JPH09110922A - Olefin polymerization catalyst and production of olefin polymer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an olefin polymn. catalyst capable of producing an olefin polymer having an excellent moldability and a very high crystallinity in a high yield. SOLUTION: This catalyst comprises a solid catalyst component contg. Ti, Mg, a halogen, and an electron-donating compd., an organoaluminum compd., an organosilicon compd., and a sulfonic ester represented by the formula: R<4> SO3 R<5> (wherein R<4> and R<5> are each a hydrocarbon group).

Description

Detailed Description of the Invention

[Background of the Invention]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer using the same. More specifically, the present invention has excellent moldability,
The present invention also relates to an olefin polymerization catalyst capable of obtaining a polymer having extremely high stereoregularity, particularly an olefin polymer having 3 or more carbon atoms, in a high yield, and a method for producing an olefin polymer using this catalyst.

[0002]

2. Description of the Related Art In recent years, many proposals have been made for producing a highly stereoregular polymer of propylene in a high yield by using a solid component containing titanium, magnesium and halogen as essential components (for example, a special method). Kaisho 57-6331
No. 0, No. 57-63311, No. 57-63312,
58-138706, 58-138711, 58-138705).

[0003]

However, these catalyst systems are not known to the inventors of the present invention to have sufficient stereoregularity of the polymer, and in addition, since the molecular weight distribution is narrow, the moldability is low. Since it was bad, further improvement was required.

[0004]

[Means for Solving the Problems]

[Outline of the Invention] The present invention is excellent in moldability by using a polymerization catalyst in which a specific solid catalyst component and an organic aluminum compound component are combined with an organic silicon compound and a specific sulfonic acid ester as an external donor. To provide a propylene polymer having extremely high stereoregularity. <Summary> That is, the olefin polymerization catalyst according to the present invention is characterized by comprising the following components (A), (B), (C) and (D) in combination.

Component (A): Solid catalyst component containing titanium, magnesium, halogen and electron donating compound as essential components Component (B): Organoaluminum compound Component (C): Organosilicon compound Component (D): Formula The sulfonic acid ester represented by R ⁴ SO ₃ R ⁵ (in the formula, R ⁴ and R ⁵ are hydrocarbon groups). Further, the method for producing an olefin polymer according to the present invention is the above-mentioned catalyst for olefin polymerization. The olefin is brought into contact with the polymer to polymerize the olefin. <Effect> According to the present invention, it is possible to obtain an olefin polymer having excellent moldability and extremely high crystallinity in a high yield. Such an olefin polymer is suitably used for applications such as automobile parts, home electric appliance parts, and packaging materials for which high rigidity is required.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION

[Detailed Description of the Invention] [Catalyst for Olefin Polymerization] The catalyst for olefin polymerization according to the present invention comprises a specific component (A), component (B) and component (C).
And the component (D) in combination. Here, "combined" does not mean only a combination of the listed components (that is, A, B, C, and D) and does not impair the effects of the present invention. Do not exclude the combination of ingredients other than the listed ingredients. <Component (A)> The component (A) is titanium, magnesium,
It is a solid catalyst component containing halogen and an electron donating compound as essential components.

Here, "comprising as essential components" means that other components or elements for the purpose other than the four components listed above may be contained, and that these components are bound to each other. It indicates that it may exist.

The magnesium compound used as the magnesium source in the present invention is preferably magnesium halide, dialkoxymagnesium, alkoxymagnesium halide, magnesium oxyhalide, dialkylmagnesium, magnesium oxide, magnesium hydroxide and a carboxylate of magnesium. Etc. Of these, magnesium halide is preferable. As alkyl or alkoxy in these compounds, those having 1 to 6 carbon atoms, particularly ethyl and butyl are preferable.

The titanium compound serving as the titanium source is, for example, a compound of the formula Ti (OR ') _4-m X _m (wherein R'is a hydrocarbon group, preferably having 1 to 10 carbon atoms, X Represents halogen, and m represents a number of 0 ≦ m ≦ 4).

Preferred specific examples of such a titanium compound include, for example, TiCl ₄ , TiBr ₄ , and Ti (O
_{C 2 H 5) Cl 3,} Ti (OC 2 H 5) 2 Cl 2, Ti
_{(OC 2 H 5) 3 Cl} , Ti (O-iC 3 H 7) C
_{l 3, Ti (O-nC} 4 H 9) Cl 3, Ti (O-nC
₄ H ₉ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) Br ₃ , Ti
_{(OC 2 H 5) (O} -nC 4 H 9) 2 Cl, Ti (O-
nC ₄ H ₉ ) ₃ Cl, Ti (OC ₆ H ₅ ) Cl ₃ , Ti
_{(O-iC 4 H 9)} 2 Cl 2, Ti (O-nC 5 H 11)
_{Cl 3, Ti (O-nC} 6 H 13) Cl 3, Ti (OC 2
_{H 5) 4, Ti (O} -nC 3 H 7) 4, Ti (O-nC
_{4 H 9) 4, Ti (} O-iC 4 H 9) 4, Ti (O-n
Such as C ₆ H _{13) 4} and _{Ti (O-nC 8 H 17} ) 4 and the like.

