JPH08151407A - Olefin polymerization catalyst and production of olefin polymer - Google Patents

Abstract

PURPOSE: To produce an olefin polymer having excellent practical performance by providing an olefin polymerization catalyst free from an organosilicom compound being a source of generating a silanol compound or a siloxane deteriorative to the properties particularly rigidity of apolymer. CONSTITUTION: The catalyst used in a process for producing an olefin polymer by polymerizing an olefin is an olefin polymerization catalyst comprising a solid catalyst component essentially consisting of titanium, magnesium and halogen, an organoaluminum compound and an electron-donating compound represented by the formula (wherein R<1> is a 1-20C hydrocarbon group; R<2> is a 1-20C hydrocarbon group; R<3> is a 1-20C hydrocarbon group; and R<4> is a 3C or higher branched hydrocarbon).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin polymerization catalyst for producing homopolymerization of ethylene or .alpha.-olefin or a copolymer thereof, and a process for producing the olefin polymer.

[0002]

It is well known to use an electron donating compound as a cocatalyst component of a magnesium chloride-supported Ziegler catalyst. It has been reported that benzoic acid esters, piperidines, acetals, and organosilicon compounds (alkoxysilanes) are effective as electron-donating compounds. However, among the above compounds, (1) benzoic acid esters or piperidines have a peculiar odor, and therefore, when these compounds are used as electron-donating compounds, residual odor in the product becomes a problem. Often. (2) Since the catalytic activity of the acetal compound is severely deactivated, the catalyst cost is high. Therefore, usually, an organosilicon compound (alkoxysilane) is often used for the above purpose, but generally, an organosilicon compound, especially an alkoxysilane compound, is easily hydrolyzed by moisture in the air to give a corresponding silanol. It is well known to provide compounds or siloxane compounds. Therefore, when an organosilicon compound is used as the electron-donating compound of the catalyst, a silanol compound or a siloxane compound is often contained in the polymer.

Conventionally, such catalyst residues and the like have been removed by a deashing process. However, in recent olefin polymerization plants, deashing-free and non-pelletizing processes are becoming mainstream, so catalyst residues and the like are produced as they are. It has been increasingly marketed in the state of remaining in the polymer. However, the silanol compound or siloxane compound microdispersed in the polymer often contributes to a decrease in the physical properties of the polymer, especially the rigidity thereof, so that 100% of the physical properties originally possessed by the polymer are not always expressed. could not. Therefore, it has been earnestly desired to develop a new catalyst system which exhibits high performance without using an organosilicon compound as a source of a silanol compound or a siloxane compound as an electron-donating compound component of an olefin polymerization catalyst.

[0004]

The object of the present invention is to exhibit high activity and high stereoregularity in a method for producing a polyolefin using a supported Ziegler catalyst, and to bring about a decrease in the physical properties of the polymer, particularly rigidity. It is an object of the present invention to provide a catalyst for olefin polymerization and a method for producing an olefin polymer which does not use an organosilicon compound which is a generation source of a silanol compound or siloxanes.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies on the electron donating compound used for the supported Ziegler catalyst in order to solve these problems, and as a result, polymerize olefins in the presence of the catalyst. In the method for producing an olefin polymer, a component (A) is a solid catalyst component containing titanium, magnesium and halogen as essential components. Component (B) Organoaluminum Compound, and Component (C) General Formula (1)

Embedded image (Here, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrocarbon group having 1 to 20 carbon atoms, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a carbon group. It is a branched hydrocarbon group having a number of 3 or more.) As a result of polymerizing an olefin using an olefin polymerization catalyst characterized by being formed from an electron donating compound represented by As a result, they have found that a polymer which is practically excellent can be obtained in high yield, and the present invention has been completed.

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; and carboxylates of magnesium such as magnesium laurate and magnesium stearate. And alkyl magnesium such as butylethyl magnesium can be exemplified. 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.

