JPH09169781A - Organic silicon compound useful as olefin polymerization catalyst component and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the subject new compound consisting of a specific 1,3-bis(trialkylsiloxy)propane compound and useful e.g. as an olefin polymerization catalyst component having high activity and high stereospecificity and giving an olefin polymer having broad molecular weight distribution. SOLUTION: The objective new organic silicon compound is expressed by the formula I (R<1> and R<2> are each a 3-20C saturated hydrocarbon group; R<3> to R<8> are each H or a 1-20C hydrocarbon group which may contain a halogen, O, N, P or S atom; R<9> to R<12> are each H or a 1-10C hydrocarbon group), e.g. 2,2-diisobutyl-1,3-bis(trimethylsiloxy)propane. It is useful as a solid catalyst component for olefin polymerization having high activity and stereospecificity and giving an olefin polymer having broad molecular weight distribution. The compound can be produced by the dehydrohalogenation reaction of a diol compound of the formula II (e.g. 2,2-diisobutyl-1,3-propanediol) with a corresponding halogenated organic silicon compound (e.g. trimethylchlorosilane).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel organosilicon compound useful as a catalyst component for olefin polymerization, a solid catalyst component for olefin polymerization using the same, a catalyst for olefin polymerization and a method for producing an olefin polymer.

[0002]

2. Description of the Related Art Conventionally, a solid catalyst containing a magnesium compound, a titanium compound, a halogen-containing compound and an electron donating compound as essential components as a catalyst component for producing a homopolymer or a copolymer of ethylene or α-olefin. Many ingredients have been proposed. It is also known that these catalysts show a high activity in the polymerization of olefins and give a polymer having a high stereoregularity in the polymerization of α-olefins. In particular, when an aromatic ester represented by a phthalate ester compound is used as an electron-donating compound in the preparation of the solid catalyst component, a polymer exhibiting high activity and high stereoregularity is obtained. It is also known that it can be obtained (for example, Japanese Unexamined Patent Publication No.
7-63310). In recent years, a catalyst system using a compound having two ether bonds existing through a plurality of atoms as the electron-donating compound in the above (JP-A-3-294)
304) is also proposed. However, the olefin polymer obtained from the catalyst system using this solid catalyst component has a problem that it is difficult to obtain a polymer having a narrow molecular weight distribution and excellent moldability and rigidity. Further, in recent years, a method of producing an olefin polymer having a wide molecular weight distribution by adding an organosilicon compound having a specific structure as a cocatalyst to the above solid catalyst component has been proposed (JP-A-4-359904). Although an olefin polymer having a considerably wide molecular weight distribution can be produced by this method, establishment of a method for producing an olefin polymer having a wider molecular weight distribution is desired.

[0003]

The object of the present invention is to provide a novel electron-donating compound which provides a catalyst for olefin polymerization, which exhibits high activity, can produce an olefin polymer having a high stereoregularity and a wide molecular weight distribution. Another object of the present invention is to provide a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the electron-donating compound.

[0004]

Means for Solving the Problems The inventors of the present invention have made diligent studies to solve the above problems and succeeded in producing a novel organosilicon compound having an electron donating property, as well as a magnesium compound, a titanium compound, a halogen-containing compound and an electron. The inventors have found that the above-mentioned problems can be solved by using the organosilicon compound as at least a part of the electron-donating compound in the solid catalyst component for olefin polymerization composed of the donating compound, and have reached the present invention.

The present invention firstly provides a novel organosilicon compound, which is characterized in that it has a chemical structure represented by the following general formula (1).

[0006]

Embedded image

(In the formula, R ¹ and R ² are each independently a branched saturated hydrocarbon group having 3 to 20 carbon atoms or a cyclic saturated hydrocarbon group, and R ³ to R ⁸ are each independently. Is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an atom of halogen, oxygen, nitrogen, phosphorus or sulfur, and R ⁹ to R
¹² is independently hydrogen or has 1 to 10 carbon atoms.
Is a hydrocarbon group. )

Secondly, the present invention provides a solid catalyst component for olefin polymerization, wherein the solid catalyst component comprises a magnesium compound, a titanium compound, a halogen-containing compound and the above organosilicon compound. To do.

Thirdly, the present invention provides a method for producing a solid catalyst component for olefin polymerization, which comprises adding the organosilicon compound to a catalyst component comprising a magnesium compound, a titanium compound and a halogen-containing compound. It is characterized in that they are brought into contact with each other.

