JP2732478B2 - Olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an olefin polymerization method capable of obtaining a high-molecular-weight olefin polymer having excellent particle properties and uniformity in particle size in a high yield.

Technical background of the invention and its problems If a olefin is polymerized or copolymerized using a TiCl ₃ -based catalyst, a polymer having a high molecular weight can be obtained. There was a problem that an ash process was required.

In addition, when polymerizing or copolymerizing an olefin by using a highly active catalyst system, a polymer having a high molecular weight can be obtained by lowering the polymerization temperature. There was a problem that it would.

By the way, many proposals have already been made on a method for producing a solid titanium catalyst component containing magnesium, titanium, a halogen and an electron donor as essential components, and such a solid catalyst component is polymerized with an α-olefin having 3 or more carbon atoms. It is also known that a polymer having high stereoregularity can be produced in a high yield by using together with an organoaluminum compound catalyst component and an organosilicon compound catalyst component.

However, when an α-olefin having 3 or more carbon atoms is polymerized or copolymerized using the above-mentioned olefin polymerization catalyst proposed so far, a high molecular weight and excellent stereoregularity are obtained. There was a problem that it was difficult to obtain an α-olefin polymer.

The present inventors have intensively studied to obtain a high molecular weight α-olefin polymer having 3 or more carbon atoms while maintaining excellent polymerization activity of the catalyst while maintaining excellent stereoregularity. If an α-olefin having 3 or more carbon atoms is homopolymerized or copolymerized using an olefin polymerization catalyst comprising an olefin polymerization catalyst and an organoaluminum compound and a specific organosilicon compound catalyst component, excellent stereoregularity and polymerization of the catalyst can be obtained. The inventors have found that an α-olefin polymer having a high molecular weight can be obtained while maintaining the activity, and have completed the present invention.

An object of the present invention is to solve the problems associated with the prior art as described above, and it is an object of the present invention to provide a high-molecular-weight and highly stereoregular α-olefin (co) polymer having 3 or more carbon atoms. It is an object of the present invention to provide a method for polymerizing an olefin so that a coalesced product can be produced in a high yield.

In addition, the present invention, while maintaining a high polymerization activity of the catalyst,
It is an object of the present invention to provide an olefin polymerization method capable of obtaining an α-olefin (co) polymer having excellent particle size distribution, particle properties, bulk specific gravity, and the like.

SUMMARY OF THE INVENTION The olefin polymerization method according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component, and [C] general formula _{^{[I] (R 1 3 C}} ) 2 Si (OR 2) 2 ... [I] ( wherein, R ^1, R ² is a hydrocarbon group.) are formed from an organic silicon compound catalyst component represented by Olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst
It is characterized by producing an olefin polymer of l / g or more.

In the polymerization method according to the present invention, as described above, the catalyst formed from the solid titanium catalyst component [A], the organoaluminum compound catalyst component [B], and the specific organosilicon compound catalyst component [C] has 3 carbon atoms. Since the above α-olefin is polymerized, an olefin polymer having a high molecular weight, excellent uniformity in particle shape and particle size, and excellent stereoregularity can be produced in high yield.

The prepolymerized catalyst according to the present invention comprises: [A] a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, [B] an organoaluminum compound catalyst component, and [C] a general formula [I]. ^{_{(R 1 3 C) 2 Si}} (OR 2) 2 ··· [I] ( wherein, R ^1, R ² is a hydrocarbon group.) the presence of a catalyst consisting of an organic silicon compound catalyst component represented by Below, it is characterized by being obtained by prepolymerizing an olefin.

By performing the main polymerization using the prepolymerization catalyst according to the present invention, a powder polymer having a large bulk density can be obtained, and the particle size of the polymer becomes uniform, and when the slurry polymerization is performed, the polymer is obtained. Is excellent in properties of the slurry containing.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the olefin polymerization method according to the present invention and the olefin polymerization catalyst used at this time will be specifically described.

In the present invention, the term polymerization may be used in a sense that encompasses not only homopolymerization but also copolymerization,
In addition, the term polymer is sometimes used to mean not only a homopolymer but also a copolymer.

In the olefin polymerization method according to the present invention, olefin polymerization or copolymerization is carried out in the presence of the following olefin polymerization catalyst.

