JPH075803B2 - Method for producing highly stereoregular polypropylene composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a highly stereoregular polypropylene composition,
More specifically, the present invention relates to a highly stereoregular polypropylene composition containing a crystalline non-linear olefin polymer and excellent in transparency and having a wide molecular weight distribution, a method for producing the same, and a molded article using the composition. .

[Conventional technology and its problems] Polypropylene has excellent heat resistance, chemical resistance, and electrical properties, and further has good rigidity, tensile strength, optical characteristics, and processability. Widely used for blow molding.

However, in the known ordinary polypropylene, there are restrictions on the application due to the limitations of physical properties and processing surface, and towards the solution, improvement of performance of polypropylene, especially retention of strength at high temperature strength, durability, It is strongly desired to improve moldability and transparency.

Regarding the improvement of the above-mentioned performances, the stereoregularity of polypropylene is increased to improve the physical properties such as heat resistance, rigidity and strength, and the molecular weight distribution is broadened to enhance the strength and durability depending on the high molecular weight part. Further, efforts are being made to improve moldability such as extrusion molding and blow molding, and to improve transparency by adding a nucleating agent.

The applicant of the present invention has already disclosed in JP-A-59-22,913 and JP-A-63
No. 191,809 (hereinafter, both may be referred to as prior inventions) proposes a polypropylene having a high molecular weight distribution and high stereoregularity. By using the polypropylene, a molded product having significantly higher rigidity and durability than the conventionally known polypropylene can be obtained, and the use in a certain field of application can be expanded, but further improvement in rigidity is desired. It is rare. Further, the molded product was semi-transparent like the conventional polypropylene molded product.

On the other hand, as a technique for providing polypropylene with improved transparency, a catalyst composed of a titanium compound and an organoaluminum compound is used to produce a non-polymer such as vinylcyclohexane, 4-vinylcyclohexene-1,4,4-dimethylpentene-1. A polypropylene composition containing a crystalline non-linear olefin polymer obtained by a method of preliminarily polymerizing a linear olefin and then mixing polypropylene obtained by polymerizing propylene with an ordinary polypropylene. 60-139,731 JP, JP 62-1,738 JP, JP Sho
63-68,648, etc.).

Although the polypropylene molded article obtained by using the composition shows a certain degree of improvement in transparency, it has a problem such as inhomogeneity due to the method for producing the composition, and has insufficient stereoregularity. Since the molecular weight distribution was narrow, it was inferior in rigidity and durability.

In view of the above-mentioned state of the art, the inventors of the present invention can obtain a molded article having excellent transparency, rigidity, and durability by a usual molding method, have a wide molecular weight distribution, and have extremely stereoregularity. An intensive research was conducted to find a high polypropylene composition.

As a result, having a certain physical property value typified by the polypropylene of the above-mentioned prior invention, the specific polypropylene has a transparency and a rigidity when a polypropylene composition containing a crystalline non-linear olefin polymer is molded and processed. The present invention has been completed by knowing that a molded product having extremely excellent durability can be obtained.

As is apparent from the above description, the object of the present invention is to provide a highly stereoregular polypropylene composition having excellent transparency and a wide molecular weight distribution, a method for producing the same, and a molded article using the composition. is there.

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

(1) (A) Organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ) is reacted with titanium tetrachloride to produce a solid product. The substance (II) is polymerized with a linear olefin,
Alternatively, a titanium trichloride composition (II) obtained by further reacting an electron donor (B ₂ ) with an electron acceptor without polymerization treatment (II
I) with an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E), or Si-O-
The melt flow rate (MFR) obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a C bond and / or a mercapto group is combined is 0.1.
~ 100 (g / 10min, load 2.16kgf) Isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) is 7 to Obtained by reacting 30 polypropylene with (B) an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ) with titanium tetrachloride. A method of polymerizing the solid product (II) with a non-linear olefin, or a linear olefin and a non-linear olefin in one step or in multiple steps, and further reacting the electron donor (B ₂ ) with the electron acceptor. Titanium trichloride composition (IV) obtained by
And an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E), or Si-O-
Melt flow rate (MFR) containing a crystalline non-linear olefin polymer obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a C bond and / or a mercapto group is combined. ) Is 0.1 to 100 (g
/ 10 min, load 2.18 kgf), isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, polypropylene having weight average molecular weight / number average molecular weight (Q) of 7 to 30 A method for producing a highly stereoregular polypropylene composition, characterized in that the composition contains a crystalline non-linear olefin polymer in an amount of 0.1 wt ppm to 2 wt%.

(2) The organoaluminum compound (A ₁ ) has a general formula of AlR ⁸ pR ⁹ _{p ′} X _{3- (p + p ′)} (wherein R ⁸ and R ⁹ are carbon atoms such as alkyl groups, cycloalkyl groups and aryl groups). A hydrogen group or an alkoxy group, X represents halogen, and 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.

(3) As the non-linear olefin, CH ₂ ═CH—R ¹ (wherein, R ¹ has a saturated cyclic structure of a hydrocarbon that may contain silicon, and a carbon that may contain silicon) Number 3
It represents a saturated ring hydrocarbon group from 1 to 18. The manufacturing method as described in said 1st item using the saturated ring hydrocarbon monomer shown by these.

(4) As the non-linear olefin, (In the formula, R ² has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ³ , R ⁴ ,
R ⁵ represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ³ , R ⁴ and R ⁵ may be hydrogen. The manufacturing method of said 1st item which uses the branched chain olefins shown by these.

(5) As the non-linear olefin, the following formula: (In the formula, n is 0, 1, m is 1, 2; R ⁶ represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon; and R ⁷ represents silicon. C1 which may contain
Represents a hydrocarbon group from 1 to 12, hydrogen, or halogen, and when m is 2, each R ⁷ may be the same or different. The manufacturing method of the said 1st term using the aromatic-type monomer shown by these.

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

(7) In place of the titanium trichloride composition (III), the titanium trichloride composition (III) is combined with an organoaluminum compound, and a catalyst component pre-activated by reacting a small amount of olefin is used. The manufacturing method described in.

(8) In place of the titanium trichloride composition (IV), the titanium trichloride composition (IV) is combined with an organoaluminum compound, and a catalyst component pre-activated by reacting a small amount of olefin is used. The manufacturing method described in.

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

The highly stereoregular polypropylene composition according to the present invention is a polypropylene composition containing a crystalline non-linear olefin polymer and having a wide molecular weight distribution and an extremely high stereoregularity, and its production method will be described.

Examples of the method for producing the highly stereoregular polypropylene according to the present invention include the following (1) to (3).

(1) A solid product (II) obtained by reacting titanium tetrachloride with an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ). ) Is polymerized with a linear olefin, or is not polymerized, and is further reacted with an electron donor (B ₂ ) and an electron acceptor to obtain a titanium trichloride composition (III) and an organoaluminum compound ( A ₂ ) and an aromatic carboxylic acid ester (E), or an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group, and obtained by polymerizing propylene using a catalyst. Melt flow rate (MFR) 0.1 to 100 (g / 10 minutes,
Load 2.16 kgf), isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) is 7
A crystalline non-linear olefin polymer obtained by polymerizing a non-linear olefin with polypropylene of 30 to 30 (hereinafter sometimes abbreviated as polypropylene (A)) using a Ziegler-Natta catalyst. How to mix.

(2) Polypropylene (A) and polypropylene (A)
Using a catalyst similar to that used to obtain propylene, the catalyst is pre-activated in one or more stages with non-linear olefins, or with linear and non-linear olefins, and then propylene is polymerized. Melt flow rate (MFR) containing crystalline non-linear olefin polymer obtained
Is 0.1 to 100 (g / 10 minutes, load 2.16 kgf), isotactic pentad fraction (P) is 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) A method of mixing polypropylene of 7 to 30.

(3) Obtained by reacting polypropylene (A) with an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ) with titanium tetrachloride. The solid product (II) is polymerized with a non-linear olefin, or a linear olefin and a non-linear olefin in a single-stage or multi-stage polymerization, and the electron donor (B ₂ ) and the electron acceptor are reacted with each other. titanium trichloride composition obtained Te (IV) and the organoaluminum compound (a ₂₎ and an aromatic carboxylic acid ester (E), or Si-O
-Containing a crystalline non-linear olefin polymer obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a -C bond and / or a mercapto group is combined, and a melt flow rate ( MFR) 0.1 to 100
(G / 10 min, load 2.16 kgf), isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) is 7 to 30 Of polypropylene (hereinafter sometimes abbreviated as polypropylene (B)).

However, the method (3) is most preferable from the viewpoint of the homogeneity of the composition and the transparency and rigidity of the molded product produced by using the composition. Next, the method (3) will be described in more detail.

A method for producing polypropylene (A) is disclosed in Japanese Patent Application Laid-Open No. 58-104, which is described in the description of the previously filed invention and other applications of the applicant.
907, JP 63-121,523, Japanese Patent Application 63-123,673
The details of each specification of Japanese Patent Application No. 63-136,821 are as follows.

The titanium trichloride composition (III) used for producing polypropylene (A) is prepared as follows.