Examples of the titanium compound used in the present invention include 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-
Alcohols having 1 to 20 carbon atoms such as ethylhexyl alcohol, benzyl alcohol, cumyl alcohol, diphenylmethanol and triphenylmethanol,
(B) Phenols having 6 to 25 carbon atoms, which may have an alkyl group, such as phenol, cresol, ethylphenol, propylphenol, cumylphenol, nonylphenol and naphthol,

(C) Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, and other ketones having 3 to 15 carbon atoms, (d) acetaldehyde, propionaldehyde, tolualdehyde,
Aldehydes having 2 to 15 carbon atoms such as naphthaldehyde,

(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 benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, diheptyl phthalate, dineopentyl phthalate, γ-butyrolactone, γ-palerolactone, coumarin, phthalide, diethyl carbonate, ortho. C2 to C20 organic acid esters such as methyl formate and ethyl orthoformate,

(H) 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 Propionic acid n-
Octyl, dodecyl 3-ethoxypropionate, pentamethylphenyl 3-ethoxypropionate, ethyl 3- (i-propoxy) propionate, butyl 3- (i-propoxy) propionate, allyl 3- (n-propoxy) propionate ,
Cyclohexyl 3- (n-butoxy) propionate, ethyl 3-neopentyloxypropionate, butyl 3- (n-octyloxy) propionate, octyl 3- (2,6-dimethyldecyloxy) propionate, 4-ethoxy Ethyl acetate,
Cyclohexyl 4-ethoxybutyrate, Octyl 5- (n-propoxy) valerate, Ethyl 12-ethoxylaurate, 3- (1-
Indenoxy) ethyl propionate, methyl 3-methoxyacrylate, methyl 2-ethoxyacrylate, ethyl 3-phenoxyacrylate, ethyl 2-methoxypropionate,
N-Butyl 2- (i-propoxy) butyrate, methyl 2-ethoxyisobutyrate, phenyl 2-cyclohexyloxyisovalerate,
Butyl 2-ethoxy-2-phenylacetate, Allyl 3-neopentyloxybutyrate, 3-Ethoxy-3- (o-methylphenyl)
Methyl propionate, ethyl 3-ethoxy-2- (o-methylphenyl) propionate, ethyl 4-ethoxy-2-methyl-1-naphthylnonanoate, ethyl 2-methoxycyclopentanecarboxylic acid, 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, 2- (phenoxy)
Methyl acetate, ethyl 3- (p-crezoxy) propionate,
Methyl 4- (2-naphthoxy) butyrate, Butyl 5-carbaloxyvalerate, Methyl 2-phenoxypropionate, Ethyl 3- (4-methylphenoxy) -2-phenylpropionate, 2-Phenoxycyclohexanecarboxylic acid ethyl ester, Thiophene -3-ethyl oxyacetate, 2- (2-picolinoxymethyl) -ethyl cyclohexanecarboxylate, ethyl 3-furfuryloxypropionate, 2,2-diisobutyl-3-methoxy-ethyl propionate, 2-isopropyl- Methyl 2-isopentyl-3-methoxy-propionate, 2-isopropyl-2-isopentyl-3-methoxy-ethyl propionate, 2-isopropyl-2-cyclopentyl-3-methoxy-
Methyl propionate, 2-isopropyl-2-cyclopentyl-3-methoxy-ethyl propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-methyl propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-
Alkoxy esters such as ethyl propionate, methyl 2,2-dicyclopentyl-3-methoxy-propionate and ethyl 2,2-dicyclopentyl-3-methoxy-propionate.

(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, ethyl 3- (i-propionyl) propionate, butyl 3- (i-propionyl) propionate, Allyl 3- (i-propionyl) propionate, 3-
Cyclohexyl (i-propionyl) propionate, ethyl 3-neopenanoylpropionate, butyl 3-n-laurylpropionate, methyl 3- (2,6-dimethylhexanoyl) propionate, ethyl 4-propionylbutyrate, 4- Cyclohexyl propionyl butyrate, octyl 5-butyryl valerate, ethyl 12-butyryl laurate, methyl 3-acetylacrylate, methyl 2-acetylacrylate, ethyl 3-benzoylpropionate, methyl 3-benzoylpropionate, 3-methyl Ethyl benzoylpropionate, Butyl 3-toluylbutyrate, Ethyl o-benzoylbenzoate, Ethyl m-benzoylbenzoate, Ethyl p-benzoylbenzoate, o-
Butyl toluyl benzoate, ethyl o-toluyl benzoate,
Ethyl m-toluylbenzoate, ethyl p-toluylbenzoate, ethyl o- (2,4,6-trimethylbenzoyl) benzoate, ethyl m- (2,4,6-trimethylbenzoyl) benzoate, p- (2 , 4,6-Trimethylbenzoyl) ethyl benzoate, ethyl o-ethylbenzoylbenzoate, ethyl o-acetylbenzoate, ethyl o-propionylbenzoate, ethyl o-laurylbenzoate, ethyl o-cyclohexanoylbenzoate, Ketoesters such as o-dodecylbenzoate.