As the titanium compound, a complex compound of TiX ' ₄ (where X'represents halogen) and an electron-donating compound (detailed later) can also be used. Specific examples of such complex compounds include, for example, TiCl ₄ .CH.
₃ CO ₂ C ₂ H ₅ , TiCl ₄ · C ₆ H ₅ COCl, T
iCl ₄ .C ₆ H ₅ CO ₂ C ₂ H _{5 and the} like.
Among these titanium compounds, TiCl ₄ is preferable.
And _{Ti (O-nC 4 H 9} ) _4.

The halogen is usually supplied from the above-mentioned magnesium and / or titanium halogen compounds, but in combination with known halogenating agents such as aluminum compounds, silicon halides, and phosphorus halides. In some cases, they can also be supplied. Halogen contained in the constituents and usually X in the above compounds may be fluorine, chlorine, bromine, iodine or mixtures thereof, with chlorine being particularly preferred.

The electron-donating compounds include (a) oxygen-containing electron donors such as alcohols, phenols, ethers, ketones, aldehydes, carboxylic acids, organic acid or inorganic acid esters, and acid halides. , Acid amides, acid anhydrides, and (b) nitrogen-containing electron donors such as amine, nitrile, and isocyanate. Preferred among these are ethers, organic acid esters and organic acid halides. Particularly preferred are organic acid esters and organic acid halides.

As the ethers, monoethers, diethers or triethers having 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms, preferably monoethers or diethers, particularly monoethers such as methyl ether, ethyl ether and isopropyl ether. , Butyl ether, amyl ether, tetrahydrofuran, anisole, diphenyl ether, 2,2-dimethyl-1,3-
Dimethoxypropane, 2,2-diisopropyl-1,3
-Dimethoxypropane, 2,2-diisobutyl-1,3
-Dimethoxypropane, 2-isopropyl-2-isobutyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxypropane, 2-
t-Butyl-2-methyl-2-1,3-dimethoxypropane, 2-t-butyl-2-isopropyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3
-Dimethoxypropane, 2,2-dicyclohexyl-
1,3-dimethoxypropane, 2,2-diphenyl-
1,3-dimethoxypropane, 2,2-dimethyl-1,
3-diethoxypropane, 2,2-diisobutyl-1,
An example is 3-diethoxypropane.

As the organic acid ester, an aliphatic carboxylic acid ester, particularly an aliphatic mono- or di-carbon compound having about 2 to 20 carbon atoms, preferably a mono- or carboxylic acid alkyl ester having about 1 to 10 carbon atoms, for example, acetic acid is used. Ethyl, ethyl acetate cellosolve, phenyl acetate, cyclohexyl acetate,
Ethyl propionate, methyl butyrate, methyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate and ethyl crotonic acid, ethyl cyclohexylcarboxylate, etc., and aromatic carboxylic acid esters, especially having 7 to 15 carbon atoms. Alkyl esters of aromatic mono- or dicarboxylic acids having about 1 to 10 carbon atoms, such as ethyl benzoate, methyl toluate, ethyl toluate, methyl anisate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, phthalic acid Dibenzyl etc. can be illustrated. Among these organic acid esters, phthalic acid esters are particularly preferable.

Examples of the organic acid halide include halides of the above-mentioned aliphatic or aromatic carboxylic acids such as aliphatic carboxylic acid chlorides such as acetyl chloride, and aromatic carboxylic acid chlorides such as benzoyl chloride, toluic acid chloride and anise. Acid chloride,
Examples thereof include phthaloyl chloride and isophthalic chloride. Among these organic acid halides, phthaloyl chloride is particularly preferable.

The amounts of the above components used are arbitrary as long as the effects of the present invention can be observed, but generally the following ranges are preferred.

The amount of titanium compound used is 0.001 to 1 in molar ratio with respect to the amount of magnesium compound used.
The range of 00 is preferable, and the range of 0.01 to 10 is more preferable. When a compound therefor is used as a halogen source, the amount used is a titanium compound and / or
Regardless of whether or not the magnesium compound contains halogen, the molar ratio is preferably 0.01 to 1000 with respect to the amount of the magnesium compound used, and
A range of 100 is more preferable.

The amount of the electron donating compound used is 0.001 to 1 in molar ratio with respect to the amount of the magnesium compound used.
The range of 0 is preferable, and the range of 0.01 to 5 is more preferable.

