JPH0780957B2 - High-rigidity polypropylene manufacturing method - Google Patents

Description

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

[Prior Art and Problems Thereof] The present inventors previously used a catalyst obtained by combining a titanium trichloride composition obtained by a specific method with an organoaluminum compound and a specific silicon compound in a specific use ratio. To produce high-rigidity polypropylene
63-121523, Japanese Patent Application 63-123673, Japanese Patent Application 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 monomer was preliminarily activated and pre-activated to obtain a specific organosilicon compound. The polypropylene obtained by polymerizing propylene using a catalyst in which the amounts are combined is not only significantly more transparent than the polypropylene obtained by the method of the invention of the prior application, but also further improved in rigidity. As a result, they have come to 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 the Problems] The present invention has the following configurations.

(1) Titanium trichloride composition (III), organoaluminum compound (A ₁ ), and Si—O—C bond and / or
Alternatively, in a method for producing polypropylene by polymerizing propylene using a catalyst composed of an organosilicon compound (S) having a mercapto group, an organoaluminum compound (A ₂ ) or an organoaluminum compound is used as the titanium trichloride composition (III). The solid product (II) obtained by reacting the reaction product (I) of (A ₂ ) and the electron donor (B ₁ ) with titanium tetrachloride is polymerized with α-olefin, or polymerized. And a titanium trichloride composition (III) obtained by further reacting an electron donor (B ₂ ) with a halide of an element of Group III to VI of the periodic table
By combining the titanium trichloride composition (III) with an organoaluminum compound (A ₁ ), which has a saturated cyclic structure of a hydrocarbon which may contain silicon and a C═C bond. A cyclic monomer having 5 to 20 carbon atoms, which may contain, per 1 g of the titanium trichloride composition (III),
0.001 g to 100 g of a pre-activated catalyst component obtained by a polymerization reaction, an additional organoaluminum compound (A ₁ ) if necessary, and an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group. In combination with the Si--O--C
The molar ratio of the organosilicon compound (S) having a bond and / or a mercapto group to the titanium trichloride composition (III) is (S) / (III) = 1.0 to 10.0, and the organoaluminum compound (A ₁ ) A method for producing high-rigidity polypropylene, which comprises polymerizing propylene using a catalyst having a molar ratio (A ₁ ) / (III) of the titanium trichloride composition (III) of 0.1 to 200.

(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
A1R ¹ _p R ² _{p ′} X _{3− (p + p ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; p, p ′
Represents an arbitrary number of 0 <p + p ′ ≦ 3. The manufacturing method of said 1st item using the organoaluminum compound represented by these.

(4) The melt flow rate (MFR) of the obtained polypropylene and the absorbance ratio (IR
-Τ: The ratio of absorbance at infrared wave numbers 997 cm ^-1 and 973 cm ^-1 is A ₉₉₇ / A ₉₇₃ ). Polymerization is carried out so that the relation with IR-τ ≥ 0.0203 log MFR + 0.950 is satisfied. The manufacturing method described in.

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 shown below.

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).
At -20 ° C to 200 ° C, preferably -10 ° C to 100 ° C for 30 seconds to 5 hours. The order of addition of (A ₂ ), (B ₁ ), and (D) is not limited, and the amount ratio used is 0.1 to 8 mol, preferably 1 to 4 mol, and 0.5 to 5 mol of the electron donor per 1 mol of organic aluminum. ~ 5 l, preferably 0.5-2 l are 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 (II) is polymerized, 2) After the reaction of the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride, α-olefin is added to polymerize the solid product (II). Treatment method, (3) After completion of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product is obtained. There is a method of suspending the substance (II) in a solvent, further adding an organoaluminum compound and an α-olefin, and polymerizing.

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 atmospheric pressure or at a pressure of 10 kg / cm ² G or less at 30 to 90 ° C. for 5 minutes to 10 hours. 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.
To 100 ml to 2,000 ml of a solvent, 0.5 g to 500 g of an organoaluminum compound, a reaction temperature of 30 to 90 ° C. for 5 minutes to 10 hours, and an α-olefin of 0 to 10 kg / cm ² G of 10 to 5,000 g. It is desirable to add 0.05 to 1,000 g and polymerize.

