JPH1142664A - Polypropylene resin composition for injection molding and injection-molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polypropylene resin compsn. for an injection-molded product having lightweight properties and high rigidity and excellent in heat resistance and scratch resistance. SOLUTION: A polypropylene resin compsn. for injection molding is based on polypropylene and has the following characteristics, that is, (1) an isotactic pentad measured by<13> C-NMR is 98.0% or more, (2) Mw/Mn measured by gel permeation chromatography is 20 or more and Mz/Mw is 8 or more, (3) specific gravity (ASTM D1505) by an underwater replacing method is 0.910 or less, (4) flexural modulus (ASTM D790) is 2500 MPa or more, (5) thermal deformation temp. (ASTM D648, load; 0.45 MPa) is 150 deg.C or higher and (6), when a resin is injected into a mold of 60 deg.C at 190 deg.V and held for 30 sec in the mold to mold an injection molded product, the thickness of the skin layer formed on the surface of the injection-molded product is 380 ×m or more.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition for injection molding and an injection-molded article comprising the composition.

[0002]

2. Description of the Related Art Polypropylene is used in various fields such as automobile parts, machine parts, electric parts, daily necessities, kitchenware, packaging films, and the like. Improvements in physical properties have been made. For example, to improve rigidity and heat resistance, an inorganic filler such as talc is blended. However, the composition containing talc has problems that the specific gravity is increased, the surface of the molded article is easily damaged, and the damaged portion is easily whitened.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polypropylene resin composition for injection molding which is lightweight, has high rigidity, and is excellent in heat resistance and scratch resistance, and injection molding comprising this composition. To provide goods.

[0004]

The present invention provides the following polypropylene resin composition for injection molding and an injection molded article. (1) A polypropylene resin composition for injection molding comprising polypropylene as a main component and having the following characteristics. Isotactic pentad fraction (mmmm fraction) measured by ¹³ C-NMR is 98.0% or more. Gel permeation chromatography (GPC)
Mw / Mn is 20 or more, and Mz / Mw is 8 or more, specific gravity (ASTM D1505) by water displacement method is 0.910 or less. Flexural modulus (ASTM D790) is 2500 MPa.
Heat deformation temperature (ASTM D648, load 0.45MP)
a) is 150 ° C. or more When a resin temperature is 190 ° C., the mixture is injected into a mold at 60 ° C., and is held in the mold for 30 seconds to mold an injection molded product. 380μm thick
(2) An injection molded article obtained by injection molding the composition according to (1).

The polypropylene resin composition of the present invention contains polypropylene as a main component, and has an isotactic pentad fraction (mmmm fraction) of 98.0% or more, preferably 98.0 to 99.0%, The molecular weight distribution represented by Mw / Mn (weight average molecular weight / number average molecular weight) is 20
As described above, the molecular weight distribution is preferably 22 to 26 and represented by Mz / Mw (z average molecular weight / weight average molecular weight) of 8
Above, preferably 9 to 10, and specific gravity of 0.910
Or less, preferably 0.906 to 0.910, and a flexural modulus of 2500 MPa or more, and preferably 2600 to 200 MPa.
2800MPa, heat deformation temperature is 150 ° C or more,
It is preferably a polypropylene resin composition having a temperature of 150 to 155 ° C. and a skin layer thickness of 380 μm or more, preferably 390 to 600 μm.

The isotactic pentad fraction (m
(mmm fraction) is an isotactic chain in a pentad unit in a polypropylene molecular chain measured by using ¹³ C-NMR, and is located at the center of a chain in which five propylene monomer units are consecutively meso-bonded. It is a fraction of propylene monomer units. Specifically, it is a value determined as a mmmm peak fraction in all absorption peaks in a methyl carbon region of a ¹³ C-NMR spectrum.

The above-mentioned Mw / Mn and Mz / Mw are values measured by gel permeation chromatography. When Mw / Mn and Mz / Mw are in the above ranges, a small amount of polypropylene having an ultrahigh molecular weight, for example, 1 × 10 ⁶ to 1 × 10 ⁷ or more, for example, 0.5 to 20% by weight is contained in the composition. .

The specific gravity is determined according to ASTM D by a water displacement method.
It is a value measured under the conditions based on 1505. The flexural modulus is a value measured under conditions according to ASTM D790. The heat distortion temperature is a value measured under a load of 0.45 MPa in accordance with ASTM D648.

The thickness of the skin layer is determined by injecting the polypropylene resin composition into a mold at a resin temperature of 190.degree. C. at 60.degree. C. and holding it in the mold for 30 seconds to form an injection molded product. This is the thickness of the skin layer formed on the surface of the molded article. Here, the skin layer is a layer in which molecules are highly oriented on the surface of the injection-molded article, no spherulites are observed, and the crystal structure at the center of the molded article is different. This skin layer is measured by observing a vertical cross section of the molded article with an optical microscope.

The polypropylene which is the main component of the polypropylene resin composition of the present invention is usually preferably composed of only units derived from propylene.
It may contain a unit derived from another monomer of 0 mol% or less, preferably 5 mol% or less.

Other monomers include, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-
Heptene, 1-octene, 1-nonene, 1-decene, 1
Α-olefins other than propylene such as dodecene; vinyl compounds such as styrene, vinylcyclopentene, vinylcyclohexane and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids such as maleic anhydride or derivatives thereof; conjugated dienes; Non-conjugated polyenes such as cyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene. Among these, ethylene, an α-olefin having 4 to 10 carbon atoms, and the like are preferable. Two or more of these may be copolymerized.

The polypropylene resin composition of the present invention comprises a branched olefin such as 3-methyl-1-butene,
3,3-dimethyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4,4-
Dimethyl-1-pentene, 4-ethyl-1-hexene,
3-ethyl-1-hexene, 3,5,5-trimethyl-
1-hexene, vinylcyclopentane, vinylcyclohexane, vinylcycloheptane, vinylnorbornane,
A homopolymer or a copolymer such as allyl norbornane, styrene, dimethyl styrene, allyl benzene, allyl toluene, allyl naphthalene, or vinyl naphthalene is contained as a prepolymer in an amount of 0.1% by weight or less, preferably 0.05% by weight or less. Is preferred. Among them, 3-methyl-1-butene and the like are particularly preferable. Since the prepolymer derived from such branched olefins acts as a nucleating agent for polypropylene, the isotactic pentad fraction can be increased and the moldability can be improved.

The polypropylene resin composition of the present invention is a composition containing polypropylene as a main component so as to satisfy the above-mentioned characteristics. It may be. As the polypropylene, if a polypropylene satisfying the above characteristics can be obtained by one-stage polymerization, the polypropylene can be used as it is as the polypropylene resin composition of the present invention. A composition blended with high molecular weight polypropylene is used. In this case, it is possible to separately produce polypropylenes having different molecular weights and melt-knead them, and blend them. However, it is preferable to blend polypropylenes having different molecular weights by producing polypropylenes having different molecular weights by multi-stage polymerization.