The olefin polymerization catalyst according to the present invention is formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and a specific organosilicon compound catalyst component [C].

FIG. 1 shows an example of a flowchart of a method for preparing a catalyst used in the present invention.

The solid titanium catalyst component [A] used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen and an electron donor as essential components.

Such a solid titanium catalyst component [A] is, for example,
It is prepared by contacting a magnesium compound, a titanium compound and an electron donor as described below.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component [A] includes, for example, Ti (OR) _g X
_4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti ( _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On Monohalogenated trialkoxy titanium such as -C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H) ₉ ) Tetraalkoxy titanium such as ₄ and the like.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of the magnesium compound having such a reducing property include dimethylmagnesium,
Diethyl magnesium, dipropyl magnesium, dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl Magnesium halide and the like can be mentioned. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of the non-reducing magnesium compound include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyoxymagne such as phenoxymagnesium and dimethylphenoxymagnesium Um; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

In the present invention, the magnesium compound is, in addition to the magnesium compound having a reducing property and the magnesium compound having no reducing property, a complex compound of the magnesium compound and another metal, a double compound or another metal compound. May be used. Further, a mixture of two or more of the above compounds may be used.

In the present invention, among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

In the present invention, when preparing the solid titanium catalyst component [A], it is preferable to use an electron donor. Specific examples of such an electron donor include alcohols, phenols, ketones, aldehydes, and the like. Examples thereof include oxygen-containing electron donors such as esters, ethers, acid amides and acid anhydrides of carboxylic acids, organic acids and inorganic acids, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates.

More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, 2
Alcohols having 1 to 18 carbon atoms such as ethylhexanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropylbenzyl alcohol; phenol;
Cresol, xylenol, ethylphenol, propylphenol, cumylphenol, nonylphenol,
C6 to C25 phenols which may have an alkyl group such as naphthol; C3 to C15 ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone and benzophenone; acetaldehyde, propionaldehyde, octylaldehyde Aldehydes having 2 to 15 carbon atoms such as benzene, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, stearic acid Ethyl, methyl chloroacetate,
Ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, dibutyl maleate, diethyl butylmalonate, diethyl dibutylmalonate, ethyl cyclohexanecarboxylate, diethyl 1,2-cyclohexanedicarboxylate, di-2-1,2-cyclohexanedicarboxylate Ethylhexyl, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate , Methyl anisate, ethyl anisate, ethyl ethoxybenzoate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone,
Coumarin, phthalide, organic acid esters having 2 to 30 carbon atoms, including esters described below, which are desirably contained in titanium catalyst components such as ethylene carbonate; inorganic acid esters such as ethyl silicate and butyl silicate; acetyl chloride; Acid halides having 2 to 15 carbon atoms such as benzoyl chloride, toluic acid chloride, anisic acid chloride and phthalic acid dichloride; carbons such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether Ethers of formulas 2 to 20; acid amides such as acetic acid amide, benzoic acid amide and toluic acid amide; acid anhydrides such as benzoic anhydride and phthalic anhydride; methylamine, ethylamine, doethylamine, tributylamine, piperidine, Tribenzylamido , Amines, pyridine, picoline, tetramethylethylenediamine;
Nitriles such as acetonitrile, benzonitrile, and trinitrile; and the like.

Further, as the electron donor, an organosilicon compound represented by the following general formula [I] can be used.

R _n Si (OR ′) _4-n [I] wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specific examples of the organosilicon compound represented by the above general formula [I] include trimethylmethoxysilane,
Trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-
Butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis-tolyldimethoxysilane, bism-tolyldimethoxysilane, bis-p-tolyldimethoxysilane,
Bis-p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n -Propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-
Chloropropyltrimethoxysilane, methyltoluethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-amino Propyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxy Silane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxy (allyloxy) silane, vinyl tris (β-methoxyethoxysilane) Vinyltriacetoxysilane, dimethyltetraethoxydicycloxane, dicyclohexylmethyldimethoxysilane, cyclopentylmethyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane, di-n-propyldiethoxysilane, di-t-butyldiethoxysilane And cyclopentyltriethoxysilane.

Among them, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane Preferred are silane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, and diphenyldiethoxysilane.

