JPH0791334B2 - Manufacturing method of high-rigidity polypropylene - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing high-rigidity polypropylene. More specifically, it relates to a method for producing a high-rigidity polypropylene having extremely excellent transparency.

[Prior Art and Its Problems] The present inventors previously combined the titanium trichloride composition obtained by a specific method with an organoaluminum compound and a specific organosilicon compound in a specific usage ratio. For producing high-rigidity polypropylene using the following catalysts (Japanese Patent Application Nos. 63-121523, 63-123673 and 63-136821)
No., hereinafter referred to as the prior invention. According to the method of the invention of the prior application, it has become possible to produce polypropylene capable of obtaining a molded article having extremely high rigidity without adding any special additive.

However, although the polypropylene obtained by the method of the invention of the prior application has high rigidity as described above, it is semi-transparent, so the commercial value may be impaired in the field of use, and improvement in transparency is desired. It was rare.

The present inventors diligently studied a method for producing a high-rigidity polypropylene having improved transparency. As a result, a titanium trichloride composition similar to that used in the prior invention was combined with an organoaluminum compound, and a small amount of a specific branched chain olefin was preliminarily activated and pre-activated to obtain a specific organosilicon compound. The polypropylene obtained by polymerizing propylene using a catalyst formed by combining specific amounts has not only extremely excellent transparency as compared with the polypropylene obtained by the method of the prior invention, but also in rigidity. The inventors have found that it is improved and have reached the present invention.

As is apparent from the above description, an object of the present invention is to provide a method for producing a high-rigidity polypropylene having remarkably excellent transparency. Another object is to provide a high rigidity polypropylene having remarkably excellent transparency.

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

(1) Propylene is polymerized using a catalyst composed of a titanium trichloride composition (III), an organoaluminum compound (A ₁ ), and an organosilicon compound (S) having a Si—OC bond and / or a mercapto group, In the method for producing polypropylene, as a titanium trichloride composition (III), a reaction product (I) of an organoaluminum compound (A ₂ ) or an organoaluminum compound (A ₂ ) and an electron donor (B ₁ ) is added. The solid product (II) obtained by reacting titanium chloride is polymerized with α-olefin, or is not polymerized, and further, an electron donor (B ₂ ) and an element of Group III to VI of the periodic table. Titanium trichloride composition obtained by reacting with a halide of (III)
By combining the titanium trichloride composition (III) and the organoaluminum compound (A ₁ ) with the following formula: (In the formula, R ¹ has 1 to 3 carbon atoms which may contain silicon.
Represents a hydrocarbon group or a silicon, up, represents a R ^2, R ^3, R ⁴ is a hydrocarbon group having silicon from carbon atoms which may contain 1 to 6, the R ^2, R ^3, R ⁴ Either one may be hydrogen. ) A pre-activated catalyst component obtained by polymerizing 0.001 g to 100 g of a branched chain olefin represented by the formula (1) per 1 g of the titanium trichloride composition (III), and an additional organoaluminum compound (A ₁ ) if necessary. , An organosilicon compound (S) further having a Si-O-C bond and / or a mercapto group
And a molar ratio (S) / (III) of the organosilicon compound (S) having the Si—O—C bond and / or mercapto group and the titanium trichloride composition (III) = 1.0 to 10%.
And the molar ratio of the organoaluminum compound (A ₁ ) to the titanium trichloride composition (III) (A ₁ ) / (III) = 0.1 to 200
A process for producing high-rigidity polypropylene, which comprises polymerizing propylene using the catalyst described in 1.

(2) The production method according to the above item 1, wherein a dialkylaluminum monohalide is used as the organoaluminum compound (A ₁ ).

(3) The general formula for the organoaluminum compound (A ₂ ) is
AlR ⁵ _p R ⁶ _{p ′} X _{3- (p + p ′ )} (wherein R ⁵ and R ⁶ 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 p, p ′ is 0 <
It represents an arbitrary number of p + p'≤3. The manufacturing method of said 1st item using the organoaluminum compound represented by these.

(4) Melt flow rate (MFR) of polypropylene and absorbance ratio by infrared absorption spectroscopy (IR-τ: absorbance ratio at infrared wave number 997 cm ^-1 and 973 cm ^-1 , A ₉₉₇ / A
₉₇₃ ), wherein the relation with IR-τ ≧ 0.0203 log MFR + 0.950 is satisfied.

The structure of the present invention will be described in detail below.

As the titanium trichloride composition (III) used in the present invention,
A titanium trichloride composition similar to that used in the prior invention is used. The details of the manufacturing method are detailed in the specification of the prior invention, but are as follows.

A solid product (II) obtained by reacting titanium tetrachloride with an organoaluminum compound (A ₂ ) or a reaction product (I) of an organoaluminum compound (A ₂ ) and an electron donor (B ₁ ) is reacted. , A polymerization treatment with an α-olefin, or without a polymerization treatment, the electron donor (B ₂ ) and the electron acceptor are further reacted to give a titanium trichloride composition (II
I) is obtained. Details of each step are as follows.

