JPH0657775B2 - Polypropylene resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polypropylene resin composition. More specifically, the present invention relates to a polypropylene resin composition having extremely excellent transparency, which comprises polypropylene and polypropylene obtained by polymerizing propylene using a titanium catalyst component for olefin polymerization containing an alkenylsilane polymer as a solid catalyst component.

[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. Therefore, various molded products such as films and sheets are manufactured. Widely used in.

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 effect of improving transparency is insufficient. , When using a benzylidene sorbitol derivative, some improvement in transparency was observed, but there was a strong odor during processing, and the bleeding phenomenon of additives (embossing)
There was a problem such as occurrence of.

In order to improve the above problems when adding the nucleating agent, a method of copolymerizing α-olefin having 4 to 18 carbon atoms of propylene and 3-methylbutene-1 (Japanese Patent Publication No. 45-32430) and vinyl A method for carrying out multi-stage polymerization of cyclohexane and propylene has been proposed (Japanese Patent Laid-Open No. 60-139710).
When polypropylene was manufactured, the effect of improving transparency was insufficient in all cases. Furthermore, many voids were generated in the film produced using the obtained polypropylene, which impaired the commercial value.

Furthermore, a method using the same method to obtain a highly crystalline polypropylene by polymerizing a small amount of trialkylvinylsilane such as vinyltrimethylsilane or trialkylallylsilane, and then polymerizing propylene (JP-A-63- No. 15804, JP-A-63-37104, JP-A-63-37105) have been proposed, but the data of the transparency of the obtained polypropylene are not shown in the specification of the publication. Other than that, there was a problem that voids were generated in the film.

The present inventors have earnestly studied polypropylene having improved transparency and having less voids when a film is manufactured.

As a result, polypropylene obtained by polymerizing propylene using a catalyst obtained by combining an alkenylsilane polymer-containing titanium catalyst component for olefin polymerization, an organoaluminum compound, and, if necessary, an electron donor is converted into a normal polypropylene. The present invention has been accomplished by knowing that the polypropylene resin composition obtained by addition has remarkably improved transparency and crystallinity as compared with conventional polypropylene, and generation of voids is extremely small.

It is an object of the present invention to provide a polypropylene resin composition having extremely high transparency and crystallinity and extremely few voids.

[Means for solving problems and their actions]

 The present invention has the following configurations.

(1) (A) polypropylene, (B) the following formula, (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Propylene using a catalyst containing a combination of an olefin polymerization titanium catalyst component, an organoaluminum compound (AL ₁ ), and an electron donor (E ₁ ) if necessary,
Alternatively, a composition comprising polypropylene obtained by polymerizing propylene and an α-olefin other than propylene, wherein the content of the alkenylsilane polymer is 0.1 wt ppm to 2 wt% with respect to the total composition. A characteristic polypropylene resin composition.

(2) (A) polypropylene is a propylene homopolymer,
The composition according to item 1, which is one or more polymers selected from a propylene-α-olefin random copolymer and a propylene-α-olefin block copolymer.

(3) The titanium catalyst component for olefin polymerization containing an alkenylsilane polymer is an organoaluminum compound (A
L ₂ ), or a reaction product (I) of an organoaluminum compound (AL ₂ ) and an electron donor (E ₂ ) is reacted with titanium tetrachloride to obtain a solid product (II), The expression is (Wherein n is an integer from 0 to 2 and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group). The composition according to the above item 1, which is a titanium catalyst component for olefin polymerization obtained by reacting an electron donor (E ₃ ) and an electron acceptor with the solid product (II) that has undergone the polymerization step. .

(4) An olefin polymerization titanium catalyst component containing an alkenylsilane polymer is obtained by contacting a liquefied magnesium compound with a depositing agent, a halogen compound, an electron donor (E ₄ ) and a titanium compound (T ₁ ). In the presence of the organoaluminum compound (AL ₃ ) for the solid product (III), (Wherein n is an integer from 0 to 2 and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group). To obtain a solid product (IV), and the solid product (IV)
The composition according to item 1, which is a titanium catalyst component for olefin polymerization, obtained by reacting a titanium halide compound (T ₂ ) with.

The polypropylene (A) used in the present invention is a combination of a titanium-containing solid 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, using a so-called Ziegler-Natta catalyst in which an electron donor component is combined as the third component of the catalyst, slurry polymerization performed in an inert catalyst, bulk polymerization using propylene itself as a solvent, or propylene gas as a main component Known propylene homopolymers, propylene-α-olefin random copolymers, propylene-α-olefin block copolymers obtained by polymerizing propylene or propylene and α-olefins other than propylene by gas phase polymerization or the like. One or more types of are used.

(B) which is the other component constituting the composition of the present invention.
Polypropylene has the following formula: (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) By polymerizing propylene, or propylene and an α-olefin other than propylene, using a catalyst containing a combination of a titanium catalyst component and an organoaluminum compound (AL ₁ ) contained, and optionally an electron donor (E ₁ ). can get.

The titanium catalyst component containing an alkenylsilane polymer, in the method for producing a titanium catalyst component comprising a multi-step process, polymerization conditions in any intermediate step, the general formula, (Wherein n is an integer from 0 to 2 and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group). The titanium catalyst component contains the alkenylsilane polymer obtained through the subsequent steps with respect to the solid that has undergone the polymerization step.

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 solid product (II) obtained by reacting the reaction product (I) with Titanium tetrachloride is polymerized with the alkenylsilane compound represented by the above general formula, and the polymerization process is performed. It is obtained by reacting the solid product (II) with an electron donor (E ₃ ) and an electron acceptor.

