JPH0959312A - Production of propylene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polypropylene copolymer excellent in balance between transparency and rigidity. SOLUTION: Propylene is copolymerized with ethylene in the presence of a catalyst comprising a catalyst solid component consisting essentially of magnesium, titanium, a halogen element and an electron donor as a component [A], an organoaluminum compound component as a component [B] and an organosilicon compound represented by the formula R<1> n Si(OR<2> )4-n-m (NR<3> R<4> )m or R<1> nSi(OR<2> )4-n-m R<5> m [R<1> , R<2> , R<3> and R<4> denote each a 1-24C hydrocarbon group; R<5> denotes a cyclic amino group; (n) is 0-2; (m) is 1-2] to produce a propylene copolymer with 0.01-10wt.% ethylenecontent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a propylene copolymer having an excellent balance of transparency and rigidity by randomly copolymerizing propylene and a small amount of ethylene using a specific catalyst component. is there.

[0002]

2. Description of the Related Art In recent years, a solid catalyst component which requires magnesium, titanium, a halogen element, and an electron donor in order to polymerize propylene, an organometallic compound of Group I to III metal of the periodic table, and a third component. A highly active catalyst system comprising an electron donor as a compound is disclosed in JP-A-57-63310 and JP-A-58-8.
Many proposals have been made in 3016, JP 59-58010, JP 60-44507, and the like. Furthermore, JP-A-62-1
1705, JP 63-258907, JP 4-370103
Japanese Unexamined Patent Publications and the like disclose a polymerization catalyst characterized by using a specific silicate as the third component.

Further, JP-A-7-109304 and JP-A-7-11
Japanese Patent No. 8320 discloses a polymerization catalyst using an aminosilane having a specific structure.

Generally, a highly crystalline polypropylene obtained by using a highly stereoregular polymerization catalyst is a milky white resin having excellent rigidity and heat resistance, and transparency may be desired in some applications. As a method of improving transparency,
It is known to copolymerize a small amount of ethylene with propylene. However, when the copolymerization ratio of ethylene is increased, the transparency is improved, but there is a problem that the crystallinity of the obtained polymer is lowered and the rigidity is lowered.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a polypropylene copolymer having an excellent balance of transparency and rigidity.

[0006]

In the present invention, a solid component of a catalyst which essentially contains magnesium, titanium, a halogen element and an electron donor as a component [A], an organoaluminum compound component as a component [B], and a component [B]. C] as general formula (1) or general formula (2) R ¹ _n Si (OR ² ) _4-nm (NR ³ R ⁴ ) _m (1) R ¹ _n Si (OR ² ) _4-nm R ⁵ _m ( 2) (In the formula, R ¹ , R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 24 carbon atoms, R ⁵ represents a cyclic amino group, n is 0 to 2 and m is 1
~ 2. The present invention provides a method for producing a propylene copolymer having an ethylene content of 0.01 to 10% by weight, which comprises copolymerizing propylene and ethylene in the presence of a catalyst composed of an organosilicon compound represented by

In the present invention, a solid catalyst component containing magnesium, titanium, a halogen element, and an electron donor as essential components is used as the component [A]. The method for producing the catalyst solid component is not particularly limited, and examples thereof include JP-A-54-94590, JP-A-56-55405, JP-A-56-45909, and JP-A-56-163.
102 publication, 57-63310 publication, 57-115408 publication,
58-83006, 58-83016, 58-138707, 59-149905, 60-23404, 60-3.
The methods proposed in JP 2805, JP 61-18330, JP 61-55104, JP-A-2-77413 and JP 2-117905 can be used. As a typical manufacturing method,
(1) A method of co-milling a magnesium compound such as magnesium chloride, an electron donor, and a titanium halide compound such as TiCl ₄ , (2) a magnesium compound and an electron donor are dissolved in a solvent, and the titanium halide is added to this solution. Examples thereof include a method of adding a compound to deposit a catalyst solid.

As the component [A], the catalyst solid components described in JP-A-60-152511, JP-A-61-31402 and JP-A-62-81405 are particularly preferable for achieving the effect of the present invention. preferable. According to these production methods, aluminum halide and a silicon compound are reacted with each other, and a magnesium compound is further reacted therewith to precipitate a solid. As the aluminum halide that can be used in the above reaction, anhydrous aluminum halide is preferable, but it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a small amount of water should also be used. You can Specific examples of aluminum halides include aluminum trichloride, aluminum tribromide and aluminum triiodide, with aluminum trichloride being particularly preferred.