First, the reaction between the organoaluminum compound (A ₂ ) and the electron donor (B ₁ ) to obtain the reaction product (I) is carried out by using the solvent (D).
In -20 ℃ ~ 200 ℃, preferably -10 ℃ ~ 100 ℃ 30 seconds ~
Do it for 5 hours. There is no limitation on the order of addition of (A ₂ ), (B ₁ ), and (D), and the amount ratio used is 0.1 to 8 mol, preferably 1 to 4 mol, of an electron donor based on 1 mol of organoaluminum.
A solvent of 0.5 to 5 l, preferably 0.5 to 2 l is suitable. Aliphatic hydrocarbons are preferred as the solvent. Thus, the reaction product (I) is obtained. The reaction product (I) can be subjected to the next reaction in a liquid state in which the reaction is completed (sometimes referred to as reaction product liquid (I)) without separation.

Next, the reaction between the reaction product (I) or the organoaluminum compound (A ₂ ) and titanium tetrachloride (C) is 0 to 200
C., preferably 10 to 90.degree. C., for 5 minutes to 8 hours. Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The mixing of (A ₂ ) or (I), (C) and the solvent may be performed in any order, and the total amount is 5
It is preferable to finish within the time. The amount of each used in the reaction is 1 mol of titanium tetrachloride, the solvent is 0 to 3,
000 ml of the organoaluminum compound (A ₂ ) or the reaction product (I) has a ratio (Al / Ti) of the number of Al atoms in the (A ₂ ) or the (I) to the number of Ti atoms in the titanium tetrachloride. 0.05-1
It is 0, preferably 0.06 to 0.3.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and the solid product (II) thus obtained is further washed with a solvent, and the obtained solid product (II) is suspended in the solvent to the next step. It may be used, or may be dried and taken out as a solid to be used.

Further, the solid product (II) obtained by reacting the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride is polymerized with α-olefin and used in the next reaction. Is also possible.

In the present invention, "polymerizing" means that a small amount of α-olefin is brought into contact with the solid product (II) to polymerize the α-olefin. By this polymerization treatment, the solid product (II) is in a state of being coated with the polymer. As a method of polymerizing with an α-olefin, (1) a solid product obtained by adding α-olefin in any process of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride A method of polymerizing (II), (2) after the reaction of the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride, α-olefin is added to give a solid product (II). Polymerization method, (3) Solid obtained after completion of reaction of organoaluminum compound (A ₂ ) or reaction product (I) with titanium tetrachloride, separation and removal of liquid portion by filtration or decantation There is a method in which the product (II) is suspended in a solvent, an organoaluminum compound and α-olefin are further added, and a polymerization treatment is carried out.

When an α-olefin is added at any stage of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride, and when the organoaluminum compound (A ₂ ) or the reaction product (I) and When the α-olefin is added after the reaction with titanium chloride, the reaction temperature
The α-olefin is added at 30 to 90 ° C. for 5 minutes to 10 hours at atmospheric pressure or at a pressure of 10 kg / cm ² G or less. The amount of α-olefin to be added is 0.05 g to 1,000 g using 10 to 5,000 g of α-olefin based on 100 g of the solid product (II).
g It is desirable to polymerize.

After the completion of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride in the polymerization treatment with α-olefin, the liquid portion is separated and removed by filtration or decantation, and the obtained solid is obtained. When the product (II) is suspended in a solvent, 100 g of the solid product (II) is used.
Solvent 100 ml ~ 2,000 ml, organoaluminum compound 0.5 g ~
5,000g was added and the reaction temperature was 30-90 ℃ for 5 minutes-10 hours.
Add 10 to 5,000 g of olefin at 0 to 10 kg / cm ² G and add 0.05
It is desirable to polymerize up to 1,000 g.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as or different from that used for (A ₂ ). 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) (Sometimes called) may be used in the next step in the state of being suspended in the solvent, and may be further dried and taken out as a solid to be used.

The solid product (II) or (II-A) is then reacted with an electron donor (B ₂ ) and an electron acceptor (F). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results. The amount to be used is (B ₂ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, based on 100 g of the solid product (II) or (II-A),
(F) 0.1 g to 1,000 g, preferably 0.2 g to 500 g, solvent 0
It is 3,000 ml, preferably 100 to 1,000 ml. As the reaction method, a solid product (II) or (II-A) is reacted with an electron donor (B ₂ ) and an electron acceptor (F) at the same time, or (F) is added to (II) or (II-A). ), And then reacting with (B ₂ ), (II) or (II-
After reacting the (B ₂₎ in A), after reacting method, the (B ₂₎ and (F) reacting (F), there is a method of reacting (II) or (II-A) Either method is acceptable. The reaction conditions are 40 in the above method.
It is desirable that the reaction is carried out at 30 ° C to 200 ° C, preferably 50 ° C to 100 ° C for 30 seconds to 5 hours. In the method, the reaction of (II) or (II-A) and (B ₂ ) is performed at 0 ° C to 50 ° C. After reacting for 1 minute to 3 hours, (F) is reacted under the same conditions as described above. In the other method, (B ₂ ) and (F)
Is reacted at 10 ° C. to 100 ° C. for 30 minutes to 2 hours, then cooled to 40 ° C. or lower, (II) or (II-A) is added, and then the reaction is performed under the same conditions as described above. Solid product (II)
Alternatively, after the reaction of (II-A), (B ₂ ) and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and then the washing with a solvent is repeated to obtain the titanium trichloride composition used in the present invention. The object (III) is obtained.