The above organoaluminum compound (AL ₂ ) and electron donor (E ₂ )
The reaction with -20 ° C to 200 ° C, preferably -1 in a solvent (D ₁ ).
It is carried out at 0 ° C to 100 ° C for 30 seconds to 5 hours. 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 organoaluminum compound (AL ₂ ) and the electron donor (E ₂ ) 0.1. Mol to 8 mol, preferably 1 to 4 mol, solvent 0.5 L to 5 L, preferably 0.5 L to 2 L. Thus, the reaction product (I) is obtained. Reaction product (I)
Can be used for the next reaction in a liquid state (sometimes referred to as a reaction product liquid (I)) after completion of the reaction without separation.

A step of polymerizing an alkenylsilane compound with a solid product (II) obtained by reacting the reaction product (I) with titanium tetrachloride or the organoaluminum compound (AL ₂ ) with titanium tetrachloride; As a method of carrying out, the reaction product (I) or the organoaluminum compound (AL ₂ )
Of the alkenylsilane compound in any step of the reaction of alkanol with titanium tetrachloride to polymerize the solid product (II), the reaction product (I), or the organoaluminum compound (AL ₂ ) With titanium tetrachloride, the solid product (II) is obtained by adding an alkenylsilane compound.
To carry out the step of polymerizing, and after completion of the reaction between the reaction product (I) or the organoaluminum compound (AL ₂ ) and titanium tetrachloride, after removing the liquid portion by filtration or decantation There is a method of suspending the obtained solid product (II) in a solvent, adding an organoaluminum compound and an alkenylsilane compound, and polymerizing the alkenylsilane compound.

Reaction product (I) or organoaluminum compound (A
The reaction of L ₂ ) with titanium tetrachloride is -1 with or without the addition of an alkenylsilane compound at any stage of the reaction.
It is carried out at 0 ° C to 200 ° C, preferably 0 ° C to 100 ° C for 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 alkenylsilane compound 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
~ 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 10, preferably 0.06 to 0.3. Is.

The step of polymerizing the alkenylsilane compound is carried out when the alkenylsilane compound is added at any stage of the reaction between the reaction product (I) or the organoaluminum compound (AL ₂ ) and titanium tetrachloride, and the reaction product (I) Or, when the alkenylsilane compound is added after the reaction between the organoaluminum compound (AL ₂ ) and titanium tetrachloride, 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.
0.1 g to 10 per 100 g of the solid product (II) under the condition of f / cm ² G.
Polymerization is carried out using 0 kg of the alkenylsilane compound so that the content of the alkenylsilane polymer in the final titanium catalyst component is 0.1% by weight to 99% by weight. When the content of the alkenylsilane polymer is less than 0.1% by weight, the effect of improving the transparency and crystallinity of the obtained polypropylene resin composition is insufficient, and when it exceeds 99% by weight, the improving effect is remarkable. It becomes economically disadvantageous.

The step of polymerizing the alkenylsilane compound was obtained after the reaction product (I) or the organoaluminum compound (AL ₂ ) and titanium tetrachloride were reacted and then the liquid portion was separated and removed by filtration or decantation. Solid product (I
If the suspension of (I) in a solvent is carried out, the solid product (I
I) To 100 g, add 100 ml to 5,000 ml of a solvent and 0.05 g to 5,000 g of an organoaluminum compound, and add 1 at a reaction temperature of 0 ° C to 90 ° C.
Minutes to 10 hours, the reaction pressure is atmospheric pressure to 10 kgf / cm ² G, 0.1 g to 100 kg of the alkenylsilane compound per 100 g of the solid product (II) is used in the final titanium catalyst component. Polymerization is performed so that the content of the silane polymer is 0.1% by weight to 99% by weight. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound is used for obtaining the reaction product (I) or used for 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 after the polymerization step (hereinafter referred to as solid product (II-A) (In some cases) 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 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, and preferably 100 g, based on 100 g of the solid product (II-A).
0.2g-500g, solvent 0-3,000ml, preferably 100-1,000m
is l. As a reaction method, a solid product (II-A)
A method of simultaneously reacting an electron donor (E ₃ ) and an electron acceptor (F), (II-A) is reacted with (F), and then (E)
A method of reacting _3), (after reacting the (E ₃₎ in II-A), (a method of reacting F), after reacting the (E ₃₎ and (F), (II-A) There is a method of reacting with, but any method may be used. The reaction conditions are 40 ° C. to 200 ° C., preferably 50 ° C. to 100 ° C. for 30 seconds to 5 in the above method.
It is desirable to react for 2 hours, and in the method of (II-A) and (E ₃ ) are reacted at 0 ° C to 50 ° C for 1 minute to 3 hours, and (F) is the same as the above. React under conditions. In the other method, (E ₃ ) and (F) are heated at 10 ℃
After reacting at -100 ° C for 30 minutes to 2 hours, it is cooled to 40 ° C or lower, (II-A) is added, and then the reaction is conducted under the same conditions as described above. After the reaction of the solid products (II-A), (E ₃ ), and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is repeated to contain an alkenylsilane polymer. A titanium catalyst component is obtained.

The organoaluminum compound (AL ₂ ) used for producing the titanium catalyst component containing the alkenylsilane polymer has a general formula of A
lR ⁴ _m R ⁵ _m · X _{3- (m + m ′)} (wherein R ⁴ and R ⁵ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen. , And m and m ′ are 0 <m +
Represents an arbitrary number of m ′ ≦ 3. ),
Specific examples thereof include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, tri
Tri-alkyl aluminums such as n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum, tri n-octyl aluminum, and tri n-decyl aluminum, diethyl aluminum Monochloride, di-n-propylaluminum monochloride, di
Dialkyl aluminum monohalides such as i-butyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide, diethyl aluminum monoiodide, etc., dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride Alkyl aluminum sesquihalides such as, aluminum aluminum dichloride, monoalkyl aluminum dihalides such as i-butyl aluminum dichloride, and the like. In addition, alkoxyalkyl aluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum are used. You can also 2 of these organoaluminums
It is also possible to use a mixture of more than one type.