The polypropylene may be a propylene block copolymer such as a propylene / ethylene block copolymer. In this case, the polypropylene is preferable because it has excellent rigidity and impact resistance. The type of the propylene block copolymer is not particularly limited, but the intrinsic viscosity [η] of the rubber part (ethylene / propylene copolymer) is 0.5 to 10 dl / g.
And a propylene / ethylene block copolymer having an ethylene content of 40% by weight or less is particularly preferred.

As a preferred method for producing the polypropylene resin composition of the present invention, for example, propylene alone or propylene and other monomers are subjected to two- or more-stage multistage polymerization in the presence of a catalyst for producing highly stereoregular polypropylene. A method of producing by polymerization can be given. As a specific method of the multi-stage polymerization, in the first stage, 135 ° C.
The intrinsic viscosity [η] measured in decalin is 8 to 12 dl /
g of polypropylene having a relatively high molecular weight is produced in an amount of 0.5 to 20% by weight in the finally obtained polypropylene resin composition.
３3 dl / g of a relatively low molecular weight polypropylene in the finally obtained polypropylene resin composition.
A method of two-stage polymerization for producing 9.5% by weight, or a method in which the production sequence of polypropylene in the above method is reversed.

As another multi-stage polymerization method, a polypropylene having an intrinsic viscosity [η] of 8 to 20 dl / g measured in decalin at 135 ° C. in the first stage may be used in a polypropylene resin composition which is finally obtained. 0.5 to 15% by weight, and in the second stage, the intrinsic viscosity [η]
Is produced in an amount of 0.5 to 30% by weight in the finally obtained polypropylene resin composition, and the intrinsic viscosity [η] is 0.8 to 4. A three-stage polymerization method in which 0 dl / g of polypropylene is produced in an amount of 99 to 55% by weight in the finally obtained polypropylene resin composition, or a method in which the production sequence of polypropylene is reversed or changed in the above method. .

Still another production method includes a method in which polypropylene having the intrinsic viscosity is separately produced, and these are melt-kneaded. The method for producing the polypropylene resin composition of the present invention is preferably a multi-stage polymerization, particularly preferably a two-stage or three-stage polymerization.

Examples of the highly stereoregular polyolefin production catalyst include (a) magnesium, titanium,
A catalyst comprising a solid titanium catalyst component containing a halogen and an electron donor, (b) an organometallic compound, and (c) an electron donor can be used.

The solid titanium catalyst component (a) as described above
Represents a magnesium compound (a-1), a titanium compound (a
-2) and an electron donor (a-3). Magnesium compound (a-
Examples of 1) include a magnesium compound having a reducing ability and a magnesium compound having no reducing ability.

The magnesium compound having reducing ability (a-
As 1), a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond can be mentioned. Specifically, dimethyl magnesium, diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy Magnesium, ethyl butyl magnesium, butyl magnesium hydride and the like can be given.

The magnesium compound having no reducing ability (a
-1) includes, for example, magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; Magnesium halides; allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride; alkoxymagnesiums such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; phenoxymagnesium, dimethylphenoxy Alloxymagnesium such as magnesium;
Examples thereof include magnesium carboxylate such as magnesium laurate and magnesium stearate.

The magnesium compound (a-1) having no reducing ability may be a compound derived from the magnesium compound (a-1) having reducing ability, or a compound derived at the time of preparing the catalyst component. In order to derive the magnesium compound (a-1) having no reducing ability from the magnesium compound (a-1) having the reducing ability, for example, the magnesium compound (a-1) having the reducing ability is converted into a polysiloxane compound, Halogen-containing silane compounds, halogen-containing aluminum compounds, esters, alcohols,
The compound may be brought into contact with a compound having an active carbon-oxygen bond such as a halogen-containing compound or a ketone.

The magnesium compound (a-1) can be derived from metallic magnesium during the preparation of the catalyst. The magnesium compound (a-1) can be used in combination of two or more kinds. The magnesium compound (a-1) as described above may form a complex compound or a double compound with another metal such as aluminum, zinc, boron, beryllium, sodium, and potassium, or may be formed of another metal compound. And a mixture thereof.

In the present invention, many magnesium compounds other than those described above can be used, but it is preferable that the finally obtained solid titanium catalyst component (a) be in the form of a halogen-containing magnesium compound. When using a halogen-free magnesium compound,
It is preferable to carry out a contact reaction with a halogen-containing compound in the process of preparing the catalyst component.

Among them, the magnesium compound (a-1) having no reducing ability is preferred, the halogen-containing magnesium compound is more preferred, and magnesium chloride, alkoxymagnesium chloride and allyloxymagnesium chloride are particularly preferred.

In the present invention, when preparing the catalyst component, the magnesium compound (a-1) is preferably used in a liquid state.
Among them, when the magnesium compound (a-1) is a solid, it can be brought into a liquid state by using an electron donor. As the liquefying agent, alcohols, phenols, ketones, aldehydes, ethers, amines, pyridines and the like as described later as an electron donor, and further tetraethoxytitanium, tetra-n-propoxytitanium,
Metal acid esters such as tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium can also be used. Among these, alcohols and metal acid esters are particularly preferably used.

The liquefaction reaction of the solid magnesium compound (a-1) is generally carried out by bringing the solid magnesium compound into contact with the above-mentioned liquefying agent and heating as necessary. This contact is usually carried out at 0 to 200 ° C., preferably at 20 ° C.
To 180 ° C, more preferably at a temperature of 50 to 150 ° C.

In the liquefaction, a hydrocarbon solvent and the like may coexist, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, tetradecane and kerosene; cyclopentane, methylcyclopentane Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, cyclooctane and cyclohexene; halogenated hydrocarbons such as dichloroethane, dichloropropane, trichloroethylene and chlorobenzene; aromatic hydrocarbons such as benzene, toluene and xylene Can be

In preparing the solid titanium catalyst component (a), it is preferable to use, for example, a tetravalent titanium compound represented by the following general formula (1) as the titanium compound (a-2). Ti (OR) _g X _4-g (1) (In the formula (1), R is a hydrocarbon group, X is a halogen atom, 0
≦ g ≦ 4. Specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC _{2
H 5) 2 Cl 3, Ti} (On-C 4 H 9) Cl 3, Ti (OC
_{2 H 5) Br 3, Ti} (O-iso-C 4 H 9) trihalide, alkoxy titanium such as _{Br 3; Ti (OCH 3)} 2 C
_{l 2, Ti (OC 2 H} 5) 2 Cl 2, Ti (On-C 4 H 9) 2 Cl
₂ , dihalogenated dialkoxy titanium such as Ti (OC ₂ H ₅ ) ₂ Br ₂ ; Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ C
1, monohalogenated trialkoxy titanium such as Ti (On-C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OC
_{H 3) 4, Ti (OC} 2 H 5) 4, Ti (On-C 4 H 9) 4, Ti
Tetraalkoxy titanium such as (O-iso-C ₄ H ₉ ) ₄ and Ti (O-2-ethylhexyl) ₄ .