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 a preferable result. The amount used is based on 100 g of the solid product (II) or (II-A),
(B ₂ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, (F) 0.
1g-1,000g, preferably 0.2g-500g, solvent 0-3,000m
l, preferably 100-1,000 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). ) After reacting
A method of reacting (B _2), was reacted with (B ₂₎ to (II) or (II-A), a method of reacting (F),
After reacting (B ₂ ) with (F), (II) or (II-A)
There is a method of reacting with, but any method may be used. The reaction conditions are 40 ° C. to 200 ° C. in the above method.
C., preferably 50 to 100.degree. C. for 30 seconds to 5 hours. In the method of (II) or (II
-A) and (B ₂ ) are reacted at 0 ° C to 50 ° C for 1 minute to 3 hours, and then (F) is reacted under the same conditions as described above. In another method, (B ₂ ) and (F) are
After reacting at 100 ° C. for 30 minutes to 2 hours, cooling to 40 ° C. or lower, adding (II) or (II-A), and then reacting under the same conditions as above. After completion of the reaction of the solid products (II) or (II-A), (B ₂ ) and (F), the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is repeated. The titanium trichloride composition (III) used for is obtained.

The organoaluminum compound (A ₂ ) used in the production of the titanium trichloride composition (III) used in the present invention has a general formula of AlR ¹ _p R ² _{p ′} X _{3 − (p + p ′)} (wherein R ¹ , R ² represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and p,
p'represents an arbitrary number of 0 <p + p'≤3. ) Is used.

Specific examples thereof include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum,
Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminium monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum halides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Other examples include monoalkylaluminum dihalides. Roh ethoxy diethylaluminum,
Alkoxyalkyl aluminums such as diethoxy monoethyl aluminum can also be used. 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-hexyl ether, di-n-octyl ether, di-i-. Ethers such as octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol,
Alcohols such as cresol, xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, aluminum acetate,
Vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anilate, 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. , Fatty acids such as propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, 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, 2,4,6-trimethyl Amines such as pyridine, N, N, N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N ′ -Β
-Dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide amides, ureas such as N, N, N'N'-tetramethylurea, phenylisocyanate, isocyanates such as toluyl isocyanate, azo such as azobenzene Compounds, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, trin -Phosphites such as butylphosphite and triphenylphosphite, phosphinites such as ethyldiethylphosphinite, ethylbutylphosphinite and phenyldiphenylphosphinite, diethylthioacetate Le, diphenyl thioether,
Methyl phenyl thioether, ethylene sulfide,
Examples thereof include thioethers such as propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used as a mixture.
The electron donor (B ₁ ) for obtaining the reaction product (I) and the solid product (II-A) reacted (B ₂ ) 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 mesitylene which is a derivative thereof,
Durene, ethylbenzene, isopropylbenzene, 2
Alkyl-substituted compounds such as -ethylnaphthalene and 1-phenylnaphthalene, and halides such as monochlorobenzene, chlorotoluene, chlorxylene, chloroethylbenzene, dichlorobenzene and bromobenzene are shown.

As the α-olefin used in the polymerization treatment, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, and heptene-1, 4-methyl-pentene-1,2-methyl- 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 titanium trichloride composition (III) obtained as described above is combined with an organoaluminum compound (A ₁ ), and a saturated cyclic structure of a hydrocarbon which may contain silicon and a C═C bond are combined therewith. A cyclic monomer having 5 to 20 carbon atoms which may contain silicon (hereinafter sometimes abbreviated as cyclic monomer) per 1 g of the titanium trichloride composition (III), 0.001 g to 100 g of a pre-activated catalyst component which has been polymerized, an additional organoaluminum compound (A ₁ ) if necessary, and an organosilicon compound (S) having a Si—O—C bond and / or a methylcapto group (S) ( Hereinafter, the organosilicon compound (S) may be abbreviated as ") 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 cyclic monomer 0.001g-1, 00
Use 0g.

The polymerization reaction temperature is 0 ° C to 100 ° C for 1 minute to 20 hours, and the cyclic monomer is reacted to give 0.001 per 1 g of the titanium trichloride composition (III).
It is desirable to polymerize g to 100 g, preferably 0.01 to 100 g of cyclic monomer. If the polymerization reaction amount is less than 0.001 g, the effect of improving transparency is insufficient, and if it exceeds 100 g, the effect is not significantly improved, which is economically disadvantageous.

