JP2562947B2 - Polypropylene resin composition, its production method and use - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polypropylene resin composition. More specifically, the present invention relates to a highly crystalline polypropylene resin composition having excellent transparency, which contains a crystalline dimethylstyrene polymer, a method for producing the same, and uses thereof.

[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 application field, and improvement of transparency has been desired.

Therefore, attempts have been made to improve the transparency of polypropylene. For example, aluminum salts of aromatic carboxylic acids (Japanese Patent Publication No. 40-1652) and benzylidene sorbitol derivatives (Japanese Patent Publication No. 51-22740). 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 was seen in transparency, there were problems such as strong odor during processing and bleeding of the additive (embossing).

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

As a result, the polypropylene resin composition containing a crystalline dimethylstyrene polymer, transparency and significantly improved in crystallinity as compared with conventional polypropylene, and also the problems such as odor and bleeding during molding. The present invention has been completed by knowing that it will be solved.

An object of the present invention is to provide a polypropylene resin composition excellent in transparency and crystallinity which does not generate odor or bleed during molding, a method for producing the same, and a use thereof.

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

(1) Crystalline dimethylstyrene polymer 0.1 wtppm to 2 wt% is included in polypropylene to make the total amount 100 wt%
The polypropylene resin composition as described above.

(2) The crystalline dimethylstyrene polymer is a crystalline 2,4-dimethylstyrene polymer, a crystalline 2,5-dimethylstyrene polymer, a crystalline 3,4-dimethylstyrene polymer, and a crystalline 3,5- 1 selected from dimethyl styrene polymers
Said first being one or more crystalline dimethylstyrene polymers
The composition according to Item.

(3) Crystallinity obtained by polymerizing dimethylstyrene using a catalyst composed of (A) polypropylene, (B) titanium catalyst component, organoaluminum compound (AL ₁ ) and electron donor (E ₁ ). By mixing with dimethyl styrene polymer, 0.1 wt p of crystalline dimethyl styrene polymer was added.
A method for producing a polypropylene resin composition, characterized in that the content of pm is 2% by weight.

(4) Using a polymer composed of (A) polypropylene, (B) titanium catalyst component, organoaluminum compound (AL ₁ ) and electron donor (E ₁ ), dimethylstyrene is polymerized and then propylene, or By mixing polypropylene obtained by multi-stage polymerization of propylene and an α-olefin other than propylene, or a polypropylene-α-olefin copolymer, by mixing with a crystalline dimethylstyrene polymer, crystalline A method for producing a polypropylene resin composition, which comprises 0.1 wt ppm to 2 wt% of a dimethylsultile polymer.

(5) Using a catalyst composed of (A) polypropylene, (B) a titanium catalyst component containing a crystalline dimethylstyrene polymer, an organoaluminum compound (AL ₁ ), and an electron donor (E ₁ ), propylene Or by mixing polypropylene obtained by polymerizing propylene with an α-olefin other than propylene, or a polypropylene-α-olefin copolymer, thereby containing 0.1 wt ppm to 2 wt% of a crystalline dimethylstyrene polymer. A method for producing a polypropylene resin composition, characterized by comprising:

(6) As a titanium catalyst component containing a crystalline dimethylstyrene polymer, a titanium catalyst component obtained by separately adding a crystalline dimethylstyrene polymer obtained by polymerization during the production of the titanium catalyst component. The manufacturing method according to the fifth item, wherein

(7) As a titanium catalyst component containing a crystalline dimethylstyrene polymer, a titanium catalyst component was separately produced during the production thereof and subjected to a polymerization treatment using dimethylstyrene under polymerization conditions, and was obtained through a subsequent step. The production method according to the above item 5, wherein a titanium catalyst component is used.

(8) As dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene,
And the production method according to the above item 3, item 4, or item 7, wherein one or more kinds of dimethylstyrene selected from 3,5-dimethylstyrene are used.

(9) (A) polypropylene is a propylene homopolymer,
6. The production method according to the above 3, 4, or 5, which is one or more polymers selected from a propylene-α-olefin random copolymer and a propylene-α-olefin block copolymer. .

(10) A molded product using the polypropylene resin composition according to the above item 1.

(11) The molded product according to item 10, wherein the molded product is an injection molded product.

(12) The molded product according to item 10, wherein the molded product is a stretched film.

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

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

The polypropylene resin composition of the present invention is a polypropylene resin composition containing a crystalline dimethylstyrene polymer, and its production method will be described.

The method for producing the polypropylene resin composition of the present invention comprises mixing (i) a crystalline dimethylstyrene polymer with ordinary polypropylene (A) obtained by a known method, or
Alternatively, (ii) the crystalline dimethylstyrene polymer is mixed with polypropylene to incorporate the crystalline dimethylstyrene polymer into the polypropylene resin composition.

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 as a main component. It can be obtained by polymerizing propylene or propylene and an α-olefin other than propylene by vapor phase polymerization or the like.

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

The crystalline dimethylstyrene polymer used in the above-mentioned method (i) uses a catalyst composed of a titanium catalyst component, an organoaluminum compound (AL ₁ ) and, if necessary, an electron donor (E ₁ ), Obtained by polymerizing dimethylstyrene.

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 it is preferably used in industrial production.
59-28573, JP-A-58-17104, etc., titanium catalyst component containing titanium trichloride as a main component obtained by the method described in JP-A-62-104810, JP-A-62-1004811. The titanium catalyst component in which titanium tetrachloride is supported on the magnesium compound described in JP-A-62-104812 and the like is used.

The organoaluminum compound (AL ₁ ) has a general formula of AlR ¹ _m R ² _{m ′} X _{3- (m + m ′)} (wherein R ¹ , R ²
Represents a hydrocarbon group or an alkoxy group represented by an alkyl group, a cycloalkyl group, an aryl group, X represents a halogen, and m and m ′ represent any 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,
Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminium monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride Monoalkyl aluminum dihalides such as Monoethoxy diethylaluminum, can also be used alkoxyalkyl aluminum such as diethoxy monoethyl aluminum. Two or more kinds of these organoaluminum compounds may be mixed and used.

