JP3361579B2 - Olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polyolefin polymerization containing a novel organosilicon compound, in which the activity of the catalyst is not significantly decreased during the polymerization and the activity can be maintained for a long time to obtain a polymer in good yield. The present invention relates to a catalyst and a method for producing a polyolefin.

[0002]

2. Description of the Related Art It is known that, when an organosilicon compound is used as a co-catalyst component of a supported Ziegler catalyst in the polymerization of olefins, the stereoregularity of the produced polymer is improved. For example, diphenyldimethoxysilane compounds (JP-A-57-63310, JP-A-57-63311,
JP-A-58-138708, JP-A-59-13870
8, JP-A-61-296006, JP-A-63-1750
08, JP-A-63-289004), diisobutyldimethoxysilane compound (JP-A-62-18406, JP-A-63-258907, JP-A-2-70708, JP-A-2-70708).
-1731010, JP-A-3-33103), diisopropyldimethoxysilane compound (JP-A-63-25890).
7, JP-A-2-229807, JP-A-3-33102,
JP-A-3-33103), dicyclopentyldimethoxysilane compound (JP-A-2-229807), di-t-butyldimethoxysilane compound (JP-A-2-70708, JP-A-2-229806, JP-A-3-33102), dicyclohexyldimethoxysilane. Compound (JP-A-63-2
58907), cyclohexylmethyldimethoxysilane compound (JP-A-2-170803, JP-A-2-2298).
07), cyclohexylethyldimethoxysilane compound (JP-A-2-163104), t-butylmethyldimethoxysilane compound (JP-A-62-1705, JP-A-61-1705).
2-20507, JP-A-63-92615, JP-A-2-
229807), t-butylpropyldimethoxysilane (JP-A-4-202505, JP-A-5-17319),
Phenyltriethoxysilane compound (JP-A-57-63
311, JP-A-58-83006, JP-A-62-205.
07, JP-A-61-296006), ethyltriethoxysilane compound (JP-A-57-63310), butyltriethoxysilane compound (JP-A-2-170803),
t-Butyltrimethoxysilane compound (JP-A-63-1
1705, JP-A-63-92615, JP-A-63-25
8907, JP-A-3-33106, JP-A-3-3310.
5, JP-A-2-70708), t-butyl (t-butoxy) dimethoxysilane compound (JP-A-3-11900).
4), an isobutyltrimethoxysilane compound (JP-A-3
-33106), t-butyltriethoxysilane compound (JP-A-2-229807), norbornanetrimethoxysilane compound (JP-A-63-92615), and the like.

However, a compound having a benzene ring on the silicon atom, such as a diphenyldimethoxysilane compound, causes benzene which is harmful to the human body due to the decomposition of the compound and remains in the product polymer, which is a sanitary problem. . Alternatively, diisopropyldimethoxysilane,
Dicyclopentyldimethoxysilane and dicyclohexyldimethoxysilane, di-t-butyldimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, t
-Butylmethyldimethoxysilane compounds and the like have no hygienic problems because the substituents on silicon are aliphatic hydrocarbon groups, but there are many synthetic problems because they have bulky substituents. , Very expensive. Further, diisobutyldimethoxysilane, cyclohexylmethyldimethoxysilane and cyclohexylethyldimethoxysilane compounds can be synthesized by a hydrosilylation reaction to obtain the desired product, which is inexpensive, but the stereoregularity of the produced polymer is not It did not meet the demand.

On the other hand, trialkoxysilane compounds (for example, phenyltriethoxysilane, ethyltriethoxysilane, butyltriethoxysilane, t-butyltrimethoxysilane, isobutyltrimethoxysilane, t-butyltriethoxysilane, norbornanetrimethoxysilane). It is well known that the catalyst activity significantly deactivates the catalytic activity. In recent years, in order to prevent a decrease in catalytic activity when such a trimethoxy compound is used, it is used in combination with a dimethoxysilane compound or the like (JP-A-2-70708, JP-A-3-33).
103, JP-A-3-33105, JP-A-3-3310
There are several techniques for performing 6), but all of them are accompanied by a decrease in stereoregularity, and a plurality of tanks for storing and supplying each organosilicon compound in a manufacturing plant are provided. It creates new problems such as need. As an even more important problem, a magnesium chloride-supported catalyst using a conventionally proposed dialkoxysilane compound and trialkoxysilane compound as a co-catalyst component has an extremely high initial activity of polymerization, but the activity may rapidly decrease thereafter. Well known.

