JP2020090621A - Manufacturing method of propylene polymer - Google Patents

Abstract

To provide a manufacturing method capable of considering manufacturing cost while providing a propylene polymer having constant or more of high stereoregularity.SOLUTION: The manufacturing method of a propylene polymer is a method for manufacturing the propylene polymer by polymerizing propylene in presence of an olefin polymerization catalyst, in which the olefin polymerization catalyst is a catalyst [A] containing (i) a specific solid titanium catalyst component, (ii) a specific organic silicon compound component represented by the formula RSi(OR)(NRR), wherein n is 0 or 1, and (iii) a specific organic metal compound component, or a catalyst [B] containing a preliminary polymerization catalyst (p) in which propylene is preliminary polymerized to the catalyst [A], the organic silicon compound component (ii) and the organic metal compound component (iii).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a method for producing a propylene-based polymer, more specifically, a method for producing a propylene-based polymer having high stereoregularity.

Conventionally, a Ziegler-Natta catalyst composed of a titanium catalyst component and an organoaluminum compound has been widely used as a polyolefin production catalyst.
In particular, when producing a highly stereoregular polyolefin such as polypropylene, a solid titanium catalyst component containing an internal donor (internal electron donor), an organoaluminum compound, and an external donor (external electron donor) are usually used. A catalyst consisting of is used. For example, an olefin polymerization catalyst comprising a magnesium chloride-supported solid titanium catalyst containing carboxylic acid esters as an internal donor and an organic silicon compound as an external donor is known (for example, Patent Document 1). And 2).

However, when olefins are polymerized using a catalyst containing a solid titanium catalyst component as described above, a so-called "residual titanium compound" causes by-production of highly stereoregular polyolefin and low stereoregular polyolefin. There was a point (JP-A-59-124909).

On the other hand, in recent years, the automobile industry has been actively developing environment-friendly fuel-efficient vehicles, and in the field of automobile materials, there has been a demand for resin materials and further thinner walls for the purpose of weight reduction. For this reason, there are great expectations for improvements in propylene-based materials, which have a large track record as automotive materials such as bumper materials, and have high rigidity and high heat resistance of propylene-based materials with unprecedented high stereoregularity. Coalition is required.

Japanese Patent Laid-Open No. 08-003215 JP-A-08-143620 JP-A-59-124909

In view of the above-mentioned conventional techniques, it is an object of the present invention to provide a method for producing a propylene polymer having a high stereoregularity above a certain level.

The present inventors have conducted extensive studies to solve the above problems, and when polymerizing a propylene-based polymer, it is sufficient to combine a specific solid titanium catalyst component and a specific organosilicon compound as an external donor. The inventors have found that a propylene-based polymer having extremely high stereoregularity can be obtained, and completed the present invention.

The present invention relates to the following [1] to [5].
[1]
A method for producing a propylene-based polymer by polymerizing propylene in the presence of an olefin polymerization catalyst,
The olefin polymerization catalyst,
(I) a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor and satisfying the following requirements (k1) to (k4):
(Ii) an organosilicon compound component represented by the following formula (II),
(Iii) a catalyst [A] containing an organometallic compound component containing an element belonging to Group 1, 2 or 13 of the periodic table,
Or
A prepolymerized catalyst (p) in which propylene is prepolymerized on the catalyst [A],
The organosilicon compound component (ii),
Catalyst [B] containing the organometallic compound component (iii)
A method for producing a propylene-based polymer characterized by:
(K1) The titanium content is 2.5% by weight or less;
(K2) the content of the electron donor is 8 to 30% by weight;
(K3) the electron donor/titanium (weight ratio) is 5 or more;
(K4) Titanium is not substantially desorbed by washing with hexane at room temperature.
R ¹ _n Si(OR ² ) ₂ (NR ³ R ⁴ ) _2-n ...(II)
[In the formula (II), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms or A hydrogen atom, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁴ may combine with each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms. , N is 0 or 1. ]

[2]
The solid titanium catalyst component (i) is
(A) Solid titanium containing magnesium, titanium, halogen and an electron donor, and titanium is not desorbed by washing with hexane at room temperature,
(B) aromatic hydrocarbon,
The production method according to the above [1], which is produced by a method including a step of contacting (c) liquid titanium and (d) an electron donor.

[3]
In the above formula (II), the production method according to [1] or [2], wherein R ¹ is a branched or linear alkyl group having 1 to 20 carbon atoms.

[4]
In the formula (II), the production according to any one of [1] to [3], wherein R ³ and R ⁴ are bonded to each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms. Method.

[5]
The production method according to any one of [1] to [4], wherein the electron donor is a compound represented by the following formula (IV).

In formula (IV), R represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms, and R′ represents 1 to 10 carbon atoms. A linear or branched alkyl group is shown, and n is an integer of 0-4.

According to the production method of the present invention, a propylene polymer having high stereoregularity can be produced stably with high activity, and the amount of low stereoregular polypropylene produced as a by-product is small.

Hereinafter, the present invention will be described in detail.
[Olefin polymerization catalyst]
The olefin polymerization catalyst that can be used in the present invention is
(I) a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor and satisfying the following requirements (k1) to (k4):
(Ii) an organosilicon compound component represented by the following formula (II),
(Iii) A catalyst [A] containing an organometallic compound component containing an element belonging to Group 1, 2 or 13 of the periodic table, or
A prepolymerized catalyst (p) in which propylene is prepolymerized on the catalyst [A],
The organosilicon compound component (ii),
Catalyst [B] containing the organometallic compound component (iii)
Is.

(K1) The titanium content is 2.5% by weight or less.
(K2) The content of the electron donor is 8 to 30% by weight.
(K3) The electron donor/titanium (weight ratio) is 5 or more.
(K4) Titanium is not substantially desorbed by washing with hexane at room temperature.

R ¹ _n Si(OR ² ) ₂ (NR ³ R ⁴ ) _2-n ...(II)
In formula (II), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Represents an atom, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁴ may be bonded to each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms, n is 0 or 1.

Hereinafter, each component constituting the olefin polymerization catalyst will be described.
<Solid titanium catalyst component (i)>
The solid titanium catalyst component (i) is
(A) Solid titanium containing magnesium, titanium, halogen and an electron donor, and titanium is not desorbed by washing with hexane at room temperature,
(B) aromatic hydrocarbon,
It can be prepared by a method including a step of bringing (c) liquid titanium into contact with (d) an electron donor.

<<(a) Solid titanium>>
The solid titanium (a) is contacted with a magnesium compound, a titanium compound, an electron donor (internal donor) and the like by various methods to prepare a known solid titanium catalyst component (for example, JP-A-4-0969911). JP-A-58-83006, JP-A-8-143580, etc.).

The magnesium compound is preferably used in the solid state. The magnesium compound in the solid state may be the magnesium compound itself in the solid state, or may be an adduct with an electron donor. Examples of the magnesium compound include magnesium compounds described in JP-A-2004-2742, specifically, magnesium chloride, magnesium ethoxy chloride, butoxy magnesium and the like. Examples of the electron donor include compounds having a magnesium compound solubilizing ability described in JP 2004-2742 A, specifically, alcohols, aldehydes, amines, carboxylic acids and mixtures thereof. The amount of the magnesium compound and the electron donor used varies depending on the kind, contact conditions, etc., but the magnesium compound is used in an amount of 0.1 to 20 mol/liter, preferably 0.5 to It can be used in an amount of 5 mol/liter.

The titanium compound is preferably used in a liquid state. Examples of such a titanium compound include a tetravalent titanium compound represented by the following formula (III).
Ti(OR ⁵ ) _g X _4-g・・・(III)
In the formula (III), R ⁵ is a hydrocarbon group, X is a halogen atom, and 0≦g≦4.

As the titanium compound, titanium tetrachloride is particularly preferable. Moreover, you may use the said titanium compound in combination of 2 or more type.
Examples of the electron donor (internal donor) include compounds represented by the following formula (IV) (hereinafter also referred to as “compound (IV)”).

In formula (IV), R represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms, and R′ represents 1 to 10 carbon atoms. A linear or branched alkyl group is shown, and n is an integer of 0-4. In the present invention, a compound in which n is 0 is preferable.

Examples of the alkyl group of R and R′ include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, a pentyl group, a hexyl group and a heptyl group. Group, octyl group, nonyl group, decyl group and the like.

Specific examples of the compound (IV) include dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, n-propyl phthalate, diisopropyl phthalate, di n-butyl phthalate, diisobutyl phthalate, di n-phthalate. Pentyl, Dineopentyl phthalate, Di-n-hexyl phthalate, Di-n-heptyl phthalate, Di(methylhexyl) phthalate, Di(dimethylpentyl) phthalate, Di(ethylpentyl) phthalate, Di(2, phthalate) 2,3-trimethylbutyl), di-n-octyl phthalate, di-2-ethylhexyl phthalate and the like. Of these, diisobutyl phthalate is particularly preferable.

In the present invention, as the electron donor (internal donor), another electron donor other than the compound (IV) may be used. As another electron donor, for example, a compound having two or more ether bonds existing via a plurality of atoms (hereinafter also referred to as “polyether compound”) can be mentioned.

Examples of the polyether compound include a compound in which an atom existing between ether bonds is carbon, silicon, oxygen, nitrogen, sulfur, phosphorus, boron, or two or more kinds of atoms selected from these. .. Of these, compounds having a relatively bulky substituent bonded to the atom between the ether bonds and having a plurality of carbon atoms in the atoms existing between the two or more ether bonds are preferable. For example, a polyether compound represented by the following formula (3) is preferable.

