JP4163220B2 - Olefin polymerization catalyst and olefin polymerization method using the catalyst - Google Patents

Description

  The present invention relates to an olefin polymerization catalyst and an olefin polymerization method using the catalyst.

  Conventionally, a catalyst containing a titanium compound supported on an active magnesium halide as a catalyst used for producing an olefin copolymer such as an α-olefin homopolymer or an ethylene / α-olefin copolymer It has been known. As such an olefin polymerization catalyst, a catalyst comprising a solid titanium catalyst component comprising magnesium, titanium, halogen and an electron donor and an organometallic compound catalyst component is known.

A polymer having high stereoregularity by using such a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components at the time of polymerization of an α-olefin having 3 or more carbon atoms. It is also known that can be produced in high yield.

  The solid titanium catalyst component may be prepared by, for example, contacting a hydrocarbon solution of a halogen-containing magnesium compound with a liquid titanium compound to form a solid product, or carbonizing a magnesium halide compound and a titanium compound. A method of forming a solid product after forming a hydrogen solution and forming the solid product in the presence of an electron donor is known.

As described above, many proposals have been made on methods for preparing a solid titanium catalyst component, but little research has been conducted on the properties of the obtained solid titanium catalyst component.
Under such circumstances, the present inventors have conducted research for the purpose of obtaining a solid titanium catalyst component capable of obtaining an olefin (co) polymer having high stereoregularity with higher polymerization activity. , Microcrystal size of the solid titanium catalyst component (magnesium halide microcrystal size forming the solid titanium catalyst component), pore volume of radius 0.1 μm or less, radius 0.1-7.5 μm When the pore volume and the average catalyst particle size are in a specific range, the olefin polymerization catalyst containing this solid titanium catalyst component can produce an olefin (co) polymer with high polymerization activity and carbon atoms. The inventors have found that an olefin (co) polymer having high stereoregularity can be obtained when polymerizing α-olefins of several or more, and have completed the present invention.

  The present invention has been made in view of the above situation, and provides an olefin polymerization catalyst capable of (co) polymerizing olefins with high polymerization activity and an olefin polymerization method using the catalyst. The purpose is to do.

The solid titanium catalyst component used in the present invention is
It can be prepared by contacting a liquid magnesium compound and a liquid titanium compound in the presence of a diether compound having a fluorene ring represented by the following general formula (i);

(In the formula, R ^a and R ^b may be the same or different from each other and each represents an alkyl group having 1 to 6 carbon atoms, and X and Y may be the same or different from each other, and Represents an alkyl group of 1 to 6 or a halogen atom, m is 0 ≦ m ≦ 4, and n is 0 ≦ n ≦ 4.

The solid titanium catalyst component is obtained by contacting a liquid magnesium compound with a diether compound having a fluorene ring represented by the above general formula (i),
Subsequently, it can prepare by contacting the solution obtained above and the titanium compound of a liquid state.

  The liquid magnesium compound can be prepared, for example, by bringing a magnesium compound into contact with a compound capable of dissolving the magnesium compound selected from the group consisting of alcohol, ester, and ether in a hydrocarbon solvent.

The olefin polymerization catalyst according to the present invention comprises:
(A) the solid titanium catalyst component,
It is characterized by comprising (B) an organometallic compound catalyst component containing a metal selected from Group I to Group III of the periodic table, and (C) an electron donor.

In the olefin polymerization catalyst according to the present invention, an olefin may be prepolymerized.
The olefin polymerization method according to the present invention is characterized in that an olefin is polymerized or copolymerized in the presence of the olefin polymerization catalyst.

  The olefin polymerization catalyst and olefin polymerization method of the present invention can polymerize olefins with high polymerization activity. Further, when an α-olefin having 3 or more carbon atoms is polymerized, an olefin (co) polymer having high stereoregularity is obtained.

  Hereinafter, the solid titanium catalyst component for olefin polymerization according to the present invention, a production method thereof, an olefin polymerization catalyst containing the catalyst component, and an olefin polymerization method using the catalyst will be specifically described.

  In the present specification, the term “polymerization” is sometimes used in the meaning including not only homopolymerization but also copolymerization, and the term “polymer” refers not only to homopolymer but also to copolymerization. It may be used in the meaning that also includes coalescence.

Solid titanium catalyst component The solid titanium catalyst component for olefin polymerization according to the present invention comprises titanium, magnesium and halogen as essential components.