Fourthly, the present invention provides an olefin polymerization catalyst, which is characterized in that it comprises the solid catalyst component and the organoaluminum compound in the above third.

Fifth, the present invention provides a method for producing an olefin polymer, which is characterized in that at least one olefin is polymerized in the presence of the catalyst according to the fourth aspect. It is a thing.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The novel organosilicon compound, the solid catalyst component for olefin polymerization, the catalyst for olefin polymerization and the method for producing an olefin polymer of the present invention will be specifically described below. The novel organosilicon compound according to the present invention is a compound having the chemical structure represented by the above general formula (1).

In the formula, R ¹ to R ¹² are as described above,
The organosilicon compound of the present invention is characterized in that R ¹ and R ² are non-linear hydrocarbon groups, particularly branched saturated hydrocarbon groups having 3 to 20 carbon atoms or cyclic hydrocarbon groups. . Specific examples of R ¹ and R ² include an isopropyl group, an isobutyl group, an isopentyl group, an isohexyl group,
Examples include cyclopentyl group and cyclohexyl group.

Specific examples of the organosilicon compound of the present invention are shown by compound name: 2,2-diisobutyl-1,3-bis (trimethylsiloxy) propane, 2,2-diisopentyl-1,3-bis (trimethylsiloxy). )propane,
2,2-diisohexyl-1,3-bis (trimethylsiloxy) propane, 2,2-dicyclopentyl-1,3
-Bis (trimethylsiloxy) propane, 2,2-dicyclohexyl-1,3-bis (trimethylsiloxy) propane, 2-isopropyl-2-isobutyl-1,3-
Bis (trimethylsiloxy) propane, 2-isopropyl-2-isopentyl-1,3-bis (trimethylsiloxy) propane, 2-isopropyl-2-isohexyl-1,3-bis (trimethylsiloxy) propane, 2-
Isobutyl-2-isopentyl-1,3-bis (trimethylsiloxy) propane, 2-isobutyl-2-isohexyl-1,3-bis (trimethylsiloxy) propane, 2-isobutyl-2-cyclopentyl-1,3-bis ( Trimethylsiloxy) propane, 2-isobutyl-
2-cyclohexyl-1,3-bis (trimethylsiloxy) propane, 2-isopentyl-2-isohexyl-
1,3-bis (trimethylsiloxy) propane, 2-isopentyl-2-cyclopentyl-1,3-bis (trimethylsiloxy) propane, 2-isopentyl-2-cyclohexyl-1,3-bis (trimethylsiloxy) propane, 2 , 2-diisobutyl-1,3-bis (ter
t-butyldimethylsiloxy) propane, 2,2-diisobutyl-1,3-bis (dimethylsiloxy) propane, 2,2-diisobutyl-1,3-bis (phenyldimethylsiloxy) propane, 2-isopropyl-2-isopentyl -1,3-bis (tert-butyldimethylsiloxy) propane, 2-isopropyl-2-isopentyl-1,3-bis (dimethylsiloxy) propane, 2
-Isopropyl-2-isopentyl-1,3-bis (phenyldimethylsiloxy) propane, 2,2-dicyclohexyl-1,3-bis (tert-butyldimethylsiloxy) propane, 2,2-dicyclohexyl-1,3
-Bis (dimethylsiloxy) propane, 2,2-dicyclohexyl-1,3-bis (phenyldimethylsiloxy) propane, 2-isopropyl-2-isopentyl-
1,3-bis (3,3,3-trifluoropropyldimethylsiloxy) propane, 2-isopropyl-2-isopentyl-1,3-bis ((tert-butylamino)
Dimethylsiloxy) propane, 2-isopropyl-2-
Examples thereof include isopentyl-1- (tert-butyldimethylsiloxy) -3- (trimethylsiloxy) propane and 2-isopropyl-2-isopentyl-1- (phenyldimethylsiloxy) -3- (trimethylsiloxy) propane. Among them, particularly preferred are 2,2-diisobutyl-1,3-bis (trimethylsiloxy) propane, 2,2-diisopentyl-1,3-bis (trimethylsiloxy) propane, 2,2-diisohexyl-1,
3-bis (trimethylsiloxy) propane, 2,2-diclopentyl-1,3-bis (trimethylsiloxy) propane, 2,2-dicyclohexyl-1,3-bis (trimethylsiloxy) propane, 2-isopropyl-2-
Examples include isopentyl-1,3-bis (trimethylsiloxy) propane.