As the electron donor used in the production of the alkenylsilane polymer-containing titanium catalyst component used in the present invention, various electron donors shown below are shown, but ethers are mainly used as (E ₂ ) (E ₃ ). It is preferable that the other electron donor is used together with the ethers. What is used as an electron donor is
Organic compounds having any atom of oxygen, nitrogen, sulfur and phosphorus, 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,
Thio alcohols and the like. Specific examples include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-
Pentyl ether, di-n-hexyl ether, di-hexyl ether, di-n-octyl ether, di-octyl ether, di-n-todecyl ether, diphenyl ether, ethylene glycol monoethyl ether, ethers such as tetrahydrofuran, methanol, Ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerol and other alcohols, phenol, cresol, xylenol, ethylphenol, naphthol and other phenols, methacrylic acid Methyl, methyl formate, methyl acetate,
Methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate, i-propyl acetate, butyl formate, amyl acetate, n-acetate
Butyl, octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-benzoic acid
Ethylhexyl, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphthoate 2 -Monocarboxylic acid esters such as ethylhexyl and ethyl phenylacetate, aliphatic polycarboxylic acid esters such as diethyl succinate, dibutyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate and diethyl butylmaleate , Monomethyl fitarate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-phthalate
n-butyl, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, isophthalic acid Dipropyl, 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 and benzoic acid, acid anhydrides such as benzoic anhydride, phthalic anhydride and tetrahydrophthalic anhydride, acetone , Methyl ethyl ketone,
Ketones such as methyl isobutyl ketone and benzophenone, nitriles such as acetonitrile and benzonitrile,
Methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, 2,2,6,6-tetramethyl Piperidine, 2,
Amine such as 2,5,5-tetramethylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N', N ' , N ″ -pentamethyl-N′-β-dimethylaminomethylphosphoric triamide, amides such as octamethylpyrophosphoramide, ureas such as N, N, N ′, N′-tetramethylurea, phenyl isocyanate, Isocyanates such as toluyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, phosphines such as triphenylphosphine oxide, dimethylphosphite, di-n -Octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, Phosphites such as rephenylphosphite, phosphinites such as ethyldiethylphosphinite, ethylbutylphosphinite, and phenyldiphenylphosphinite, diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide, thioethers such as propylene sulfide , Ethyl thioether,
Examples include thioalcohols such as n-propyl thioether and thiophenol.

These electron donors can also be used as a mixture.
The electron donor (E ₂ ) for obtaining the reaction product (I) and (E ₃ ) reacted with the solid product (II-A) may be the same or different. The electron acceptor (F) reacted with the solid product (II-A) is represented by a halide of an element of Group 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 solvents are used. 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. It is also possible to use halogenated hydrocarbons such as dichloroethane, trichloroethylene, and tetrachloroethylene. As aromatic compounds, 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, chlorxylene. , Halides such as chloroethylbenzene, dichlorobenzene, and bromobenzene are shown.

The alkenylsilane compound used for carrying out the step of polymerizing has the general formula (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Vinyltrimethylsilane, vinyltriethylsilane, vinyltrin-
Butylsilane, vinyldimethylcyclohexylsilane,
Examples thereof include vinyldimethylphenylsilane, allyltrimethylsilane, allyltriethylsilane, allyltripropylsilane, 3-butenyltrimethylsilane, and 3-butenyltriethylsilane.

In addition to the titanium catalyst component containing the alkenylsilane polymer obtained as described above, for example, a liquefied magnesium compound and a depositing agent, a halogen compound, an electron donor (E ₄ )
And solid products obtained by contacting titanium compounds (T ₁ )
For (III), in the presence of an organoaluminum compound (AL ₃ ),
It is obtained by carrying out a step of polymerizing an alkenylsilane compound to obtain a solid product (IV) and reacting the solid product (IV) with a titanium halide compound (T ₂ ). A titanium catalyst component containing an alkenylsilane polymer can also be used.
The method for producing the titanium catalyst component will be described below.

The term "liquefaction" of the magnesium compound referred to 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, or reacts with another compound, 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 substance in the form of a Colorado or a semi-dissolved substance other than the case where it is 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 ⁶ _r R ⁷ _s (M is aluminum, zinc, boron or beryllium atom, R ⁶ and R ⁷ are hydrocarbon residues, p, q, r, s> 0, v
Is the valence of M, there is a relation of r + s = vp + 2q. ) Can be formed (for example, JP-A-50-139885) and dissolved in a hydrocarbon solvent to be liquefied.

Furthermore, when metallic magnesium is used, a method of liquefying with alcohol and ethyl orthotitanate (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 magnesium compounds as described above, for example, the case of dissolving magnesium chloride in a hydrocarbon solvent (D ₂ ) using titanic acid ester and alcohol is described as follows: , 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 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 minutes to 7 hours, preferably 10 minutes to 5 hours. Ti as titanate
Orthotitanate represented by (OR ⁸ ) ₄ and R
⁹ O—Ti (OR ¹⁰ ) (OR ¹¹ ) _t OR ¹² is a polytitanate ester. Where R ⁸ , R ⁹ ,
R ¹⁰ , R ¹¹ and R ¹² are an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group 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 orthottanate, phenyl orthotitanate and cyclohexyl orthotitanate, methyl polytitanate, ethyl polytitanate, n-propyl polytitanate, polytitanate
Use polytitanate esters such as i-propyl, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate, and cyclohexyl polytitanate. You can The amount of polytitanate used is converted to orthotitanate,
An equivalent amount of orthotitanate may be used.