(H) Inorganic acid esters such as methyl borate, butyl titanate, butyl phosphate, diethyl phosphite and di (2-phenylphenyl) phosphorochloridate,
(I) Number of carbon atoms such as 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
2 to 25 ethers, (nu) acetic acid amides, benzoic acid amides, toluic acid amides and other C2 to C20 acid amides, (l) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, chloride C2 to C20 acid halides such as phthaloyl and isophthalic acid chloride, (wo) acetic anhydride, C2 to C20 acid anhydrides such as phthalic anhydride, (wa) monomethylamine, monoethylamine, diethylamine, Amine having 1 to 20 carbon atoms such as tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, etc., (C) Acetonitrile, benzonitrile, nitriles having 2 to 20 carbon atoms such as trinitrile, ( Yo) Ethylthioalcohol, Butylthioalcohol, Phenylthio Thiols having 2 to 20 carbon atoms such as thiols, thioethers having 4 to 25 carbon atoms such as (ta) diethyl thioether and diphenyl thioether, and sulfate esters having 2 to 20 carbon atoms such as (le) dimethyl sulfate and diethyl sulfate. , (So) phenylmethyl sulfone, diphenyl sulfone, etc.
20 sulfonic acids, (T) phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, triphenylmethoxysilane, hexamethyl Examples thereof include silicon-containing compounds having 2 to 24 carbon atoms such as disiloxane, octamethyltrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, and lower alkyl silicate (especially ethyl silicate). . Two or more kinds of these electron donating compounds can be used. Among these, preferable are organic acid esters, alkoxyesters, ketoesters and the like.

The catalyst preparation method used in the present invention is not particularly limited, but the following examples can be given. 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 magnesium halide and an organic or inorganic compound (which may contain the above-mentioned electron-donating compound) is prepared, and the above-mentioned electron-donating compound and titanium compound are successively contacted (the order may be changed). To obtain a catalyst component. Contacting the above-mentioned electron donating compound with a magnesium compound (or further containing a titanium compound),
A method of obtaining a catalyst component by carrying out a contact with a titanium compound and / or a halogenation treatment at the same time or in a subsequent stage (including the use of the titanium compound at any stage).
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 1000 in molar ratio to titanium.
, Preferably in the range of 2 to 200, the content of halogen in the molar ratio to titanium is in the range of 1 to 100, and when the electron-donating compound is used, its content is in the molar ratio to titanium. Within 10 or less, preferably 0.1
It may be in the range of ~ 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 in general, it is in the range of 0.1 to 200 microns, preferably 1 to 100 microns, and more preferably Preferably 10 to
It is 100 microns.

The organoaluminum compound in the present invention is represented by the following general formulas (2) to (4). AlR ⁵ R ⁶ R ⁷ (2) R ⁸ R ⁹ Al-O-AlR ¹⁰ R ¹¹ (3)

Embedded image

[Chemical 4] In the expressions (2), (3) and (4), R ⁵ , R ⁶
And R ⁷ may be the same or different and may have a large number of carbon atoms.
12 hydrocarbon groups, R ⁸ , R ⁹ , R ¹⁰ , and R
¹¹ may be the same or different and are hydrocarbon groups having at most 12 carbon atoms. R ¹² is a hydrocarbon group having at most 12 carbon atoms, and n is an integer of 1 or more. Typical examples of the organoaluminum compound represented by the formula (2) include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum, and further diethylaluminum hydride and Alkyl aluminum hydrides such as diisobutyl aluminum hydride and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride are included. Representative examples of the organoaluminum compound represented by the formula (3) include alkyl dialumoxanes such as tetraethyl dialumoxane and tetrabutyl dialumoxane. The formula (4) represents an aluminoxane, which is a polymer of an aluminum compound. R ¹² includes methyl, ethyl, propyl, butyl, benzyl and the like, preferably methyl and ethyl groups. The value of n is preferably 1-10. 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 organoaluminum used in the polymerization system is generally 10 ⁻⁴ mmol / min.
1 or more, preferably 10 ^-2 mmol / l or more. In addition, the ratio of titanium atom used in the solid catalyst component is
The molar ratio is generally 0.5 or more, preferably 2 or more,
Especially, 10 or more is preferable. 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 organic ester compound having a structure represented by the general formula (1).