The method for producing the organosilicon compound of the present invention is not particularly limited. An example of the production method is described below, but it goes without saying that these do not limit the production method of the organosilicon compound of the present invention.

As an example, the corresponding diol compound (1
Mention may be made of a dehydrohalogenation reaction between a) and the corresponding halogenated organosilicon compound (1b). The corresponding diol compound (1a) can be represented by the following formula (1a).

[0017]

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(In the formula, R ¹ , R ² , R ⁹ to R ¹² are as described above.)

The corresponding diol compound (1a) can be produced by a known appropriate method. For example, EUROP
IAN PATENTS APPLICATION 36
As described in 1493, it can be obtained by introducing substituents R ¹ and R ² into a malonic acid ester compound and then reducing the ester group portion. Also, EUR
OPIAN PATENTS APPLICATION
As described in 487035, an aldehyde compound having a double bond can also be obtained by subjecting an aldol condensation reaction to a hydrogenation reaction or a Cannizzaro reaction.

The corresponding halogenated organosilicon compound (1
b) can be represented by the following formula (1b).

[0021]

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(R ³ to R ⁵ are as described above.
X is a halogen atom and may be any of fluorine, chlorine, bromine and iodine. )

The dehydrohalogenation reaction between the diol compound (1a) and the halogenated organosilicon compound (1b) may be carried out by bringing these compounds into contact with each other in an appropriate solvent. As the solvent, ethers such as diethyl ether and tetrahydrofuran, amides such as N, N-dimethylformamide, and nitriles such as acetonitrile can be used. A basic nitrogen-containing organic compound such as triethylamine, imidazole, pyridine or urea may be added to accelerate the dehydrohalogenation reaction.

In the dehydrohalogenation reaction, the halogenated organosilicon compound (1b) may be brought into contact with the diol compound (1a) in an amount of at least twice the equivalent amount. Moreover, after contacting 1 equivalent of the halogenated organosilicon compound (1b) with 1 equivalent of the diol compound (1a),
The asymmetric organosilicon compound (1) may be synthesized by contacting with one or more equivalents of different halogenated organosilicon compounds (1b). Moreover, after protecting one hydroxyl group of the diol compound (1a) with a so-called "protecting group" (eg, tosyl group, tetrahydropyran-2-yl group, methoxymethyl group, acetyl group, etc.), the other hydroxyl group is protected. A group of the halogenated organosilicon compound (1
It may be allowed to react with b), followed by a "deprotection reaction", and then with a different halogenated organosilicon compound (1b).

The solid catalyst component for olefin polymerization according to the present invention is obtained by bringing one or more of the above-mentioned organosilicon compounds into contact with a catalyst component comprising a magnesium compound, a titanium compound and a halogen-containing compound.
As the magnesium compound, the titanium compound and the halogen-containing compound, the same compounds as those in the conventionally known solid catalyst component using them can be used, but each of them will be further described below.

Magnesium compounds used in the present invention include magnesium halides such as magnesium chloride and magnesium bromide: alkoxy magnesium such as ethoxy magnesium and isopropoxy magnesium; magnesium laurate and magnesium stearate. Carboxylic acid salt of magnesium: alkyl magnesium such as butylethyl magnesium and the like can be exemplified. Further, these compounds may be a mixture of two or more kinds. Among them, magnesium halides or those forming magnesium halides at the time of catalyst preparation are preferable, and particularly preferable are those in which the above halogen is chlorine.

The titanium compound used in the present invention includes titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, titanium tetraiodide: trichloromethoxytitanium, trichloroethoxytitanium, trichloro-n.
-Trihalogenated alkoxy titanium such as butoxy titanium, trichloro-iso-butoxy titanium, and tribromoethoxy titanium: dichlorodimethoxy titanium, dichlorodiethoxy titanium, dichlorodi (n-butoxy) titanium,
Dihalogenated dialkoxy titanium such as dichlorodi (iso-butoxy) titanium and dibromodiethoxy titanium: trimethoxy titanium chloride, triethoxy titanium chloride, tri (n-butoxy) titanium chloride, tri (iso-butoxy) titanium chloride, triethoxy Trialkoxy titanium halides such as titanium bromide:
Examples thereof include titanium tetraalkoxides such as titanium tetramethoxide, titanium tetraethoxide, titanium tetra n-butoxide, and titanium tetra iso-butoxide. Further, these compounds may be a mixture of two or more kinds. Of these, tetravalent titanium compounds containing halogen are preferable, and titanium tetrachloride is particularly preferable.

