JPH08301920A - Process for polymerization of alpha-olefin - Google Patents

Abstract

PURPOSE: To obtain an α-olefin polymer having a high activity and being capable of giving an α-olefin polymer having a high stereoregularity and a broad molecular weight distribution. CONSTITUTION: A process for polymerizing an α-olefin in the presence of a catalyst comprising a solid catalyst component [A] essentially consisting of magnesium, titanium, halogen and an electron donor, an organoaluminum compound component [B], an organosilicon compound component [C] represented by the general formula: Si(OR<1> )2 (NR<2> R<3> )2 (wherein R<1> , R<2> and R<3> are each a 1-10C hydrocarbon group), and another organosilicon compound component [D].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a homopolymer of an α-olefin having a high stereoregularity and a wide molecular weight distribution, or a copolymer with another α-olefin.

[0002]

2. Description of the Related Art In recent years, in order to polymerize .alpha.-olefins, a solid catalyst component which requires magnesium, titanium, a halogen element, and an electron donor as an essential component, and an organometallic group I to III metal. A supported high activity catalyst system comprising a compound and an electron donor as a third component is disclosed in JP
57-63310, JP-A-58-83016, JP-A-59-580
Many have been proposed in Japanese Patent Laid-Open No. 10-44, Japanese Patent Laid-Open No. 60-44507 and the like. Furthermore, JP-A-62-11705 and JP-A-63-25
JP-A-8907, JP-A-2-84404, JP-A-4-202505, JP-A-4-370103, and the like, a polymerization catalyst characterized by using a specific organosilicon compound as a third component It is disclosed.

However, the olefin polymer obtained by using the above-mentioned supported catalyst system generally has a narrow molecular weight distribution, has a small viscoelasticity when the polymer is melted, and may cause a problem in moldability depending on the use. is there. In order to improve this problem, a means for broadening the molecular weight distribution is adopted by carrying out polymerization using a plurality of polymerization vessels or multi-stage polymerization. However, such a method requires complicated operations, and a method capable of obtaining an α-olefin polymer having a wide molecular weight distribution by single-stage polymerization is desired. In addition, Japanese Patent Laid-Open No. 3-7703
The gazette describes different MFRs as electron donors for the third component.
Although a polymerization method using a mixture of two electron donors that give the above is disclosed, further improvement is desired.

[0004]

OBJECTS OF THE INVENTION The present invention uses a highly active supported catalyst to
-Providing a method for polymerizing an olefin to produce an α-olefin polymer having a wide range of stereoregularity and molecular weight distribution.

[0005]

Technical Solution for Solving the Problems The present invention is directed to [A] a solid catalyst component essentially containing magnesium, titanium, a halogen element, and an electron donor, [B] an organoaluminum compound component, and [C] a general formula. Si (OR ¹ ) ₂ (NR ² R ³ ) ₂ (where
R ¹ , R ² and R ³ represent a hydrocarbon group having 1 to 10 carbon atoms. )
There is provided a method for polymerizing an α-olefin in the presence of a catalyst consisting of an organosilicon compound component represented by and a [D] organosilicon compound component (excluding the organosilicon compound of the [C] component).

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, an aluminum halide is reacted with an organosilicon compound, and then a Grignard compound is reacted 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 the aluminum halide include aluminum trichloride, aluminum tribromide and aluminum triiodide. Aluminum trichloride is particularly preferable.

Specific examples of the organosilicon compound used in the above reaction include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane, Examples thereof include dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonoethoxysilane, and trimethylmonobutoxysilane. In particular, methylphenyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and dimethyldiethoxysilane are preferable.

The amount of the compound used in the reaction between the aluminum halide and the organosilicon compound depends on the element ratio (Al / Si).
Is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3, and it is preferable to use an inert solvent such as hexane or toluene in the reaction. Reaction temperature is usually 10-100
℃, preferably 20 ~ 80 ℃, the reaction time is usually 0.2 ~
5 hours, preferably 0.5 to 3 hours.

Specific examples of the Grignard 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, ethyl. Examples include magnesium iodide. As the solvent of the Grignard compound, for example, an aliphatic ether such as diethyl ether, dibutyl ether, diisopropyl ether, diisoamyl ether, or an aliphatic cyclic ether such as tetrahydrofuran can be used.