Two or more of these electron donors can be used.

The electron donor that is desirably contained in the titanium catalyst component is an ester, and more preferably an electron donor represented by the general formula: (Where R ¹ is a substituted or unsubstituted hydrocarbon group, R ² ,
R ⁵ and R ⁶ are hydrogen or a substituted or unsubstituted hydrocarbon group, and R ³ and R ⁴ are hydrogen or a substituted or unsubstituted hydrocarbon group, and preferably at least one of them is a substituted or unsubstituted hydrocarbon group. It is a hydrogen group. R ³ and R ⁴ may be connected to each other. The substituted hydrocarbon group for R ^{1 to} R ⁵ includes a hetero atom such as N, O, or S.
-O-C, COOR, COOH, OH, SO 3 H, -C-N-C-, NH
_It has a group such as ₂ . ) Can be exemplified.

Particularly preferred among these are diesters of dicarboxylic acids in which at least one of R ¹ and R ² is an alkyl group having 2 or more carbon atoms.

Specific examples of the polycarboxylic acid ester include diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, dibutyl methyl malonate, diethyl malonate, diethyl ethyl malonate, and diethyl isopropyl malonate. Diethyl butylmalonate, Diethyl phenylmalonate, Diethyl diethylmalonate, Diethyl allylmalonate Diethyldiisobutylmalonate, Dinormal butylmalonate Diethylmaleate Dimethylmaleate Monooctyl, Dioctylmaleate, Dibutylmaleate, Butylmaleate Dibutyl, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, dibutyl itaconate, cyto Aliphatic polycarboxylic esters such as dioctyl laconate and dimethyl citraconic acid, 1,2
Alicyclic polycarboxylic acid esters such as diethyl cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadicate, monoethyl phthalate, dimethyl phthalate, methylethyl phthalate, monophthalate Isobutyl,
Mono-n-butyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, ethyl n-butyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, di-isobutyl phthalate, di-n-heptyl phthalate, Di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, triethyl trimellitate, trimellitic acid Examples include aromatic polycarboxylic acid esters such as dibutyl and heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

As the polyhydric hydroxy compound ester, specifically, 1,2-diacetoxybenzene, 1-methyl-2,3-
Examples include diacetoxybenzene, 2,3-diacetoxynaphthalene, ethylene glycol dipivalate, butanediol pivalate, and the like.

Specific examples of the hydroxy-substituted carboxylic acid include benzoylethyl salicylate, acetylisobutyl salicylate, and acetylmethyl salicylate.

Examples of the polyvalent carboxylic acid ester that can be supported on the titanium catalyst component include, in addition to the above compounds, diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, sebacine Esters of long-chain dicarboxylic acids such as di-n-octyl acid and di-2-ethylhexyl sebacate can be used.

Among these polyfunctional esters, compounds having a skeleton of the above-mentioned general formula are preferred, and more preferred are esters of phthalic acid, maleic acid, substituted malonic acid and the like with alcohols having 2 or more carbon atoms, and especially phthalic acid. Diesters of acids and alcohols having 2 or more carbon atoms are preferred.

Another electron donor component that can be supported on the titanium catalyst component is RCOOR ′ (R and R ′ are hydrocarbyl groups which may have a substituent, and at least one of them is a branched (aliphatic) ) Or a ring-containing chain group).
Specifically, as R and _{R ', (CH 3) 2} CH-, C 2 H 5 CH (CH 3) -, (CH 3) 2 CHCH 2 -,
_{(CH 3) 3 C-, C} 2 H 5 CH, (CH 3) CH 2 -, And the like. If either R or R 'is the above group, the other may be the above group, or may be another group such as a linear or cyclic group.

Specifically, various monoesters such as dimethylacetic acid, trimethylacetic acid, α-methylbutyric acid, β-methylbutyric acid, methacrylic acid and benzoylacetic acid, and various monocarboxylic acid esters of alcohols such as isopropanol, isobutyl alcohol and tert-butyl alcohol Can be exemplified.

Carbonic esters can also be selected as electron donors. Specifically, diethyl carbonate, ethylene carbonate, diisopropyl carbonate, phenylethyl carbonate, diphenyl carbonate and the like can be exemplified.