First, a reaction product (I) of an organoaluminum compound (A ₁ ) or an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ) is reacted with titanium tetrachloride to obtain a solid product (II).
To get

The reaction between the organoaluminum compound (A ₁ ) and the electron donor (B ₁ ) to obtain the reaction product (I) is carried out in the solvent (D) at −20 ° C. to 200 ° C., preferably −10 ° C. to 100 ° C. Perform at 30 ° C for 5 to 5 hours.

The order of addition of (A ₁ ), (B ₁ ), and (D) is not limited, and the amount ratio used is 1 mol of organoaluminum to an electron donor.
0.1-8 mol, preferably 1-4 mol, solvent 0.5-5,
Preferably 0.5 to 2 is suitable. Aliphatic hydrocarbons are preferred as the solvent. Thus, the reaction product (I) is obtained. The reaction product (I) is in a liquid state in which the reaction is completed without separation (sometimes referred to as reaction product liquid (I)).
Can be used for the next reaction.

Next, the reaction between the reaction product (I) or the organoaluminum compound (A ₁ ) 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 ₁ ) 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 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the organoaluminum compound (A
₁ ) or the reaction product (I) has a ratio (Al / Ti) of the number of Al atoms in (A ₁ ) or (I) to the number of Ti atoms in titanium tetrachloride of 0.05 to 10, preferably 0.06. ~ 0.3.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is repeated, and the obtained solid product (II) is used in the next step while being suspended in the solvent. Alternatively, it may be dried and taken out as a solid to be used.

Further, the solid product (II) obtained by reacting the organoaluminum compound (A ₁ ) or the reaction product (I) with titanium tetrachloride is polymerized with a linear olefin and used in the next reaction. Is also possible.

In the present invention, "polymerizing" means to polymerize a linear olefin or a non-linear olefin by contacting the solid product (II) with a linear olefin or a non-linear olefin under conditions capable of polymerizing. Say.

Here, as a method of polymerizing with a linear olefin, (1) a linear olefin is added at any stage of the reaction between the organoaluminum compound (A ₁ ) or the reaction product (I) and titanium tetrachloride to give a solid. A method of polymerizing the product (II), (2) after completion of the reaction between the organoaluminum compound (A ₁ ) or the reaction product (I) and titanium tetrachloride, a linear olefin is added to obtain a solid product (II And (3) after the reaction between the organoaluminum compound (A ₁ ) or the reaction product (I) and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation, and thus obtained. There is a method in which the solid product (II) is suspended in a solvent, an organic aluminum compound and a linear olefin are further added, and a polymerization treatment is carried out.

When a linear olefin is added at any stage of the reaction between the organoaluminum compound (A ₁ ) or the reaction product (I) and titanium tetrachloride, and the addition of the organoaluminum compound (A ₁ ) or the reaction product (I) When adding a linear olefin after the reaction with titanium chloride, the reaction temperature
The linear 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 linear olefin added is 100 g of solid product (II)
In comparison with 10-5,000 g of linear olefin, 0.05 g-
It is desirable to polymerize 1,000 g.

After the completion of the reaction between the organoaluminum compound (A ₁ ) or the reaction product (I) and titanium tetrachloride in the polymerization treatment with the linear 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 and 0.5 g to 5,000 g of an organoaluminum compound, a reaction temperature of 30 to 90 ° C. for 5 minutes to 10 hours, and a linear olefin of 10 to 5,000 g at 0 to 10 kg / cm ² G. It is desirable to add 0.05 to 1,000 g and polymerize.

The solvent is preferably an aliphatic hydrocarbon and may be the same as or different from the one used for the organoaluminum compound (A ₁ ). After the completion of the reaction, the liquid portion was separated and removed by filtration or decantation, and after further washing with a solvent, the obtained solid product subjected to the polymerization treatment (hereinafter referred to as solid product (II-A) May be used in the next step in the state of being suspended in the solvent, 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 of (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
The reaction method is 3,000 ml, preferably 100 to 1,000 ml. As a reaction method, a solid product (II) or (II-A) is simultaneously reacted with an electron donor (B ₂ ) and an electron acceptor (F), (II) or (II-A) is reacted with (F) and then (B ₂ ) is reacted, (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 ° C. to 20 ° C. in the above method.
It is desirable to carry out the reaction at 0 ° C, preferably 50 ° C to 100 ° C for 30 seconds to 5 hours. In the method of (II) or (II
After reacting the reaction of (A) with (B ₂ ) at 0 ° C to 50 ° C for 1 minute to 3 hours, the reaction with (F) is performed under the same conditions as described above. In the other method, (B ₂ ) and (F) are heated at 10 ° C.
After reacting at -100 ° C for 30 minutes to 2 hours, cooled to 40 ° C or lower, and after adding (II) or (II-A),
React under the same conditions as.

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 to obtain polypropylene ( A titanium trichloride composition (III) used for the production of A) is obtained.

The organoaluminum compound (A ₁ ) used for producing the titanium trichloride composition (III) has a general formula of AlR ⁸ pR ⁹ _{p ′.}
X _{3- (p + p ')} (In the formula, R ⁸ and R ⁹ represent a hydrocarbon group or an alkoxy group represented by an alkyl group, a cycloalkyl group or an aryl group, X represents a halogen, and p and p'are 0. An organic aluminum compound represented by <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 hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Monoalkyl aluminum dihalides of Monoethoxy diethylaluminum, alkoxyalkyl aluminum such as diethoxy monoethyl aluminum can also be used to.

Two or more kinds of these organoaluminum compounds may be mixed and used.

As the electron donor used in the production of the titanium trichloride composition (III), various ones shown below are shown.
It is preferable that ethers are mainly used as (B ₁ ) and (B ₂ ), and other electron donors are shared with the ethers.

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. And amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, 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, amyl 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 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 , 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 acid triamide, amides of octamethylpyrophosphoramide, ureas such as N, N, N ', N'-tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate, azo such as azobenzene Compounds, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, solyphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, triethylphosphite, triethylphosphite Phosphites such as n-butyl phosphite and triphenyl phosphite, phosphinites such as ethyl diethyl phosphinite, ethyl dibutyl phosphinite, and phenyl diphenyl phosphinite; Be ether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide, thioethers such as propylene sulfide, ethyl thio alcohol, n- propyl thio alcohol, also the like thio alcohols such as thiophenol.

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.

Electron acceptor (F) used for the production of titanium (III) trichloride
Is represented by halides of elements of groups III to VI of the periodic table. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like. These can also be used as a mixture. Most preferred is titanium tetrachloride.

The following 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 an aromatic compound, an aromatic hydrocarbon such as naphthalene,
And alkyl derivatives such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene and 1-phenylnaphthalene which are derivatives thereof, halogen such as monochlorobenzene, chlorotoluene, chlorxylene, chloroethylbenzene, dichlorobenzene and bromobenzene. Compounds are shown.

As the linear olefin used for the polymerization treatment, ethylene,
Propylene, butene-1, pentene-1, hexene-
Linear olefins such as 1, octene-1 and the like are used, and particularly ethylene and propylene are preferably used. One or more kinds of these linear olefins are used.

The titanium trichloride composition (III) and organoaluminum compound (A ₂ ) obtained as described above, and an aromatic carboxylic acid ester (E) or an organosilicon having a Si—O—C bond and / or a mercapto group. The compound (S) is combined with a predetermined amount described below to form a catalyst used for the production of the polypropylene of the present invention, or more preferably, a catalyst pre-activated by reacting an olefin.

Pre-activation is based on 1 g of titanium trichloride composition (III),
Organoaluminum compound 0.005 g to 500 g, solvent 0 to 50,
Using 0 to 1,000 ml of hydrogen and 0.01 g to 5,000 g of olefin, preferably 0.05 g to 3,000 g, the olefin is reacted at 0 ° C. to 100 ° C. for 1 minute to 20 hours to prepare a titanium trichloride composition (II
I) It is desirable to polymerize 0.01 g to 2,000 g, preferably 0.05 g to 200 g of olefin per 1 g.

The reaction of olefins for preactivation is n-pentane,
It can be carried out in an aliphatic or aromatic hydrocarbon solvent such as n-hexane, n-heptane, or toluene, or in a liquefied olefin such as liquefied propylene or liquefied butene-1 without using a solvent. The reaction can also be carried out in advance, or it can be carried out in the presence of an olefin polymer and hydrogen in advance.

In the preliminary activation, it is also possible to add an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group in advance.

Examples of the olefin used for preactivating include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methyl-pentene-1. , Branched-chain monoolefins such as 2-methyl-pentene-1 and the like,
One or more olefins are used. Further, as the organoaluminum compound, the same ones as the above-mentioned (A ₁ ) can be used, but a dialkylaluminum monohalide similar to the below-mentioned (A ₂ ) is preferably used.

After the preliminary activation reaction is completed, a predetermined amount of the aromatic carboxylic acid ester (E) or the organosilicon compound (S) having a Si—O—C bond and / or a mercapto group (S) is added to the preliminary activation catalyst component slurry. The added catalyst can be used as it is for the polymerization of propylene.

Also, coexisting solvent, unreacted olefin and organoaluminum compound are removed by filtration or decantation,
A dried powder or granules or a suspension of the powder or granules is prepared by adding a solvent to the powder and the organoaluminum compound (A ₂ )
And a method in which (E) or (S) is used in combination as a catalyst for the polymerization of propylene, a coexisting solvent,
And unreacted olefins are evaporated and removed by distillation under reduced pressure or by an inert gas flow, and the powder or granules or the powder and granules are suspended by adding a solvent to the granules. It is also possible to add the compound (A ₂ ) and further combine it with (E) or (S) to form a catalyst, which can be used for the polymerization of propylene.