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. Titanium compound (a-
2) can be used in combination of two or more kinds. Further, the titanium compound (a-2) can be used after being diluted with a hydrocarbon compound, a halogenated hydrocarbon compound, or the like.

Examples of the electron donor (a-3) used in preparing the solid titanium catalyst component (a) include alcohols, phenols, ketones, aldehydes, esters of organic or inorganic acids, organic acid halides, and the like. Examples include ethers, acid amides, acid anhydrides, ammonia, amines, nitriles, isocyanates, nitrogen-containing cyclic compounds, and oxygen-containing cyclic compounds. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol,
C1-C18 alcohols such as octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumyl C6 to C20 phenols which may have a lower alkyl group such as phenol and naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone and benzoquinone; acetaldehyde ,
Aldehydes having 2 to 15 carbon atoms such as propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and the like can be mentioned.

Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, crotonic acid Ethyl, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate,
Propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate,
Amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, phthalate Di-n-butyl acid, di-2-ethylhexyl phthalate, γ-
Organic acid esters having 2 to 30 carbon atoms such as butyrolactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; Methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether,
C2-C20 ethers such as anisole and diphenyl ether epoxy-p-menthane; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; acid anhydrides such as acetic anhydride, phthalic anhydride and benzoic anhydride ;
Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine; nitriles such as acetonitrile, benzonitrile, tolunitrile; pyrrole, methylpyrrole, dimethylpyrrole, etc. Pyrroles, pyrroline, pyrrolidine, indole, pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridines such as pyridine chloride, piperidines, quinolines,
Nitrogen-containing cyclic compounds such as isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, dihydropyran and the like And cyclic oxygen-containing compounds.

As the organic acid ester used as the electron donor (a-3), a polycarboxylic acid ester having a skeleton represented by the following general formula (2) can be mentioned as a particularly preferred example.

Embedded image

In the formula (2), R ¹ is a substituted or unsubstituted hydrocarbon group, R ² , R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted Or an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. Also R ³
And R ⁴ may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{1 to} R ⁶ are substituted, the substituent contains a different atom such as N, O, S, etc.
-C, COOR, COOH, OH, SO 3 H, -C-N
-C-, having a group such as NH _2.

Specific examples of such a polycarboxylic acid ester include diethyl succinate, dibutyl succinate,
Diethyl methyl succinate, diisobutyl α-methyl glutarate, diethyl methyl malonate, diethyl ethyl malonate, diethyl isopropyl malonate, diethyl butyl malonate, diethyl phenyl malonate, diethyl diethyl malonate, diethyl dibutyl malonate, monooctyl maleate Dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate,
Aliphatic polycarboxylic acid esters such as diethyl itaconate and dioctyl citraconic acid; alicyclic polycarboxylic acids such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate and diethyl nadicate ester;
Monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate,
Diisobutyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, naphthalene Aromatic polycarboxylic acid esters such as dibutyl dicarboxylate, triethyl trimellitate and dibutyl trimellitate; heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid;

Examples of the polycarboxylic acid esters include long-chain dicarboxylic acids such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, and di-2-ethylhexyl sebacate. Acid esters and the like can also be mentioned.

Further, as the electron donor (a-3),
It is also possible to use an organic silicon compound or a polyether compound described below used as an electron donor of the component (c), water, or an anionic, cationic or nonionic surfactant.

In the present invention, among the above, it is preferable to use a carboxylic acid ester, and it is particularly preferable to use a polycarboxylic acid ester, especially a phthalic acid ester. Two or more electron donors (a-3) can be used in combination.

The titanium compound (a-2), magnesium compound (a-1) and electron donor (a-
When contacting 3), other reaction reagents such as silicon, phosphorus, and aluminum may coexist, and a carrier-supported solid titanium catalyst component (a) may be prepared using a carrier. .

As such a carrier, Al ₂ O ₃ , Si
O ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , ZnO, Sn
Resins such as O ₂ , BaO, ThO, and styrene-divinylbenzene copolymer are exemplified. Among these, A
l ₂ O _3, SiO _2, a styrene - divinylbenzene copolymer are preferably used.

The solid titanium catalyst component (a) can be prepared by any method including known methods, and will be briefly described below with several examples. (1) A hydrocarbon solution of a magnesium compound (a-1) containing an electron donor (a liquefying agent) (a-3) is brought into contact with an organometallic compound to precipitate a solid, or while depositing a solid. A method of causing a contact reaction with a titanium compound (a-2). (2) Magnesium compound (a-1) and electron donor (a
A method of contacting and reacting the complex comprising -3) with an organometallic compound, and then contacting and reacting the titanium compound (a-2). (3) A method in which a contact product of an inorganic carrier and an organomagnesium compound (a-1) is contact-reacted with a titanium compound (a-2) and an electron donor (a-3). At this time, the contacted product may be brought into contact with a halogen-containing compound and / or an organometallic compound in advance.

(4) Loading of the magnesium compound (a-1) from a mixture of the magnesium compound (a-1) solution, the electron donor (a-3) and the carrier containing a liquefying agent and a hydrocarbon solvent as the case may be. A method of contacting the titanium compound (a-2) after obtaining the prepared carrier. (5) A method in which a carrier and a solution containing a magnesium compound (a-1), a titanium compound (a-2), an electron donor (a-3) and, in some cases, a hydrocarbon solvent are further contacted. (6) A method of contacting a liquid organomagnesium compound (a-1) with a halogen-containing titanium compound (a-2). At this time, the electron donor (a-3) is used at least once.

(7) Liquid organomagnesium compound (a
-1) a method of contacting a halogen-containing compound with a titanium compound (a-2). In this process, the electron donor (a-3) is used at least once. (8) Alkoxy group-containing magnesium compound (a-1)
And a halogen-containing titanium compound (a-2). At this time, at least one electron donor (a-3) is used.
Use the times. (9) Alkoxy group-containing magnesium compound (a-1)
And a method comprising contacting a complex comprising an electron donor (a-3) with a titanium compound (a-2).

