JPH0655869B2 - Polypropylene composition, method for producing the same, and molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polypropylene composition. More specifically, a highly crystalline highly transparent polypropylene composition containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, a method for producing the same, and the polypropylene composition are provided. It relates to a molded product used.

[Conventional technology and its problems] Compared with other plastics, polypropylene is superior in lightness, moldability, mechanical strength, chemical stability, etc., and is also economically advantageous. It is widely used in the manufacture of various molded products such as the first one.

However, polypropylene is translucent, which may impair the commercial value in the field of application, and improvement in transparency has been desired.

For this reason, attempts have been made to improve the transparency of polypropylene, for example, aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1,652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22,740). There is a method of adding a nucleating agent such as) to polypropylene, but when an aluminum salt of an aromatic carboxylic acid is used, the dispersibility is poor and the improvement in transparency is insufficient, and, When a benzylidene sorbitol derivative is used, although some improvement in transparency can be seen, it has a strong odor during processing and the bleeding phenomenon of additives (embossing).
There was a problem such as occurrence of.

The present inventors have earnestly studied polypropylene having improved transparency and solving the above-mentioned problems when the nucleating agent is used.

As a result, a polypropylene composition containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer is significantly improved in transparency and crystallinity as compared with conventional polypropylene. The present invention has been completed by knowing that problems such as odor and bleeding during processing can be solved.

It is an object of the present invention to provide a polypropylene composition excellent in transparency and crystallinity that does not generate odor or bleed during molding, a method for producing the same, and a molded article using the polypropylene composition. .

[Means for Solving the Problems] The present invention has the following configurations.

(1) A polypropylene composition comprising polypropylene containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer in an amount of 0.1% by weight to 2% by weight so that the total amount is 100% by weight.

(2) Using a catalyst composed of (A) polypropylene, (B) titanium catalyst component, organoaluminum compound (AL ₁ ) and, if necessary, an electron donor (E ₁ ), a dialkyldiallylsilane and / or a trialkyldiallylsilane. Crystalline dialkyldiallylsilane polymer obtained by polymerizing alkylsilylstyrene and /
Alternatively, the crystalline dialkyldiallylsilane polymer and / or the crystalline trialkylsilylstyrene polymer is mixed with the crystalline trialkylsilylstyrene polymer so that the composition contains 0.1% by weight to 2% by weight of the composition. A method for producing a polypropylene composition, comprising:

(3) Using a catalyst composed of (A) polypropylene, (B) titanium catalyst component, organoaluminum compound (AL ₁ ) and, if necessary, an electron donor (E ₁ ), a dialkyldiallylsilane and / or a trialkyldiallylsilane. A crystalline dialkyldiallylsilane polymer and / or a crystalline polymer is prepared by polymerizing alkylsilylstyrene and then mixing propylene or polypropylene obtained by polymerizing propylene and α-olefins other than propylene in multiple stages. A method for producing a polypropylene composition, characterized in that a trialkylsilylstyrene polymer is contained in the composition in an amount of 0.1% by weight to 2% by weight.

(4) A titanium catalyst component containing (A) polypropylene and (B) a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, an organoaluminum compound (AL ₁ ) and, if necessary, Using a catalyst composed of an electron donor (E ₁ ), propylene, or polypropylene obtained by polymerizing propylene and an α-olefin other than propylene, is mixed to give a crystalline dialkyldiallylsilane polymer and / or Alternatively, a method for producing a polypropylene composition is characterized in that the composition contains a crystalline trialkylsilylstyrene polymer in an amount of 0.1% by weight to 2% by weight.

(5) Crystalline dialkyldiallylsilane polymer and /
Alternatively, as a titanium catalyst component containing a crystalline trialkylsilylstyrene polymer, a crystalline dialkyldiallylsilane compound obtained by separately polymerizing dialkyldiallylsilane and / or trialkylsilylstyrene during the production of the titanium catalyst component is used. 5. The production method according to the above item 4, wherein a titanium catalyst component obtained by adding a coalesced and / or crystalline trialkylsilylstyrene polymer to the titanium catalyst component during the production is used.

(6) Crystalline dialkyldiallylsilane polymer and /
Alternatively, as a titanium catalyst component containing a crystalline trialkylsilylstyrene polymer, a dialkyldiallylsilane and / or
Alternatively, the production method according to the above item 4, wherein the titanium catalyst component in the course of production is polymerized with trialkylsilylstyrene, and the titanium catalyst component obtained through the subsequent step is used.

(7) A molded product obtained by using the polypropylene composition as described in the above item 1.

(8) The molded product according to item 7, wherein the molded product is an injection molded product.

(9) The molded product according to item 7, wherein the molded product is a stretched film.

(10) The molded product according to item 7, wherein the molded product is a sheet.

Hereinafter, the configuration of the present invention will be described in detail.

The polypropylene composition of the present invention is a polypropylene composition containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer (hereinafter sometimes referred to as a specific silicon-containing polymer). The manufacturing method thereof will be described.

The method for producing the polypropylene resin composition of the present invention is the same as (A) polypropylene obtained by a known method.
(i) Crystalline dialkyldiallylsilane polymer and / or crystalline trialkylsilylstyrene polymer is mixed, or (ii) Crystalline dialkyldiallylsilane polymer and / or crystalline trialkylsilylstyrene polymer is contained. The crystalline dialkyldiallylsilane polymer and / or the crystalline trialkylsilylstyrene polymer is added to the polypropylene composition by mixing the polypropylene.

The polypropylene (A) used in the present invention is a combination of a titanium catalyst component (a solid compound containing titanium trichloride as a main component or a solid compound having titanium tetrachloride supported on a carrier such as magnesium chloride) and an organoaluminum compound. In some cases, a so-called Ziegler-Natta catalyst in which an electron donor component is combined as the third component of the catalyst is used to perform slurry polymerization in an inert solvent, bulk polymerization using propylene itself as a solvent, or propylene gas-based gas. It is obtained by polymerizing propylene or propylene and an α-olefin other than propylene by phase polymerization or the like.

More specifically, known propylene homopolymers, propylene-α-olefin random copolymers, propylene-α
-One or more types of olefin block copolymers may be mentioned.

The crystalline dialkyldiallylsilane polymer and / or crystalline trialkylsilylstyrene polymer used in the above-mentioned method (i) contains a titanium catalyst component, an organoaluminum compound (AL ₁ ), and optionally an electron donor. It is obtained by polymerizing a dialkyldiallylsilane and / or a trialkylsilylstyrene (hereinafter sometimes referred to as a specific silicon-containing monomer) using a catalyst composed of the body (E ₁ ).

As the titanium catalyst component, any known solid can be used as long as it is a titanium-containing solid for the production of stereoregular polyolefin, but from the viewpoint of industrial production, it is preferable to use JP-B-59-2.
8573 official method, titanium catalyst component containing titanium trichloride as a main component obtained by the method described in JP-A-58-17104, JP-A-62-104810, JP-A-62-104811 A titanium catalyst component obtained by supporting titanium tetrachloride on a magnesium compound described in JP-A-62-104812 is used.

The organoaluminum compound (AL ₁ ) has the general formula
AlR ¹ _m R ² _m ′ X _{3- (m + m} ′ ₎ (In the formula, R ¹ and R ² are a hydrocarbon group or an alkoxy group represented by an alkyl group, a cycloalkyl group or an aryl group, and X is a halogen. To show
m and m'represent an arbitrary number of 0 <m + m'≤3. ) Is used.

Specific examples include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum, tri n- Trialkylaluminums such as octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-i-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum mono Dialkylaluminum monohalides such as iodide, dialkylaluminum hydrides such as diethylaluminum hydride, methylaluminium Examples include sesquichloride, alkylaluminum sesquihalides of ethylaluminum sesquichlorides, monoalkylaluminum dihalides such as ethylaluminum dichloride and i-butylaluminum dichloride, and monoethoxydiethylaluminum, diethoxymonoethylaluminum, etc. Alkoxyalkylaluminums of can also be used. Two or more kinds of these organoaluminum compounds may be mixed and used.