The titanium trichloride composition (III) obtained as described above is combined with an organoaluminum compound (A ₁ ), and this is combined with the following formula, (In the formula, R ¹ has 1 to 3 carbon atoms which may contain silicon.
Represents a hydrocarbon group up to, or silicon, and R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ² , R ³ and R ⁴ Either one may be hydrogen. Preliminary activation catalyst obtained by polymerizing 0.001 g to 100 g of a branched chain olefin represented by the formula (hereinafter sometimes abbreviated as branched chain olefin) per 1 g of the titanium trichloride composition (III). Ingredients and, if necessary, additional organoaluminum compound (A ₁ ), Si-OC bond and / or
Or an organosilicon compound (S) having a mercapto group
(Hereinafter, it may be abbreviated as organosilicon compound (S).) To form a catalyst used in the present invention.

Pre-activation is based on 1 g of titanium trichloride composition (III),
Organoaluminum compound (A ₁ ) 0.005 g to 500 g, solvent 0
50l, hydrogen 0-1,000ml, and branched chain olefins 0.01g
Use ~ 1,000g.

The polymerization reaction temperature is 0 ° C. to 100 ° C. for 1 minute to 20 hours, and the branched chain olefins are reacted to give 0.001 g to 100 g, preferably 0.01 g to 100 g of branched chain olefins per 1 g of the titanium trichloride composition (III). It is desirable to polymerize. Polymerization reaction amount is 0.001g
If it is less than 100g, the effect of improving transparency and rigidity is insufficient, and 100g
If it exceeds, the improvement of the effect will not be significant and it will be economically disadvantageous.

The preactivation can be carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane or toluene, and hydrogen may coexist during the preactivation. It is also possible to add the organosilicon compound (S) in advance in the preliminary activation.

After completion of the pre-activation reaction, the catalyst prepared by adding a predetermined amount of the organosilicon compound (S) to the pre-activation catalyst component slurry can be used as it is for the polymerization of propylene, or the coexisting solvent, Branched chain olefins of the reaction,
And the organoaluminum compound (A ₁ ) are removed by filtration,
A solvent is added to the dried powder or granules to make it in a suspended state, and this is combined with an additional organoaluminum compound (A ₁ ) and an organosilicon compound (S) to form a catalyst. Method for polymerization, coexisting solvent, and unreacted branched chain olefins under reduced pressure,
Or by an inert gas flow or the like, it is evaporated and removed, and the powder or granules or the powder or granules is suspended by adding a solvent, and an organoaluminum compound (A ₁ ) is added to the powder or granules if necessary. Further, it can be used as a catalyst in combination with an organosilicon compound (S) for the polymerization of propylene.

During the polymerization of propylene, the titanium trichloride composition (III), the total amount of the organoaluminum compound (A ₁ ) including the additional organoaluminum compound (A ₁ ) and the amount of the organosilicon compound (S) used. The molar ratio (S) / (III) of the organosilicon compound (S) to the titanium trichloride composition (III) is 1.0 to 10.0, and the organoaluminum compound (A ₁ ) is the titanium trichloride composition. It is used in a range that the molar ratio (A ₁ ) / (III) of (III) is 0.1 to 200.

When the addition amount of the organosilicon compound (S) is small, the crystallinity is insufficiently improved, so that the rigidity is not high, and when the addition amount is too large, the polymerization activity decreases, which is not practical. The number of moles of the titanium trichloride composition (III) is substantially included in (III).
Ti gram means the number of atoms.

The organoaluminum compound (A ₂ ) used for producing the titanium trichloride composition (III) used in the present invention has a general formula:
AlR ⁵ _p R ⁶ _{p ′} X _{3- (p + p ′)} (wherein R ⁵ and R ⁶ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and p represents ,
p'represents an arbitrary number of 0 <p + p'≤3. ) Is used.

Specific examples thereof include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum and tri n-
Butyl aluminum, tri i-butyl aluminum, tri
Tri-alkyl aluminums such as 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-propyl aluminum 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 Two or more kinds of these organoaluminum compounds may be mixed and used.

As the electron donor used in the present invention, various ones shown below are shown. As (B ₁ ) and (B ₂ ), ethers are mainly used, and other electron donors are shared with ethers. Is preferred. What is used as an electron donor is an organic compound 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,
Examples include phosphinites, hydrogen sulfide or thioethers, and thioalcohols. Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether,
Diisoamyl 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, tetrahydrofuran, etc. Ethers, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol,
Alcohols such as cresol, xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate,
Vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid
2-ethylhexyl, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate , 2-ethylhexyl naphthoate,
Esters such as ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, fatty acids such as acrylic acid and maleic acid, aromatic acids such as benzoic acid, methyl ethyl ketone, Methyl isobutyl ketone, ketones such as benzophenone, nitriles such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline,
Amine such as 2,4,6-trimethylpyridine, N, N, N ′, N′-tetramethylethylenediamine, aniline and dimethylaniline, foarumamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N "-pentamethyl-N'-β-
Amides such as dimethylaminomethylphosphoric acid triamide and octamethylpyrophosphoramide, ureas such as N, N, N′-N′-tetramethylurea, 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 -Phosphites such as octyl phosphite, triethyl phosphite, tri-n-butyl phosphite and triphenyl phosphite, phosphinites such as ethyl diethyl phosphinite, ethyl butyl phosphinite and phenyl diphenyl phosphinite, diethyl thioether , Diphenyl thioether, methyl phenyl thioether, ethylene sulfide, propylene sulfide and other thioethers, ethyl thioalcohol, n-propyl thiol Thio alcohols such as alcohol and thiophenol can also be mentioned. These electron donors can also be used as a mixture. The electron donor (B ₁ ) for obtaining the reaction product (I) and (B ₂ ) reacted with the solid product (II-A) may be the same or different.