The preliminary activation can be carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane or toluene, and hydrogen may be allowed to coexist during the preliminary activation. 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, The cyclic monomer of the reaction and the organoaluminum compound (A ₁ ) were removed by filtration, and the dried powder or granules or a solvent was added to the powder to give a suspended state. A ₁ ) and an organosilicon compound (S) are used as a catalyst to provide a catalyst for the polymerization of propylene, a coexisting solvent, and unreacted cyclic monomer are distilled under reduced pressure or by an inert gas flow, etc. is evaporated off, the state of being suspended by adding a solvent to the powder or granular material or powder granules, add the organoaluminum compound (a ₁₎ as necessary to the ones, further organosilicon compounds (S) and a combination of a catalyst, it is also possible to use in 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 cyclic monomer used for preactivation has a saturated cyclic structure of a hydrocarbon that may contain silicon and a C = C bond. It is a cyclic monomer having 5 to 20 carbon atoms which may contain silicon. Specific examples thereof include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane,
3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methylvinylcyclohexane, 4-methylvinylcyclohexane,
In addition to vinylcycloalkanes such as vinylcycloheptane, allylcyclopentane, allylcycloalkanes such as allylcyclohexane, etc., cyclotrimethylenevinylsilane, cyclotetramethylenevinylsilane, cyclopentamethylenevinylsilane, cyclohexamethylenevinylsilane, cyclopentamethyleneallylsilane Cyclic monomer having a silicon atom in a saturated cyclic structure such as cyclohexylvinylsilane, cyclohexylallylsilane,
Examples thereof include cyclic monomers containing silicon in addition to the saturated cyclic structure such as 4-trimethylsilylvinylcyclohexane and 4-trimethylsilylallylcyclohexane. One or more kinds of these cyclic monomers are used.

Dialkylaluminum monohalide is preferably represented by titanium trichloride composition (III) chloride and combined with the organoaluminum compound (A _1), and the general formula AlR ³ as the organic aluminum compound (A ₁₎ used optionally R ⁴ X . In the formula, R ³ and R ⁴ 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. n-propyl aluminum monochloride, di i-butyl aluminum monochloride, di n-butyl aluminum monochloride, diethyl aluminum monoiodide,
Examples include diethyl aluminum monobromide.

Specific examples of the organosilicon compound (S) having a Si—O—C bond and / or a mercapto group, which is another component constituting the catalyst, include methyltrimethoxysilane, vinyltrimethoxysilane, and allyl. Trimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, Propyltriethoxysilane, allyltriethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, - triethoxysilyl-2
Norbornene, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltri i-propoxysilane, dimethyldi i-
Propoxysilane, trimethyl i-propoxysilane,
Tetra n-butoxysilane, methyltri n-butoxysilane, tetra (2-ethylbutoxy) silane, methyltriphenoxysilane, dimethylphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxysilane, triethoxychlorosilane, tri i-propoxy. Chlorosilane, tri-n-butoxychlorosilane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxysilane. Acetoxysilane, trimethylacetoxysilane, triethylacetoxysilane, phenyldimethylacetoxysilane, triphenylacetate Kishishiran, bis (trimethylsilyl) adipate, trimethylsilyl benzoate,
Organosilicon compounds having a Si—O—C bond such as triethylsilylbenzoate, mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, 3-
Mercaptopropyltrimethylsilane, 4-mercapto-n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptopropyltriethylsilane, 1-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3 An organic silicon compound having a mercapto group such as mercaptopropylethylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane, and 3-mercaptopropylmethyldiphenylsilane; and mercaptomethyltrimethoxysilane,
Mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyldiethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, dimethoxy- Three
-Mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, diethoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-
An organosilicon compound having a Si—O—C bond and a mercapto group such as 2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, and 3-mercaptopropoxytrimethylsilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxy. Silane, 3-
Aminopropyldiethoxymethylsilane, 3-aminopropyldimethylethoxyirane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3- (2-aminoethylaminopropyl)
An organosilicon compound having a Si—O—C bond and an amino group, such as dimethoxymethylsilane, 2-aminoethylaminomethylbenzyloxydimethylsilane, and 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxysilane. Etc.

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

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; Absorbance ratio at infrared wave number 997 cm ^-1 and 973 cm ^-1 is related to A ₉₉₇ / A ₉₇₃ , IR-τ ≧ 0.0203 log MFR +
Characterized by satisfying the equation of 0.950.

The higher the crystallinity of the polymer, the higher the IR-τ, and the MFR
The higher is, the higher IR-τ tends to be.

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 to 50 kg / cm ² G and usually 30 minutes to 1
It will be carried out for about 5 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 contains a polymer having a highly stereoregular cyclic structure in a dispersed state, so that the polymer having the cyclic structure exhibits a nucleating action during melt molding. As a result, the crystallization of polypropylene is promoted, and as a result, the transparency and crystallinity of the polypropylene as a whole are enhanced.