Aliphatic saturated and unsaturated alcohols can be used as alcohols. Specifically, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, n-amyl alcohol, i-amyl alcohol, n-hexyl alcohol, n-
In addition to monohydric alcohols such as octyl alcohol, 2-ethylhexyl alcohol 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), pentane, hexane, heptane, nonane, aliphatic hydrocarbons such as decane and kerosene, benzene, aromatic hydrocarbons such as toluene and xylene, tetrachloride hydrocarbon, 1,2 -Dichloroethane, 1,1,2-trichloroethane, chlorobenzene and 0-
Mention may be made of halogenated carbon hydrogen such as dichlorobenzene. Of these, aliphatic hydrocarbons are preferable.

The solid product (III) is a liquefied magnesium compound and a precipitant (X ₁ ), a halogen compound (X ₂ ), an electron donor (E ₄ ).
And a titanium compound (T ₁ ) in contact with each other. Precipitating agent (X
_{As 1} ), halogen, halogenated hydrocarbon, halogen-containing silicon compound, halogen-containing aluminum compound,
Examples of the halogenating agent include a halogen-containing titanium compound, a halogen-containing zirconium compound, and a halogen-containing vanadium compound. When the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen, such as alcohol or polysiloxane having a Si—H bond, can be used. The amount of these depositing agents (X ₁ ) used is 0.1 to 50 mol per 1 mol of the magnesium compound. Also, halogen compounds
Examples of (X ₂ ) include halogen and compounds containing halogen, the same halogenating agents as examples of the precipitating agent can be used, and when a halogenating agent is used as the precipitating agent, Does not necessarily require a new use of the halogen compound (X ₂ ). The amount of the halogen compound (X ₂ ) used is 0.1 mol to 50 mol per 1 mol of the magnesium compound.
Use mol.

Examples of the electron donor (E ₄ ) include those similar to those used as (E ₂ ) and (E ₃ ) described above, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldi Ethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltriethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxy Examples of the organic silicon compound having a Si-OC bond such as silane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrii-propoxysilane, and vinyltriacetoxysilane are preferable, and aromatic monocarboxylic acid esters are preferable. , Aromatic polyvalent carboxylic acid esters, alkoxysilanes, and particularly preferably aromatic polyvalent carboxylic acid esters are used.

One or more kinds of these electron donors (E ₄ ) are used, and the amount used is 0.01 mol to 5 mol per 1 mol of the magnesium compound.
It is a mole.

The titanium compound (T ₁ ) necessary for the preparation of the solid product (III) is
General formula Ti (OR ¹³ ) _4-u X _u (wherein R ¹³ represents an alkyl group, a cycloalkyl group or an aryl group, X represents a halogen, and u
Is an arbitrary 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, diethoxy titanium dibromide, dibutoxy titanium dibromide, chloride Examples thereof include trimethoxy titanium, triethoxy titanium chloride, tributoxy titanium chloride, and triphenoxy titanium 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, but the titanium compound (T ₁ )
When a titanium halide compound is used as the compound, since it has halogen, the depositing agent (X ₁ ) and the halogen compound (X _{1
Use of 2} ) is optional. Further, even when a titanate ester is used in the liquefaction of the magnesium compound, the new use of the titanium compound (T ₁ ) is optional. The amount of the titanium compound (T ₁ ) used is 0.1 mol to 100 mol per 1 mol of the magnesium compound.

Liquefied magnesium compound, precipitation agent (X ₁ ), halogen compound (X ₂ ), electron donor (E ₄ ) and titanium compound
(T ₁ ) is contacted with stirring to obtain a solid product (III). At the time of contact, an inert hydrocarbon solvent (D ₃ ) may be used, or each component may be diluted in advance and used. Examples of the inert hydrocarbon solvent (D ₃ ) used include the same ones as the above-mentioned (D ₂ ). The amount used is 0 to 5,000 ml per mol of the magnesium compound. There are various methods of contact, for example, (X ₁ ) is added to a liquefied magnesium compound to precipitate a solid, and (X ₂ ) is added to the solid.
A method of contacting (E ₄ ) and (T ₁ ) 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. Liquefied magnesium compound and
After contacting (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, if a titanate ester is used to liquefy a magnesium compound,
(T ₁₎ is, in the case of using a halogen-containing titanium compound as a precipitating agent (X ₁₎ (X ₂₎ and the case (T ₁₎ is, by using a halogenating agent as a precipitation agent (X ₁₎ (X ₂ ) are optional components.

The contact temperature of each component is −40 ° C. to + 180 ° C., preferably
The contact time is -20 ° C to + 150 ° C, and the contact time is 5 minutes to 8 hours, preferably 1 at each reaction pressure of atmospheric pressure to 10 kg / cm ² G.
It is from 0 minutes to 6 hours.

A solid product (III) is obtained in the above catalytic 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 method is subjected to a step of polymerizing an alkenylsilane compound in the presence of the organoaluminum compound (AL ₃ ) to obtain a solid product (IV).