When supporting these electron donors, it is not always necessary to use them as starting materials, and it is also possible to use compounds that can be changed to these during the preparation of the titanium catalyst component.

In the titanium catalyst component, other electron donors may coexist, but if they coexist in an excessively large amount, they have an adverse effect, so they should be suppressed to a small amount.

In the present invention, the solid titanium catalyst component [A] can be produced by bringing the above-mentioned magnesium compound (or metallic magnesium) into contact with an electron donor and a titanium compound. In order to produce the solid titanium catalyst component [A], a known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and an electron donor can be employed. The above components may be brought into contact with each other in the presence of another reaction reagent such as silicon, phosphorus, and aluminum.

The method for producing the solid titanium catalyst component (A) will be briefly described below with several examples.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. This reaction may be performed in the presence of a grinding aid or the like. Further, when reacting as described above, the solid compound may be pulverized.

(2) a liquid magnesium compound having no reducing property;
A method in which a liquid titanium compound is reacted in the presence of an electron donor to precipitate a solid titanium complex.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) A method in which an electron donor and a titanium compound are further reacted with the reaction product obtained in (1) or (2).

(5) A solid compound obtained by pulverizing a magnesium compound or a complex compound comprising a magnesium compound and an electron donor in the presence of a titanium compound is treated with any of a halogen, a halogen compound and an aromatic hydrocarbon. how to. In this method, a magnesium compound or a complex compound comprising a magnesium compound and an electron donor may be ground in the presence of a grinding aid or the like. Alternatively, a magnesium compound or a complex compound composed of a magnesium compound and an electron donor may be ground in the presence of a titanium compound, pre-treated with a reaction aid, and then treated with a halogen or the like. In addition, examples of the reaction assistant include an organic aluminum compound and a halogen-containing silicon compound.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(7) A method of contacting a reaction product of a metal oxide, dihydrocarbylmagnesium and a halogen-containing alcohol with an electron donor and a titanium compound.

(8) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

Among the methods for preparing the solid titanium catalyst component [A] described in the above (1) to (8), a method using a liquid titanium halide during the catalyst preparation, a method using a titanium compound, or a method using a titanium compound In this case, a method using a halogenated hydrocarbon is preferable.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is about 0.01 to 5 per mole of the magnesium compound. Moles, preferably 0.05 to 2 moles, and the titanium compound is used in an amount of about 0.01 to 500 moles, preferably 0.05 to 300 moles.

The solid titanium catalyst component [A] thus obtained
Contains magnesium, titanium, halogen and an electron donor as essential components.

In this solid titanium catalyst component [A], halogen /
The titanium (atomic ratio) is about 4-200, preferably about 5-100, and the electron donor / titanium (molar ratio) is about 0.1-1.
0, preferably about 0.2 to about 6, and magnesium / titanium (atomic ratio) of about 1 to 100, preferably about 2 to 50.

This solid titanium catalyst component [A] contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 50 m ² / g or more, preferably about 60 to 1000 m ² / g, More preferably about 100
~800m is a ² / g. The solid titanium catalyst component [A] does not substantially change its composition by washing with hexane since the above components are integrated to form a catalyst component.

Such a solid titanium catalyst component [A] may be used alone, or may be used after being diluted with an inorganic compound or an organic compound such as a silicon compound, an aluminum compound, or a polyolefin. In addition, when a diluent is used, even if it is smaller than the above-mentioned specific surface area, it shows high catalytic activity.

For a method of preparing such a highly active titanium catalyst component, see, for example, JP-A-50-108385 and JP-A-50-126590.
No. 51-20297, No. 51-28189, No. 51
No. 64586, No. 51-92885, No. 51-136625, No. 52-87489, No. 52-100596, No. 52-1
No. 47688, No. 52-104593, No. 53-2580, No. 53-40093, No. 53-40094, No. 53-43
No. 094, No. 55-135102, No. 55-135103, No. 55-152710, No. 56-811, No. 56-119
No. 08, No. 56-18606, No. 58-83006,
JP-A-58-138705, JP-A-58-138706, JP-A-58-138707
JP-A-58-138708, JP-A-58-138709,
Nos. 58-138710, 58-138715, 60-23404
No. 61-21109, No. 61-37802, No. 61
And -37803.

