JP3408596B2 - Olefin polymerization solid catalyst component, olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-performance catalyst which exhibits a high activity when subjected to the polymerization or copolymerization of olefins, and is particularly applied to the polymerization of α-olefins having 3 or more carbon atoms. In the case of, a solid catalyst component for olefin polymerization capable of obtaining a highly stereoregular polymer in high yield,
The present invention relates to a method for producing an olefin polymerization catalyst and an olefin polymerization method.

[0002]

2. Description of the Related Art A Ziegler catalyst supported on magnesium chloride has been conventionally known as a catalyst used for producing an olefin polymer such as polymerization or copolymerization of α-olefin. As such an olefin polymerization catalyst, many production methods using a solid catalyst component composed of magnesium, titanium, halogen and an electron donating compound have been proposed. In particular, it is well known that excellent performance is exhibited when an organic carboxylic acid ester compound such as a phthalic acid ester is used as the electron donating compound (JP-A-57-63311 and JP-A-3-311).
294302, JP-A 3 -706, JP 2-2896
04, JP-A-3-43407). However, in these catalyst systems, it was necessary to use a large amount of expensive organosilicon compound as a co-catalyst component other than the organoaluminum compound during polymerization. Recently, a catalyst system using a compound having two or more ether bonds existing through a plurality of atoms as the electron-donating compound (JP-A-3-2943).
04) is also proposed, but even if these catalyst systems are used, they do not have industrially satisfactory performance in terms of activity and stereoregularity, and it is desired to develop a catalyst with higher performance. Was there.

[0003]

The object of the present invention is to provide a catalyst system which gives a highly active and highly stereoregular polymer, which has been insufficient in the above-mentioned prior art.

[0004]

The solid catalyst component for olefin polymerization according to the present invention is (A) titanium, magnesium,
It is formed by bringing a solid catalyst component containing halogen and an electron donating compound (D1) into contact with (B) an alkoxyester compound represented by the general formula (1) and an organoaluminum compound. . _{^{(R 1 O) i (R}} 2 O) j (R 3 O) k -Z-COOR 4 (1) ( ^{wherein, R 1, R 2, R} 3 and R ⁴ or a methyl group
Ethyl group , Z is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms whose hydrogen atom may be substituted with an aromatic group or a polycyclic group, and i, j, k are 0 or 1 And i,
The sum of j and k is 1 . According to the solid catalyst component for olefin polymerization according to the present invention, when the alkoxy ester compound as described above is used, the activity is high even when an electron donating compound such as an organosilicon compound is not used during the polymerization. Further, it is possible to obtain an olefin polymerization catalyst capable of producing a polymer having high stereoregularity. Further, according to the solid catalyst component for olefin polymerization according to the present invention, it is possible to obtain an olefin polymerization catalyst capable of producing a polymer having higher stereoregularity by using an electron donating compound during the polymerization. . The catalyst for olefin polymerization according to the present invention is [1] a solid catalyst component containing (A) magnesium, titanium, halogen and an electron donating compound (D1),
(B) A solid catalyst component for olefin polymerization, which is formed by bringing an alkoxyester compound represented by the general formula (1) and an organoaluminum compound into contact, and (R ¹ O) _i (R ² O) ) _J (R ³ O) _k —Z—COOR ⁴ (1) (wherein R ¹ , R ² , R ³ and R ⁴ are methyl groups or
Ethyl group , Z is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms whose hydrogen atom may be substituted with an aromatic group or a polycyclic group, and i, j, k are 0 or 1 And i,
The sum of j and k is 1 . [2] It is characterized in that it is formed from an organoaluminum compound. Further, the olefin polymerization method according to the present invention is characterized by polymerizing or copolymerizing ethylene and / or α-olefin using the above-mentioned olefin polymerization catalyst. According to the olefin polymerization catalyst and the olefin polymerization method of the present invention, the organoaluminum compound [2] is used together with the solid catalyst component [1] of the present invention.
By using, it is possible to obtain a polymer having high stereoregularity in addition to having high catalytic activity and being able to carry out the polymerization reaction efficiently without using an electron donating compound such as an organosilicon compound during the polymerization. . Further, the olefin polymerization catalyst and the olefin polymerization method according to the present invention use a catalyst containing an electron donating compound together with the organoaluminum compound [2] in addition to the above-mentioned two components to obtain a polymer having higher stereoregularity. You can get it.