Further, as the electron donor (E ₁ ) used if necessary, a known electron donor used for the purpose of improving stereoregularity in ordinary α-olefin polymerization is used.

What is used as an electron donor (E ₁ ) is oxygen, nitrogen,
Organic compounds having any of sulfur and phosphorus atoms, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates , Azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, silanols, and organosilicon compounds having a Si—OC bond.

Specific examples include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether,
Di-i-amyl ether, di-n-pentyl ether, di-
n-hexyl ether, di-i-hexyl ether, di-n-
Octyl ether, di-i-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, ethers such as tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2 -Alcohols such as ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenols such as phenol, cresol, xylenol, ethylphenol, naphthol, methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, Vinyl acetate, n-propyl acetate, i-propyl acetate, butyl formate, amyl acetate, n-butyl acetate, octyl acetate,
Phenyl acetate, ethyl propionate, methyl benzoate,
Ethyl benzoate, propyl benzoate, butyl benzoate,
Octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propion anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate,
Propyl naphthoate, butyl naphthoate, naphthoic acid 2-
Monocarboxylic acid esters such as ethylhexyl and ethyl phenylacetate, diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate,
Butyl polymaleic acid esters such as diethyl maleate, monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate , Phthalic acid di-i-
Butyl, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, Aromatic polyvalent carboxylic acid esters such as dipropyl terephthalate, dibutyl terephthalate and di-i-butyl naphthalene dicarboxylate, aldehydes such as acetaldehyde, propionaldehyde and benzaldehyde,
Carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid, acid anhydrides such as benzoic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, acetone , Methyl ethyl ketone, methyl isobutyl ketone, benzophenone and other ketones, acetonitrile, benzonitrile and other nitriles, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino)
Ethanol, pyridine, quinoline, α-picoline, 2,4,
Amine such as 6-trimethylpyridine, 2,2,6,6-tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, aniline and dimethylaniline , Formamide, hexamethylphosphoric triamide, N, N, N ', N', N "-pentamethyl-N'-β-
Amides such as dimethylaminomethylphosphoric acid triamide and octamethylpyrophosphoramide, ureas such as N, N, N ′, N′-tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate, azo such as azobenzene Compounds, phosphines such as ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, tri-n-butylphosphite, tri Phosphites such as phenylphosphite, ethyldiethylphosphinite, ethylbutylphosphinite, phosphinites such as phenyldiphenylphosphinite, diethylthioether, diphenylthioether, methylphenyl Thioethers such as ethers, ethylthioalcohol, n-propylthioalcohol, thioalcohols and thiophenols such as thiophenols, silanols such as trirutylsilanol, triethylsilanol and triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane , Methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyl Triethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltri-i-propoxysilane, vinyltriacetate Organosilicon compounds having a Si-OC bond such Shishiran the like.

The amount of each catalyst component used is the same as in ordinary α-olefin polymerization, but specifically, to 1 g of the titanium catalyst component,
The organoaluminum compound (AL ₁ ) 0.005 g to 500 g and the electron donor (E ₁ ) 0 to 500 g are used. A specific silicon-containing monomer is polymerized using a catalyst in which the above predetermined amounts are combined. The polymerization temperature of the polymerization reaction is 0 ° C. to 150 ° C., the polymerization pressure is atmospheric pressure to 50 kg / cm ² G, and the specific silicon-containing monomer is supplied for 5 minutes in the presence or absence of an inert solvent. Polymerize for ~ 50 hours. It is also possible to make hydrogen coexist during the polymerization. After completion of the polymerization, it is possible to remove the catalyst residue by carrying out a purification treatment with alcohol or the like.

The dialkyldiallylsilane and / or trialkylsilylstyrene usable in the main polymerization reaction has a general formula (C
H ₂ = CH-CH ₂ ) ₂ SiR ³ R ⁴ or (In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are the same or different and each represents an alkyl group having 1 to 6 carbon atoms.), Which is a specific silicon-containing monomer. . In particular,
Examples thereof include dimethyldiallylsilane, ethylmethyldiallylsilane, diethyldiallylsilane, p-trimethylsilylstyrene, m-trimethylsilylstyrene, p-triethylsilylstyrene, m-triethylsilylstyrene and p-ethyldimethylsilylstyrene.

Further, for the method for producing a polypropylene containing a specific silicon-containing polymer used in the above-mentioned method (ii),
The following methods are available.

(1) titanium catalyst component, organoaluminum compound (AL ₁ ),
And a method of polymerizing a specific silicon-containing monomer, and then polymerizing propylene or propylene and an α-olefin other than propylene in multiple stages, using a catalyst composed of an electron donor (E ₁ ) if necessary.

(2) A titanium catalyst component obtained by adding a specific silicon-containing polymer obtained by polymerization according to the method (i) separately during the production of the titanium catalyst component for α-olefin polymerization, an organoaluminum compound A method of polymerizing propylene, or propylene and an α-olefin other than propylene, using a catalyst composed of (AL ₁ ) and optionally an electron donor (E ₁ ).

(3) During the production of the titanium catalyst component for α-olefin polymerization, a polymerization treatment is performed using a specific silicon-containing monomer under polymerization conditions, and a titanium catalyst component and an organoaluminum compound obtained through the subsequent steps (AL ₁ ), and optionally a catalyst consisting of an electron donor (E ₁ ), propylene,
Alternatively, it is a method of polymerizing propylene and an α-olefin other than propylene.

The above methods (1) to (3) will be described in detail.

The method of (1), using the same catalyst as that used in the method of obtaining the specific silicon-containing polymer of (i) described above,
The specific silicon-containing monomer is polymerized under the same polymerization conditions as in (i), but the polymerization reaction amount of the specific silicon-containing monomer is 0.001 g to 100 g per 1 g of the titanium catalyst component. To Then, main polymerization of propylene is carried out.
Before that, α-olefin was added per 1 g of the titanium catalyst component.
After 0.1 g to 100 g of reaction and preliminary activation, propylene or propylene and an α-olefin other than propylene may be polymerized.

After the completion of the polymerization of the specific silicon-containing monomer or after the pre-activation with the α-olefin, the unreacted monomers and the like are washed away with an inert hydrocarbon solvent to further remove the organoaluminum compound and necessary components. After adding an electron donor according to the above, propylene, or propylene and an α-olefin other than propylene may be polymerized, or the reaction mixture after the reaction may be used as it is for propylene or propylene and an α-olefin other than propylene. It may be used for the polymerization of olefins.

Propylene, or α other than propylene and propylene
-Polymerization of olefins is carried out under known polymerization conditions, that is, a polymerization temperature of 20 ° C to 150 ° C and a polymerization pressure of atmospheric pressure to 50 kg / cm ² G under conditions of gas phase polymerization, bulk polymerization, slurry polymerization,
Polymerization may be carried out for 20 minutes to 20 hours using a method combining these.

Examples of each catalyst component and the specific silicon-containing monomer used in this method include the same ones as those used for obtaining the specific silicon-containing polymer of (i) described above.

Next, in the method of (2), the method is a titanium catalyst component used when polymerizing propylene or propylene and an α-olefin other than propylene. This is a method of using the titanium catalyst component obtained by adding the specific silicon-containing polymer obtained by the method of i).

Explaining specifically the method for producing such a titanium catalyst component, for example, a method of co-milling a specific silicon-containing polymer obtained by the method of titanium trichloride and (i) with an electron donor, if necessary, Alternatively, when titanium tetrachloride is reduced with an organoaluminum compound, a method of allowing the specific silicon-containing polymer obtained by the method (i) to coexist, or in the presence or absence of a carrier such as a magnesium compound and an electron donor The specific silicon-containing polymer obtained by the method (i) below is co-ground and then treated with titanium tetrachloride, or a liquefied magnesium compound is obtained by the specific method obtained by the method (i). Examples include a method in which a silicon-containing polymer is dispersed, then treated with a depositing agent such as a halogen compound, and then treated with an electron donor and titanium tetrachloride.