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

What is used as the electron donor (E ₁ ) is an organic compound having any atom of oxygen, nitrogen, sulfur and phosphorus, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, Nitriles, aminos, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, silanols and Si-O-C bonds And an organic silicon compound having

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-ethylhexanol, allyl alcohol,
Alcohols such as 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, benzoic acid 2 -Ethylhexyl, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, naphthoate propyl, naphthobutyl, naphthoate Acid 2-ethylhexyl, ethyl phenylacetate and other monocarboxylic acid esters, diethyl succinate, methyl methyl malonate, diethyl butyl malonate, dibutyl maleate, diethyl butyl maleate, and other aliphatic polycarboxylic acid esters, phthalate Acid monomethyl, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate , Di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate,
Aromatic polyvalent carboxylic acid esters such as di-2-ethylhexyl isophthalate, diethyl terephthalate, 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, ketones such as benzophenone, acetonitrile, nitriles such as benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α -Picoline,
2,4,6-trimethylpyridine, 2,2,6,6-tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, N, N,
N ', N'-tetramethylethylenediamine, aniline,
Amine such as dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, etc. Amides, N,
Urea such as N, N ′, N′-tetramethylurea, phenyl isocyanate, isocyanate such as toluyl isocyanate, azo compound such as azobenzene, ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenyl Phosphines such as phosphine oxide, dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite,
Phosphites such as tri-n-butyl phosphite and triphenyl phosphite; phosphinites such as ethyl diethyl phosphinite, ethyl butyl phosphinite and phenyldiphenyl phosphinite; diethyl thioether, diphenyl thioether, methyl phenyl thioether, etc. Thioethers, ethylthioalcohol,
Thioalcohols and thiophenols such as n-propylthioalcohol and thiophenol, silanols such as trimethylsilanol, triethylsilanol and triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane,
Diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diphenylethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxy Silane, phenyltriethoxysilane, ethyltri i-propoxysilane,
Examples thereof include organosilicon compounds having a Si—O—C bond such as vinyltriacetoxysilane.

The amount of each catalyst component used is the same as in ordinary α-olefin polymerization, but specifically, with respect to 1 g of titanium catalyst component,
An organoaluminum compound (AL ₁ ), 0.01 g to 500 g, and an electron donor (E ₁ ) 0 to 500 g are used. Dimethylstyrene 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, and the polymerization pressure is atmospheric pressure to 5 ° C.
Dimethylstyrene is fed at 0 kg / cm ² G in the presence or absence of an inert solvent and polymerization is carried out for 5 minutes to 50 hours. It is also possible to supply hydrogen during the polymerization.
At the end of the polymerization, it is possible to remove the catalyst residue by carrying out a purification treatment with alcohols or the like.

Dimethylstyrene that can be used in this polymerization reaction is 2,4-
One or more dimethylstyrenes selected from dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5-dimethylstyrene.

Thus, a crystalline dimethylstyrene polymer is obtained.

In addition, as a method for producing a polypropylene containing a crystalline dimethylstyrene polymer used in the above-mentioned method (ii), the following method can be mentioned.

(1) Titanium catalyst component, organoaluminum compound (A
A method in which dimethylstyrene is polymerized and then propylene or propylene and an α-olefin other than propylene are polymerized in multiple stages using a catalyst composed of L ₁ ), and optionally an electron donor (E ₁ ).

(2) A titanium catalyst component obtained by adding the crystalline dimethylstyrene polymer obtained by polymerization by the method (i) separately during the production of the titanium catalyst component for α-olefin polymerization, organoaluminum A method of polymerizing propylene, or propylene and an α-olefin other than propylene, using a catalyst comprising a compound (AL ₁ ) and, if necessary, an electron donor (E ₁ ).

(3) A titanium catalyst component, an organoaluminum compound (AL ₁ ), which is obtained by subjecting a titanium catalyst component for α-olefin polymerization to a polymerization treatment under a polymerization condition using dimethylstyrene under a polymerization condition and then performing a subsequent step. And a method of polymerizing propylene, or propylene and an α-olefin other than propylene, using a catalyst composed of an electron donor (E ₁ ) if necessary.

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

The method (1) uses the same catalyst as that used in the method for obtaining the crystalline dimethylstyrene polymer of (i) described above to polymerize dimethylstyrene under the same polymerization conditions as (i). The polymerization reaction amount of the dimethylstyrene is adjusted to 0.001 g to 100 g per 1 g of the titanium catalyst component. Subsequently, propylene is subjected to main polymerization, but before that, 0.1 g of α-olefin is added per 1 g of the titanium catalyst component.
After reacting 100 g and preactivating, propylene or propylene and an α-olefin other than propylene may be polymerized.

After completion of the polymerization of dimethylstyrene, or after further preactivating with α-olefin, unreacted monomers and the like are washed away with an inert hydrocarbon solvent to remove the organic aluminum compound and, if necessary, an electron donor. After the addition of propylene, propylene, or the polymerization of propylene and an α-olefin other than propylene may be carried out, and the reaction mixture after the reaction is used as it is for the polymerization of propylene or propylene and an α-olefin other than propylene. Good.

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

As each catalyst component and dimethylstyrene used in this method, the same ones as those used for obtaining the crystalline dimethylstyrene polymer of (i) described above can be mentioned.

Next, as the method (2), the method is as a titanium catalyst component used when polymerizing propylene or propylene and an α-olefin other than propylene. Is a method of using the titanium catalyst component obtained by adding the crystalline dimethylstyrene polymer obtained by the above method.

A method for producing such a titanium catalyst component will be specifically described. For example, a method of co-milling a polymer of titanium trichloride and crystalline dimethylstyrene obtained by the method (i) together with an electron donor as necessary. Or a method of coexisting with the crystalline dimethylstyrene polymer obtained by the method (i) when reducing titanium tetrachloride with an organoaluminum compound, or in the presence or absence of a carrier such as a magnesium compound and an electron donor The crystalline dimethylstyrene polymer obtained by the method (i) below is co-pulverized and then treated with titanium tetrachloride, or the liquefied magnesium compound is obtained by the method (i). Examples thereof include a method in which a styrene polymer is dispersed, then treated with a precipitation agent such as a halogen compound, and then treated with an electron donor and titanium tetrachloride.

Here, the amount of the crystalline dimethylstyrene polymer used is in the range of 0.01% to 50% by weight of the polymer in the titanium catalyst component.