The solid catalyst component for olefin polymerization, the catalyst for olefin polymerization and the olefin polymerization method according to the present invention will be specifically described below. The olefin polymerization catalyst component [1] according to the present invention is obtained by contacting a solid catalyst component (A) containing magnesium, titanium, halogen and an electron donating compound (D1) with an alkoxy ester compound and an organoaluminum compound. The resulting catalyst component. The olefin polymerization catalyst according to the present invention comprises such a solid catalyst component [1] and an organoaluminum compound [2].
And are formed in contact with each other. In the present invention, the solid catalyst component (A) used for preparing the solid catalyst component [1] is
For example, a titanium compound and a magnesium compound, and an electron donating compound (D
It is prepared by contacting these compounds with 1) and. 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 mentioned above 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 to the titanium compound and the magnesium compound. In the solid catalyst component (A) contained in the olefin polymerization catalyst according to the present invention, in addition to the compound as described above, an electron donating compound (D1) may be an alkoxy ester compound and / or an electron donating property other than the alkoxy ester compound. A compound is used.

The alkoxy ester compound used in the preparation of the solid catalyst component (A) used in the present invention has the general formula (1): (R ¹ O) _i (R ² O) _j (R ³ O) _k -Z- It is represented by COOR ⁴ (1). R ¹ , R ² , R ³ and R ⁴ are each a methyl group or
It is a chill group . These are, it may also be the same or different
Yes .

[0008]

[0009]

Z is preferably an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom of which may be substituted with an aromatic group having 1 to 18 carbon atoms or a polycyclic group. Specifically, methylene, ethylene, ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, propenylene and the like, and substituted examples include methylmethylene, n-butylmethylene, ethylethylene,
Isopropyl ethylene, tert-butyl ethylene, s
ec-Butylethylene, tert-amylethylene, adamantaneethylene, bicyclo [2,2,1] heptylethylene, phenylethylene, tolylethylene, xylylethylene, diphenyltrimethylene, 1,2-cyclopentylene, 1,3- Cyclopentylene, 3-cyclohexene-
1,2-ylene, dimethylethylene, indenyl-1,2-
Ilene and the like can be exemplified. A hydrogen atom may be replaced with a halogen atom.

[0011] By way of specific compounds, methyl methoxyacetate, ethyl methoxyacetate, main butoxy phenyl acetate, ethoxyethyl acetate, ethoxyethyl acetate, 3 - methyl methoxypropionate, 3-methoxypropionate, ethyl 3 - ethoxypropionate ethyl, 4 - ethoxyethyl acetate, 1 2-ethoxyethyl lauric ethyl phosphate, 3 - methoxy methyl acrylate, 2-ethoxyethyl acrylate, methyl 2 - methoxy ethyl propionate, 2 - Etokishiiso butyric acid methyl, 3 - ethoxy-3- ( Methyl o-methylphenyl) propionate, ethyl 3-ethoxy-2- (o-methylphenyl) propionate, 4-ethoxy-2
- methyl-1 Nafuchirunonan ethyl, 2-methoxy-cyclopentanecarboxylic acid ethyl ester, 3 - can be exemplified ethoxy norbornane-2-carboxylic acid methyl ester le like.

Of these, the following general formula (2) is preferred.

[Chemical 2] It is an alkoxy ester compound represented by. Where R
⁵ is a methyl group or an ethyl group , R ⁶ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms , and R ⁷ is hydrogen.
An atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms , R
⁸ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms, Y is a chain hydrocarbon group having 1 to 4 carbon atoms, an aliphatic hydrocarbon group , an aromatic hydrocarbon group or a polycyclic hydrocarbon group. The group is a substituted group or an alicyclic hydrocarbon group having 1 to 12 carbon atoms. Particularly preferred is an alkoxy ester in which Y is a chain hydrocarbon and has a bulky substituent having 4 or more carbon atoms at the 2-position or 3-position counted from the carboxyl group. Again 4
An alkoxy ester compound having a cycloalkane having a member ring to an 8-membered ring is also preferable. Specifically, 3-ethoxy-
Ethyl 2-phenylpropionate, 3-ethoxy-2-
Tolyl-propionic acid ethyl, 3-ethoxy-2-mesityl pro pyrone ethyl, 3 - ethoxy -3-tert-butyl propionate, 3-ethoxy-3-adamantyl propionic acid ethyl, 3-ethoxy -2-tert- Ethyl butylpropionate, ethyl 3-ethoxy-2-tert-amylpropionate, ethyl 3-ethoxy-2-adamantylpropionate, ethyl 3-ethoxy-2-bicyclo [2,2,1] heptylpropionate, 2- Examples thereof include ethyl ethoxy-cyclohexanecarboxylate, methyl 2- (ethoxymethyl) -cyclohexanecarboxylate, and methyl 3-ethoxynorbornane-2-carboxylate.