The component (A) is produced in the absence of oxygen, for example, by the following production method using the above components. (A) A method of bringing a magnesium halide, an electron donating compound and a titanium compound into contact with each other. (B) A method of treating alumina or magnesia with a phosphorus halide compound and contacting it with a magnesium halide, an electron donating compound, or a titanium halogen-containing compound. (C) A titanium halogen compound and / or a halogen compound of silicon are brought into contact with a solid component obtained by bringing a magnesium halide, a titanium tetraalkoxide, and a specific polymer silicon compound into contact with each other. A method of contacting a donor compound.

As the polymer silicon compound, those represented by the following formula are suitable.

[0022]

Embedded image (Here, R represents a hydrocarbon group having 1 to 10 carbon atoms, p represents a degree of polymerization such that the viscosity of the polymer silicon compound is in the range of 1 to 100 centistokes.) Specific examples of the polymer silicon compound include: Examples include methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, cyclohexyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane and 1,3,5,7,9. -Pentamethylcyclopentasiloxane and the like are preferable. (D) A method in which a magnesium compound is dissolved in titanium tetraalkoxide and an electron-donating compound, and the titanium compound is brought into contact with a solid component precipitated with a halogenating agent or a titanium halogen compound. (E) A method in which an organomagnesium compound such as a Grignard reagent is allowed to act with a halogenating agent, a reducing agent, etc., and then an electron donating compound and a titanium compound are brought into contact therewith. (F) A method of bringing a halogenating agent and / or a titanium compound into contact with an alkoxymagnesium compound in the presence of an electron donating compound.

Among the methods for producing the above component (A), (a)
Or (c) is preferable.

The component (A) used in the present invention may be the solid component obtained as described above as it is, or the solid component may be added in the presence or absence of an organoaluminum compound to give a small amount of olefins. It may be subjected to a prepolymerization treatment which comprises contacting with and polymerizing this.

When the component (A) is preliminarily polymerized, the prepolymerization conditions of the olefins for producing the component (A) are not particularly limited, but the following conditions are generally used. preferable. The polymerization temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. As the polymerization amount, 0.001 to 50 g of olefins is preferably polymerized per 1 g of the solid component, and 0.1 to 10 g of olefins is more preferably polymerized. The preliminary polymerization conditions are usually milder than the main polymerization conditions, and for example, the polymerization temperature is usually lower than that in the main polymerization.

As the organoaluminum compound component which may be used during the prepolymerization, those generally known as Ziegler type organoaluminum compounds can be used. As a specific example, the compound shown in the section of the description of the component (B) described later, that is, an organoaluminum compound can be used.

The amount of the organoaluminum component used in the prepolymerization is such that Al / T is used with respect to the Ti component in the solid component (A).
The i (molar ratio) is preferably from 1 to 20, more preferably from 2 to 10.

Examples of the olefins used in the prepolymerization include ethylene, propylene, 1-butene, 1-hexene and 3-methyl-1-butene. <Component (B)> The component (B) is an organoaluminum compound. Specific examples of organoaluminum compounds suitable for use as component (B) include R ⁶ _3-q AlX _q or R ⁷ _3-r Al (OR ⁸ ) _r (wherein R ⁶ and R
⁷ is a hydrocarbon group or hydrogen atom having 1 to 20 carbon atoms which may be the same or different, R ⁸ is a hydrocarbon group having 1 to 4 carbon atoms, X is halogen, q and r are 0 ≦ q <, respectively.
3, 0 <r <3).
Specifically, (a) trialkylaluminum, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum,
Trioctylaluminum, and tridecylaluminum, and the like, (b) alkylaluminum halides, such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride, and (c) dialkylaluminum hydrides, such as diethylaluminum hydride and (D) aluminum alkoxides such as dibutyl aluminum hydride, such as diethyl aluminum ethoxide and diethyl aluminum phenoxide.

In addition to these organoaluminum compounds (a) to (d), other organometallic compounds such as R ⁹ _3-a Al (O
R ¹⁰ ) _a (where a is 1 ≦ a ≦ 3, and R ⁹ and R ¹⁰ are hydrocarbon groups having 1 to 20 carbon atoms which may be the same or different), and Can be used together. For example, combined use of triethyl aluminum and diethyl aluminum alkoxide, combined use of diethyl aluminum monochloride and diethyl aluminum ethoxide, combined use of ethyl aluminum dichloride and diethyl aluminum ethoxide, combined use of triethyl aluminum and diethyl aluminum ethoxide and diethyl aluminum monochloride, etc. Is mentioned.