Polymerization of propylene, or propylene and an α-olefin other than propylene, using the catalyst obtained by combining the titanium catalyst component obtained by the above method, the organoaluminum (AL ₁ ) and, if necessary, the electron donor (E ₁ ). Obtained.

Next, the method (3) will be described. In the method, as a titanium catalyst component used when polymerizing propylene or propylene and an α-olefin other than propylene, dimethylstyrene is subjected to a polymerization treatment under polymerization conditions during the production of the titanium catalyst component, and This is a method using a titanium catalyst component obtained through the subsequent steps.

A method for producing such a titanium catalyst component will be specifically described. For example, an organoaluminum compound (AL ₂ ) or a reaction product (I) of an organoaluminum compound (AL ₂ ) and an electron donor (E ₂ ). It is obtained by polymerizing the solid product (II) obtained by reacting titanium tetrachloride with dimethylstyrene and further reacting the electron donor (E ₂ ) with the electron acceptor.

The reaction between the organoaluminum compound (AL ₂ ) and the electron donor (E ₂ ) described above 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. To do. There is no limitation on the order of addition of the organoaluminum compound (AL ₂ ), (E ₂ ), and (D ₁ ), and the amount ratio used is 1 mol of the electron donor (E ₂ ) to 1 mol of the organoaluminum compound (AL ₂ ). -8 mol, preferably 1-4 mol, solvent 0.5L-5L, preferably
It is 0.5L-2L. 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.

As a method for polymerizing the solid product (II) obtained by reacting the reaction product (I) with titanium tetrachloride or the organoaluminum compound (AL ₂ ) with titanium tetrachloride with dimethylstyrene, A method of polymerizing the solid product (II) by adding dimethylstyrene at any stage of the reaction of the reaction product (I) or the organoaluminum compound (AL ₂ ) with titanium tetrachloride, the reaction product (I ) Or an organoaluminum compound (AL ₂ ) and titanium tetrachloride, and then polymerizing the solid product (II) by adding dimethylstyrene, and a reaction product (I) or an organoaluminum compound. (A
After completion of the reaction between L ₂ ) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (II) is suspended in a solvent. There is a method of adding and polymerizing.

The reaction of the reaction product (I) or the organoaluminum compound (AL ₂ ) with titanium tetrachloride can be carried out with or without the addition of dimethylstyrene in any step of the reaction.
C. to 200.degree. C., preferably 0.degree. C. to 100.degree. C. for 5 minutes to 10 hours. It is preferable not to use a solvent, but an aliphatic or aromatic hydrocarbon can also be used. The mixing of (I) or the organoaluminum compound (AL ₂ ), titanium tetrachloride and the solvent may be performed in any order, and dimethylstyrene may be added at any stage. The mixing of the total amount of (I) or the organoaluminum compound (AL ₂ ), titanium tetrachloride, and the solvent is preferably 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 mol of titanium tetrachloride, and the solvent is 0 to
3,000 ml, the ratio of the number of Al atoms in the reaction product (I) or the organoaluminum compound (AL ₂ ) to the number of Ti atoms in titanium tetrachloride (Al / Ti) is 0.05 to 0.3.

The polymerization treatment with dimethylstyrene is carried out by adding dimethylstyrene in any process of the reaction between the reaction product (I) or the organoaluminum compound (AL ₂ ) and titanium tetrachloride, and the reaction product (I) or the organoaluminum. After the reaction with the compound (AL ₂ ) titanium tetrachloride,
When dimethylstyrene is added, the reaction temperature is 0 ° C to
The final titanium catalyst component was prepared by using 0.01 g to 100 kg of dimethylstyrene per 100 g of the solid product (II) under the conditions of 90 ° C. for 1 minute to 10 hours and the reaction pressure of atmospheric pressure to 10 kg / cm ² G. The content of the crystalline dimethyl styrene polymer is 0.01% by weight to 99
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 the polymerization treatment with dimethylstyrene, the liquid portion is separated and removed by filtration or decantation, and the obtained solid is formed. When the product (II) is suspended in a solvent, 100 ml-5,000 ml of the solvent and 0.5 g-5,000 g of an organoaluminum compound are added to 100 g of the solid product (II), and the reaction temperature is 0 ° C-90 ° C. 1 minute to 10 hours at a reaction pressure of atmospheric pressure to 10 kg / cm ² G, 0.01 g to 100 kg of dimethylstyrene per 100 g of the solid product (II) was used in the final titanium catalyst component. Crystalline dimethylstyrene polymer content 0.01% to 99% by weight
Polymerize so that The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound is the one used for obtaining the reaction product (I) or the reaction with titanium tetrachloride directly without reacting with the electron donor (E ₂ ). It may be the same as or different from the one. After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further washing with a solvent, the obtained solid product subjected to polymerization treatment (hereinafter referred to as solid product (II-
A) may be used in the next step in the state of being suspended in the solvent, or may be dried and taken out as a solid.

Solid product: (II-A) reacts an electron donor (E ₂ ) with an electron acceptor (F). This reaction can be carried out without using a solvent, but the use of an aliphatic hydrocarbon gives better results. The amount used is (E ₃ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, and (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 simultaneously reacted with an electron donor (E ₂ ) and an electron acceptor (F). After reacting (II-A) with (F), (E) ₃ )
Reacting (II-A) with (E ₃ ) and then reacting with (F), reacting (E ₃ ) with (F), and then reacting with (II-A) There is a method of making it possible, but either method may be used.

The reaction conditions are 40 ° C to 40 ° C in the above method.
It is desirable to react at 200 ° C., preferably 50 ° C. to 100 ° C. for 30 seconds to 5 hours, and in the method of (II-A) and (E ₃ ) the reaction is performed at 0 ° C. to 50 ° C. for 1 minute to 3 hours. After the reaction, (F) is reacted under the same conditions as described above. In the other method, (E ₃ ) and (F) are heated at 10 ° C to 10
After reacting at 0 ℃ for 30 minutes to 2 hours, cool to 40 ℃ or below (I
After adding IA), the reaction is carried out under the same conditions as described above. The solid product (II-A), (E 3) and (F)
After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is further repeated to obtain a titanium catalyst component containing a crystalline dimethylstyrene polymer.