Examples of the electron-donating compound (D1) other than the alkoxy ester compound used when preparing the solid catalyst component (A) used in the present invention 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, cumyl alcohol, diphenylmethanol, triphenylmethanol and the like. Alcohols having 1 to 20 carbon atoms, (b) phenol,
Cresol, ethylphenol, propylphenol,
C6 to C25 phenols which may have an alkyl group such as cumylphenol, nonylphenol and naphthol, (C) acetone, methylethylketone, methylisobutylketone, acetophenone, cyclohexanone and other C3 to C15 ketones, (D) C2-C15 aldehydes such as acetaldehyde, propionaldehyde, tolualdehyde, and naphthaldehyde; (f) methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, methyl acetate Cellosolve, 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 crotonic acid, ethyl cyclohexanecarboxylate, methyl phenylacetate, methyl phenylbutyrate,
Propyl phenylbutyrate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, cellosolve benzoate, methyl toluate, ethyl toluate, toluic acid Amyl, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, diethyl phthalate, diisobutyl phthalate, diheptyl phthalate, dineopentyl phthalate, γ-butyrolactone, γ-palerolactone, coumarin, phthalide, diethyl carbonate , Organic acid esters having 2 to 20 carbon atoms, such as methyl orthoformate and ethyl orthoformate,

(H) 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.

Inorganic acid esters such as (g) methyl borate, butyl titanate, butyl phosphate, diethyl phosphite, 2,2-diphenylphosphorochloridate, (th) methyl ether, ethyl ether, isopropyl ether ,
Ethers having 2 to 25 carbon atoms such as butyl ether, amyl ether, tetrahydrofuran anisole, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol diphenyl ether, and 2,2-dimethoxypropane, (ri) 2- (2-ethylhexyl) 1,3- Dimethoxypropane, 2-isopropyl-
1,3-dimethoxypropane, 2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3- Dimethoxypropane, 2-cumyl-1,3-dimethoxypropane, 2-
(Phenylethyl) -1,3-dimethoxypropane, 2
-(2-Cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3-dimethoxypropane, 2- (diphenylmethyl) -1,3-
Dimethoxypropane, 2- (1-naphthyl) -1,3-
Dimethoxypropane, 2- (2-fluorophenyl)-
1,3-dimethoxypropane, 2- (1-decahydronaphthyl) -1,3-dimethoxypropane, 2- (pt)
-Butylphenyl) -1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane,
2,2-dibutyl-1,3-dimethoxypropane, 2-
Methyl-2-propyl-1,3-dimethoxypropane,
2-Methyl-2 - benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-methyl-2 -Phenyl-1,3-dimethoxypropane, 2-methyl-2-cyclohexyl-
1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-
Bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2 , 2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, Diethers such as 3-dimethoxypropane, (nu) acetic acid amide, benzoic acid amide,
Acid amides having 2 to 20 carbon atoms such as toluic acid amide, and acid halides having 2 to 20 carbon atoms such as (l) acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, and isophthaloyl chloride, (Wo) acetic anhydride, phthalic anhydride and other acid anhydrides having 2 to 20 carbon atoms, (wa) monomethylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethyl C1-C20 amines such as ethylenediamine, (C) acetonitrile, benzonitrile, trinitrile and other C2-C20 nitriles, (yo) ethylthioalcohol, butylthioalcohol, phenylthiol and other C2
To 20 thiols, (ta) diethyl thioether, diphenyl thioether, etc., having 4 to 25 carbon atoms
Thioethers, dimethyl sulfate (2), sulfates having 2 to 20 carbon atoms such as diethyl sulfate, sulfonic acids having 2 to 20 carbon atoms such as (so) phenylmethyl sulfone and diphenyl sulfone, and (tsu) phenyl trimethoxy Silane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxysilane, triphenylmethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, trimethylsilanol, Examples include silicon-containing compounds having 2 to 24 carbon atoms such as phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, and lower alkyl silicate (especially ethyl silicate). It can be. Among these, preferred are organic acid esters, ketoesters, diethers and the like. The electron-donating compound (D1) does not necessarily have to be used as a starting material and can be produced in the process of preparing the solid catalyst component (A).