[0005]

The object of the present invention is to solve the above-mentioned problems in the prior art in a method for producing a polyolefin using a supported Ziegler catalyst, and to reduce the activity of the catalyst during the polymerization, thereby reducing the activity. It is an object of the present invention to provide a catalyst for olefin polymerization containing a novel organosilicon compound and a method for producing a polyolefin, which enables a polymer to be obtained in good yield by maintaining it for a long time.

[0006]

[Means for Solving the Problems] The inventors of the present invention have conducted diligent studies on a co-catalyst used for a supported Ziegler catalyst, particularly an external donor, in order to solve these problems. In the method for producing an olefin polymer by polymerizing, a solid catalyst component containing component (A) titanium, magnesium, and halogen as essential components, component (B) organoaluminum compound, and component (C) general formula (1),

[Chemical 2] (Wherein R ¹ is a secondary or tertiary amino residue) is formed from a novel organosilicon compound, and the olefin is polymerized using a catalyst for olefin polymerization. The inventors have found that a polymer which is practically excellent can be obtained in good yield by solving all of the above-mentioned problems and reached the present invention.

The effects of the present invention can be obtained only by using a novel organosilicon compound having a specific structure as a cocatalyst, especially as an external donor.

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.

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 to the titanium compound and the magnesium compound.

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. C6 to C25 phenols, (C) acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone and other C3 to C15 ketones, (d) acetaldehyde, propionaldehyde, tolualdehyde, naphthaldehyde and other carbons Aldehydes of the numbers 2 to 15, methyl (e) formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl cellosolve acetate, cellosolve acetate, Ethyl pionate, methyl n-butyrate, methyl isobutyrate, ethyl isobutyrate, isopropyl isobutyrate, ethyl valerate, butyl valerate, ethyl stearate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl methacrylate, croton Ethyl acid, ethyl cyclohexanecarboxylate, methyl phenylacetate, methyl phenylbutyrate, propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoic acid Benzyl, cellosolve benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, lid Diheptyl, dineopentyl phthalic acid, γ- butyrolactone, γ
-C2 to C20 organic acid esters such as parerolactone, coumarin, phthalide, diethyl carbonate, methyl orthoformate 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 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 di (2-phenylphenyl) phosphorochloridate,
(I) Ethers having 2 to 25 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, and 2,2-dimethoxypropane; ) Acetamide, benzoic acid amide, toluic acid amide or the like having 2 to 2 carbon atoms
0 acid amides, (l) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthalic acid and other acid halides having 2 to 20 carbon atoms, (wo) acetic anhydride, phthalic anhydride Such as C2 to C20 acid anhydrides, (wa) monomethylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylethylenediamine, etc. Amines, (f) acetonitrile, benzonitrile, trinitrile and other nitriles having 2 to 20 carbon atoms, (yo) ethylthioalcohol, butylthioalcohol, phenylthiol and other thiols having 2 to 20 carbon atoms, (ta) Diethyl thioether, diphe Number 4 to 25 thioethers carbon, such as thioether, (Les) dimethyl sulfate, sulfates of from 20 C 2 -C such as diethyl sulfate,
(So) phenylmethyl sulfone, diphenyl sulfone and other sulfonic acids having 2 to 20 carbon atoms, (T) phenyltrimethoxysilane, phenyltriethoxysilane,
Phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, triphenylmethoxysilane, hexamethyldisiloxane,
Octamethyltrisiloxane, trimethylsilanol,
Examples thereof include silicon-containing compounds having 2 to 24 carbon atoms such as 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 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 a 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 effects of the present invention are recognized, but generally 0.1 to 2
It is in the range of 00 microns, preferably 1-100 microns, more preferably 10-100 microns.

