 1.02, CXS = 0.2 wt%), and the polymerization ratio of the polymer component (2) of Example 1 In order to approach X, the content of the EP part was adjusted to 20% by weight. The adjusted polymer was evaluated according to the physical property measurement methods described in (6) to (9) above. The evaluation results are shown in Table 2.

[Comparative Example 2]
The polymerization operation described in Production Example 2 was performed twice, and these were mixed with homopolypropylene ([η] = 1.02, CXS = 0.2 wt%), and the polymerization ratio of the polymer component (2) of Example 1 In order to approach X, the content of the EP part was adjusted to 15% by weight. The adjusted polymer was evaluated according to the physical property measurement methods described in (6) to (10) above. Table 2 shows the evaluation results for (6) to (9), and Table 3 shows the evaluation results for (10).

As described above, the propylene-based block copolymer obtained in Example 1 is superior in rigidity such as tensile strength and bending strength as compared with the propylene-based block copolymer obtained in Comparative Examples 1 and 2. In addition, it was confirmed that the impact resistance measured by Izod impact strength was also excellent. In Example 1, it is considered that the impact resistance was improved because [η] EP was high and the particle diameter Dv of the polymer component (2) was small.

Claims (4)

In the presence of a polymerization catalyst obtained by contacting a solid catalyst component (A) having a titanium atom, a magnesium atom and a halogen atom as essential components, an organoaluminum compound (B), and an electron donating compound (C). Polymerization step (I) in which propylene is homopolymerized or copolymerized with propylene and an olefin other than propylene to produce a polymer component (1) having a content of monomer units based on propylene of 90% by weight or more. After the polymerization, propylene and an olefin other than propylene are further copolymerized to produce a polymer component (2) in which the content of monomer units based on propylene is 10 to 90% by weight (II) ) To produce a propylene-based block copolymer,
The compound (D) represented by the following general formula (d) and the ether group-containing linear hydrocarbon compound (E) are reacted in the reaction system during the polymerization step (II) or before the polymerization step (II). A process for producing a propylene-based block copolymer, which is added to
M (OR ¹ ) _p X _q (d)
[In formula (d), M represents a Zr or Hf atom, R ¹ represents a hydrocarbon group, and X represents a hydrogen atom, a halogen atom or a hydrocarbon group. p represents a number satisfying 0 ≦ p ≦ m, q represents a number satisfying 0 ≦ q ≦ m, and p + q = m. Here, m represents the valence of M. ]   The compound (D) represented by the general formula (d) and the ether group-containing linear hydrocarbon compound (E) are added after the polymerization step (I) and before the polymerization step (II). The method for producing a propylene-based block copolymer according to claim 1, wherein the compound (D) represented by the formula (d) and the ether group-containing linear hydrocarbon compound (E) are added to the reaction system in this order. . The compound (D) represented by the general formula (d) includes a compound represented by the following general formula (d-1) or a compound represented by the following general formula (d-2). The manufacturing method of the propylene-type block copolymer of 2.
Zr (OR ¹ ) ₄ (d-1)
Hf (OR ¹ ) ₄ (d-2)
[In Formula (d-1) and Formula (d-2), R ¹ represents a hydrocarbon group. ] A solid catalyst component (A) having a titanium atom, a magnesium atom and a halogen atom as essential components,
A solid catalyst component precursor (a) obtained by reducing a titanium compound represented by the following general formula (i) with an organic magnesium compound in the presence of an organosilicon compound having a Si-O bond;
A halogen-containing compound (b);
An electron donor (c);
The manufacturing method of the propylene-type block copolymer as described in any one of Claims 1-3 which is a solid catalyst component obtained by making it contact.

[In Formula (i), a represents the number of 1-20, R represents a C1-C20 hydrocarbon group. X represents a halogen atom or a hydrocarbon oxy group having 1 to 20 carbon atoms, and all Xs may be the same or different. ]