The solid 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. 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 solid catalyst component (A) is arbitrary as long as the effects of the present invention are recognized, but the following ranges are generally preferred. The content of magnesium in the solid catalyst component (A) is in the range of 0.1 to 1000, preferably 2 to 2 in terms of molar ratio to titanium.
00, the halogen content may be in the range of 1 to 100 by molar ratio to titanium, and the electron donating compound
The content of (D1) may be within a range of 10 or less, preferably within a range of 0.1 to 5, in terms of molar ratio to titanium. The solid catalyst component [1] for olefin polymerization according to the present invention is formed by bringing the solid catalyst component (A) as described above into contact with the above-mentioned alkoxy ester compound and organoaluminum compound.

The organoaluminum compound component used in preparing the solid catalyst component [1] used in the present invention is represented by the following general formulas (3) to (5). AlR ⁹ R ¹⁰⁰ R ¹¹ (3) R ¹² R ¹³ Al-O-AlR ¹⁴ R ¹⁵ (4)

[Chemical 2] 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 examples of the organoaluminum compound represented by the formula (3) include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum,
Trialkylaluminums such as triisopentylaluminium and trioctylaluminum, alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and alkylaluminums such as diethylaluminum chloride, diethylaluminum bromide and ethylaluminum sesquichloride and ethylaluminum sesquichloride. Halide is given. Further, among the organoaluminum compounds represented by the formula (4), typical ones are alkyldialumoxanes such as tetraethyl dialumoxane and tetrabutyl dialumoxane. The formula (5) represents an aluminoxane, which is a polymer of an aluminum compound. R ¹⁶ 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.

When the solid catalyst component (A) is contacted with the alkoxy ester compound and the organoaluminum compound to obtain the solid catalyst component [1], the alkoxy ester compound is 1 mol of titanium atom of the solid catalyst component (A). 0.1-50 mol, preferably 0.5-30 mol,
More preferably, it is used in an amount of 1 to 10 mol. The amount of the organoaluminum compound is preferably 0.1 to 100 mol, particularly preferably 1 to 50 mol, per titanium atom of the solid catalyst component (A). The olefin polymerization catalyst according to the present invention is formed from such a solid catalyst component [1], an organoaluminum compound [2] and, if necessary, an electron donating compound. As the organoaluminum compound [2] in the present invention, the same compounds as the above-mentioned organoaluminum compounds can be used.

[0020] In the touch for olefin polymerization medium according to the present invention if necessary, the electron donor compound is used as the electron-donating compound, an organic silicon compound having an alkoxy ester compounds and alkoxy groups described above It is possible to use, and it is particularly preferable to use an alkoxy ester compound and an organosilicon compound having an alkoxy group. Specific examples of the organosilicon compound having an alkoxy group include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, and ethylisopropyl. Dimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di (tert-butyl) dimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane , Tert-butylisopropyldimethoxysilane, tert-butylbutyldimetho Shishiran, te
rt-butylisobutyldimethoxysilane, tert-
Butyl (sec-butyl) dimethoxysilane, tert
-Butylamyldimethoxysilane, tert-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, t
tert-butyldecyldimethoxysilane, tert-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, tert-butyl (cyclopentyl) dimethoxysilane, tert-butyl (cyclohexyl) dimethoxysilane, dicyclopentyldimethoxysilane, bis ( 2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, mesityltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, Butyltrimethoxysilane,
i-butyltrimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane,
Amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl (te
rt-butoxy) dimethoxysilane, isopropyl (t
ert-butoxy) dimethoxysilane, tert-butyl (isobutoxy) dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, thexyltrimethoxysilane, thexyl (i-propoxy) dimethoxysilane, thexyl (tert-butoxy) dimethoxysilane. Etc. The amount of the electron donating compound used is a molar ratio of component [electron donating compound] / component [2] = 0.0.
It is 01 to 5, preferably 0.01 to 1.