  In the solid titanium catalyst component for olefin polymerization according to the present invention, titanium is 0.3 to 10% by weight, preferably 0.5 to 8% by weight, more preferably 0.8 to 6% by weight, and still more preferably 1 to 1. 5% by weight of magnesium, 5 to 35% by weight, preferably 8 to 30% by weight, more preferably 10 to 28% by weight, still more preferably 12 to 25% by weight, and halogen. 30 to 75% by weight, preferably 35 to 75% by weight, more preferably 38 to 72% by weight, and still more preferably 40 to 70% by weight.

  The solid titanium catalyst component of the present invention preferably contains an electron donor in addition to the titanium, magnesium and halogen. In this case, the electron donor is 0.5 to 30% by weight, preferably 1 to It is desirable that it is contained in a proportion of 27% by weight, more preferably 3 to 25% by weight, still more preferably 5 to 23% by weight.

Examples of the electron donor include an electron donor (a) as described later, and among them, a diether compound having a fluorene ring represented by the following general formula (i) is preferable.
The composition of the solid titanium catalyst component was as follows. The solid titanium catalyst component was thoroughly washed with a large amount of hexane, dried at 0.1 to 1 Torr at room temperature for 2 hours or more, then ICP (atomic absorption analysis), GC It is determined by measuring (gas chromatography).

  The solid titanium catalyst component according to the present invention has a crystallite size calculated from the peak of the (110) plane by X-ray diffraction of the magnesium halide (microcrystal) forming the catalyst component is 3 to 100 mm, preferably 5 It is in the range of ˜80 よ り, more preferably in the range of 10˜40 Å, and still more preferably in the range of 10˜30 Å.

  When the crystallite size is much smaller than 3 mm, the particle shape of the catalyst is deteriorated, the apparent bulk density of the olefin (co) polymer to be produced may be lowered, and when the crystallite size is much larger than 100 mm. , The polymerization activity may decrease, or the stereoregularity of the olefin (co) polymer produced may decrease.

The solid titanium catalyst component according to the present invention, the volume of the following pore radius 0.1μm is 0.20 cm ³ / g or less, preferably 0.15 cm ³ / g or less, more preferably 0.01 cm ³ / g or less More preferably, it is 0.005 cm ³ / g or less, and the volume of pores having a radius of 0.1 to 7.5 μm is 0.30 cm ³ / g or more, preferably 0.40 cm ³ / g or more, more preferably 0. .45 cm ³ / g or more, particularly preferably 0.50 cm ³ / g or more.

When the volume of pores having a radius of 0.1 μm or less is much larger than 0.20 cm ³ / g, the polymerization activity may decrease, or the stereoregularity of the generated olefin (co) polymer may decrease,
When the volume of pores having a radius of 0.1 to 7.5 μm is much smaller than 0.30 cm ³ / g, the polymerization activity may be lowered.

  The solid titanium catalyst component according to the present invention has an average catalyst particle size (volume standard) measured by a light transmission precipitation method of 0.5 to 80 μm, preferably 3 to 70 μm, more preferably 3 to 35 μm. .

If the average catalyst particle size is much smaller than 0.5 μm, the resulting olefin (co) polymer may contain fine powder.
Here, the crystallite size, pore volume and average catalyst particle size are measured as follows.

[Microcrystal size]
The crystallite size is measured with an X-ray diffractometer (RU-300, manufactured by Rigaku Corporation) by measuring the full width at half maximum (FWHM) of the (110) plane, and a known Scherrer equation (where 0.9 is a constant) Obtained by applying K). All samples used for measuring the crystallite size were handled under a nitrogen atmosphere. The method for measuring the crystallite size using Scherrer's equation is detailed in “Karrit X-ray diffraction theory (translated by Gentaro Matsumura) published by Agne”.

[Pore volume]
About 0.3 g of the pore volume test sample was precisely weighed under a nitrogen atmosphere, placed in a measurement cell, deaerated at room temperature (approx. 0.7 Pa reached), and then mercury was injected. This cell was attached to the apparatus and measured. The measurement conditions are shown below.

Equipment: Porosimeter 2000 made by Carlo Elba
Measurement pressure range: about 1000 kPa to 190 MPa
Measurement mode: Pressure increase process in the above pressure range Cell volume: 15 cm ³
[(Method) for measuring (number) average catalyst particle size]
The number average catalyst particle size was measured by applying a known Stokes equation (the following equation) by a light transmission sedimentation method. As an apparatus, an automatic particle size distribution measuring apparatus CAPA-300 type (manufactured by Horiba) was used. As the dispersant, a mixed solution of decalin and triolein (decalin / triolein = 1/4 (weight ratio)) was used.

D: catalyst particle size (cm)
η ₀ : Dispersion medium viscosity coefficient (piose)
ρ: Sample density (g / cm ³ )
ρ ₀ : Dispersion medium density (g / cm ³ )
t: Settling time (sec.)
X ₁ : Distance from the center of rotation to the settled surface (cm)
X ₂ : Distance from the center of rotation to the measurement surface (cm)
ω: rotational angular velocity (rad / sec.)

