JPH08151406A - Olefin polymerization catalyst and production of olefin polymer - Google Patents

Abstract

PURPOSE: To produce a polyolefin having a very small amount of boiling-acetone solubles which are low-molecular-weight components by using a supported Ziegler/Natta catalyst of a composition containing a specified cocatalyst. CONSTITUTION: This catalyst is prepared by mixing a solid catalyst component (A) essentially consisting of titanium, magnesium in an amount to give a molar ratio of 0.1-1000 to the titanium, and a halogen in an amount to give a molar ratio of 1-10 to the titanium, an organoaluminum compound (B) in an amount to give a molar ratio of 0.5 or above to the titanium, an organosilicon compound (C) represented by formula I (wherein R<1> is a 1-4C hydrocarbon group; R<2> is an H or 1-6C hydrocarbon group; and R<3> and R<4> are each a 1-6C hydrocarbon group) and used in an amount to give a molar ratio of 0.001-5 to component B and an organosilicon compound (D) represented by formula II (wherein R<5> is a 1-4C hydrocarbon group; and R<6> to R<8> are each an H or a 1-6C hydrocarbon group) and used in an amount to give a molar ratio of 0.001-0.1 to component C. This catalyst is useful for the stereospecific polymerization of a propylene- based monomer mixture.

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 polyolefin having a very low content of low molecular weight components and a catalyst. Among the low molecular weight components, the present invention relates to a method for producing a polyolefin and a catalyst in which the content of a boiling acetone-soluble component that causes a decrease in the rigidity of a polymer is extremely small.

[0002]

It is known that when an organosilicon compound is used as a co-catalyst component of a supported Ziegler catalyst, the stereoregularity of the produced polymer is improved. Polyolefins having high stereoregularity are very useful because they can be highly rigid materials. Therefore, many organosilicon compounds have been proposed so far as co-catalyst components that exhibit high stereospecificity. However, among the proposed organosilicon compounds, there are those that are costly to synthesize, those that produce substances harmful to the human body, those with low polymer yield, etc. Very few show performance.

An organosilicon compound represented by the above general formula (1) has been proposed as a cocatalyst component showing practical and excellent performance (Japanese Patent Laid-Open No. 5-287019). However, the low molecular weight component contained in a very small amount is said to reduce the rigidity of the obtained polymer, and in order to meet the needs for high rigidity materials in recent years, an olefin polymer having a lower low molecular weight component is further required. Was required. Among low molecular weight components,
It is said that the components soluble in boiling acetone particularly reduce the rigidity of the polymer. As a method of removing such low molecular weight components, a method of washing with an organic solvent is well known. However, since the cleaning process is expensive,
It has been desired to develop a method for removing low molecular weight components that does not require it.

[0004]

The object of the present invention is to produce a polymer having an extremely low content of low molecular weight components in a method for producing a polyolefin using a supported Ziegler catalyst without passing through a polymer washing step. Is to provide a way to do. Specifically, it is to provide a method for producing a polyolefin having a very small amount of a boiling acetone-soluble component in a polymerization step.

[0005]

Means for Solving the Problems In order to solve these problems, the present inventors have conducted extensive studies on a cocatalyst used in a supported Ziegler catalyst, particularly an electron donor (external donor) added at the time of polymerization. In the method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, the catalyst used is a component (A) a solid catalyst component containing titanium, magnesium and halogen as essential components (B) an organoaluminum compound component (C) an organosilicon compound represented by the general formula (1), and

Embedded image (Here, R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom,
R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms. R
² , R ³ and R ⁴ may be the same or different. ) Component (D) Organosilicon compound represented by the general formula (2)

[Chemical 4] (Here, R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms, R ⁶ ,
R ⁷ and R ⁸ are hydrocarbon groups having 1 to 6 carbon atoms or hydrogen atoms, and R ⁶ , R ⁷ and R ⁸ may be the same or different. As a result of polymerizing an olefin using a catalyst for olefin polymerization consisting of (1), it was found that a polymer having an extremely low content of a boiling acetone-soluble component can be obtained by solving the problems described above, and the present invention was reached.

The effect of the present invention can be obtained only by using a plurality of organosilicon compounds having a specific structure as a cocatalyst, particularly as an external donor. The cause is that the component (D) (organosilicon compound represented by the general formula (2)) added in a small amount poisons the active sites, which may generate low molecular weight components, due to various phenomena, or It is expected that the active site is converted into an active site that produces a high molecular weight component, but the detailed reason is unknown.

The present invention will be specifically described below. Examples of the magnesium compound used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide; alkoxy magnesium such as ethoxy magnesium and isopropoxy magnesium; carboxylic acids of magnesium such as magnesium laurate and magnesium stearate. Examples thereof include salts; alkyl magnesium such as butyl ethyl magnesium, and the like. Further, it may be a mixture of two or more kinds of these compounds. Preferably, magnesium halide is used, or magnesium halide is formed during catalyst formation. More preferably, the halogen is chlorine.