Further, since the polymer having a cyclic structure 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: Indicates polymerization activity, and represents polymer yield (g) per 1 g of titanium catalyst component. (Unit: g / g) (2) MFR: Melt flow rate JIS K 7210 Table 1 conditions
14 (Unit: g / 10 minutes) (3) IR-τ: The sample was formed into a film with a pressure molding machine at 200 ° C for 1 minute of preheating and 1 minute of pressing, and then immediately cooled to 20 ° C with water. A film having a thickness of about 40μ was obtained. 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 were cut out from the annealed film, and each of these small films was used as a measurement sample to obtain 997 cm ⁻¹ and 973 cm ^−1.
Absorbance ratio of (A ₉₉₇ / A ₉₇₃ ) is measured and the average value is calculated as I
Let R-τ value. This IR-τ measurement is based on Perkin Elmer 783
Type infrared spectrophotometer.

(4) Internal haze: The haze inside the film excluding the effect of the surface, using a press machine at a temperature of 200 ° C and a pressure of 200 kg.
A polypropylene film with a thickness of 150μ was prepared under the condition of / cm ² G, and liquid paraffin was applied to both sides of the film.
The haze was measured according to SK 7105. (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'-hydroxyphenyl) propionate] methane 0.
1 part by weight and 0.1 part by weight of calcium stearate 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 K 7203 compliant (Unit: kgf / cm ² ) (b) Tensile strength: JIS K 7113 compliant (Unit: kgf / cm ² ) (C) Rockwell hardness (R scale): JIS In accordance with K 7202 (d) Heat distortion temperature (HDT): In accordance with JIS K 7207 (unit: ° C) Example 1 (1) Preparation of titanium trichloride composition (III) n-hexane 6l, diethylaluminum monochloride ( DEAC) 5.0 mol, diisoamyl ether 12 mol at 25 ° C
And mixed for 1 minute at room temperature 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., 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 0 ° C., the reaction was continued for 1 hour, the mixture was cooled to room temperature, the supernatant was removed, 20 l of n-hexane was added, and the supernatant was removed by decantation was repeated 4 times to obtain a solid product (II) 1.9. k
got g.

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 give 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 polymerization treatment was added to 6 l of n-hexane. After suspension, 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, 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 preactivated 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 diethylaluminum monochloride, a titanium trichloride composition obtained in (1) (III) (450 g) at room temperature, and then the temperature in the reactor was adjusted to 4
The mixture was heated to 0 ° C., 0.7 kg of vinylcyclohexane was added, and the reaction was carried out at 40 ° C. for 2 hours (1.0 g of vinylcyclohexane was reacted per 1 g of the titanium trichloride composition (III)).

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

(3) Polymerization of propylene After replacing the stainless steel reactor with an internal volume of 500 liter with a stirrer with nitrogen gas, 200 liter of n-hexane, 50 g of diethylaluminum monochloride, (2) preactivated catalyst obtained at room temperature Ingredients as titanium trichloride composition (III) 15
g, 33 g of 3-aminopropyltriethoxysilane and 150 Nl of hydrogen. 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, 100l of pure water
Was added, the mixture was stirred for 10 minutes, and the aqueous layer was extracted twice. After that, the polymer slurry was extracted, filtered, and dried to obtain a polymer. Since the obtained polymer was a lump having a diameter of 1 to 2 cm, the whole amount of the polymer was pulverized by a pulverizer to obtain 48.6 kg of MFR 1.7 polypropylene.

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 240 Nl (Example 2) and 440 Nl (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 charging amount was changed to 220 Nl (Comparative Example 2) and 390 Nl (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 vinylcyclohexane, and thereafter, the same as in (3) of Example 1. Polymerization of propylene was performed to obtain polypropylene.

Comparative Example 5 In (3) of Example 1, 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 (2) of Example 1, 3-methylvinylcyclohexane was used instead of vinylcyclohexane, and the usage amounts thereof were 0.1 g (Comparative Example 6) and 45 g (Example 4), respectively. ), 1.4 kg (Example 5) to carry out the pre-activation reaction, and instead of 3-aminopropyltriethoxysilane in (3), phenyltriethoxysilane was used.
Polypropylene was obtained in the same manner as in Example 1 except that 29 g was used.