Process for preparing a solid titanium catalyst for olefin polymerization solid titanium catalyst component according to the adjustment invention components is not particularly limited, for example, can be prepared by such the following method.
(1) A method in which a liquid magnesium compound is brought into contact with a liquid titanium compound in the presence of an electron donor (a).
(2) A liquid magnesium compound and an electron donor (a) are contacted, and then the obtained solution and a titanium compound in a liquid state are contacted, and then an electron donor (b) if necessary. And a method of contacting with a titanium compound in a liquid state.

Next, each raw material used for preparation of such a solid titanium catalyst component will be described.
Liquid Magnesium Compound The liquid magnesium compound can be prepared from a magnesium compound having a reducing ability and a magnesium compound not having a reducing ability.

Here, as the magnesium compound having reducing ability, for example, the formula X _n MgR _2-n
(In the formula, n is 0 ≦ n <2, R is hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, for example, an alkyl group, an aryl group, or a cycloalkyl group, and when n is 0, R may be the same or different and X is a halogen)
The organic magnesium compound represented by these can be mentioned.

Specifically, as an organomagnesium compound having such reducing ability,
Dimethyl magnesium, 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,
Examples thereof include butyl ethoxy magnesium, ethyl butyl magnesium, octyl butyl magnesium, butyl magnesium hydride and the like. These magnesium compounds may be used alone or may form a complex compound with an organoaluminum compound described later. These magnesium compounds may be liquid or solid.

Further, as an organomagnesium compound having no reducing ability, specifically,
Magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride;
Alkoxy magnesium halides such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxymagnesium halides such as phenoxymagnesium chloride and methylphenoxymagnesium chloride;
Alkoxy magnesium such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium, 2-ethylhexoxy magnesium;
Allyloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium;
Examples thereof include magnesium carboxylates such as magnesium laurate and magnesium stearate.

  These magnesium compounds having no reducing ability may be compounds derived from the above-described magnesium compounds having reducing ability or compounds derived at the time of preparation of the catalyst component. In order to derive a magnesium compound having no reducing ability from a magnesium compound having a reducing ability, for example, a magnesium compound having a reducing ability is converted into a halogen such as a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester or an alcohol. What is necessary is just to make it contact with the compound which has a containing compound, OH group, and an active carbon-oxygen bond.

  The magnesium compound is a complex compound of the above magnesium compound and another metal, a complex compound or a mixture of another metal compound in addition to the magnesium compound having the reducing ability and the magnesium compound not having the reducing ability. May be. Furthermore, the composite material which combined 2 or more types of said compound may be sufficient.

  Among these, a magnesium compound having no reducing ability is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxy magnesium chloride, and allyloxy magnesium chloride are preferable, and magnesium chloride is particularly preferably used.

Examples of the compound that can solubilize the solid magnesium compound include at least one compound selected from the group consisting of alcohols, ethers, and esters.
Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol Alcohol having 1 to 18 carbon atoms, such as ethylene glycol;
Halogen-containing alcohols having 1 to 18 carbon atoms, such as trichloromethanol, trichloroethanol, trichlorohexanol;
Ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, ethyl benzyl ether, dibutyl ether, anisole, diphenyl ether;
Examples thereof include metal acid esters such as tetraethoxytitanium, tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium, tetrahexoxytitanium, tetrabutoxyzirconium, and tetraethoxyzirconium.

Among these, alcohol is preferable, and 2-ethylhexanol is particularly preferable.
The compound capable of solubilizing the magnesium compound is an electron donor (a) described later,
Also used as (b).

  Specific examples of hydrocarbon solvents used for the preparation of liquid magnesium compounds include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. And alicyclic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof. Of these, aliphatic hydrocarbons are preferable, and decane and hexane are particularly preferable.

Electron donor (a)
Examples of the electron donor (a) used for the preparation of the solid titanium catalyst component include alcohols, ethers, metal acid esters exemplified as compounds capable of solubilizing magnesium compounds, and alcohols other than those described above, phenol, Examples include ketones, aldehydes, amines, pyridine, organic acid esters, aliphatic carboxylic acids, acid anhydrides, aliphatic carbonates, organic silicon compounds, organic phosphorus compounds, polyvalent carboxylic acid esters, diethers, and polyethers.