The amount of the specific silicon-containing polymer used here is in the range such that the polymer is 0.01% by weight to 50% by weight in the titanium catalyst component.

The polypropylene composition of the present invention comprises a titanium catalyst component obtained by the above method, an organoaluminum compound (AL ₁ ), and optionally a catalyst in which an electron donor (E ₁ ) is combined with propylene, or propylene. And an α-olefin other than propylene are polymerized.

Next, the method (3) will be described. The method, as a titanium catalyst component used when polymerizing propylene, or α-olefin other than propylene,
This is a method of using a titanium catalyst component obtained through a polymerization treatment under a polymerization condition using a specific silicon-containing monomer during the production of the titanium catalyst component, and the subsequent steps.

The method for producing such a titanium catalyst component will be specifically described in detail, for example, an organoaluminum compound (AL ₂ ) or an organoaluminum compound (AL ₂ ) and an electron donor (E ₂ )
The fixed product (II) obtained by reacting titanium tetrachloride with the reaction product (I) with is subjected to a polymerization treatment with a specific silicon-containing monomer, and further subjected to electron donation (E ₃ ) and electron acceptance. The titanium catalyst component is produced as the final solid product (III) obtained by reacting with the body. .

The above-mentioned organoaluminum compound (AL ₂ ) and electron donor (E ₂ )
The reaction with is carried out in a solvent (D ₁ ) at −20 ° C. to 200 ° C., preferably −10 ° C. to 100 ° C. for 30 seconds to 5 hours. The addition order of the organoaluminum compound (AL ₂ ), (E ₂ ), (D ₁ ) is not limited,
The amount ratio to be used is 0.1 mol to 8 mol of the electron donor (E ₂ ), preferably 1 to 1 mol of the organoaluminum compound (AL ₂ ).
4 mol, solvent 0.5 L to 5 L, preferably 0.5 L to 2 L. Thus, the reaction product (I) is obtained. The reaction product (I) can be used for the next reaction in a liquid state as it is after completion of the reaction (sometimes referred to as the reaction product liquid (I)) without separation.

The reaction product (I) and titanium tetrachloride or the solid product (II) obtained by reacting the organoaluminum compound (AL ₂ ) and titanium tetrachloride are polymerized with a specific silicon-containing monomer. The reaction product (I),
Alternatively, a method of polymerizing the solid product (II) by adding a specific silicon-containing monomer to the reaction mixture at any stage of the reaction between the organoaluminum compound (AL ₂ ) and titanium tetrachloride, the reaction product ( I) or the reaction of the organoaluminum compound (AL ₂ ) with titanium tetrachloride, and then adding a specific silicon-containing monomer to the reaction mixture to give a solid product (II)
And the reaction product (I) or the reaction between the organoaluminum compound (AL ₂ ) and titanium tetrachloride is completed, and the reaction mixture is filtered or decanted to separate and remove a liquid portion. There is a method of suspending the obtained solid product (II) in a solvent, further adding an organoaluminum compound and a specific silicon-containing monomer, and performing a polymerization treatment.

Reaction product (I) or organoaluminum compound (A
The reaction of L ₂ ) with titanium tetrachloride may be carried out with or without the addition of a particular silicon-containing monomer to the reaction mixture at any stage of the reaction, from −10 ° C. to 200 ° C., preferably 0 ° C. 100 ° C
5 minutes to 10 hours. Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The mixing of (I) or the organoaluminum compound (AL ₂ ), titanium tetrachloride, and the solvent may be performed in any order, and the addition of the specific silicon-containing monomer may be performed at any stage. (I) or organoaluminum compound (A
It is preferable that the mixing of all of L ₂ ), titanium tetrachloride, and the solvent be completed within 5 hours, and the reaction is performed during the mixing. It is preferable to continue the reaction within 5 hours after mixing the whole amount. The amount of each used in the reaction is 1 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the reaction product (I) or the Al in the organic aluminum compound (AL ₂ ) is used.
The ratio of the number of atoms to the number of Ti atoms in titanium tetrachloride (Al / Ti) is 0.
It is from 05 to 10, preferably from 0.06 to 0.3.

The polymerization treatment with the specific silicon-containing monomer is carried out when the specific silicon-containing monomer is added at any stage of the reaction between the reaction product (I) or the organoaluminum compound (AL ₂ ) and titanium tetrachloride, and When a specific silicon-containing monomer is added after the reaction of the reaction product (I) or the organoaluminum compound (AL ₂ ) with titanium tetrachloride, the reaction temperature is 0 ° C to 90 ° C for 1 minute to 10 hours. , Reaction pressure is atmospheric pressure ~ 10k
0.01 g per 100 g of solid product (II) under the condition of gf / cm ² G
Using g to 100 kg of the specific silicon-containing monomer, the content of the specific silicon-containing polymer in the final solid product (III), that is, the titanium catalyst component used in the present invention, is 0.01% to 99% by weight.
Polymerization is performed so that the weight% is reached.

After the reaction of the reaction product (I) or the organoaluminum compound (AL ₂ ) with titanium tetrachloride is completed by a polymerization treatment with a specific silicon-containing monomer, the liquid portion is separated and removed by filtration or decantation, When the obtained solid product (II) is suspended in a solvent, 100 ml-5,000 ml of solvent and 0.5 g-5,000 g of organoaluminum compound are added to 100 g of the solid product (II) at the reaction temperature. 0 ℃ ~ 90
0.01g to 100kg per 100g of solid product (II) under the condition of 1 minute to 10 hours at ℃, and reaction pressure from atmospheric pressure to 10kgf / cm ² G.
The specific silicon-containing monomer is used to polymerize the final solid product (III) so that the content of the specific silicon-containing polymer is 0.01% by weight to 99% by weight. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound is the one used for obtaining the reaction product (I), or the electron donor (E ₂ )
It may be the same as or different from the one used for the reaction with titanium tetrachloride directly without reacting with.
After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further repeating washing with a solvent, the obtained solid product subjected to polymerization treatment (hereinafter referred to as solid product (II-A) (May be said) may be used in the next step while being suspended in the solvent, or may be dried and taken out as a solid to be used.

The solid product (II-A) is then provided with an electron donor (E ₃ ).
React with the electron acceptor (F). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results. The amount used is (E ₃ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, (F) 0.1 g to 1,000 g, preferably 0.2 g, based on 100 g of the solid product (II-A).
˜500 g, solvent 0˜3,000 ml, preferably 100˜1,000 ml. As a reaction method, a solid product (II-A) is reacted with an electron donor (E ₃ ) and an electron acceptor (F) at the same time. After reacting (II-A) with (F), a method of reacting E _3), was reacted with (E ₃₎ to (II-a), (F )
The reaction of (E ₃ ) and (F), then (II
There is a method of reacting -A), but any method may be used.

The reaction conditions are 40 ° C to 2 ° C in the above method.
It is desirable to carry out the reaction at 00 ° C, preferably 50 ° C to 100 ° C for 30 seconds to 5 hours, and in the method of (II-A) and (E
_After reacting the reaction of ₃ ) at 0 ° C to 50 ° C for 1 minute to 3 hours,
(F) is reacted under the same conditions as above. In the other method, (E ₃ ) and (F) are heated at 10 ℃ ~ 100 ℃ for 30 minutes ~
After reacting for 2 hours, the mixture is cooled to 40 ° C. or lower, (II-A) is added, and then reacted under the same conditions as described above. After completion of the reaction of the solid products (II-A), (E ₃ ) and (F), the liquid portion is separated and removed by filtration or decantation, and the solid product (II
I), that is, the titanium catalyst component containing the specific silicon-containing polymer used in the present invention is obtained.