The amount of the component (B) used is 1 / Al (molar ratio) with respect to the titanium component constituting the component (A).
It is in the range of 1000, preferably in the range of 10 to 500. <Component (C)> The component (C) is an organosilicon compound. A compound having a Si—O—C bond is generally used, but a typical compound is a compound represented by the formula (I). R ¹ R ² _3-n Si (OR ³ ) _n (I) Here, R ¹ is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group, preferably an α-carbon having 3 to 12 carbon atoms. Is a secondary or tertiary branched aliphatic hydrocarbon group, or a cycloaliphatic hydrocarbon group having 5 to 12 carbon atoms, and particularly preferably a branched aliphatic group having 4 to 10 carbon atoms and a tertiary α carbon. It is a hydrocarbon group or a C 5-7 cycloaliphatic hydrocarbon group. R ² is the same or different from R ¹ and has 1 to 1 carbon atoms.
2 branched aliphatic, cycloaliphatic or linear hydrocarbon groups. R ³ is a branched or linear hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. n is 2
≦ n ≦ 3.

Specific examples of the silicon compound include the following substances. (CH ₃ ) ₃ CSi
_{(CH 3) (OCH 3)} 2, (CH 3) 3 CSi (CH
(CH ₃ ) ₂ ) (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi
_{(CH 3) (OC 2 H} 5) 2, (C 2 H 5) 3 CSi
_{(CH 3) (OCH 3)} 2, (CH 3) (C 2 H 5) C
_{HSi (CH 3) (OCH 3} ) 2, ((CH 3) 2 CH
CH ₂ ) ₂ Si (OCH ₃ ) ₂ , (CH ₃ ) ₃ CSi
(OCH ₃ ) ₃ , (CH ₃ ) ₃ CSi (OC
_{2 H 5) 3, (C} 2 H 5) 3 CSi (OCH 3) 3,
(CH ₃ ) (C ₂ H ₅ ) CHSi (OCH ₃ ) ₃ , (C
_{2 H 5) (CH 3)} 2 CSi (OC 2 H 5) 3,

[0032]

Embedded image

[0033]

Embedded image <Component (D)> The component (D) is a sulfonate represented by the formula R ⁴ SO ₃ R ⁵ .

Here, R ⁴ and R ⁵ are hydrocarbon groups. R ⁴ forming the sulfonic acid moiety of this sulfonic acid ester is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, a cycloaliphatic hydrocarbon group having 5 to 15 carbon atoms, or a branched group having 3 to 20 carbon atoms. Aliphatic hydrocarbon group, more preferably aromatic hydrocarbon group having 6 to 10 carbon atoms, 5 to 1 carbon atoms
A cycloaliphatic hydrocarbon group having 0 or a branched aliphatic hydrocarbon group having 3 to 8 carbon atoms, particularly preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Thus, the preferred sulfonic acid is an aromatic sulfonic acid.

R ⁵ forming the alcohol-corresponding portion of the sulfonic acid ester is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and more preferably, the number of carbon atoms. It is a branched aliphatic hydrocarbon group having 3 to 20 or a cyclic aliphatic hydrocarbon group having 5 to 15 carbon atoms. This R ⁵ is particularly preferably a branched aliphatic hydrocarbon group having 3 to 15 carbon atoms or a branched aliphatic hydrocarbon group having 5 to 10 carbon atoms, which is branched at the α-position carbon atom, and more preferably, It is a branched aliphatic hydrocarbon group having 3 to 8 carbon atoms.
Among these, it is preferable that R ⁴ is the above-mentioned aromatic hydrocarbon group, and R ⁵ is the above-mentioned branched aliphatic hydrocarbon group or cyclic aliphatic hydrocarbon group.

Specifically, the following compounds can be exemplified.