In the formula (3), m is an integer of 1 to 10, preferably an integer of 3 to 10, and more preferably an integer of 3 to 5. R ¹¹ , R ¹² , and R ^{31 to} R ³⁶ are each independently a hydrogen atom or at least one selected from carbon, hydrogen, oxygen, fluorine, chlorine, bromine, iodine, nitrogen, sulfur, phosphorus, boron, and silicon. It is a substituent having a seed element. R ¹¹ and R ¹² are each independently preferably a hydrocarbon group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 6 carbon atoms. R ^{31 to} R ³⁶ are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

Specific examples of R ¹¹ and R ¹² include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2 Examples thereof include an ethylhexyl group, a decyl group, a cyclopentyl group, and a cyclohexyl group. Among these, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group are preferable. Specific examples of R ^{31 to} R ³⁶ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. Among these, a hydrogen atom and a methyl group are preferable. Any of R ¹¹ , R ¹² , and R ^{31 to} R ³⁶ (preferably R ¹¹ and R ¹² ) may together form a ring other than a benzene ring, and the main chain contains an atom other than carbon. It may be.

Specific examples of the polyether compound include 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2 ,2-dibutyl-1,3-dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl- 1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-1,3-dimethoxypropane, 2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1 , 3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2,2-bis(cyclohexylmethyl)-1, 3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2, 2-di-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-dimethoxypropane, 2-isopropyl-2 -Isopentyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4- Diethoxybutane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3 -Methoxymethyldioxane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxy Ethane, 1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane, 2,2-pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3 -Dimethoxypropane, 1,2-bis(methoxymethyl)cyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-di Ethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl 2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2 -Ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-2 -Ethoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane and the like can be exemplified. ..

Among these, 1,3-diethers are preferable, and 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis(cyclohexylmethyl)1,3-dimethoxypropane are more preferred. These compounds may be used alone or in combination of two or more.

<<Preparation of solid titanium (a)>>
The solid titanium (a) can be prepared by contacting the magnesium compound, the titanium compound, and the electron donor. At this time, it is preferable to suspend the magnesium compound in a solid state in a hydrocarbon solvent before use. When contacting these components, the titanium compound in liquid form may be used once to produce the solid (1), and the obtained solid (1) is further contacted with the titanium compound in liquid form. You may let it be made to produce a solid substance (2). Furthermore, it is preferable to prepare the solid titanium (a) after washing the solid (1) or (2) with a hydrocarbon solvent, if necessary.

The contact of each component as described above is usually performed at a temperature of -70°C to +200°C, preferably -50°C to +150°C, more preferably -30°C to +130°C. The amount of each component used when preparing the solid titanium (a) varies depending on the preparation method and cannot be specified unconditionally, but for example, the electron donor is 0.01 to 10 mol, preferably 0, per mol of the magnesium compound. The titanium compound can be used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol, in an amount of 0.1 to 5 mol.

In the present invention, the solid matter (1) or (2) thus obtained can be used as it is as the solid titanium (i), and this solid matter is washed with a hydrocarbon solvent at 0 to 150°C. Preferably.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane and cetane, non-halogenated aromatic hydrocarbon solvents such as toluene, xylene and benzene, or halogen-containing aromatic solvents. A hydrocarbon solvent or the like is used. Among these, aliphatic hydrocarbon solvents or halogen-free aromatic hydrocarbon solvents are preferably used.

When washing the solid matter, the hydrocarbon solvent is used in an amount of usually 10 to 500 ml, preferably 20 to 100 ml, relative to 1 g of the solid matter. The solid titanium (a) thus obtained contains magnesium, titanium, halogen and an electron donor. In this solid titanium (a), the electron donor/titanium (weight ratio) is preferably 6 or less.
In the solid titanium (a) thus obtained, titanium is not desorbed by washing with hexane at room temperature.

<<(b) Aromatic hydrocarbon>>
Examples of the aromatic hydrocarbon (b) used for contacting with the solid titanium (a) include benzene, toluene, xylene, ethylbenzene, and halogen-containing hydrocarbons thereof. Among these, xylene (particularly paraxylene) is preferable. By contacting the solid titanium (a) with such an aromatic hydrocarbon (b), it is possible to reduce the so-called "residual titanium compound" that is a by-product of the low stereoregular component.

<<(c) Liquid titanium>>
Examples of the liquid titanium (c) used for contacting with the solid titanium (a) include the same titanium compounds as those used for preparing the solid titanium (a). Among them, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable.

<<(d) Electron Donor>>
Examples of the electron donor (d) used for the contact with the solid titanium (a) include the same ones as the electron donor (internal donor) described above. Among them, it is preferable to use the same electron donor as that used for preparing the solid titanium (a).

<<Preparation Method of Solid Titanium Catalyst Component (i)>>
The solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (d) are brought into contact with each other at a temperature of usually 110 to 160°C, preferably 115°C to 150°C for 1 minute. It is carried out for 10 hours, preferably for 10 minutes to 5 hours.

In this contact, the aromatic hydrocarbon (b) is usually used in an amount of 1 to 10000 ml, preferably 5 to 5000 ml, more preferably 10 to 1000 ml, relative to 1 g of solid titanium (a). The liquid titanium (c) is used in an amount of usually 0.1 to 50 ml, preferably 0.2 to 20 ml, and particularly preferably 0.3 to 10 ml with respect to 100 ml of the aromatic hydrocarbon (b). The electron donor (d) is generally used in an amount of 0.01 to 10 ml, preferably 0.02 to 5 ml, particularly preferably 0.03 to 3 ml, based on 100 ml of the aromatic hydrocarbon (b).

The order of contacting the solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (d) is not particularly limited, and they can be contacted simultaneously or sequentially.
The solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (d) are preferably contacted with each other in an inert gas atmosphere with stirring. For example, a slurry of solid titanium (a), aromatic hydrocarbon (b), liquid titanium (c) and electron donor (d) is stirred at the above temperature in a glass flask equipped with a stirrer that is sufficiently replaced with nitrogen. The solid titanium (a), the aromatic hydrocarbon (b), the liquid titanium (c) and the electron donor (a) are stirred by rotating the stirrer at a rotation speed of 100 to 1000 rpm, preferably 200 to 800 rpm for the above time. It is desirable to contact d).

The solid titanium (a) and the aromatic hydrocarbon (b) after contact can be separated by filtration.
By contacting such solid titanium (a) with the aromatic hydrocarbon (b), a solid titanium catalyst component (i) having a titanium content lower than that of the solid titanium (a) is obtained. Specifically, a solid titanium catalyst component (i) having a titanium content of 25% by weight or more, preferably 30 to 95% by weight, and more preferably 40 to 90% by weight less than that of the solid titanium (a) is obtained.

The solid titanium catalyst component (i) obtained as described above contains magnesium, titanium, halogen and an electron donor, and satisfies the following requirements (k1) to (k4), preferably the following requirement (k5): Meets more.

(K1) The titanium content of the solid titanium catalyst component (i) is 2.5% by weight or less, preferably 2.2 to 0.1% by weight, more preferably 2.0 to 0.2% by weight, and particularly preferably. Is 1.8 to 0.3% by weight, most preferably 1.5 to 0.4% by weight.

The content of the electron donor (k2) is 8 to 30% by weight, preferably 9 to 25% by weight, more preferably 10 to 20% by weight.
(K3) The electron donor/titanium (weight ratio) is 5 or more, preferably 7.5 to 35, more preferably 8 to 30, and particularly preferably 8.5 to 25.

In the solid titanium catalyst component (i) (k4), titanium is not substantially desorbed by washing with hexane at room temperature. The hexane washing of the solid titanium catalyst component (i) means washing with hexane in an amount of usually 10 to 500 ml, preferably 20 to 100 ml, for 5 minutes with respect to 1 g of the solid titanium catalyst component (i). Say. Room temperature is 15 to 25°C. Further, the fact that titanium is not substantially desorbed means that the titanium concentration in the hexane cleaning liquid is 0.1 g/liter or less.

The solid titanium catalyst component (i) (k5) has an average particle size of 5 to 70 μm, preferably 7 to 65 μm, more preferably 8 to 60 μm, and particularly preferably 10 to 55 μm.

Here, the amounts of magnesium, halogen, titanium, and electron donor are each% by weight per unit weight of the solid titanium catalyst component (i), and magnesium, halogen, and titanium are measured by plasma emission spectroscopy (ICP method). , The electron donor is quantified by gas chromatography. The average particle size of the catalyst is measured by the centrifugal sedimentation method using a decalin solvent.

When the solid titanium catalyst component (i) as described above is used as a catalyst component for olefin polymerization, propylene can be polymerized with high activity, and the production amount of polypropylene having low stereoregularity is small, resulting in high stereoregularity. It is possible to stably produce a polypropylene having good properties.

<Organosilicon compound component (ii)>
In the production method according to the present invention, the organosilicon compound component (ii) functions as an external donor (external electron donor) to the solid titanium catalyst component (i).

The organosilicon compound component (ii) constituting the olefin polymerization catalyst of the present invention is represented by the following formula (II).
R ¹ _n Si(OR ² ) ₂ (NR ³ R ⁴ ) _2-n ...(II)
In formula (II), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms or hydrogen. Represents an atom, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁴ may be bonded to each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms, n is 0 or 1.

Here, the hydrocarbon group constituting R ¹ may be a primary hydrocarbon group, a secondary hydrocarbon group, or a tertiary hydrocarbon group. Examples of R ¹ include an alicyclic hydrocarbon group having 3 to 20 carbon atoms, a branched or linear alkyl group having 1 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and the like.

Among these, as the alicyclic hydrocarbon group having 3 to 20 carbon atoms, for example, these groups having a cyclobutyl group, a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a cyclohexyl group, a cyclohexynyl group, and a substituent. And so on. Further, the alicyclic hydrocarbon group may be a polycyclic group such as an adamantyl group or a methyladamantyl group.

On the other hand, of the hydrocarbon groups that can form R ^1, for the branched or straight-chain alkyl group having 1 to 20 carbon atoms and the aralkyl group having 7 to 20 carbon atoms, the carbon adjacent to Si is It may be primary carbon, secondary carbon, or tertiary carbon.