The step of polymerizing the alkenylsilane compound is a solid product.
(III) relative to 100 g, an inert hydrocarbon solvent (D ₄₎ 100ml~5,00
0 ml of organoaluminum compound (AL ₃ ) 5 g to 5,000 g was added, the reaction temperature was 0 ° C. to 90 ° C. for 1 minute to 10 hours, and the reaction pressure was atmospheric pressure to 10 kg / cm ² G under the conditions of alkenylsilane compound. Add 0.1 to 100 kg, and polymerize so that the content of the alkenylsilane polymer in the final titanium catalyst component will be 0.1 to 99% by weight. The alkenylsilane polymer content is 0.1
If the amount is less than 10% by weight, the effect of improving the transparency and crystallinity of the obtained polypropylene resin composition is insufficient, and 99
When the content is more than weight%, the improvement effect is not remarkable and it is economically disadvantageous.

In the step of carrying out the step of polymerizing, carboxylic acid esters such as ethyl benzoate, methyl toluate and ethyl anisate, silane compounds such as phenyltriethoxysilane, diphenyldimethoxysilane and methyltriethoxysilane, etc. It is also possible to coexist with a representative electron donor. Their usage is
0 to 5,000 g per 100 g of solid product (III).

Organoaluminum compound used when carrying out the polymerization step
As (AL ₃ ), the solvent (D ₄ ) and the alkenylsilane compound, the same ones as the above-mentioned (AL ₂ ), (D ₂ ) and the alkenylsilane compound are used.

As described above, the step of polymerizing with the alkenylsilane compound is performed, and the solid product (IV) is obtained by washing with the above-mentioned inert hydrocarbon solvent.

Subsequently, the solid product (IV) was added to the titanium halide compound (T ₂ ).
To obtain a titanium catalyst component containing an alkenylsilane polymer. As the titanium halide compound (T ₂ ), the general formula Ti (OR ¹³ ) _4-u X given as an example of the titanium compound (T ₁ ) necessary for the preparation of the solid product (III) described above is used.
_A titanium halide compound represented by _u (wherein R ¹³ represents an alkyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and u is an arbitrary number of 0 <u ≦ 4) is used. Although similar examples can be given as specific examples, titanium tetrachloride is most preferable.

The reaction of the solid product (IV) and the titanium halide compound (T _2), relative to the magnesium compound 1 mol in the solid product (IV), using a titanium halide compound (T ₂₎ 1 mole or more The reaction temperature is 20 ℃ to 200 ℃, the reaction pressure is atmospheric pressure to 10kg / cm.
^The reaction is carried out under ² G for 5 minutes to 6 hours, preferably 10 minutes to 5 hours. Further, during the reaction, an inert hydrocarbon solvent (D ₅ )
It is also possible to carry out the reaction in the presence of an electron donor (E ₅ ) or an electron donor, and specifically, the same inert solvent and electron donor as those described above for (D ₁ ) to (D ₄ ) and (E ₄ ). Is used. The usage of these is
It is desirable that (D ₅ ) be 0 to 5,000 ml per 100 g of the solid product (IV) and that (E ₅ ) be 0 to 2 mol per 1 mol of the magnesium compound in the solid product (IV). After reaction of 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, and unreacted. By removing substances or by-products, a titanium catalyst product is obtained.

The titanium catalyst component containing the alkenylsilane polymer obtained by various methods as described above can be used in the same manner as the known titanium catalyst component for olefin polymerization such as propylene.

The alkenylsilane polymer-containing titanium catalyst component is combined with an organoaluminum compound (AL ₁ ) and optionally an electron donor (E ₁ ) to form a catalyst, or a small amount of α-olefin is further preliminarily activated. As a catalyst, by the same polymerization method as the known propylene polymerization method described above,
Propylene, or α other than propylene and propylene
-(B) polypropylene is obtained by polymerizing olefins.

As the organoaluminum compound (AL ₁ ), the same organoaluminum compounds as (AL ₂ ) and (AL ₃ ) used for obtaining the titanium catalyst component described above can be used. Further, the electron donor (E ₁ ) used as necessary is an organic acid ester, an organosilicon compound having a Si-OC bond such as an alkoxysilane compound or an aryloxysilane compound, an ether, a ketone, an acid anhydride, or an amine. Etc. are preferably used. Specific examples thereof include the same as those exemplified as the electron donors (E ₂ ) to (E ₅ ) used when producing the titanium catalyst component described above.

The amount of the titanium catalyst component containing the alkenylsilane polymer, the organoaluminum compound (AL ₁ ) and the electron donor (E ₁ ) used is 0.005 g to 500 g of the organoaluminum compound (AL ₁ ) per ₁ g of the titanium catalyst component. , Electron donor (E ₁ ) 0-500 g
Is.

Further, α-olefin used in the pre-activation and copolymerization with propylene, in addition to propylene, ethylene, butene-1, pentene-1, hexene-1, heptene-1,
Examples include straight chain monoolefins such as octene-1, and branched chain monoolefins such as 4-methyl-pentene-1 and 2-methyl-pentene-1. The polypropylene produced using the thus obtained (B) alkenylsilane-containing titanium catalyst component is added to the above-mentioned (A) known polypropylene to obtain the polypropylene resin composition of the present invention.
Regarding the addition amount, it is added so that the content of the alkenylsilane polymer becomes 0.1 wtppm to 2 wt% with respect to the entire composition. When the content of the alkenylsilane polymer is less than 0.1 ppm by weight, the effect of improving the transparency and crystallinity of the obtained composition is insufficient, and when it exceeds 2% by weight, the effect is not remarkable. Not 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, Henschel mixer (trade name),
A high speed stirring device such as a super mixer may be used,
As a kneading device, a Banbury mixer, a roll, a co-kneader, a 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.

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, within the range not significantly impairing the object of the present invention. Examples of the filler include inorganic or organic fillers such as glass fiber, talc, mica, wood powder and synthetic fiber.