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

[Chemical 3] In the expressions (2), (3) and (4), R ² , R ³
And R ⁴ may be the same or different and each is a hydrocarbon group having at most 12 carbon atoms, and R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and may have at most 12 carbon atoms. It is a hydrocarbon group. R ⁹ 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 and ethyl aluminum sesquichloride. Further, among the organoaluminum compounds represented by the formula (3), typical ones include alkyl dialumoxane such as tetraethyl dialumoxane and tetrabutyl dialumoxane. The formula (4) 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 preferably 1 to 10. Of these organoaluminum compounds, trialkylaluminum,
Alkyl aluminum hydrides and alkyl alumoxanes are preferred because they give particularly favorable 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 4] (Wherein R ¹ is a secondary or tertiary amino residue) Specific examples of such compounds are shown below. Thexyl (dimethylamino) dimethoxysilane, Thexyl (methylpropylamino) dimethoxysilane, Thexyl (methylbutylamino) dimethoxysilane, Thexyl (methylisobutyl) dimethoxysilane, Thexyl (methylsec-butylamino) dimethoxysilane, Thexyl (methyltert- Butylamino) dimethoxysilane, thexyl (methylcyclopentylamino) dimethoxysilane, thexyl (methylcyclohexylamino) dimethoxysilane, thexyl (diethylamino) dimethoxysilane, thexyl (ethylpropylamino) dimethoxysilane, thexyl (ethylbutylamino) dimethoxysilane, thexyl (Ethylisobutyl) dimethoxysilane, thexyl (ethyl sec-butylamino) dimethoxysilane, thexyl Ethyl tert- butylamino)
Dimethoxysilane, Thexyl (ethylcyclopentylamino) dimethoxysilane, Thexyl (ethylcyclohexylamino) dimethoxysilane, Thexyl (dipropylamino) dimethoxysilane, Thexyl (propylbutylamino) dimethoxysilane, Thexyl (propylisobutyl) dimethoxysilane, Thexyl (propyl) sec-
Butylamino) dimethoxysilane, thexyl (propyl tert-butylamino) dimethoxysilane, thexyl (propylcyclopentylamino) dimethoxysilane,
Thexyl (propylcyclohexylamino) dimethoxysilane, Thexyl (diisopropylamino) dimethoxysilane, Thexyl (isopropyl n - propylamino)
Dimethoxysilane, thexyl (isopropyl-butylamino) dimethoxysilane, thexyl (isopropyl isobutyl amino) dimethoxysilane, thexyl (isopropyl sec- butylamino) dimethoxysilane, thexyl (isopropyl tert- butylamino) dimethoxysilane, thexyl (isopropyl cyclopentylamino)
Dimethoxysilane, thexyl (isopropylcyclohexylamino) dimethoxysilane, thexyl (dibutylamino) dimethoxysilane, thexyl (butyl sec-butylamino) dimethoxysilane, thexyl (butyl te
rt-butylamino) dimethoxysilane, thexyl (butylcyclopentylamino) dimethoxysilane, thexyl (butylcyclohexylamino) dimethoxysilane,
Thexyl (diisobutylamino) dimethoxysilane, Thexyl (dicyclopentylamino) dimethoxysilane,
Thexyl (dicyclohexylamino) dimethoxysilane, Thexyl (methylamino) dimethoxysilane, Thexyl (ethylamino) dimethoxysilane, Thexyl (propylamino) dimethoxysilane, Thexyl (isopropylamino) dimethoxysilane, Thexyl (butylamino) dimethoxysilane, Thexyl ( Isobutylamino)
Dimethoxysilane, thexyl (sec-butylamino)
Dimethoxysilane, thexyl (ter-butylamino)
Dimethoxysilane, thexyl (cyclopentylamino)
Dimethoxysilane, thexyl (cyclohexylamino)
Dimethoxysilane, thexyl (pyrrolidyl) dimethoxysilane, thexyl (2-methylpyrrolidyl) dimethoxysilane, thexyl (2,5-dimethylpyrrolidyl) dimethoxysilane, thexyl (piperidyl) dimethoxysilane, thexyl (2-methylpiperidyl) dimethoxy Silane, thexyl (2,6-dimethylpiperidyl) dimethoxysilane, thexyl (4-methylpiperidyl) dimethoxysilane, thexyl (pyrazolyl) dimethoxysilane,
Thexyl (piperazyl) dimethoxysilane, Thexyl (indolyl) dimethoxysilane, Thexyl (isoindolyl) dimethoxysilane, Thexyl (morpholyl)
These are dimethoxysilane, thexyl (pyrrolinyl) dimethoxysilane, thexyl (imidazolinyl) dimethoxysilane, and thexyl (pyrazolidinyl) dimethoxysilane.

Of these, preferred are thexyl (dimethylamino) dimethoxysilane, thexyl (diethylamino) dimethoxysilane and thexyl (dipropylamino).
Dimethoxysilane, thexyl (dibutylamino) dimethoxysilane, thexyl (cyclohexylmethylamino)
Dimethoxysilane, thexyl (t-butylamino) dimethoxysilane, thexyl (pyrrolidyl) dimethoxysilane, thexyl (2-methylpyrrolidyl) dimethoxysilane, thexyl (piperidyl) dimethoxysilane, thexyl (2,6-dimethylpiperidyl) dimethoxysilane, Thexyl (2-methylpiperidyl) dimethoxysilane. The amount of the component (C) used is a molar ratio of the component (C).
/ Component (B) = 0.001 to 5, preferably 0.01 to
It is 1.