Among these, the hydrocarbon group in which the carbon adjacent to Si is a primary carbon is carbon number such as ethyl group, propyl group, n-butyl group, n-amyl group, i-butyl group, i-amyl group. 1-20 primary alkyl groups, and benzyl groups and the like can be mentioned.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include secondary alkyl groups having 1 to 20 carbon atoms such as i-propyl group, s-butyl group and s-amyl group, and α-methyl Examples thereof include a benzyl group.

As the hydrocarbon group in which the carbon adjacent to Si is a tertiary carbon, a tertiary alkyl group having 1 to 20 carbon atoms such as a tert-butyl group and a tert-amyl group, and an α,α-dimethylbenzyl group ( Cumyl group) and the like.

Of these, a cyclopentyl group and a cyclobutyl group are preferable. In one of the preferred embodiments of the present invention R ¹ is a cyclobutyl group.
However, when the practical aspect, for example, the balance between the high steric controllability and the cost of the obtained propylene-based polymer is emphasized, R ¹ is a branched or straight chain having 1 to 20 carbon atoms. It can be said that an alkyl group is one of the preferable embodiments of the present invention. Here, as will be confirmed in Examples of the present application to be described later, when the branched or linear alkyl group having 1 to 20 carbon atoms is adopted as R ¹ , such an alkyl group is a primary alkyl group. In the case of, a propylene-based polymer having practically sufficiently high stereoregularity can be provided as in the case of the secondary alkyl group. Among the branched or linear alkyl groups having 1 to 20 carbon atoms, ethyl group, i-propyl group, n-propyl group and i-butyl group are preferable.

Examples of R ² include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, iso- Examples thereof include a pentyl group, a cyclopentyl group, an n-hexyl group and a cyclohexyl group. Of these, a methyl group and an ethyl group are particularly preferable.

Examples of R ³ include hydrogen, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, Examples thereof include iso-pentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and octyl group. Of these, an ethyl group is particularly preferable.

Examples of R ⁴ include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, sec-butyl group, n-pentyl group, iso- Examples thereof include a pentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group and an octyl group. Of these, an ethyl group is particularly preferable.

Further, in the present invention, R ³ and R ⁴ may be bonded to each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms, and even in such a case, it is a preferred embodiment of the present invention. There is one. In this case, the group represented by NR ³ R ⁴ can also be regarded as a cyclic secondary amino group having 3 to 20 carbon atoms. Examples of such a divalent hydrocarbon group include propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, octane. Examples thereof include a -1,8-diyl group. The groups represented by NR ³ R ⁴ are, for example, azetidino group (trimethyleneimino group), pyrrolidino group, piperidino group, azepano group (hexamethyleneimino group), azonano group (octamethyleneimino group), etc. Corresponds to the case. In a preferred aspect of the present invention, the divalent hydrocarbon group is a butane-1,4-diyl group.

Among the organosilicon compounds represented by the formula (II), specific examples of the compound in which n is 1 include cyclobutyl(diethylamino)dimethoxysilane, cyclopentyl(diethylamino)dimethoxysilane, cyclopentenyl(diethylamino)dimethoxysilane, cyclopenta. Dienyl(diethylamino)dimethoxysilane, cyclohexyl(diethylamino)dimethoxysilane, ethyl(diethylamino)dimethoxysilane, n-propyl(diethylamino)dimethoxysilane, isopropyl(diethylamino)dimethoxysilane, n-butyl(diethylamino)dimethoxysilane, isobutyl(diethylamino) ) Dimethoxysilane, tert-butyl(diethylamino)dimethoxysilane, ethyl(piperidinodiethylamino)dimethoxysilane, isopropyl(diethylamino)dimethoxysilane, tert-butyl(diethylamino)dimethoxysilane, isopropylpyrrolidinodimethoxysilane, isopropylpiperidinodimethoxysilane Examples include silane.

Among the organosilicon compounds represented by the formula (II), specific examples of the compound in which n is 0 include dipyrrolidinodimethoxysilane, dipiperidinodimethoxysilane, bis(dimethylamino)dimethoxysilane, and bis(diethylamino). ) Dimethoxysilane, diethylamino(methylethylamino)dimethoxysilane, piperidino(diethylamino)dimethoxysilane, piperidino(dimethylamino)dimethoxysilane and the like can be mentioned.

Among the organosilicon compounds represented by the above formula (II), ethyl(diethylamino)dimethoxysilane and cyclopentyldiethylaminodimethoxysilane are preferable from the viewpoint of high stereoregularity, particularly, a point of increasing a long meso chain length. Further, as shown in the following examples, isopropylpyrrolidinodimethoxysilane also tends to be relatively preferable.

In one of the preferred embodiments of the present invention, the organosilicon compound represented by the above formula (II) is ^{one in} which R ¹ is a primary hydrocarbon group having 1 to 20 carbon atoms, or NR ³ R ⁴ The group represented is an organosilicon compound having a cyclic secondary amino group having 3 to 20 carbon atoms.

The organosilicon compound component (ii) described above may be used alone or in combination of two or more.
By using the solid titanium catalyst component (i) and the organosilicon compound component (ii) in combination, a propylene polymer having a high level of high stereoregularity can be obtained.

<Organometallic compound component (iii)>
The organometallic compound component (iii) that constitutes the olefin polymerization catalyst of the present invention is an organometallic compound containing a metal belonging to Group 1, 2 or 13 of the periodic table, such as an organoaluminum compound and a first group. Examples thereof include complex alkyl compounds of a group metal and aluminum, organometallic compounds of a group 2 metal, and the like. The organometallic compound component (iii) may be used in combination of two or more kinds.

≪Organoaluminum compound≫
The organoaluminum compound is represented by the following formula, for example.
R ^a _n AlX _3-n
In the formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is halogen or hydrogen, and n is 1 to 3.

R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, Examples include octyl, cyclopentyl group, cyclohexyl, phenyl and tolyl.

Moreover, as the said organoaluminum compound, the compound shown by the following formula can also be mentioned.
^Ra _n AlY _3-n
In the formula, R ^a is the same as above, Y is —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group or —N(R ^g )AlR. ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group or the like, and R ^e is And hydrogen, a methyl group, an ethyl group, an isopropyl group, a phenyl group, a trimethylsilyl group and the like, and R ^f and R ^g are a methyl group, an ethyl group and the like.

Specific examples of such organoaluminum compounds include the following compounds.
Compounds represented by R ^a _n Al(OR ^b ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like.

_{^{· R a n Al (OSiR c}} ) a compound represented by _3-n, e.g., _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), (iso-Bu) 2 Al (OSiEt 3) Such.
_{^{· R a n Al (OAlR d}} 2) 3-n Et 2 AlOAlEt 2, such as _{(iso-Bu) 2 AlOAl (} iso-Bu) 2.
Among the above organoaluminum compounds, the organoaluminum compound represented by R ^a ₃ Al is preferably used.

[Method for producing catalyst for olefin polymerization]
The olefin polymerization catalyst can be produced by a method including a step of bringing the solid titanium catalyst component (i), the organosilicon compound component (ii), and the organometallic compound component (iii) into contact with each other. ..

In the present invention, when forming an olefin polymerization catalyst from each of these components (i), (ii), and (iii), other components may be used as necessary.
In the present invention, the prepolymerization catalyst (p) may be formed from the above components. The prepolymerization catalyst (p) is formed by prepolymerizing propylene in the presence of the above-mentioned components (i), (ii), (iii) and other components used as necessary. Such a prepolymerization catalyst (p) usually forms an olefin polymerization catalyst together with the organosilicon compound (ii) and the organometallic compound (iii), but only the prepolymerization catalyst (p) is used as the olefin polymerization catalyst. Sometimes you can.

[Method for producing propylene-based polymer]
In the method for producing a propylene-based polymer of the present invention, propylene is polymerized in the presence of the above-mentioned olefin polymerization catalyst. That is, the method for producing a propylene-based polymer of the present invention includes a step of polymerizing propylene in the presence of the above-mentioned olefin polymerization catalyst.

Here, when carrying out the polymerization of propylene, in addition to propylene, a small amount of an olefin other than propylene or a small amount of a diene compound may coexist in the polymerization system to produce a random copolymer. As such other olefins other than propylene, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 3-methyl- C2-C8 olefins, such as 1-butene, are mentioned. Of these, ethylene is preferred. In the case of a random copolymer, the content of a comonomer other than propylene is preferably 6 mol% or less, more preferably 3 mol% or less.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method. When the polymerization takes a reaction form of slurry polymerization, an inert organic solvent can be used as a reaction solvent, or an olefin which is liquid at the reaction temperature can be used.

Specific examples of the inert organic solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons; aromatic hydrocarbons; halogenated carbonization. Examples thereof include hydrogen, and contact products thereof. Of these, it is particularly preferable to use an aliphatic hydrocarbon.

In the polymerization, the solid titanium catalyst component (i) or the prepolymerization catalyst (p) is usually about 1×10 ⁻⁵ to 1 mmol, preferably about 1×, in terms of titanium atom per 1 liter of polymerization volume. It is used in an amount of 10 ^{−4 to} 0.1 mmol.

The organosilicon compound (ii) is generally used in an amount of about 0.001 mol to 10 mol, preferably 0.01 mol to 5 mol, based on 1 mol of the metal atom of the organometallic compound (iii).
The organometallic compound (iii) is used in an amount such that the metal atom in the compound (iii) is usually about 1 to 2000 mol, preferably about 2 to 500 mol, based on 1 mol of the titanium atom in the polymerization system. Be done.

When the prepolymerization catalyst (p) is used during this polymerization, it may not be necessary to add the organosilicon compound (ii) and/or the organometallic compound (iii). When the olefin polymerization catalyst is formed from the prepolymerization catalyst (p), the component (ii) and the component (iii), these respective components (ii) and (iii) can be used in the amounts as described above.