As the organoaluminum compound (AL ₂ ) used for the production of the titanium catalyst component, the same ones as (AL ₁ ) exemplified in the above-mentioned methods (i), (1) and (2) are used. The electron donor (E ₂₎ (E ₃₎ usable as also the description (E ₁₎
Although the same examples can be exemplified, ethers are mainly used as (E ₂ ) and (E ₃ ), and other electron donors are preferably shared with ethers. These electron donors can also be used as a mixture. Reaction with an electron donor (E ₂ ) to obtain a reaction product (I), a solid product (II-A) (E ₃ ).
May be the same or different.

The electron acceptor (F) reacted with the solid product (II-A) is
It is represented by halides of elements of groups III to VI of the periodic table. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like. These can also be used as a mixture. Most preferred is titanium tetrachloride.

The following are used as the solvent (D ₁ ). As the aliphatic hydrocarbon, n-pentane, n-hexane, n-heptane,
n-octane, i-octane, etc. are shown, and halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene, etc. may be used instead of or together with the aliphatic hydrocarbons. it can.

As an aromatic compound, an aromatic hydrocarbon such as naphthalene,
And its derivatives, mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene,
Alkyl-substituted compounds such as 1-phenylnaphthalene, halides such as monochlorobenzene, chlorotoluene, chlorxylene, chloroethylbenzene, dichlorobenzene and bromobenzene are shown.

The specific silicon-containing monomer used in the polymerization treatment may be the same as those used in the methods (i) and (1) described above.

In addition to the titanium catalyst component obtained as described above, for example, it is obtained by contacting a liquefied magnesium compound with a precipitating agent, a halogen compound, an electron donor (E ₄ ) and a titanium compound (T ₁ ). The solid product (IV) is polymerized with a specific silicon-containing monomer in the presence of the organoaluminum compound (AL ₃ ) to obtain a solid product (V), and the solid product (V) is halogenated. The solid product (IV) obtained by reacting the titanium oxide compound (T ₂ ) can be used as the titanium catalyst component. The method for producing the titanium catalyst component will be described below.

The term “liquefaction” of the magnesium compound as used in the present invention means that the magnesium compound itself becomes a liquid, the case where the magnesium compound itself is soluble in a solvent to form a solution, and the case where the magnesium compound reacts with other compounds. Alternatively, it also includes the case where a solution is formed by being solubilized in a solvent as a result of forming a complex. Further, the solution may be in the state of containing a colloidal or semi-dissolved substance in addition to the case of being completely dissolved.

The magnesium compound to be liquefied may be any as long as it can be in the above-mentioned "liquefied" state, for example, magnesium dihalide, alkoxy magnesium halide, aryloxy magnesium halide, dialkoxy magnesium, diaryloxy. In addition to magnesium, magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate, dialkyl magnesium, alkyl magnesium halide and the like, metal magnesium can also be used.

As a method of liquefying the magnesium compound, known means are used. For example, a magnesium compound is an alcohol,
Liquefaction with aldehydes, amines or carboxylic acids (JP-A-56-811), liquefaction with orthotitanate (JP-A-54-40293), liquefaction with phosphorus compounds In addition to the method (Japanese Patent Application Laid-Open No. 58-19307) and the like, a method in which these are combined is also included. In addition, it is not possible to apply the above method, for the organomagnesium compound having a C-Mg bond, since it is soluble in ether, dioxane, pyridine, etc., it is used as a solution of these, or by reacting with an organometallic compound, The general formula is M _p
Mg _q R ⁸ _r R ⁹ _s (M is aluminum, zinc, boron or beryllium atom, R ⁸ and R ⁹ are hydrocarbon residues, p, q, r, s> 0,
When v is the valence of M, there is a relation of r + s = vp + 2q. )
It is possible to form a complex compound represented by (JP-A-50-139885, etc.) and dissolve it in a hydrocarbon solvent to liquefy it.

Furthermore, in the case of using metallic magnesium, a method of liquefying with an alcohol and an orthotitanate ester (Japanese Patent Laid-Open No. 50-51587, etc.) or reacting with an alkyl halide in ether to form a so-called Grignard reagent It can be liquefied by the method.

Among the methods for liquefying a magnesium compound as described above, for example, the case of dissolving magnesium chloride in a hydrocarbon solvent (D ₂ ) using a titanate ester and an alcohol will be described. Using 0.1 mol to 2 mol of titanic acid ester, 0.1 mol to 5 mol of alcohol, and 0.1 to 5 of solvent (D ₂ ),
The components are mixed in any order of addition and the suspension is heated with stirring at 40 ° C to 200 ° C, preferably 50 ° C to 150 ° C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to 5 hours. Examples of the titanic acid ester include an orthotitanic acid ester represented by Ti (OR ¹⁰ ) ₄ and a polytitanic acid ester represented by R ¹¹ [O-Ti (OR ¹² ) (OR ¹³ )] _t -OR ¹⁴ . Where R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ are alkyl groups having 1 to 20 carbon atoms or cycloalkyl groups having 3 to 20 carbon atoms, and t is a number of 2 to 20.

Specifically, methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, i-propyl orthotitanate, n-butyl orthotitanate, i-butyl orthotitanate, n-amyl orthotitanate, Orthotitanate such as 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, polytitanate
It is possible to use polytitanate such as i-propyl, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate and cyclohexyl polytitanate. it can. The polytitanate ester may be used in an amount equivalent to orthotitanate in terms of orthotitanate.

Aliphatic saturated and unsaturated alcohols can be used as alcohols. Specifically, methanol, ethanol, n-propanol, i-propanol, n-butanol, n-amyl alcohol, i-amyl alcohol, n-haisanol, n-octanol, 2-ethylhexanol,
In addition to monohydric alcohols such as and allyl alcohol, polyhydric alcohols such as ethylene glycol, trimethylene glycol and glycerin can also be used. Of these, aliphatic saturated alcohols having 4 to 10 carbon atoms are preferable.

As the inert hydrocarbon solvent (D ₂ ), those similar to the solvent (D ₁ ) used in the production of the titanium catalyst component can be used, and among them, aliphatic hydrocarbons are preferable.

The solid product (IV) is obtained by contacting the above liquefied magnesium compound with the precipitating agent (X ₁ ), halogen or halogen compound (X ₂ ), electron donor (E ₄ ) and titanium compound (T ₁ ). To be As the depositing agent (X ₁ ), halogen,
Examples of the halogenating agent include halogenated hydrocarbons, halogen-containing silicon compounds, halogen-containing aluminum compounds, halogen-containing titanium compounds, halogen-containing zirconium compounds and halogen-containing vanadium compounds. When the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen,
For example, alcohol, polysiloxane having a Si—H bond, or the like can be used. The amount of these precipitation agents (X ₁ ) used is 0.1 mol to 50 mol per 1 mol of the magnesium compound. In addition, halogen or halogen compound (X ₂ )
Examples of the halogenating agent include halogens and compounds containing halogen, and the same halogenating agents as examples of the precipitating agent can be used. It does not necessarily require a new use of a halogen compound (X ₂ ). The halogen or halogen compound (X ₂ ) is used in an amount of 0.1 to 50 mol based on 1 mol of the magnesium compound.

As the electron donor (E ₄ ), the above-mentioned (E ₂ ) and (E ₃ )
The same thing as is used, preferably, aromatic monocarboxylic acid esters, aromatic polycarboxylic acid esters,
Alkoxysilanes, particularly preferably aromatic polycarboxylic acid esters are used. One or more kinds of these electron donors (E ₄ ) are used, and the amount thereof is 0.01 mol to 5 mol per 1 mol of the magnesium compound.

Titanium compound (T ₁ ) required for the preparation of solid product (IV)
Is the general formula Ti (OR ¹⁵ ) _4-u X _u (wherein R ¹⁵ is an alkyl group,
A cycloalkyl group or an aryl group, X represents halogen, and u is any number of 0 <u ≦ 4. The titanium halide compound represented by the formula (1) or the orthotitanate ester or polytitanate ester mentioned in the liquefaction of the magnesium compound is used.