Examples of the aromatic sulfonic acid ester include methyl benzene sulfonate, ethyl benzene sulfonate,
Butyl benzene sulfonate, hexyl benzene sulfonate, cyclohexyl benzene sulfonate, phenyl benzene sulfonate, methyl p-toluene sulfonate, p-
Ethyl toluene sulfonate, propyl p-toluene sulfonate, butyl p-toluene sulfonate, hexyl p-toluene sulfonate, cyclohexyl p-toluene sulfonate, phenyl p-toluene sulfonate, methyl p-ethylbenzene sulfonate, p-ethylbenzene Ethyl sulfonate, p-ethylbenzene butyl sulfonate, p
-Hexyl ethylbenzenesulfonate, cyclohexyl p-ethylbenzenesulfonate, phenyl p-ethylbenzenesulfonate, methyl pt-butylbenzenesulfonate, ethyl pt-butylbenzenesulfonate, p
-Butyl tert-butylbenzenesulfonate, hexyl tert-butylbenzenesulfonate, cyclohexyl tert-butylbenzenesulfonate, phenyl pt-butylbenzenesulfonate, methyl m-toluenesulfonate,
m-toluene sulfonate, m-toluene sulfonate, hexyl m-toluene sulfonate, cyclohexyl m-toluene sulfonate, phenyl m-toluene sulfonate, methyl m-ethylbenzene sulfonate, m
-Ethyl ethylbenzene sulfonate, butyl m-ethylbenzene sulfonate, hexyl m-ethylbenzene sulfonate, cyclohexyl m-ethylbenzene sulfonate, phenyl m-ethylbenzene sulfonate, mt-
Methyl butylbenzenesulfonate, ethyl mt-butylbenzenesulfonate, butyl mt-butylbenzenesulfonate, hexyl mt-butylbenzenesulfonate, cyclohexyl mt-butylbenzenesulfonate, mt- Butyl benzene sulfonate, isopropyl benzene sulfonate, isobutyl benzene sulfonate, sec-butyl benzene sulfonate, tert-butyl benzene sulfonate, te benzene sulfonate
rt-amyl, 2-ethylhexyl benzenesulfonate, isopropyl p-toluenesulfonate, isobutyl p-toluenesulfonate, se p-toluenesulfonate
c-Butyl, tert-butyl p-toluenesulfonate, tert-amyl p-toluenesulfonate, 2-ethylhexyl p-toluenesulfonate, isopropyl p-ethylbenzenesulfonate, isobutyl p-ethylbenzenesulfonate, p-ethylbenzenesulfonate se
c-Butyl, p-ethylbenzenesulfonic acid tert-
Butyl, tert-amyl p-ethylbenzenesulfonate, 2-ethylhexyl p-ethylbenzenesulfonate, isopropyl p-tert-butylbenzenesulfonate, isobutyl p-tert-butylbenzenesulfonate, sec-p-tert-butylbenzenesulfonate sec
-Butyl, p-tert-butylbenzenesulfonic acid t
ert-butyl, tert-amyl p-tert-butylbenzenesulfonate, 2-ethylhexyl p-tert-butylbenzenesulfonate, isopropyl m-toluenesulfonate, isobutyl m-toluenesulfonate,
sec-Butyl m-toluenesulfonate, tert-butyl m-toluenesulfonate, tert-amyl m-toluenesulfonate, 2-ethylhexyl m-toluenesulfonate, isopropyl m-ethylbenzenesulfonate, isobutyl m-ethylbenzenesulfonate, sec-Butyl m-ethylbenzenesulfonate, tert-butyl m-ethylbenzenesulfonate, tert-amyl m-ethylbenzenesulfonate, 2-ethylhexyl m-ethylbenzenesulfonate, isopropyl m-tert-butylbenzenesulfonate, m-tert- Isobutyl butylbenzenesulfonate, sec-butyl m-tert-butylbenzenesulfonate, tert-butyl m-tert-butylbenzenesulfonate, m-ter
tert-amyl t-butylbenzene sulfonate and m
2-tert-butylbenzenesulfonic acid 2-ethylhexyl, and the like.

Examples of the aliphatic sulfonic acid ester include methyl cyclohexyl sulfonate, ethyl cyclohexyl sulfonate, butyl cyclohexyl sulfonate, hexyl cyclohexyl sulfonate, cyclohexyl sulfonate phenyl, cyclohexyl sulfonate phenyl, cyclopentyl sulfonate methyl, and cyclopentyl sulfonate. Ethyl, butyl cyclopentyl sulfonate,
Hexyl cyclopentyl sulfonate, cyclohexyl cyclopentyl sulfonate, phenyl cyclopentyl sulfonate, methyl isobutyl sulfonate, ethyl isobutyl sulfonate, butyl isobutyl sulfonate, hexyl isobutyl sulfonate, cyclohexyl isobutyl sulfonate, phenyl isobutyl sulfonate, t-butyl sulfonate Methyl, ethyl t-butyl sulfonate, butyl t-butyl sulfonate, hexyl t-butyl sulfonate, cyclohexyl t-butyl sulfonate, phenyl t-butyl sulfonate, methyl t-amyl sulfonate, t
-Ethyl amyl sulfonate, butyl t-amyl sulfonate, hexyl t-amyl sulfonate, cyclohexyl t-amyl sulfonate, phenyl t-amyl sulfonate,
Isopropyl cyclohexyl sulfonate, isobutyl cyclohexyl sulfonate, cyclohexyl sulfonate s
ec-butyl, tert-butyl cyclohexylsulfonate, tert-amyl cyclohexylsulfonate, 2-ethylhexyl cyclohexylsulfonate, isopropyl cyclopentylsulfonate, isobutyl cyclopentylsulfonate, sec-butyl cyclopentylsulfonate, tert-butyl cyclopentylsulfonate, cyclopentyl Tert-amyl sulfonate, 2-ethylhexyl cyclopentyl sulfonate, isopropyl isobutyl sulfonate, isobutyl isobutyl sulfonate,
Sec-Butyl isobutyl sulfonate, tert-butyl isobutyl sulfonate, ter isobutyl sulfonate
t-amyl, 2-ethylhexyl isobutyl sulfonate, tert-butyl isopropyl isopropyl, ter
Isobutyl t-butyl sulfonate, sec-butyl tert-butyl sulfonate, tert-butyl tert-butyl sulfonate, tert-butyl sulfonate ter
t-amyl, 2-ethylhexyl tert-butyl sulfonate, isopropyl tert-amyl sulfonate, t
ert-amyl sulfonate isobutyl, tert-amyl sulfonate sec-butyl, tert-amyl sulfonate tert-butyl, tert-amyl sulfonate t
Examples include ert-amyl, 2-ethylhexyl tert-amyl sulfonate, and the like.