(10) A complex comprising an alkoxy group-containing magnesium compound (a-1) and an electron donor (a-3) is brought into contact with an organometallic compound, and then a titanium compound (a
-2) a method of causing a contact reaction. (11) A method of contacting and reacting the magnesium compound (a-1), the electron donor (a-3), and the titanium compound (a-2) in an arbitrary order. Prior to this reaction, each component may be pretreated with a reaction aid such as an electron donor (a-3), an organometallic compound, or a halogen-containing silicon compound. (12) Liquid magnesium compound having no reducing ability (a
-1) and a liquid titanium compound (a-2) in the presence of an electron donor (a-3) to precipitate a solid magnesium-titanium composite.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound (a-2). (14) A method in which an electron donor (a-3) and a titanium compound (a-2) are further reacted with the reaction product obtained in (11) or (12). (15) A solid obtained by pulverizing the magnesium compound (a-1), the electron donor (a-3), and the titanium compound (a-2) is converted into a halogen, a halogen compound or an aromatic compound. A method of treating with any of hydrogen. In this method, only the magnesium compound (a-1) or the magnesium compound (a-1) and the electron donor (a
-3), or a step of pulverizing the complex compound consisting of the magnesium compound (a-1) and the titanium compound (a-2). Further, after the pulverization, a pretreatment with a reaction assistant may be performed, followed by a treatment with halogen or the like. As the reaction assistant, an organometallic compound or a halogen-containing silicon compound is used.

(16) A method in which the magnesium compound (a-1) is pulverized and then brought into contact with the titanium compound (a-2).
At the time of grinding and / or contacting the magnesium compound (a-1), an electron donor (a-3) is used together with a reaction aid as necessary. (17) A method of treating the compound obtained in the above (11) to (16) with a halogen, a halogen compound or an aromatic hydrocarbon. (18) The contact reaction product with the metal oxide, the organomagnesium (a-1) and the halogen-containing compound is converted into an electron donor (a
-3) and preferably a method of contacting with a titanium compound (a-2).

(19) A magnesium compound (a-1) such as a magnesium salt of an organic acid, alkoxymagnesium or aryloxymagnesium is replaced with a titanium compound (a-
2) a method of contacting with an electron donor (a-3) and, if necessary, a halogen-containing hydrocarbon. (20) A method of contacting a hydrocarbon solution containing a magnesium compound (a-1) and an alkoxytitanium with an electron donor (a-3) and, if necessary, a titanium compound (a-2). At this time, it is preferable to coexist a halogen-containing compound such as a halogen-containing silicon compound. (21) Liquid magnesium compound having no reducing ability (a
-1) is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) complex, and then the electron donor (a-3) and the titanium compound (a-
A method of reacting 2).

The amount of each component used for the contact varies depending on the preparation method and cannot be specified unconditionally. 10 mol, preferably 0.1 to 5
The amount of the titanium compound (a-2) is 0.01 to 10 in a molar amount.
It is desirable to use it in an amount of 00 mol, preferably 0.1 to 200 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor. In the solid titanium catalyst component (a), halogen / titanium (atom) Ratio) is about 2
200, preferably about 4-100, and the electron donor /
It is desirable that the titanium (molar ratio) is about 0.01-100, preferably about 0.02-10, and the magnesium / titanium (atomic ratio) is about 1-100, preferably about 2-50.

As the organometallic compound (b) used together with the solid titanium catalyst component (a), a compound containing a metal selected from Groups I to III of the periodic table is preferable. Such organoaluminum compounds, complex alkyl compounds of a Group I metal with aluminum, and organometallic compounds of a Group II metal can be mentioned.

Formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² are hydrocarbon groups containing usually 1 to 15, preferably 1 to 4 carbon atoms, These may be the same or different, X represents a halogen atom, 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, q
Is a number satisfying 0 ≦ q <3, and m + n + p + q = 3. The organoaluminum compound (b-1) represented by).

[0052] Formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is as defined above.) Group I metals and aluminum and the alkylated complex represented by ( b-2). General formula R ¹ R ² M ² (wherein R ¹ and R ² are the same as above, and M ² is M
g, Zn or Cd. A) a group II or group III dialkyl compound (b-3);

As the organoaluminum compound (b-1), for example, R ¹ _m Al (OR ² ) _3-m (R ¹ and R ² are the same as above, and m is preferably 1.5
≦ m ≦ 3. A compound represented _{^{by), R 1 m AlX 3-}} m (R 1 is as defined above, X is halogen, m is preferably 0 <m <3.) A compound represented by, R ¹ _m AlH _3-m (R ¹ is the same as above, and m is preferably 2 ≦ m <3
It is. R ¹ _m Al (OR ² ) _n X _q (R ¹ and R ² are the same as above, X is halogen, 0 <m
≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q
= 3. And the like.

More specifically, the organoaluminum compound (b-1) includes trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide and dibutylaluminum butoxide. dialkylaluminum _{^{alkoxide; R 1 2.5 Al (OR 2}} ) partially alkoxylated alkyl aluminum having an average composition represented _0.5 like; diethylaluminum ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui butoxide alkyl sesquichloride alkoxides such as Sid Dialkylaluminum halides such as chloride, dibutylaluminum chloride and diethylaluminum bromide; ethylaluminum Alkyl aluminum sesquihalides such as um sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride; ethylaluminum dihydride;
Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as propylaluminum dihydride; partially alkoxylated and halogenated alkyls such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide Aluminum and the like can be given.

Further, as a compound similar to (b-1)
Represents two or more aluminum atoms through an oxygen atom or a nitrogen atom
Raising the organoaluminum compound to which chromium is bound
And, for example, (C_TwoH_Five)_TwoAlOAl (C_TwoH_Five)_Two,
(C_FourH₉)_TwoAlOAl (C_FourH ₉)_Two, (C_TwoH_Five)_TwoAl
N (C_TwoH_Five) Al (C_TwoH_Five)_Two, Methylaluminoxa
And aluminoxanes such as aluminoxane.

As the complex alkylated product (b-2),
LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like can be given.

As the organometallic compound (b), an organoaluminum compound (b-1), particularly a trialkylaluminum, is preferably used. The organometallic compound (b) can be used in combination of two or more kinds.

Specific examples of the electron donor (c) used together with the solid titanium catalyst component (a) and the organometallic compound (b) include an organosilicon compound (c) represented by the following general formula (3). -1) or a compound (c-2) having two or more ether bonds existing through a plurality of atoms.

R ¹ _n Si (OR ² ) _4-n (3) (in the formula (3), n is 1, 2 or 3, and when n is 1, R ¹ is a secondary or tertiary carbonized It is a hydrogen group, n is at least one secondary or tertiary hydrocarbon group R ¹ when 2 or 3, R ¹ may be different even in the same, R ² is the number of carbon atoms 1 to 4 hydrocarbon groups,
When -n is 2 or 3, R ² may be the same or different. )

In the organosilicon compound (c-1) represented by the general formula (3), the secondary or tertiary hydrocarbon group may be a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group or a substituent. And a hydrocarbon group in which the carbon adjacent to Si is secondary or tertiary. More specifically, examples of the substituted cyclopentyl group include a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group,
-N-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethylcyclopentyl group,
2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group,
Examples thereof include a cyclopentyl group having an alkyl group such as a 2,3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes 2-methylcyclopentenyl group, 3-methylcyclopentenyl group, 2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethylcyclopentenyl group, 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, Examples thereof include a cyclopentenyl group having an alkyl group such as a tetramethylcyclopentenyl group and a tetraethylcyclopentenyl group.