As the organoaluminum compound catalyst component (B), a compound having at least one aluminum-carbon bond in the molecule can be used. Examples of such a compound include: (i) a compound represented by the general formula R ¹ _m Al (OR ² ) _{n Hp} X _q (wherein R ¹ and R ² each usually have 1 to 15 carbon atoms, preferably 1 to X is a hydrocarbon group containing four, and may be the same or different from each other, and X represents a halogen atom;
<M ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0 ≦
A number of q <3, moreover organic aluminum compound represented by a is) m + n + p + q = 3, a (ii) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, K, R ¹ Are the same as those described above), and a complex alkylated product of a Group 1 metal and aluminum.

As the organoaluminum compound represented by the formula (i), the following compounds can be exemplified.

General formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.5
≦ m ≦ 3), a general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as above; X is a halogen, m is preferably 0 <m <3); and a general formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above; m is preferably 2 ≦ m <3); and a general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² is the same as above, X is halogen, 0 <
m ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

More specifically, the aluminum compound represented by (i) includes trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; dialkylaluminums such as diethylaluminum ethoxide and dibutylaluminum butoxide. Alkyl aluminum sesquialkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum sesquibutoxide; partially alkoxylated alkyl aluminum having an average composition represented by R ¹ _2.5 Al (OR ² ) _0.5 ; diethyl aluminum chloride; Dialkylaluminum halides such as dibutylaluminum chloride and diethylaluminum bromide; Alkyl aluminum sesquihalides such as chloridochloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated alkyl aluminum such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; diethyl aluminum Dialkylaluminum hydrides such as hydride and dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Partly such as aluminum ethoxy bromide Alkoxy reduction and halogenated alkylaluminum can be exemplified.

Examples of the compound similar to (i) include an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Such compounds include, for example, (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ , (C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ , Methyl aluminoxane and the like can be mentioned.

Examples of the compound represented by the formula (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Among these, it is particularly preferable to use trialkylaluminum or alkylaluminum to which two or more aluminum compounds described above are bonded.

The organosilicon compound catalyst component [C], the general formula _{^{[I] (R 1 3 C}} ) 2 Si (OR 2) 2 ... [I] ( wherein, R ¹ is a hydrocarbon group, preferably 1 to carbon atoms R2 is preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrocarbon group having 1 to 3 carbon atoms, particularly preferably a hydrocarbon group having 1 to ² carbon atoms. Preferably, six R ¹ and two R ² may be the same or different.) An organosilicon compound represented by the formula:

As such an organosilicon compound, specifically,
Di-t-butyldimethoxysilane, di-t-butyldiethoxysilane, di-t-butylmethoxyethoxysilane, di-t
-Amyldimethoxysilane, t-butyl-t-amyldimethoxysilane, bis (1,1-diethylpropyl) dimethoxysilane and the like are used.

In the polymerization method of the present invention, the olefin is polymerized in the presence of the above-mentioned catalyst, and it is preferable to perform the following pre-polymerization before performing such polymerization (main polymerization).

By performing such preliminary polymerization, a powder polymer having a large bulk density can be obtained. In addition, when the preliminary polymerization is performed, the particle size becomes uniform, and in the case of slurry polymerization, the properties of the slurry become excellent. Therefore, according to the polymerization method of the present invention, the obtained polymer powder or polymer slurry can be easily handled.

In the preliminary polymerization, the solid titanium catalyst component [A] is usually used in combination with at least a part of the organoaluminum compound catalyst component [B]. At this time, an organosilicon compound can be allowed to coexist, and such an organosilicon compound is not limited to the compound used as the organosilicon compound catalyst component [C]. When the compound used as such a catalyst component [C] is used, a part or all of such an organosilicon compound may be allowed to coexist.

In the prepolymerization, a catalyst having a considerably higher concentration than the catalyst concentration in the system in the main polymerization can be used.

The concentration of the solid titanium catalyst component [A] in the prepolymerization is usually about 0.01 to 200 mmol, preferably about 0.05 mol, in terms of titanium atom, per inert hydrocarbon medium described later.
Desirably, it is in the range of ~ 100 mmol.