The amount ratio of the component (C) and the component (D) used can be selected in a wide range, but each is usually 0.01 in molar ratio with respect to the organoaluminum compound of the component (B).
To 1.0, preferably 0.05 to 0.5.

Component (D) is simply a polymerization additive,
That is, it can be used as a typical so-called external donor, but it is preferably used after being contacted and mixed with the component (B) in advance. In that case, the total amount of the component (B) used for the polymerization and the component (D) may be preliminarily mixed, or a part of the component (B) and the component (D) may be preliminarily mixed, and then the polymerization system is used. It may be used as an additive. As described above, in the present invention, the usage of the component (D) other than the case where the component (A) is added in the manufacturing process and incorporated into the component (A) is considered to be used as an external donor. The same applies to the component (C).

The component (C) and the component (D) may be used not only in the main polymerization but also in the preliminary polymerization.

[Catalyst Use / Polymerization] <Polymerization> The catalyst system of the present invention is of course applicable to ordinary slurry polymerization, but is substantially solvent-free liquid phase solventless polymerization or solution polymerization. Also applicable to gas phase polymerization.

As a polymerization solvent in the case of slurry polymerization,
Hydrocarbon solvents such as hexane, heptane, pentane, etc. can be used.

The polymerization temperature is preferably 30 to 200 ° C, more preferably 50 to 150 ° C, particularly preferably 60 to 1 ° C.
00 ° C. Hydrogen can also be used supplementarily as a molecular weight regulator at that time. <Olefin> The olefin used for polymerizing with the catalyst system of the present invention has 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms,
Α-olefins such as ethylene, propylene,
Linear olefins such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-
It is a branched chain α-olefin such as 1-butene. Among them, the catalyst of the present invention is particularly suitable for the polymerization of propylene, but it is also preferably used when copolymerizing ethylene or 1-butene with propylene in a random or block manner.

[0045]

【Example】

Example 1 [Preparation of component (A)] 200 ml of dehydrated and deoxygenated n-heptane was introduced into a flask thoroughly purged with nitrogen, and then 0.4 mol of MgCl ₂ and Ti (O) were added.
-NC ₄ H ₉ ) ₄ was introduced in an amount of 0.8 mol and the reaction was carried out for 2 hours while maintaining the temperature at 95 ° C. After the reaction was completed, the temperature was lowered to 40 ° C, and then methylhydrogenpolysiloxane (20
Introduced 48 ml of Centistokes),
The reaction was performed for 3 hours. The solid component formed was washed with n-heptane.

Next, 50 ml of purified n-heptane was introduced into a flask sufficiently replaced with nitrogen, and 0.24 mol of the solid component synthesized above was introduced in terms of Mg atom. Then add 25 ml of n-heptane to SiCl
₄ 0.4 mol was mixed and introduced into the flask over 60 minutes while maintaining the temperature at 30 ° C., and reacted at 90 ° C. for 3 hours.

25 ml of n-heptane was further mixed with 0.02 mol of phthalic acid chloride, and
While maintaining at 0 ° C, introduce into the flask over 30 minutes, and
The reaction was performed at 0 ° C. for 1 hour.

After the reaction was completed, the solid component was washed with n-heptane. Then, 0.24 mmol of SiCl ₄ was introduced into this and reacted at 100 ° C. for 3 hours. After the reaction,
It was thoroughly washed with n-heptane. The solid component obtained here was mainly composed of magnesium chloride, and the Ti content was 2.3% by weight.

[Polymerization of Propylene] In a stainless steel autoclave with an internal volume of 3 liters equipped with a stirrer, 1.5 liters of sufficiently purified n-heptane, 108 mg of t-butylmethyldimethoxysilane, and 380 mg of triethylaluminum and p- A solid catalyst component (A) prepared by introducing a mixture of 150 mg of butyl toluenesulfonate in advance and further producing the mixture as described above.
After introducing 20 milligrams, 500 milliliters of hydrogen were introduced.

Then, the autoclave was heated to a temperature of 65 ° C., and propylene was pressure-supplied to a pressure of 7 kg / cm ² to start the polymerization of propylene. The pressure was maintained for 3 hours to continue the polymerization.