If hydrogen is used during the polymerization, the molecular weight of the resulting propylene polymer can be adjusted, and a polymer having a large MFR can be obtained.
In the present invention, the polymerization is usually carried out at a temperature of about 20 to 150° C., preferably about 50 to 100° C. and a pressure of normal pressure to 100 kg/cm ² , preferably about ² to 50 kg/cm ^2. ..

In the present invention, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.
Further, in the present invention, a homopolymer of propylene may be produced, or an olefin other than propylene may be used in combination to produce a random copolymer or a block copolymer.

[Propylene polymer]
A propylene-based polymer can be obtained by the production method of the present invention described above in the "method for producing a propylene-based polymer".

In a typical embodiment of the present invention, the propylene polymer satisfies the following requirements (1) to (3) or the following requirements (1) to (4):
(1) Meso average chain length is 500 to 100,000;
(2) Melt flow rate (MFR) (ASTM D1238, 230° C., under 2.16 kg load) is 0.5 to 1000 g/10 minutes;
(3) The ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 4.2 to 20;
(4) The amount of n-decane-soluble component at 23° C. is 0.01 to 2% by weight.

Each requirement will be described below.
<Requirement (1)>
The propylene-based polymer of the present invention has a meso-average chain length of 500 to 100,000, preferably 700 to 50,000, and more preferably 1,000 to 10,000. When the meso-average chain length is within the above range, the stereoregularity of the propylene-based polymer becomes sufficiently high, and the propylene-based polymer has improved heat resistance and mechanical properties such as flexural modulus. The meso-average chain length can be determined by the method described in Examples below.

<Requirement (2)>
The propylene-based polymer of the present invention has an MFR (ASTM D1238, 230° C., under 2.16 kg load) of 0.5 to 1000 g/10 minutes, preferably 1.0 to 800 g/10 minutes, more preferably 1.5. ~500 g/10 minutes. When the MFR is within the above range, the moldability and mechanical strength of the propylene-based polymer will be excellent. The propylene-based polymer of the present invention is preferably 50 to 1000 g/10 minutes, more preferably 100 to 1000 g/10 minutes, particularly preferably 100 to 500 g/10 minutes even in a high MFR region. High level of stereoregularity.

<Requirement (3)>
In the propylene-based polymer of the present invention, the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by GPC is 4.2 to 20, preferably 4.5 to 15. It is preferably 4.8 to 10. When Mw/Mn is within the above range, it is preferable from the viewpoint of moldability of the propylene-based polymer.

<Requirement (4)>
In the second aspect of the propylene-based polymer of the present invention, the amount of the n-decane-soluble component at 23° C. is 0.01 to 2% by weight, preferably 0.1 to 1.8% by weight, more preferably 0.1. 2 to 1.5% by weight. When the amount of the decane-soluble component is within the above range, the highly crystalline component is sufficiently secured, and the by-product of the low stereoregular component is suppressed.

Furthermore, the propylene-based polymer obtained by the above production method preferably satisfies the following requirement (5) in addition to the above requirements (1) to (3) or the above requirements (1) to (4). It is more preferable to satisfy (5) and (6), and it is further preferable to simultaneously satisfy the following requirement (7):
(5) When the ratio of the components eluted at a temperature of 122° C. or higher by the temperature rising elution fractionation measurement method (TREF) is A% by weight and the melt flow rate of the requirement (2) is Bg/10 minutes, the following formula Satisfy (I);
100≧A≧20×EXP (−0.01×B) (I)
(6) The proportion of components eluted by TREF at a temperature of 122° C. or higher is 0.1 to 100% by weight;
(7) The mesopentad fraction (mmmm) determined by ¹³ C-NMR is 99.0 to 100%.

<Requirement (5)>
The propylene-based polymer of the present invention has the following formula (I) when the proportion of the component eluted by TREF at a temperature of 122° C. or higher is A wt% and the melt flow rate of the requirement (2) is Bg/10 minutes. ) Is satisfied.

100≧A≧20×EXP (−0.01×B) (I)
The propylene-based polymer satisfying the above formula (I) is preferable in that it has a certain degree of heat resistance and stereoregularity exhibiting a high rigidity even if the MFR is not less than a certain level.

<Requirement (6)>
In the propylene-based polymer of the present invention, the proportion A of the component eluted by TREF at a temperature of 122° C. or higher is preferably 0.1 to 100% by weight, more preferably 0.2 to 80% by weight, and particularly preferably 0. 3 to 50% by weight. When the ratio of the elution component is within the above range, the stereoregularity of the propylene-based polymer becomes sufficiently high, and the heat resistance of the propylene-based polymer and the mechanical properties such as bending elastic modulus are improved.

<Requirement (7)>
The propylene polymer of the present invention has a mesopentad fraction (mmmm) determined by ¹³ C-NMR of preferably 99.0 to 100%, more preferably 99.1 to 99.99%, and particularly preferably 99. 2 to 99.95%. When the mesopentad fraction is within the above range, the stereoregularity of the propylene-based polymer tends to be sufficiently high.

Here, the mesopentad fraction indicates the existence ratio of a pentadene isotactic structure in a molecular chain, and represents the proportion of propylene structural units at the center of a chain having a continuous meso structure of five propylene monomer units. Is the rate. The mesopentad fraction can be determined by the method described in Examples below.

[Propylene resin composition]
The propylene-based polymer obtained by the production method of the present invention can be used in the form of a propylene-based resin composition. This propylene-based resin composition is a propylene-based resin composition containing the above-described propylene-based polymer of the present invention (hereinafter also referred to as "propylene-based polymer (A)"). The components other than the propylene-based polymer (A) constituting the propylene-based resin composition of the present invention are not particularly limited, and known components can be added depending on the application.

As a preferred embodiment of the propylene resin composition of the present invention,
20 to 80% by mass of a propylene block copolymer (C) consisting of a propylene homopolymer part and a propylene/α-olefin copolymer part,
Ethylene/α-olefin copolymers (D) 1 to 50 containing 50 to 95 mol% of a structural unit derived from ethylene and 5 to 50 mol% of a structural unit derived from an α-olefin having 3 to 20 carbon atoms. Mass% and inorganic filler (E) 0-70 mass%
(Provided that the total of the components (C), (D) and (E) is 100% by mass),
In the propylene-based block copolymer (C), as the propylene homopolymer part, 60 to 99% by mass of the propylene-based polymer (A), and as the propylene/α-olefin copolymer part, in propylene. Propylene/α-olefin copolymer (B) 1 containing from 55 to 90 mol% of a structural unit derived from and from 10 to 45 mol% of a structural unit derived from an α-olefin other than propylene having a carbon number of 2 to 20 40% by mass (however, the total of components (A) and (B) is 100% by mass),
Propylene resin composition (hereinafter also referred to as "first composition");
A propylene resin composition containing 100 parts by mass of the propylene polymer (A) and 0.01 to 10 parts by mass of a nucleating agent (F) (hereinafter, also referred to as "second composition"); and
70 to 99.5 mass% of at least one component selected from the group consisting of the propylene polymer (A) and the propylene block copolymer (C),
Inorganic fiber (G) 0.5 to 30% by mass (however, the total of components (A), (C) and (G) is 100% by mass.) Propylene resin composition (hereinafter referred to as “third part”). Also referred to as "composition of".)
And so on. Hereinafter, each composition will be described.

<First composition>
The first composition of the present invention is a resin containing the propylene block copolymer (C) and the ethylene/α-olefin copolymer (D), and further containing an inorganic filler (E) if necessary. The propylene-based block copolymer (C) is a composition, and contains the propylene-based polymer (A) and the propylene/α-olefin copolymer (B). Such a first composition of the present invention can form a molded article having excellent fluidity during molding and excellent flexural modulus and impact resistance.

In the first composition of the present invention, a propylene homopolymer is used as the propylene-based polymer (A) constituting the propylene-based block copolymer (C).
In the first composition of the present invention, after the propylene-based polymer (A) and the propylene/α-olefin copolymer (B) are mixed to form a propylene-based block copolymer (C), It can be prepared by mixing the ethylene/α-olefin copolymer (D) and, if necessary, the inorganic filler (E).

<<Propylene block copolymer (C)>>
The propylene-based block copolymer (C) contains 60 to 99% by mass, preferably 70 to 97% by mass, more preferably 75 to 95% by mass of the propylene-based polymer (A) as a propylene homopolymer part. The content of the propylene/α-olefin copolymer (B) is in the range of 1 to 40% by mass, preferably 3 to 30% by mass, and more preferably 5 to 25% by mass (however, the component (A)). And (B) is 100% by mass.).

By thus forming the propylene-based block copolymer (C) using the propylene-based polymer (A) and the propylene/α-olefin copolymer (B), rigidity, heat resistance and impact resistance can be improved. It is possible to form a molded article having an excellent balance with Here, the propylene-based block copolymer (C) can be formed, for example, by melt-kneading the propylene-based polymer (A) and the propylene/α-olefin copolymer (B). ..

«Propylene/α-olefin copolymer (B)»
The propylene/α-olefin copolymer (B) is a copolymer of propylene and an α-olefin other than propylene and having 2 to 20 carbon atoms, and contains 55 to 90 mol% of a structural unit derived from propylene, It is preferably contained in the range of 60 to 85 mol %, and the constituent unit derived from the α-olefin is contained in the range of 10 to 45 mol %, preferably 15 to 40 mol% (provided that it is derived from propylene. The total of constituent units and constituent units derived from α-olefin is 100 mol %.).

Examples of the α-olefin having 2 to 20 carbon atoms other than propylene include ethylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene and 3-methyl-1. -Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. These may be used alone or in combination of two or more. Of these, ethylene is preferred.

The MFR (ASTM D1238E, measurement temperature 230° C., load 2.16 kg) of the propylene/α-olefin copolymer (B) is preferably 0.1 g/10 minutes or more, more preferably 0.3 to 20 g/10. Minutes.