Specific examples of the titanium halide compound, titanium tetrachloride, titanium tetrabromide, methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, butoxy titanium trichloride, phenoxy titanium trichloride, ethoxy titanium tribromide, Butoxy titanium tribromide, dimethoxy titanium dichloride,
Diethoxy titanium dichloride, dipropoxy titanium dichloride,
Dibutoxy titanium dichloride, diphenoxy titanium dichloride,
Examples thereof include diethoxytitanium dibromide, dibutoxytitanium dibromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, and triphenoxytitanium chloride. Examples of the orthotitanate and polytitanate include the same ones as described above.

One or more of these titanium compounds (T ₁ ) are used,
Titanium compound (When a halogenated titanium compound is used as T _1, it has halogen so that the use of the depositing agent (X ₁ ) and the halogen or the halogen compound (X ₂ ) is optional. Even when a titanate ester is used for liquefying the compound, the titanium compound (T ₁ ) may be newly used, and the amount of the titanium compound (T ₁ ) to be used is 1 mol of the magnesium compound.
It is 0.1 to 100 mol.

Liquefied magnesium compound, precipitation agent (X ₁ ),
A halogen or a halogen compound (X ₂ ), an electron donor (E ₄ ) and a titanium compound (T ₁ ) are contacted with stirring to obtain a solid product (IV). At the time of contact, an inert hydrocarbon solvent (D ₃ ) may be used, or each component may be diluted in advance and used. Inert hydrocarbon solvent used (D ₃ )
As the above, the same as the above-mentioned (D ₂ ) can be exemplified. The usage amount is 0 to 5,000 ml per mol of the magnesium compound.
Is.

There are various contact methods, for example,
(X ₁ ) is added to a liquefied magnesium compound to precipitate a solid, and (X ₂ ), (E ₄ ), and (T ₁ ) are brought into contact with the solid in any order. A method in which (X ₁ ) is added to a solution in which a liquefied magnesium compound and (E ₄ ) are brought into contact with each other to precipitate a solid, and (X ₂ ) and (T ₁ ) are brought into contact with the solid in any order. After contacting the liquefied magnesium compound with (T ₁ ), (X ₁ ) is added, and then (E ₄ ) and (X ₂ ) are contacted in any order.

The amount of each component used is within the above range, but these components may be used at one time or may be divided into several stages and used. Also, as already mentioned, if one component has an atom or group that also characterizes the other component, a new use of the other component is not necessary. For example, when a titanate ester is used for liquefying a magnesium compound (T ₁ ), when a halogen-containing titanium compound is used as a depositing agent (X ₁ ), (X ₂ ) and (T ₁ ).
However, when a halogenating agent is used as the precipitating agent (X ₁ ), (X
₂ ) are optional components.

The contact temperature of each component is −40 ° C. to + 180 ° C., preferably −
20 ℃ ~ +150 ℃, contact time is atmospheric pressure ~
5 minutes to 8 hours per step at 10 kg / cm ² G, preferably 10
Minutes to 6 hours.

A solid product (IV) is obtained in the above catalytic reaction.
The solid product (IV) may be subsequently reacted in the next step, but it is preferably washed with the above-mentioned inert hydrocarbon solvent.

Next, the solid product (IV) obtained by the above method is subjected to a polymerization treatment with a specific silicon-containing monomer in the presence of the organoaluminum compound (AL ₃ ) to obtain a solid product (V).

The polymerization treatment with a certain amount of silicon-containing monomer is performed by adding 100 ml of an inert hydrocarbon solvent (D ₄ ) to 100 g of the solid product (IV).
5,000 ml, 0.5 g to 5,000 g of organoaluminum compound (AL ₃ ) are added, the reaction temperature is 0 ° C to 90 ° C for 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 10 kg / cm ² g under specific conditions. Add 0.01 g to 100 kg of silicon-containing monomer to obtain solid product (IV)
That is, the polymerization is performed such that the content of the specific silicon-containing polymer in the final titanium catalyst component is 0.01% by weight to 99% by weight.

Further, in the polymerization treatment stage, electrons represented by carboxylic acid esters such as ethyl benzoate, methyl toluate and ethyl anisate, and organosilicon compounds such as phenyltriethoxysilane, diphenyldimethoxysilane and methyltriethoxysilane. It is also possible for the donor to coexist. Their use amount is 0 to 5,000 g per 100 g of the solid product (IV).

The solvent (D ₄ ) of the organoaluminum compound (AL ₃ ) and the specific silicon-containing monomer used in the polymerization treatment are the above-mentioned (AL ₂ ) and (D ₂ ) and the specific silicon-containing monomer, respectively. The same as is used.

As described above, the polymerization treatment with the specific silicon-containing monomer is performed, and the solid product (V) is obtained by washing with the above-mentioned inert hydrocarbon solvent.

Subsequently, the solid product (V) is reacted with a titanium halide compound (T ₂ ) to obtain a target titanium catalyst component.
As the titanium halide compound (T ₂ ), the general formula Ti (OR ¹⁵ ) _4-u X _u (given as an example of the titanium compound (T ₁ ) necessary for preparing the solid product (IV) described above is used. In the formula, R ¹⁵ is an alkyl group, a cycloalkyl group, or an aryl group, X is a halogen, and u is an arbitrary number of 0 <u ≦ 4). Although similar examples can be given as specific examples, titanium tetrachloride is most preferable.

The reaction of the solid product (V) and titanium halide compound (T _2), relative to the magnesium compound 1 mol in the solid product (V), using a titanium halide compound (T ₂₎ 1 mole or more The reaction temperature is 20 ° C. to 200 ° C. and the reaction pressure is atmospheric pressure to 10 kg / cm ² G for 5 minutes to 6 hours, preferably 10 minutes to 5 hours. The reaction can also be carried out in the presence of an inert hydrocarbon solvent (D ₅ ) or an electron donor (E ₅ ), and specifically, the above-mentioned (D ₁ ) to (D ₄ ) and An inert solvent similar to (E ₄ ) or an electron donor is used. The amount of these used is 100 g in the solid product (V)
(D ₅ ) is preferably 0 to 5,000 ml, and (E ₅ ) is preferably 0 to 2 mol per 1 mol of the magnesium compound in the solid product (V). After the reaction of the solid product (V) with the titanium halide compound (T ₂ ) and, if necessary, an electron donor, the solid is separated by filtration or decantation and washed with an inert hydrocarbon solvent. The reaction product or by-product is removed to obtain the solid product (VI), that is, the titanium catalyst component used in the present invention.

As described above, the titanium catalyst component obtained by the polymerization treatment with the specific silicon-containing monomer during the production can be used in the same manner as the known titanium catalyst component for α-olefin polymerization such as propylene.

That is, the titanium catalyst component was replaced with an organoaluminum compound (A
L ₄ ), and optionally a catalyst in combination with an electron donor (E ₆ ) or as a catalyst pre-activated by further polymerizing a small amount of α-olefin, and the known propylene polymerization method described above. By the same polymerization method, propylene, or propylene and an α-olefin other than propylene are polymerized to obtain polypropylene containing a specific silicon-containing polymer.

Organoaluminum compound (AL ₄ ) and electron donor (E ₆ ).
Examples of (AL ₁ ) and (E ₁ ) are the same as those mentioned above, and the amounts used are also the same.

In addition, pre-activation and α- used with propylene
As olefins, in addition to propylene, linear olefins such as ethylene, butene-1, hexene-1, and octene-1, branched chain olefins such as 2-methylpentene-1, 5-methylhexene-1 and the like Can be given.

The thus-obtained specific silicon-containing polymer (B) or polypropylene containing the specific silicon-containing polymer is mixed with (A) a known polypropylene to obtain the polypropylene composition of the present invention.