During the polymerization of propylene, the above-mentioned titanium trichloride composition (III), organoaluminum compound (A ₂ ), aromatic carboxylic acid ester (E) or organic compound having a Si—O—C bond and / or a mercapto group is used. Regarding the amount of the silicon compound (S) used, when an aromatic carboxylic acid ester (E) is used as the third component of the catalyst, the molar ratio (E) between the (E) and the titanium trichloride composition (III) is used. / (III)
Is 0.1 to 10.0, and when an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group is used, the molar ratio of (S) to (III) (S) / (III) 1.
0 to 10.0, and in any case, the molar ratio (A ₂ ) / (III) of the organoaluminum compound (A ₂ ) and the titanium trichloride composition (III) is 0.1 to 200, preferably Is used in the range of 0.2 to 100.

As the organoaluminum compound (A ₂ ) to be combined with the titanium trichloride composition (III) during the polymerization of propylene, a dialkylaluminum monohalide represented by the general formula of AlR ⁸ R ⁹ X is preferable.

In the formula, R ⁸ and R ⁹ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group or an alkoxy group, and X represents halogen.

As a specific example, diethyl aluminum monochloride,
Examples thereof include di-n-propyl aluminum monochloride, di-butyl aluminum monochloride, di-n-butyl aluminum monochloride, diethyl aluminum monoiodide, diethyl aluminum monobromide and the like.

Specific examples of the aromatic carboxylic acid ester (E) that can be used as the third component constituting the catalyst include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, and toluic acid. Methyl, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate Can be given.

Specific examples of the organosilicon compound (S) having a Si—O—C bond and / or a mercapto group that can be used as the third component of the catalyst instead of the aromatic carboxylic acid ester (E) include methyltrimethoxysilane. , Vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane,
Trimethylmethoxysilane, triphenylmethoxysilane, 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 i-propoxysilane, trimethyl i-propoxysilane, tetra n-butoxy. Silane, 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, trimethylacetoxysilane, triethylacetoxysilane, phenyldimethylacetoxysilane, triphenylacetoxysilane, bis (trimethylsilyl) adipate, trimethylsilylbenzoate, triethylsilyl Si-O such as benzoate
An organosilicon compound having a -C bond, mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, 3-mercaptopropyltrimethylsilane, 4
-Mercapto-n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptopropyltriethylsilane, 1-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3-mercaptopropylethylmethylphenyl Organosilicon compounds having a mercapto group such as silane, 4-mercaptobutyldiethylphenylsilane and 3-mercaptopropylmethyldiphenylsilane, mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyl Triethoxysilane, mercaptomethylethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2-meth Mercaptoethyl trimethoxysilane,
3-mercaptopropyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, diethoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane , An organosilicon compound having a Si-O-C bond and a mercapto group such as 3-mercaptopropoxytrimethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3 −
Aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 2-aminoethylaminomethyl Benzyloxydimethylsilane, 3- [2-
Examples thereof include (2-aminoethylaminoethylamino) propyl] trimethoxysilane and other organosilicon compounds having a Si—O—C bond and an amino group.

Polymerization of propylene is carried out with the catalyst thus combined or with the preactivated catalyst. Polymerization modes for polymerizing propylene include n-hexane, n
-Slurry polymerization carried out in a hydrocarbon solvent such as -heptane, n-octane, benzene or toluene, or bulk polymerization carried out in liquefied propylene or gas phase polymerization carried out in a gas phase.

The polymerization temperature is usually 20 ° C to 85 ° C, preferably 20 ° C to 80 ° C, and particularly preferably 40 ° C to 75 ° C, which is a relatively low temperature. If the polymerization temperature is too high, it becomes difficult to increase the stereoregularity of the obtained polypropylene, and if the polymerization temperature is too low, the polymerization rate of propylene becomes slow, which is not practical. The polymerization pressure is normal pressure (0 Kgf / cm ² G) to 50 Kgf / cm ² G, and the polymerization time is usually about 30 minutes to 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 propylene polymerization method.

The polypropylene (A) used in the present invention is not always obtained as long as it is within the range of the molar ratio of each catalyst component described above and the above-mentioned polymerization conditions.
It is necessary to confirm the polymerization temperature and the specific type of (E) or (S) to be used and the molar ratio to (III)), and to select the polypropylene (A) so as to satisfy the physical property requirements.

The above-mentioned propylene polymerization can be carried out by either batch polymerization or continuous polymerization. After completion of the polymerization, the polypropylene (A) used in the present invention is obtained after a known post-treatment step such as a catalyst deactivation step and a catalyst residue removal step, if necessary.

The polypropylene (A) thus obtained must have the following physical property requirements. That is, the melt flow rate (MF
R) is 0.1 when the load is 2.16Kgf under the temperature condition of 230 ℃.
g / 10 minutes to 100 g / 10 minutes, preferably 0.5 g / 10 minutes to 80 g /
10 minutes. If the MFR is less than 0.1 g / 10 minutes, the fluidity at the time of melting will be insufficient, and if it exceeds 100 g / 10 minutes, the strength of the obtained molded product will be insufficient.

The isotactic pentad fraction (P), which is a measure of stereoregularity, which is the most characteristic physical property of polypropylene (A), is 0.960 to 0.990. Here, the isotactic pentad fraction (P) is defined by A. Zambelli et al.
It is the isotactic fraction in pentad units in polypropylene molecules measured using the method published in Macromolecules 6 925 (1973), ie ¹³ C-NMR.

However, the method for determining the attribution of the NMR absorption peaks described above is based on Macromo
lecules 8 687 (1975). The value of the isotactic pentad fraction (P) in the present invention is
It is the value of stereoregular polypropylene as it is, not the value of polypropylene after extraction, fractionation, etc.

If P is less than 0.960, the desired high rigidity and high heat resistance cannot be achieved. The upper limit for P is not limited, but P = 0.990 due to the restrictions on the production of the polypropylene according to the present invention.
Something is practically available at the present time of the present invention.

Further, the number of the weight average molecular weight, which is the other characteristic property of polypropylene (A), which is a measure of the molecular weight distribution, is the ratio to the average molecular weight, and the weight average molecular weight / number average molecular weight (Q) is 7 to 30. Regarding the molecular weight distribution,
Generally, the ratio of the weight average molecular weight to the number average molecular weight, the weight average molecular weight / number average molecular weight (Q) is used as a scale, and the larger the ratio (Q), the wider the molecular weight distribution. When Q is less than 7, the durability of the resulting molded article is poor, and when it exceeds 30, the workability is poor.

Examples of the polypropylene (B) used in the composition according to the present invention include a reaction product (I) of an organoaluminum compound (A ₁ ) or an organoaluminum compound (A ₁ ) and an electron donor (B ₂ ) with tetrachloride. The solid product (II) obtained by reacting titanium is subjected to one-stage or multi-stage polymerization treatment with a non-linear olefin, or a linear olefin and a non-linear olefin, and further with an electron donor (B ₂ ). Titanium trichloride composition obtained by the method of reacting with an electron acceptor (I
V) and an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E), or an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group are used to produce propylene. It contains a crystalline non-linear olefin polymer obtained by polymerization and has a melt flow rate (MFR) of 0.1 to 100 (g / 10
Min, load 2.16 kgf), isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) is 7
~ 30 polypropylene is used.

As is clear from the above, polypropylene (B) has the same physical properties as polypropylene (A), except that polypropylene (B) is crystalline due to the titanium trichloride composition (IV) used. That is, it contains a non-linear olefin polymer. Next, the polypropylene (B)
The manufacturing will be described.

The titanium trichloride composition (IV) as the titanium-containing catalyst component used for the production of polypropylene (B) is prepared as follows.

Preparation of the titanium trichloride composition (IV) is one of the methods for preparing the titanium trichloride composition (III) described above, which is an organoaluminum compound (A ₁ ) or an organoaluminum compound (A ₁ ).
The method includes a step of polymerizing a solid product (II) obtained by reacting titanium tetrachloride with the reaction product (I) of a styrene and an electron donor (B ₁ ) with a linear olefin. Instead of the step of polymerizing with the linear olefin, it is carried out by introducing a step of polymerizing the non-linear olefin, or the linear olefin and the non-linear olefin in one stage or in multiple stages.

The polymerization treatment step will be described in detail since it is the same as the preparation of the titanium trichloride composition (III) except the polymerization treatment step.

Embodiment of the above-mentioned polymerization step, that is, the reaction product (I) of the organoaluminum compound (A ₁ ) and the electron donor (B ₁ ) and titanium tetrachloride, or the organoaluminum compound (A ₁ )
Solid product (I
As a method of polymerizing I) with a non-linear olefin, or a linear olefin and a non-linear olefin, a reaction product (I) or an organoaluminum compound (A ₁ ) can be used.
With a non-linear olefin, or a linear olefin and a non-linear olefin in any step of the reaction of the solid product (II) with a polymerization treatment, the reaction product (I) or Organoaluminum compound (A ₁ )
After completion of the reaction between styrene and titanium tetrachloride, a method of polymerizing the solid product (II) by adding a non-linear olefin, or a linear olefin and a non-linear olefin, a reaction product (I) or an organoaluminum compound After the reaction of (A ₁ ) with titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, the obtained solid product (II) is suspended in a solvent, and an organoaluminum compound is further added. After that, there is a method of adding a non-linear olefin, or a linear olefin and a non-linear olefin, and polymerizing.