The electron acceptor (F) used in the present invention is represented by the periodic table III to V.
It is represented by halides of Group I elements. 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 carbon hydrogen 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.

Examples of the α-olefin used in the polymerization treatment include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1, 4-methyl-pentene-1, 2-methyl-olefin. Branched chain monoolefins such as pentene-1 are used. These α-olefins may be used as a mixture of two or more α-olefins.

The branched chain olefins used for pre-activation are represented by the following formula, (In the formula, R ¹ has 1 to 3 carbon atoms which may contain silicon.
Represents a hydrocarbon group up to, or silicon, and R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ² , R ³ and R ⁴ Either one may be hydrogen. ) Is a branched chain olefin. Specific examples thereof include 3-position branched chain olefins such as 3-methylbutene-1, 3-methylpentene-1, and 3-ethylpentene-1, 4-ethylhexene-1,4,4-dimethylpentene-
4-position branched chain olefin such as 1,4,4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltrin-butylsilane, vinyldimethylcyclohexylsilane, vinyldimethylphenylsilane, allyltrimethylsilane, allyldimethylcyclohexylsilane, Examples include alkenylsilanes such as allyltriethylsilane, allyltrin-propylsilane, 3-butenyltrimethylsilane and 3-butenyltriethylsilane, and diallylsilanes such as dimethyldiallylsilane, ethylmethyldiallylsilane and diethyldiallylsilane. To be
One or more kinds of these branched chain olefins are used.

Dialkylaluminum monohalide is preferably represented by titanium trichloride composition (III) and combined with the organoaluminum compound (A _1), and an organic aluminum compound optionally used (A ₁₎ as the general formula AlR ⁷ R ⁸ X . In the formula, R ⁷ and R ⁸ represent a hydrocarbon group such as an alkyl group, an aryl group, an alkaryl group, a cycloalkyl group or an alkoxy group, X represents a halogen, and specific examples thereof include diethylaluminum monochloride and diamine. Examples thereof include n-propylaluminum monochloride, di-i-butylaluminum monochloride, di-n-butylaluminum monochloride, diethylaluminum monoiodide and diethylaluminum monobromide.

Organosilicon compound (S) having Si-OC bond and / or mercapto group which is another component constituting the catalyst
As specific examples that can be used as, methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxy. Silane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, allyltriethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n- Octadecyltriethoxysilane, 6-triethoxysilyl-2-norbornene, dimethyldiethoxysilane, diethyldiethoxysilane,
Diphenyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltri i-
Propoxysilane, dimethyldi-propoxysilane, trimethyli-propoxysilane, tetra-n-butoxysilane, methyltri-n-butoxysilane, tetra (2-ethylbutoxy) silane, methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane,
Trimethoxysilane, triethoxysilane, triethoxychlorosilane, tri i-propoxychlorosilane, tri
n-butoxychlorosilane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxysilane, Organosilicon compounds having a Si-OC bond such as trimethylacetoxysilane, triethylacetoxysilane, phenyldimethylacetoxysilane, triphenylacetoxysilane, bis (trimethylsilyl) adibate, trimethylsilylbenzoate and triethylsilylbenzoate, and mercaptomethyltrimethylsilane, 2- Mercaptoethyltrimethylsilane, 3-mercaptopropyltrimethylsilane, 4-
Mercapto-n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptopropyltriethylsilane, 1-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3-mercaptopropylethylmethylphenylsilane An organosilicon compound having a mercapto group such as 4-mercaptobutyldiethylphenylsilane and 3-mercaptopropylmethyldiphenylsilane,
Further, mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyldiethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2-mercaptoethyltrimethoxysilane, 3- Mercaptopropyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, diethoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, 3 -Organosilicon compounds having Si-OC bonds and mercapto groups such as mercaptopropoxytrimethylsilane and 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3 -(2-aminoethylaminopropyl) dimethoxymethylsilane, 2-aminoethylaminomethylbenzyloxydimethylsilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane and other Si-OC bonds and Examples thereof include organic silicon compounds having an amino group.

The catalyst thus obtained for use in the present invention is used for the polymerization of propylene. The propylene can be polymerized by slurry polymerization in a hydrocarbon solvent such as n-hexane, n-heptane, n-octane, benzene or toluene, or bulk polymerization and gas phase polymerization in liquefied propylene. It can be carried out.