The titanium compound used in the present invention includes titanium halides such as titanium tetrachloride and titanium trichloride; titanium alkoxides such as titanium butoxide and titanium ethoxide; and alkoxytitanium halides such as phenoxytitanium chloride. It can be illustrated. Also,
It may be a mixture of two or more of these compounds. The halogen-containing compound used in the present invention is halogen, which is fluorine, chlorine, bromine, or iodine, preferably chlorine, and the specific compounds actually exemplified are halogenated compounds such as titanium tetrachloride and titanium tetrabromide. Titanium, silicon tetrachloride, silicon halides such as silicon tetrabromide, phosphorus trichloride, phosphorus halides such as phosphorus pentachloride are typical examples, but depending on the preparation method, halogenated hydrocarbons, halogen molecules, Hydrohalic acid (eg, HCl, HBr, HI, etc.) may be used. These may be common with titanium compounds and magnesium compounds.

In preparing the solid catalyst component (A) used in the present invention, various electron donors (internal donors) may or may not be added. As an electron donor,
Examples thereof include oxygen-containing compounds and nitrogen-containing compounds. More specifically, (a) methanol, ethanol, propanol, butanol, heptanol, hexanol, octanol, dodecanol, octadecyl alcohol, 2
-Ethyl-hexyl alcohol, benzyl alcohol,
It may have an alkyl group having 1 to 20 carbon atoms such as cumyl alcohol, diphenylmethanol and triphenylmethanol, and (b) phenol, cresol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol. Phenols having 6 to 25 carbon atoms,

(C) Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and other ketones having 3 to 15 carbon atoms; (d) acetaldehyde, propionaldehyde, tolualdehyde, naphthaldehyde, and other aldehydes having 2 to 15 carbon atoms. Kind,

(V) Methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl propionate, methyl n-butyrate, methyl isobutyrate, ethyl isobutyrate , Isopropyl isobutyrate, ethyl valerate, butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
Ethyl methacrylate, ethyl crotonate, cyclohexanecarboxylate, methyl phenylacetate, methyl phenylbutyrate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, benzoate Acid phenyl, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate,
Ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, diheptyl phthalate, dineopentyl phthalate, diethyl malonate, isopropyl isopentyl malonate, diethyl diisobutyl malonate, organic acid esters having 2 to 20 carbon atoms such as γ-butyrolactone, γ-parerolactone, coumarin, phthalide, diethyl carbonate, methyl orthoformate, ethyl orthoformate,

(F) Methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, phenyl methoxyacetate,
Methyl ethoxyacetate, Ethyl ethoxyacetate, Butyl ethoxyacetate, Phenyl ethoxyacetate, Ethyl n-propoxyacetate, Ethyl i-propoxyacetate, Methyl n-butoxyacetate, Ethyl i-butoxyacetate, n-Hexyloxyacetate, sec-Hexyl Octyl oxyacetate, methyl 2-methylcyclohexyloxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, butyl 3-methoxypropionate, ethyl 3-ethoxypropionate, butyl 3-ethoxypropionate, 3-ethoxy N-Octyl propionate, dodecyl 3-ethoxypropionate, pentamethylphenyl 3-ethoxypropionate, ethyl 3- (i-propoxy) propionate, 3-
Butyl (i-propoxy) propionate, Allyl 3- (n-propoxy) propionate, 3- (n-Butoxy)
Cyclohexyl propionate, ethyl 3-neopentyloxypropionate, butyl 3- (n-octyloxy) propionate, octyl 3- (2,6-dimethyldecyloxy) propionate, ethyl 4-ethoxyacetate,
Cyclohexyl 4-ethoxybutyrate, octyl 5- (n-propoxy) valerate, ethyl 12-ethoxylaurate, ethyl 3- (1-indenoxy) propionate, 3
-Methyl methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, ethyl 2-methoxypropionate, 2- (i-propoxy) butyrate n
-Butyl, methyl 2-ethoxyisobutyrate, phenyl 2-cyclohexyloxyisovalerate, 2-ethoxy-2-
Butyl phenylacetate, allyl 3-neopentyloxybutyrate, methyl 3-ethoxy-3- (o-methylphenyl) propionate, ethyl 3-ethoxy-2- (o-methylphenyl) propionate, 4-ethoxy-2- Methyl-
Ethyl 1-naphthylnonanoate, 2-methoxycyclopentanecarboxylic acid ethyl ester, 2-ethoxycyclohexanecarboxylic acid butyl ester, 3- (ethoxymethyl) tetralin-2-acetic acid isopropyl ester, 8-
Butoxy-decalin-1-carboxylic acid ethyl ester,
3-Ethoxynorbornane-2-carboxylic acid methyl ester, methyl 2- (phenoxy) acetate, ethyl 3- (p-crezoxy) propionate, 4- (2-naphthoxy)
Methyl butyrate, Butyl 5-carbaloxyvalerate, Methyl 2-phenoxypropionate, Ethyl 3- (4-methylphenoxy) -2-phenylpropionate, Ethyl 2-phenoxycyclohexanecarboxylic acid, Ethyl thiophene-3-oxyacetate, Alkoxy esters such as ethyl 2- (2-picolinoxymethyl) -cyclohexanecarboxylate and ethyl 3-furfuryloxypropionate,