Specific examples of the silicon compound used in the above reaction include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane and dimethyl. Diethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane,
Trimethylmonoethoxysilane and trimethylmonobutoxysilane can be exemplified. Particularly, methylphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and dimethyldiethoxysilane are preferable.

The amount of the compound used in the reaction between the aluminum halide and the silicon compound is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3 in terms of element ratio (Al / Si). Preference is given to using active solvents. The reaction temperature is generally 10 to 100 ° C, preferably 20 to 80 ° C, and the reaction time is generally 0.2 to 5 hours, preferably 0.5 to 3 hours.

Specific examples of the magnesium compound used in the above reaction include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, propyl magnesium bromide, butyl magnesium bromide and ethyl. Examples include magnesium iodide. As the solvent for the magnesium compound, for example, aliphatic ethers such as diethyl ether, dibutyl ether, diisopropyl ether and diisoamyl ether, and aliphatic cyclic ethers such as tetrahydrofuran can be used.

The amount of the magnesium compound used is usually 0.5 to 3, preferably 1.5 to 2.3 in terms of the element ratio (Mg / Al) to the aluminum halide used in the preparation of the reaction product of the aluminum halide and the silicon compound. It is a range. The reaction temperature is usually -50 to 100 ° C, preferably-
20 to 50 ° C, reaction time is usually 0.2 to 5 hours, preferably
0.5 to 3 hours.

The white solid obtained in the reaction between the aluminum halide and the silicon compound and subsequently in the reaction with the Grignard compound is contact-treated with an electron donor and a titanium halide compound. As a method of contact treatment,
(1) a method in which a solid is treated with a titanium halide compound, then treated with an electron donor, and further treated with a titanium halide compound, and (2) the solid is coexisted with a titanium halide compound and an electron donor. , And then a treatment with a titanium halide compound. For example, the above solid is dispersed in an inert solvent and the electron donor or / and the titanium halide compound is dissolved therein, or an electron donor or / and a liquid titanium halide compound is used without using an inert solvent. Disperse the solid in. In this case, the contact treatment between the solid and the electron donor or / and the titanium halide compound can be carried out under stirring at a temperature of usually 50 to 150 ° C. and a contact time of 0.2 to 5 hours, although there is no particular limitation. Further, this contact processing can be performed a plurality of times.

Specific examples of the titanium halide compound that can be used in the contact treatment include tetrachlorotitanium, tetrabromotitanium, trichloromonobutoxytitanium, tribromomonoethoxytitanium, trichloromonoisopropoxytitanium, dichlorodiethoxytitanium, dichlorodititanium. Examples thereof include butoxy titanium, monochlorotriethoxy titanium, and monochlorotributoxy titanium. Particularly, tetrachlorotitanium and trichloromonobutoxytitanium are preferred.

The electron donor used in the above contact treatment is preferably an aromatic ester, particularly orthophthalic acid diester. Specific examples of the diester include diethyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, dihexyl orthophthalate, di-2-ethylhexyl orthophthalate, and di-n-heptyl orthophthalate. After the above-mentioned catalytic treatment, the treated solid is generally separated from the treated mixture and thoroughly washed with an inert solvent, and the obtained solid is used as the catalyst solid component [A] of the present invention as an α-olefin polymerization catalyst. be able to.

As the organoaluminum compound as the component [B] of the present invention, alkylaluminum, halogenoalkylaluminum and the like can be used, but alkylaluminum is preferred. Trialkylaluminum is particularly preferable, and specific examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum and the like. Any of the above-mentioned organoaluminum compounds can be used as a mixture. Further, a polyaluminoxane obtained by a reaction between an alkyl aluminum and water can be used in the same manner. The amount of the organoaluminum compound used as the α-olefin polymerization catalyst is 0.1 to 500, preferably 0.5 to 500 in terms of the element ratio (Al / Ti) to titanium of the catalyst solid component [A].
It is 150.