Regarding the crystallinity of the polymer capable of exerting the effect of the present invention for the polypropylene obtained by the above-mentioned various polymerization modes, the melt flow rate (MF of polypropylene)
R) and the absorbance ratio by infrared absorption spectroscopy (IR-τ
And; the absorbance ratio at infrared wave numbers 997 cm ^-1 and 973 cm ^-1 ,
The relationship with A ₉₉₇ / A ₉₇₃ ) is characterized by satisfying the formula IR−τ ≧ 0.0203log MFR + 0.950.

The higher the crystallinity of the polymer, the higher the IR-τ, and the higher the MFR, the higher the IR-τ.

Practically, the MFR is practically 0.05 to 200, preferably 0.1 to 100.

The polymerization temperature is usually 20 to 100 ° C, preferably 40 to 85 ° C. If the temperature is too low, the polymerization activity becomes low, which is not practical, and if the temperature is high, it becomes difficult to increase the crystallinity. Polymerization pressure is normal pressure ~ 50kg / cm ² G, usually 30 minutes ~
It will be carried out for about 15 hours. At the time of polymerization, the addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as the conventional polymerization method.

Thus, the polypropylene obtained by the method of the present invention is a high-rigidity polypropylene having remarkably high transparency, and is used for various molded articles by the known techniques such as injection molding, vacuum molding, extrusion molding and blow molding. It

[Action] The high-rigidity polypropylene obtained by the method of the present invention is a highly stereoregular branched chain olefin polymer that exhibits a nucleating action, thereby promoting crystallization of polypropylene,
It improves the transparency and crystallinity of the entire polypropylene.

Further, since the branched chain olefin 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.

〔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.

(1) CY: Titanium trichloride composition (III) showing polymerization activity
It represents the polymer yield (g) per gram.

(2) MFR: Melt flow rate JIS K7210 Conditions in Table 1 14
(Unit: g / 10 minutes) (3) IR-τ: Preheat the sample with a pressure molding machine at 200 ° C for 1 minute-
After being formed into a film with a pressure of 1 minute, it was immediately water-cooled to 20 ° C. to obtain a film of about 40 μm. Then, the film is put in an annealing tube, sucked in a vacuum, and annealed in an oil bath at 135 ° C. for 1 hour. Three small films are cut out from the annealed film, the absorbance ratio of ₉₉₇ cm ⁻¹ and 973 cm ⁻¹ , (A ₉₉₇ / A ₉₇₃ ) is measured by using each of these small films as a measurement sample, and the average thereof is measured. Let the value be the IR-τ value. This IR- [tau] measurement was performed with a Perkin Elmer 783 type infrared spectrophotometer.

(4) Internal haze: The internal haze excluding the influence of the surface, using a press machine at a temperature of 200 ° C and a pressure of 200 kg.
After making polypropylene film of 150μ thickness under the condition of / cm ² G and applying liquid paraffin on both sides of the film,
The haze was measured according to JIS K7105. (Unit:%) (5) Crystallization temperature: Measured with a differential scanning calorimeter at a descending rate of 10 ° C / min.

(Unit: ° C) (6) Rigidity: Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'] based on 100 parts by weight of polypropylene
Hydroxyphenyl) propionate] methane (0.1 parts by weight) and calcium stearate (0.1 parts by weight) were mixed, and the mixture was granulated using an extruder having a screw diameter of 40 mm. Then, the granulated product is made into a JIS type test piece at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine, and the test piece is left for 72 hours in a room at a humidity of 50% and a room temperature of 23 ° C. Was measured by the following method.

(A) Flexural modulus: JIS K7203 compliant (Unit: kgf / cm ² ) (B) Tensile strength: JIS K7113 compliant (Unit: kgf / cm ² ) (C) Rockwell hardness (R scale): JIS K7202 Compliant (d) Heat distortion temperature (HDT): Compliant with JIS K7207 (Unit:
C.) Example 1 (1) Preparation of titanium trichloride composition (III) n-hexane 6 l, diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 12 mol were added at 25 ° C.
The mixture was mixed for 1 minute at room temperature and reacted for 5 minutes at the same temperature to obtain a reaction product (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., and the whole amount of the reaction product solution (I) was added dropwise to this in 30 minutes, and then kept at the same temperature for 30 minutes, and 75 ° C. The temperature was raised to 1, the reaction was continued for 1 hour, the mixture was cooled to room temperature, the supernatant was removed, 2 l of n-hexane was added, and the operation of removing the supernatant by decantation was repeated 4 times to obtain solid product (II) 1.9 I got kg.

The whole amount of this (II) was suspended in 30 liters of n-hexane, 200 g of diethylaluminum monochloride was added, 1.0 kg of propylene was added at 30 ° C., and the mixture was reacted for 1 hour to obtain a solid product (II-A ) (Propylene reaction amount 0.6k
g). After the reaction, the supernatant liquid was removed, 30 l of n-hexane was added, and the operation of removing by decantation was repeated twice. 2.5 kg of the solid product (II-A) subjected to the above-mentioned polymerization treatment in 6 l of n-hexane. Then, 3.5 kg of titanium tetrachloride was added at room temperature for about 1 minute and reacted at 80 ° C. for 30 minutes, 1.6 kg of diisoamyl ether was further added, and the mixture was reacted at 80 ° C. for 1 hour. After the reaction was completed, the supernatant was removed by decantation, 40 l of n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand, and the operation of removing the supernatant was repeated 5 times, and then dried under reduced pressure. A titanium chloride composition (III) was obtained. The titanium content in 1 g of the titanium trichloride composition (III) was 192 mg.