As the organoaluminum (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₎ is (E ₃₎ similar ones can be exemplified as usable also previously described (E ₁₎ as, (E ₂₎
It is preferable that ethers are mainly used as (E ₃ ), and other electron donors are shared with the ethers. These electron donors can also be used as a mixture. Electron donor (E ₂ ) for obtaining reaction product (I), solid product (II
Each is reacted -A) (E ₃₎ may be different even in the same.

Electron acceptor (F) reacted with solid product (II-A)
Are 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,
Examples thereof include zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like, and these may be used in combination. Most preferred is titanium tetrachloride.

The following are used as the solvent (D ₁ ). Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, i-octane and the like, and carbon tetrachloride, chloroform instead of or together with the aliphatic hydrocarbon. Also, halogenated hydrocarbons such as dichloroethane, trichloroethylene and terrachlorethylene can be used.

Examples of the aromatic compound include aromatic hydrocarbons such as naphthalene, and their derivatives such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, alkyl-substituted compounds such as 1-phenylnaphthalene, monochlorobenzene, chlorotoluene, and chloro. Xylene,
Examples thereof include halides such as chloroethylbenzene, dichlorobenzene, and bromobenzene.

The dimethylstyrene used in the polymerization treatment may be the same as those used in the methods (i) and (l) described above.

In addition to the titanium catalyst component obtained as described above,
For example, a solid product (III) 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 ) is treated with an organoaluminum compound (AL ₃ In the presence of), a solid product (IV) is obtained by polymerization treatment with dimethylstyrene, and the solid product (IV) is reacted with a titanium halide compound (T ₂ ). A titanium catalyst component can be used. The method for producing the titanium catalyst component will be described below.

The "liquefaction" of the magnesium compound referred to in the present invention
Means that the magnesium compound itself becomes liquid,
When it itself is soluble in a solvent and forms a solution,
It also includes the case of forming a solution by being solubilized in a solvent as a result of reacting with another compound or 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 gnesium, magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate, dialkyl magnesium, alkyl magnesium halide and the like, metal magnesium can be used.

As a method of liquefying the magnesium compound, known means are used. For example, a method of liquefying a magnesium compound with an alcohol, an aldehyde, an amine or a carboxylic acid (JP-A-56-811, etc.) and a method of liquefying a magnesium compound with an orthotitanate (JP-A-54-40293, etc.) ), A method of liquefying with a phosphorus compound (JP-A-58-19307)
No. gazette, etc.), etc., as well as methods combining these. Also, the above method cannot be applied,
Since the organomagnesium compound having a C-Mg bond is soluble in ether, dioxane, pyridine, etc., it can be used as a solution of these, or can be reacted with an organometallic compound to give a compound of the general formula M _p Mg _q R ³ _r R ⁴ _s (M is aluminum,
Zinc, boron, or perillium atom, R ³ and R ⁴ are hydrocarbon residues, and r + s = vp, where p, q, r, s> o, v is the valence of M
There is a relationship of + 2q. ) Can be formed (JP-A-50-139885, etc.), dissolved in a hydrocarbon solvent, and liquefied.

Furthermore, when metallic magnesium is used, a method of liquefying with an alcohol and an orthotitanate ester (JP-A-50-51587, etc.) or reaction with an alkyl halide in ether to form a so-called Grignard reagent It can be liquefied by a method.

In the method of liquefying the magnesium compound as described above, for example, the case of dissolving magnesium chloride in a hydrocarbon solvent (D ₂ ) using titanic acid ester and alcohol will be described. , 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 ) are used to mix the respective components in an arbitrary addition order, and the suspension is stirred. Heating is performed at 40 ° C to 200 ° C, preferably 50 ° C to 150 ° C. The time required for the reaction and dissolution is 5 to 7 hours, preferably 10 minutes to 5 hours. Examples of the titanate ester include an orthotitanate ester represented by Ti (OR ⁵ ) ₄ and a polytitanate ester represented by R ⁶ [O—Ti (OR ⁷ ) (OR ⁸ )] _t —OR ^9. . Where R ⁵ ,, R ⁶ ,, R ⁷ ,, R ⁸
And R ⁹ is an alkyl group having 1 to 20 carbon atoms, or 3 carbon atoms
To 20 cycloalkyl groups, and t is a number from 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, i-propyl polytitanate, N-Butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n polytitanate
-Polytitanate esters such as octyl, phenyl polytitanate, and cyclohexyl polytitanate can be used. The polytitanate ester may be used in an amount equivalent to orthotitanate in terms of orthotitanate.

As the alcohol, aliphatic saturated and unsaturated alcohols can be used. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i
In addition to monohydric alcohols such as -propyl alcohol, n-butyl alcohol, n-amyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, and allyl alcohol, ethylene glycol, triglyceride Polyhydric alcohols such as methylene 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 ₂ ) used in the production of the titanium catalyst component can be used, but among them, aliphatic hydrocarbons are preferable.

The solid product (III) is obtained by contacting the liquefied magnesium compound with the precipitating agent (X ₁ ), the halogen compound (X ₂ ), the electron donor (E ₄ ) and the titanium compound (T ₁ ). Examples of the precipitant (X ₁ ) include halogenating agents such as halogens, halogenated hydrocarbons, halogen-containing silicon compounds, halogen-containing aluminum compounds, halogen-containing titanium compounds, halogen-containing zirconium compounds, and halogen-containing vanadium compounds. Further, 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 the precipitating agent (X ₁₎ is 0.1 mol to 50 mol, relative to 1 mol of the magnesium compound. Further, examples of the halogen compound (X ₂ ) include halogen and compounds containing halogen, and the same halogenating agents as the examples of the precipitating agent can be used. When used, it does not necessarily require a new use of the halogen compound (X ₂ ). The halogen compound (X ₂ ) is used in an amount of 0.1 mol to 50 mol per mol of the magnesium compound.

As the electron donor (E ₄ ), those similar to the above-mentioned (E ₂ ) and (E ₃ ) are used, and 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 to 5 mol per 1 mol of the magnesium compound.

The titanium compound (T ₁ ) necessary for the preparation of the solid product (III) has the general formula Ti (OR ¹⁰ ) _4-u X _u (wherein R ¹⁰ is an alkyl group, a cycloalkyl group, or an aryl group, X represents halogen, and u is an arbitrary number satisfying 0 <u ≦ 4.)
The titanium halide compound represented by or the orthotitanate ester and polytitanate ester mentioned at the time of liquefying the magnesium compound are used.