Embedded image In the formula, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrocarbon group having 1 to 5 carbon atoms.
It is a hydrocarbon group of 1 to 3, specifically, a methyl group, an ethyl group or a propyl group. R ² has 1 to 20 carbon atoms
A hydrocarbon group, preferably a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrocarbon group having 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group,
2-ethylhexyl group, cyclopentyl group, cyclohexyl group and the like. R ³ is a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl Group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group, pentadecyl group, cyclopentyl group, cyclohexyl group and the like. R ⁴ is a branched hydrocarbon group having 3 or more carbon atoms, specifically, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, sec-pentyl group, tert-pentyl group, 2-ethylhexyl group, thexyl group, cyclopentyl group, cyclohexyl group and the like.

As the above compound, 2-methyl-2-
Isopropyl-3-methoxy-methyl propionate, 2-methyl-2-isopropyl-3-methoxy-ethyl propionate, 2-methyl-2-isopropyl-3-methoxy-propionic acid (iso-butyl), 2-methyl- 2-Isopropyl-3-methoxy-propionic acid (tert-butyl), 2-methyl-2-
Isopropyl-3-methoxy-propionic acid (2-ethylhexyl), 2-methyl-2-isopropyl-3-ethoxy-methyl propionate, 2-methyl-2-isopropyl-3-ethoxy-ethyl propionate, 2-methyl- 2-isopropyl
-3-Ethoxy-butyl propionate, 2-Ethyl-2-isopropyl-3-methoxy-ethyl propionate, 2-Ethyl-2-isopropyl-3-Ethoxy-butyl propionate, 2-Ethyl-2-isopropyl-3 -Methoxy-propionic acid (tert-butyl), 2-ethyl-2-isopropyl-3-
Methoxy-propionic acid (2-ethylhexyl), 2,2-
Diisopropyl-3-methoxy-ethyl propionate,
2,2-Diisopropyl-3-methoxy-butyl propionate, 2-isopropyl-2-isobutyl-3-methoxy-methyl propionate, 2-isopropyl-2-isobutyl-3-methoxy-ethyl propionate, -isopropyl-2 -Isobutyl-3-methoxy-butyl propionate, 2-isopropyl-2-isobutyl-3-methoxy-propionic acid (2-ethylhexyl), 2-isopropyl-2-isopentyl-3-
Methoxy-methyl propionate, 2-isopropyl-2-isopentyl-3-methoxy-ethyl propionate, 2-isopropyl-2-isopentyl-3-methoxy-butyl propionate, 2-isopropyl-2-isopentyl-3-methoxy
-Propionic acid (2-ethylhexyl), 2-isopropyl
-2-Cyclopentyl-3-methoxy-methyl propionate, 2-isopropyl-2-cyclopentyl-3-methoxy-
Ethyl propionate, 2-isopropyl-2-cyclopentyl-3-methoxy-butyl propionate, 2-isopropyl
-2-Cyclopentyl-3-methoxy-propionic acid (2-ethylhexyl), 2-butyl-2-isopropyl-3-methoxy-propionic acid (2-ethylhexyl), 2-butyl-2-
Isobutyl-3-methoxy-ethyl propionate, 2-butyl-2-isobutyl-3-methoxy-propionic acid (2-ethylhexyl), 2-butyl-2-isopentyl-3-methoxy
-Ethyl propionate, 2-Butyl-2-isopentyl-3-
Methoxy-propionic acid (2-ethylhexyl), 2-butyl-2-cyclopentyl-3-methoxy-ethyl propionate, 2,2-diisobutyl-3-methoxy-ethyl propionate, 2,2-diisobutyl-3-methoxy- Propionic acid (2-ethylhexyl), 2-isobutyl-2-isopentyl
-3-Methoxy-ethyl propionate, 2-isobutyl-2-
Isopentyl-3-methoxy-propionic acid (2-ethylhexyl), 2-isobutyl-2-cyclopentyl-3-methoxy-ethyl propionate, 2-isobutyl-2-cyclopentyl-3-methoxy-propionic acid (2-ethylhexyl), 2-Cyclopentyl-2-isopentyl-3-methoxy-
Methyl propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-ethyl propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-butyl propionate, 2-Cyclopentyl-2-isopentyl-3-methoxy-
Examples include propionic acid (2-ethylhexyl) and ethyl 2,2-dicyclopentyl-3-methoxy-propionate. The amount of the component (C) used is a component (C) / component (B) = 0.001-5, preferably 0.01-1 in molar ratio.