The halogen-containing compound used in the present invention is a compound in which the halogen is fluorine, chlorine, bromine or iodine, preferably chlorine. The form of the compound used depends on the catalyst preparation method, but is usually titanium halide such as titanium tetrachloride or titanium tetrabromide, silicon halide such as silicon tetrachloride or silicon tetrabromide: phosphorus trichloride, phosphorus pentachloride, etc. Phosphorus halide: 2,2,2-trichloroethanol, 2,2,2-trifluoroethanol and other halogen-containing alcohols are typical examples. Depending on the preparation method, halogenated hydrocarbon, halogen molecule, hydrohalic acid (eg, HCl, HBr, HI) or the like can be used.

The method for preparing the solid catalyst component used in the present invention is not particularly limited, but the following method can be exemplified as a preferable method. That is, a method in which magnesium halide, titanium halide and the organosilicon compound are co-pulverized and then halogenated, magnesium halide alone or magnesium halide and a silicon compound or phosphorus compound are co-pulverized, and then the organosilicon In the coexistence of the compound, a titanium compound treatment, a further halogenation treatment, a magnesium carboxylate or alkoxy magnesium and a titanium compound, a halogenating agent and a method of heat-treating the organosilicon compound, magnesium halide is dissolved in an organic solvent or the like. In the presence of a titanium compound, during or after precipitation, the organosilicon compound is allowed to act, and further, when the alkylmagnesium and the halogenating agent are brought into contact with each other, the organosilicon compound or the titanium compound is added.

As the organoaluminum compound in the present invention, compounds represented by the following general formulas (2) to (4) are preferable. AlR ¹³ R ¹⁴ R ¹⁵ (2) R ¹⁶ R ¹⁷ Al-O-AlR ¹⁸ R ¹⁹ (3)

[0031]

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In equations (2), (3) and (4),
R ¹³ , R ¹⁴ and R ¹⁵ are each independently a hydrocarbon group having at most 12 carbon atoms, a halogen atom or a hydrogen atom, at least one of which is a carbon-hydrogen group, R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrocarbon group having at most 12 carbon atoms. R ²⁰ 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 triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum and trioctylaluminum, and further trialkylaluminums. Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride and alkyl aluminum halides such as diethyl aluminum chloride, diethyl aluminum bromide and ethyl aluminum sesquichloride.

Further, among the organoaluminum compounds represented by the formula (3), typical ones include alkyldialuminoxanes such as tetraethyldialuminoxane and tetrabutyldialuminoxane.

The formula (4) represents an aluminoxane, which is a polymer of an aluminum compound. R ²⁰ includes a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group, and preferably a methyl group or an ethyl group. The value of n is preferably 1 to 10.

Of these organoaluminum compounds,
Trialkylaluminums, alkylaluminum halides and alkylaluminoxanes are preferred, and trialkylaluminums are particularly preferred because they give favorable results.

An electron donating compound (ED) is optionally used in the preparation of the olefin polymerization catalyst according to the present invention. The electron donating compound (ED) is Organosilicon compounds having an alkoxy group, nitrogen-containing compounds, phosphorus-containing compounds and oxygen-containing compounds can be used.

Specific examples of the organosilicon compound having an alkoxy group include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane and triethylethoxysilane. , Ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di (t
(tert-butyl) dimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylethyldimethoxysilane, tert-butylpropyldimethoxysilane, tert-butylisopropyldimethoxysilane, tert-butylisopropyldiethoxysilane,
tert-butylbutyldimethoxysilane, tert-
Butylisobutyldimethoxysilane, tert-butyl (sec-butyl) dimethoxysilane, tert-butylamyldimethoxysilane, tert-butyltert
-Amyldimethoxysilane, tert-butylhexyldimethoxysilane, tert-butylheptyldimethoxysilane, tert-butyloctyldimethoxysilane, tert-butylnonyldimethoxysilane, ter
t-butyldecyldimethoxysilane, tert-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, tert-butyl (cyclopentyl) dimethoxysilane, tert-butyl (cyclohexyl) dimethoxysilane, tert-butylphenyldimethoxysilane, sec-butylisopropyldimethoxysilane,
sec-butyl tert-butyldimethoxysilane, s
ec-butyl tert-amyldimethoxysilane, se
c-butylthexyldimethoxysilane, sec-butylcyclopentyldimethoxysilane, sec-butylcyclohexyldimethoxysilane, sec-butylphenyldimethoxysilane, tert-amylisopropyldimethoxysilane, tert-amylcyclopentyldimethoxysilane, tert-amylcyclohexyldimethoxysilane, tert-amylphenyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylisopropyldimethoxysilane,
Cyclohexylphenyldimethoxysilane, bis (2-
Methylcyclopentyl) dimethoxysilane, bis (2,
3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenylisopropyldimethoxysilane, phenyltriethoxysilane, mesityltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltri Methoxysilane, tert-butyltrimethoxysilane, se
c-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornenyltrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, cyclopentyl ( tert-butoxy) dimethoxysilane, isopropyl (tert-butoxy)
Dimethoxysilane, tert-butyl (isobutoxy)
Examples thereof include dimethoxysilane, tert-butyl (tert-butoxy) dimethoxysilane, thexyltrimethoxysilane, thexyl (isopropoxy) dimethoxysilane, and thexyl (tert-butoxy) dimethoxysilane.