The amount of the organoaluminum catalyst component [B] may be an amount such that 0.1 to 500 g, preferably 0.3 to 300 g of a polymer is produced per 1 g of the solid titanium catalyst component [A]. About 0.1 to 1 per mole of titanium atom
Desirably, the amount is 00 moles, preferably about 0.5-50 moles.

The prepolymerization is preferably carried out under mild conditions by adding an olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Among these inert hydrocarbon media, 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.

When such an olefin is used for prepolymerization, a highly crystalline polymer can be obtained from an α-olefin having 2 to 10, preferably 3 to 10 carbon atoms.

In the present invention, a liquid α is used in place of part or all of the inert hydrocarbon medium used in the preliminary polymerization.
-Olefins can be used.

The reaction temperature for the prepolymerization may be any temperature at which the resulting prepolymer does not substantially dissolve in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about -20 to + 8 ° C.
The temperature is desirably in the range of 0 ° C, more preferably 0 to + 40 ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer in an amount such that the intrinsic viscosity [η] of the polymer obtained by the prepolymerization measured in decalin at 135 ° C. is about 1 dl / g or more, preferably about 2 to 20 dl / g.

As described above, the pre-polymerization was conducted using 1 g of titanium catalyst component [A]
Desirably, about 0.1 to 1000 g, preferably about 0.3 to 500 g, of polymer is produced. If the prepolymerization amount is too large, the production efficiency of the olefin polymer in the main polymerization may decrease.

The prepolymerization can be performed in a batch system or a continuous system.

After or without pre-polymerization as described above, it is formed from the aforementioned solid titanium catalyst component [A], organoaluminum catalyst component [B] and organosilicon compound catalyst component [C]. The main polymerization of olefin is carried out in the presence of an olefin polymerization catalyst.

Examples of the olefin that can be used in the main polymerization include α-olefins having 3 or more carbon atoms, such as propylene, 1-butene, 4-methyl-1-pentene, and 1-octene. In the polymerization method of the present invention, these olefins can be used alone or in combination. Of these olefins, it is preferable to perform homopolymerization using propylene or 1-butene, or to copolymerize using a mixed olefin containing propylene or 1-butene as a main component. When such a mixed olefin is used, the content of propylene or 1-butene as the main component is usually 50%.
It is preferably at least 70 mol%, preferably at least 70 mol%.

Further, in the present invention, the above-mentioned α-olefin having 3 or more carbon atoms and ethylene can be copolymerized. At this time, the α-olefin having 3 or more carbon atoms is desirably present in the obtained copolymer in an amount of 60 mol%, preferably 80 mol% or more.

In the polymerization method of the present invention, a polymer having an [η] of 6 dl / g or more, preferably 8 dl / g or more, and a high stereoregularity index is obtained by polymerizing an α-olefin having 3 or more carbon atoms. Can be produced with high catalyst efficiency.

When performing homopolymerization or copolymerization of these olefins, a compound having a polyunsaturated bond such as a conjugated diene or a non-conjugated diene can be used as a polymerization raw material.

In the polymerization method of the present invention, the main polymerization of the olefin,
Usually, the reaction is performed in a gas phase or a liquid phase.

When the main polymerization takes a reaction mode of slurry polymerization, the above-mentioned inert hydrocarbon can be used as the reaction solvent, and an olefin liquid at the reaction temperature can be used.

In the polymerization method of the present invention, the titanium catalyst component [A] is used in an amount of usually about 0.005 to 0.5 mmol, preferably about 0.01 to 0.5 mmol, in terms of Ti atom per polymerization volume. The metal component in the organoaluminum compound catalyst component [B] is usually about 1 to 2000 per mole of the titanium atom in the titanium catalyst component [A] in the polymerization system. Moles, preferably about 5-500 moles. Further, the organosilicon compound catalyst component [C] is usually about 0.001 to 10 moles in terms of Si atoms in the organosilicon compound catalyst component [C] per mole of metal atom in the organoaluminum compound catalyst component [B]. It is preferably used in an amount of about 0.01 to 2 mol, particularly preferably about 0.05 to 1 mol.

In the polymerization method of the present invention, the titanium catalyst component [A], the organoaluminum compound catalyst component [B], and the organosilicon compound catalyst component [C] may be brought into contact at the time of the main polymerization. You may contact at the time of superposition | polymerization. In the contact before the main polymerization, only arbitrary two members may be freely selected and contacted, or a part of each component may be contacted with two or three members.