The amount of the Grignard 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 organosilicon compound. Is the 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 of treating a solid with a titanium halide compound, then treating with an electron donor, and then again treating with a titanium halide compound, and (2) treating the solid with a titanium halide compound and an electron donor. Then, a well-known method such as a method of treating with a titanium halide compound after the treatment with 1 can be adopted. 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 treatment can be performed multiple times.

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

The electron donor used in the above contact treatment is preferably an aromatic ester, particularly an 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 contact treatment, the treated solid is generally separated from the treated mixture and thoroughly washed with an inert solvent to obtain a solid which is α-as the catalyst solid component [A] of the present invention.
It can be used as a polymerization catalyst for olefins.

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 organoaluminum compounds may be used as a mixture. Further, polyaluminoxane obtained by the reaction of alkylaluminum and water can be used as well.

The amount of the organoaluminum compound used as the α-olefin polymerization catalyst is 0.1 to 500, preferably the element ratio (Al / Ti) to titanium of the catalyst solid component [A].
It is 0.5 to 150.

The component [C] of the present invention is represented by the general formula Si (OR ¹ ) ₂ (NR ² R ³ ) ₂ (wherein R ¹ , R ² and R ³ are hydrocarbon groups having 1 to 10 carbon atoms). Is an organosilicon compound represented by.

Hydrocarbon groups preferred as R ¹ , R ² and R ³ are unsaturated or saturated aliphatic hydrocarbon groups having 1 to 10 carbon atoms, and particularly preferably unsaturated or saturated ones having 1 to 8 carbon atoms. It is an aliphatic hydrocarbon group. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, n-amyl, n-hexyl, isoamyl, cyclopentyl, cyclohexyl, phenyl and octyl groups. .

Among them, preferred as R ¹ are methyl, ethyl, propyl, isopropyl, isobutyl group, R ² and
Preferred as R ³ are methyl, ethyl, n-propyl, isopropyl, n-butyl and t-butyl groups.
R ² and R ³ may be the same or different.

Further, as the organosilicon compound of the component (C) of the present invention, different organosilicon compounds having the same NR ² R ^{3 of two} amino groups bonded to a silicon atom are different. It may be an organic silicon compound.

Specific examples of the organosilicon compound having the same NR ² R ^{3 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 ² R ³ groups different from each other include (diethylamino) (di-n-propylamino) dimethoxysilane,
Examples of organic silicon compounds include (diisopropylamino) (di-n-propylamino) dimethoxysilane.

Specific examples of the organosilicon compound having different R ² and R ³ include 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-
Butylamino) diethoxysilane, bis (di-t-butylamino) diethoxysilane and the like.

Among the above compounds, the component [C] is bis (dimethylamino) dimethoxysilane (BDMDM).
S), bis (diethylamino) dimethoxysilane (BDEDM
S), bis (di-n-propylamino) dimethoxysilane (B
DNPADMS) can be preferably used. Particularly, bis (diethylamino) dimethoxysilane (BDEDMS) is preferable.

[0026]

Embedded image

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.

The component [D] of the present invention is the above-mentioned component [C].
The organosilicon compounds other than the organosilicon compounds of. The organosilicon compound of the component [D] has the general formula R ⁴ _n Si
(OR ⁵ ) _4-n (In the formula, R ⁴ represents a hydrocarbon group having 1 to 10 carbon atoms or an amino group, R ⁵ represents a hydrocarbon group having 1 to 10 carbon atoms, and n
Is 1 to 3. ) And organosilicon compounds. Furthermore, R ⁴ ₂ Si (OR ⁵ ) ₂ is more preferable, and R ⁴ ₂ Si (OMe) ₂ is particularly preferable.

When two R ^{4 s} are hydrocarbon groups, at least one R ⁴ is preferably a hydrocarbon in which carbon of Si—C bond forms a secondary, tertiary or ring. Specific examples include isopropyl group, sec-butyl group, t-butyl group, cyclopentyl group,
And a cyclohexyl group.