Comparative Examples 7 to 9 and Examples 6 and 7 In Example 1, (2), vinylcyclohexane was used instead of vinylcyclohexane, and in (3), 3-aminopropyltriethoxysilane was used instead. In addition, using dimethoxy-3-mercaptopropylmethylsilane, except that the molar ratio of the dimethoxy-3-mercaptopropylmethylsilane to the titanium trichloride composition (III) is changed as shown in the table, respectively.
Polypropylene was obtained in the same manner as in Example 1. However, in Comparative Examples 7 and 8, 10 g of a titanium trichloride composition (III) was used as the pre-activating catalyst component during the propylene polymerization of (3),
And 33.3 g of diethylaluminum monochloride was used.

Example 8 (1) Preparation of titanium trichloride composition (III) 8 l of n-heptane, 16 mol of di-n-butylaluminum monochloride and 10 mol of di-n-butyl ether were mixed at 30 ° C for 10 minutes and reacted for 20 minutes. Then, a reaction product liquid (I) was obtained.

The whole amount of this reaction product liquid (I) was added dropwise to a solution consisting of 5 liters of toluene and 64 mol of titanium tetrachloride kept at 45 ° C for 60 minutes, then heated to 85 ° C and further reacted for 2 hours. The mixture was cooled to room temperature, the supernatant was removed, 30 l of n-heptane was added, and the operation of removing the supernatant by decantation was repeated twice to obtain 4.9 kg of a solid product (II).

The whole amount of this (II) was suspended in 30 l of n-heptane, 2.0 kg of di-n-butyl ether and 15 kg of titanium tetrachloride were added at room temperature for about 20 minutes, and the mixture was reacted at 90 ° C for 2 hours, cooled, and then decanted. The supernatant was removed by filtration, washed with n-heptane and dried to obtain a titanium trichloride composition (III). The content of titanium atoms in 1 g of the titanium trichloride composition (III) was 255.
It was 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)
A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that 450 g was used and 4.4 kg of vinylcyclopentane was used instead of vinylcyclohexane.

(3) Polymerization of Propylene In (3) of Example 1, 27 g (15 g of titanium trichloride composition (III)) of the pre-activated catalyst component obtained in the above (2) was used as the pre-activated catalyst component. Polypropylene was obtained by polymerizing propylene in the same manner as in (3) of Example 1 except that 29 g of allyltriethoxysilane was used instead of 3-aminopropyltriethoxysilane.

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.

Comparative Example 11 In the example 2 (2), the titanium trichloride composition (II
Preliminarily activated catalyst components were obtained in the same manner except that 450 g of titanium trichloride (AA) obtained by reducing titanium tetrachloride with metallic aluminum instead of I) and crushing activation was used.
After that, the pre-activated catalyst component is used to carry out (3) of Example 8.
Polypropylene was obtained in the same manner as in.

Comparative Example 12 In the reaction for obtaining the solid product (II) in (1) of Example 8, 16 mol of diethylaluminum monochloride was used in place of the reaction product solution (I), and the reaction was carried out at 0 ° C. instead of 45 ° C. In the same manner as (1) of Example 8, after dropping, the temperature was raised to 75 ° C., the mixture was stirred and reacted for 1 hour, and then refluxed at the boiling temperature of titanium tetrachloride (about 136 ° C.) for 4 hours to change to purple, cooled, and filtered. After drying, titanium trichloride (RA) was obtained. A polypropylene was obtained in the same manner as in Comparative Example 11 except that this titanium trichloride was replaced with titanium trichloride (AA) in Comparative Example 11.

Example 9 (1) Preparation of titanium trichloride composition (III) 27.0 mol of titanium tetrachloride was added to 12 liters of n-hexane and the temperature was 1 ° C.
After cooling to 1, 22.5 l of n-hexane containing 27.0 mol of diethylaluminum monochloride was further added dropwise at 1 ° C for 4 hours. After the completion of dropping, the temperature was kept at the same temperature for 15 minutes for reaction, then the temperature was raised to 65 ° C over 1 hour, and the temperature was further increased to 1 ° C.
Reacted for hours. Then, the supernatant was removed, and n-hexane 10
The procedure of adding l and removing by decantation was repeated 5 times. Of 5.7 kg of the obtained solid product (II), 1.8 kg
-Suspended in hexane 11 to which 1.6 l diisoamyl ether was added. After stirring this suspension at 35 ° C for 1 hour,
It was washed 5 times with 3 l of n-hexane to obtain a treated solid. The treated solid obtained was treated with 6 l of n-hexane solution containing 40% by volume of titanium tetrachloride.
Suspended in.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, 20 l of n-hexane was used once and 3
The solid thus obtained was washed 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
A pre-activated catalyst component was obtained in the same manner as in (2) of Example 1 except that I) 450 g was used and cyclopentymethylene vinyl silane 2.0 kg was used instead of vinyl cyclohexane.