As the nitrogen-containing compound, specifically,
2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl-2,2,
2,6-substituted piperidines such as 6,6-tetramethylpiperidine, 2,5-diisopropylazolidine, N-
2,5-Substituted azolidine such as methyl-2,2,5,5-tetramethylazolidine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetraethylmethylene Substituted methylenediamines such as diamines, substituted imidazolines such as 1,3-dibenzylimidazolidine, and 1,3-dibenzyl-2-phenylimidazolidine are available.

Specific examples of the phosphorus-containing compound include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite and diethyl n.
-Phosphite esters such as butyl phosphite and diethyl phenyl phosphite.

As the oxygen-containing compound, specifically,
2,2,6,6-tetramethyltetrahydrofuran,
2,6-Substituted tetrahydrofurans such as 2,2,6,6-tetraethyltetrahydrofuran, 1,1-dimethoxy-2,3,4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, diphenyldimethoxymethane, etc. Acetal compounds, etc.

Of these, it is particularly preferable to use an organosilicon compound having an alkoxy group. Particularly preferred are tert-butylcyclopentyldimethoxysilane, tert-butylcyclohexyldimethoxysilane, tert-butylphenyldimethoxysilane and se.
c-Butylisopropyldimethoxysilane, sec-butyltert-butyldimethoxysilane, sec-butylthexyldimethoxysilane, dicyclopentyldimethoxysilane, cyclopentylisopropyldimethoxysilane, cyclopentylcyclohexyldimethoxysilane, cyclopentylphenyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexyl Isopropyldimethoxysilane, tert-butyltrimethoxysilane, sec-butyltrimethoxysilane, te
rt-butylisobutoxydimethoxysilane, tert
-Butyl tert-butoxydimethoxysilane, thexyltrimethoxysilane, thexyl (isopropoxy) dimethoxysilane, and thexyl (tert-butoxy) dimethoxysilane.

The olefin used for the polymerization is generally an olefin having at most 18 carbon atoms, and typical examples thereof include ethylene, propylene, 1-butene, 4-methyl-1-pentene and 1-. Examples include hexene and 1-octene. In carrying out the polymerization, these olefins may be homopolymerized, or two or more olefins may be copolymerized (for example, copolymerization of ethylene and propylene).

In the polymerization of olefin, the amount of the organic aluminum compound used in the polymerization system is preferably 10 ^{-4 to} 20 mmol / L. The molar ratio to the titanium atom in the solid catalyst component is usually 0.5 to 5000. It is preferably 2 to 2000, particularly preferably 10 to 100.
0. When this value is 0.5 or less, the polymerization activity is significantly reduced. Moreover, even if it is 5000 or more, the catalyst performance is not further improved.

The amount of the titanium-containing solid catalyst component used is usually 0.01 to 5, and preferably 0.01 to 1, in molar ratio with respect to the organoaluminum compound.

The amount of the electron-donating compound (ED) used is usually 0.001 to 5, preferably 0.01 to 1, in terms of molar ratio with respect to the organoaluminum compound.

In the olefin polymerization method according to the present invention,
It is preferable that the olefin is preliminarily polymerized by the olefin polymerization catalyst.

The olefin used in the preliminary polymerization may be the same as or different from the olefin used in the main polymerization described later, but it is preferable to use propylene. The reaction temperature during the prepolymerization is in the range of -20 to 100 ° C, preferably -20 to 60 ° C. In the prepolymerization, a molecular weight regulator such as hydrogen can be used.
The prepolymerization is 0.1 to 1 g of the olefin polymerization catalyst.
It is desirable to carry out so that 1000 g, preferably 0.3 to 500 g, and particularly preferably 1 to 200 g of polymer are produced.