The olefin used for olefin 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 and the like, which are advantageous for stereospecific polymerization of alpha olefins containing 3 or more carbon atoms such as mixtures thereof and ethylene and mixtures thereof. 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 Thereof 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; such as toluene, xylene, ethylbenzene, isopropylbenzene, ethyltoluene, n-propylbenzene, diethylbenzene and mono- or dialkylnaphthalene. Alkyl aromatic hydrocarbons; halogenated and hydrogenated aromatic hydrocarbons such as chlorobenzene, 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 dialkylnaphthalenes; 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.

The gas phase polymerization method in which the present invention is useful can use a stirred bed reactor, a fluidized bed reactor system and the like. A typical gas phase olefin polymerization reactor system is
Olefin monomer and catalyst components can be added,
It consists of a reaction vessel equipped with a stirrer and contains 1 catalyst component.
It is added to the reaction vessel together or separately from one or more valve control ports. 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 from the viewpoint of obtaining good catalyst performance and high production rate, 20 ° C to 100 ° C is preferable, and more preferably 50 ° C to 80 ° C. Is.

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 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. ℃. 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%) was prepared by dissolving 2 g of the polymer in 200 ml of xylene at 135 ° C., cooling the solution to room temperature, and filtering the precipitated polymer under reduced pressure. The filtrate was subjected to rotary evaporation to distill off the solvent. The residue obtained by drying this was measured. The value of the polymerization activity was calculated by the following formula.

[Equation 1] XSRT% 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. In each example, each compound used for producing and polymerizing the solid catalyst component (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, silicon compound, etc.)
Are substantially free of water. 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 in the polymerization were used as 1.0 M / l and 0.1 M / l hexane solutions, respectively.

[Synthesis Example of Organosilicon Compound] [Synthesis of Thexyl (dibutylamino) dimethoxysilane] 100 ml of dehydrated THF (tetrahydrofuran) was added to a 300 ml three-necked flask equipped with a dropping funnel, Dimroth and a magnetic stirrer under a nitrogen stream. Dibutylamine 1
Add 2.9 g (0.1 mol) and put the contents in an ice bath at 0 ° C.
Cooled to. n-Butyl lithium (59ml, 1.7M /
L hexane solution) was added dropwise over 30 minutes. Then the ice bath was removed and the reaction mixture was stirred at room temperature for 1 hour. Separately, in a 500 ml three-necked flask equipped with a dropping funnel, a Dimroth and a magnetic stirrer under a nitrogen stream, dehydrated THF 10
0 ml and 20.6 g of thexyltrimethoxysilane
(0.1 mol) was charged and the contents were cooled to 0 ° C. in an ice bath. The lithium amide solution prepared above was added dropwise over 1 hour. After removing the ice bath and warming to room temperature, the reaction mixture was refluxed for 2 hours. The reaction mixture is cooled to room temperature,
The white precipitate was filtered off with a glass filter (G4). The solvent was removed by a rotary evaporator, and the target compound was distilled under reduced pressure to obtain 19.7 g (0.065 mol,
Yield 65%). Boiling point 119-123 ° C / 7mmH
g, GC = 98.3%, GC-MS; m / z = 303.
By the same method, by changing the amine compound used, thexyl (dipropyl) aminodimethoxysilane, thexyl (cyclohexylmethylamino) dimethoxysilane, thexyl (tert-butylamino) dimethoxysilane, thexyl (pyrrolidyl) dimethoxysilane, thexyl (piveridyl) ) Dimethoxysilane and thexyl (2,6-dimethylpiperidyl) dimethoxysilane compounds were synthesized, respectively. The physical properties of each compound are shown in Table 1.