The propylene/α-olefin copolymer (B) is produced by various known production methods, for example, by copolymerizing propylene with an α-olefin having 2 to 20 carbon atoms other than propylene in the presence of a metallocene catalyst. can do.
The propylene/α-olefin copolymer (B) may be used alone or in combination of two or more.

≪Ethylene/α-olefin copolymer (D)≫
The ethylene/α-olefin copolymer (D) is a random copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, and has a structural unit derived from ethylene of 50 to 95 mol%, preferably 55. To 90 mol%, and the constituent unit derived from the α-olefin is contained in 5 to 50 mol%, preferably 10 to 45 mol%. By blending the ethylene/α-olefin copolymer (D) with the propylene block copolymer (C), impact resistance can be further improved.

Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned. These may be used alone or in combination of two or more. Among these, propylene, 1-butene, 1-hexene and 1-octene are preferable, and 1-butene and 1-octene are more preferable.

The MFR (ASTM D1238E, measurement temperature 230°C, load 2.16 kg) of the ethylene/α-olefin copolymer (D) is preferably 0.1 to 50 g/10 minutes, more preferably 0.3 to 20 g/. It is 10 minutes, more preferably 0.5 to 10 g/10 minutes. The density of the ethylene/α-olefin copolymer (D) is preferably 0.850 to 0.920 kg/m ³ , and more preferably 0.855 to 0.900 kg/m ³ .

As the ethylene/α-olefin copolymer (D), a product produced by a known method may be used, or a commercially available product may be used. Preferable commercially available products include, for example, “Toughmer (registered trademark) A” series and “Toughmer (registered trademark) H” series manufactured by Mitsui Chemicals, Inc., and “Engage (registered trademark)” series manufactured by DuPont Dow. , ExxonMobil's "Exact (registered trademark)" series and the like.
The ethylene/α-olefin copolymer (D) may be used alone or in combination of two or more.

<<Inorganic filler (E)>>
Examples of the inorganic filler (E) include talc, clay, mica, calcium carbonate, magnesium hydroxide, ammonium phosphate, silicates, carbonates, carbon black, magnesium sulfate fiber, glass fiber, carbon fiber and the like. Can be mentioned. These may be used alone or in combination of two or more. In the first composition of the present invention, it is preferable to use talc as the inorganic filler (E).

The content of the components (C) to (E) in the first composition of the present invention is 20 to 80 when the total of the components (C) to (E) is 100% by mass. % By mass, preferably 25 to 75% by mass, more preferably 30 to 70% by mass, and the component (D) is 1 to 50% by mass, preferably 5 to 40% by mass, more preferably 10 to 30% by mass. And the component (E) is 0 to 70% by mass, preferably 5 to 60% by mass, and more preferably 10 to 50% by mass.

<Second composition>
The second composition of the present invention is a resin composition containing the propylene polymer (A) and the nucleating agent (F), and can form a molded article excellent in rigidity, heat resistance and flexural modulus. it can.

The propylene-based polymer (A) used in the second composition of the present invention may be a propylene homopolymer or a random copolymer containing a monomer other than propylene as a copolymerization component.

Examples of the nucleating agent (F) include sorbitol-based nucleating agents, phosphate-based nucleating agents (organic phosphate metal salts), aromatic carboxylic acid metal salts, aliphatic carboxylic acid metal salts, rosin compounds, and the like. Organic nucleating agents; inorganic nucleating agents such as inorganic compounds. These may be used alone or in combination of two or more.

Commercially available products of the nucleating agent (F) include a phosphate-based nucleating agent "ADEKA STAB NA-11" (manufactured by ADEKA) and a rosin-based nucleating agent "Pine Crystal KM1610" (Arakawa Chemical Co., Ltd.). (Manufactured by Mirken Co., Ltd.), a nucleating agent “Hyperfoam HPN-20E” (manufactured by Milliken) made of a metal salt of an aliphatic carboxylic acid, and a sorbitol-based nucleating agent “Mirad NX8000” (manufactured by Milliken).

The content of the nucleating agent (F) in the second composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 100 parts by mass of the propylene-based polymer (A). ˜5 parts by mass, more preferably 0.1 to 1.0 parts by mass.

<Third composition>
The second composition of the present invention contains at least one component selected from the group consisting of the propylene polymer (A) and the propylene block copolymer (C), and an inorganic fiber (G). Since it is a resin composition, it is possible to form a molded article having an excellent balance of rigidity, heat resistance and flexural modulus.

The propylene-based polymer (A) used in the third composition of the present invention may be either a propylene homopolymer or a random copolymer, but the above-mentioned propylene-based block copolymer (C) constituting the propylene-based block copolymer (C) is used. The propylene polymer (A) is a propylene homopolymer.

Examples of the inorganic fiber (G) include magnesium sulfate fiber, glass fiber, carbon fiber and the like. These may be used alone or in combination of two or more.
When magnesium sulfate fibers are used, the average fiber length thereof is preferably 5 to 50 μm, more preferably 10 to 30 μm. Further, the average fiber diameter of the magnesium sulfate fiber is preferably 0.3 to 2 μm, and more preferably 0.5 to 1 μm. Examples of commercially available products include "Mosheiji" (trade name, manufactured by Ube Materials Co., Ltd.).

As glass fibers, glass fibers such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass) and alkali-resistant glass are melt-spun to form filament fibers. I can list the ones I made. The glass fibers are contained in the composition in the form of short fibers of 1 mm or less or long fibers of 1 mm or more.

Examples of the carbon fibers include polyacrylonitrile (PAN)-based carbon fibers made from polyacrylonitrile and pitch-based carbon fibers made from pitch. These carbon fibers can be used as so-called chopped carbon fibers obtained by cutting the fiber raw yarn into a desired length, and may be subjected to a convergent treatment using various sizing agents as necessary. ..

The content of the inorganic fiber (G) in the third composition of the present invention is preferably 1 to 30% by mass, more preferably 2 when the total amount of the component (A) and the component (G) is 100% by mass. -25% by mass, more preferably 5-20% by mass.

<Other ingredients>
The propylene-based resin composition of the present invention is a resin, a rubber, a filler, a weather resistance stabilizer, a heat resistance stabilizer, an antistatic agent other than the above-mentioned components (A) to (G) within a range not impairing the object of the present invention. Other components such as an agent, an antislip agent, an antiblocking agent, an antifogging agent, a lubricant, a pigment, a dye, a plasticizer, an antiaging agent, a hydrochloric acid absorbent, an antioxidant and a crystal nucleating agent can be added. The blending amount of the other components in the propylene-based resin composition of the present invention is not particularly limited as long as it does not impair the object of the present invention.

<Method for producing propylene resin composition>
The propylene-based resin composition of the present invention can be manufactured by blending the above-mentioned components. The components may be sequentially blended in any order, or may be mixed at the same time. Further, a multi-stage mixing method may be employed in which some components are mixed and then other components are mixed. However, regarding the first composition of the present invention, as described above, the propylene-based block copolymer is prepared by mixing the propylene-based polymer (A) and the propylene-α-olefin copolymer (B). After forming (C), it is produced by mixing the ethylene/α-olefin copolymer (D) and, if necessary, the inorganic filler (E) and other components. Also, in the third composition of the present invention, when the propylene block copolymer (C) is used, similarly, after the propylene block copolymer (C) is previously formed, other components are mixed. It is manufactured by

As a method for blending each component, for example, a method of mixing or melting and kneading each component simultaneously or sequentially using a mixing device such as a Banbury mixer, a single screw extruder, a twin screw extruder, a high speed twin screw extruder. Is mentioned.

[Molded body]
The molded product of the present invention is formed using the propylene polymer of the present invention or the propylene resin composition of the present invention described above. The propylene-based polymer of the present invention has a level of high stereoregularity which has never been achieved, and also has high rigidity and high heat resistance. Therefore, the molded article of the present invention has a small dimensional change due to temperature change and is dimensionally stable. It has excellent properties. Therefore, the molded product of the present invention can be suitably used in various fields such as automobile parts, home electric appliance parts, food containers, and medical containers. Examples of the automobile parts include automobile interior/exterior members such as bumpers and instrumental panels, and outer plate materials such as roofs, door panels, and fenders. In particular, the first composition of the present invention is suitable for automobile bumpers, instrument panels, and fenders, and the second composition of the present invention is suitable for automobile interior members (for example, door panels, pillars, etc.), The third composition of the present invention is suitable as an automobile functional member (for example, an engine fan, a fan shroud, etc.), but is not limited thereto.

The method for molding the molded article of the present invention is not particularly limited, and various known methods for polymer molding can be adopted, but injection molding and press molding are particularly preferable.

Hereinafter, the present invention will be described more specifically based on Examples, but the present invention is not limited to these Examples. The methods for measuring various physical properties described in the examples are as follows.

<Meso pentad fraction (mmmm (noise removal method))>
1. Measurement condition apparatus: Bruker BioSpin AVANCE III cryo-500 type nuclear magnetic resonance apparatus Measurement nucleus: ¹³ C (125 MHz)
Measurement mode: Single pulse proton broadband decoupling Pulse width: 45° (5.00 microseconds)
Repeat time: 5.5 seconds Number of integrations: 256 times Measurement solvent: o-dichlorobenzene/deuterated benzene (80/20% by volume) mixed solvent Sample concentration: 50 mg/0.6 mL
Measurement temperature: 120°C
Chemical shift standard: 21.59 ppm (mesopentad methyl peak shifts)

2. Calculation method One of the indicators of the stereoregularity of the polymer, the mesopentad fraction (mmmm,%) for examining its microtacticity is the peak intensity of the ¹³ C-NMR spectrum obtained under the above measurement conditions 1. It was calculated from the ratio.