In carrying out the polymerization, the solid catalyst component of the present invention and the organoaluminum compound may be separately introduced into the polymerization vessel or may be mixed in advance. The polymerization can be carried out in an inert solvent, in a liquid monomer (olefin) or in the gas phase. Further, a molecular weight modifier (generally hydrogen) may coexist. The polymerization temperature is -10.
˜180 ° C., preferably 20˜130 ° C.
In addition, with respect to the form of the polymerization reactor, the method of controlling the polymerization, the method of post-treatment, etc., there are no limitations specific to the present catalyst system, and known appropriate methods and conditions can be applied.

[0050]

The present invention will be described in more detail with reference to the following examples. The melt index (that is, MFR) in Examples and Comparative Examples is JIS K-6758.
Measured according to -1968.

Heptane index (hereinafter referred to as "H.
R. Represents the remaining amount in% by weight after the obtained polymer was extracted with boiling n-heptane for 6 hours. Weight average molecular weight (Mw) and number average molecular weight (M
n) was measured by gel permeation chromatography (hereinafter referred to as “GPC”) using orthodichlorobenzene as a solvent at a temperature of 140 ° C. The initial flexural modulus (FM) is measured according to ASTM-D-790-66.
It went according to. In each of the examples, the compounds (organic solvent, olefin, hydrogen, titanium compound, magnesium compound, etc.) used in the production and polymerization of the solid catalyst component are all substantially free of moisture. Further, the preparation and polymerization of the solid catalyst component were carried out in the absence of water and in an inert atmosphere such as nitrogen.

The names and the abbreviations of the additives and the electron-donating compounds (ED) in the solid catalyst components used as the organosilicon compounds or their substitutes used in Examples and Comparative Examples are shown below. It was 2-isopropyl-2
-Isopentyl-1,3-bis (trimethylsiloxy)
Propane (A), 2,2-diisobutyl-1,3-bis (trimethylsiloxy) propane (B), diisobutyl phthalate (C), ethyl 2-benzoylbenzoate (D), cyclopentyl tert-butyldimethoxysilane (E ), Thexylisopropoxydimethoxysilane (F).

Example 1 Synthesis of 2-isopropyl-2-isopentyl-1,3-bis (trimethylsiloxy) propane After replacing the inside of a 200 ml flask equipped with a stirrer and a dropping funnel with nitrogen, 50 ml of diethyl ether was added. It was EUROPEAN PATENTS APPLICA
5 g (26.6 mmol) of 2-isopropyl-2-isopentyl-1,3-dihydroxypropane synthesized by the method described in TION 487035, and 6.5 g (60 m of trimethylchlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd.)).
mol) was added to the flask. 0 this flask
Cooled to ° C. 50m of diethyl ether in the dropping funnel
l and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) 10.
1 g (100 mmol) of a mixed solution was added and added dropwise to the flask. After stirring for about 1 hour, 200 ml of water was added, and this solution was extracted with diethyl ether. After the ether layer was collected, it was distilled under reduced pressure to obtain 6.5 g of the target product.
I got The reaction yield was 74%.

Bp124-125 ° C./10 mmHg, G
C> 99.5%, ¹ H-NMR (400 MH, CDCl ₃ ); 3.37
7 (dd, 4H, OCH2). 1.690 (sept,
1H), 1.378 (sept, 1H), 1.176-
1.140 (m, 2H, CH2), 1.097-1.0
59 (m, 2H, CH2), 0.851 (d, 6H, C
H3), 0.835 (d, 6H, CH3), 0.040
4 (s, 18H, Si- CH3) ppm, 13 C-NMR (100 MH, CDCl 3); 63.7
54, 42.909, 32.476, 29.170, 2
8.055, 22.739, 17.842, -0.59
2 ppm, ²⁹ Si-NMR (CDCl ₃ ); 15.405 ppm,