(2) Preparation of pre-activated catalyst component After replacing a stainless steel reactor with an inclined blade with an internal volume of 80 l with nitrogen gas, 40 l of n-hexane, 200 g of diethylaluminium monochloride, and the titanium trichloride composition obtained in (1) After adding 450 g of compound (III) at room temperature, the temperature in the reactor is adjusted to 40
℃, add allyl trimethylsilane 1.3Kg, 40 ℃ 2
Reacted for 1 hour (per 1 g of titanium trichloride composition (III),
Allyltrimethylsilane 1.0g reaction).

After completion of the reaction, unreacted allyltrimethylsilane, solvent and the like were removed by filtration, washed with n-hexane and dried to obtain a preactivated catalyst component in the form of powder.

(3) Polymerization of propylene After replacing the stainless reactor equipped with a stirrer with an internal volume of 500 liters with nitrogen gas, 200 liters of n-hexane, 50 g of diethylaluminum monochloride, and the preactivated catalyst obtained in (2) at room temperature 15 g as a titanium trichloride composition (III),
33 g of 3-aminopropyltriethoxysilane and 150 Nl of hydrogen were added. Subsequently, propylene was polymerized at a polymerization temperature of 70 ° C. and a propylene partial pressure of 10 kg / cm ² G for 3 hours. After completion of the reaction, 10 l of methanol was supplied and treated at 70 ° C for 30 minutes, and then unreacted propylene and unreacted hydrogen were discharged. Further, 100 g of a 20 wt% sodium hydroxide aqueous solution was added, and the mixture was treated at 70 ° C for 20 minutes. Subsequently, 100 l of pure water was added, and after stirring for 10 minutes, the operation of extracting the aqueous layer was performed twice, and then the polymer slurry was extracted, filtered and dried to obtain a polymer. Since the obtained polymer contained lumps, it was crushed with a crusher to powderize the whole amount of the polymer,
55.5 kg of R1.8 polypropylene was obtained.

Comparative Example 1 The titanium trichloride composition (II) obtained in (1) of Example 1 was used in place of the pre-activated catalyst component in (3) of Example 1.
Polypropylene was obtained in the same manner except that 15 g of I) was used.

Examples 2 and 3 Polypropylene was obtained in the same manner as in Example 1 except that the amount of hydrogen charged was changed to 230 l (Example 2) and 430 l (Example 3) in (3) of Example 1.

Comparative Examples 2 and 3 Polypropylene was obtained in the same manner as in Comparative Example 1 except that the hydrogen charge amount was changed to 220 l (Comparative Example 2) and 390 l (Comparative Example 3) in (3) of Example 1.

Comparative Example 4 A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that 560 g of propylene was used instead of allyltrimethylsilane, and then (3) of Example 1 was used.
Polymerization of propylene was carried out in the same manner as above to obtain polypropylene.

Comparative Example 5 In Comparative Example 1 (3), the catalyst component 3-aminopropyltriethoxysilane was not used, the titanium trichloride composition (III) was used in an amount of 10 g, and the amount of diethylaluminum monochloride was changed. Polypropylene was obtained in the same manner except that the amount was 33.3 g.

Comparative Example 6 and Examples 4 and 5 In Example 1 (2), dimethyldiallylsilane was used in place of allyltrimethylsilane, and the amounts thereof were changed to 0.4 g, 160 g, and 4.8 kg, respectively, to carry out pre-activation. A polypropylene was obtained in the same manner as in Example 1 except that the reaction was performed and 29 g of phenyltriethoxysilane was used instead of 3-aminopropyltriethoxysilane in (3).

Comparative Examples 7-9 and Examples 6,7 In (2) of Example 1, using 0.7 kg of 3-methylbutene-1 instead of allyltrimethylsilane,
Further, in (3), instead of 3-aminopropyltriethoxysilane, dimethoxy-3-mercaptopropylmethylsilane was used, and the molar ratio of dimethoxy-3-mercaptopropylmethylsilane to the titanium trichloride composition (III) was changed. Polypropylene was obtained in the same manner as in Example 1 except that the changes were made as shown in the table. However, Comparative Example 7,
In Example 8, 10 g of the pre-activated catalyst component was used as the titanium trichloride catalyst component and 33.3 g of diethylaluminum monochloride was used during the propylene polymerization of (3).