Here, in the case of polypropylene having an unprecedented level of stereoregularity such as the measurement target in the present invention, when the rmmr, mmrm, rmrr, rmrm, and mrrr regions are included in the integrated value, the integration of “noise” is performed. It is considered that there is a problem that the degree of influence on the value increases and S2 in a general calculation method is overestimated, that is, mmmm (%) is underestimated. Even in Prog. Polym. Sci. 26 (2001), 443-533, in the case of polypropylene having 95% or more stereoregularity, the integrated values of the rmmr, mmrm, rmrr, rmrm, and mrrr regions are as long as certain requirements are satisfied. Theoretically, it is reported that the total is 0.1% or less, which suggests that it leads to overestimation of S2 in a general calculation method.

Therefore, in the present invention, the calculation is performed according to the following (formula 1). The rmmr, mmrm, rmrr, rmrm, and mrrr regions were excluded from the calculation according to the suggestions of Prog. Polym. Sci. 26 (2001), 443-533. Hereinafter, the calculation method in this specification is referred to as a “noise removal method”.

mmmm (noise removal method) (%)=S1/S2*100 (Equation 1)
S1=(peak containing mmmm, mmmr)-(n-propyl end)-(n-butyl end)-mrm*2
S2 = S1 + mmmr + mmrr + mrrm + rrrr
= S1 + 5 * mrrm + rrrr

In the calculation by the above (Formula 1), the following attributions were made as examples. The mmmm peak overlaps with mmmr peaks (n-propyl end) and (n-butyl end).
Peaks including mmmm and mmmr: Peak area of 21.2 to 22.0 ppm mmmr = mrrm*2
mmrr = mrrm * 2
mrrm: 19.5 to 19.7 ppm peak area rrrr: 20.0 to 20.2 ppm peak area n-propyl end: (A1 + A3)/2
A1: 14.2 ppm peak area A3: 39.4 ppm peak area n-butyl end: 36.7 ppm peak area

<Meso average chain length>
The meso-average chain length Ln(m) was calculated based on the following formula.
Ln(m)=3+5X/(1-X)
X=mmmm (noise removal method) (%)/100

<Molecular weight distribution>
The Mw/Mn value, which is an index of the molecular weight distribution, was obtained by analyzing a chromatogram measured under the following conditions by a known method.
Apparatus: Waters gel permeation chromatograph Alliance GPC2000 type Column: Tosoh TSKgel GMH6-HT x2 + TSKgel GMH6-HTL x2
Mobile phase: o-dichlorobenzene (containing 0.025% BHT)
Flow rate: 1.0 ml/min
Temperature: 140℃
Column calibration: Tosoh monodisperse polystyrene Sample concentration: 0.15% (w/v)
Injection volume: 0.4 ml <Melt flow rate (MFR)>
According to ASTM D1238E, the measurement temperature was 230°C.

<Amount of soluble components in decane>
A glass measuring container was charged with about 6 g of propylene polymer (this weight is expressed as b (gram) in the following formula), 500 ml of decane, and a small amount of a heat-resistant stabilizer soluble in decane, and a nitrogen atmosphere. Under stirring, the temperature was raised to 150° C. for 2 hours while stirring with a stirrer to dissolve the propylene polymer, and the mixture was held at 150° C. for 2 hours and then gradually cooled to 23° C. over 8 hours. The obtained liquid containing the precipitate of the propylene polymer was filtered under reduced pressure with a glass filter of 25G-4 standard manufactured by Iwata Glass Co., Ltd. A 100 ml portion of the filtrate was collected and dried under reduced pressure to obtain a part of the decane-soluble component. This weight is expressed as a (gram) in the following formula. After this operation, the amount of decane-soluble component was determined by the following formula.
Decane soluble component content (% by weight)=100×(500×a)/(100×b)

<Melting point (Tm)>
Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., about 5 mg of a sample was packed in an aluminum pan for measurement, heated to 230° C. at 50° C./min, and held at 230° C. for 5 minutes, and then 10° C. The temperature was decreased to −100° C./min, and the temperature was maintained for 5 minutes, and then the temperature was increased to 200° C. at 10° C./min. The melting point (Tm) was determined from the endothermic curve at the time of this final temperature rise.

<Flexural modulus>
The flexural modulus (MPa) was measured under the following conditions according to ISO 178.
Temperature: 23 ℃
Test piece: 10 mm (width) x 4 mm (thickness) x 80 mm (length)
Bending speed: 2 mm/min Span: 64 mm
<Charpy impact test>
According to JIS K7111, the Charpy impact strength with notch was measured under the following conditions.
"Test condition"
Temperature: -30°C and 23°C
Test piece: 10 mm (width) x 80 mm (length) x 4 mm (thickness)
The notch is machined.

[Example 1]
<Preparation of solid titanium (a-1)>
A high-speed stirring device (made by Tokushu Kika Kogyo Co., Ltd.) having an internal volume of 2 liters was thoroughly replaced with nitrogen, and then 700 ml of purified kerosene, 10 g of magnesium chloride, 24.2 g of ethanol and sorbitan distearate (produced by Kao Atlas Co., Ltd.) 3 g of Emazol 320") was charged. The system was heated under stirring and stirred at 120° C. and 800 rpm for 30 minutes. Using a Teflon (registered trademark) tube having an inner diameter of 5 mm, the mixture was transferred to a 2 liter glass flask (with a stirrer) filled with 1 liter of purified kerosene that had been cooled to -10°C under high speed stirring. The obtained solid was filtered and sufficiently washed with purified n-hexane to obtain a solid adduct in which 2.8 mol of ethanol was coordinated with 1 mol of magnesium chloride.

Next, the solid adduct (45 mmol in terms of magnesium atom) was suspended in 20 ml of decane, and then the whole amount was introduced into 195 ml of titanium tetrachloride kept at -20°C with stirring. The temperature of this mixed solution was raised to 80° C. over 5 hours, and 1.8 ml (6.2 mmol) of diisobutyl phthalate was added. Subsequently, the temperature was raised to 110° C. and the mixture was stirred for 1.5 hours.

After completion of the reaction for 1.5 hours, the solid part was collected by hot filtration and washed with decane at 100° C. and hexane at room temperature until titanium was not detected in the filtrate. Thus, solid titanium (a-1) containing 3.8% by weight of titanium, 16% by weight of magnesium, 18.2% by weight of diisobutyl phthalate and 1.1% by weight of ethanol residue was obtained. Obtained.

<Preparation of solid titanium catalyst component (i-1)>
In a 200 ml glass reactor sufficiently replaced with nitrogen, 6.8 g of the obtained solid titanium (a-1), 113 ml of paraxylene, 11 ml of decane, 2.5 ml (23 mmol) of titanium tetrachloride and diisobutylphthalein were added. -0.34 ml (1.2 mmol) was added. The temperature in the reactor was raised to 130° C., the mixture was stirred at that temperature for 1 hour to perform contact treatment, and then the solid portion was collected by hot filtration. This solid part was resuspended in 101 ml of paraxylene, and 1.7 ml (15 mmol) of titanium tetrachloride and 0.22 ml (0.8 mmol) of diisobutyl phthalate were further added.

Then, the temperature was raised to 130° C., and the reaction was carried out by stirring for 1 hour while maintaining the temperature. After completion of the reaction, solid-liquid separation was performed again by hot filtration, and the obtained solid part was washed with decane at 100° C. and hexane at room temperature until the content of paraxylene in the catalyst was 1% by weight or less. Thus, a solid titanium catalyst component (i-1) containing 1.3% by weight of titanium, 20% by weight of magnesium, 13.8% by weight of diisobutyl phthalate and 0.8% by weight of diethyl phthalate was obtained.

In addition, the present inventor confirmed that the diethyl phthalate detected in the solid titanium catalyst component (i-1) is probably diisobutyl phthalate and the solid titanium (a-1) in the production process of the solid titanium catalyst component. It is speculated that this may be due to the accompanying transesterification with the ethanol used to produce ).

<Preparation of prepolymerization catalyst (p-1)>
In a nitrogen-substituted 200 ml glass reactor, 50 ml of hexane, 5.0 mmol of triethylaluminum, 0.75 mmol of isopropylpyrrolidinodimethoxysilane, and 0 to 5 parts of the solid titanium catalyst component (i-1) in terms of titanium atom were converted. After charging 0.25 mmol, propylene was fed at an amount of 1.47 liter/hour for 1 hour while maintaining the temperature in the system at 20°C. By this operation, a prepolymerized catalyst (p-1) in which 3 g of propylene was prepolymerized per 1 g of the solid titanium catalyst component (i-1) was obtained.

The molar ratio of triethylaluminum, isopropylpyrrolidinodimethoxysilane, and the titanium atom in the solid titanium catalyst component (i-1) used in the preparation of the prepolymerization catalyst (p-1) was 20/3/ It was 1.

<Main polymerization>
An autoclave having an internal volume of 2 liters was charged with 500 g of propylene and 4.5 liters of hydrogen, and the temperature inside the system was raised to 60°C. Then, 0.5 mmol of triethylaluminum, 0.1 mmol of isopropylpyrrolidinodimethoxysilane, and 0.002 mmol of the prepolymerization catalyst (p-1) obtained above in terms of titanium atoms were added to initiate polymerization. did. Polymerization was carried out for 1 hour while maintaining the temperature in the system at 70°C. Next, the polymerization was stopped by adding ethanol, and unreacted propylene was purged to obtain 199 g of polypropylene (A-1). Table 1 shows the results of evaluation of the physical properties of the obtained polypropylene (A-1).

The molar ratio of triethylaluminum used in the main polymerization, isopropylpyrrolidinodimethoxysilane and the titanium atom in the prepolymerization catalyst (p-1) was 250/50/1.

[Example 2]
<Preparation of prepolymerization catalyst (p-2)>
Except that cyclobutyl(diethylamino)dimethoxysilane was used instead of isopropylpyrrolidinodimethoxysilane, the same procedure as in "Preparation of prepolymerization catalyst (p-1)" in Example 1 was carried out to prepare a solid titanium catalyst component ( i-1) A prepolymerized catalyst (p-2) in which 3 g of propylene per 1 g was prepolymerized was obtained.