(To) Methyl acetyl acetate, ethyl acetyl acetate, butyl acetyl acetate, methyl propionyl acetate, phenyl acetyl acetate, ethyl propionyl acetate,
Ethyl propionyl acetate, Phenyl propionyl acetate,
Butyl propionyl acetate, ethyl butyryl acetate, ethyl i-butanoyl acetate, ethyl pentanoyl acetate, methyl 3-acetylpropionate, ethyl 3-acetylpropionate, butyl 3-acetylpropionate, ethyl 3-propionylpropionate, 3-propionylpropionate Butyl acid, n-octyl 3-propionylpropionate, dodecyl 3-propionylpropionate, pentamethylphenyl 3-propionylpropionate, 3- (i
-Ethyl propionyl) propionate, butyl 3- (i-propionyl) propionate, allyl 3- (i-propionyl) propionate, cyclohexyl 3- (i-propionyl) propionate, ethyl 3-neopenanoylpropionate, 3 Butyl -n-lauryl propionate, methyl 3- (2,6-dimethylhexanoyl) propionate, ethyl 4-propionyl butyrate, cyclohexyl 4-propionyl butyrate, octyl 5-butyryl valerate, ethyl 12-butyryl laurate, 3 -Methyl acetyl acrylate, methyl 2-acetyl acrylate, 3-
Ethyl benzoylpropionate, methyl 3-benzoylpropionate, ethyl 3-methylbenzoylpropionate, butyl 3-toluylbutyrate, ethyl o-benzoylbenzoate, ethyl m-benzoylbenzoate, ethyl p-benzoylbenzoate, o-toluyl Butyl benzoate, o-
Ethyl toluylbenzoate, ethyl m-toluylbenzoate, ethyl p-toluylbenzoate, o- (2,4,6-
Trimethylbenzoyl) ethyl benzoate, m- (2,
4,6-Trimethylbenzoyl) ethyl benzoate, p-
Ethyl (2,4,6-trimethylbenzoyl) benzoate, ethyl o-ethylbenzoylbenzoate, ethyl o-acetylbenzoate, ethyl o-propionylbenzoate,
Ketoesters such as ethyl o-laurylbenzoate, ethyl o-cyclohexanoylbenzoate and ethyl o-dodecylbenzoate,

(H) Inorganic acid esters such as methyl borate, butyl titanate, butyl phosphate, diethyl phosphite and diphenylphosphorochloridate,

(Ri) methyl ether, ethyl ether,
Isopropyl ether, butyl ether, amyl ether, tetrahydrofuran anisole, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, 2,2-dimethoxypropane, 1,3-dimethoxypropane, 1,3-diethoxypropane, 2-isopropyl-2- Isopentyl-
1,3-dimethoxypropane, 2,2-diisobutyl-
2 to 25 carbon atoms such as 1,3-dimethoxypropane
Ethers,

(N) Acid amides having 2 to 20 carbon atoms such as acetic acid amide, benzoic acid amide, toluic acid amide,
(L) Acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthaloyl chloride and other acid halides having 2 to 20 carbon atoms, (wo) acetic anhydride, phthalic anhydride and other carbon atoms having 2 to 2 carbon atoms 20 acid anhydrides, (wa) monomethylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
Amines having 1 to 20 carbon atoms such as picoline and tetramethylethylenediamine, nitriles having 2 to 20 carbon atoms such as (mo) acetonitrile, benzonitrile and trinitrile,

(Yo) Ethylthioalcohol, butylthioalcohol, phenylthiol, etc. having 2 to 2 carbon atoms
0 thiols, (ta) diethyl thioether, diphenyl thioether and other thioethers having 4 to 25 carbon atoms,

(R) C2-C20 sulfuric acid esters such as dimethyl sulfate and diethyl sulfate; C2-C20 sulfonic acids such as (so) phenylmethyl sulfone and diphenyl sulfone; and (P) phenyltrimethoxysilane. , Phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane,
Carbon number 2 such as phenyldimethylethoxysilane, triphenylmethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, lower alkyl silicate (especially ethyl silicate) To 24 silicon-containing compounds. 2 of these electron-donating compounds
More than one species can be used. Among these, preferable are organic acid esters, alkoxyesters, ketoesters and the like.