As the substituted cyclopentadienyl group, 2
-Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group,
2-n-butylcyclopentadienyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2,5-dimethylcyclopentadienyl group, 2,3-diethylcyclo Pentadienyl group,
2,3,4-trimethylcyclopentadienyl group, 2,
3,5-trimethylcyclopentadienyl group, 2,3
4-triethylcyclopentadienyl group, 2,3,4
5-tetramethylcyclopentadienyl group, 2,3
4,5-tetraethylcyclopentadienyl group, 1,
Cyclopentadienyl groups having an alkyl group such as 2,3,4,5-pentamethylcyclopentadienyl group and 1,2,3,4,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl, s-butyl,
Examples thereof include an s-amyl group and an α-methylbenzyl group. Examples of the hydrocarbon group in which the carbon adjacent to Si is a tertiary carbon include a t-butyl group, a t-amyl group, α, α ′
-Dimethylbenzyl group, admantyl group and the like.

In the organosilicon compound (c-1) represented by the general formula (3), when n is 1, cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyl Trialkoxy such as trimethoxysilane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane and 2-norbornanetriethoxysilane Examples include silanes.

When n is 2, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, Examples thereof include dialkoxysilanes such as cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane, and dimethoxy compounds represented by the following general formula (4).

[0066]

Embedded image In the formula (4), R ¹ and R ² are each independently adjacent to a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or Si A hydrocarbon group in which carbon is a secondary or tertiary carbon.

As the dimethoxy compound represented by the general formula (4), for example, dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, di (2- Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane, di (2,3-dimethylcyclopentyl) dimethoxysilane, di (2,4-dimethylcyclopentyl)
Dimethoxysilane, di (2,5-dimethylcyclopentyl) dimethoxysilane, di (2,3-diethylcyclopentyl) dimethoxysilane, di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5
-Trimethylcyclopentyl) dimethoxysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane, di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl)
Dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3,4-trimethylcyclopentenyl) dimethoxysilane, di (2
3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl)
Dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxysilane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane , Di (2-n-butylcyclopentenyl) dimethoxysilane, di (2,3-
Dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl)
Dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxy Silane, di (2,3,4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-
Tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5
-Pentamethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethyl) Benzyl) dimethoxysilane, di (admantyl) dimethoxysilane,
Madmantyl-t-butyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, di-s-butyldimethoxysilane,
Di-s-amyldimethoxysilane, isopropyl-s-
Butyldimethoxysilane and the like.

In the general formula (3), when n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethyl Monoalkoxysilanes such as methoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane and the like can be mentioned.

As the electron donor (c), dimethoxysilanes, particularly dimethoxysilanes represented by the above general formula (4), are preferred. Specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di ( 2-
Preferred are methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di-t-amyldimethoxysilane and the like. The organosilicon compound (c-1) can be used in combination of two or more kinds.

Compound having two or more ether bonds existing through a plurality of atoms used as electron donor (c) (hereinafter sometimes referred to as polyether compound)
In (c-2), the atoms present between the ether bonds are one or more selected from carbon, silicon, oxygen, sulfur, phosphorus, and boron, and the number of atoms is two or more. Of these, relatively bulky substituents on the atoms between ether bonds, specifically those having 2 or more carbon atoms, preferably 3 or more,
A substituent having a branched or cyclic structure, more preferably a substituent having a branched or cyclic structure, is preferred. In addition, the atom existing between two or more ether bonds may have a plurality of, preferably 3 to 20, more preferably 3
Compounds containing from 10 to 10, particularly preferably from 3 to 7, carbon atoms are preferred.

Such a polyether compound (c-2)
Examples thereof include a compound represented by the following general formula (5).

Embedded image

In the formula (5), n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen,
A substituent having at least one element selected from sulfur, phosphorus, boron and silicon, and any of R ^{1 to} R
²⁶ , preferably R ^{1 to} R ²ⁿ may together form a ring other than a benzene ring, and the main chain may contain atoms other than carbon.

As the polyether compound (c-2) represented by the general formula (5), specifically, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3 -Dimethoxypropane, 2-butyl-
1,3-dimethoxypropane, 2-s-butyl-1,3
-Dimethoxypropane, 2-cyclohexyl-1,3-
Dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl)- 1,3
-Dimethoxypropane, 2- (p-chlorophenyl)-
1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-dimethoxypropane, 2- (2-fluorophenyl) -1,3-dimethoxy Propane, 2- (1
-Decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt-butylphenyl) -1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl -1,3
-Dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane, 2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1 , 3-Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3
-Dimethoxypropane, 2-methyl-2-ethyl-1,
3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl-2
-Cyclohexyl-1,3-dimethoxypropane, 2,
2-bis (p-chlorophenyl) -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-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-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- (1-methylbutyl) -2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s- Butyl-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-
Phenyl-2-isopropyl-1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-dimethoxypropane, 2-benzyl-2-isopropyl-1,
3-dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-
Benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1 , 3-Dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2
-Isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3- Dicyclohexyl-1,4-diethoxybutane, 2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxy Butane, 2,2-bis (p-methylphenyl) -1,4-dimethoxybutane, 2,3-
Bis (p-chlorophenyl) -1,4-dimethoxybutane, 2,3-bis (p-fluorophenyl) -1,4-
Dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl-1,5-dimethoxypentane, 2,4-diisobutyl-1, 5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3-diisobutoxypropane, 1,2-diisobutoxypropane,
1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 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, 2,8-
Dioxaspiro [5,5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5- Oxononane, 6,6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane, 1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,
2,1] heptane, 1,1-dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane, 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-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane Isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3
-Dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenylbis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-butylbis (methoxymethyl) silane, Cyclohexyl-t-butylbis (methoxymethyl) silane, i-propyl-t-butylbis (methoxymethyl)
Silane and the like.

Of these, 1,3-diethers are preferably used, and in particular, 2,2-diisobutyl-1,3
-Dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferred. Used.

Two or more polyether compounds (c-2) can be used in combination. Further, the organosilicon compound (c-
1) and the polyether compound (c-2) can be used in combination.

Further, an organosilicon compound (d) represented by the following general formula (6) can be used in combination. R _n Si (OR ² ) _4-n (6) (In the formula (6), R and R ² are hydrocarbon groups, and 0 <
n <4, and among the organosilicon compounds represented by this formula, the organosilicon compound represented by the general formula (3) (c)
-1) is not included. )

More specifically, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane , Bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane , Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
n-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris (Β-methoxyethoxysilane), vinyltriacetoxysilane and the like. Further, as similar compounds, ethyl silicate, butyl silicate, dimethyltetraethoxydicycloxane and the like can be used.