Further, the above-mentioned non-linear olefin, or the polymerization treatment with the linear olefin and the non-linear olefin may be a polymerization treatment with the non-linear olefin alone. Polymerization with an olefin followed by polymerization with a non-linear olefin gives the resulting titanium trichloride composition (II
It is a preferred method from the viewpoints of polymerization operability during use of I) and improvement of rigidity and homogeneity of the obtained polypropylene.

Furthermore, as the polymerization treatment, as described above, the linear olefin and the non-linear olefin are used at least once each, and two or more times, for example, the non-linear olefin is polymerized, and then the linear olefin is further added to perform the polymerization. It is also possible to perform processing.

The reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride is carried out at -10 ° C to 200 ° C with or without addition of a linear olefin and a non-linear olefin at any stage of the reaction. C., preferably 0.degree. C. to 100.degree. C. for 5 minutes to 10 hours. Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used.

The reaction product (I) or the organoaluminum compound (A ₁ ), titanium tetrachloride, and the solvent may be mixed in any order, and the linear olefin and the non-linear olefin may be added at any stage.

Mixing of the reaction product (I) or the organoaluminum compound (A ₁ ), titanium tetrachloride, and the solvent is preferably completed within 5 hours, and the reaction is performed during the mixing. It is preferable to continue the reaction within 5 hours after mixing the whole amount.

The amount of each used in the reaction is 1 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the reaction product (I) or the organoaluminum compound (A ₁ ) is the (I) or organoaluminum compound (A ₁ ) The ratio of the number of Al atoms in the titanium to the number of Ti atoms in titanium tetrachloride (Al / Ti) is 0.02 to 10, preferably 0.0.
6 to 0.3.

Polymerization treatment with a non-linear olefin, or a linear olefin and a non-linear olefin is carried out in any step of the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride. When a chain olefin and a non-linear olefin are added, and a reaction product (I) or an organoaluminum compound (A ₁ )
When the non-linear olefin, or the linear olefin and the non-linear olefin are added after the reaction between the olefin and titanium tetrachloride is completed, the reaction temperature is 0 ° C. 1 minute at 90 ℃
10 hours, reaction pressure is atmospheric pressure (0 kgf / cm ² G) to 10 kgf / cm ² G
Under the conditions of 100 g of solid product (II), 0.1 g to 100 kg of linear olefins and 0.01 g to 100 kg of non-linear olefins
In the case of the non-linear olefin homopolymerization treatment in the final titanium trichloride composition (III), the content of the non-linear olefin polymer is 0.01% by weight to 99% by weight,
When a linear olefin and a non-linear olefin are used, the content of the linear olefin polymer block is 0.1
Polymerization is performed so that the content of the non-linear olefin polymer block is 0.01% to 49.5% by weight, and the content of the non-linear olefin polymer block is 0.01% to 49.5% by weight.

When the content of the non-linear olefin polymer is less than 0.01% by weight, the effect of improving the rigidity of the polypropylene produced by using the obtained titanium trichloride composition (III) is insufficient and exceeds the above range. And, the improvement of the effect becomes unnoticeable, which is an operational and economic disadvantage.

As described above, it is preferable to use not only the non-linear olefin but also the linear olefin in the polymerization treatment. In this case, the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is In consideration of the balance between the effect of improving drivability and the effect of improving rigidity and impact resistance, it is preferably 98/2 or less.

After completion of the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride, the liquid portion is separated by filtration or decantation through polymerization treatment with a non-linear olefin, or a linear olefin and a non-linear olefin. When the solid product (II) thus obtained is suspended in a solvent after being separated and removed, 100 g of the solid product (II) can be used in any polymerization treatment with a linear olefin or a non-linear olefin. On the other hand, in the presence of a solvent of 100 ml to 5,000 ml and an organic aluminum compound of 0.5 g to 5,000 g, a reaction temperature of 0 ° C. to 90 °
1 minute to 10 hours at ℃, reaction pressure is atmospheric pressure (0kgf / cm ² G) to 1
Under the condition of 0 kgf / cm ² G, 0.1 g to 100 kg of a linear olefin and 0.0 to a non-linear olefin per 100 g of the solid product (II).
Final titanium trichloride composition (III) using 1g-100kg
In the case of the non-linear olefin homopolymerization treatment, the content of the non-linear olefin polymer is 0.01% by weight to 99% by weight.

When a linear olefin and a non-linear olefin are used, the content of the linear olefin polymer block is 0.1
% To 49.5% by weight, the content of the non-linear olefin polymer block is 0.01% to 49.5% by weight, and the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is 98/2 or less. Polymerize to

In any of the above-mentioned polymerization treatments, the reaction mixture can be used as it is for the next-stage polymerization treatment after the completion of the polymerization treatment in each step with the linear olefin or the non-linear olefin. Further, the coexisting solvent, unreacted linear olefin, or non-linear olefin, and the organoaluminum compound are removed by filtration or decantation, and the solvent and the organoaluminum compound are added again, and the next step It may be used for a polymerization treatment with a non-linear olefin or a linear olefin.

The solvent used during the polymerization treatment is preferably an aliphatic hydrocarbon,
The organoaluminum compound may be the same as that used in obtaining the reaction product (I) or the one used in the reaction with titanium tetrachloride directly without reacting with the electron donor (B ₁ ), It can be different.

As the linear olefin used for the polymerization treatment, ethylene,
Propylene, butene-1, pentene-1, hexene-1
And other linear olefins are used, and ethylene and propylene are particularly preferably used. One or more kinds of these linear olefins are used.

The non-linear olefin used in the polymerization treatment has the following formula: CH
₂ ═CH—R ¹ (wherein R ¹ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and 3 to 18 which may contain silicon)
Represents a saturated ring hydrocarbon. ) A saturated ring hydrocarbon monomer represented by the following formula, (In the formula, R ² has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ³ ,
R ⁴ and R ⁵ represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ³ , R ⁴ and R ⁵
The individual may be hydrogen. ) Branched-chain olefins represented by (In the formula, n is 0, 1 or m is 1, 2 and R ⁶
Represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ⁷ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. , M is 2, each R ⁷ may be the same or different. ) Is an aromatic monomer.

Specific examples thereof include vinylcyclopropane, vinylcyclobutane, butynylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane and 3- In addition to vinylcycloalkanes such as methylvinylcyclohexane, 4-methylvinylcyclohexane and vinylcycloheptane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane,
Cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, cyclotetramethylenevinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, Saturated ring hydrocarbons having a silicon atom in the saturated ring structure such as cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylenemethylallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethylenemethylallylsilane, and cyclopentamethyleneethylallylsilane. Polymer, cyclobutyldimethylvinylsilane, cyclopen Didimethylvinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylallylsilane, cyclohexyldiethylallylsilane , 4-trimethylsilylvinylcyclohexane, 4-trimethylsilylallylcyclohexane, and the like, and saturated ring-containing hydrocarbon monomers containing a silicon atom in addition to the saturated cyclic structure.

Examples of the branched chain olefins include 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
3-position branched olefin such as 1, 4-ethylhexene-1,
4,4-dimethylpentene-1,4,4-dimethylhexene-
4-position branched olefin such as 1, vinyltrimethylsilane,
Alkenylsilanes such as vinyltriethylsilane, vinyltrin-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethylsilane, allyltriethylsilane, allyltrin-propylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane. Examples thereof include diallylsilane such as dimethyldiallylsilane, ethylmethyldiallylsilane, and diethyldiallylsilane.

As the aromatic monomer, styrene, and alkylstyrenes such as o-methylstyrene and pt-butylstyrene, which are derivatives thereof, 2,4-dimethylstyrene, 2,5-dimethylstyrene, Dialkylstyrenes such as 3,4-dimethylstyrene and 3,5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-
Halogen-substituted styrenes such as 4-chlorostyrene, o-fluorostyrene, p-fluorostyrene, p-trimethylsilylstyrene, m-triethylsilylstyrene,
Trialkylsilylstyrenes such as p-ethyldimethylsilylstyrene, o-allyltoluene, allyltoluenes such as p-allyltoluene, 2-allyl-p-xylene, 4-allyl-o-xylene, 5-allyl-m. -Allylxylenes such as xylene, vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane,
Alkenylphenylsilanes such as allylethylmethylphenylsilane, and 4- (o-tolyl) -butene-1
And 1-vinylnaphthalene, etc., and one or more kinds of these non-linear olefins are used.

After completion of the reaction, the liquid portion was separated and removed by filtration or decantation, and after further washing with a solvent, the obtained solid product subjected to the polymerization treatment (hereinafter, referred to as solid product (II-B) May be used in the next step in the state of being suspended in the solvent, or may be dried and taken out as a solid to be used.