Example 8 (1) Preparation of titanium trichloride composition (III) n-heptane 8l, di-n-butylaluminum monochloride
16 mol and 10 mol of di-n-butyl ether were mixed at 30 ° C. for 10 minutes and reacted for 20 minutes to obtain a reaction product liquid (I). The whole amount of this reaction product liquid (I) was mixed with toluene 5 kept at 45 ° C.
l, dropped into a solution consisting of 64 mol of titanium tetrachloride in 60 minutes, heated to 85 ° C and reacted for 2 hours, cooled to room temperature, removed the supernatant, and added 30 l of n-heptane. The operation of removing the supernatant liquid by decantation was repeated twice to obtain 4.9 kg of a solid product (II) obtained. The total amount of this (II) is n-
Suspend in 30 liters of heptane, add 2.0 kg of di-n-butyl ether and 15 kg of titanium tetrachloride at room temperature for about 20 minutes, and add 2 at 90 ° C.
After reacting for a period of time and cooling, the supernatant was removed by decantation, washing with n-heptane and drying were performed to obtain a titanium trichloride composition (III). The content of titanium atoms in 1 g of the titanium trichloride composition (III) was 255 mg.

(2) Preparation of pre-activated catalyst component In (2) of Example 1, the titanium trichloride composition (II
Titanium trichloride composition (III) obtained in (1) above as I)
Example 1 except that 450 g was used and 0.6 kg of 3-methylpentene-1 was used instead of allyltrimethylsilane.
A preactivated catalyst component was obtained in the same manner as in (2).

(3) Polymerization of Propylene Using 27 g of the pre-activated catalyst component (15 g of the titanium trichloride composition (III)) obtained in (2) above as the pre-activated catalyst component in (3) of Example 1, Further, propylene was polymerized in the same manner as in (3) of Example 1 except that 29 g of allyltriethoxysilane was used instead of 3-aminopropyltriethoxysilane to obtain polypropylene.

Comparative Example 10 The titanium trichloride composition (II) obtained in (1) of Example 8 in place of the pre-activated catalyst component in (3) of Example 8 (II
Polypropylene was obtained in the same manner except that 15 g of I) was used.

Example 9 (1) Preparation of titanium trichloride composition (III) After adding 27.0 mol of titanium tetrachloride to 12 l of n-hexane and cooling to 1 ° C., diethyl aluminum monochloride was further added.
12.5 L of n-hexane containing 27.0 mol was added dropwise at 1 ° C. over 4 hours. After completion of the dropping, the reaction was carried out at the same temperature for 15 minutes, the temperature was raised to 65 ° C. over 1 hour, and the reaction was further performed at the same temperature for 1 hour. Next, the supernatant liquid was removed, 10 l of n-hexane was added,
The operation of removing by decantation was repeated 5 times, and 1.8 kg of 5.7 kg of the obtained solid product (II) was added to n-hexane 11
Suspended in this, to which was added 1.6 l diisoamyl ether. This suspension was stirred at 35 ° C. for 1 hour and then washed 5 times with 3 l of n-hexane to obtain a treated solid. The obtained treated solid was suspended in 6 l of a 40% by volume titanium tetrachloride solution in n-hexane.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After completion of the reaction, 20 l of n-hexane was used once, the solid obtained was washed three times, and then dried under reduced pressure to obtain a titanium trichloride composition (III).

(2) Preparation of pre-activated catalyst component Titanium trichloride composition (III) in (2) of Example 1
As the titanium trichloride composition (II
I) 450 g, and preliminarily activated catalyst component was obtained in the same manner as in (2) of Example 1 except that 6.0 kg of 4,4-dimethylhexene-1 was used instead of allyltrimethylsilane. It was

(3) Polymerization of Propylene In (3) of Example 1, 45 g (15 g of titanium trichloride composition (III)) of the pre-activated catalyst component obtained in (2) above was used as the pre-activated catalyst component, and (3) of Example 1 except that 37 g of dimethyldiacetoxysilane was used instead of 3-aminopropyltriethoxysilane.
Polypropylene was obtained in the same manner as in.

Comparative Example 11 The titanium trichloride composition (II) obtained in (1) of Example 9 in place of the pre-activated catalyst component in (3) of Example 9 (II
Polypropylene was obtained in the same manner except that 15 g of I) was used.

Example 10 (1) Preparation of titanium trichloride composition (III) n-heptane 4l, diethylaluminum monochloride 5.
The reaction solution obtained by reacting 0 mol, 9.0 mol of diisoamyl ether and 5.0 mol of di-n-butyl ether at 18 ° C for 30 minutes was added dropwise to 27.5 mol of titanium tetrachloride at 40 ° C for 300 minutes, and then the same. After reacting at the temperature for 1.5 hours, the temperature was raised to 65 ° C., the reaction was carried out for 1 hour, the supernatant was removed, 20 l of n-hexane was added, and the operation of removing by decantation was repeated 6 times to obtain the solid product ( II) 1.8 kg was suspended in 50 liters of n-hexane, and 200 g of diethylaluminum monochloride was added.
1.0 kg of propylene was added at 0 ° C. and the mixture was reacted for 1 hour to obtain a solid product (II-A) subjected to polymerization treatment (reaction amount of propylene: 0.5 kg). After the reaction, the supernatant was removed and then 30-l of n-hexane was added.
The solid product (II-A) (2.3 kg) which has been subjected to the above-mentioned polymerization treatment by repeating the operation of adding and removing by decantation twice.
Suspended in 4 liters of n-hexane, titanium tetrachloride 1.8 kg, n-
Butyl ether (1.8 kg) was added, and the mixture was reacted at 60 ° C for 3 hours. After the reaction was completed, the supernatant was removed by decantation, 20 l of n-hexane was added, and the mixture was stirred for 5 minutes and allowed to stand, and the operation of removing the supernatant was repeated 3 times, followed by drying under reduced pressure and trichloride. A titanium composition (III) was obtained. The content of titanium atoms in 1 g of the titanium trichloride composition (III) was 200 mg.