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

Polymerization Method and Conditions Therefor In carrying out the polymerization, the solid catalyst component of the present invention, the organoaluminum compound or these and the organosilicon compound may be introduced individually into a polymerization vessel, but two kinds of them or The whole may be mixed in advance, typically, after adding an inert solvent, an organoaluminum compound and an organosilicon compound described below to a dropping funnel substituted with nitrogen, and after mixing for a certain time or more (about 1 minute or more) It is preferable that the mixture is brought into contact with the solid catalyst component, further reacted for a certain period of time (about 1 minute or more), and then added to the polymerization reaction vessel. As the inert solvent used at this time,
Alkanes and cycloalkanes such as pentane, hexane, heptane, n-octane, isooctane, cyclohexane and methylcyclohexane; toluene, xylene,
Alkyl aromatic hydrocarbons such as ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene and mono- or dialkylnaphthalenes; halogenated and hydrogen such as chlorobenzene, chloronaphthalene, orthodichlorobenzene, tetrahydronaphthalene, decahydronaphthalene. Aromatic hydrocarbons; 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 3600 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 diluting 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. -Propylbenzene,
Alkyl aromatic hydrocarbons such as diethylbenzene and mono- or dialkylnaphthalenes; halogenated and hydrogenated aromatic hydrocarbons such as chlorobenzene, chloronaphthalene, ortho-dichlorobenzene, tetrahydronaphthalene, decahydronaphthalene; high molecular weight liquid paraffins or thereof There are mixtures, 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. Generally, but not required, with water, alcohol, acetone or other suitable catalyst deactivators known as catalyst poisons when the polymerization is complete or when the polymerization is terminated or the deactivation of the invention is carried out. It is possible by contact. The polymerization temperature is generally -10 ° C to 180 ° C, but 20 ° C to 100 ° C from the viewpoint of obtaining good catalytic performance and high production rate.
Is preferred, and more preferably in the range of 50 ° C to 80 ° C.

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 not limited to the compound used as the catalyst component (C). 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 the inert hydrocarbon solvent described later. The amount of the organoaluminum compound component (B) is 0.1 to 50 per 1 g of the solid titanium catalyst component (A).
The amount is such that 0 g of polymer is produced, preferably 0.1 to 300 g of polymer. 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 resulting 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. ℃
Is. A molecular weight modifier such as hydrogen may be used in the prepolymerization. The prepolymerization can be carried out batchwise or continuously. In addition, the polymerization control method, the post-treatment method, and the like are not limited to those specific to the present catalyst system, and all known methods can be applied.

[0026]

[Examples] Xylene-soluble matter (%) at room temperature of polymer
(XSRT%) is 2 g of polymer in 200 ml of xylene at 135 ° C.
Was dissolved, and then the solution was cooled to room temperature, and the precipitated polymer was filtered under reduced pressure. The solvent was distilled off from the filtrate using a rotary evaporator, and the residue was dried to measure the residue. XSRT% 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 melt flow rate (that is, MFR) at a load of 2.16 Kg is JIS K-
Measured according to 6758-1968. Initial flexural modulus (F
M) was measured according to ASTM-D-790-6600. The content of silicon atoms contained in the polymer was measured by a fluorescent X-ray analyzer. In each of the examples, each compound (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, electron donating compound, etc.) used for the production and polymerization of the solid catalyst component was substantially free of water. Further, regarding the production and polymerization of the solid catalyst component,
Substantially no water was present and the operation was performed under a nitrogen atmosphere. The organoaluminum compound and the electron donating compound used during the polymerization were used as 1.0 M / L and 0.1 M / L hexane solutions, respectively.

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. Add 0.39 g of phthalic anhydride to the solution and
The mixture is stirred and mixed at ℃ for 2 hours, and phthalic anhydride is dissolved in the homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, titanium tetrachloride 72 held at -20 ° C.
Add all of the solution dropwise to the solution over 1 hour. After charging, raise the temperature of this mixture to 110 ° C over 4 hours,
When reaching 110 ℃, diisobutyl phthalate 0.91 g
Is added and the mixture is maintained at the same temperature for 2 hours with stirring.
After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 72 ml of titanium tetrachloride, and then again 11
Heat reaction at 0 ℃ for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, washed sufficiently with decane and hexane so that the free titanium compound was not detected in the washing liquid, and dried under reduced pressure. [Polymerization] Into a 6.0-liter stainless steel autoclave, 4.8 mg of the solid component produced by the above method, 1.6 ml of ethyl 2-isopropyl-2-isopentyl-3-methoxy-propionate (0.1 M / L hexane solution) Then, 1.6 ml of triethylaluminum (1.0 M / L hexane solution) was added, and then 1020 g of propylene and 0.09 g of hydrogen were added. The temperature of the autoclave was raised and the internal temperature was kept at 770 ° C.
After 2 hours, the content gas was released to terminate the polymerization. The results are shown in Table 1.