Specific examples of the titanium halide compound include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, and trititanium trichloride. Butoxy titanium bromide, dimethoxy titanium dichloride, diethoxy titanium dichloride, dipropoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy titanium dibromide, dibutoxy titanium dibromide, trichloride Examples thereof include methoxy titanium, triethoxy titanium chloride, tryptoxy titanium chloride, and trienoxy titanium chloride. Examples of the orthotitanate and polytitanate include the same ones as described above.

One or more of these titanium compounds (T ₁ ) may be used. When a titanium halide compound is used as the titanium compound (T ₁ ), it has a halogen and therefore a depositing agent (X ₁ ) and a halogen compound ( The use of X ₂ ) is optional. Also, when a titanate ester is used during liquefaction of a magnesium compound, a new use of a titanium compound (T ₁ ) is optional. Titanium compound (T ₁ )
The amount used is 0.1 mol to 100 mol per 1 mol of the magnesium compound.

The above liquefied magnesium compound, precipitating agent (X ₁ ), halogen compound (X ₂ ), electron donor (E ₄ ) and titanium compound (T ₁ ) are contacted with stirring to give a solid product (III). obtain. When contacting, use an inert hydrocarbon solvent (D
₃ ) may be used, or each component may be diluted in advance and used, and as the inert hydrocarbon solvent (D ₃ ) to be used, the same ones as the above-mentioned (D ₂ ) can be exemplified. The usage is
It is 0 to 5,000 ml per mol of the magnesium compound.

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) 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 liquefying and bringing the magnesium compound into contact 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 used in several stages. 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 ) is an optional component to be used.

The contact temperature of each component is −40 ° C. to + 180 ° C., preferably −20 ° C. to + 150 ° C., and the contact time is 5 minutes to 8 hours for each step when the reaction pressure is atmospheric pressure to 10 kg / cm ² G. , Preferably 10 minutes to 6 hours.

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

Next, the solid product (III) obtained by the above-mentioned method,
Polymerization treatment with dimethylstyrene in the presence of the organoaluminum compound (AL ₃ ) gives a solid product (IV).

Polymerization with dimethylstyrene gives a solid product (II
I) 100 g to 100 g of inert hydrocarbon solvent (D ₄ ) -5,00
0 ml, 0.5 g to 5,000 g of an organoaluminum compound (AL ₃ ) are added, dimethylstyrene is added under the conditions of a reaction temperature of 0 ° C. to 90 ° C. for 1 minute to 10 hours and a reaction pressure of atmospheric pressure to 10 kg / cm ² G. 0.01
˜100 kg is added and polymerized so that the content of the crystalline dimethylstyrene polymer in the final titanium catalyst component is 0.01% by weight to 99% by weight.

Further, in the polymerization treatment stage, electron donation represented by carboxylic acid esters such as ethyl benzoate, methyl toluate and ethyl anisate, and silane compounds such as phenyltriethoxysilane, diphenyldimethoxysilane and methyltriethoxysilane. It is also possible for the body to coexist. The amount of them used is the solid product (II
I) 0 to 5,000 g per 100 g.

Organoaluminum compound used for polymerization (A
L _3), the solvent (D ₄₎ and dimethyl styrene, previously described, respectively _{(AL 2), (D 2} ) and those similar to dimethyl styrene is used.

Polymerization with dimethylstyrene is performed as described above, and the solid product (IV) is obtained by washing with the aforementioned inert hydrocarbon solvent.

Subsequently, the solid product (IV) 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 ¹⁰ ) _4-u X _u (as described above as an example of the titanium compound (T ₁ ) necessary for preparing the solid product (III) is used. In the formula, R ¹⁰ is an alkyl group, a cycloalkyl group, or an aryl group, X is a halogen, and u is an arbitrary number satisfying 0 <u ≦ 4. Similar examples can be given, but titanium tetrachloride is most preferable.

The reaction between the solid product (IV) and the titanium halide compound (T ₂ ) is carried out by using the magnesium compound 1 in the solid product (IV).
1 mol or more of the titanium halide compound (T ₂ ) is used per mol, 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
React for 5 minutes to 5 hours. It is also possible to carry out the reaction in the presence of an inert hydrocarbon solvent (D ₅ ) or an electron donor (E ₅ ), and specifically, the above-mentioned (D ₁ ) to
An inert solvent or electron donor similar to (D ₄ ) or (E ₄ ) is used. The amount of these used is 0 to 5,000 ml (D ₅ ) per 100 g in the solid product (IV), and 0 to 2 mol (E ₅ ) per 1 mol of the magnesium compound in the solid product (IV). The range of is desirable. After reacting the solid product (IV) 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-products are removed to obtain a titanium catalyst component.

As described above, the titanium catalyst component obtained by polymerizing with dimethylstyrene 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 is used as a catalyst by combining it with an organoaluminum compound (AL ₄ ) and, if necessary, an electron donor (E ₅ ), or a catalyst incompletely activated by polymerizing a small amount of α-olefin. And, by the same polymerization method as the known propylene polymerization method described above, propylene,
Alternatively, polypropylene containing a crystalline dimethylstyrene polymer can be obtained by polymerizing propylene and an α-olefin other than propylene.

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

Also, pre-activation and α used with propylene
-As olefins, in addition to propylene, ethylene,
Examples thereof include straight chain olefins such as butene-1, hexene-1 and octene-1, and branched chain olefins such as 2-methylpentene-1,5-methylhexene-1.

The thus obtained (B) crystalline dimethylstyrene polymer or polypropylene containing the crystalline dimethylstyrene polymer is mixed with (A) known polypropylene to obtain the polypropylene resin composition of the present invention.

Regarding the mixing ratio, the content of the crystalline dimethylstyrene polymer is 0.1 wtppm to 2 wt% with respect to the total composition. When the content of the crystalline dimethylstyrene polymer is less than 0.1 ppm by weight, the effect of improving transparency and crystallinity of the obtained composition is insufficient, and when it exceeds 2% by weight, the effect is remarkably improved. It is no longer economical.

