JP3426664B2 - 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 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-7-706, JP-A-2-2896
04, JP-A-3-43407). However, in these catalyst systems, it was necessary to use a large amount of an organosilicon compound or the like as a promoter 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-3-29430).
Although 4) has been proposed, even if these catalyst systems are used, they do not have industrially satisfactory performances in terms of activity and stereoregularity, and it is desired to develop higher performance catalysts. Was there.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst system which economically gives a highly active and highly stereoregular olefin polymer, which has been insufficient in the prior art. It is a thing.

[0004]

The solid catalyst component for olefin polymerization according to the present invention is (A) titanium, magnesium,
It is formed by contacting a solid catalyst component containing a halogen and an electron donating compound (D1) with (B) an aminoalkoxysilane compound represented by the general formula (1) and an organoaluminum compound. There is. R ¹ R ² Si (OMe) ₂ (1) (wherein R ¹ is a secondary or tertiary amino residue, and R ² is a thexyl (—C (CH ₃ ) ₂ CH (CH ₃ ) ₂ ) group. According to the solid catalyst component for olefin polymerization according to the present invention, a polymer having high activity and high stereoregularity can be produced without using an electron donating compound as a cocatalyst or an external donor during the polymerization. It is possible to obtain a catalyst for olefin polymerization. Further, according to the solid catalyst component for olefin polymerization according to the present invention, by further using the above-mentioned aminoalkoxysilane compound or a specific electron-donating compound during the polymerization, it is possible to produce a polymer having higher stereoregularity. It is possible to obtain a catalyst for use.
Olefin polymerization catalyst according to the present invention is characterized by (1) minute olefin polymerization solid catalyst component according to the present invention, it is formed from [2] an organoaluminum compound. The method for producing an olefin polymer 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 (production of olefin polymer) of the present invention, when the organoaluminum compound [2] is used together with the solid catalyst component [1] of the present invention, further It is possible to obtain a polymer having high stereoregularity as well as having high catalytic activity and efficient polymerization reaction without using an electron-donating compound. Further, the olefin polymerization catalyst and the olefin polymerization method according to the present invention use a catalyst containing an aminoalkoxysilane compound (B) or a specific electron donating compound together with the organoaluminum compound [2] in addition to the above two components. Further, a polymer having higher stereoregularity can be obtained.

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 comprises contacting a solid catalyst component (A) containing magnesium, titanium, a halogen and an electron donating compound (D1) with an aminoalkoxysilane compound and an organoaluminum compound. This is the catalyst component obtained. The olefin polymerization catalyst according to the present invention is formed by bringing such a solid catalyst component [1] into contact with an organoaluminum compound [2]. In the present invention, the solid catalyst component (A) used for preparing the solid catalyst component [1] is prepared, for example, by using a titanium compound and a magnesium compound and an electron donating compound (D1) and bringing these compounds into contact with each other. To be done. 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 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, an electron donating compound (D1) is used in addition to the compound as described above.

The electron-donating compound (D1) used when preparing the solid catalyst component (A) used in the present invention is
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 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, Methyl 3-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.

(To) Ethyl 3-ethoxy-2-phenylpropionate, ethyl 3-ethoxy-2-tolylpropionate, ethyl 3-ethoxy-2-mesitylpropionate, 3-butoxy-2- (methoxyphenyl) ) Ethyl propionate, methyl 3-i-propoxy-3-phenylpropionate, ethyl 3-ethoxy-3-tert-butylpropionate, ethyl 3-ethoxy-3-adamantylpropionate, 3-ethoxy-2-tert- Ethyl butylpropionate, ethyl 3-ethoxy-2-tert-amylpropionate, ethyl 3-ethoxy-2-adamantylpropionate, 3-ethoxy-2-bicyclo [2,2,2]
1] Ethyl heptylpropionate, ethyl 2-ethoxy-cyclohexanecarboxylate, 2- (ethoxymethyl)
-Alkoxy esters such as methyl cyclohexanecarboxylate and methyl 3-ethoxynorbornane-2-carboxylate.

(H) Inorganic acid esters such as methyl borate, butyl titanate, butyl phosphate, diethyl phosphite, 2,2-diphenylphosphorochloridate, (ri) 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,