As the component [C] of the present invention, a compound represented by the general formula (1)
Or the general formula (2) R ¹ _n Si (OR ² ) _4-nm (NR ³ R ⁴ ) _m (1) R ¹ _n Si (OR ² ) _4-nm R ⁵ _m (2) (wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 24 carbon atoms, R ⁵ represents a cyclic amino group, n is 0 to 2 and m is 1
~ 2. ) An organosilicon compound represented by

R ¹ in the formula (1) or (2) is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a cyclopentyl group or a cyclohexyl group. It is a hydrocarbon group selected from the group consisting of:

R ² , R ³ and R ⁴ are hydrocarbon groups having 1 to 8 carbon atoms. It is preferably an unsaturated or saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms, and particularly preferably the number of carbon atoms.
1 to 4 unsaturated or saturated aliphatic hydrocarbon groups.
Specific examples are methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, iso-butyl group, t-butyl group, n-pentyl group, n-amyl group, n-hexyl group, iso-amyl group, cyclopentyl group, cyclohexyl group, phenyl group, octyl group Groups and the like.

Preferred as R ² are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group and the like. Preferred as R ³ and R ⁴ are methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, t-butyl group and the like. R ³ and
R ⁴ may be the same or different.

A preferred cyclic amino group for R ⁵ is
The thing derived from a secondary cyclic amine compound is mentioned.

Examples of secondary cyclic amine compounds include pyrrolidine compounds, pyrrole compounds, pyrroline compounds, piperidine compounds, pyridine compounds, indoline compounds, indole compounds, quinoline compounds, carbazole compounds,
Examples thereof include ethyleneimine compounds, hexamethyleneimine compounds, and derivatives thereof.

Among the secondary cyclic amine compounds, piperidine, pyrrolidine and hexamethyleneimine are preferable.

General formula (1) R ¹ _n Si (OR ² ) _4-nm (NR ³ R
⁴ ) As the organosilicon compound represented by _m , n is 1 and
General formula (3) in which m is 1 is an alkyl (dialkylamino) alkoxysilane represented by R ¹ Si (OR ² ) ₂ (NR ³ R ⁴ ), or a general formula in which n is 0 and m is 2 ( 4)
A bis (dialkylamino) alkoxysilane represented by Si (OR ² ) ₂ (NR ³ R ⁴ ) ₂ is preferably used.

General formula (2) R ¹ _n Si (OR ² ) _4-nm R ⁵ _m
As the organosilicon compound represented by, n is 1 and m is 1
Is an alkyl (cyclic amino) alkoxysilane represented by the general formula (5) R ¹ Si (OR ² ) ₂ R ⁵ , or n is 0
And m is a is Formula ^{2 (6) Si (OR 2} ) represented by bis ₂ R ⁵ ₂ (cyclic amino) alkoxysilanes are preferably used.

Specific compounds of the alkyl (dialkylamino) alkoxysilane represented by the general formula (3) R ¹ Si (OR ² ) ₂ (NR ³ R ⁴ ) include ethyl (diethylamino).
Dimethoxysilane (EDEADMS), n-propyl (diethylamino) dimethoxysilane (NPDEADMS), iso-propyl (diethylamino) dimethoxysilane (IPDEADMS), n-butyl (diethylamino) dimethoxysilane (NBDEADMS), iso-
Butyl (diethylamino) dimethoxysilane (IBDEADM
S), cyclopentyl (diethylamino) dimethoxysilane (CPDEADMS), cyclohexyl (diethylamino) dimethoxysilane (CHDEADMS) and the like.

Further, methyl (dimethylamino) dimethoxysilane (MDMADMS), methyl (diethylamino) dimethoxysilane (MDEADMS), methyl (di-n-propylamino)
Examples thereof include dimethoxysilane (MDNPADMS) and methyl (isopropylamino) dimethoxysilane (MDIPADMS).

Further, iso-propyl (dimethylamino) dimethoxysilane, iso-propyl (methylethylamino)
Dimethoxysilane, iso-propyl (methylpropylamino) dimethoxysilane, iso-propyl (dipropylamino) dimethoxysilane, iso-propyl (propylethylamino) dimethoxysilane, iso-butyl (dimethylamino) dimethoxysilane, iso-butyl ( Methylethylamino) dimethoxysilane, iso-butyl (diethylamino)
Dimethoxysilane, iso-butyl (dipropylamino) dimethoxysilane, cyclopentyl (dimethylamino) dimethoxysilane, cyclopentyl (methylethylamino) dimethoxysilane, cyclopentyl (dipropylamino) dimethoxysilane, cyclohexyl (dimethylamino) dimethoxysilane, cyclohexyl ( Examples thereof include methylethylamino) dimethoxysilane and cyclohexyl (dipropylamino) dimethoxysilane.

The bis (dialkylamino) alkoxysilane represented by the general formula (4) Si (OR ² ) ₂ (NR ³ R ⁴ ) ₂ includes NR of two amino groups bonded to a silicon atom.
³ R ⁴ may be the same organosilicon compound or different organosilicon compounds.