In producing the composition of the present invention, it is sufficient to mix predetermined amounts of the above-mentioned components (A) and (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 include room temperature to 100 ° C,
The temperature is 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. As the filler, for example, glass fiber, talc, mica, wood powder,
Inorganic or organic materials such as synthetic fibers can be used.

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

[Operation] Since the polypropylene resin composition of the present invention contains the highly stereoregular dimethylstyrene polymer in a dispersed state, the harmful crystalline dimethylstyrene polymer exhibits a nucleating action during melt molding, As a result of reducing the spherulite size of polypropylene and promoting crystallization, the transparency and crystallinity of the entire polypropylene resin composition are increased.

Further, since the crystalline dimethylstyrene 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 min) Crystallization temperature: measured with a differential scanning calorimeter at a temperature decreasing rate of 10 ° C./min. (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:%) Transparency: The LS value (narrow-angle diffuse transmission value) measured using a "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 crystalline dimethylstyrene polymer-containing polypropylene Preparation of titanium catalyst component n-Hexane 6, diethyl aluminum monochloride (DEAC) 5.0 mol, and diisoamyl ether 12.0 mol were mixed at 25 ° C for 1 minute. The reaction product solution (I) (diisoamyl ether / DEAC molar ratio is reacted for 5 minutes at the same temperature.
2.4) was obtained. Titanium tetrachloride 40 in a reactor purged with nitrogen
After adding mols and heating to 35 ° C., the whole amount of the above reaction product liquid (I) was added dropwise thereto over 180 minutes, then kept at the same temperature for 60 minutes, heated to 80 ° C. and further reacted for 1 hour at room temperature. The mixture was cooled to 40 ° C., the supernatant was removed, 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, and 21 kg of 2,4-dimethylstyrene was added at 40 ° C.
Polymerization was performed at 2 ° C. for 2 hours. After treatment, heat up to 50 ℃,
The operation of removing the supernatant liquid and adding n-hexane 30 and decanting the supernatant liquid was repeated 4 times to obtain a solid product (II-A) subjected to polymerization treatment. With the total amount of this solid product suspended in n-hexane 9, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes and reacted at 80 ° C for 30 minutes, and then diisoamyl ether was added. 1,6 kg was added and reacted at 80 ° C. for 1 hour. After completion of the reaction, the operation of removing the supernatant was repeated five times, and then dried under reduced pressure to obtain a titanium trichloride composition. 2, in the obtained titanium trichloride composition,
The 4-dimethylstyrene polymer content was 50.0% by weight and the titanium content was 12.6% by weight.

Preparation of pre-activated catalyst After replacing a stainless steel reactor with an inclined blade with an internal volume of 80 with nitrogen gas, n-hexane 40, diethyl aluminum monochloride 28.5 g, (1) obtained titanium trichloride composition 450 g Was added at room temperature, 0.9 Nm ^{3 of} ethylene was supplied at 30 ° C. for 2 hours to cause a reaction (reaction of 2.0 g of ethylene per 1 g of the titanium trichloride composition), and then unreacted ethylene was removed. After washing with hexane, it was dried to obtain a preactivated catalyst.

Polymerization of Propylene L / D = 3 equipped with a stirrer with an internal volume of 80 and nitrogen substitution
After 20 kg of polypropylene powder of MFR2.0 was charged into the horizontal polymerization vessel of, n-hexane was added to the pre-activated catalyst obtained in (2) above to make a 4.0 wt% n-hexane suspension.
6.41 mg atom / hr in terms of titanium atom of the suspension,
And diethyl aluminum monochloride 3.8g / hr
And continuously supplied from the same pipe.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 1.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G.
It went on continuously for hours. 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 50% by volume. The polymer extracted 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 the crystalline 2,
MFR1.8 containing 122 weight ppm of 4-dimethylstyrene polymer
Of polypropylene (B).

(2) Production of polypropylene resin composition 5.0 kg of polypropylene (B) containing the crystalline 2,4-dimethylstyrene polymer obtained in (1) in a Henschel mixer (trade name) having an internal volume of 50, the above (1) ), The titanium catalyst component obtained by omitting the step of polymerizing with 2,4-dimethylstyrene in the production of the titanium catalyst component is used to obtain the crystallinity. 5.0 kg of normal polypropylene (A) with MFR1.8 containing no 2,4-dimethylstyrene polymer, tetrakis [methylene-3-]
5 g of (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane and 5 g of calcium stearate were added and mixed with stirring for 5 minutes. Subsequently, using a single-screw extruder with an inner diameter of 40 mm, the melt-kneading temperature is 230 ° C.
Was extruded, cooled with water, and then cut to obtain a pellet-shaped polypropylene resin composition.

(3) Manufacture of molded product The composition obtained in (2) was melted at a resin temperature of 230 using an injection molding machine.
A JIS type test piece was injection-molded at ℃ and mold temperature of 50 ℃. The test piece was allowed to stand for 72 hours at room temperature of humidity 50% and room temperature 23 ° C for 72 hours, and the flexural modulus was measured to be 14,1.
It was 00 kgf / 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 to give a temperature of 20 ° C.
A sheet having a thickness of 1 mm was prepared with the cooling roll of. The sheet is heated with hot air of 150 ° C. for 70 seconds, and using a biaxial stretching machine,
The film was stretched 7 times in both longitudinal and transverse directions to obtain a biaxially stretched film having a thickness of 20 μm.

Comparative Example 1 In (2) of Example 1, a polypropylene catalyst (B) containing a crystalline 2,4-dimethylstyrene polymer was not used, and a titanium catalyst component which had not been subjected to a 2,4-dimethylstyrene polymerization treatment was used. A composition was obtained in the same manner except that 10 kg of the usual polypropylene (A) obtained above was used. A molded article was produced from the obtained composition in the same manner as in Example 1 (3).

Comparative Example 2 and Examples 2 and 3 The mixing ratio of the polypropylene (B) containing the crystalline 2,4-dimethylstyrene polymer and the ordinary polypropylene (A) in (2) of Example 1 was changed as shown in the table. A composition was obtained in the same manner as above, except that a molded article was obtained in the same manner as in (3) of Example 1.

Example 4 (1) In a stainless steel reactor equipped with a stirrer, decane 3, anhydrous magnesium chloride 480 g, n-butyl orthotitanate 1.7 kg and 2-ethyl-1-hexanol.
1.95 kg were mixed and heated to 130 ° C. for 1 hour with stirring to dissolve the mixture into a uniform solution. The homogeneous solution was brought 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, which 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 (III).