Specific compounds include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane. , Methylphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonoethoxysilane, trimethylmonobutoxysilane and the like.

Further, t-butylmethyldimethoxysilane,
sec-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyldimethoxysilane,
Other examples include branched hydrocarbon group-containing organosilicon compounds such as di-t-butyldimethoxysilane and diisopropyldimethoxysilane.

Examples of the organosilicon compound as the component [D] include alicyclic hydrocarbon group-containing organosilicon compounds such as dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, cyclopentyltrimethoxysilane and cyclohexyltrimethoxysilane. .

Further, among R ⁴ of the general formula R ⁴ _n Si (OR ⁵ ) _4-n , an organic silicon compound in which at least one is a cyclic amino group can be mentioned. Preferred cyclic amino groups for R ⁴ include those derived from secondary cyclic amine compounds.

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.

Specific examples of the secondary cyclic amine compound include the compounds represented by the following formulas.

[0036]

Embedded image

[0037]

Embedded image

[0038]

[Chemical 4]

[0039]

Embedded image

The above cyclic amino group-containing organosilicon compound can be obtained by the reaction of a secondary cyclic amine compound and a silicon halide compound. Alternatively, it can be obtained by reacting an alkali metal salt or alkaline earth metal salt of a secondary cyclic amine compound with tetraalkoxysilane.

As the silicon halide compound, Si (OM
e)₂Cl₂, Si (OMe)₂Br₂, Si (OEt)₂Cl ₂, Si (OEt)₂Br₂
Can include dihalodialkoxysilanes such as
It

Examples of the alkali metal salt or alkaline earth metal salt of the secondary cyclic amine compound include lithium salt and magnesium salt of the secondary cyclic amine compound. As the tetraalkoxysilane, Si (OMe) ₄ ,
Si (OEt) ₄ etc. can be mentioned.

Specific examples of the organosilicon compound containing two cyclic amino groups include:

[0044]

[Chemical 6]

Compounds such as

Specific examples of the organosilicon compound having one cyclic amino group include:

[0047]

[Chemical 7]

[0048]

Embedded image

And the like.

[0050] As the organic silicon compound of the component (D), like the general formula R ⁴ ₂ Si (OR ⁵⁾ Alternative one R ⁴ in ₂ is a hydrocarbon radical R ⁴ is an amino group compound is To be Specific examples include ethyl (diethylamino) dimethoxysilane (EDEADMS), n-propyl (diethylamino) dimethoxysilane (NPDEADMS), isopropyl (diethylamino)
Dimethoxysilane (IPDEADMS), n-butyl (diethylamino) dimethoxysilane (NBDEADMS), isobutyl (diethylamino) dimethoxysilane (IBDEADMS), t-butyl (diethylamino) dimethoxysilane (TBDEADMS), cyclopentyl (diethylamino) dimethoxysilane (CPDEADM)
S), cyclohexyl (diethylamino) dimethoxysilane (CHDEADMS), vinyl (diethylamino) dimethoxysilane (VDEADMS), phenyl (diethylamino) dimethoxysilane (PHDEADMS) and the like.

[0051]

[Chemical 9]

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

[0053]

[Chemical 10]

Further, isopropyl (dimethylamino) dimethoxysilane, isopropyl (methylethylamino)
Dimethoxysilane, isopropyl (methylpropylamino) dimethoxysilane, isopropyl (dipropylamino) dimethoxysilane, isopropyl (propylethylamino) dimethoxysilane, isobutyl (dimethylamino) dimethoxysilane, isobutyl (methylethylamino) dimethoxysilane, isobutyl (diethylamino) )
Dimethoxysilane, isobutyl (dipropylamino) dimethoxysilane, t-butyl (dimethylamino) dimethoxysilane, t-butyl (methylethylamino) dimethoxysilane, cyclopentyl (dimethylamino) dimethoxysilane, cyclopentyl (methylethylamino) dimethoxysilane, Cyclopentyl (dipropylamino) dimethoxysilane, cyclohexyl (dimethylamino) dimethoxysilane, cyclohexyl (methylethylamino)
Examples thereof include dimethoxysilane and cyclohexyl (dipropylamino) dimethoxysilane.