Specific examples of the organosilicon compound having the same NR ³ R ⁴ of two amino groups include bis (dimethylamino) dimethoxysilane, bis (diethylamino) dimethoxysilane and bis (di-n- Propylamino)
Dimethoxysilane, bis (diisopropylamino) dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (di-t-butylamino) dimethoxysilane, bis (diethylamino) diethoxysilane, bis (di-n-propyl) Amino) diethoxysilane, bis (diisopropylamino) diethoxysilane, bis (di-n-
Examples of the organic silicon compound include butylamino) diethoxysilane and bis (di-t-butylamino) diethoxysilane.

Specific examples of the organosilicon compound having two NR ³ R ⁴ groups different from each other include (diethylamino) (di-n-propylamino) dimethoxysilane,
Examples of organic silicon compounds include (diisopropylamino) (di-n-propylamino) dimethoxysilane.

Further, a specific compound of the organic silicon compound in which R ³ and R ⁴ are different is bis (methylethylamino)
Dimethoxysilane, bis (methyl-n-propylamino)
Dimethoxysilane, bis (ethyl-n-propylamino)
Dimethoxysilane, bis (ethylisopropylamino)
Dimethoxysilane, bis (di-n-butylamino) dimethoxysilane, bis (di-t-butylamino) dimethoxysilane, bis (diethylamino) diethoxysilane, bis (di-n-propylamino) diethoxysilane, bis ( Diisopropylamino) diethoxysilane, bis (di-n-
Examples include butylamino) diethoxysilane and bis (di-t-butylamino) diethoxysilane.

Among the above compounds, bis (dimethylamino) dimethoxysilane (BDMDMS), bis (diethylamino) dimethoxysilane (BDEDMS) and bis (di-n-propylamino) dimethoxysilane (BDNPADMS) are preferably used. it can. Particularly, bis (diethylamino) dimethoxysilane (BDEDMS) is preferable.

Specific compounds of the alkyl (cyclic amino) alkoxysilane represented by the general formula (5) R ¹ Si (OR ² ) ₂ R ⁵ include methyl (pyrrolidino) dimethoxysilane.
(MPYRDMS), methyl (piperidino) dimethoxysilane (M
PIPDMS), methyl (hexamethyleneimino) dimethoxysilane (MHMIDMS), methyl (2-methylpiperidino) dimethoxysilane (M2MPIPDMS), methyl (3-methylpiperidino) dimethoxysilane (M3MPIPDMS), methyl (4-methylpiperidino) dimethoxysilane (M4MPIPDMS) , Methyl (2,6-dimethylpiperidino) dimethoxysilane (M26DMPI
PDMS), methyl (3,5-dimethylpiperidino) dimethoxysilane (M35DMPIPDMS),

Ethyl (piperidino) dimethoxysilane (E
PIPDMS), n-propyl (piperidino) dimethoxysilane
(NPPIPDMS), iso-propyl (piperidino) dimethoxysilane (IPPIPDMS), n-butyl (piperidino) dimethoxysilane (NBPIPDMS), iso-butyl (piperidino) dimethoxysilane (IBPIPDMS), cyclopentyl (piperidino) dimethoxysilane (CPPIPDMS), Examples thereof include cyclohexyl (piperidino) dimethoxysilane (CHPIPDMS).

The general formula (6) Si bis represented by (OR ^{₂₎ 2} R ^{5 2} Specific compounds of (cyclic amino) alkoxysilanes, di pyrrolidinopyridine dimethoxysilane (DPYRDMS)
, Dipiperidinodimethoxysilane (DPIPDMS), dihexamethyleneiminodimethoxysilane (DHMIDMS), di (2-
Methylpiperidino) dimethoxysilane (D2MPIPDMS), di (3-methylpiperidino) dimethoxysilane (D3MPIPDMS)
, Di (4-methylpiperidino) dimethoxysilane (D4MPIP
DMS), di (2,6-dimethylpiperidino) dimethoxysilane (D26DMPIPDMS), di (3,5-dimethylpiperidino) dimethoxysilane (D35DMPIPDMS) and the like.

The amount of the component [C] used is the element ratio of the silane of the component [C] to the aluminum of the component [B] (Si / Al).
0.01 to 1 is preferable, and 0.05 to 0.33 is particularly preferable.