In the present invention, when a polypropylene is produced using the above-mentioned catalyst comprising the solid titanium catalyst component (a), the organometallic compound (b) and the electron donor (c), preliminary polymerization is carried out in advance. You can do it too. In the prepolymerization, the olefin is polymerized in the presence of the solid titanium catalyst component (a), the organometallic compound (b), and, if necessary, the electron donor (c).

As the prepolymerized olefin, ethylene,
Linear olefins such as propylene, 1-butene, 1-octene, 1-hexadecene, and 1-eicosene;
Methyl-1-butene, 3-methyl-1-pentene, 3-
Ethyl-1-pentene, 4-methyl-1-pentene, 4
-Methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-
1-hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilane Olefins having a branched structure such as olefins can be used, and these may be copolymerized.

Among them, as mentioned above, branched olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like. Is particularly preferably used. In particular, 3-methyl-1-
It is preferable to use a catalyst obtained by prepolymerizing butene, because the resulting polypropylene has high rigidity.

In the prepolymerization, the solid titanium catalyst component (a)
About 0.1 to 1000 g per gram, preferably 0.3 to 1000 g
Desirably, the reaction is performed so that about 500 g of a polymer is produced. If the prepolymerization amount is too large, (co)
The production efficiency of the polymer may decrease. In the prepolymerization, the catalyst can be used at a considerably higher concentration than the catalyst concentration in the system in the main polymerization.

The solid titanium catalyst component (a) is usually used in an amount of about 0.01 to 200 in terms of titanium atom per liter of polymerization volume.
Desirably, it will be used at a concentration of millimolar, preferably about 0.05-100 millimolar. Organometallic compound (b)
Is generally about 0.1 to 100 mmol, preferably about 0.1 mol per mol of titanium atom in the solid titanium catalyst component (a).
Preferably, it is used in an amount of 5 to 50 mmol. The electron donor (c) may or may not be used at the time of the prepolymerization, but is used in an amount of 0.1 to 50 mol, preferably 0.5 to 50 mol per mol of titanium atom in the solid titanium catalyst component (a). 30
Moles, more preferably 1 to 10 moles.

The prepolymerization is preferably carried out under mild conditions by adding the prepolymerized olefin and the above catalyst component to an inert hydrocarbon medium. As an inert hydrocarbon medium,
For example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane; aromatics such as benzene, toluene and xylene Hydrocarbons; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; mixtures thereof; In particular, it is preferable to use an aliphatic hydrocarbon.

The prepolymerization temperature may be a temperature at which the produced prepolymer is not substantially dissolved in an inert hydrocarbon medium, and is usually -20 to + 100 ° C, preferably -2.
0 to + 80 ° C, more preferably about 0 to + 40 ° C. The prepolymerization can be performed in a batch system, a continuous system, or the like. At the time of prepolymerization, the molecular weight can be adjusted using hydrogen or the like.

In the present invention, when producing polypropylene,
The solid titanium catalyst component (a) (or prepolymerized catalyst) was converted to titanium atoms per liter of polymerization volume by about 0.0
001 to 50 mmol, preferably about 0.001 to 10
Desirably, it is used in millimolar amounts. The organometallic compound (b) is used in an amount of about 1 to 2000 mol, preferably about 2 to 500 mol, per 1 mol of titanium atom in the polymerization system.
It is desirable to use it in a molar amount. The electron donor (c) is used in an amount of about 0.001 to 50 mol, preferably about 0.01 to 0.1 mol, per 1 mol of metal atom of the organometallic compound (b).
It is desirable to use it in an amount of about 20 mol.

In the case where propylene is subjected to multi-stage polymerization using the above-mentioned catalyst, propylene and other monomers as described above may be used at any stage or all stages as long as the object of the present invention is not impaired. May be copolymerized.

In the case of multistage polymerization, in each stage, propylene is homopolymerized or propylene and other monomers are copolymerized to produce polypropylene.
In each stage, it is desirable to produce more than 90 mole%, preferably 95 to 100 mole%, of the units derived from propylene. The molecular weight of the polypropylene in each stage can be adjusted, for example, by changing the amount of hydrogen supplied to the polymerization system.

In the present invention, in addition to the step of forming the polypropylene component by such multi-stage polymerization, a copolymerization step of propylene and ethylene is further performed to form a propylene / ethylene copolymer rubber component, and the propylene block copolymer is formed. Can also be manufactured.

The polymerization is carried out by a gas phase polymerization method or a solution polymerization method,
Any of liquid phase polymerization methods such as a suspension polymerization method may be performed, and each of the above steps may be performed by a separate method. The process may be performed in any of a batch system, a semi-continuous system, and a continuous system, and each of the above stages may be performed by dividing into a plurality of polymerization vessels, for example, 2 to 10 polymerization vessels.

As the polymerization medium, an inert hydrocarbon may be used, or liquid propylene may be used as the polymerization medium. The polymerization conditions in each stage are such that the polymerization temperature is about -50 to 20.
0 ° C., preferably in the range of about 20 to 100 ° C., and the polymerization pressure is appropriately selected in the range of normal pressure to 100 kg / cm ² (gauge pressure), preferably about ^{2 to} 50 kg / cm ² (gauge pressure). You.

At the time of propylene polymerization, the solid titanium catalyst component (a) (or pre-polymerization catalyst) is mixed with a polymerization volume of 1 lit.
It is desirable to use about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, in terms of titanium atom per er. The organometallic compound (b) has a metal atomic weight of about 1 to 1 mole of titanium atom in the polymerization system.
It is desirable to use 2,000 moles, preferably about 2 to 500 moles. The electron donor (c) is used in an amount of about 0.001 to 5 per mole of the metal atom of the organometallic compound (b).
It is desirable to use it in an amount of 0 mol, preferably about 0.01 to 20 mol.

When a prepolymerized catalyst is used, a solid titanium catalyst component (a) and an organometallic compound (b) can be newly added as necessary. The organometallic compound (b) in the pre-polymerization and the main polymerization may be the same or different.

The electron donor (c) is used at least once in either the prepolymerization or the main polymerization, and is used only in the main polymerization or in both the prepolymerization and the main polymerization. Used. The electron donor (c) in the pre-polymerization and the main polymerization may be the same or different.

The above-described catalyst components need not be newly added in the subsequent subsequent steps, but may be appropriately added. When the above-mentioned catalyst is used, even when hydrogen is used at the time of polymerization, the crystallinity or stereoregularity index of the obtained polypropylene does not decrease, and the catalyst activity does not decrease.