Regarding the mixing ratio, it is added so that the content of the specific silicon-containing polymer becomes 0.1 wtppm to 2 wt% with respect to the entire composition. The content of the specific silicon-containing polymer is 0.1% by weight.
If it is less than ppm, the effect of improving the transparency and crystallinity of the obtained composition is insufficient, and if it exceeds 2% by weight, the effect is not significantly improved and it is not economical.

In producing the composition of the present invention, the above (A) and
It is sufficient to mix a predetermined amount of the component (B) and then sufficiently knead. As a mixing device, a high-speed stirring device such as a Henschel mixer (trade name) or a super mixer may be used, and as a kneading device, a Banbury mixer, roll, cokneader, single-screw or twin-screw extruder, etc. may be used. . The mixing conditions are not limited, but are room temperature to 100 ° C., preferably room temperature to 60 ° C., for 1 minute to 1 hour, preferably 3 minutes to 30 minutes. The kneading conditions are also not limited, but the residence time in the extruder is 10 seconds to 5 minutes, preferably 20 seconds to
2 minutes. The kneading temperature is 180 to 300 ° C, preferably 200 to 280 ° C.

After kneading, it is desirable to cool and cut and use as a pelletized composition.

In the composition of the present invention, various additives which are usually added to polypropylene as required, for example, an antioxidant, an antistatic agent, an ultraviolet absorber, a copper damage inhibitor, a flame retardant, a pigment, etc. may be used in combination. You can Further, the composition of the present invention may contain a polymer such as polyethylene, polybutene, ethylene-propylene rubber and the like, and an optional filler as long as the object of the present invention is not significantly impaired. Examples of the filler include inorganic or organic fillers such as glass fiber, talc, mica, wood powder and synthetic fiber.

The polypropylene composition of the present invention thus obtained is used for injection-molded articles, non-stretched films, stretched films, sheets and other molded articles by known molding techniques such as injection molding, vacuum molding, extrusion molding, blow molding and stretching. Be used for.

[Operation] Since the polypropylene resin composition of the present invention contains a specific silicon-containing polymer having high stereoregularity dispersed therein, the specific silicon-containing polymer exhibits a nucleating action during melt molding. This reduces the spherulite size of polypropylene and promotes crystallization, resulting in an increase in the transparency and crystallinity of the entire polypropylene composition.

Further, since the specific silicon-containing polymer introduced by the method of the present invention is a stereoregular high molecular weight polymer as described above, it does not bleed on the surface.

[Examples] Hereinafter, the present invention will be described with reference to Examples. The definitions of terms used in Examples and Comparative Examples and the measuring methods are as follows.

MFR: Melt flow index According to ASTM D-1238 (L). (Unit: g / 10 minutes) Crystallization temperature: Measured at a temperature decreasing rate of 10 ° C./minute using a differential scanning calorimeter. (Unit: ° C) Flexural modulus: The flexural modulus was measured according to JIS K7203. (Unit: kgf / cm ² ) Transparency: Four films were stacked and haze was measured according to JIS K6714. (Unit:%) Permeability: Shown as LS value (narrow-angle diffuse transmission value) measured using "visual transparency tester" manufactured by Toyo Seiki Seisakusho. (Unit:%) In addition, the lower the haze value and the LS value, the more excellent the transparency and the transparent feeling.

Example 1 (1) Production of specific silicon-containing polymer-containing polypropylene Preparation of titanium catalyst component n-hexane 6, diethylaluminum monochloride
(DEAC) 5.0 mol, diisoaluminum ether 12.0 mol at 25 ° C
At room temperature for 15 minutes and reacted at the same temperature for 15 minutes to obtain a reaction product liquid (I) (diisoamyl ether / DEAC molar ratio 2.4). Put 40 moles of titanium tetrachloride in a reactor purged with nitrogen, heat to 35 ° C, drop the whole amount of the above reaction product solution (I) into the reactor in 180 minutes, and then keep at the same temperature for 60 minutes, then to 80 ° C. The temperature was raised and the reaction was allowed to proceed for another 1 hour, the mixture was cooled to room temperature, the supernatant was removed, and n-hexane 20 was added and the operation of removing the supernatant by decantation was repeated 4 times to obtain a solid product (II).
The whole amount of this (II) was suspended in n-hexane 30, 400 g of diethylaluminum monochloride was added, 15 kg of dimethyldiallylsilane was added at 40 ° C., and a polymerization treatment was carried out at 40 ° C. for 2 hours. After the treatment, the temperature was raised to 50 ° C., the supernatant was removed, n-hexane 30 was added, and the supernatant was removed by decantation was repeated 4 times to obtain a solid product (II
-A) was obtained. The total amount of this solid product was n-hexane 9
In the suspended state, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes and reacted at 80 ° C for 30 minutes, then 1.6 kg of diisoamyl ether was further added and reacted at 80 ° C for 1 hour. Let After the completion of the reaction, the operation of removing the supernatant was repeated 5 times and then dried under reduced pressure to obtain a solid product (III), which was used as a titanium catalyst component for the present invention. The content of the crystalline dimethylalkyldiallylsilane polymer in the titanium catalyst component was 50.0% by weight, and the titanium content was 12.6% by weight.

Preparation of pre-activated catalyst After replacing the stainless reactor with an inclined blade with an internal volume of 80 with nitrogen gas, n-hexane 40, diethylaluminium monochloride 28.5g, obtained in (1), the titanium catalyst component
After adding 450 g at room temperature, add ethylene at 30 ° C for 2 hours.
After supplying 0.9 Nm ³ and reacting it (reaction of ethylene 2.0 g per 1 g of titanium catalyst component), unreacted ethylene was removed,
After washing with n-hexane, it was dried to obtain a preactivated catalyst.

Polymerization of Propylene After adding 20 kg of polypropylene powder of MFR 2.0 to a horizontal polymerization vessel of L / D = 3 equipped with a stirrer with an internal volume of 80 and substituted with nitrogen, n- was added to the pre-activated catalyst obtained in (2) above. Hexane was added to obtain a 4.0 wt% n-hexane suspension, and the suspension was continuously converted into 6.3 mg atom / hr in terms of titanium atom and 3.8 g / hr of diethylaluminum monochloride continuously from the same pipe. Supplied.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 1.0% by volume, and propylene was supplied so that the total pressure was 23 kg / cm ² G, and the gas phase polymerization of propylene was carried out at 70 ° C for 120 hours. It went continuously. During the polymerization period, the polymer was continuously extracted from the polymerization vessel at 10 kg / hr so that the level of the retained polymer in the polymerization vessel was 50% by volume. The extracted polymer was subsequently subjected to contact treatment with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C for 15 minutes, and then MFR containing 120 ppm by weight of crystalline dimethyldiallylsilane polymer.
Obtained as a polypropylene (B) of 8.

(2) Production of polypropylene composition 5.0 kg of polypropylene (B) containing the crystalline dimethyldiallylsilane polymer obtained in (1) in a Henschel mixer (trade name) with an internal volume of 50, titanium in the above (1) Using a titanium catalyst component obtained by omitting the step of polymerizing treatment with dimethyldiallylsilane in producing the catalyst component, and subsequently obtained in the same manner as in (1) above, containing a crystalline dimethyldiallylsilane polymer. Not MFR 1.8 Normal Polypropylene
(A) 0.5 kg, tetrakis [methylene-3- (3 ', 5'-di-t-
Butyl-4'-hydroxyphenyl) propionate] methane (5 g) and calcium stearate (5 g) were added and the mixture was stirred and mixed for 5 minutes. Subsequently, using a single-screw extruder having an inner diameter of 40 mm, the mixture was extruded at a melt-kneading temperature of 230 ° C., cooled with water, and cut to obtain a polypropylene composition in the form of pellets.