In the olefin polymerization method according to the present invention, olefin polymerization is carried out using the olefin polymerization catalyst according to the present invention. In the olefin polymerization method according to the present invention, prepolymerization is not always necessary, but it is also preferable to carry out prepolymerization, and the solid catalyst component [1] is usually used.
Is used in combination with at least a part of the organoaluminum compound component [2]. At this time, an electron donating compound can be allowed to coexist. The concentration of the solid catalyst component [1] in the prepolymerization is usually 0.01 to 2 in terms of titanium atom per liter of an inert hydrocarbon solvent described later.
It is desirable to set it in the range of 00 millimole. The amount of the organoaluminum compound component [2] is the solid catalyst component [1] 1
The amount may be such that 0.1 to 500 g of polymer is produced per g, and preferably the amount is such that 0.1 to 300 g of 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. As the inert hydrocarbon solvent used at this time, specifically, propane, butane,
Aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, kerosene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; Aromatic hydrocarbons such as benzene, toluene, xylene; Ethylene chloride , Halogenated hydrocarbons such as chlorobenzene, 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 the olefin polymerization method of the present invention, the amount of the organoaluminum compound used in the main polymerization is generally 10 ^-4 mmol / l or more, and 10 ^-2 mmol / l.
The above is suitable. 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. The amount of organoaluminum used in the polymerization system is 20 mmol / l or more, and the ratio to titanium atoms is 1000 in terms of molar ratio.
In the above cases, even if these values are further increased, the catalyst performance is not further improved.

The olefin used in the polymerization method according to the present invention is generally an olefin having at most 12 carbon atoms, and a typical example thereof is ethylene,
Examples include propylene, butene-1, 4-methylpentene-1, hexene-1, octene-1, and the like, and mixtures thereof, and alpha olefins containing three or more carbon atoms such as ethylene and mixtures thereof. Is advantageous for the stereospecific polymerization of 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.

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 lower than the vapor pressure at the polymerization temperature of the olefin to be polymerized, but generally the monomer pressure is in the range of atmospheric pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² . is there. The polymerization can be carried out either in an inert solvent, in a liquid monomer (olefin) or in the gas phase. Also, the polymerization is performed in a batch system,
It can be carried out by either a semi-continuous method or a continuous method. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions. A molecular weight regulator (generally hydrogen) to obtain a polymer with a workable melt flow.
May coexist. In the case of the batch method, the polymerization time is
It is generally from 30 minutes to several hours, and in the case of continuous processes it is the corresponding average residence time. 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 10 ° C.
0 degreeC is suitable, More preferably, it is the range of 50 degreeC-80 degreeC.

In addition, the polymerization control method, the post-treatment method, etc. are not limited to those specific to the present catalyst system, and all known methods can be applied.

[0028]

[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. XSRT
% Was calculated by the following formula.

[Equation 1] In the examples and comparative examples, the load is 2.16k.
The melt index (i.e., MFR) in g was measured according to JIS K-6758-1968. In each example, each compound used in the production and polymerization of the solid catalyst component (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, electron donating compound,
Organosilicon compounds, etc.) are all 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.

Example 1 [Preparation of solid 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. Phthalic anhydride 0.39 in solution
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 was raised to 110 ° C. over time, and when it reached 110 ° C., 0.97 g of dibutyl phthalate was added.
Hold at the same temperature for a period of time with stirring. After completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was collected with 72 ml Ti.
After resuspending with Cl ₄ , heating reaction is performed again at 110 ° 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. The content of titanium atoms in this solid catalyst component (A) was 1.9% by weight. [Preparation of solid catalyst component [1]] 500 ml under nitrogen stream
Purified hexane 100 in a 3-necked flask equipped with a magnetic stirrer
ml, triethylaluminum 5 mmol, ethyl 3-ethoxy-2-tert-butylpropionate 1.
0.4 millimoles of 0 mmol and the above solid catalyst component (A) in terms of titanium atom were added, and the mixture was stirred and mixed at 25 ° C. for 1 hour and then left to stand to remove the supernatant. After washing twice with purified hexane, purified hexane 100m
1 was added to obtain a hexane suspension solution. [Polymerization] To a 6.0 liter stainless steel autoclave, 0.005 mmol of the solid catalyst component [1] prepared above and 1 mmol of triisobutylaluminum in terms of titanium atom were added, and then 1020 g of the solution. Propylene and 0.09 g hydrogen were charged. 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. As a result, 585 g of powdery polypropylene was obtained.
Therefore, the activity is 117,000 g-PP / mmol-Ti, MFR =
It was 4.4 g / 10 min and XSRT = 1.4%.