In the above production method, polypropylene can be produced in a high yield per unit amount of the solid titanium catalyst component (a), so that the amount of the catalyst in the polypropylene, particularly the halogen content, is relatively reduced. Can be. Therefore, the operation of removing the catalyst from the polypropylene can be omitted, and rust is less likely to occur in the mold when the molded article is formed using the finally obtained polypropylene resin composition.

The polypropylene resin composition of the present invention includes:
As long as the object of the present invention is not impaired, additives, other polymers and the like may be blended as necessary. For example, a rubber component may be blended in an appropriate amount to improve impact strength.

Specific examples of the rubber component include ethylene / propylene copolymer rubber, ethylene / 1-butene copolymer rubber, ethylene / 1-octene copolymer rubber, propylene / ethylene copolymer rubber and the like. Amorphous or low-crystalline α-olefin copolymer containing no diene component: ethylene-propylene-dicyclopentadiene copolymer rubber; ethylene-propylene-1,4-hexadiene copolymer rubber, ethylene-propylene・ Cyclooctadiene copolymer rubber, ethylene propylene methylene norbornene copolymer rubber, ethylene propylene
Ethylene / propylene / non-conjugated diene copolymer rubber such as ethylidene norbornene copolymer rubber; and ethylene / butadiene copolymer rubber.

The additives include a nucleating agent, an antioxidant,
Hydrochloric acid absorber, heat stabilizer, weather stabilizer, light stabilizer, ultraviolet absorber, slip agent, antiblocking agent, antifogging agent, lubricant, antistatic agent, flame retardant, pigment, dye, dispersant,
Copper damage inhibitors, neutralizers, foaming agents, plasticizers, foam inhibitors, crosslinkers, peroxide and other flow improvers, weld strength improvers, natural oils, synthetic oils, waxes, inorganic fillers, etc. I can give it.

The polypropylene resin composition of the present invention includes:
The above-mentioned prepolymer may be contained as a nucleating agent, or various other known nucleating agents may be blended, or the prepolymer may be blended with another nucleating agent. By containing or blending a nucleating agent, the crystal grains are finely divided, and the crystallization speed is improved to enable high-speed molding.

For example, when the polypropylene resin composition contains a nucleating agent, crystal grains can be miniaturized, the crystallization speed can be improved, and high-speed molding can be performed. As the nucleating agent other than the prepolymer, various conventionally known nucleating agents, for example, phosphate nucleating agents, sorbitol nucleating agents, metal salts of aromatic or aliphatic carboxylic acids, inorganic compounds and the like are particularly limited. Used without.

As the inorganic filler, talc, silica,
Mica, calcium carbonate, glass fiber, glass beads,
Barium sulfate, magnesium hydroxide, walasunite, calcium silicate fiber, carbon fiber, magnesium oxysulfate fiber, potassium titanate fiber, titanium oxide,
Examples thereof include calcium sulfite, white carbon, clay, and calcium sulfate. These inorganic fillers can be used alone or in combination of two or more.

When talc is used among the inorganic fillers, the rigidity and impact resistance of the obtained molded product are increased.
Talc is preferably used. Especially when the average particle diameter is 0.1
Talc of ３3 μm, preferably 0.5-2.5 μm,
This is desirable because the contribution to the improvement of rigidity and impact resistance is remarkable.

The polypropylene resin composition of the present invention is lightweight, has high rigidity, is excellent in heat resistance and scratch resistance, and has impact resistance, surface gloss, chemical resistance, abrasion resistance and the like. It is used as a raw material resin for injection molding.

When the polypropylene resin composition of the present invention is used as a raw material resin for injection molding, the raw material resin may contain other components such as the rubber component and additives. By blending the rubber component, the impact resistance of the molded article can be improved. By adding talc, particularly talc having the above average particle diameter, the rigidity and impact resistance of the molded product can be improved.

When the injection-molded article is a part for automobiles or a part for home appliances, the polypropylene resin composition 40 to 100
Parts by weight, preferably 55 to 85 parts by weight,
It is desirable to add ５０50 parts by weight, preferably 10-35 parts by weight, and 0-60 parts by weight, preferably 5-25 parts by weight of the inorganic filler. Particularly in the case of an automotive trim material, the polypropylene resin composition is 50 to 100 parts by weight, the rubber component is 0 to 40 parts by weight, preferably 0 to 25 parts by weight, and the inorganic filler is 0 to 40 parts by weight, preferably 0 to 0 parts by weight. It is desirable to add 25 parts by weight.

The raw material resin for the injection-molded article includes 0.05 to 1 part by weight of an antioxidant, 0 to 1 part by weight of a light stabilizer, and 0 to 1 part by weight of an ultraviolet absorber with respect to 100 parts by weight of a polypropylene resin composition. Parts by weight, 0 to 1 part by weight of antistatic agent, 1 to 1 lubricant
0.5 parts by weight, 0 to 1 part by weight of a copper damage inhibitor and the like can be added.

The injection-molded article of the present invention is an injection-molded article obtained by injection-molding the above-mentioned polypropylene resin composition of the present invention or a resin composition obtained by mixing other components with this polypropylene resin composition. The injection molded product of the present invention can be manufactured by injection molding a raw material resin into various shapes using a known injection molding apparatus under known conditions.

The injection-molded article of the present invention is lightweight and hardly charged, and is excellent in rigidity, heat resistance, scratch resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, appearance, etc. , Home appliances and other molded products.

Specific examples of the injection molded article of the present invention include an armrest, an indicator panel lower, an indicator panel core, an indicator panel upper, a car cooler housing, a console box, a grab outdoor, a glove box, a trim, a door trim, and a door pocket. , Speaker grill, high mount, relay fuse box, lamp housing, meter case,
Automotive interior materials such as meter hoods, pillars, and center pillars; automotive exterior materials such as bumpers, front grille side, license plates, louver garnishes, side moldings, bumper corners, bumper sides, and side mudguards; air cleaner cases, junction boxes, siroccos Fan, corrugated tube, connector, fan shroud, protector, lamp housing, reserve tank (cap), air purifier,
Other car parts such as battery case; cleaner pipe, dishwasher parts, washing machine parts, home appliances such as housing, hot plate, rice cooker body; other syringes,
Caps, connectors, containers, daily necessities, medical supplies, miscellaneous goods, and the like.

[0110]

Since the polypropylene resin composition for injection molding of the present invention has specific physical properties, it is lightweight, has high rigidity, and is excellent in heat resistance and scratch resistance. Since the injection molded article of the present invention is composed of the above composition, it is lightweight, has high rigidity, and is excellent in heat resistance, scratch resistance and appearance.

[0111]

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1 [Preparation of solid titanium catalyst component] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C for 2 hours to form a homogeneous solution. 21.3 phthalic anhydride was added to this solution.
g was added and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride.