The molar ratio of triethylaluminum, cyclobutyl(diethylamino)dimethoxysilane used in the preparation of the prepolymerization catalyst (p-2) to the titanium atom in the solid titanium catalyst component (i-1) was 20/3. It was /1.

<Main polymerization>
3. The above prepolymerization catalyst (p-2) is used in place of the prepolymerization catalyst (p-1), cyclobutyl(diethylamino)dimethoxysilane is used in place of isopropylpyrrolidinodimethoxysilane, and the hydrogen charging amount is 4. 220 g of polypropylene (A-2) was obtained in the same manner as in the "main polymerization" of Example 1, except that the amount was changed from 5 liters to 4.0 liters. Table 1 shows the results of evaluating the physical properties of the obtained polypropylene (A-2).

The molar ratio of triethylaluminum, cyclobutyl(diethylamino)dimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-2) was 250/50/1.

[Example 3]
<Preparation of prepolymerization catalyst (p-3)>
Except that ethyl(diethylamino)dimethoxysilane was used in place of isopropylpyrrolidinodimethoxysilane, the same procedure as in "Preparation of prepolymerization catalyst (p-1)" in Example 1 was carried out to prepare a solid titanium catalyst component ( i-1) A prepolymerized catalyst (p-3) in which 3 g of propylene per 1 g was prepolymerized was obtained.

The molar ratio of triethylaluminum and ethyl(diethylamino)dimethoxysilane used for the preparation of the prepolymerization catalyst (p-3) to the titanium atom in the solid titanium catalyst component (i-1) was 20/3. It was /1.

<Main polymerization>
3. The above prepolymerization catalyst (p-3) was used in place of the prepolymerization catalyst (p-1), ethyl(diethylamino)dimethoxysilane was used in place of isopropylpyrrolidinodimethoxysilane, and the hydrogen charging amount was 4. 217 g of polypropylene (A-3) was obtained in the same manner as in the "main polymerization" of Example 1, except that the amount was changed from 5 liters to 3.5 liters. Table 1 shows the results of evaluating the physical properties of the obtained polypropylene (A-3).

The molar ratio of triethylaluminum and ethyl(diethylamino)dimethoxysilane used in the main polymerization to the titanium atom in the prepolymerization catalyst (p-3) was 250/50/1.

[Comparative Example 1]
<Preparation of prepolymerization catalyst (p-c1)>
Except that cyclohexylmethyldimethoxysilane was used in place of isopropylpyrrolidinodimethoxysilane, the same procedure as in "Preparation of prepolymerization catalyst (p-1)" in Example 1 was carried out to prepare a solid titanium catalyst component (i- 1) A prepolymerized catalyst (p-c1) in which 3 g of propylene was prepolymerized per 1 g was obtained.

The molar ratio of triethylaluminum, cyclohexylmethyldimethoxysilane used in the preparation of the prepolymerization catalyst (p-c1) and the titanium atom in the solid titanium catalyst component (i-1) was 20/3/1. Met.

<Main polymerization>
In the same manner as in Example 1, except that the prepolymerization catalyst (p-c1) was used instead of the prepolymerization catalyst (p-1), and cyclohexylmethyldimethoxysilane was used instead of isopropylpyrrolidinodimethoxysilane. Polymerization” was carried out in the same manner as above to obtain 230 g of polypropylene (a-1). Table 1 shows the results of evaluation of the physical properties of the obtained polypropylene (a-1).

The molar ratio of triethylaluminum, cyclohexylmethyldimethoxysilane used in the main polymerization to the titanium atom in the prepolymerization catalyst (p-c1) was 250/50/1.

[Example 4]
In the main polymerization, the charging amount of hydrogen was changed from 4.5 liters to 11.0 liters, the temperature in the system during the polymerization was changed from 70° C. to 60° C., and the addition amount of triethylaluminum was 0. 0.5 mmol to 1.0 mmol, the amount of isopropylpyrrolidinodimethoxysilane added to 0.1 mmol to 0.2 mmol, and the amount of the prepolymerization catalyst (p-1) added to 0.002 mmol in terms of titanium atom. Was carried out in the same manner as in Example 1 except that the content of polypropylene (A-4) was changed to 0.004 mmol. Table 1 shows the results of evaluation of physical properties of the obtained polypropylene (A-4).

The molar ratio of triethylaluminum used in the main polymerization, isopropylpyrrolidinodimethoxysilane and the titanium atom in the prepolymerization catalyst (p-1) was 250/50/1.

[Example 5]
In this polymerization, 234 g of polypropylene (A-5) was obtained in the same manner as in Example 2 except that the charged amount of hydrogen was changed from 4.0 liters to 9.0 liters. Table 1 shows the results of evaluating the physical properties of the obtained polypropylene (A-5).

The molar ratio of triethylaluminum, cyclobutyl(diethylamino)dimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-2) was 250/50/1.

[Example 6]
In the main polymerization, the charged amount of hydrogen was changed from 4.0 liter to 10.5 liter, the added amount of triethylaluminum was changed from 0.5 mmol to 1.0 mmol, and the added amount of cyclobutyl(diethylamino)dimethoxysilane was changed. Was changed from 0.1 mmol to 1.0 mmol, and the addition amount of the prepolymerization catalyst (p-2) was changed from 0.002 mmol to 0.004 mmol in terms of titanium atom. In the same manner, 295 g of polypropylene (A-6) was obtained. Table 1 shows the results of evaluating the physical properties of the obtained polypropylene (A-6).

The molar ratio of triethylaluminum, cyclobutyl(diethylamino)dimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-2) was 250/250/1.

[Example 7]
In this polymerization, 207 g of polypropylene (A-7) was obtained in the same manner as in Example 3, except that the charging amount of hydrogen was changed from 3.5 liters to 8.5 liters. Table 1 shows the results of evaluating the physical properties of the obtained polypropylene (A-7).

The molar ratio of triethylaluminum and ethyl(diethylamino)dimethoxysilane used in the main polymerization to the titanium atom in the prepolymerization catalyst (p-3) was 250/50/1.

[Example 8]
In the main polymerization, the charged amount of hydrogen was changed from 3.5 liter to 11.0 liter, the added amount of triethylaluminum was changed from 0.5 mmol to 1.0 mmol, and the added amount of ethyl(diethylamino)dimethoxysilane was changed. The procedure of Example 3 was repeated except that the amount of propylene was changed from 0.1 mmol to 1.0 mmol, to obtain 186 g of polypropylene (A-8). Table 1 shows the results of evaluating the physical properties of the obtained polypropylene (A-8).

The molar ratio of triethylaluminum and ethyl(diethylamino)dimethoxysilane used in the main polymerization to the titanium atom in the prepolymerization catalyst (p-3) was 250/250/1.

The meanings of the symbols relating to the "organosilicon compound component (ii)" of the "olefin polymerization catalyst" in Table 1 and Table 2 below are as follows.
ii-1: Isopropylpyrrolidinodimethoxysilane
ii-2: Cyclobutyl(diethylamino)dimethoxysilane
ii-3: Ethyl(diethylamino)dimethoxysilane
cii-1: cyclohexylmethyldimethoxysilane
cii-2: Diethylaminotriethoxysilane

[Example 9]
<Preparation of prepolymerization catalyst (p-4)>
90 g of the solid titanium catalyst component (i-1), 82.1 ml of triethylaluminum, 19.2 ml of isopropylpyrrolidinodimethoxysilane, and 14.3 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 20 L, and the internal temperature was 15 to 20°C. 1000 g of propylene was added and the reaction was carried out while stirring for 120 minutes. After the polymerization was completed, the solid component was allowed to settle, and the supernatant was removed and washing with heptane was performed twice. The prepolymerization catalyst (p-4) was obtained by the above operation.

The obtained prepolymerized catalyst (p-4) was resuspended in purified heptane to prepare a slurry with heptane so that the solid catalyst component concentration was 0.7 g/L.
The molar ratio of triethylaluminum, isopropylpyrrolidinodimethoxysilane used in the preparation of the prepolymerization catalyst (p-4) to the titanium atom in the solid titanium catalyst component (i-1) was 20/3/ It was 1.

<Main polymerization>
300 L of propylene was charged into a vessel polymerization vessel equipped with a stirrer having an internal capacity of 500 L, and while maintaining this liquid level, 100 kg/hour of propylene was added to the slurry of the prepolymerized catalyst (p-4) catalyst obtained above as a solid catalyst component. Of 0.970 g/hour, 10.9 ml/hour of triethylaluminum, and 3.40 ml/hour of isopropylpyrrolidinodimethoxysilane as an external donor were continuously supplied, and polymerization was carried out at a temperature of 70°C. Further, hydrogen was continuously supplied so that the concentration of hydrogen in the gas phase in the polymerization tank would be 6.90 mol %. After deactivating the obtained slurry, propylene was evaporated to obtain polypropylene (A-9) in the form of powder.

The obtained polypropylene (A-9) was vacuum dried at 80°C.
Table 2 shows the results of evaluating the physical properties of the obtained polypropylene (A-9).
The molar ratio of triethylaluminum, isopropylpyrrolidinodimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-4) was 250/50/1.

[Example 10]
In the main polymerization, polypropylene (A-10) was obtained in the same manner as in Example 9, except that the supply amount of isopropylpyrrolidinodimethoxysilane was changed from 3.40 ml/hour to 6.80 ml/hour. .. Table 2 shows the results of evaluating the physical properties of the obtained polypropylene (A-10).

The molar ratio of triethylaluminum, isopropylpyrrolidinodimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-4) was 250/100/1.

[Example 11]
In the main polymerization, polypropylene (A-11) was obtained in the same manner as in Example 9 except that the temperature in the system during the polymerization was changed from 70°C to 60°C. Table 2 shows the results of evaluation of the physical properties of the obtained polypropylene (A-11).