(L) Acetic acid amides, benzoic acid amides, acid amides having 2 to 20 carbon atoms such as toluic acid amides,
(Wo) Acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride, phthaloyl chloride, isophthaloyl chloride and other acid halides having 2 to 20 carbon atoms, (wa) acetic anhydride, phthalic anhydride and other carbon atoms to 2 to 20 acid anhydrides, (f) monomethylamine, monoethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine,
C1-C20 amines such as picoline and tetramethylethylenediamine, (Yo) acetonitrile, benzonitrile, trinitrile and other C2-C20 nitrites, (ta) ethylthioalcohol, butylthioalcohol, phenylthiol, etc. 2 to 2 carbons
0 thiols, (re) diethyl thioether, diphenyl thioether and other thioethers having 4 to 25 carbon atoms, (so) dimethyl sulfate, diethyl sulfate and other C 2 to 20 sulphate esters, and (T) phenylmethyl sulfone , Sulfonic acids having 2 to 20 carbon atoms such as diphenyl sulfone, (ne) phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, vinyltriethoxysilane, diphenyldiethoxysilane, phenyldimethylmethoxysilane, phenyldimethylethoxy Silane, triphenylmethoxysilane, hexamethyldisiloxane, octamethyltrisiloxane, trimethylsilanol, phenyldimethylsilanol, triphenylsilanol, diphenylsilanediol, silicic acid Having 2 to carbon atoms, such as grade alkyl (especially ethyl silicate) and the like silicon-containing compound of 24. Of these, preferred are organic acid esters, alkoxyesters, ketoesters,
Diethers and the like. The electron donating compound (D1) is
It is not always necessary to use it as a starting material, and it 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 mentioned. A method of obtaining a catalyst component by bringing magnesium halide, titanium halide and the above-mentioned electron donating compound into contact with each other by co-grinding or by dispersing or dissolving in a solvent. A method of preparing a complex of magnesium halide and an organic or inorganic compound (which may contain the above-mentioned electron-donating compound), and bringing this into contact with a titanium halide or a complex of the above-mentioned electron-donating compound to obtain a catalyst component. . A complex of 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 can be recognized, but generally the following ranges are preferable. 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 aminoalkoxysilane compound (B) and the organoaluminum compound. The aminoalkoxysilane compound according to the present invention is an aminoalkoxysilane compound represented by the general formula (1). ^{R 1 R 2 Si (OMe)} 2 (1) wherein, R ¹ is 2 or tertiary amino residue, R ² Te <br/> hexyl _{(-C (CH 3) 2 CH} (CH 3) 2 ) Is a group. Specific examples of such compounds are shown below. Te hexyl (dimethylamino) dimethoxysilane, thexyl (methylpropylamino) dimethoxysilane, thexyl (methyl-butylamino) dimethoxysilane, thexyl (methyl isobutyl amino) dimethoxysilane, thexyl (methyl cyclopentylamino) dimethoxysilane, thexyl (methylcyclohexylamino )
Dimethoxysilane, Thexyl (diethylamino) dimethoxysilane, Thexyl (ethylpropylamino) dimethoxysilane, Thexyl (ethylbutylamino) dimethoxysilane, Thexyl (dipropylamino) dimethoxysilane, Thexyl (propylbutylamino) dimethoxysilane, Thexyl (diisopropylamino) ) Dimethoxysilane, thexyl (dibutylamino) dimethoxysilane,
Thexyl (diisobutylamino) dimethoxysilane, Thexyl (dicyclopentylamino) dimethoxysilane,
Thexyl (dicyclohexylamino) dimethoxysilane, Thexyl (isopropylamino) dimethoxysilane, Thexyl (diisobutylamino) dimethoxysilane, Thexyl (isopropylamino) dimethoxysilane, Thexyl (butylamino) dimethoxysilane, Thexyl (isobutylamino) dimethoxysilane, Thexyl ( tert-butylamino) dimethoxysilane, thexyl (cyclopentylamino) dimethoxysilane, thexyl (cyclohexylamino) dimethoxysilane, thexyl (pyrrolidyl) dimethoxysilane, thexyl (piperidyl) dimethoxysilane, thexyl (2-methylpiperidyl) dimethoxysilane, thexyl ( 2,6-Dimethylpiperidyl) dimethoxysilane, thexyl (4-methylpiperidyl) dimethoxysilane , Texyl (pyrazolyl)
These are dimethoxysilane, thexyl (piperazyl) dimethoxysilane, thexyl (indolyl) dimethoxysilane, thexyl (isoindolyl) dimethoxysilane, thexyl (morpholyl) dimethoxysilane, thexyl (imidazolinyl) dimethoxysilane, and thexyl (pyrazolidinyl) dimethoxysilane. Preferably in this, Te <br/> cyclohexyl (dimethylamino) dimethoxysilane, thexyl (diethylamino) dimethoxysilane, thexyl (dipropylamino) dimethoxysilane, thexyl (dibutylamino) dimethoxysilane, thexyl (cyclohexylmethyl-amino) dimethoxysilane Silane, texyl
-Butylamino) dimethoxysilane, thexyl (pyrrolidyl) dimethoxysilane, thexyl (2-methylpyrrolidyl) dimethoxysilane, thexyl (piperidyl) dimethoxysilane, thexyl (2,6-dimethylpiperidyl)
Dimethoxysilane, thexyl (2-methylpiperidyl)
It is dimethoxysilane.