Comparative Example 1 A catalyst was prepared and polymerized in the same manner as in Example 1 except that the type of the catalyst component (C) used was changed as shown in Table 1. The results are shown in Table 1.

Example 2 [Preparation of solid Ti catalyst component (A)] 5 g of diethoxymagnesium, 3-methoxy-2-tert-amyl-ethyl propionate were placed in a 300 ml round bottom flask which was thoroughly dried under a nitrogen stream. 1.30 g and 25 ml methylene chloride were added. It was stirred under reflux for 1 hour and then the suspension was pumped into room temperature 200 ml titanium tetrachloride. The temperature was gradually raised to 110 ° C. and the reaction was carried out with stirring for 2 hours. After the reaction was completed, the precipitated solid was filtered off, and 11
It was washed 3 times with 200 ml of n-decane at 0 ° C. Titanium tetrachloride (200 ml) was newly added and reacted at 120 ° C for 2 hours. After the reaction was completed, the precipitated solid was separated by filtration, washed with 200 ml of n-decane three times, and washed with hexane at room temperature until chlorine ions were not detected in n-hexane. [Polymerization] Into a 6.0 liter stainless steel autoclave, 5.2 mg of the solid component produced by the above method, 1.6 ml of ethyl 2-isopropyl-2-isopentyl-3-methoxy-propionate (0.1 M / L hexane solution) , 1.6 ml of triethylaluminum (1.0 M / L hexane solution) was added, and then 340 g of propylene and 0.09 g of hydrogen were added. The temperature of the autoclave was raised and the internal temperature was kept at 80 ° C. 2
After a while, the content gas was released to terminate the polymerization. The results are shown in Table 1.

Comparative Example 2, Examples 3-5 A catalyst was prepared and polymerized in the same manner as in Example 5 except that the type of the catalyst component (C) used was changed as shown in Table 1. The results are shown in Table 1.

[0031]

[Table 1]

[0032]

Industrial Applicability According to the method of the present invention, it is possible to produce an olefin polymer which does not contain a silanol compound or siloxanes which have a great influence on the physical properties of the polymer and as a result has practically excellent performance. became.

[Brief description of drawings]

FIG. 1 is a flow chart for adjusting a catalyst according to the present invention.

Claims (3)

[Claims] 1. A catalyst used in a method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, component (A) a solid catalyst component containing titanium, magnesium and halogen as essential components. Component (B) Organoaluminum Compound, and Component (C) General Formula (1) (Here, R ¹ is a hydrocarbon group having 1 to 10 carbon atoms, R ² is a hydrocarbon group having 1 to 20 carbon atoms, R ³ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ is a carbon group. It is a branched hydrocarbon group having a number of 3 or more.) An olefin polymerization catalyst comprising an electron-donating compound represented by the formula: 2. An electron-donating compound represented by the general formula (1), wherein R ¹ is a methyl group, an ethyl group, a propyl group, or R.
² is a hydrocarbon group having 1 to 10 carbon atoms, R ³ is a methyl group, ethyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, Decyl group, pentadecyl group, cyclopentyl group, cyclohexyl group, and R ⁴
Is isopropyl group, isobutyl group, sec-butyl group, tert
-Butyl group, isopentyl group, sec-pentyl group, tert-
The catalyst for olefin polymerization according to claim 1, which is any one of a pentyl group, a 2-ethylhexyl group, a texyl group, a cyclopentyl group, and a cyclohexyl group. 3. The electron-donating compound represented by the general formula (1) is ethyl 2,2-diisobutyl-3-methoxy-propionate or 2-isopropyl-2-isopentyl-3-methoxy-.
Methyl propionate, 2-isopropyl-2-isopentyl
-3-Methoxy-ethyl propionate, 2-isopropyl-2
-Cyclopentyl-3-methoxy-methyl propionate,
2-isopropyl-2-cyclopentyl-3-methoxy-ethyl propionate, 2-cyclopentyl-2-isopentyl-3
-Methoxy-methyl propionate, 2-cyclopentyl-2
-Isopentyl-3-methoxy-ethyl propionate, 2,
3. 2-dicyclopentyl-3-methoxy-methyl propionate or at least one compound selected from 2,2-dicyclopentyl-3-methoxy-ethyl propionate, wherein the compound is at least one compound. Olefin polymerization catalyst.