Among the organosilicon compounds of the above component [D], compounds such as dicyclopentyldimethoxysilane, cyclopentyl (diethylamino) dimethoxysilane, cyclopentylpyrrolidinodimethoxysilane and pyrrolidinodimethoxysilane can be preferably used.

As the combination of the components [C] and [D] of the present invention, the melt flowability MFR _(C) of the polymer obtained by using the organosilicon compound [C] together with the components (A) and (B). The melt flowability MFR _(D) of the polymer obtained by using the organosilicon compound [D] together with the components (A) and (B) preferably satisfies MFR _(C) / MFR _(D) ≧ 2. , MFR _(C) / MFR _{(D )} ≧ 5 is more preferable, and MFR _(C) / MFR _(D) ≧ 10 is particularly preferable.

The amounts of the components [C] and [D] used are
The element ratio (Si / Al) of the component [C] and the component [D] silane to the component [B] aluminum is preferably 0.01 to 1, and more preferably 0.05 to 0.33.

The mixing ratio of the amounts of the components [C] and [D] used is preferably 4-0.25 in terms of the molar ratio of [C] and [D],
Particularly, 2 to 0.5 is preferable.

In the present invention, a chain transfer agent such as hydrogen can be used. The amount of hydrogen used for producing an α-olefin polymer having a desired stereoregularity (HI) and melt fluidity (MFR) can be appropriately determined depending on the polymerization method and the polymerization conditions. 0.2-10
It is in the range of kg / cm ² .

In the present invention, during the α-olefin polymerization,
The order of contact of the catalyst components is not particularly limited, but it is not so preferable that only the organosilicon compounds of the components [C] and [D] and the catalyst solids of the component [A] are in direct contact.

Examples of the α-olefin used in the present invention include propylene, 1-butene, 1-hexene, 4-methylpentene-1,1-octene and the like. In the present invention, the above α-olefin can be homopolymerized or copolymerized, and further the above α-olefin and ethylene can be copolymerized. In the present invention, propylene can be homopolymerized, and then ethylene or a mixture of ethylene and propylene can be copolymerized in the presence of the homopolymer to produce a propylene block copolymer.

As the polymerization method in the present invention, a slurry polymerization method using a non-polar solvent such as hexane or heptane, a gas phase polymerization method in which a monomer is brought into contact with a catalyst in a gas state, or a monomer in a liquid state as a solvent is used. A bulk polymerization method or the like in which the polymerization is performed can be adopted. Polymerization pressure is 1
~ 200kg / cm ² , preferably 10 ~ 80kg / cm ² , the polymerization temperature is usually 10 ~ 100 ℃, preferably 30 ~ 90 ℃, the polymerization time is usually
It is in the range of 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 olefin according to the above-mentioned various polymerization methods. In the prepolymerization, the catalyst solid component [A] is preliminarily contact-treated with the organoaluminum compound component [B] and the organosilicon compound components [C] and [D] before the main polymerization is carried out, and the solid is washed to bring them into contact with each other. Solids can be prepared. Further, using the catalyst solid component [A] or the above-mentioned catalytically treated solid, in the presence of the organoaluminum compound component [B] and the organosilicon compound components [C] and [D], a limited amount of α-olefin is obtained. It can also be prepolymerized. When the contact-treated solid is used, the organosilicon compound components [C] and [D] 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-mentioned contact-treated solid or prepolymerized solid is used as the catalyst solid component in the main polymerization, the organosilicon compound components [C] and [D] can be omitted in the main polymerization.

As the contact treatment of the present invention, the component [A],
The component [B] and the components [C] and [D] are mixed, and usually 0
React at ~ 100 ° C for 0.1-10 hours. The mixing order of each component is not particularly limited, but in general, the order of the component [A], the component [B], and the components [C] and [D] 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 separated and then used in the main polymerization, or the main polymerization can be continuously carried out without separation.