The preparation method of the solid catalyst component used in the present invention is not particularly limited, but the following examples can be mentioned. A method of obtaining a catalyst component by bringing magnesium halide, titanium halide and the above-mentioned electron donating compound into contact with each other by co-grinding or by dispersing or dissolving in a solvent. A method of preparing a complex of magnesium halide and an organic or inorganic compound (which may contain the above-mentioned electron-donating compound), and bringing this into contact with a titanium halide or a complex of the above-mentioned electron-donating compound to obtain a catalyst component. . A complex of a magnesium halide and an organic or inorganic compound (which may contain the above-mentioned electron-donating compound) is formed, and the above-mentioned electron-donating compound and the titanium compound are sequentially brought into contact therewith (the order may be changed)
To obtain a catalyst component. A method for obtaining a catalyst component by contacting a magnesium compound (or a titanium compound further) with the above-mentioned electron donating compound, and at the same time or at a subsequent stage contact with a titanium compound and / or halogenation treatment to obtain a catalyst component (titanium at any stage) Including the use of compounds).

The above-mentioned catalyst component may be produced by a method of supporting or impregnating it on a substance generally used as a catalyst carrier, for example, silica or alumina.

The quantitative relationship of each component in the component (A) is as follows:
It is optional as long as the effects of the present invention can be observed, but the following ranges are generally preferred. The content of magnesium in the component (A) is 0.1 to 1 in terms of molar ratio to titanium.
It may be in the range of 000, preferably in the range of 2 to 200, and the content of halogen is 1 to 10 in terms of molar ratio to titanium.
It may be in the range of 0, and when the electron-donating compound is used, its content is within the range of 10 or less in terms of molar ratio to titanium.
It may be preferably in the range of 0.1 to 5.

The average particle size of the solid catalyst component used in the present invention is arbitrary as long as the effect of the present invention can be recognized, but it is generally in the range of 0.1 to 200 microns, preferably 1 ~ 100 microns, more preferably 10-1
It is 00 microns.

The organoaluminum compound in the present invention is represented by the following general formulas (3) to (5). AlR ⁹ R ¹⁰ R ¹¹ (3) R ¹² R ¹³ Al-O-AlR ¹⁴ R ¹⁵ (4)

Embedded image In formulas (3), (4) and (5), R ⁹ and R ¹⁰
And R ¹¹ may be the same or different and is a hydrocarbon group having at most 12 carbon atoms, and R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ may be the same or different and may have at most 12 carbon atoms. Is a hydrocarbon group. R ¹⁶ has at most 1 carbon atom
It is two hydrocarbon groups and n is an integer of 1 or more.

Typical of the organoaluminum compounds represented by the formula (3) are trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, and diethyl. Alkyl aluminum hydrides such as aluminum hydride and diisobutyl aluminum hydride and alkyl aluminum hydrides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride and ethyl aluminum sesquichloride.

Further, among the organoaluminum compounds represented by the formula (4), typical ones include alkyl dialumoxane such as tetraethyl dialumoxane and tetrabutyl dialumoxane.

The formula (5) represents an aluminoxane, which is a polymer of an aluminum compound. R ⁹ includes methyl, ethyl, propyl, butyl, benzyl and the like, preferably methyl and ethyl groups. n is 1 to 1
0 is preferred. Of these organoaluminum compounds, trialkylaluminums, alkylaluminum hydrides and alkylalumoxanes are preferable because they give particularly preferable results.

In the polymerization of olefins, the amount of organic aluminum used in the polymerization system is generally 10 ^-4 mmol / l or more, preferably 10 ^-2 mmol / l or more. The molar ratio of titanium atom to the solid catalyst component is generally 0.5 or more, preferably 2 or more, and more preferably 10 or more. If the amount of organoaluminum used is too small, the polymerization activity will be significantly reduced. When the amount of organoaluminum used in the polymerization system is 20 mmol / l or more and the ratio with respect to titanium atoms is 1000 or more in molar ratio, the catalyst performance is further improved even if these values are further increased. I can't see that.

The component (C) of the catalyst used in the present invention is
It is an organosilicon compound having a structure represented by the general formula (1).

[Chemical 6] (Here, R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom,
R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms. R
² , R ³ and R ⁴ may be the same or different. )

Specific examples of such compounds are shown below. Isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, isopropyltriisopropoxysilane,
t-butyltrimethoxysilane, t-butyltriethoxysilane, t-butyltripropoxysilane, t-butyltriisopropoxysilane, thexyltrimethoxysilane (2,3-dimethyl-2-trimethoxysilylbutane), textile Siltriethoxysilane, texyltripropoxysilane, texyltriisopropoxysilane,
2,3-dimethyl-2-trimethoxysilylpentane,
2,3-dimethyl-2-triethoxysilylpentane,
2,3-dimethyl-2-tripropoxysilylpentane, 2,3-dimethyl-2-triisopropoxysilylpentane, 2-methyl-3-ethyl-2-trimethoxysilylpentane, 2-methyl-3-ethyl- 2-triethoxysilylpentane, 2-methyl-3-ethyl-2-
Tripropoxysilylpentane, 2-methyl-3-ethyl-2-triisopropoxysilylpentane, 2,3
4-trimethyl-2-trimethoxysilylpentane,
2,3,4-trimethyl-2-triethoxysilylpentane, 2,3,4-trimethyl-2-tripropoxysilylpentane, 2,3,4-trimethyl-2-triisopropoxysilylpentane, 2,3- Dimethyl-2-trimethoxysilylhexane, 2,3-dimethyl-2-triethoxysilylhexane, 2,3-dimethyl-2-tripropoxysilylhexane, 2,3-dimethyl-2-
Triisopropoxysilylhexane, 2,4-dimethyl-3-ethyl-2-trimethoxysilylpentane, 2,
4-dimethyl-3-ethyl-2-triethoxysilylpentane, 2,4-dimethyl-3-ethyl-2-tripropoxysilylpentane, 2,4-dimethyl-3-ethyl-2-triisopropoxysilylpentane, 2,4-Dimethyl-3-isopropyl-2-trimethoxysilylpentane, 2,4-dimethyl-3-isopropyl-2-triethoxysilylpentane, 2,4-dimethyl-3-isopropyl-2-tripropoxysilylpentane , 2,
4-dimethyl-3-isopropyl-2-triisopropoxysilylpentane and the like can be mentioned. Of these, thexyltrimethoxysilane is particularly preferable. The amount of the component (C) used is the molar ratio of the component (C) / component (B) =
0.001-5 are preferable, and more preferably 0.01-
It is 1.