The solid product (II-B) is then reacted with an electron donor (B ₂ ) and an electron donor (F). The reaction conditions are solid product (II) or (II-A) (B ₂ ) and (F)
The conditions are the same as those for the reaction. Thus, a titanium trichloride composition (IV) containing a crystalline non-linear olefin polymer
Is obtained.

The polypropylene (B) used for producing the composition according to the present invention includes the titanium trichloride composition (IV) obtained by the above method, the organoaluminum compound (A ₂ ), and the aromatic carboxylic acid ester (E), Alternatively, it can be obtained by polymerizing propylene using a catalyst in combination with an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group.

That is, the titanium trichloride composition (II used as the titanium-containing solid catalyst component when the above-mentioned polypropylene (A) was obtained (II
Polypropylene (B) is obtained by polymerizing propylene under the same conditions except that the titanium trichloride composition (IV) is used in place of I). At this time, the respective polymerization conditions such as the used molar ratio of each catalyst component and the polymerization temperature are also in the same range as in the production of the polypropylene (A) described above.

As described above, containing a non-linear olefin polymer,
And the melt flow rate (MR) is 0.1 to 100 (g / 10min, load 2.16kgf), isotactic pentad fraction (P)
Of 0.960 to 0.990, the ratio of the weight average molecular weight to the number average molecular weight, and the weight average molecular weight / number average molecular weight (Q) of 7 to 30 are obtained.

The polypropylene composition of the present invention is obtained by mixing the polypropylene (A) thus obtained with the polypropylene (B).

The mixing ratio of polypropylene (A) and polypropylene (B) is such that the crystalline non-linear olefin polymer is 0.
Any content may be used as long as the content is 1 wt ppm to 2 wt%, but generally, the total amount is 100 wt%, polypropylene (A) 10 wt% to 99.995 wt, polypropylene (B) 90 wt% to 0.005 Mix at a weight percentage.

When the content of the crystalline non-linear olefin polymer is less than 0.1 wtppm, the transparency of the molded article produced by using the obtained composition is insufficient, and when it exceeds 2 wt%, the transparency is high. It is not economical because the improvement of is not remarkable.

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

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

Various additives that are usually added to polypropylene in the composition according to the present invention, such as antioxidants, antistatic agents, ultraviolet absorbers, copper damage inhibitors, flame retardants, pigments and the like are used in combination as appropriate. can do. Furthermore, in the composition according to the present invention, in the range not significantly impairing the object of the present invention,
Polymers such as polyethylene, polybutene, ethylene-propylene rubber and the like and optional fillers can be included. Examples of the filler include inorganic or organic fillers such as glass fiber, talc, mica, wood powder and synthetic fiber.

Thus obtained high stereoregular polypropylene composition according to the present invention, injection molding, vacuum molding, extrusion molding, blow molding, molding such as stretching, injection molding products by the technique,
It is used for molded products such as stretched films and sheets.

[Operation] Polypropylene (A) and polypropylene (B) constituting the highly stereoregular polypropylene composition according to the present invention
Has extremely high stereoregularity, and thus the molded article obtained using the composition according to the present invention is remarkably excellent in heat resistance, rigidity and strength. Further, since it has a wide molecular weight distribution, it has extremely high durability. Furthermore, since the molded product has a high degree of crystallinity and exhibits a fine spherulite morphology, it is also excellent in transparency.

The characteristic properties of polypropylene constituting the composition according to the present invention are as described above, which acts on the excellent performance of the molded article obtained by using the highly stereoregular polypropylene composition according to the present invention. Although the details of the production action of the polypropylene according to the present invention that supports the characteristic physical properties are not clear, it is estimated as follows.

The titanium trichloride compositions (III) and (IV) relating to the production of polypropylene constituting the composition according to the present invention, an organoaluminum compound (A ₂ ), an aromatic carboxylic acid ester (E), or Si—O. Performance of a catalyst in which an organosilicon compound (S) having a -C bond and / or a mercapto group is combined, and in particular, the production performance of polypropylene having a high isotactic pentad fraction possessed by the titanium trichloride composition (III). , The production of polypropylene having a higher isotactic pentad fraction possessed by the titanium trichloride composition (IV) due to the introduction of a polymerization treatment step to further impart stereospecificity, aromatic as the third component Carboxylic acid ester (E) or Si-O
The polypropylene having a wide molecular weight distribution and a high isotactic pentad fraction possessed by the organosilicon compound (S) having a -C bond and / or a mercapto group has the above-mentioned properties in the polypropylene constituting the composition of the present invention. It seems that it imparts physical properties.

Furthermore, in the polypropylene (B) constituting the highly stereoregular polypropylene composition according to the present invention, the crystalline non-linear chain resulting from the polymerization treatment step during the production of the titanium trichloride composition (IV) according to the present invention is used. Since the olefin polymer is dispersed, the polymer exerts a nucleating action during the molding of the polypropylene composition, thereby exhibiting fine spherulite morphology and improving transparency.

In particular, in the above-mentioned polymerization treatment step, when the polymerization treatment with the linear olefin is performed before the polymerization treatment with the non-linear olefin, the produced linear olefin of the crystalline linear olefin-linear olefin block copolymer is produced. Due to the compatibility of the polymer block with polypropylene, the dispersibility of the non-linear olefin polymer block in polypropylene is highly improved.

Therefore, the homogeneity of the composition is further improved, and the nucleating action of the non-linear olefin polymer block is remarkably exhibited. Therefore, the homogeneity, rigidity and strength of the molded article produced by using the obtained polypropylene are improved. It is estimated that the transparency, etc. is further improved.

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

(1) MFR: Melt flow rate JIS K 7210 Table 1 conditions
According to 14. (Unit: g / 10 min) (2) Isotactic pentad fraction (P): Measured using JEOL GX-270 manufactured by JEOL Ltd. based on the method described above.

(3) Weight average molecular weight / number average molecular weight (Q): Measured and determined by GPC-150C type gel permeation chromatography manufactured by Waters.

(4) Rigidity, strength, heat resistance:
The strength and heat resistance were evaluated.

Flexural modulus: The flexural modulus was measured at 23 ° C. and 80 ° C. according to JIS K 7203. (Unit: kgf / cm ² ) Tensile Strength: Tensile strength was measured at 23 ° C. according to JIS K 7113. (Unit: kgf / cm ² ) Heat distortion temperature: The heat distortion temperature was measured according to JIS K 7202. (Unit: ° C) (5) Durability: Tensile creep test (load 248 Kgf / cm ² ) was performed according to JIS K 7115, and creep rupture time was measured to evaluate durability. (Unit: time) (6) Transparency: Four films were stacked and haze was measured according to JIS K 6714 to evaluate transparency. (Unit:%) Example 1 (1) Production of polypropylene (A) Preparation of titanium trichloride composition (III) n-hexane 6, diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 12 mol 25
The mixture was mixed at 1 ° C for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (I) (diisoamyl ether / DEAC molar ratio 2.4). 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35 ° C, and the whole amount of the above reaction product solution (I) was added dropwise to this in 30 minutes, and then kept at the same temperature for 30 minutes, and then to 75 ° C. The temperature was raised and the reaction was continued for another 1 hour, the mixture was cooled to room temperature, the supernatant was removed, n-hexane 20 was added and the supernatant was removed by decantation was repeated 4 times to obtain 1.9K of solid product (II).
got g.

The whole amount of this (II) was suspended in n-hexane 30, 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 ) Got. (Propylene reaction amount
0.6 kg).

After the reaction, the supernatant liquid was removed, and n-hexane 30 was added and the operation of removing by decantation was repeated twice, and 2.5 kg of the solid product (II-A) subjected to the above-mentioned polymerization treatment was added to n-hexane 6 After suspending in it, 3.5 kg of titanium tetrachloride was added at room temperature for about 1 minute and reacted at 80 ° C for 30 minutes, then 1.6 kg of diisoamyl ether was further added and reacted at 80 ° C for 1 hour. .

After the reaction was completed, the supernatant was removed by decantation.
N-Hexane was added, and 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 to obtain a titanium trichloride composition (III). The titanium content in 1 g of the titanium trichloride composition (III) was 192 mg.

Preparation of pre-activated catalyst component A stainless steel reactor with an internal volume of 150 equipped with a stirrer with inclined blades was replaced with nitrogen gas, and then n-hexane 100,
2.61 Kg of diethyl aluminum monochloride and 1.8 kg of the titanium trichloride composition (III) obtained above were added at room temperature. Then, the temperature in the reactor was set to 30 ° C. Subsequently, 1 kg of propylene was added and reacted at the same temperature for 2 hours (0.5 g of propylene per 1 g of the titanium trichloride composition (III)).
After the reaction), unreacted propylene was removed to obtain a preactivated catalyst component in a slurry state.

Production of propylene In a polymerization vessel equipped with a stirrer and equipped with a two-stage turbine blade with an internal volume of 150 and nitrogen substitution, the preactivated catalyst component slurry (note, including diethylaluminum monochloride) obtained above was converted into titanium atoms. 11.4 mg atom / hr,
Further, n-hexane was continuously supplied at 13 Kg / hr from the same pipe as another catalyst or from another pipe so that the molar ratio of methyl p-toluate to titanium atom was 1.8, as a catalyst. Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 11% by volume, and propylene was supplied so that the total pressure was maintained at 10 kg / cm ² G, and slurry polymerization of propylene was performed at 60 ° C. for 120 hours. , Went continuously.