In the present invention, the proportion of propylene and ethylene used is such that the ethylene content in the resulting copolymer is
It is appropriately set to 0.01 to 10% by weight, preferably 0.1 to 8% by weight.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used to produce a propylene copolymer having the desired stereoregularity (HI) and melt flowability (MFR) can be appropriately determined depending on the polymerization method and polymerization conditions, but usually hydrogen Partial pressure 0.
It is in the range of 05 to 1.0.

In the present invention, the order of contact of the catalyst components during polymerization is not particularly limited, but it is less preferred that only the organosilicon compound of the component [C] and the catalyst solid of the component [A] come into direct contact.

As the polymerization method in the present invention, a slurry polymerization method using a nonpolar solvent such as hexane or heptane,
A vapor phase polymerization method in which a monomer is brought into contact with a catalyst in a gas state, a bulk polymerization method in which a monomer in a liquid state is used as a solvent to perform polymerization, or the like can be adopted. Polymerization pressure is 1 to 200 kg / cm
² , preferably 10 to 80 kg / cm ² , the polymerization temperature is usually 10 to 100
C., preferably 30 to 90.degree. C., and the polymerization time is usually 0.1 to 10 hours, preferably 0.5 to 7 hours.

Further, in the present invention, it is preferable to carry out the main polymerization after prepolymerizing the monomer according to the above-mentioned various polymerization methods. In the pre-polymerization, the catalyst solid component [A] is contact-treated with the organoaluminum compound component [B] and the organosilicon compound component [C] in advance, and the contact-treated solid is prepared by washing the solid before carrying out the main polymerization. be able to. Further, the catalyst solid component [A] or the above-mentioned catalytically treated solid may be used to prepolymerize a limited amount of the monomer in the presence of the organoaluminum compound component [B] and the organosilicon compound component [C]. . When the contact-treated solid is used, the organosilicon compound component [C] can be omitted in the prepolymerization. By using these contact-treated solids, prepolymerized solids, or washed solids after prepolymerization in the main polymerization, the polymerization activity per catalyst solid and the stereoregularity of the polymer can be improved.

In the present invention, when the above contact-treated solid or prepolymerized solid is used as the catalyst solid component in the main polymerization, the organosilicon compound component [C] can be omitted in the main polymerization.

As the contact treatment of the present invention, the component [A],
The component [B] and the component [C] are mixed and usually 0 to 100
React at 0.1 ℃ for 10 to 10 hours. The order of mixing each component is not particularly limited, but in general, the order of the component [A], the component [B], and the component [C] is preferable. After the contact treatment, the solid is washed with an inert hydrocarbon solvent, filtered and separated to be used as a catalyst solid component in prepolymerization or main polymerization.

The prepolymerization in the present invention can be carried out by a gas phase method, a slurry method, a bulk method or the like. The solid obtained in the prepolymerization can be used after the separation in the main polymerization, or the main polymerization can be carried out without separation.

The amount of the organoaluminum component used in the prepolymerization is usually Al / Ti with respect to the titanium atom of the catalyst solid component.
The molar ratio is 0.5 to 1000, preferably 1 to 100. The amount of the organosilicon compound used is usually 0.01 to Si / Al molar ratio to the aluminum atom of the organoaluminum compound component.
1, preferably 0.1 to 0.5. Further, hydrogen can be allowed to coexist in the preliminary polymerization, if necessary.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION 【Example】

EXAMPLES Examples of the present invention will be described below. The melt flowability (MFR) of a polymer represents the weight (g) of the melt polymer measured at 230 ° C. according to ASTM D-1238 under a load of 2.16 kg for 10 minutes.

The ethylene content in the copolymer was determined by press molding using a 0.2 mm-thick film, and using an infrared absorption spectrum method, a calibration curve was obtained using 2,6,10,14-tetramethylpentadecane. Created and attributed to 3 methylene groups 730 cm ^-1
It was determined from the absorbance ratio of.

The flexural modulus of the copolymer was measured according to ASTM-D790. B as an antioxidant in polymer powder
0.1% by weight of HT (2,6-ditertiarybutyl-4-methylphenol) and 0.2% by weight of IRGANOX 1010 [tetrakis- (methylene-3,5-ditertiarybutyl-4-hydroxy-cinnamate) methane] were added, After melt-kneading into pellets, test pieces were prepared by injection molding.

The haze was measured according to ASTM-D1003.
For the measurement, a 1.0 mm thick sheet prepared by injection molding was used.