The component (D) of the catalyst used in the present invention is
It is an organosilicon compound having a structure represented by the general formula (2).

[Chemical 7] (Here, R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms, R ⁶ ,
R ⁷ and R ⁸ are hydrocarbon groups having 1 to 6 carbon atoms or hydrogen atoms, and R ⁶ , R ⁷ and R ⁸ may be the same or different. )

Specific examples of such compounds are shown below. n-propyltrimethoxysilane, n-
Propyltriethoxysilane, n-propyltripropoxysilane, n-propyltriisopropoxysilane,
n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltripropoxysilane, n-butyltriisopropoxysilane, 2,3-dimethylbutyl-trimethoxysilane, 2,3-dimethylbutyl-triethoxysilane 2,3-dimethylbutyl-tripropoxysilane, 2,3-dimethylbutyl-triisopropoxysilane, 2,3-dimethylpentyl-trimethoxysilane, 2,3-dimethylpentyl-triethoxysilane, 2,3- Dimethylpentyl-tripropoxysilane, 2,3-dimethylpentyl-triisopropoxysilane, 2-methyl-3-ethylpentyl-trimethoxysilane, 2-methyl-3-ethylpentyl-triethoxysilane, 2-methyl-3 -Ethylpentyl-tripropoxysilane, 2- Tyl-3-ethylpentyl-triisopropoxysilane, 2,3,4-trimethylpentyl-trimethoxysilane, 2,3,4-trimethylpentyl-triethoxysilane, 2,3,4-trimethylpentyl-tripropoxysilane 2,3,4-trimethylpentyl-triisopropoxysilane, 2,3-dimethylhexyl-trimethoxysilane, 2,3-dimethylhexyl-triethoxysilane, 2,3-dimethylhexyl-tripropoxysilane, 2, 3-dimethylhexyl-triisopropoxysilane, 2,4-dimethyl-3
-Ethylpentyl-trimethoxysilane, 2,4-dimethyl-3-ethylpentyl-triethoxysilane, 2,
4-dimethyl-3-ethylpentyl-tripropoxysilane, 2,4-dimethyl-3-ethylpentyl-triisopropoxysilane, 2,4-dimethyl-3-isopropylpentyl-trimethoxysilane, 2,4-dimethyl- 3-isopropylpentyl-triethoxysilane,
2,4-dimethyl-3-isopropylpentyl-tripropoxysilane, 2,4-dimethyl-3-isopropylpentyl-triisopropoxysilane and the like can be mentioned.

Component (D) is preferably one selected from the structural isomers of component (C). Therefore, it is preferable to consider the selection of the component (D) in combination with the component (C). A particularly preferred combination uses thexyltrimethoxysilane as component (C) and 2,3-dimethylbutyl-trimethoxysilane (2,3-dimethyl-1-trimethoxysilyl-butane) as component (D). It was a combination that I had. The amount of component (D) used is a molar ratio of component (D) / component (C) = 0.001 to
0.1, preferably 0.01 to 0.05.

The olefin used for the polymerization is generally an olefin having at most 12 carbon atoms, and typical examples thereof include ethylene, propylene and butene-.
1,4-methylpentene-1, hexene-1, octene-1, and the like, and mixtures thereof, and stereospecific α-olefins containing 3 or more carbon atoms such as ethylene and mixtures thereof. It is advantageous for sexual polymerization. More preferably, it is particularly effective for stereospecific polymerization of propylene or mixtures of propylene and up to about 20 mol% ethylene or higher α-olefins, with propylene homopolymerization being most preferred.