During the polymerization, the retention level of the polymer slurry in the polymerization vessel is
The polymer slurry was continuously withdrawn from the polymerization vessel so as to be 75% by volume into a flash tank having an internal volume of 50. While depressurizing in a flash tank to remove unreacted hydrogen and propylene, methanol was supplied at 1 Kg / hr and contact treatment was performed at 70 ° C. Subsequently, the polymer slurry was neutralized with an aqueous sodium hydroxide solution, and the polymer was washed with water, separated, and dried to obtain polypropylene (A) at 10 kg / hr.

When the polypropylene (A) was analyzed, the MFR was 4.0
(G / 10min), isotactic pentad fraction (P) is
The weight average molecular weight / number average molecular weight (Q) was 0.973 and 10.7.

(2) Production of polypropylene (B) Preparation of titanium trichloride composition (IV) A solid product (II) was obtained in the same manner as in the above (1).

The whole amount of this (II) was suspended in n-hexane 30, 400 g of diethylaluminum monochloride was added, 1.5 kg of propylene was added at 30 ° C., and polymerization was carried out at the same temperature for 1 hour. After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 30 n-hexane.

Subsequently, n-hexane 30 and 400 g of diethylaluminum monochloride were added, the temperature was raised to 40 ° C., 5.7 kg of vinylcyclohexane was added, and polymerization was carried out at 40 ° C. for 2 hours. After the reaction was completed, the supernatant was removed and n-hexane 30
Was added and the operation of removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (II-B) which had been subjected to a multistage polymerization treatment with propylene-vinylcyclohexane.

With the total amount of this solid product (II-B) suspended in n-hexane 9, 3.5 kg of titanium tetrachloride was added at room temperature to about 10 kg.
After adding for 1 minute and reacting at 80 ° C. for 30 minutes, 1.6 kg of diisoamyl ether was further added and reacted at 80 ° C. for 1 hour. After the reaction was completed, the operation of removing the supernatant was repeated 5 times, and then dried under reduced pressure to obtain a titanium trichloride composition (IV).

In the obtained titanium trichloride composition (IV), the propylene polymer block content was 16.7% by weight, the vinylcyclohexane polymer block content was 50.0% by weight, and the titanium content was 4.8% by weight.

Preparation of pre-activated catalyst component In the above (1), the titanium trichloride composition (III)
In place of the above, the titanium trichloride composition (IV) obtained above was used, and a pre-activated catalyst component slurry was obtained in the same manner except that the amount of diethylaluminum monochloride used was 1.14 Kg.

Polymerization of Propylene Propylene was produced in the same manner as in (1) except that the pre-activated catalyst component slurry obtained above as the pre-activated catalyst component slurry was fed to the polymerization vessel at 11.5 milmol atom / hr in terms of titanium atom. After the polymerization of (1), polypropylene (B) was obtained through the same post-treatment process.

The polypropylene (B) contained a crystalline vinylcyclohexane polymer block in an amount of 328 ppm by weight and had an MFR of 4.0 (g / 10
Min), isotactic pentad fraction (P) is 0.98
5, the weight average molecular weight / number average molecular weight (Q) was 13.5.

(3) Production of polypropylene composition 17 kg of polypropylene (A) obtained in (1), 3 kg of polypropylene (B) obtained in (2), and tetrakis [methylene-containing] in a Henschel mixer (trade name) with an internal volume of 100. 3-
10 g of (3 ′, 5′-tert-butyl-4′-hydroxyphenyl) propionate] methane and 10 g of calcium stearate were added and mixed with stirring for 5 minutes. Subsequently, using a single-screw extruder with an inner diameter of 40 mm, the mixture was melt-kneaded at 230 ° C. and extruded, cooled with water, and cut, and a crystalline vinylcyclohexane polymer block in a pellet-like high stereoregular content of 49 wt ppm A polypropylene composition was obtained.

(4) Manufacture of Molded Article The polypropylene composition obtained in (3) was injection molded into a JIS type test piece at a molten resin temperature of 230 ° C and a mold temperature of 50 ° C. About the test piece, humidity 50%, 23
After standing at room temperature of 96 ° C. for 96 hours, the rigidity, strength, heat resistance and durability were evaluated by the methods described above.

Further, the composition obtained in (3) was extruded at a molten resin temperature of 250 ° C. using a T-die type film forming machine, and made into a sheet having a thickness of 1 mm by a cooling roll at 20 ° C. The sheet with hot air at 150 ° C
It was heated for 70 seconds and stretched 7 times in both longitudinal and transverse directions using a biaxial stretching machine to obtain a biaxially stretched film having a thickness of 20 μm.

Comparative Examples 1 and 2 and Examples 2 and 3 (1) In (3) of Example 1, the content of the crystalline vinylcyclohexane polymer was changed by changing the mixing ratio of polypropylene (A) and polypropylene (B). A polypropylene composition was obtained in the same manner except that it changed as shown in the table below, and thereafter, a molded article was produced in the same manner as in (4) of Example 1.

Comparative Example 3 (1) In a stainless steel reactor equipped with a stirrer, decane 3, anhydrous magnesium chloride 480 g, n-butyl orthotitanate 1.7 kg and 2-ethyl-1-hexanol.
1.95 Kg was mixed and heated at 130 ° C. for 1 hour with stirring to dissolve the solution to obtain a uniform solution. The homogenous solution was heated to 70 ° C., 180 g of di-n-butyl phthalate was added with stirring, and after 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, which was further heated to 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (V).

The whole amount of the solid product (V) was mixed with titanium tetrachloride 15 dissolved in 1,2-dichloroethane 15, then 360 g of n-butyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours with stirring. The liquid phase was removed by decantation at the same temperature, 1,2-dichloroethane 15 and titanium tetrachloride 15 were added again, and the mixture was stirred at 100 ° C for 2 hours, washed with hexane and dried to obtain a titanium-containing supported catalyst component. It was

After replacing the stainless steel reactor with an inclined blade with an internal volume of 30 with nitrogen gas, n-hexane 20, 150 g of triethylaluminum, and 100 g of the titanium-containing supported catalyst component obtained in the above were added at room temperature. Subsequently, 60 g of propylene was added and reacted at 40 ° C. for 2 hours (0.5 g reaction of propylene per 1 g of titanium-containing supported catalyst component).

After completion of the reaction, the unreacted propylene and the liquid phase part were removed, the solid was washed with n-hexane and further dried to obtain a preactivated catalyst component.

In (1) of Example 1, n-hexane was added to the pre-activated catalyst component obtained above as a pre-activated catalyst to prepare a 4.0 wt% n-hexane slurry, and the slurry was converted into titanium atom. At 0.19 mg atom / hr
And triethylaluminum as the organoaluminum compound, and diphenyldimethoxysilane as the third component of the catalyst in a molar ratio of 20 to each titanium atom.
Supply the catalyst to the polymerization part from the same pipe so that it becomes 0 and 30, and adjust the hydrogen concentration in the gas phase in the polymerization vessel.
Propylene was polymerized in the same manner except that the content was 1.2% by volume to obtain polypropylene.

The polypropylene MFR was 4.0 (g / 10 minutes), the isotactic pentad fraction (P) was 0.956, and the weight average molecular weight / number average molecular weight (Q) was 4.4.

(2) A titanium-containing supported catalyst component was obtained in the same manner as in (1) above.

A pre-activated catalyst component was obtained in the same manner as in the above (1) except that 350 g of vinylcyclohexane was used instead of propylene. (Titanium-containing supported catalyst component 1g
Vinylcyclohexane 2.0 g reaction) In the above (1), the pre-activated catalyst component obtained above as the pre-activated catalyst component was converted into titanium atom of 0.
Polymerization of propylene was carried out in the same manner except that 27 milgram atom / hr was supplied to the polymerization reactor, and the produced bulk polymer clogged the polymer slurry withdrawing pipe from the polymerization reactor. The propylene polymerization had to be stopped in 6 hours. The content of the crystalline vinylcyclohexane polymer in the polypropylene is
86 weight ppm, MFR was 3.0, isotactic pentad fraction (P) was 0.960, and weight average molecular weight / number average molecular weight (Q) was 4.5.

(3) The polypropylene obtained in (1) above was replaced by 8K in place of polypropylene (A) in (3) of Example 1.
A polypropylene composition containing 52 ppm by weight of a crystalline vinylcyclohexane polymer was obtained in the same manner except that 12 kg of polypropylene obtained in (2) above was used in place of g and polypropylene (B).

(4) A molded article was produced in the same manner as in (4) of Example 1 except that the polypropylene composition obtained in (3) above was used as the polypropylene composition.

Comparative Example 4 (2) In Comparative Example 3 (1), anhydrous magnesium chloride, n-butyl orthotitanate, and 2-ethyl-1-.
To a homogeneous solution of hexanol and decane, di-phthalate
Separately, before adding butyl, 500 g of titanium trichloride composition (III) obtained in the same manner as in (1) of Example 1 and 100 g of diethylaluminum monochloride were used as catalysts in n-hexane 100. After 1.5 kg of vinylcyclohexane added to the above was polymerized at 60 ° C. for 2 hours, washed with methanol, further washed with n-hexane, and dried to obtain 1.1 kg of a crystalline vinylcyclohexane polymer.
A titanium-containing supported catalyst component was obtained in the same manner except that it was pulverized in a vibration mill of 0 at room temperature for 5 hours and then suspended in the above homogeneous solution.