In the polymerization method of the present invention, before the polymerization, the respective contact components may be brought into contact with each other in an inert gas atmosphere, or the respective catalyst components may be brought into contact with the olefin atmosphere.

When the organic aluminum compound catalyst component [B] and a part of the organosilicon compound catalyst component [C] are used in the prepolymerization, the catalyst used in the prepolymerization is used together with the remaining catalyst. In this case, the catalyst used in the prepolymerization may contain a prepolymerization product.

In the present invention, the polymerization temperature of the olefin is usually about
The pressure is usually set at normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² , at ²⁰ to 200 ° C., preferably about 50 to 180 ° C. In the polymerization method of the present invention, the polymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be carried out in two or more stages by changing the reaction conditions.

The olefin polymer thus obtained may be any of a homopolymer, a random copolymer and a block copolymer.

In the present invention, since the yield of the polymer having stereoregularity per unit amount of the solid catalyst component is high, the catalyst residue in the polymer,
In particular, the halogen content can be relatively reduced. Therefore, the operation of removing the catalyst in the polymer can be omitted, and rusting of the metal mold can be effectively prevented when the formed article is formed using the produced olefin polymer.

The olefin polymer obtained by the polymerization method of the present invention has an average particle diameter of 150 to 5000 μm, preferably 200 to
3000 μm, and the amount of finely divided polymer particles of 100 μm or less is preferably 5% by weight or less, more preferably 1% by weight.
It is as follows. Further, the geometric standard deviation σ _g calculated based on the particle size distribution determined by sieving the produced polymer particles is 2.0 or less, preferably 1.5 or less, particularly preferably
1.3 or less. Thus, since the olefin polymer obtained by the polymerization method of the present invention is a granular powder having a narrow particle size distribution and a uniform particle diameter, an operation of pelletizing the obtained olefin polymer is required. It can be omitted.

Effect of the Invention The olefin polymerization method of the present invention uses a specific polymerization catalyst formed from a solid titanium catalyst component [A], an organoaluminum compound catalyst component [B], and a specific organosilicon compound catalyst component [C]. Since the polymerization of α-olefins having 3 or more carbon atoms is performed, particularly high-molecular-weight olefin polymers can be produced in high yield.

The olefin polymer obtained by the polymerization method of the present invention has a high stereoregularity and a narrow particle size distribution,
Moreover, it has a uniform particle size and a high bulk density.

Furthermore, according to the polymerization method of the present invention, an olefin polymer having the above-mentioned excellent properties can be efficiently produced, and the catalyst activity does not decrease with the lapse of polymerization time.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 [Preparation of solid titanium catalyst component [A]] Anhydrous magnesium chloride (7.14 g, 75 mmol), decane 3
7.5 ml and 35.1 ml of 2-ethylhexyl alcohol (225
(Mmol) at 130 ° C for 2 hours to obtain a homogeneous solution. Then, 1.67 g of phthalic anhydride (1
(1.3 mmol), and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride in the above homogeneous solution.

After cooling the thus obtained homogeneous solution to room temperature, 200 ml (1.8 mol) of titanium tetrachloride kept at -20 ° C
The whole amount was dropped over 1 hour. After the dropwise addition, the temperature of the obtained solution was raised to 110 ° C. over 4 hours, and when the temperature reached 110 ° C., 5.03 ml (18.8 mmol) of diisobutyl phthalate was added.

Stir at the above temperature for another 2 hours. After completion of the reaction for 2 hours, a solid portion was collected by filtration under hot conditions, and the solid portion was collected for 275 m.
After re-suspending with 1 l of TiCl ₄ , a heating reaction was performed again at 110 ° C. for 2 hours.

After completion of the reaction, a solid portion was collected again by hot filtration, and
Washed with decane and hexane. This washing,
The process was performed until no titanium compound was detected in the washing solution.

The solid titanium catalyst component [A] synthesized as described above was obtained as a hexane slurry. A part of the catalyst was collected and dried. When the dried product was analyzed, the composition of the solid titanium catalyst component [A] obtained as described above was as follows: titanium 2.5% by weight, chlorine 58% by weight, magnesium 18% by weight, and diisobutyl phthalate 13.8%.
% By weight.