The molar ratio of triethylaluminum, isopropylpyrrolidinodimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-4) was 250/50/1.

[Example 12]
<Preparation of prepolymerization catalyst (p-5)>
160 g of the solid titanium catalyst component (i-1), 146 ml of triethylaluminum, 39.1 ml of ethyl(diethylamino)dimethoxysilane, and 14.3 L of heptane were inserted into an autoclave with a stirrer having an internal volume of 20 L, and the internal temperature was adjusted to 15 to 20°C. 1,000 g of propylene was added and the reaction was carried out while stirring for 120 minutes. After the polymerization was completed, the solid component was allowed to settle, and the supernatant was removed and washing with heptane was performed twice. The prepolymerization catalyst (p-5) was obtained by the above operation.

The obtained prepolymerized catalyst (p-5) was resuspended in purified heptane to prepare a slurry with heptane so that the solid catalyst component concentration was 0.7 g/L.
The molar ratio of triethylaluminum and ethyl(diethylamino)dimethoxysilane used for the preparation of the prepolymerization catalyst (p-5) to the titanium atom in the solid titanium catalyst component (i-1) was 20/3. It was /1.

<Main polymerization>
300 L of propylene was charged into a vessel polymerization vessel with an internal capacity of 500 L equipped with a stirrer, and while maintaining this liquid level, 100 kg/hour of propylene was added to the slurry of the prepolymerized catalyst (p-5) catalyst obtained above as a solid catalyst component. 1.50 g/hour, triethylaluminum 17.1 ml/hour, and ethyl(diethylamino)dimethoxysilane 6.12 ml/hour as an external donor were continuously supplied, and the temperature was 64° C. for polymerization. Further, hydrogen was continuously supplied so that the hydrogen concentration in the gas phase in the polymerization tank was 4.0 mol %. The obtained slurry was deactivated and then propylene was evaporated to obtain powdery polypropylene (A-12).

The obtained polypropylene (A-12) was vacuum dried at 80°C.
Table 2 shows the results of evaluating the physical properties of the obtained polypropylene (A-12).
The molar ratio of triethylaluminum, ethyl(diethylamino)dimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-5) was 250/50/1.

[Example 13]
In this polymerization, polypropylene (A-13) was obtained in the same manner as in Example 12, except that the amount of hydrogen supplied was changed so that the hydrogen concentration was 7.0 mol %. Table 2 shows the results of evaluating the physical properties of the obtained polypropylene (A-13).

The molar ratio of triethylaluminum, ethyl(diethylamino)dimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-5) was 250/50/1.

[Example 14]
In this polymerization, polypropylene (A-14) was obtained in the same manner as in Example 12, except that the hydrogen supply amount was changed so that the hydrogen concentration was 16.2 mol %. Table 2 shows the results of evaluation of the physical properties of the obtained polypropylene (A-14).

The molar ratio of triethylaluminum, ethyl(diethylamino)dimethoxysilane used in the main polymerization and the titanium atom in the prepolymerization catalyst (p-5) was 250/50/1.

[Comparative example 2]
<Preparation of prepolymerization catalyst (p-c2)>
Preliminary polymerization catalyst (p-c2) was performed in the same manner as in “Preparation of prepolymerization catalyst (p-5)” in Example 12 except that diethylaminotriethoxysilane was used instead of ethyl(diethylamino)dimethoxysilane. ) Got.

The obtained prepolymerized catalyst (p-c2) was resuspended in purified heptane to prepare a slurry with heptane so that the solid catalyst component concentration was 0.7 g/L.
The molar ratio of triethylaluminum, diethylaminotriethoxysilane, and the titanium atom in the solid titanium catalyst component (i-1) used in the preparation of the prepolymerization catalyst (p-c2) was 20/3/1. Met.

<Main polymerization>
The prepolymerization catalyst (p-5) was used in place of the prepolymerization catalyst (p-5), diethylaminotriethoxysilane was used in place of ethyl(diethylamino)dimethoxysilane, and the hydrogen concentration was 1.9 mol%. Polypropylene (a-2) was obtained in the same manner as in the “main polymerization” in Example 12, except that the amount of hydrogen supplied was changed. Table 2 shows the results of evaluating the physical properties of the obtained polypropylene (a-2).

The molar ratio of triethylaluminum used in the main polymerization, diethylaminotriethoxysilane and the titanium atom in the prepolymerization catalyst (p-c2) was 250/50/1.

[Preparation of pellets made of polypropylene only and evaluation of physical properties]
Only the polypropylene obtained in the above Examples or Comparative Examples was melt-kneaded under the following conditions in a twin-screw extruder to prepare pellets. The obtained pellets were injection-molded by an injection molding machine under the following conditions to prepare test pieces. Table 3 shows the physical properties of the obtained injection-molded article (test piece).

1. Melt-kneading conditions Bi-directional kneading machine in the same direction: Product number KZW-15, manufactured by Techno Bell Co., Ltd. Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 40 rpm
2. Injection molding conditions Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds Cooling time: 15 seconds

[Preparation of Pellets Containing Polypropylene and Inorganic Filler and Evaluation of Physical Properties]
The polypropylene and the inorganic filler (E) obtained in the above-mentioned Examples or Comparative Examples were mixed so as to have the composition shown in Table 4 below, and the obtained mixture was melt-kneaded with a twin-screw extruder to form pellets. Was produced. The obtained pellets were injection-molded with an injection molding machine to prepare test pieces.

Here, the melt-kneading and the injection molding were performed under the conditions described in “1. Melt-kneading conditions” and “2. Injection-molding conditions” in “Preparation of pellets made of polypropylene only and evaluation of physical properties”, respectively. ..

Table 4 shows the physical properties of the obtained injection-molded article (test piece).

The meanings of the symbols relating to the component (E) in Table 4 are as follows.
E-1: Talc (trade name: JM209, manufactured by Asada Milling Co., Ltd.)
[Preparation of pellets containing propylene block copolymer and inorganic filler and evaluation of physical properties]
First, the polypropylene obtained in the above-mentioned Examples or Comparative Examples and the propylene/α-olefin copolymer (B) were mixed in the amounts shown in Table 5, and then melted in a twin-screw extruder under the following conditions. A propylene-based block copolymer was prepared by kneading. Next, the obtained propylene-based block copolymer was mixed with the ethylene/α-olefin copolymer (D) and the inorganic filler (E) in the amounts shown in Table 5, and the conditions were as follows under a twin-screw extruder. Was melt-kneaded to prepare a pellet-shaped propylene-based resin composition. The obtained pellets were injection-molded by an injection molding machine under the following conditions to prepare test pieces. Table 5 shows the physical properties of the obtained injection-molded article (test piece).

<Melting and kneading conditions>
Bi-directional kneading machine in the same direction: product number KZW-15, manufactured by Techno Bell Co., Ltd. Kneading temperature: 190°C
Screw rotation speed: 500 rpm
Feeder rotation speed: 40 rpm
<Injection molding conditions>
Injection molding machine: EC40 (trade name, manufactured by Toshiba Machine Co., Ltd.)
Cylinder temperature: 190℃
Mold temperature: 40℃
Injection time-holding time: 13 seconds Cooling time: 15 seconds

The meanings of the symbols relating to the components (B), (D) and (E) in Table 5 are as follows.
B-1: Propylene/ethylene copolymer (trade name: Toughmer S4020, manufactured by Mitsui Chemicals, Inc.)
D-1: Ethylene/butene copolymer (trade name: Tufmer A1050S, manufactured by Mitsui Chemicals, Inc.)
E-1: Talc (trade name: JM209, manufactured by Asada Milling Co., Ltd.)

Claims (5)

A method for producing a propylene-based polymer by polymerizing propylene in the presence of an olefin polymerization catalyst,
The olefin polymerization catalyst,
(I) a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor and satisfying the following requirements (k1) to (k4):
(Ii) an organosilicon compound component represented by the following formula (II),
(Iii) a catalyst [A] containing an organometallic compound component containing an element belonging to Group 1, 2 or 13 of the periodic table,
Or
A prepolymerized catalyst (p) in which propylene is prepolymerized on the catalyst [A],
The organosilicon compound component (ii),
Catalyst [B] containing the organometallic compound component (iii)
A method for producing a propylene-based polymer characterized by:
(K1) The titanium content is 2.5% by weight or less;
(K2) the content of the electron donor is 8 to 30% by weight;
(K3) the electron donor/titanium (weight ratio) is 5 or more;
(K4) Titanium is not substantially desorbed by washing with hexane at room temperature.
R ¹ _n Si(OR ² ) ₂ (NR ³ R ⁴ ) _2-n ...(II)
[In the formula (II), R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms, R ² represents a hydrocarbon group having 1 to 4 carbon atoms, and R ³ represents a hydrocarbon group having 1 to 12 carbon atoms or A hydrogen atom, R ⁴ represents a hydrocarbon group having 1 to 12 carbon atoms, and R ³ and R ⁴ may combine with each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms. , N is 0 or 1. ] The solid titanium catalyst component (i) is
(A) Solid titanium containing magnesium, titanium, halogen and an electron donor, and titanium is not desorbed by washing with hexane at room temperature,
(B) aromatic hydrocarbon,
The manufacturing method according to claim 1, which is manufactured by a method including a step of contacting (c) liquid titanium and (d) an electron donor. The production method according to claim ¹ , wherein in the formula (II), R ¹ is a branched or linear alkyl group having 1 to 20 carbon atoms. The production method according to claim 1, wherein in the formula (II), R ³ and R ⁴ are bonded to each other to form a divalent hydrocarbon group having 3 to 20 carbon atoms. . The method according to any one of claims 1 to 4, wherein the electron donor is a compound represented by the following formula (IV).

In formula (IV), R represents a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 3 to 6 carbon atoms, and R′ represents 1 to 10 carbon atoms. A linear or branched alkyl group is shown, and n is an integer of 0-4.