In Comparative Example 3 (1), the titanium-containing supported catalyst component obtained above was used as the titanium-containing supported catalyst component 30.
A preactivated catalyst component was obtained in the same manner except that 0 g was used.

In Comparative Example 3 (1), the pre-activated catalyst component obtained above was used as a pre-activated catalyst in terms of titanium atom.
Propylene was polymerized in the same manner except that 0.20 mg atom / hr was supplied to the polymerization vessel to obtain polypropylene. The polypropylene contained 64 weight ppm of crystalline vinylcyclohexane polymer, MFR was 3.5 (g / 10 minutes), isotactic pentad fraction (P) was 0.956, and weight average molecular weight / number average molecular weight (Q) was It was 4.4.

(3) In (3) of Example 1, 4 kg of polypropylene obtained in (1) of Comparative Example 3 was used instead of polypropylene (A), and 16 kg of polypropylene obtained in (2) was used instead of polypropylene (B). A polypropylene composition containing 51 ppm by weight of a crystalline vinylcyclohexane polymer was obtained in the same manner except that it was used.

(4) A molded article was produced in the same manner as in (4) of Example 1 except that the polypropylene composition obtained in (3) above was used as the polypropylene composition.

Comparative Example 5 (1) In (1) of Example 1, the preactivated catalyst component slurry was 6.9 mg atom / equivalent to titanium atom without supplying the third component of the catalyst, methyl p-toluate.
Polymerization of propylene was carried out in the same manner except that the hydrogen concentration was supplied to the polymerization vessel in hr and the hydrogen concentration in the gas phase in the polymerization vessel was 5.2% by volume to obtain polypropylene. The polypropylene had an MFR of 4.2 (g / 10 min), an isotactic pentad fraction (P) of 0.951, and a weight average molecular weight / number average molecular weight (Q) of 5.5.

(2) In (2) of Example 1, the pre-activated catalyst slurry was fed to the polymerization reactor at 7.0 mg atom / hr in terms of titanium atom without feeding the third component of the catalyst, methyl p-toluate. Polymerization of propylene was carried out in the same manner except that the hydrogen concentration in the gas phase in the polymerization vessel was set to 5.2% by volume to obtain polypropylene. The polypropylene has a crystalline vinylcyclohexane polymer block of 20
The content was 0 ppm by weight, the MFR was 4.0 (g / 10 min), the isotactic pentad fraction (P) was 0.967, and the weight average molecular weight / number average molecular weight (Q) was 6.0.

(3) The polypropylene obtained in (1) above was replaced by 15k in place of the polypropylene (A) in (3) of Example 1.
g, and 50 wt ppm of the crystalline vinylcyclohexane polymer block in the same manner except that the polypropylene (B) was replaced by 5 kg of the polypropylene obtained in (2) above.
The polypropylene composition containing was obtained.

(4) A molded article was produced in the same manner as in (4) of Example 1 except that the polypropylene composition obtained in (3) above was used as the polypropylene composition.

Example 4 (1) Production of polypropylene (A) In (1) of Example 1, the hydrogen concentration in the gas phase in the polymerization vessel was set to 3.2% by volume, and each catalyst component was added to the entire polymerization vessel. After carrying out slurry polymerization of propylene at 60 ° C. in the same manner except that the pressure is maintained at 10 kg / cm ² G and supplied to the respective polymerization vessels, a similar post-treatment step is obtained.
Polypropylene (A) was obtained at 10 kg / hr.

When the polypropylene (A) was analyzed, the MFR was 0.5.
(G / 10min), isotactic pentad fraction (P) is
The weight average molecular weight / number average molecular weight (Q) was 0.972 and 10.4.

(2) Production of polypropylene (B) Preparation of titanium trichloride composition (IV) n-heptane 4, 5.0 moles of diethylaluminum monochloride, 9.0 moles of diisoamyl ether, 5.0 moles of di-n-butyl ether at 18 ° C for 30 minutes. The reaction solution obtained by the reaction was added dropwise to 27.5 mol of titanium tetrachloride at 40 ° C over 300 minutes, and then the reaction was maintained at the same temperature for 1.5 hours, and then 65
The temperature was raised to ℃ and the reaction was carried out for 1 hour. The operation of removing the supernatant liquid, adding n-hexane 20 and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (II) was added to n-hexane 4
The suspension was suspended in 0, 500 g of diethylaluminum monochloride was added, 0.9 kg of propylene was added at 30 ° C., and the mixture was reacted for 1 hour to carry out the first stage polymerization treatment.

After the lapse of reaction time, the supernatant was removed and n-hexane 20 was added.
Was added and the operation of removing by decantation was repeated twice. Subsequently, after adding n-hexane 40 and 500 g of diethylaluminum monochloride, 7.6 kg of allyltrimethylsilane was added, and the reaction was carried out at 40 ° C for 2 hours to carry out a second stage polymerization treatment, and multistage polymerization with propylene-allyltrimethylsilane. A treated solid product (II-B) was obtained.

After the reaction, the supernatant liquid was removed, and then the operation of adding n-hexane 20 and removing by decantation was repeated twice, and the solid product (II-B) subjected to the above-mentioned polymerization treatment was added to n-hexane 7
The mixture was suspended in the mixture, 1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added, and the mixture was reacted at 60 ° C for 3 hours. After completion of the reaction, the supernatant was removed by decantation, and then 20 n-
Hexane was added, and the mixture was stirred for 5 minutes and allowed to stand, and the procedure of removing the supernatant was repeated 3 times, and then dried under reduced pressure to obtain a titanium trichloride composition (IV).

Preparation of pre-activated catalyst component In (2) of Example 1, the titanium trichloride composition (IV) obtained above was used as the titanium trichloride composition (IV), and the amount of diethylaluminum monochloride was used. A preactivated catalyst component slurry was obtained in the same manner except that the amount was 1.4 kg.

Polymerization of Propylene In (2) of Example 1, the pre-activated catalyst component slurry obtained above as the pre-activated catalyst component slurry was fed to the polymerization vessel at 12.0 mg atom / hr in terms of titanium atom, and polymerization Set the hydrogen concentration in the gas phase inside the vessel to 3.2.
Propylene (B) was obtained at a rate of 10 kg / hr after slurry polymerization of propylene was carried out at 60 ° C. in the same manner except that the volume% was used, and then the same post-treatment step was performed.

The polypropylene (B) contained 225 ppm by weight of a crystalline allyltrimethylsilane polymer block and had an MFR of 0.5 (g / g
10 minutes), isotactic pentad fraction (P) is 0.98
1, the weight average molecular weight / number average molecular weight (Q) was 11.8.

(3) In (3) of Example 1, the polypropylene (A) obtained in the above (1) was used as the polypropylene (A).
A crystalline allyltrimethylsilane polymer block was prepared in the same manner except that 15 kg, and 5 kg of the polypropylene (B) obtained in (2) above were used as the polypropylene (B).
A highly stereoregular polypropylene composition containing ppm by weight was obtained.

(4) A molded article was produced in the same manner as in (4) of Example 1 except that the polypropylene composition obtained in (3) above was used as the polypropylene composition.

Comparative Example 6 A polypropylene composition was obtained in the same manner as in Example 4 (3) except that 20 kg of polypropylene (A) was used without using polypropylene (B) as polypropylene. Using this, a molded product was produced in the same manner as in (4) of Example 4.

Example 5 (1) Production of polypropylene (A) Preparation of titanium trichloride composition (III) 27.0 mol of titanium tetrachloride was added to n-hexane 12 and 1 ° C.
After cooling to 1, the n-hexane 12.5 containing 27.0 mol of diethylaluminum monochloride was further added dropwise at 1 ° C. over 4 hours. After the 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 procedure of removing the supernatant liquid, adding n-hexane 10 and removing by decantation was repeated 5 times, and out of 5.7 kg of the obtained solid product (II), 1.8 kg was suspended in n-hexane 11. To this was added diisoamyl ether 1.2 and ethyl benzoate 0.4. This suspension was stirred at 35 ° C. for 1 hour and then washed 5 times with n-hexane 3 to obtain a treated solid. The treated solid obtained was suspended in n-hexane solution 6 containing 40% by volume of titanium tetrachloride and 10% by volume of silicon tetrachloride.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, n-hexane 20 was used once and 3
The solid thus obtained was washed and then dried under reduced pressure to obtain a titanium trichloride composition (III).

Preparation of pre-activated catalyst component The titanium trichloride composition (III) obtained above as the titanium trichloride composition (III) in (1) of Example 1
Was used, and a mixture of 2.0 kg of diethylaluminum monochloride and 1.6 kg of diethylaluminum monoiodide was used as the organoaluminum compound to obtain a preactivated catalyst component in a slurry state in the same manner.