(3) Manufacture of molded product The composition obtained in (2) was melted at a resin temperature of 230 ° C using an injection molding machine.
A JIS type test piece was injection molded at a mold temperature of 50 ° C.
The test piece has a humidity of 50% and a room temperature of 23 ° C.
After leaving it for an hour, the flexural modulus was measured to be 14,300 kg.
It was f / cm ² . Further, the composition obtained in (2) was extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine, and a sheet having a thickness of 1 mm was prepared with a cooling roll at 20 ° C. 150 ℃
Was heated with hot air for 70 seconds and stretched 7 times in both the longitudinal and transverse directions using a biaxial stretching machine to obtain a biaxially stretched film having a thickness of 20 μm.

COMPARATIVE EXAMPLE 1 (2) of Example 1 was obtained by using a titanium catalyst component not polymerized with dimethyldiallylsilane without using the polypropylene (B) containing the crystalline dimethyldiallylsilane polymer. Polypropylene (A) 10kg
A composition was obtained in the same manner except that was used. A molded product was produced from the obtained composition in the same manner as in Example 1 (3).

Comparative Example 2 and Examples 2 and 3 In Example 1 (2), the mixing ratio of the polypropylene (B) containing the crystalline dimethyldiallylsilane polymer and the normal polypropylene (A) was changed to obtain crystalline dimethyldiylsilane. A composition was obtained in the same manner except that the allylsilane polymer content was as shown in the table below, and thereafter a molded article was obtained in the same manner as in (3) of Example 1.

Example 4 (1) Decane 3, anhydrous magnesium chloride 480 g, orthotitanic acid n- in a stainless steel reactor equipped with a stirrer
1.7 kg of butyl and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated at 130 ° C. for 1 hour with stirring to dissolve them to obtain a uniform solution. The homogeneous solution was heated to 70 ° C., 180 g of diisobutyl phthalate was added with stirring, and after 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid,
It was further heated to 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (IV).

450 g of triethylaluminum and 145 g of diphenyldimethoxysilane in which the total amount of the solid product (IV) was kept at 30 ° C.
After suspending it in hexane 10 containing dimethyl ether, 2.9 kg of dimethyldiallylsilane was added, and the mixture was stirred at the same temperature for 2 minutes.
Polymerization was performed for a time. After the treatment, the operation of removing the supernatant liquid, adding n-hexane 6 and removing the supernatant liquid by decantation was repeated 4 times to obtain a polymerized solid product (V).

The whole amount of the solid product (V) was mixed with titanium tetrachloride 5 dissolved in 1,2-dichloroethane 5, then 180 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring, The liquid phase was removed by decantation at the same temperature, 1,2-dichloroethane 5 and titanium tetrachloride 5 were added again, and the mixture was stirred at 100 ° C for 2 hours, washed with hexane and dried to obtain a solid product (VI). Obtained and used as the titanium catalyst component used in the present invention. The titanium catalyst component had a particle shape close to a sphere, and contained 1.5% by weight of titanium and 50.0% by weight of a crystalline dimethyldiallylsilane polymer.

After replacing a stainless steel reactor with an inclined blade with an internal volume of 30 with nitrogen gas, n-hexane 20, 1.5 kg of triethylaluminum, 480 g of diphenyldimethoxysilane and 200 g of the titanium catalyst component obtained from the above were added at room temperature. Reactor
Hold ethylene at 30 ℃ and keep ethylene at 18 ℃ for 2 hours.
After supplying 0 N and reacting (1.0 g of ethylene per 1 g of titanium catalyst component reaction), unreacted ethylene was removed to obtain a preactivated catalyst.

20 kg of polypropylene powder of MFR2.0 was charged into the polymerization vessel used in (1) of Example 1, and the pre-activated catalyst slurry (containing triethylaluminum and diphenyldimethoxysilane in addition to the titanium catalyst component) was added to titanium atom. It was continuously supplied at a rate of 0.285 mg atom / hr. Also, hydrogen was supplied so that the concentration in the gas phase was maintained at 0.15% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G, and the gas phase polymerization of propylene was continuously performed at 70 ° C for 120 hours. went. During the polymerization period, the polymer was continuously withdrawn from the polymerization vessel at 10 kg / hr so that the level of the retained polymer in the polymerization vessel was 60% by volume. The extracted polymer was then treated in the same manner as in (1) of Example 1 to obtain MF containing 46 wt ppm of crystalline dimethyldiallylsilane polymer.
Obtained as R 2.0 polypropylene (B).

(2) In (2) of Example 1, 5.0 kg of polypropylene (B) containing the crystalline dimethyldiallylsilane polymer obtained in (1) above as polypropylene (B), and ordinary polypropylene (A) As the above, using a titanium catalyst component obtained in the same manner except that the step of polymerizing with dimethyldiallylsilane in the above (1) is omitted,
A polypropylene composition was obtained in the same manner except that 5.0 kg of a polypropylene containing no crystalline dimethyldiallylsilane polymer obtained in the same manner as in (1) was used.

(3) A molded article was obtained in the same manner as in Example 1 (3) except that the polypropylene composition obtained in (2) above was used as the polypropylene composition.

Comparative Example 3 In the same manner as in Example 2 (2), a polypropylene catalyst (B) containing a crystalline dimethyldiallylsilane polymer was not used, but a titanium catalyst component not polymerized with dimethyldiallylsilane was used. Polypropylene (A) 10kg
A composition was obtained in the same manner except that was used. A molded product was produced from the obtained composition in the same manner as in Example 4 (3).

Example 5 (1) n-heptane 4, diethylaluminum monochloride 5.0 mol, diisoamyl ether 9.0 mol, di n-
The reaction solution obtained by reacting 5.0 moles of butyl ether at 18 ° C for 30 minutes was added dropwise to 27.5 moles of titanium tetrachloride at 40 ° C over 300 minutes, and after keeping the same temperature for 1.5 hours to react,
The temperature was raised to 65 ° C and the reaction was carried out for 1 hour. The operation of removing the supernatant liquid, adding n-hexane 20 and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (II) was added to n-hexane 7
The mixture was suspended in the mixture, 1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added, and the mixture was reacted at 60 ° C for 3 hours. After the reaction was completed, the supernatant was removed by decantation, 20 n-hexane was added, and the mixture was stirred for 5 minutes, allowed to stand and the supernatant was removed 3 times. A catalyst component was obtained.

After replacing the stainless steel reactor with an inclined blade with an internal volume of 80 with nitrogen gas, n-hexane 40, diethylaluminum monochloride 200g, titanium catalyst component 450g obtained with
Was added at room temperature, the temperature in the reactor was adjusted to 40 ° C, 4.3 kg of dimethyldiallylsilane was added, and the reaction was carried out at 40 ° C for 2 hours (per 1 g of titanium catalyst component, dimethyldiallylsilane).
1.2g reaction). After completion of the reaction, unreacted dimethyldiallylsilane, solvent and the like were removed by filtration, washed with n-hexane and dried to obtain a preactivated catalyst in the form of powder.

After replacing the stainless steel reactor with a stirrer with an internal volume of 500 with nitrogen gas, at room temperature n-hexane 200, diethylaluminum monochloride 96 g, the preactivated catalyst obtained as a titanium catalyst component 10 g, and hydrogen 100N
Was added. Then, the polymerization temperature was 70 ° C and the propylene partial pressure was 10
Propylene was supplied so that the concentration was kg / cm ² G, and ethylene was supplied so that the concentration in the gas phase of the polymerization vessel was kept at 0.2% by volume, and propylene-ethylene copolymerization was carried out for 2 hours and 30 minutes.

After completion of the reaction, add 1.0 kg of methanol to carry out the catalyst deactivation reaction.
After 30 minutes at 70 ° C., it was cooled to room temperature and the obtained polymer was dried. Since the dried polymer contained lumps, it was crushed to powder the whole amount of the polymer,
A MFR1.7 propylene-ethylene copolymer containing 273 ppm by weight of a crystalline dimethyldiallylsilane polymer was obtained.