Preparation of Solid Catalyst Component 1 Anhydrous magnesium chloride (commercial anhydrous magnesium chloride was dried at about 500 ° C. in a dry hydrogen chloride gas stream under a nitrogen atmosphere.
9.5 g (0.1 mol) of decane 50 ml and 2-
Add to a round bottom flask containing a mixture of 39 g (0.3 mol) of ethylhexyl alcohol, and add 2 at 130 ° C.
The mixture was heated and dissolved for an hour. 2.1 g of phthalic anhydride was added, and the mixture was further heated at 130 ° C. for 1 hour. The solution was cooled to room temperature, 20 ml was charged into a dropping funnel, and -2 over 30 minutes.
The solution was dropped into 80 ml of titanium tetrachloride at 0 ° C., and 11
Raised to 0 ° C. 2-isopropyl-2-isopentyl-1,3-bis (trimethylsiloxy) propane 1.6 as an organosilicon compound was added to 5 ml of hexane.
A container to which 6 g (0.005 mol) was added was slowly added dropwise. After completion of the dropwise addition, the reaction was performed at 110 ° C. for 2 hours.
After removing the supernatant, 80 ml of titanium tetrachloride was newly introduced and heated at 110 ° C. for 2 hours. Then, after washing 3 times with 100 ml of decane at 110 ° C, hexane 100 was added at room temperature.
Washed 3 times with ml. After separating the solid by filtration, hexane was distilled off under vacuum at room temperature to obtain a solid catalyst component. The titanium atom content of this catalyst component was 2.4% by weight.

Polymerization and Physical Properties of Polymer: In a stainless steel autoclave having an internal volume of 1.5 L, 4 mg of the solid catalyst component produced by the above method and 3 ml of a 1M hexane solution of triethylaluminum (3 mmo)
l), 9 ml (0.9 mmol) of a 0.1 M hexane solution of cyclopentyl tert-butyldimethoxysilane as an electron-donating compound (ED) was added, and then 34
0 g of propylene and 0.1 g of hydrogen were charged. The temperature of the autoclave was raised and the internal temperature was kept at 70 ° C. After one hour, the content gas was released to terminate the polymerization. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 2 The procedure of Example 1 was repeated, except that thexylisopropoxydimethylsilane was used as the electron-donating compound (ED) during the polymerization. The results are shown in Table 1.

Example 3 Synthesis of 2,2-diisobutyl-1,3-bis (trimethylsiloxy) propane Stirrer, 2 equipped with dropping funnel
After replacing the inside of the 00 ml flask with nitrogen, 50 ml of diethyl ether was added. EUROPIAN PATE
5 g (26.6 mmol) of 2,2-diisobutyl-1,3-dihydroxypropane synthesized by the method described in NT APPLICATION 361493, and 6.5 g of trimethylchlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd.).
(60 mmol) was added to the flask. The flask was cooled to 0 ° C. 50 ml of diethyl ether and triethylamine (Wako Pure Chemical Industries, Ltd.) in the dropping funnel
(Manufactured by Manufacture) 10.1 g (100 mmol) of a mixed solution was added, and the mixture was added dropwise to the flask. After stirring for about 1 hour, water 20
0 ml was added and the solution was extracted with diethyl ether. The ether layer was collected and then distilled under reduced pressure to obtain 6.0 g of the desired product. The reaction yield was 68%. bp120-123 ° C / 10 mmHg, GC> 99.5
%, ¹ H-NMR (400 MH, CDCl ₃ ); 3.307
(Dd, 4H, OCH2), 1.695 (sept, 2
H), 1.135 (d, 4H, CH2), 0.900
(D, 12H, CH3), 0.067 (s, 18H, S
i-CH3) ppm,

Preparation of solid catalyst component 2 As the organosilicon compound, 2,2-diisobutyl-1,
The procedure of Preparation 1 of the solid catalyst component described in Example 1 was repeated, except that 3-bis (trimethylsiloxy) propane was used.

Polymerization and Physical Properties of Polymer Produced The same procedure as in Example 1 was carried out. The results are shown in Table 1.

Example 4 The same procedure as in Example 1 was carried out, except that thexylisopropoxydimethylsilane was used as the electron-donating compound (ED) during the polymerization. The results are shown in Table 1.

Comparative Examples 1 to 4 Diisobutyl phthalate or 2-benzoylbenzoic acid was used as a substitute for the organosilicon compound, and the compounds shown in Table 1 were used as the electron donating compound (ED) added at the time of polymerization. The same procedure as in Example 1 was performed except that the above was performed. The results are shown in Table 1.