Thereafter, the introduction of the monomers was stopped, unreacted monomers were purged, the produced polymer was filtered from heptane, and dried. As a result, 491 g of powdery polypropylene was obtained. When n-heptane was removed by heating from the filtrate, 0.82 g of a polymer was obtained. Therefore, the catalyst yield of this catalyst system was 24600 g-polypropylene / g-solid catalyst (g-PP / g-CAT). Melt flow rate (MFR) is 5.5g / 10
The resulting polymer had a bulk density of 0.51 g / cm ³ . The Q value measured by GPC was 5.1, and the density of the press sheet was 0.9097 g / cm ³ . The Olsen bending elastic modulus was measured by the method of ASTM D-747-70, and was found to be 15300 kg / cm ² . Comparative Example 1 Propylene was polymerized in the same manner as in Example 1 except that butyl p-toluenesulfonate was not used. The obtained results are as shown in Table 1. Example 2 Propylene was polymerized in the same manner as in Example 1 except that butyl p-toluenesulfonate was not separately mixed with triethylaluminum but separately added to the polymerization tank. The obtained results are as shown in Table 1. Comparative Examples 2 and 3 Propylene was polymerized in the same manner as in Example 2 except that the compound shown in Table 1 was used as the component (D) in place of butyl p-toluenesulfonate. The obtained results are as shown in Table 1. Examples 3 and 4 Propylene was polymerized in the same manner as in Example 1 except that the compounds shown in Table 1 were used as the component (D) in place of butyl p-toluenesulfonate. The obtained results are as shown in Table 1. Example 5 [Production of Propylene Block Copolymer] A stirring autoclave having an internal volume of 200 liters was sufficiently replaced with propylene, and then 50 liters of purified n-heptane and t-
3.0 g of butylmethyldimethoxysilane was introduced, then 10.5 g of triethylaluminum and 4.2 g of butyl p-toluenesulfonate were premixed, and 8.7 g of the solid catalyst component prepared in Example 1 was introduced. 60 ℃
It was introduced under a propylene atmosphere while maintaining the above.

The first-stage polymerization was started by heating the autoclave to 65 ° C. and then introducing propylene at a feed rate of 9.0 kg / hr while maintaining the hydrogen concentration at 2.5 vol%.

After 231 minutes, the introduction of propylene was stopped. The pressure inside the autoclave at this time was 5.8 kg / cm ^2.
G. Further, the polymerization was continued at 65 ° C. for 90 minutes. Then, 0.2 kg / cm ² G of propylene in the vapor phase
Purged until

Next, after the autoclave was cooled to 60 ° C., post-stage polymerization was introduced at a feed rate of 3.78 kg / hr of propylene and 2.52 kg / hr of ethylene for 31 minutes, and then the polymerization was continued for 30 minutes. The obtained slurry was filtered and dried to obtain 33.4 kg of a powdery block copolymer.

Details of the results are shown in Table 2. In the table, the weight ratio of the first-stage polymerization and the second-stage polymerization and the weight ratio of propylene and ethylene in the second-stage polymerization are calculated values on a feed basis. Comparative Example 4 A block copolymer was produced in the same manner as in Example 5, except that butyl p-toluenesulfonate was not used. As a result, the pressure in the autoclave at the end of the propylene feed in the first-stage polymerization was 5.8 kg / cm.
² G, and 32.2 kg of a powdery block copolymer was obtained. Details of the obtained results are as shown in Table 2. Comparative Example 5 Electron Donor (Phthalic Acid Chloride) during Preparation of Component (A)
Propylene was polymerized in the same manner as in Example 1 except that was not used. The obtained results are as shown in Table 1. Example 6 In the polymerization of propylene of Example 1, p-toluenesulfonic acid s was used instead of butyl p-toluenesulfonate.
An experiment was conducted in the same manner as in Example 1 except that ec-butyl was used. As a result, 510 g of powdery polypropylene was obtained. When n-heptane was removed from the filtrate by heating, 0.71 g of a polymer was obtained. Therefore, the catalyst yield of this catalyst system is 25500 g-polypropylene /
It was a g-solid catalyst (g-PP / g-CAT). The melt flow rate (MFR) was 5.7 g / 10 minutes, and the bulk density of the produced polymer was 0.51 g / cm ³ . GPC
The measured Q value was 5.1, and the density of the press sheet was 0.9100 g / cm ³ . The Olsen flexural modulus was measured by the method of ASTM D-747-70,
It was 15500 kg / cm ² . Example 7 Propylene was polymerized in the same manner as in Example 6 except that sec-butyl p-toluenesulfonate was not separately mixed with triethylaluminum but separately added to the polymerization tank. The results obtained are as shown in Table 3. Examples 8 and 9 Polymerization of propylene was carried out in the same manner as in Example 1 except that the compound shown in Table 3 was used as the component (D) instead of sec-butyl p-toluenesulfonate. It was The results obtained are as shown in Table 3. Example 10 [Production of Propylene Block Copolymer] A stirring autoclave having an internal volume of 200 liters was sufficiently replaced with propylene, and then 50 liters of purified n-heptane and t-
3.0 g of butylmethyldimethoxysilane were introduced, then 10.5 g of triethylaluminum and 4.2 g of sec-butyl p-toluenesulfonate were introduced in advance, and the solid catalyst component 8 prepared in Example 1 was further introduced. 0.7 g
Was maintained at 60 ° C. and was introduced under a propylene atmosphere.