The polypropylene resin composition of the present invention thus obtained, injection molding, vacuum molding, extrusion molding, blow molding,
It is provided for manufacturing films, sheets, containers, etc. by known techniques such as stretching.

〔The invention's effect〕

The polypropylene resin composition of the present invention is extremely excellent in transparency and crystallinity. Furthermore, the film produced using the composition of the present invention has very few voids.

As is apparent from the examples shown below, the internal haze of the press film obtained by using the composition of the present invention is higher than that of the known polypropylene obtained by using the titanium catalyst component containing no alkenylsilane polymer. It is about 1/7 to 2/7, and has extremely high transparency. Further, the crystallinity as well as the transparency is remarkably improved, and the crystallization temperature is increased and the flexural modulus is improved. (See Examples 1 to 7 and Comparative Examples 1 and 5 to 6) Further, even if the alkenylsilane polymer is contained, it is obtained by multi-stage polymerization of the alkenylsilane compound and propylene under the catalyst system already formed. The composition using the obtained polypropylene (see Comparative Examples 2 and 4) has many voids in the film due to poor dispersion of the alkenylsilane polymer,
The improvement in transparency and crystallinity is also insufficient as compared with the composition of the present invention.

〔Example〕

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
Internal haze: It is the internal haze of the film excluding the influence of the surface, and the composition is made into a film having a thickness of 150μ under the conditions of a temperature of 200 ° C and a pressure of 200 kg / cm ² G using a press machine. After coating liquid paraffin on both sides, JISK7105
The haze was measured according to. (Terminal:%) Crystallization temperature: measured with a differential scanning calorimeter at a temperature decreasing rate of 10 ° C./min. (Unit: ° C) Flexural modulus: The composition was melted on an injection molding machine at a temperature of 230
℃, mold temperature 50 ℃, make a JIS type test piece,
The test piece is 72% in a room with a humidity of 50% and a room temperature of 23 ° C.
After standing for a time, the flexural modulus was measured according to JIS K7203. (Unit: kgf / cm ² ) Void: The composition 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 of 20 ° C. The sheet was heated with hot air at 150 ° C. for 70 seconds and stretched 7 times in both longitudinal and transverse directions using a biaxial stretching machine to obtain a 20 μ thick biaxially stretched film. The film was observed with an optical microscope, and the number of voids having a diameter of 10 μm or more was measured, and less than 20 per 1 cm ² was indicated by ◯, 20 or more and less than 50 by Δ, and 50 or more by x.

Example 1 (1) Production of polypropylene (B) using titanium catalyst component containing alkenylsilane polymer Production of titanium catalyst component containing alkenylsilane polymer n-Hexane 6 Diethylaluminum Monochloride (D
EAC) 5.0 mol and diisoamyl ether 12.0 mol were mixed at 25 ° C. for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (I) (diisoamyl ether / DEAC molar ratio 2.4). 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35 ° C., the whole amount of the above reaction product liquid (I) was added dropwise to this in 180 minutes, and then kept at the same temperature for 60 minutes and then to 80 ° C. The temperature was raised and the reaction was continued for another hour, then cooled to room temperature, the supernatant was removed, n-hexane 20 was added and the supernatant was removed by decantation was repeated 4 times to obtain a solid product (II). It was The whole amount of this (II) was suspended in n-hexane 60, 600 g of diethylaluminum monochloride was added, 35 kg of allyltrimethylsilane was added at 40 ° C., and polymerization was carried out at 40 ° C. for 2 hours. After carrying out this step, the temperature was raised to 50 ° C., n-hexane 30 excluding the supernatant was added, and the operation of removing the supernatant by decantation was repeated 4 times to carry out the step of polymerizing a solid product ( II-A) was obtained. 3.5 kg of titanium tetrachloride was added in a state where the whole amount of the solid product was suspended in n-hexane 25 at room temperature for about 10 minutes and reacted at 80 ° C. for 30 minutes, and then diisoamyl ether 1.6 was added. 8 kg added
The reaction was carried out at 0 ° C for 1 hour. After the reaction was completed, the supernatant was removed by decantation, 40 n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand and the supernatant was removed 5 times. The ingredients are obtained. The content of polyallyltrimethylsilane in the obtained titanium catalyst component was 8
The content was 5.7% by weight and the titanium content was 3.6% by weight.

Preparation of pre-activated catalyst After replacing the stainless steel reactor with an inclined blade with an internal volume of 100 with nitrogen gas, n-hexane 70, diethyl aluminum monochloride 11.4 g, obtained titanium catalyst component 1.26 k
After adding g at room temperature, add ethylene to 1.2 at 30 ° C for 2 hours.
After supplying 5 Nm ³ and reacting (1.0 g of ethylene per 1 g of titanium catalyst component reaction), unreacted ethylene was removed to obtain a preactivated catalyst.

Polymerization of Propylene L / D = 3 equipped with a stirrer with an internal volume of 80 and nitrogen substitution
Horizontal Polymerizer MFR2.0 Polypropylene Powder 20k
After the addition of g, the above pre-activated catalyst was continuously supplied at 6.5 mg atom / hr in terms of titanium atom, and a 30 wt% n-hexane solution of diethylaluminum monochloride at 3.8 g / hr as diethylaluminum monochloride.

Hydrogen was supplied so that the concentration in the gas phase was maintained at 1.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G, and gas phase polymerization of propylene was continuously performed at 70 ° C for 120 hours. I went. During the polymerization period, the polymer was continuously withdrawn from the polymerization vessel at 10 kg / hr so that the retention level of the 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 for 30 minutes at 95 ° C., and then as polypropylene (B) of MFR1.8 containing 741 ppm by weight of polyallyltrimethylsilane. Was obtained.