Example 5 Preparation of solid catalyst component 2 12.8 g (0.53 mol) of metallic magnesium, 88 ml (0.53 mol) of ethyl orthoformate and 0.5 ml of 1,2-dibromoethane as a reaction initiator were added and suspended. The suspension was kept at 55 ° C., and 5 ml of a solution prepared by dissolving 80 ml (0.80 mol) of n-butyl chloride in 100 ml of hexane was added and stirred for 50 minutes, and the rest was added dropwise over 80 minutes. The reaction was carried out at 70 ° C. for 4 hours with stirring to obtain a solid product. Washed six times with hexane at 50 ° C.

6.3 g of the solid product and 50 ml of decane
Was placed in a reactor at room temperature, a mixed solution of 2.0 ml of 2,2,2-trichloroethanol and 11 ml of decane was added dropwise over 30 minutes, and after completion, the mixture was stirred at 80 ° C. for 1 hour. The solid was separated by filtration, washed with 100 ml of hexane four times, and then with toluene 100
Washed twice with ml.

40 ml of toluene and 60 ml of titanium tetrachloride were added to the solid and the temperature was raised to 90 ° C. to obtain 2.49 g of 2-isopropyl-2-isopentyl-1,3-bis (trimethylsiloxy) propane as an organosilicon compound (0.4. 00
(75 mol) and toluene (5 ml) were added dropwise over 5 minutes, and the mixture was stirred at 120 ° C for 2 hours. Then, the solid
It was filtered off at ℃ and washed twice with toluene at 90 ℃. Further, 40 ml of toluene and 60 ml of titanium tetrachloride were added to the solid, and the mixture was stirred at 120 ° C. for 2 hours. The obtained solid was separated by filtration at 110 ° C. and washed seven times with 100 ml of hexane at room temperature. After separating this solid by filtration, hexane was distilled off under vacuum at room temperature to obtain a solid catalyst component. The titanium atom content of this catalyst component was 2.5% by weight.

Polymerization and Physical Properties of Polymers Polymerization was evaluated by the polymerization method described in Example 1 except that 4 mg of the solid catalyst component obtained by the above method was used.
The results are shown in Table 1.

Examples 6 to 8 and Comparative Examples 5 to 8 are shown in Table 1 as an additive and an electron donating compound (ED) in the solid catalyst component used as an alternative to the organosilicon compound. The same procedure as in Example 5 was carried out except that the above compound was used. The results are shown in Table 1.

[0068]

[Table 1]

[0069]

EFFECT OF THE INVENTION It is possible to provide an olefin polymer exhibiting high activity and high stereospecificity and having a wide molecular weight distribution.

[Brief description of the drawings]

FIG. 1 ¹ H-NMR of an organosilicon compound obtained in an example.
Fig.

FIG. 2 ¹³ C-NMR of the organosilicon compound obtained in the example.
Fig.

FIG. 3: ²⁹ Si-NM of organosilicon compounds obtained in the examples
R diagram.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Shintaro Inazawa Oita City, Oita Pref.

Claims (8)

[Claims] 1. An organosilicon compound represented by the following general formula (1): Embedded image (In the formula, R ¹ and R ² are each independently a branched saturated hydrocarbon group having 3 to 20 carbon atoms or a cyclic saturated hydrocarbon group, and R ³ to R ⁸ are independently hydrogen. Alternatively, it is a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain an atom of halogen, oxygen, nitrogen, phosphorus or sulfur, and R ⁹ to R ¹² are independently hydrogen or hydrogen. It is a hydrocarbon group having 1 to 10 carbon atoms.) 2. Organosilicon according to claim 1, wherein R ¹ and R ^{2 in} the general formula (1) are each independently a branched saturated hydrocarbon group having 3 to 6 carbon atoms. Compound. 3. The organosilicon compound according to claim 1, wherein R ⁹ to R ^{12 in} the general formula (1) are each hydrogen. 4. A solid catalyst component for olefin polymerization, which comprises a magnesium compound, a titanium compound, a halogen-containing compound and the organosilicon compound according to any one of claims 1 to 3. 5. A method for producing a solid catalyst component for olefin polymerization, which comprises bringing the organosilicon compound according to claim 1 into contact with a catalyst component comprising a magnesium compound, a titanium compound and a halogen-containing compound. Method. 6. An olefin polymerization catalyst comprising the solid catalyst component for olefin polymerization according to claim 4 and an organoaluminum compound. 7. The catalyst for olefin polymerization according to claim 6, further comprising an electron donating compound other than the organosilicon compound. 8. At least one olefin.
Or a method for producing an olefin polymer, which is characterized in that the olefin polymerization catalyst according to any one of 7) is present.