[0028]

[Table 1]

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 was added, and the mixture was stirred and mixed at 130 ° C. for 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 di (2-ethylhexyl) phthalate is added, and the mixture is kept under stirring at the same temperature for 2 hours. Two
After completion of the reaction for a certain period of time, a solid portion was collected by hot filtration, and the solid portion was resuspended in 72 ml of TiCl ₄ and then again 11
Heat reaction is performed at 0 ° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration, washed sufficiently with decane and hexane until no free titanium compound was detected in the washing liquid, and then dried under reduced pressure. [Polymerization] Into a 6.0-liter stainless steel autoclave, 5.8 mg of the solid component produced by the above method and 1.6 ml of thexyl (pyrrolidyl) dimethoxysilane
(0.1 M / l hexane solution), 1.6 ml of triethylaluminum (1 M / l hexane solution) were added, and then 1020 g of propylene and 0.09 g of hydrogen were added. Raise the temperature of the autoclave and set the internal temperature to 80 ° C.
Kept at. After 2 hours, the content gas was released to terminate the polymerization. The results are shown in Table 2.

Comparative Examples 1 and 2, Examples 2 to 4 Catalysts were 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 2. The results are shown in Table 2.

[0031]

[Table 2]

Example 5 [Preparation of solid Ti catalyst component (A)] In a 300 ml round-bottomed flask that had been thoroughly dried under a nitrogen stream, 5 g of diethoxymagnesium and 3-methoxy-2-t-amylpropionic acid (t- Butyl) 1.42 g and methylene chloride 25 ml were added. Stir at reflux for 1 hour, then pump the suspension into 200 ml TiCl ₄ at room temperature. Gradually 110
The temperature was raised to 0 ° C. and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the precipitated solid was filtered off and n-decane 2 at 110 ° C was added.
It was washed 3 times with 00 ml. 200 ml of new TiCl ₄
Was added and reacted at 120 ° C. for 2 hours. After the reaction was completed, the precipitated solid was filtered off and washed with 200 ml of n-decane three times,
It was washed with hexane at room temperature until no chlorine ion was detected with n-hexane. [Polymerization] 2.3 mg of the solid component produced by the above method and 1.6 ml of thexyl (pyrrolidyl) dimethoxysilane were placed in a 6.0-liter stainless steel autoclave.
(0.1 M / l hexane solution), 1.6 ml of triethylaluminum (1 M / l hexane solution) were 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. After 2 hours, the content gas was released to terminate the polymerization.
The results are shown in Table 3.

Comparative Examples 3 and 4, Examples 6 and 11 Catalyst preparation and polymerization were carried out in the same manner as in Example 5 except that the type of the catalyst component (C) used was changed as shown in Table 3. The results are shown in Table 3.

Examples 12 and 14 A catalyst was prepared and polymerized in the same manner as in Example 5 except that the amount of the catalyst component (C) used was changed as shown in Table 4. The results are shown in Table 4.

Examples 15 and 16 Example 5 except that the amount of hydrogen used was changed as shown in Table 5.
The catalyst was prepared and polymerized in the same manner as in. The results are shown in Table 5.

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

As described above, according to the method of the present invention, there is little decrease in the catalytic activity during the polymerization, and the activity can be maintained for a long time. As a result, the olefin polymer which is excellent in practical use is obtained. Can be manufactured economically.

[Brief description of drawings]

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

Claims (9)

(57) [Claims] 1. A catalyst used in a method for producing an olefin polymer by polymerizing olefins in the presence of a catalyst, wherein the catalyst is component (A) a solid catalyst component containing titanium, magnesium and halogen as essential components, (B) Organoaluminum compound, and component (C) Formula (1), (Here, R ¹ is a secondary or tertiary amino residue) A catalyst for olefin polymerization comprising a novel organosilicon compound. 2. The catalyst for olefin polymerization according to claim 1, wherein the organosilicon compound is a thexyl (dipropylamino) dimethoxysilane compound. 3. The catalyst for olefin polymerization according to claim 1, wherein the organosilicon compound is a thexyl (dibutylamino) dimethoxysilane compound. 4. The catalyst for olefin polymerization according to claim 1, wherein the organosilicon compound is a thexyl (cyclohexylmethylamino) dimethoxysilane compound. 5. The organosilicon compound is texyl (ter)
The catalyst for olefin polymerization according to claim 1, which is a -butylamino) dimethoxysilane compound. 6. The catalyst for olefin polymerization according to claim 1, wherein the organosilicon compound is a thexyl (pyrrolidyl) dimethoxysilane compound. 7. The catalyst for olefin polymerization according to claim 1, wherein the organosilicon compound is a thexyl (piperidyl) dimethoxysilane compound. 8. The organosilicon compound is thexyl (2,6
A catalyst for olefin polymerization according to claim 1, which is a -dimethylpiperidyl) dimethoxysilane compound. 9. A method for producing an olefin polymer, which comprises using the catalyst for olefin polymerization according to claim 1.