(2) Production of polypropylene resin composition A polypropylene (B) containing the polyallyltrimethylsilane obtained in (1) (3.0 kg) in a Henschel mixer (trade name) with an internal volume of 50, and a normal propylene single weight of MFR1.8 7.0 kg of the combined powder, 5 g of tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, and 5 g of calcium stearate were added,
Stir-mix 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. to obtain a pellet-shaped polypropylene resin composition. The evaluation results of the obtained composition are shown in the table.

Comparative Example 1 A composition was obtained in the same manner as in Example 1 (2) except that polypropylene containing polyallyltrimethylsilane was not used and 10 kg of a normal propylene homopolymer was used. The evaluation results of the obtained composition are shown in the table.

Comparative Example 2 (1) Production of Polypropylene Containing Alkenylsilane Polymer The solid product (II) in Example 1 (1) was used without carrying out the step of polymerizing allyltrimethylsilane. -A) A titanium catalyst component was obtained in the same manner except that it was an equivalent product.

N-Hexane 60 was added to the reactor used in (1) of Example 1.
Then, 60 g of diethylaluminum monochloride and 360 g of the titanium catalyst component obtained above were added at room temperature, 3.8 kg of allyltrimethylsilane was added, and the mixture was reacted at 40 ° C. for 2 hours. (Reaction of 4.0 g per 1 g of titanium catalyst component) Propylene was obtained in the same manner as in (1) of Example 1 except that the catalyst slurry obtained by reacting allyltrimethylsilane obtained above was used in place of the preactivated catalyst. When the polymerization was carried out, the generated bulk polymer clogged the extraction pipe, and therefore the production had to be stopped 14 hours after the start of the polymerization. After the polymerization was stopped, the reactor was opened after cooling to room temperature, the lump polymer was taken out, and pulverized with a pulverizer to give 769 polyallyltrimethylsilane.
A polypropylene with MFR 1.5 containing ppm by weight was obtained.

(2) Polypropylene (B) obtained by using the titanium catalyst component containing the alkenylsilane polymer in (2) of Example 1
A polypropylene resin composition was obtained in the same manner except that 3.0 kg of the polypropylene obtained in (1) above was used instead of.

Comparative Example 3 and Examples 2 and 3 The polypropylene (B) containing polyallyltrimethylsilane and the ordinary propylene homopolymer in (2) of Example 1 were changed to have different polyallyltrimethylsilane contents. 0.01 wtppm, 12 wtppm, 371 wtppm
To obtain a polypropylene resin composition.

Example 4 (1) Production of polypropylene (B) using titanium catalyst component containing alkenylsilane polymer Production of titanium catalyst component Decane 3 was added in a stainless reactor equipped with a stirrer.
, 480 g of anhydrous magnesium chloride, 1.7 kg of n-butyl orthotitanate and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated to 130 ° C. for 1 hour with stirring to dissolve 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.
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 145 g of diphenyldimethoxysilane in which the total amount of the solid product (III) was kept at 30 ° C.
After suspending it in hexane 30 containing hexane, 11.5 kg of allyltrimethylsilane was added, and the mixture was stirred at the same temperature for 2 minutes.
The step of polymerizing for a time was carried out. After processing, remove the supernatant and n-
Hexane 20 was added and the operation of removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (IV) subjected to the step of polymerizing.

The total amount of the solid product (IV) was mixed with titanium tetrachloride 15 dissolved in 1,2-dichloroethane 15, then 360 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours while stirring, and then at the same temperature. In 1, the liquid phase part was removed by decantation, 1,2-dichloroethane 15 and titanium tetrachloride 15 were again 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 had a particle shape close to a sphere and contained 0.33% by weight of titanium and 88.9% by weight of polyallylsilane.

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 50, triethylaluminum 1.5 kg, diphenyldimethoxysilane 480 g, and titanium catalyst component 900 g obtained in room temperature were added. Added in. Reactor
Maintain ethylene at 30 ° C and 81
After supplying 0 Nl and reacting (1.0 g of ethylene per 1 g of titanium catalyst component reaction), unreacted ethylene was removed to obtain a preactivated catalyst.

Polymerization of Propylene After 20 kg of polypropylene powder of MFR2.0 was charged into the polymerization vessel used in (1) of Example 1, the preactivated catalyst slurry obtained above (in addition to the titanium catalyst component, triethylaluminum and diphenyldimethoxysilane) was used. including)
Was continuously supplied at 0.298 mg atom / hr in terms of titanium atom.

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 G, and 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 retained level of the polymer in the polymerization vessel was 60% by volume. The extracted polymer was subsequently subjected to a contact treatment with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 30 minutes, and then MFR2.0 polypropylene (B) containing 381 ppm by weight of polyallyltrimethylsilane. Was obtained as.

(2) Production of polypropylene resin composition In (2) of Example 1, 3.5 kg of polypropylene (B) obtained in (1) above as polypropylene (B) containing polyallyltrimethylsilane, and ordinary propylene alone A polypropylene resin composition was obtained in the same manner except that 6.5 kg of a polymer having MFR 2.0 was used.

Comparative Example 4 (1) A titanium catalyst was prepared in the same manner as in Example 1 (1) except that the solid product (III) was converted to the solid product (IV) equivalent without being polymerized with allyltrimethylsilane. The ingredients are obtained.