450 g of triethylaluminum and diphenyldimethoxysilane in which the total amount of the solid product (III) was kept at 30 ° C.
After suspending in hexane 10 containing 145 g, 5.5 kg of 2,5-dimethylstyrene was added, and polymerization was performed for 2 hours at the same temperature while stirring. After the treatment, remove the supernatant and n-
Hexane 6 was added and the operation of removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (IV) subjected to a polymerization treatment.

The total amount of the solid product (IV) was 1,2-dichloroethane 5
Was mixed with titanium tetrachloride 5 dissolved in, followed by addition of 180 g of diisobutyl phthalate and reaction at 100 ° C. for 2 hours with stirring. Then, the liquid phase portion was removed by decantation at the same temperature, and 1, again. 2-Dichloroethane 5 and titanium tetrachloride 5 were added, and the mixture was stirred at 100 ° C. for 2 hours, washed with hexane and dried to obtain a titanium catalyst component. The titanium catalyst component has a particle shape close to a sphere, and titanium 1.5
% And 2,5-dimethylstyrene polymer 50.0% by weight
Was included.

After replacing the stainless steel reactor with an inclined blade with an internal volume of 30 with nitrogen gas, n-hexane 20, triethylaluminum 1.5 kg, diphenyldimethoxysilane 480 g,
200 g of the titanium catalyst component obtained in and were added at room temperature. The reactor was maintained at 30 ° C., 180 N of ethylene was fed at the same temperature for 2 hours to cause a reaction (reaction of 1.0 g of ethylene per 1 g of titanium catalyst component), and then unreacted ethylene was removed.
A preactivated catalyst was obtained.

After 20 kg of polypropylene powder of MFR2.0 was charged into the polymerization vessel used in (1) of Example 1, the above preactivated catalyst slurry (containing triethylaluminum and diphenyldimethoxysilane in addition to the titanium catalyst component) was used as a titanium atom. It was continuously supplied at a rate of 0.285 mg atom / hr. Further, 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, and the gas phase polymerization of propylene was continuously performed at 70 ° C. for 120 hours. It was 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 polymer thus extracted was subsequently treated in the same manner as in (1) of Example 1 to obtain MF containing 46 ppm by weight of a crystalline 2,5-dimethylstyrene polymer.
Obtained as polypropylene (B) with R1.8.

(2) In (2) of Example 1, as the polypropylene (B), the polypropylene (B) containing the crystalline 2,5-dimethylstyrene polymer obtained in the above (1) 5.
As the ordinary polypropylene (A), a titanium catalyst component obtained in the same manner as in the above (1) except that the step of polymerizing with 2,5-dimethylstyrene was omitted was used. ) Obtained in the same manner as
A polypropylene resin composition was obtained in the same manner except that 5.0 kg of polypropylene containing no 5-dimethylstyrene polymer was used.

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

Comparative Example 3 In (2) of Example 4, a titanium catalyst component not polymerized with 2,4-dimethylstyrene was used without using the polypropylene (B) containing a crystalline 2,4-dimethylstyrene polymer. A composition was obtained in the same manner except that 10 kg of the usual polypropylene (A) obtained was used. A molded product was produced from the obtained composition in the same manner as in Example 4 (3).

Example 5 (1) Titanium tetrachloride (27.0 mol) was added to n-hexane (12) and the mixture was cooled to 1 ° C. Then, n-hexane (12.5) containing 27.0 mol of diethylaluminum monochloride was added dropwise at 1 ° C over 4 hours. After completion of the dropping, the reaction was maintained 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 1.8 out of 5.7 kg of the obtained solid product (II) was obtained.
kg was suspended in n-hexane 11, to which diisoamyl ether, 1,6 was added. This suspension was stirred at 35 ° C. for 1 hour and then washed 5 times with n-hexane 3 to obtain a treated solid. The treated solid obtained was treated with 40% by volume of titanium tetrachloride in n-
Suspended in hexane solution 6. 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 and the solid obtained was washed three times and then dried under reduced pressure to obtain a titanium catalyst component.

A titanium catalyst component obtained by replacing a stainless steel reactor with an inclined blade with an internal volume of 80 with nitrogen gas, and then using n-hexane 40 and diethylaluminum monochloride 200 g.
After adding 450 g at room temperature, bring the temperature inside the reactor to 40 ° C.,
2.25 kg of 5-dimethylstyrene was added and reacted at 40 ° C. for 2 hours (reaction of 1.0 g of 3,5-dimethylstyrene per 1 g of titanium-containing solid catalyst component). After completion of the reaction, unreacted 3,5-dimethylstyrene, 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 an agitator with an internal volume of 500 with nitrogen gas, at room temperature, n-hexane 200,
36 g of diethyl aluminum monochloride, 15 g of the obtained pre-activated catalyst as a titanium catalyst component, and 1 hydrogen.
00N was added. Then, at a polymerization temperature of 70 ° C., propylene was supplied so that the propylene partial pressure was 10 kg / cm ² G, and ethylene was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 0.2% by volume, and propylene-ethylene co-polymer was added. Polymerization was carried out for 3 hours.

After completion of the reaction, 1.0 kg of methanol was added, the catalyst deactivation reaction was carried out at 70 ° C. for 30 minutes, then cooled to room temperature, and the obtained polymer was dried. The dried polymer contained lumps, so it was crushed and the whole amount of the polymer was pulverized to give 227 ppm by weight of crystalline 3.5-dimethylstyrene polymer.
A propylene-ethylene copolymer containing MFR1.5 was obtained.

(2) In (2) of Example 1, as polypropylene (B), 3.0 kg of the propylene-ethylene copolymer containing the crystalline 3,5-dimethylstyrene polymer obtained in (1) above, As the ordinary polypropylene (A), the titanium catalyst component obtained in (1) above was not subjected to the pre-activation reaction with 3,5-dimethylstyrene, but the titanium catalyst component obtained in (1) was used as a pre-activation catalyst equivalent. 7.0 kg of propylene-ethylene copolymer of MFR1.7 containing no crystalline 3,5-dimethylstyrene polymer obtained in the same manner as 1)
A polypropylene resin composition was obtained in the same manner except that was used.