(2) Preparation of pre-activated catalyst component Titanium trichloride composition (III) in (2) of Example 1
As the titanium trichloride composition (II
I) A pre-activated catalyst component was obtained in the same manner as in (2) of Example 1 except that 450 g was used and 2.3 Kg of 4,4-dimethylpentene-1 was used instead of allyltrimethylsilane. It was

(3) Polymerization of Propylene In (3) of Example 1, 37.5 g (15 g as titanium trichloride composition (III)) of the pre-activated catalyst component obtained in the above (2) was used as the pre-activated catalyst component. 21 as mercaptomethyltrimethylsilane as compound (S)
Polypropylene was obtained in the same manner except that a catalyst composed of 40 g of diethylaluminum monoiodide and 28 g of di-n-propylaluminum monochloride as the organoaluminum compound was used.

Comparative Example 12 The titanium trichloride composition (II) obtained in (1) of Example 10 in place of the pre-activated catalyst component in (3) of Example 10 (II
Polypropylene was obtained in the same manner except that 15 g of I) was used.

Preliminary activation conditions, polymerization conditions, polymerization results, and evaluation results according to each of the above Examples and Comparative Examples are shown in the table on the next page.

[Effect of the Invention] The main effect of the present invention is to obtain a polypropylene having extremely high transparency and rigidity.

As is apparent from the above-mentioned examples, the internal haze of the film produced using the polypropylene obtained by the method of the present invention is 1/4 to 2/2 as compared with the case where the pre-activation by the branched chain olefins is not performed. It is 5 and has extremely high transparency. Further, the crystallization temperature is increased by 3 ° C to 4 ° C as compared with the polypropylene obtained by the method of the invention of the prior application, and the crystallinity is remarkably improved, so that the flexural modulus is further improved.

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram (flow chart) for explaining the method of the present invention.

Claims (4)

[Claims] 1. Propylene is polymerized using a catalyst comprising a titanium trichloride composition (III), an organoaluminum compound (A ₁ ) and an organosilicon compound having a Si—O—C bond and / or a mercapto group. In the method for producing polypropylene, a titanium trichloride composition (III) is used as a reaction product (I) of an organoaluminum compound (A ₂ ) or an organoaluminum compound (A ₂ ) and an electron donor (B ₁ ). The solid product (II) obtained by reacting titanium tetrachloride is subjected to polymerization treatment with α-olefin, or without polymerization treatment, and further to an electron donor (B ₂ ) and a group III-VI group of the periodic table. Titanium trichloride composition obtained by reacting with elemental halide (III)
By combining the titanium trichloride composition (III) and the organoaluminum compound (A ₁ ) with the following formula: (In the formula, R ¹ has 1 to 3 carbon atoms which may contain silicon.
Represents a hydrocarbon group or a silicon, up, represents a R ^2, R ^3, R ⁴ is a hydrocarbon group having silicon from carbon atoms which may contain 1 to 6, the R ^2, R ^3, R ⁴ Either one may be hydrogen. ) A pre-activated catalyst component obtained by polymerizing 0.001 g to 100 g of a branched chain olefin represented by the formula (1) per 1 g of the titanium trichloride composition (III), and an additional organoaluminum compound (A ₁ ) if necessary. , An organosilicon compound (S) further having a Si-O-C bond and / or a mercapto group
And a molar ratio (S) / (III) of the organosilicon compound (S) having the Si—O—C bond and / or mercapto group and the titanium trichloride composition (III) = 1.0 to 10%.
And the molar ratio of the organoaluminum compound (A ₁ ) to the titanium trichloride composition (III) (A ₁ ) / (III) = 0.1 to 200
A process for producing high-rigidity polypropylene, which comprises polymerizing propylene using the catalyst described in 1. 2. The method according to claim 1, wherein a dialkylaluminum monohalide is used as the organoaluminum compound (A ₁ ). 3. An organoaluminum compound (A ₂ ) having a general formula of AlR ⁵ _p R ⁶ _{p ′} X _{3- (p + p ′ )} (wherein R ⁵ and R ⁶ are an alkyl group, a cycloalkyl group, A hydrocarbon group such as an aryl group or an alkoxy group, X represents halogen, and p, p '
Represents an arbitrary number of 0 <p + p ′ ≦ 3. ) An organoaluminum compound represented by
The manufacturing method described in paragraph. 4. The melt flow rate of polypropylene (MF
R) and the absorbance ratio by infrared absorption spectroscopy (IR-
τ: Absorbance ratio at infrared wave numbers 997 cm ^-1 and 973 cm ^-1 ,
The method according to claim 1, wherein polymerization is performed such that the relationship with A ₉₉₇ / A ₉₇₃ ) satisfies IR-τ ≧ 0.0203 log MFR + 0.950.