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

[Chemical 1] In the expressions (2), (3) and (4), R ³ , R ⁴
And R ⁵ may be the same or different and each is a hydrocarbon group having at most 12 carbon atoms, and R ⁶ , R ⁷ , R ⁸ and R 5
⁹ may be the same or different and is a hydrocarbon group having at most 12 carbon atoms. R ¹⁰ has at most 12 carbon atoms
Is a hydrocarbon group, and n is an integer of 1 or more.
Typical of the organoaluminum compounds represented by the formula (2) are 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 (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 ¹⁰ 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 aminoalkoxysilane compound and the organoaluminum compound (B) to obtain the solid catalyst component [1], the aminoalkoxysilane compound is the solid catalyst component (A). 0.1 to 50 moles, preferably 0.1 to 50 moles per 1 mole of the titanium atom.
It is used in an amount of 5 to 30 mol, more preferably 1 to 10 mol. The organoaluminum compound is 0.1 mol to 100 mol per titanium atom of the solid catalyst component (A),
Particularly preferably, the amount is 1 to 50 mol. The olefin polymerization catalyst according to the present invention is formed from such a solid catalyst component [1] and an organoaluminum compound component [2].

As the organoaluminum compound of the component [2], the organoaluminum compound exemplified in (B) at the time of preparation of the solid catalyst component [1] can be used.
If necessary, the electron donating compound (D2) may be used for the preparation of the olefin polymerization catalyst according to the present invention. An organosilicon compound can be used as the electron-donating compound (D2). Specifically, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane,
Tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di (tert-butyl) Dimethoxysilane, t
tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylbutyldimethoxysilane, tert-butylisobutyldimethoxysilane,
tert-butyl (sec-butyl) dimethoxysilane, tert-butylamyldimethoxysilane, ter
t-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, tert-butyldecyldimethoxysilane,
tert- butyl (3,3,3 trifluoroacetic methylpropyl) 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, te
rt-Butyltrimethoxysilane, sec-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrisilane Methoxysilane, cyclopentyl (tert-butoxy) dimethoxysilane, isopropyl (tert-butoxy) dimethoxysilane, tert-butyl (isobutoxy) dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, texyltrimethoxysilane, thexyl (i) -Propoxy) dimethoxysilane, texyl (te
rt-butoxy) dimethoxysilane and the like. The amount of the electron-donating compound (D2) used is (D) / component [2] = 0.001-5, preferably 0.01-1 in molar ratio.

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, the electron donating compound (D2) can coexist. The concentration of the solid catalyst component [1] in the prepolymerization is usually 0.
It is desirable to set it in the range of 01 to 200 mmol. The amount of the organoaluminum compound component [2] may be such that 0.1 to 500 g of a polymer is produced per 1 g of the solid catalyst component [1], and preferably 0.1 to 300 g of a polymer is produced. It is the amount to do. The prepolymerization is carried out by adding an olefin and the above catalyst component to an inert hydrocarbon solvent,
It is preferable to carry out under mild conditions. As the inert hydrocarbon solvent used at this time, specifically, propane,
Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclopentane; aromatic hydrocarbons such as benzene, toluene, xylene; Examples thereof include halogenated hydrocarbons such as ethylene chloride and 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 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. ℃. 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 according to 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, of which ethylene is representative.
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
Generally, it is from 30 minutes to several hours, and in the case of the continuous method, it is the corresponding average residence time. About 1 in autoclave type reaction
Polymerization times ranging from hours to 6 hours are typical.

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, and the like are not limited to those specific to the present catalyst system, and all known methods can be applied.

[0023]

[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 flow rate (i.e., MFR) in g was measured according to JIS K-6758-1968. 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. 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 is raised to 110 ° C. over time, and when it reaches 110 ° C., 0.97 g of diisobutyl phthalate is added, and from this, the mixture is kept under stirring at the same temperature for 2 hours. After completion of the reaction for 2 hours, a solid part was collected by hot filtration, and 72 ml of this solid part was collected.
After resuspending in TiCl 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 2.2% 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, thexyl (pyrrolidyl) dimethoxysilane 1.0 mmol and the above solid catalyst component (A) in an amount of 0.5 mmol in terms of titanium atom, and mixed by stirring at 20 ° C. for 1 hour and then allowed to stand. The supernatant was removed. After washing twice with purified hexane, 100 ml of purified hexane was added to prepare a hexane suspension solution. [Polymerization] In a 6.0 liter stainless steel autoclave, 0.003 mmol of the solid catalyst component [1] produced above in hexane was converted in terms of titanium atom, and 0.6 mmol of triisobutylaluminum as component [2]. Add, then 1020 g propylene and 0.0
9 g of hydrogen was 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, 620 g of powdery polypropylene was obtained. Therefore, the activity is 207,000 g-PP / mmol-T
i, MFR = 3.8 g / 10 min, XSRT = 0.6%
Met.