(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 Polypropylene was obtained in the same manner as in (3) of Example 1 except that 37 g of dimethyldiacetoxysilane was used instead of 3-aminopropyltriethoxysilane.

Comparative Example 13 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
The reaction solution obtained by reacting 5.0 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. After reacting at the temperature for 1.5 hours, the temperature was raised to 65 ° C and the reaction was carried out for 1 hour.
Repeat the operation of adding l and removing by decantation 6 times,
1.8 kg of the obtained solid product (II) was suspended in 50 liters of n-hexane, 200 g of diethylaluminum monochloride was added, 1.0 kg of propylene was added at 60 ° C., and the mixture was reacted for 1 hour to produce a solid product subjected to polymerization treatment. The product (II-A) was obtained (propylene reaction amount 0.5 kg). 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, and the solid product (II-A) (2.
3 kg) was suspended in 4 liters of n-hexane, and titanium tetrachloride 1.8
kg and n-butyl ether 1.8 kg were added, and the mixture was reacted at 60 ° C. for 3 hours.

After the reaction was completed, the supernatant was removed by decantation, and then 20
The procedure of adding 1-liter of n-hexane, stirring for 5 minutes, leaving still and removing the supernatant was repeated 3 times, and then dried under reduced pressure to obtain a titanium trichloride composition (III).

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) 450 g was used, and a preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that the amount of vinylcyclohexane used was 1.1 kg.

(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 consisting of 40 g of diethylaluminum monoiodide and 28 g of di-n-propylaluminum monochloride was used as the organoaluminum compound.

Comparative Example 14 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.

[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 by using the polypropylene obtained by the method of the present invention is about 1/4 to about 10% as compared with the case where the film is not pre-activated by the cyclic monomer. It is 2/5 and has extremely high transparency. Further, the crystallization temperature is increased by about 3 ° C. to about 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. A propylene using a catalyst comprising a titanium trichloride composition (III), an organoaluminum compound (A ₁ ) and an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group. In the method for producing polypropylene by polymerizing an organoaluminum compound (A ₂ ) or a reaction product of an organoaluminum compound (A ₂ ) and an electron donor (B ₁ ) as a titanium trichloride composition (III) ( The solid product (II) obtained by reacting I) with titanium tetrachloride is subjected to polymerization treatment with α-olefin, or without polymerization treatment, and further to an electron donor (B ₂ ) and a periodic table III to III. Titanium trichloride composition obtained by reacting with halide of group VI element (III)
By combining the titanium trichloride composition (III) with an organoaluminum compound (A ₁ ), which has a saturated cyclic structure of a hydrocarbon which may contain silicon and a C═C bond. A cyclic monomer having 5 to 20 carbon atoms, which may contain, per 1 g of the titanium trichloride composition (III),
0.001 g to 100 g of a pre-activated catalyst component obtained by a polymerization reaction, an additional organoaluminum compound (A ₁ ) if necessary, and an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group. In combination with the Si--O--C
The molar ratio of the organosilicon compound (S) having a bond and / or a mercapto group to the titanium trichloride composition (III) is (S) / (III) = 1.0 to 10.0, and the organoaluminum compound (A ₁ ) A method for producing high-rigidity polypropylene, which comprises polymerizing propylene using a catalyst having a molar ratio (A ₁ ) / (III) of the titanium trichloride composition (III) of 0.1 to 200. 2. The process 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 A ¹ R ¹ _p R ² _{p ′} X _{3- (p + p ′)} (wherein R ¹ and R ² are an alkyl group, a cycloalkyl group or an aryl group). A hydrocarbon group or an alkoxy group such as, X represents halogen, and p,
p ′ represents an arbitrary number of 0 <p + p ′ ≦ 3. The manufacturing method of Claim 1 which uses the organoaluminum compound represented by these. 4. The melt flow rate (MFR) of the obtained polypropylene and the 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 ). The method according to claim 1, wherein the polymerization is carried out so that the relationship of IR-τ ≧ 0.0203 log MFR + 0.950 is satisfied.