The first-stage polymerization was started by heating the autoclave to 65 ° C. and then introducing propylene at a feed rate of 9.0 kg / hr while maintaining the hydrogen concentration at 2.5 vol%.

After 231 minutes, the introduction of propylene was stopped. The pressure inside the autoclave at this time was 5.1 kg / cm ^2.
G. Further, the polymerization was continued at 65 ° C. for 90 minutes. Then, 0.2 kg / cm ² G of propylene in the vapor phase
Purged until

Next, after the autoclave was cooled to 60 ° C., post-stage polymerization was introduced at a feed rate of 3.78 kg / hr of propylene and 2.52 kg / hr of ethylene for 31 minutes, and then the polymerization was continued for 30 minutes. The obtained slurry was filtered and dried to obtain 33.6 kg of a powdery block copolymer.

Details of the results are shown in Table 2. In the table, the weight ratio of the first-stage polymerization and the second-stage polymerization and the weight ratio of propylene and ethylene in the second-stage polymerization are calculated values on a feed basis. Comparative Example 6 Electron Donor (Phthalic Acid Chloride) during Preparation of Component (A)
Propylene was polymerized in the same manner as in Example 6 except that was not used. The results obtained are as shown in Table 3. Examples 11 to 13 The same experiment as in Example 1 was carried out except that the same mole number of the compounds shown in the following table was used instead of phthaloyl chloride in the production of the component (A) of Example 1. Result is,
It is as shown in Table 4. Example 14 [Production of component (A)] In a flask thoroughly replaced with nitrogen,
100 ml of dehydrated and deoxygenated toluene was introduced, and then 10 g of Mg (OEt) ₂ was introduced to make a suspension. Then, 20 ml of TiCl ₄ was introduced, the temperature was raised to 90 ° C., 2.5 ml of di-n-butyl phthalate was introduced, and the temperature was further raised to 110 ° C. and reacted for 3 hours. After completion of the reaction, it was washed with toluene. Then T
20 ml of iCl ₄ and 100 ml of toluene were introduced and reacted at 110 ° C. for 2 hours. After completion of the reaction, it was thoroughly washed with n-heptane to obtain a solid catalyst component of component (A). The titanium content of this product is 2.6% by weight.
Met. [Polymerization of propylene] The same procedure as in Example 1 was carried out. The results are as shown in Table 1. <Practical physical property measuring method> The practical physical property measuring method in Examples 5, 10 and Comparative Example 4 was performed as follows. The following additives were added to the powdery block copolymers obtained in Examples 5, 10 and Comparative Example 4, pelletized by an extruder under the same conditions, and a sheet having a thickness of 4 mm was formed by an injection molding machine. It was created and the physical properties were evaluated. Additive 2,6-tert-butylphenol 0.10% by weight RA1010 (manufactured by Ciba Geigy) 0.05% by weight Calcium stearate 0.10% by weight Physical property measurement Various physical properties were measured by the following methods.

(A) Flexural modulus: ASTM-D790 (b) Izod impact strength (0 ° C.): ASTM-D25
6 (with notch)

[0057]

[Table 1]

[0058]

[Table 2]

[0058]

[Table 3]

[0059]

[Table 4]

EFFECTS OF THE INVENTION According to the present invention, it is possible to obtain an olefin polymer having excellent moldability and extremely high crystallinity, and an olefin polymerization catalyst capable of producing this polymer in a high yield. The above has been described in the section of “Outline of”.

Claims (4)

[Claims] 1. An olefin polymerization catalyst comprising a combination of the following components (A), (B), (C) and (D). Component (A): Solid catalyst component containing titanium, magnesium, halogen and electron-donating compound as essential components Component (B): Organoaluminum compound Component (C): Organosilicon compound Component (D): Formula R ⁴ SO ₃ Sulfonic acid ester represented by R ⁵ (in the formula, R ⁴ and R ⁵ are hydrocarbon groups) 2. R of sulfonic acid ester of component (D)
^{5. The} catalyst for olefin polymerization according to claim 1, wherein ⁵ is a branched aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. 3. A sulfonic acid ester compound as component (D), wherein R ⁴ is an aromatic hydrocarbon group and R ⁵ is a branched aliphatic hydrocarbon group or a cycloaliphatic hydrocarbon group. The olefin polymerization catalyst according to claim 1 or 2. 4. A process for producing an olefin polymer, which comprises contacting an olefin with the catalyst for olefin polymerization according to any one of claims 1 to 3 for polymerization.