Polymerization of Propylene In (1) of Example 1, as the pre-activated catalyst component slurry, the pre-activated catalyst component slurry obtained in the above (2) (Note: including diethyl aluminum monochloride and diethyl aluminum monoiodide) At 27 mg atom / hr in terms of titanium atom, and instead of methyl p-toluylate as the third component of the catalyst, 3-aminopropyltriethoxysilane is supplied to the polymerization vessel at a molar ratio of 2.8 to titanium atom. Polymerization of propylene was carried out in the same manner as above, except that the hydrogen concentration in the gas phase in the polymerization vessel was maintained at 30% by volume to obtain polypropylene (A). The MFR of the polypropylene (A) is 30.0 (g
/ 10 minutes), isotactic pentad fraction (P) is 0.9
69, the weight average molecular weight / number average molecular weight (Q) was 10.0.

(2) Production of polypropylene (B) Preparation of titanium trichloride composition (IV) A solid product (II) was obtained in the same manner as in the above (1).

Of the 5.7 kg of this solid product, 1.8 kg of n-hexane 50
Suspended in diethyl aluminum monochloride 35
0 g was added, and 3.8 kg of 3-methylbutene-1 was further added.
The polymerization reaction was carried out at 0 ° C. for 2 hours.

After the polymerization treatment, the supernatant was removed, n-hexane 30 was added, and the operation of removing by decantation was repeated twice.
The total amount of the obtained solid product (II-B) subjected to the polymerization treatment was suspended in n-hexane 11, to which diisoamyl ether 1.2 and ethyl benzoate 0.4 were added.
This suspension was stirred at 35 ° C. for 1 hour and then washed 5 times with n-hexane 3 to obtain a treated solid. The treated solid obtained was suspended in n-hexane solution 6 containing 40% by volume of titanium tetrachloride and 10% by volume of silicon tetrachloride.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, n-hexane 20 was used once and 3
The solid obtained was washed and then dried under reduced pressure to obtain a titanium trichloride composition (IV).

Preparation of pre-activated catalyst component In the above (1), the titanium trichloride composition (III)
Instead of using the titanium trichloride composition (IV) obtained above, the amount of diethyl aluminum monochloride was 1.0 kg, and the amount of diethyl aluminum monoiodide was 0.8 kg. The activated catalyst component was obtained in a slurry state.

Polymerization of Propylene Propylene was produced in the same manner as in (1) except that the pre-activated catalyst component slurry obtained above as the pre-activated catalyst component slurry was fed to the polymerization vessel at 23 mg atom / hr in terms of titanium atom. After the polymerization of (1), polypropylene (B) was obtained through the same post-treatment process.

The polypropylene (B) is crystalline 3-methylbutene-
One polymer contains 416 ppm by weight, MFR is 30.0 (g / 10 minutes),
The isotactic pentad fraction (P) was 0.980, and the weight average molecular weight / number average molecular weight (Q) was 13.0.

(3) Manufacture of polypropylene composition In (3) of Example 1, 17 kg of polypropylene (A) obtained in (1) above as polypropylene (A) and polypropylene obtained in (2) above as polypropylene (B). A high stereoregular polypropylene composition containing 62 ppm by weight of a crystalline 3-methylbutene-1 polymer was obtained in the same manner except that 3 kg of (B) was used.

(4) A molded article was produced in the same manner as in (4) of Example 1 except that the polypropylene composition obtained in (3) above was used as the polypropylene composition.

Comparative Example 7 A polypropylene composition was obtained in the same manner as in Example 5 (3) except that 20 kg of polypropylene (A) was used without using polypropylene (B) as polypropylene. Using this, a molded product was produced in the same manner as in (4) of Example 4.

Example 6 (1) The polypropylene (A) obtained in (1) of Example 1 was used.

(2) In (2) of Example 1, in the step of polymerizing the solid product (II), ethylene 400N was used instead of propylene to perform the first-stage polymerization, and then unreacted ethylene was removed. Decantation and n-
Without washing with hexane, p-trimethylsilylstyrene was subsequently used instead of vinylcyclohexane.
A titanium trichloride composition (IV) was obtained in the same manner except that the second-stage polymerization treatment was performed using 8.6 kg.

The same procedure as in (2) of Example 1 was repeated except that the titanium trichloride composition (IV) obtained above was used as the titanium trichloride composition (IV) and ethylene 900N was used instead of propylene. The activation process was performed. After completion of the reaction, the supernatant was removed by decantation, washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

In (2) of Example 1, n-hexane was added to the pre-activated catalyst component obtained above as a pre-activated catalyst component to prepare a 4.0 wt% n-hexane slurry, and the slurry was then treated with titanium atoms. 11.8 mg atom converted
Polymerization of propylene was conducted at 60 ° C in the same manner as above, except that diethyl aluminum monochloride was added to the polymerization vessel as a catalyst at a molar ratio of 3.0 to titanium atom in addition to methyl p-toluate. And then the polypropylene (B) 10
Obtained in kg / hr.

The polypropylene (B) contained 338 ppm by weight of a crystalline p-trimethylsilylstyrene polymer block and had an MFR of
3.8 (g / 10 min), isotactic pentad fraction (P) 0.980, weight average molecular weight / number average molecular weight (Q)
Was 11.2.

(3) Production of polypropylene composition In (3) of Example 1, the polypropylene (A) was the polypropylene (A) obtained in the above (1), and the polypropylene (B) was polypropylene obtained in the above (2) ( A high stereoregular polypropylene composition containing 51 ppm by weight of a crystalline p-trimethylsilylstyrene polymer block was obtained in the same manner except that B) was used.

(4) A molded article was produced in the same manner as in (4) of Example 1 except that the polypropylene composition obtained in (3) above was used as the polypropylene composition.

The physical properties of polypropylene constituting the compositions of the above Examples and Comparative Examples and the evaluation results of the compositions are shown in the table.

[Advantages of the Invention] As is apparent from the above-mentioned examples, the highly stereoregular polypropylene composition according to the present invention has a high stereoregularity, a polypropylene having a wide molecular weight distribution, and a crystalline non-linear chain which are not present in conventional polypropylene. Since it contains an olefin polymer, it has significantly higher rigidity, strength, heat resistance, durability, and transparency when compared to molded products made from conventional polypropylene. ing.

Therefore, molded articles produced by various molding methods using the highly stereoregular polypropylene composition according to the present invention can be expected to be expanded to application fields which were not used in conventional polypropylene molded articles. .

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 23:02)

Claims (8)

[Claims] 1. A method obtained by reacting titanium tetrachloride with (A) an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ). Titanium trichloride composition (III) obtained by polymerizing the solid product (II) with or without a linear olefin, or by further reacting an electron donor (B ₂ ) with an electron acceptor. And an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E), or Si-O-
The melt flow rate (MFR) obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a C bond and / or a mercapto group is combined is 0.1.
~ 100 (g / 10min, load 2.16kgf) Isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) is 7 to Obtained by reacting 30 polypropylene with (B) an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ) with titanium tetrachloride. A method of polymerizing the solid product (II) with a non-linear olefin, or a linear olefin and a non-linear olefin in one step or in multiple steps, and further reacting the electron donor (B ₂ ) with the electron acceptor. Titanium trichloride composition (IV) obtained by
And an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E), or Si-O-
Melt flow rate (MFR) containing a crystalline non-linear olefin polymer obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a C bond and / or a mercapto group is combined. ) Is 0.1 to 100 (g
/ 10 min, load 2.18 kgf), isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, polypropylene having weight average molecular weight / number average molecular weight (Q) of 7 to 30 A method for producing a highly stereoregular polypropylene composition, characterized in that the composition contains a crystalline non-linear olefin polymer in an amount of 0.1 wt ppm to 2 wt%. 2. An organoaluminum compound (A ₁ ) having a general formula of AlR ⁸ pR ⁹ _{p ′} X _{3- (p + p ′)} (wherein R ⁸ and R ⁹ are alkyl groups, cycloalkyl groups, aryl groups, etc. Is a hydrocarbon group or an alkoxy group, X is 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. 3. As the non-linear olefin, CH ₂ ═CH—R ¹ (wherein R ¹ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and may contain silicon). Good carbon number 3
It represents a saturated ring hydrocarbon group from 1 to 18. ) A saturated ring hydrocarbon monomer represented by
The manufacturing method according to item. 4. A non-linear olefin having the following formula: (In the formula, R ² has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ³ , R ⁴ ,
R ⁵ represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ³ , R ⁴ and R ⁵ may be hydrogen. The manufacturing method of Claim 1 which uses the branched chain olefins shown by these. 5. A non-linear olefin having the following formula: (In the formula, n is 0, 1, m is 1, 2; R ⁶ represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon; and R ⁷ represents silicon. C1 which may contain
Represents a hydrocarbon group from 1 to 12, hydrogen, or halogen, and when m is 2, each R ⁷ may be the same or different. The manufacturing method of Claim 1 which uses the aromatic type monomer shown by these. 6. The production method according to claim 1, wherein a dialkylaluminum monohalide is used as the organoaluminum compound (A ₂ ). 7. A catalyst component prepared by combining the titanium trichloride composition (III) with an organoaluminum compound instead of the titanium trichloride composition (III) and reacting a small amount of an olefin to pre-activate the catalyst component. The manufacturing method according to item 1 of the above. 8. A catalyst component prepared by combining a titanium trichloride composition (IV) with an organoaluminum compound instead of the titanium trichloride composition (IV) and reacting a small amount of an olefin to pre-activate the catalyst component. The manufacturing method according to item 1 of the above.