(2) As polypropylene (B) in (2) of Example 1, 3.0 k of propylene-ethylene copolymer containing the crystalline dimethyldiallylsilane polymer obtained in (1) above was used.
g, as a normal polypropylene (A), without carrying out the preactivation reaction with dimethyldiallylsilane in the above (1), the titanium catalyst component obtained in was used as a preactivation catalyst equivalent, and A polypropylene composition was obtained in the same manner except that 7.0 kg of a MFR 1.9 propylene-ethylene copolymer containing no crystalline dimethyldiallylsilane polymer obtained in the same manner as 1) was used.

(3) A molded article was obtained in the same manner as in (3) of Example 1, except that the polypropylene composition obtained in (2) above was used as the polypropylene composition.

Comparative Example 4 Obtained by using the titanium catalyst component which does not carry out the preactivation reaction with dimethyldiallylsilane without using the propylene-ethylene copolymer containing the crystalline dimethyldiallylsilane polymer in (2) of Example 5. A composition was obtained in the same manner except that 10 kg of the obtained propylene-ethylene copolymer containing no crystalline dimethyldiallylsilane polymer was used. A molded product was obtained from the obtained composition in the same manner as in Example 5 (3).

Example 6 (1) Production of Specific Silicon-Containing Polymer After replacing a stainless reactor with an inclined blade with an internal volume of 100 with nitrogen gas, n-hexane 40, 320 g of diethylaluminum monochloride 320 g, (1 of Example 1) After adding 500 g of a titanium catalyst component obtained in the same manner at room temperature except that the step of polymerizing with dimethyldiallylsilane was omitted, 10 kg of dimethyldiallylsilane was further added. Then, the temperature in the reactor was set to 50 ° C., and polymerization was carried out at the same temperature for 2 hours. After completion of the polymerization, 10 kg of methanol was added, and the mixture was treated at 60 ° C for 1 hour. Subsequently, the solvent and the like were filtered off and the polymer was dried. The dried polymer was then ground in a vibration mill for 5 hours to obtain a powdery crystalline dimethyldiallylsilane polymer.

(2) Production of polypropylene composition (1) crystalline dimethyldiallylsilane polymer obtained in 1.
0 g was dissolved in cyclohexene 1 and the solution was used as Comparative Example 1.
A uniform polypropylene powder of the same MFR 1.8 used in 10 kg was uniformly mixed. Subsequently, the mixture was dried under reduced pressure at 90 ° C. to remove cyclohexene, and then a stabilizer was added and mixed and melt-kneaded in the same manner as in (2) of Example 1 to obtain a composition.

(3) Manufacture of molded product Example 1 using the polypropylene composition obtained in (2)
A molded product was manufactured in the same manner as in (3).

Example 7 (1) Crystalline p-trimethylsilylstyrene obtained by polymerizing n-hexane 12 using p-trimethylsilylstyrene instead of dimethyldiallylsilane in the same manner as in (6) of Example 6 separately. 2.2 kg of polymer powder was suspended. Then, after adding 27.0 mol of titanium tetrachloride and cooling to 1 ° C,
Further, n-hexane 12.5 containing 27.0 mol of diethylaluminum monochloride was added dropwise at 1 ° C over 4 hours.
After completion of dropping, the reaction was carried out at the same temperature for 15 minutes, followed by raising the temperature to 65 ° C. over 1 hour, and further reacting at the same temperature for 1 hour. Next, the procedure of removing the supernatant liquid, adding n-hexane 10 and removing by decantation was repeated 5 times, and 2.5 kg of the obtained fixed product (II) of 7.9 kg was suspended in n-hexane 11. , To which was added diisoamyl ether 1.6. After stirring this suspension at 35 ° C for 1 hour, n-hexane 3 was added.
It was washed 5 times with to obtain a treated solid.

The treated solid obtained was suspended in n-hexane solution 6 containing 40% by volume of titanium tetrachloride. This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After completion of the reaction, n-hexane 20 was used once to wash the solid obtained three times, and then dried under reduced pressure to obtain a titanium catalyst component. Using the titanium catalyst component, crystalline p-
Contains 67 wtppm of trimethylsilylstyrene polymer
A polypropylene (B) with MFR 1.6 was obtained.

(2) A polypropylene composition was obtained in the same manner as in (2) of Example 1 except that 5.0 kg of the polypropylene obtained in (1) above was used as the polypropylene (B) containing the specific silicon-containing polymer. .

(3) Using the polypropylene composition obtained in (2) above, a molded article was produced in the same manner as in (3) of Example 1.

The special points and evaluation results of molded articles of the polypropylene compositions of Examples and Comparative Examples prepared as described above are shown in the table.

[Effect of the Invention] The composition of the present invention and a molded article produced using the composition are remarkably excellent in transparency and crystallinity.

As is clear from the above-mentioned examples, the four-sheet haze value of the stretched film obtained by using the composition of the present invention is 1.6% to
It is 4.1% and has a remarkably high transparency as compared with a stretched film using a normal polypropylene containing no specific silicon-containing polymer.

Further, the crystallinity is improved together with the transparency, and the crystallization temperature of the polypropylene composition is increased and the bending elastic modulus of the injection-molded test piece is improved.

Claims (10)

[Claims] 1. A polypropylene composition comprising polypropylene containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer in an amount of 0.1% by weight to 2% by weight so that the total amount is 100% by weight. 2. A catalyst comprising (A) polypropylene, (B) titanium catalyst component, organoaluminum compound (AL ₁ ), and, if necessary, an electron donor (ε ₁ ), dialkyldiallylsilane and / or Or a crystalline dialkyldiallylsilane polymer obtained by polymerizing trialkylsilylstyrene, and / or
Alternatively, the crystalline dialkyldiallylsilane polymer and / or the crystalline trialkylsilylstyrene polymer is mixed with the crystalline trialkylsilylstyrene polymer so that the composition contains 0.1% by weight to 2% by weight of the composition. A method for producing a polypropylene composition, comprising: 3. A dialkyldiallyl silane and / or a catalyst comprising (A) polypropylene, (B) a titanium catalyst component, an organoaluminum compound (AL ₁ ) and, if necessary, an electron donor (ε ₁ ). Alternatively, a crystalline dialkyldiallylsilane polymer and / or a polymer obtained by polymerizing a trialkylsilylstyrene and subsequently mixing propylene or polypropylene obtained by polymerizing propylene and an α-olefin other than propylene in multiple stages, and / or A process for producing a polypropylene composition, characterized in that the composition contains a crystalline trialkylsilylstyrene polymer in an amount of 0.1 wt ppm to 2 wt%. 4. A titanium catalyst component containing (A) polypropylene and (B) a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, an organoaluminum compound (AL ₁ ), and if necessary. Accordingly, a crystalline dialkyldiallylsilane polymer is prepared by mixing propylene or polypropylene obtained by polymerizing propylene with an α-olefin other than propylene using a catalyst composed of an electron donor (ε ₁ ). And / or a crystalline trialkylsilylstyrene polymer is contained in the composition in an amount of 0.1 ppm by weight to 2% by weight, which is a method for producing a polypropylene composition. 5. As a titanium catalyst component containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, a dialkyldiallylsilane and / or trialkylsilylstyrene is separately added during the production of the titanium catalyst component. Claims 1. Using a titanium catalyst component obtained by adding a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer obtained by polymerizing The method according to item 4. 6. A titanium catalyst component containing a crystalline dialkyldiallylsilane polymer and / or a crystalline trialkylsilylstyrene polymer, which is used during the production of the titanium catalyst component under the polymerization conditions under dialkyldiallylsilane and / or The production method according to claim 4, wherein the titanium catalyst component in the process of production is subjected to a polymerization treatment using trialkylsilylstyrene, and the titanium catalyst component obtained through a subsequent step is further used. 7. A molded article comprising the polypropylene composition according to claim 1. 8. The molded product according to claim 7, wherein the molded product is an injection molded product. 9. The molded product according to claim 7, wherein the molded product is a stretched film. 10. The molded product according to claim 7, wherein the molded product is a sheet.