Comparative Example 1 The solid catalyst component [1] was prepared and polymerized in the same manner as in Example 1 except that the aminoalkoxysilane compound was not used in preparing the solid catalyst component [1]. 132000g-PP / mmol-Ti, MFR = 32.8g / 1
0 min, XSRT = 46.3%.

Comparative Example 2 The same as Example 1 except that 2-isopropyl-2-isopentyl-1,3-dimethoxypropane was used in place of the aminoalkoxysilane compound when preparing the solid catalyst component [1]. When the solid catalyst component [1] was prepared and polymerized, the activity was 78900 g-PP / mmol-Ti, MFR.
= 5.9 g / 10 min, XSRT = 2.3%.

Example 2 (Reference Example) [Preparation of Solid Catalyst Component (A)] In a 300 ml round bottom flask which had been sufficiently dried under a nitrogen stream, 5 g of diethoxymagnesium and 3-methoxy-2-ter were added.
1.64 g of ethyl t-butylpropionate and 25 ml of methylene chloride were added. Stir at reflux for 1 hour, then pump the suspension into 200 ml TiCl ₄ at room temperature. 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 110
It was washed 3 times with 200 ml of n-decane at 0 ° C. New Ti
200 ml of Cl ₄ was added and reacted at 120 ° C. for 2 hours. After completion of the reaction, the precipitated solid was filtered off and n-decane 200 was added.
It was washed with ml three times and washed with hexane at room temperature until no chloride ion was detected with n-hexane. The content of titanium atoms in this solid catalyst component was 1.8% by weight.

[Preparation of solid catalyst component [1]] Under a nitrogen stream, 100 ml of purified hexane, 5 mmol of triethylaluminum, 0.5 mmol of tert-butyl (pyrrolidyl) dimethoxysilane and the above were placed in a 500 ml three-necked flask equipped with a magnetic stirrer. 0.5 mmol of the solid catalyst component (A) in terms of titanium atom was 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 10
0 ml was added to give a hexane suspension solution. [Polymerization] Into a 6.0-liter stainless steel autoclave, 0.005 mmol of the solid catalyst component [1] produced above in hexane suspension and 1.0 mmol of triisobutylaluminum were added, and then 1020 g 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, 480 g of powdery polypropylene was obtained. Therefore, the activity is 96000 g-PP / mmol-Ti, MFR = 5.1
g / 10 min, XSRT = 2.3%.

Example 3 A solid catalyst component (A) and a solid catalyst component [1] were prepared in the same manner as in Example 2, and during the polymerization, an electron-donating compound (D) was added.
Polymerization of propylene was carried out using 0.25 mmol of thexyltrimethoxysilane as 2). As a result, the polymerization activity was 131000 g-PP / mmol-Ti, MFR =
It was 4.7 g / 10 min and XSRT = 0.5%.

[0030]

The solid catalyst component [1] for olefin polymerization according to the present invention comprises (A) a solid catalyst component containing magnesium, titanium, halogen and an electron donating compound (D1), and (B) an aminoalkoxy. It is formed by contacting a silane compound and an organoaluminum compound. According to this solid catalyst component [1], high polymerization activity is exhibited without using an electron donating compound during polymerization,
In addition, it becomes possible to obtain an olefin polymerization catalyst capable of obtaining a polymer having high stereoregularity, and it has become possible to economically produce an olefin polymer. further,
By using an electron-donating compound at the time of polymerization, it has become possible to produce an olefin polymerization product capable of obtaining a polymer having higher stereoregularity.

[Brief description of drawings]

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

Claims (4)

(57) [Claims] 1. A solid catalyst component containing (A) titanium, magnesium, halogen and an electron-donating compound (D1), and (B) an aminoalkoxysilane compound represented by the general formula (1) and an organoaluminum compound. A solid catalyst component for olefin polymerization, which is formed by contacting with. R ¹ R ² Si (OMe) ₂ (1) (wherein R ¹ is a secondary or tertiary amino residue, and R ² is a thexyl (—C (CH ₃ ) ₂ CH (CH ₃ ) ₂ ) group. .) 2. Component [1] An olefin polymerization catalyst formed from the solid catalyst component for olefin polymerization according to claim 1 and component [2] an organoaluminum compound. 3. The catalyst for olefin polymerization according to claim 2 , which further contains an electron donating compound (D2). 4. A method for producing an olefin polymer, which comprises polymerizing or copolymerizing α-olefin and / or ethylene using the catalyst for olefin polymerization according to claim 2 or 3 .