Comparative Example 1 The solid catalyst component [1] was prepared and polymerized in the same manner as in Example 1 except that the alkoxy ester compound was not used when preparing the solid catalyst component [1].
2000g-PP / mmol-Ti, MFR = 32.8g / 10mi
n, XSRT = 46.3%. Comparative Example 2 A solid catalyst component [1] was prepared in the same manner as in Example 1 except that 2,2-diisobutyl-1,3-dimethoxypropane was used instead of the alkoxy ester compound when preparing the solid catalyst component [1]. Was prepared and polymerized, the activity was 6
4900g-PP / mmol-Ti, MFR = 7.6g / 10min
, XSRT = 3.5%.

Example 2 [Preparation of solid Ti catalyst component (A)] 5 g of diethoxymagnesium and ethyl 3-ethoxy-2-tert-butylpropionate were placed in a 300 ml round bottom flask which was sufficiently dried under a nitrogen stream. 54 g and 25 ml methylene chloride were added. Stir at reflux for 1 hour, then pump the suspension into 200 ml TiCl4 at room temperature. Gradually 11
The temperature was raised to 0 ° C. and the reaction was carried out with stirring for 2 hours.
After the reaction was completed, 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. The content of titanium atoms in this solid catalyst component was 2.1% by weight. [Preparation of solid catalyst component [1]] 500 ml under nitrogen stream
Purified hexane 100 in a 3-necked flask equipped with a magnetic stirrer
ml, triethylaluminum 5 mmol, ethyl 3-ethoxy-2-tert-butylpropionate 0.
After adding 5 mmol and 1 mmol of the above solid catalyst component (A) in terms of titanium atom, and stirring and mixing at 25 ° C. for 1 hour,
The solution was left to stand and the supernatant was removed. After washing twice with purified hexane, 100 ml of purified hexane was added to prepare a hexane suspension solution. [Polymerization] To a 6.0-liter stainless steel autoclave, 0.004 mmol of the solid catalyst component [1] prepared above and 10.8 mol of triisobutylaluminum in terms of titanium atom were added, and then 1020 g of the solution. Propylene and 0.09 g hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 70 ° C. After 1 hour, the content gas was released to terminate the polymerization. As a result, 536 g of powdery polypropylene was obtained.
Therefore, the activity is 134000 g-PP / mmol-Ti, MFR =
It was 3.5 g / 10 min and XSRT = 2.1%.

[0032]

The solid catalyst component [1] for olefin polymerization according to the present invention is a solid catalyst component containing (A) magnesium, titanium, halogen and an electron donating compound (D1), and (B) an alkoxy ester compound. Are formed by contacting. According to the solid catalyst component [1], it is possible to obtain a catalyst for olefin polymerization which can exhibit a high polymerization activity and can obtain a polymer having high stereoregularity without using an electron-donating compound during polymerization. It has become possible.

[Brief description of drawings]

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

Claims (5)

(57) [Claims] 1. A solid catalyst component containing (A) titanium, magnesium, halogen and an electron-donating compound (D1), and (B) an alkoxyester compound represented by the general formula (1) and an organoaluminum compound. A solid catalyst component for olefin polymerization, which is formed by contacting. _{^{(R 1 O) i (R}} 2 O) j (R 3 O) k -Z-COOR 4 (1) ( ^{wherein, R 1, R 2, R} 3 and R ⁴ or a methyl group
Ethyl group , Z is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms whose hydrogen atom may be substituted with an aromatic group or a polycyclic group, and i, j, k are 0 or 1 And i,
The sum of j and k is 1 . ) 2. An alkoxy ester compound having the following general formula
The olfi according to claim 1, which is represented by (2).
Solid catalyst component for polymerization. [Chemical 1] (Here, R ⁵ is a methyl group or an ethyl group, and R ⁶ is water.
An elementary atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms,
R ⁷ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms
R ⁸ is a methyl group or an ethyl group, and Y is a carbon group.
Aliphatic hydrocarbon group, aromatic hydrocarbon in the number 1 to 4 chain hydrocarbon group
A group substituted with a hydrocarbon group or a polycyclic hydrocarbon group, or
Is an alicyclic hydrocarbon group having 1 to 12 carbon atoms. ) 3. An alkoxy ester compound is 3-etoki
An ethyl cy-2-t-butylpropionate.
The solid catalyst component for olefin polymerization according to 1 or 2. 4. [1] for olefin polymerization catalyst characterized by being formed from <br/> solid catalyst component及beauty [2] The organic aluminum compound according to any one of claims 1 to 3 . 5. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an α-olefin and / or ethylene using the catalyst for olefin polymerization according to claim 4 .