Example 1 (1) Preparation of catalyst solid component [A] 15 mmol of anhydrous aluminum chloride was added to 40 ml of toluene, and then 15 mmol of methyltriethoxysilane was added dropwise with stirring. The reaction was carried out for 1 hour. After cooling the reaction product to -5 ° C, 18 ml of diisopropyl ether containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction product over 30 minutes with stirring, and the temperature of the reaction solution was adjusted to within the range of -5 to 0 ° C. I kept it. After completion of the dropwise addition, the temperature was gradually raised, and the reaction was continued at 30 ° C. for 1 hour. The precipitated solid was filtered off and washed with toluene and n-heptane. Next, 4.9 g of the obtained solid was suspended in 30 ml of toluene, and 150 mmol of titanium tetrachloride and 3.3 mmol of di-n-heptyl phthalate were suspended in this suspension.
Mmol was added, and the mixture was reacted at 90 ° C. for 1 hour with stirring.
The solid was filtered off at the same temperature and washed with toluene and then n-heptane. Furthermore, the solid was suspended again in 30 ml of toluene, 150 mmol of titanium tetrachloride was added, and the mixture was stirred at 90 ° C.
And reacted for 1 hour. The solid was filtered off at the same temperature, and the solid was washed with toluene and then n-heptane. The titanium content in the obtained catalyst solid component was 3.55% by weight. This solid was suspended in 80 ml of heptane to prepare a heptane slurry of catalyst solid components.

(2) Copolymerization of Propylene and Ethylene A glass ampoule containing a heptane slurry of catalyst solid component (7.9 mg as catalyst solid component) enclosed in an autoclave with an internal volume of 2 L equipped with a stirrer was attached, and then the autoclave was filled with nitrogen. Replaced with. Then triethyl aluminum
2.1 ml of n-heptane solution containing 2.1 mmol was charged to the autoclave. Further, as the component [C], 0.35 mmol of diperidinodimethoxysilane (DPIPDMS) is contained.
1.74 ml of n-heptane solution was charged. Then 2.0 kg / cm ²
G ² hydrogen and 3.0 kg / cm ² G ethylene were sequentially introduced, 1200 ml of liquid propylene was introduced, and the autoclave was shaken. The autoclave was cooled to 10 ° C., and when the stirring was started, the glass ampoule containing the solid catalyst component was crushed and prepolymerized for 10 minutes. Subsequently, the temperature inside the autoclave was raised to 60 ° C, and polymerization was carried out at 60 ° C for 1 hour. After the polymerization was completed, unreacted propylene gas and ethylene gas were released, and the polymer was heated to 50 ° C.
After drying under reduced pressure for 20 hours, a white powdery polypropylene copolymer was obtained. Table 1 shows the measurement results of the properties of the copolymer.

Example 2 Example 1 was repeated except that iso-propyl (piperidino) dimethoxysilane (IPPIPDMS) was used as the component [C]. Table 1 shows the measurement results of the properties of the copolymer.

Example 3 Example 1 except that iso-propyl (diethylamino) dimethoxysilane (IPDEADMS) was used as the component [C].
I went in the same way. Table 1 shows the measurement results of the properties of the copolymer.

Comparative Example 1 The procedure of Example 1 was repeated except that cyclohexylmethyldimethoxysilane (CMDMS) was used as the component [C]. Table 1 shows the measurement results of the properties of the copolymer.

[0057]

[Table 1]

[0058]

Industrial Applicability The catalyst of the present invention can be used to produce a polypropylene copolymer having an excellent balance of transparency and rigidity.

[Brief description of drawings]

FIG. 1 is a flow chart showing a preparation process and a polymerization method of a catalyst component of the present invention.

Claims (1)

[Claims] 1. A catalyst solid component essentially comprising magnesium, titanium, a halogen element and an electron donor as the component [A], an organoaluminum compound component as the component [B], and a general formula (1) as the component [C]. Or the general formula (2) R ¹ _n Si (OR ² ) _4-nm (NR ³ R ⁴ ) _m (1) R ¹ _n Si (OR ² ) _4-nm R ⁵ _m (2) (wherein R ¹ , R ² , R ³ and R ⁴ represent a hydrocarbon group having 1 to 24 carbon atoms, R ⁵ represents a cyclic amino group, n is 0 to 2 and m is 1
~ 2. ) A method for producing a propylene copolymer having an ethylene content of 0.01 to 10% by weight, which comprises copolymerizing propylene and ethylene in the presence of a catalyst comprising an organosilicon compound represented by