The prepolymerization time is usually 0.1 to 10 hours,
It is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the catalyst solid component. Catalyst solid component
If it is less than 0.1 g per 1 g, the main polymerization activity will be insufficient and the amount of catalyst residue will increase, and the stereoregularity of the α-olefin polymer will be insufficient. If it exceeds 100 g, the crystallinity of the α-olefin polymer tends to decrease. The prepolymerization temperature is
It is carried out at 0 to 100 ° C, preferably 10 to 90 ° C in the presence of each catalyst component. When carrying out the prepolymerization at a high temperature exceeding 50 ° C., it is preferable to reduce the α-olefin concentration or shorten the polymerization time. Otherwise catalyst solid component
It is difficult to control the production of 0.1 to 100 g of the prepolymer per 1 g, and the crystallinity of the α-olefin polymer obtained by the main polymerization is lowered.

The amount of the organoaluminum component used in the prepolymerization is usually Al / Ti based on the titanium atom of the catalyst solid component.
The molar ratio is 0.5 to 1000, preferably 100 to 600. The amount of silicate compound used is usually 0.01 / Si molar ratio to the aluminum atom of the organoaluminum compound component.
˜1, preferably 0.1 to 0.5. For prepolymerization,
Hydrogen can coexist if necessary.

In the present invention, the molecular weight distribution Mw / M
An α-olefin polymer is obtained when n is 8 or more.

[0070]

When an α-olefin is produced using the catalyst of the present invention, an α-olefin polymer having a high activity, a high stereoregularity of the polymer and a large molecular weight distribution can be provided.

EXAMPLES Examples of the present invention will be described below. In the examples, “polymerization activity” means a catalyst solid component.
Yield (g) of polymer produced per gram.

Melt flowability (MFR) represents the weight (g) of molten polymer measured at 230 ° C. under a load of 2.16 kg for 10 minutes according to ASTM D-1238.

The melting point and crystallization temperature were measured by using DSC (SSC-5200 DSC-220C manufactured by Seiko Denshi Kogyo). The measurement method is to raise the temperature from room temperature to 230 ° C at a rate of 10 ° C / min., Hold for 5 minutes, and then from 230 ° C to 40 ° C.
Cool down at a rate of 5 ° C / min and then from 40 ° C to 230 ° C.
The temperature was raised to 10 ° C. at a rate of 10 ° C./min., And the melting point was measured.

Examples 1-2, Comparative Examples 1-2 (1) Preparation of solid catalyst 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. After completion of the dropwise addition, the mixture was reacted at 25 ° C 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 the dropping was completed, 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) Polymerization of Propylene 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 inside of the autoclave was replaced with nitrogen. . Then triethyl aluminum
2.1 ml of n-heptane solution containing 2.1 mmol was charged to the autoclave. Further, as the component [C], bis (diethylamino) dimethoxysilane (BDEADMS), and as the component [D], cyclopentyl (piperidino)
Dimethoxysilane (CPPIPDMS) was charged in the amounts shown in Table 1 (molar ratio to triethylaluminum TEA). Then, after introducing ² kg / cm ² of hydrogen, 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. Then, raise the temperature inside the autoclave to 70 ° C and
Polymerization was carried out for 1 hour.

After completion of the polymerization, unreacted propylene gas was released and the polymer was dried under reduced pressure at 50 ° C. for 20 hours to obtain white powdery polypropylene. Table 2 shows the measurement results of the polymerization activity and the characteristics of the polymer.

Examples 3 to 4 and Comparative Example 3 Bis (diethylamino) dimethoxysilane (BDEADMS) as the component [C] and dicyclopentyldimethoxysilane (DCPDMS) as the component [D] are shown in Table 3, respectively. Example 1 was repeated except that the amount (molar ratio to triethylaluminum TEA) was charged. Table 4 shows the measurement results of the polymerization activity and the characteristics of the polymer.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

[Table 4]

[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 solid catalyst component essentially comprising [A] magnesium, titanium, a halogen element, and an electron donor,
[B] organoaluminum compound component, [C] general formula Si
(OR ¹ ) ₂ (NR ² R ³ ) ₂ (in the formula, R ¹ , R ² and R ³ are each a carbon number of 1 to
10 hydrocarbon groups are shown. ), And an organosilicon compound component [D] (however,
A method of polymerizing an α-olefin in the presence of a catalyst consisting of [C] component other than the organosilicon compound).