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

Comparative Example 4 In (5) of Example 5, the propylene-ethylene copolymer containing the crystalline 3,5-dimethylstyrene polymer was not used, and the preactivation reaction with 3,5-dimethylstyrene was not carried out. A composition was obtained in the same manner except that 10 kg of a propylene-ethylene copolymer containing no crystalline 3,5-dimethylstyrene polymer obtained using a titanium catalyst component was used. About the obtained composition, (3) of Example 5
A molded product was obtained in the same manner as in.

Example 6 (1) Production of crystalline dimethylstyrene polymer After replacing a stainless steel reactor with an inclined blade with an internal volume of 100 with nitrogen gas, n-hexane 40, diethylaluminum monochloride 320 g, (1 of Example 1) In ()), 500 g of the titanium catalyst component obtained in the same manner was added at room temperature except that the step of polymerizing with 2,4-dimethylstyrene was omitted, and then 10 kg of 2,4-dimethylstyrene was 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 vibrating mill for 5 hours and powdered crystalline 2,4-
A dimethylstyrene polymer was obtained.

(2) Production of polypropylene resin composition 1.0 g of the crystalline 2,4-dimethylstyrene polymer obtained in (1) was dissolved in cyclohexene 1, and the solution was the same MFR1.8 as used in Comparative Example 1. Was uniformly mixed with 10 kg of ordinary polypropylene powder. Then, after drying under reduced pressure at 90 ° C. to remove cyclohexene, 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 A molded product was manufactured in the same manner as in (3) of Example 1 using the polypropylene composition obtained in (2).

Example 7 (1) In (1) of Example 1, the reaction product liquid (I)
In reacting titanium tetrachloride with titanium tetrachloride, 3,5 instead of 2,4-dimethylstyrene in (1) of Example 6 was separately prepared.
-Crystalline 3, obtained by polymerization using dimethyl styrene,
By suspending 1.0 kg of 5-dimethylstyrene polymer powder in titanium tetrachloride and omitting the step of polymerizing the solid product (II) with 2,4-dimethylstyrene, the total amount of the solid product (II) was A titanium catalyst component having a crystalline 3,4-dimethylstyrene polymer content of 34.5% by weight was obtained in the same manner except that the solid product (II-A) was used. Using the titanium catalyst component, the same procedure as in Example 1 was followed except that the crystalline 3,4-dimethylstyrene polymer was contained in an amount of 81 ppm by weight.
A polypropylene (B) having MFR 1.7 was obtained.

(2) A polypropylene resin composition was obtained in the same manner as in (2) of Example 1, except that 5.0 kg of the polypropylene obtained in the above (1) was used as the polypropylene (B) containing the crystalline dimethylstyrene polymer. It was

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

[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 apparent from the above-mentioned Examples, the four-sheet haze value of the stretched film obtained by using the composition of the present invention is 3.0%.
It is up to 4.1%, and has significantly higher transparency as compared with a stretched film using a normal polypropylene that does not contain a crystalline dimethylstyrene polymer.

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

Claims (13)

(57) [Claims] 1. Crystalline dimethylstyrene polymer 0.1 wt ppm
Include 2% by weight of polypropylene in 100%
Polypropylene resin composition as a weight percentage. 2. The crystalline dimethylstyrene polymer is crystalline 2,
One or more crystallinity selected from 4-dimethylstyrene polymer, crystalline 2,5-dimethylstyrene polymer, crystalline 3,4-dimethylstyrene polymer, and crystalline 3,5-dimethylstyrene polymer The composition of claim 1 which is a dimethyl styrene polymer. 3. Obtained by polymerizing dimethylstyrene using a catalyst comprising (A) polypropylene, (B) titanium catalyst component, organoaluminum compound (AL ₁ ) and electron donor (E ₁ ). By mixing with the crystalline dimethylstyrene polymer, the crystalline dimethylstyrene polymer is added at 0.1 ppm by weight.
The method for producing a polypropylene resin composition is characterized in that the content is ˜2% by weight. 4. A polymer comprising (A) polypropylene, (B) a titanium catalyst component, an organoaluminum compound (AL ₁ ) and an electron donor (E ₁ ) is used to polymerize dimethylstyrene and subsequently propylene. , Or polypropylene obtained by multi-stage polymerization of propylene and an α-olefin other than propylene, or by mixing with a polypropylene-α-olefin copolymer, by mixing with a crystalline dimethylstyrene polymer, A method for producing a polypropylene resin composition, characterized in that the crystalline dimethylstyrene polymer is contained in an amount of 0.1 ppm by weight to 2% by weight. 5. A catalyst comprising (A) polypropylene, (B) a titanium catalyst component containing a crystalline dimethylstyrene polymer, an organoaluminum compound (AL ₁ ) and an electron donor (E ₁ ). , Propylene, or polypropylene obtained by polymerizing propylene and an α-olefin other than propylene, or a polypropylene-α-olefin copolymer to obtain a crystalline dimethylstyrene polymer in an amount of 0.1 ppm by weight to 2% by weight. % Of the polypropylene resin composition. 6. A titanium catalyst component containing a crystalline dimethylstyrene polymer, which is obtained by separately adding a crystalline dimethylstyrene polymer obtained by polymerization during the production of the titanium catalyst component. The manufacturing method according to claim 5, wherein a catalyst component is used. 7. A titanium catalyst component containing a crystalline dimethylstyrene polymer, which is separately obtained during the production of the titanium catalyst component under a polymerization condition using dimethylstyrene, and is then subjected to a subsequent step. The method according to claim 5, wherein the titanium catalyst component is used. 8. A dimethylstyrene selected from 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5-dimethylstyrene.
Claim 3 wherein at least one kind of dimethylstyrene is used.
The manufacturing method according to item 4, item 4, or item 7. 9. (A) Polypropylene is a propylene homopolymer, a propylene-α-olefin random copolymer,
The production method according to claim 3, 4, or 5, which is one or more polymers selected from propylene-α-olefin block copolymers. 10. A molded product obtained by using the polypropylene resin composition according to claim 1. 11. The molded product according to claim 10, wherein the molded product is an injection molded product. 12. The molded product according to claim 10, wherein the molded product is a stretched film. 13. A molded article is a sheet.
The molded article according to item 10.