[Preliminary polymerization] 200 ml of purified hexane was placed in a 400-ml glass reactor purged with nitrogen, and 20 mmol of triethyl aluminum was added.
After adding 4 mmol of di-t-butyldimethoxysilane and 2 mmol of the titanium catalyst component [A] in terms of titanium atom, propylene was supplied for 1 hour at a rate of 5.9 Nl / hour, and per 1 g of the Ti catalyst component [A], 2.8 g of propylene were polymerized.

After completion of the prepolymerization, the liquid part was removed by filtration, and the separated solid part was dispersed again in decane.

[Main Polymerization] An autoclave having an internal volume of 2 was charged with 750 ml of purified hexane, and 0.75 mmol of trimethylaluminum and 0.7 g of di-t-butyldimethoxysilane were added in a propylene atmosphere at room temperature.
075 mmol and the prepolymerized product of the catalyst component [A] were added in an amount of 0.015 mmol in terms of titanium atom (equivalent to 4.46 mg in terms of the catalyst component [A]). Then 70
C., and propylene polymerization was performed for 2 hours. The pressure during the polymerization was kept at 7 kg / cm ² G.

After completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white granular polymer and a liquid phase. Boiling after drying n-
Table 1 shows the residual extraction ratio with heptane, intrinsic viscosity [η], apparent bulk specific gravity, polymerization activity, II of all polymers, average particle size, and geometric standard deviation of particle size distribution.

Examples 2-3 In the polymerization of Example 1, the polymerization temperature was 40 ° C and 90 ° C.
The polymerization of polypropylene was carried out in the same manner as in Example 1 except that the polymerization was changed to.

 Table 1 shows the results.

Example 4 In the prepolymerization of Example 1, the amount of triethylaluminum was changed from 20 mmol to 6 mmol and di-t-
Polypropylene was polymerized in the same manner as in Example 1 except that butyldimethoxysilane was not added.

 Table 1 shows the results.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of a catalyst preparation method in the olefin polymerization method according to the present invention.

Claims (8)

(57) [Claims] 1. A [A] magnesium, the solid titanium catalyst component containing titanium, a halogen and an electron donor as essential ingredients, [B] an organoaluminum compound catalyst component, and [C] the general formula [I] (R ¹ ₃ C) ₂ Si (OR ² ) ₂ ... [I] wherein R ¹ and R ² are hydrocarbon groups. In the presence, the olefin is polymerized or copolymerized and [η] is 6dl /
A method for polymerizing olefins, which comprises producing an olefin polymer having a weight of at least g. 2. The method according to claim 1, wherein the olefin is polymerized or copolymerized in the presence of the prepolymerized catalyst after the olefin is prepolymerized. 3. The method according to claim 1, wherein the olefin is an α-olefin. 4. The compound of the above formula [C], wherein R ² has 1 carbon atom.
The method for polymerizing an olefin according to claim 1 or 2, wherein the hydrocarbon group is a hydrocarbon group of (1) to (3). 5. The compound of the above formula [C], wherein R ¹ has 1 carbon atom.
The method for polymerizing an olefin according to claim 4, wherein the hydrocarbon group is any one of the hydrocarbon groups described above. 6. [A] magnesium, the solid titanium catalyst component containing titanium, a halogen and an electron donor as essential ingredients, [B] an organoaluminum compound catalyst component, and [C] the general formula [I] (R ¹ ₃ C) ₂ Si (OR ² ) ₂ ... [I] (wherein, R ¹ and R ² are hydrocarbon groups) in the presence of a catalyst comprising an organosilicon compound catalyst component represented by the formula: A catalyst for olefin polymerization obtained by prepolymerizing olefin. 7. The compound represented by the general formula for component [C], wherein R ² has 1 carbon atom.
The catalyst for olefin polymerization according to claim 6, wherein the catalyst is a hydrocarbon group of (1) to (3). 8. The compound of the above general formula for component [C], wherein R ¹ has 1 carbon atom.
The catalyst for olefin polymerization according to claim 7, which is a hydrocarbon group of (1) to (3).