The homogeneous solution thus obtained was heated at 23 ° C.
After cooling to 75 ° C., 75 ml of this homogeneous solution was
Was dropped into 200 ml of titanium tetrachloride held for 1 hour. After the dropwise addition, the temperature of the obtained mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 5.22 g of diisobutyl phthalate (DIBP) was added.
From this, the same temperature was maintained while stirring for 2 hours. Next, a solid portion was collected by filtration while hot, and the solid portion was removed in an amount of 275 ml.
And reheated at 110 ° C. for 2 hours.

After the heating, the solid portion was collected again by hot filtration and washed with decane and hexane at 110 ° C. until no titanium compound was detected in the washing solution. The solid titanium catalyst component prepared as described above was stored as a hexane slurry. Further, a part of them was dried to examine the catalyst composition. As a result, the solid titanium catalyst component contained 2.5% by weight of titanium, 58% by weight of chlorine, 18% by weight of magnesium, and 13.8% by weight of DIBP.

[Polymerization] Into an autoclave having an internal volume of 17 liters, 3 kg of propylene was charged, and the temperature was raised to 60 ° C. Then, 7.0 mmol of triethylaluminum and 7.0 of dicyclopentyldimethoxysilane (DCPMS) were added.
The solid titanium catalyst component obtained above was added in an amount of 0.7 mmol in terms of titanium atoms. 70 temperature
After the temperature was raised to ° C., polymerization was carried out for 10 minutes. Next, the vent valve was opened, and unreacted propylene was purged through an integrating flow meter (the first-stage propylene homopolymerization was completed).

After completion of the purge, the vent valve was closed, 3 kg of propylene and 0.7 liter of hydrogen were charged, the temperature was raised to 70 ° C., and the mixture was held for 5 minutes to carry out polymerization. Next, the vent valve was opened, and unreacted propylene was purged through an integrating flow meter (the second-stage propylene homopolymerization was completed). Table 1 shows the physical properties of the obtained polypropylene resin composition.
Shown in The intrinsic viscosity [η] of the polypropylene obtained in the first stage was 9.5 dl / g as a result of sampling a portion of the polypropylene after the completion of the first stage.
The proportion of the polypropylene obtained by the first stage polymerization in the finally obtained polypropylene resin composition is 1%.
It was 5% by weight. Various physical properties of the finally obtained polypropylene resin composition were measured. Table 1 shows the results.

The finally obtained polypropylene resin composition was subjected to a prescribed additive formulation, and was melt-kneaded at 200 ° C. in a single screw extruder (manufactured by Ishinaka Iron Works Co., Ltd.) to obtain pellets. These pellets are made by J100SA manufactured by Japan Steel Works, Ltd.
Resin temperature 190 ° C, mold temperature 60 ° C with II type injection molding machine
To obtain an injection molded product. The injection moldability was good.

Comparative Example 1 In Example 1, dicyclopentyldimethoxysilane (DCPMS) was changed to cyclohexylmethyldimethoxysilane (CMDMS), and hydrogen was fed also in the first-stage homopolymerization. A polypropylene was obtained in the same manner as in Example 1 except for polymerization. The physical properties of this polypropylene were measured in the same manner as in Example 1.
Table 1 shows the results.

Comparative Example 2 Polypropylene B170 and B168 produced as described below were melt-blended at a weight ratio of 85:15 to produce a polypropylene resin composition. The physical properties of this composition were measured in the same manner as in Example 1. Table 1 shows the results.

Polypropylene B170: In the same manner as in Example 1, the propylene homopolymerization in the first and second stages was polymerized in the same manner, and finally a polypropylene having an MFR of 50 g / 10 min was obtained. Polypropylene B168: In Example 1, the propylene homopolymerization in the first and second stages was polymerized in the same manner to finally obtain a polypropylene having an MFR of 2 g / 10 minutes.

Comparative Example 3 The following polypropylenes B176 and B178 were melt-blended at a weight ratio of 79:21 to produce a polypropylene resin composition. The physical properties of this composition were determined in Example 1.
The measurement was performed in the same manner as described above. Table 1 shows the results.

Polypropylene B176: The polar root viscosity [η] of the polypropylene obtained in the first stage in Example 1
Is the same as Example 1 except that the ratio is 2.0 dl / g and a ratio of 40 wt%. Polypropylene B178: In Example 1, the polypropylene obtained in the first stage had a root viscosity [η] of 4.0 dl.
Example 1 is the same as Example 1 except that the ratio is 38 wt% in / g.

Comparative Example 4 Titanium tetrachloride was reduced with metallic aluminum, and this was further polymerized using diisobutyl phthalate and a solid catalyst component composed mainly of pulverized titanium trichloride to obtain a polypropylene resin composition. Obtained. The physical properties of this polypropylene resin composition were measured in the same manner as in Example 1. Table 1 shows the results.

[0123]

[Table 1]

Notes in Table 1 * 1 Measured by DSC * 2 Measured by DSC * 3 Measured by DSC * 4 Measured by GPC * 5 Measured by ¹³ C-NMR * 6 Dissolved in hot xylene, cooled to 20 ° C., and filtered The solute is concentrated and the weight of the soluble matter is measured. * 7 Measured under the conditions according to ASTM D1238. * 8 Measured by the water substitution method under the conditions according to ASTM D1505. * 9 Measured under the conditions according to ASTM D790. * 10 ASTM. Measured under the condition of 230 ° C according to D256 * 11 Load 0.45 according to ASTM D648
Measured under MP condition * 12 Measured on R-scale according to ASTM D785 * 13 Measured under 1 kg load condition according to JIS K-5400 * 14 Incident and received angles according to ASTM P523 Measured at 60 ° * 15 Injected into 60 ° C mold at 190 ° C resin temperature
A vertical section of an injection molded product having a thickness of 1/8 inch, which was molded by holding it in a mold for 0 second, was observed and observed with an optical microscope. * 16 Wide angle X-ray diffraction measurement transmission method, measurement surface 110 * 17 Wide angle X-ray Diffraction measurement reflection method

Claims (2)

[Claims] Claims: 1. Mainly comprising polypropylene, the following:
A polypropylene resin composition for injection molding having the following characteristics: Isotactic pentad fraction (mmmm fraction) measured by ¹³ C-NMR is 98.0% or more. Gel permeation chromatography (GPC)
Mw / Mn is 20 or more, and Mz / Mw is 8 or more, specific gravity (ASTM D1505) by water displacement method is 0.910 or less. Flexural modulus (ASTM D790) is 2500 MPa.
Heat deformation temperature (ASTM D648, load 0.45MP)
a) is 150 ° C. or more When a resin temperature is 190 ° C., the mixture is injected into a mold at 60 ° C., and is held in the mold for 30 seconds to mold an injection molded product. 380μm thick
that's all 2. An injection molded article obtained by injection molding the composition according to claim 1.