In carrying out the polymerization, the solid catalyst component of the present invention, the organoaluminum compound, or these and the organosilicon compound may be separately introduced into a polymerization vessel, but two or all of them may be mixed in advance. Alternatively, typically, a dropping funnel replaced with nitrogen is mixed with an inert solvent, an organoaluminum compound and an organosilicon compound, which will be described later, and mixed, and after a certain time or more (about 1 minute or more), the mixture is solidified. It is preferable that the catalyst component is brought into contact with the catalyst component, reacted for a certain period of time (about 1 minute or more), and then added to the polymerization reaction vessel. The inert solvent used at this time is pentane, hexane, heptane, n-
Alkanes and cycloalkanes such as octane, isooctane, cyclohexane and methylcyclohexane; alkylaromatic hydrocarbons such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene and mono or dialkylnaphthalenes; chlorobenzene, Halogenated and hydrogenated aromatic hydrocarbons such as chloronaphthalene, orthodichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquid paraffins or mixtures thereof can be used.

The olefin polymerization according to the present invention is carried out at atmospheric pressure or at a monomer pressure above atmospheric pressure. In gas phase polymerization, the monomer pressure should not be below the vapor pressure at the polymerization temperature of the olefin to be polymerized, but generally the monomer pressure is in the range of about 20 to 600 PSI. The polymerization can be carried out either in an inert solvent, in a liquid monomer (olefin) or in the gas phase. Further, the polymerization can be carried out by any of batch method, semi-continuous method and continuous method. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. In order to obtain a polymer having a practicable melt flow, a molecular weight modifier (generally hydrogen) may coexist. The polymerization time is generally 30 minutes to several hours in the case of the batch method, and the corresponding average residence time in the case of the continuous method. Polymerization times of about 1 to 6 hours are typical in autoclave type reactions.

In the slurry method, the polymerization time is preferably 30 minutes to several hours. Suitable diluent solvents for use in slurry polymerization include alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane and methylcyclohexane; toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n. -Alkyl aromatic hydrocarbons such as propylbenzene, diethylbenzene and mono- or dialkylnaphthalene; halogenated and hydrogenated aromatic hydrocarbons such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquids There are paraffins or mixtures thereof, and other well known diluent solvents.

In the gas phase polymerization method in which the present invention is useful, a stirred tank reactor, a fluidized bed reactor system or the like can be used. A typical gas phase olefin polymerization reactor system consists of a reaction vessel to which olefin monomer and catalyst components can be added and which is equipped with a stirrer, the catalyst components being reacted together or separately from one or more valve control ports. Added to the container. Olefin monomer is typically a method in which unreacted monomer removed as exhaust gas and fresh feed monomer are mixed and supplied to a reactor through a recycle gas system that is pressed into a reaction vessel.

Although not generally required, water, alcohol, acetone or any other suitable catalyst deactivation is known as a catalyst poison when the polymerization is complete or when it is terminated or when the deactivation of the invention is carried out. It is possible by contacting with an agent. The polymerization temperature is generally -10 ° C to 18 ° C.
Although it is 0 ° C., 20 ° C. to 100 ° C. is preferable from the viewpoint of obtaining good catalyst performance and high production rate, and more preferably 50 ° C. to 80 ° C.

Prepolymerization Prepolymerization is not always necessary, but it is also preferable to carry out prepolymerization, and usually the solid catalyst component (A) is used in combination with at least a part of the organoaluminum compound component (B). . At this time, an organosilicon compound or an acetal compound can coexist. Such an organosilicon compound is the catalyst component (C)
Alternatively, it is not limited to the compound used as (D). The concentration of the solid catalyst component (A) in the prepolymerization is preferably in the range of usually 0.01 to 200 mmol in terms of titanium atom per liter of an inert hydrocarbon solvent described later. The amount of the organoaluminum compound component (B) was 0.1% per 1 g of the solid titanium catalyst component (A).
The amount is such that 1 to 500 g of the polymer is produced, and preferably the amount is such that 0.1 to 300 g of the polymer is produced. The prepolymerization is preferably carried out under mild conditions by adding an olefin and the above catalyst component to an inert hydrocarbon solvent. Specific examples of the inert hydrocarbon solvent used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; benzene, toluene, xylene, and other aromatic hydrocarbons; ethylene chloride, chlorobenzene, and other halogenated hydrocarbons, and mixtures thereof. Of these inert hydrocarbon solvents, it is particularly preferable to use aliphatic hydrocarbons. The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below. The reaction temperature of the prepolymerization may be a temperature at which the produced prepolymer is not substantially dissolved in the inert hydrocarbon solvent, and is usually about -10 ° C to 100 ° C, preferably about -10 ° C to 80 ° C. ℃. In the prepolymerization, a molecular weight modifier such as hydrogen can be used. The prepolymerization can be carried out batchwise or continuously.

In addition, with respect to the method of controlling polymerization, the method of post-treatment, etc., there is no limitation specific to the present catalyst system, and all known methods can be applied.

[0041]

EXAMPLES The content (A-sol) of the boiling acetone-soluble component in the polymer was measured by the following method. First, the obtained polymer is placed in a vacuum oven under vacuum at 60 ° C.
And dried for 8 hours or more. Take a known amount of this sample,
This was placed in a Soxhlet extractor and extracted with boiling acetone for 6 hours. Then, it was sufficiently dried in a vacuum oven, and the weight of the polymer after extraction was measured. A-sol
(wt%) was calculated by the following formula.