N-heptane 30 was added to the reactor used in (4) of Example 4.
, 100 g of the titanium catalyst component obtained above, 400 g of diethylaluminum monochloride, 120 g of diphenyldimethoxysilane and 1.6 kg of allyltrimethylsilane were added to 40
The reaction was carried out at 0 ° C for 2 hours. (Reaction of allyltrimethylsilane 6.5 g per 1 g of titanium catalyst component) Then, the solid was washed with n-heptane and filtered to obtain a solid. Furthermore, after adding n-heptane 30, diethylaluminum monochloride 400g, and diphenyldimethoxysilane 55g, propylene 280g was supplied and it was made to react at 30 degreeC for 1 hour. (Propylene 1.8g Reaction per 1g of Titanium Catalyst Component) In place of the preactivated catalyst slurry in (1) of Example 4, the catalyst slurry obtained above was further added with triethylaluminum 1.7g / hr and diphenyldimethoxysilane. At 0.30 g / hr, propylene was polymerized in the same manner except that it was supplied from different supply ports, and the produced bulk polymer blocked the powder extraction pipe, so that 12 I had to stop manufacturing in time. After stopping, the same treatment as in (1) of Comparative Example 2 was carried out to give polyallyltrimethylsilane 401
A polypropylene with MFR 1.5 containing ppm by weight was obtained.

(2) Polypropylene (B) obtained by using the alkenylsilane polymer-containing titanium catalyst component in (2) of Example 4
A polypropylene resin composition was obtained in the same manner except that 3.5 kg of the polypropylene obtained in (1) above was used instead of.

Example 5 (1) A solid solution was prepared by using a mixed solution of 1.8 kg of silicon tetrachloride and 2.0 kg of titanium tetrachloride instead of titanium tetrachloride in (1) of Example 1 and using 2.2 kg of diisoamyl ether. A titanium catalyst component was obtained in the same manner except that the product (II-A) was reacted, and then polypropylene (B) was obtained in the same manner as in (1) of Example 1.

(2) 2.5 kg of the polypropylene (B) obtained in the above (1) as the polypropylene (B) obtained by the titanium catalyst component containing the alkenylsilane polymer, and MFR1.8 as a normal polypropylene, and the content of ethylene unit is 0.2. weight%
A composition was obtained in the same manner as in (2) of Example 1 except that 7.5 kg of the propylene-ethylene random copolymer of was used.

Comparative Example 5 Instead of the polypropylene (B) obtained by the alkenylsilane polymer-containing titanium catalyst component in (5) of Example 5, a conventional polypropylene homopolymer of MFR1.8, 2.5k, was used.
A composition was obtained in the same manner except that g was used.

Example 6 (1) In the same manner as in (1) of Example 4, 376 weight parts of polyallyltrimethylsilane was similarly added except that ethylene was further supplied so that the concentration in the gas phase was kept at 0.2% by volume during the propylene polymerization. % MFR 1.7 propylene-ethene random copolymer was obtained.

(2) Polypropylene (B) obtained by using the alkenylsilane polymer-containing titanium catalyst component in (2) of Example 4
A polypropylene resin composition was obtained in the same manner as above except that 3.5 kg of the propylene-ethylene random copolymer obtained in (1) above was used.

Comparative Example 6 Without using the propylene-ethylene random copolymer obtained by using the alkenylsilane polymer-containing titanium catalyst component in (6) of Example 6, the usual propylene-ethylene copolymer was adjusted to 10 kg. A composition was obtained in the same manner except for the above.

Example 7 A titanium catalyst component was obtained in the same manner as in (1) of Example 1 except that 30 kg of 3-butenyltrimethylsilane was used instead of allyltrimethylsilane. Polypropylene (B) was manufactured and a polypropylene resin composition was manufactured.

Claims (4)

[Claims] 1. (A) polypropylene; (B) the following formula: (In the formula, n is an integer from 0 to 2, and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group.) Propylene using a catalyst containing a combination of an olefin polymerization titanium catalyst component, an organoaluminum compound (AL ₁ ), and an electron donor (E ₁ ) if necessary,
Alternatively, a composition comprising polypropylene obtained by polymerizing propylene and an α-olefin other than propylene, wherein the content of the alkenylsilane polymer is 0.1 wt ppm to 2 wt% with respect to the total composition. A characteristic polypropylene resin composition. 2. (A) Polypropylene is a propylene homopolymer, propylene-α-olefin random copolymer,
The composition according to claim 1, which is one or more kinds of polymers selected from propylene-α-olefin block copolymers. 3. A titanium catalyst component for olefin polymerization containing an alkenylsilane polymer is an organoaluminum compound.
(AL ₂ ) or a reaction product (I) of an organoaluminum compound (AL ₂ ) and an electron donor (E ₂ ) is reacted with titanium tetrachloride to obtain a solid product (II), The general formula is (Wherein n is an integer from 0 to 2 and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group). The solid catalyst (II) which has undergone the polymerization step and is further reacted with an electron donor (E ₃ ) and an electron acceptor to obtain a titanium catalyst component for olefin polymerization. Composition. 4. An olefin polymerization titanium catalyst component containing an alkenylsilane polymer is contacted with a liquefied magnesium compound and a depositing agent, a halogen compound, an electron donor (E ₄ ) and a titanium compound (T ₁ ). The solid product obtained (II
In the presence of the organoaluminum compound (AL ₃ ) for I), the general formula (Wherein n is an integer from 0 to 2 and R ¹ , R ² , and R ³ represent an alkyl group, a cycloalkyl group, or an aryl group). To obtain a solid product (IV), and the solid product (IV)
The composition according to claim 1, which is a titanium catalyst component for olefin polymerization, obtained by reacting a titanium halide compound (T ₂ ) with.