[Equation 1] The value of the polymerization activity was calculated by the following formula.

[Equation 2] In the examples and comparative examples, the load is 2.16k.
The melt flow rate (i.e., MFR) in g was measured according to JIS K-6758-1968. The initial flexural modulus (FM) is ASTM-D-790-
It carried out according to 66. In each of the examples, each compound (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, silicon compound, etc.) used in the production and polymerization of the solid catalyst component is substantially from which water has been removed. In addition, the production and polymerization of the solid catalyst component were carried out under a nitrogen atmosphere in which substantially no water was present. The organoaluminum compound and the organosilicon compound used during the polymerization are 1.0 M / l and 0.1 M / l, respectively.
Used as a hexane solution.

Example 1 [Preparation of solid Ti catalyst component (A)] 1.71 g of anhydrous magnesium chloride, 9 ml of decane and 8.4 ml of 2-ethylhexyl alcohol were heated and reacted at 130 ° C. for 3 hours to form a uniform solution. 0.3% phthalic anhydride in this solution
9 g is added, and the mixture is stirred and mixed at 130 ° C. for another 2 hours to dissolve phthalic anhydride in the homogeneous solution. The homogeneous solution thus obtained is cooled to room temperature and then added dropwise to 72 ml of titanium tetrachloride kept at -20 ° C over 1 hour. After charging, the temperature of this mixed solution should be 4
The temperature is raised to 110 ° C. over time, and when the temperature reaches 110 ° C., 0.95 g of diisobutyl phthalate is added, and from this, the mixture is maintained at the same temperature for 2 hours with stirring. After completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was collected by 72 mlT.
After resuspending in iCl ₄ , again at 110 ° C. for 2 hours,
Perform heating reaction. After the reaction was completed, the solid part was collected again by hot filtration, washed sufficiently with decane and hexane until no free titanium compound was detected in the washing solution, and then dried under reduced pressure. [Polymerization] In a 1.5 liter stainless steel autoclave, 5.8 mg of the solid component produced by the above method and 5.4 mg of thexyltrimethoxysilane (0.8 ml of a 0.1 M / l hexane solution) and 2 were added. , 3-dimethylbutyl-
Trimethoxysilane 0.11 mg (2.0 mM / l hexane solution 0.8 ml), triethylaluminum 91
Add mg (0.8 ml of 1M / l hexane solution),
Then 340 g propylene and 0.03 g hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. The results are shown in Table 1.

Comparative Examples 1 and 2, Examples 2 to 4 As in Example 1, except that the types of catalyst component (C) and catalyst component (D) used were changed as shown in Table 1, Preparation and polymerization were performed. The results are shown in Table 1.

Example 5 [Preparation of solid Ti catalyst component (A)] 5 g of diethoxymagnesium, 1.22 g of ethyl 3-ethoxy-2-phenylpropionate and 300 g of a round bottom flask which had been sufficiently dried under a nitrogen stream were added. 25 ml of methylene chloride was added.
Stir at reflux for 1 hour, then add the suspension to room temperature at 200 m.
Pumped into 1 TiCl ₄ . The temperature was gradually raised to 110 ° C. and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the precipitated solid was filtered off and washed with 200 ml of n-decane at 110 ° C three times. 200 ml of TiCl _{4 is} newly added and the temperature is 120 ° C.
And reacted for 2 hours. After the reaction is completed, the precipitated solid is filtered off,
It was washed 3 times with 200 ml of n-decane and then with hexane at room temperature until chlorine ions were not detected with n-hexane. [Polymerization] 2.3 mg of the solid component produced by the above method and 5.4 mg of thexyltrimethoxysilane (0.8 ml of a 0.1 M / l hexane solution) were added to a 1.5 liter stainless steel autoclave. , 3-dimethylbutyl-
Trimethoxysilane 0.11 mg (2.0 mM / l hexane solution 0.8 ml), triethylaluminum 91
Add mg (0.8 ml of 1M / l hexane solution),
Then 340 g propylene and 0.03 g hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. The results are shown in Table 1.

Comparative Example 3 A solid catalyst component was prepared and polymerized in the same manner as in Example 5 except that the catalyst component (D) was not used. The results are shown in Table 1.
Shown in

Example 6 [Preparation of solid Ti catalyst component (A)] Magnesium metal 1
2.8g, ethyl orthoformate 88ml (0.53mo
1) and 1,2-dibromoethane 0.
5 ml was added to keep the suspension at 55 ° C and hexane 1
80 ml of n-butyl chloride (000 ml
5 ml of a solution in which 1) was dissolved was added and stirred for 50 minutes, and the rest was added dropwise over 80 minutes. The reaction was carried out at 70 ° C. for 4 hours with stirring to obtain a solid product. It was washed 6 times with hexane at 50 ° C. 6.3 g of the solid product and 50 m of decane
1 was put in the reactor, and a mixed solution of 2.0 ml of 2,2,2-trichloroethanol and 11 ml of decane was added dropwise at room temperature over 30 minutes, and after completion, the mixture was stirred at 80 ° C for 1 hour. After filtering off the solid matter, the solid matter was washed 4 times with 100 ml of hexane and further washed with toluene 10 times.
It was washed twice with 0 ml. 40 ml of toluene in the solid,
Titanium tetrachloride (60 ml) was added and the temperature was raised to 90 ° C., and diethyl isopropyl isopentylmalonate (2.04 g, 0.0
(075 mol) and 5 ml of toluene were added dropwise over 5 minutes, and the mixture was stirred at 120 ° C. for 2 hours. Then, the solid was filtered at 90 ° C and washed twice with toluene at 90 ° C. Further, 40 ml of toluene and 60 ml of titanium tetrachloride are added to the solid substance.
Was added and the mixture was stirred at 120 ° C. for 2 hours, and the solid obtained was 110
The mixture was filtered at ℃ and washed 7 times with 100 ml of hexane at room temperature to obtain a solid titanium catalyst component. [Polymerization] Into a 1.5 liter autoclave made of stainless steel, 4.0 mg of the solid component produced by the above method and 5.4 mg of thexyltrimethoxysilane (0.8 ml of 0.1 M / l hexane solution) and 2 were added. , 3-dimethylbutyl-
Trimethoxysilane 0.11 mg (2.0 mM / l hexane solution 0.8 ml), triethylaluminum 91
Add mg (0.8 ml of 1M / l hexane solution),
Then 340 g propylene and 0.03 g hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. After 1 hour, the content gas was released to terminate the polymerization. The results are shown in Table 1.

Comparative Example 4 A solid catalyst component was prepared and polymerized in the same manner as in Example 6 except that the catalyst component (D) was not used. The results are shown in Table 1.
Shown in

[0048]

[Table 1]

[0049]

The method of the present invention makes it possible to easily obtain a polyolefin having a very small amount of low molecular weight components, and as a result, it becomes possible to economically produce an olefin polymer having excellent rigidity.

[Brief description of drawings]

FIG. 1 is a flow chart diagram to assist in understanding the present invention.

Claims (11)

[Claims] 1. A catalyst used in a method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, wherein the component (A) is a solid catalyst component containing titanium, magnesium and halogen as essential components. B) Organoaluminum Compound Component (C) An organosilicon compound represented by the general formula (1), and (Here, R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, R ² is a hydrocarbon group having 1 to 6 carbon atoms or a hydrogen atom,
R ³ and R ⁴ are hydrocarbon groups having 1 to 6 carbon atoms. R
² , R ³ and R ⁴ may be the same or different. ) Component (D) An organosilicon compound represented by the general formula (2): (Here, R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms, R ⁶ ,
R ⁷ and R ⁸ are hydrocarbon groups having 1 to 6 carbon atoms or hydrogen atoms, and R ⁶ , R ⁷ and R ⁸ may be the same or different. ) An olefin polymerization catalyst comprising: 2. The organosilicon compound represented by the general formula (1), which is used as the component (C), has a carbon number of 1 to R ¹ .
4 hydrocarbon groups, and R ² , R ³ and R ⁴ have 1 to ⁴ carbon atoms
3. The olefin polymerization catalyst according to claim 1, which is an alkyl group of 3 or a hydrogen atom. 3. The organosilicon compound used as the component (D) and represented by the general formula (2), wherein R ⁵ has 1 to 1 carbon atoms.
4 hydrocarbon groups, and R ⁶ , R ⁷ and R ⁸ have 1 to ⁷ carbon atoms.
The catalyst for olefin polymerization according to claim 1 or 2, wherein the alkyl group of 3 or a hydrogen atom. 4. The organosilicon compound used as component (D) is one selected from the structural isomers of the organosilicon compound used as component (C). The catalyst for olefin polymerization according to any one of 1 to 3. 5. The catalyst for olefin polymerization according to claim 1, wherein the component (C) is thexyltrialkoxysilane. 6. The catalyst for olefin polymerization according to claim 1, wherein the component (D) is 2,3-dimethylbutyltrialkoxysilane. 7. The catalyst for olefin polymerization according to claim 1, wherein the component (C) is thexyltrimethoxysilane. 8. The catalyst for olefin polymerization according to claim 1, wherein the component (D) is 2,3-dimethylbutyltrimethoxysilane. 9. The molar ratio of the component (C) and the component (D) (component (D) / component (C)) has a value of 0.0001 to 0.1. The catalyst for olefin polymerization according to any one of 1. 10. A method for producing a propylene polymer by polymerizing propylene in the presence of a catalyst, wherein the catalyst according to any one of claims 1 to 9 is used. Method. 11. The boiling acetone-soluble component of the propylene polymer is 0.05 wt% or less.
0. The method for producing a propylene polymer described in 0.