Specifically, aliphatic alcohols such as methyl carbitol, 2-methylpentanol, 2-ethylbutanol, decanol, tetradecyl alcohol, undecenol and stearyl alcohol; alicyclic alcohols such as cyclohexanol and methylcyclohexanol; methyl Aromatic alcohols such as benzyl alcohol, α-methylbenzyl alcohol, α, α-dimethylbenzyl alcohol; aliphatics containing alkoxy groups such as n-butyl cellosolve, ethyl cellosolve, 2-butoxyethanol, 1-butoxy-2-propanol Alcohols other than those mentioned above, such as alcohol;
Phenol having 6 to 20 carbon atoms which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol;
Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl n-butyl ketone, acetophenone, benzophenone, benzoquinone, cyclohexanone;
Aldehyde having 2 to 15 carbon atoms, such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde;
Amines such as trimethylamine, triethylamine, tributylamine, tribenzylamine, tetramethylenediamine, hexamethylenediamine;
Pyridines such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, pyridine chloride;

Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, i-butyl acetate, t-butyl acetate, octyl acetate, cyclohexyl acetate, methyl chloroacetate, ethyl dichloroacetate, ethyl propionate, ethyl pyruvate, ethyl pivalate , Methyl butyrate, ethyl valerate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Carbon atoms such as benzyl acid, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide 2-1 8 organic acid esters;
Aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid;
Acid anhydrides such as acetic anhydride, phthalic anhydride, maleic anhydride, benzoic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride;
Aliphatic carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate;

Organosilicon compounds such as methyl silicate, ethyl silicate and diphenyldimethoxysilane, preferably R ¹ _x R ² _y Si (OR ³ ) _z (R ¹ and R ² may be the same or different from each other, Or halogen, R ³ is a hydrocarbon group, and 0 ≦ x <2, 0 ≦ y <2, 0 <z ≦ 4))
And organic phosphorus compounds having a P—O—C bond such as trimethyl phosphite and triethyl phosphite.

  Examples of the polyvalent carboxylic acid ester include compounds having a skeleton represented by the following general formula.

In the formula, R ⁴ represents a substituted or unsubstituted hydrocarbon group, R ⁵ , R ⁸ and R ⁹ represent hydrogen or a substituted or unsubstituted hydrocarbon group, and R ⁶ and R ⁷ represent hydrogen or a substituted group. Or an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group. R ⁶ and R ⁷ may be connected to each other to form a cyclic structure. Substituents in the case where the hydrocarbon groups R ^{4 to} R ⁹ are substituted include heteroatoms such as N, O, and S, for example, C—O—C, COOR, COOH, OH, SO ₃ H, — It has groups such as C—N—C— and NH ₂ .

As such a polyvalent carboxylic acid ester, specifically,
Diethyl succinate, dibutyl succinate, diethyl methyl succinate, diisobutyl α-methylglutarate, diethyl methylmalonate, diethyl ethylmalonate, diethyl isopropylmalonate, diethyl butylmalonate, diethyl phenylmalonate, diethyl diethylmalonate, dibutyl Diethyl malonate, monooctyl maleate, dioctyl maleate, dibutyl maleate, dibutyl butyl maleate, diethyl butyl maleate, diisopropyl β-methylglutarate, diallyl ethyl succinate, di-2-ethylhexyl fumarate, diethyl itaconate, Aliphatic polycarboxylic esters such as dioctyl citraconic acid;
Alicyclic polycarboxylic acid esters such as diethyl 1,2-cyclohexanecarboxylate, diisobutyl 1,2-cyclohexanecarboxylate, diethyl tetrahydrophthalate, diethyl nadic acid;
Monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, monoisobutyl phthalate, diethyl phthalate, ethyl isobutyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, phthalate Di-n-heptyl acrylate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dineopentyl phthalate, didecyl phthalate, benzyl butyl phthalate, diphenyl phthalate, diethyl naphthalene dicarboxylate, dibutyl naphthalene dicarboxylate, trimellit Aromatic polycarboxylic acid esters such as triethyl acid and dibutyl trimellitic acid;
And heterocyclic polycarboxylic acid esters such as 3,4-furandicarboxylic acid.

Other examples of polyvalent carboxylic acid esters include long chains such as diethyl adipate, diisobutyl adipate, diisopropyl sebacate, di-n-butyl sebacate, di-n-octyl sebacate, di-2-ethylhexyl sebacate Mention may also be made of esters of dicarboxylic acids.

  Examples of the diether compound include diether compounds having a fluorene ring represented by the following general formula (i).

In the formula, R ^a and R ^b may be the same or different from each other, and are alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl. , Tert-butyl, pentyl, hexyl and the like.

X and Y may be the same as or different from each other, and represent an alkyl group having 1 to 6 carbon atoms or a halogen atom. m is 0 ≦ m ≦ 4, and n is 0 ≦ n ≦ 4.
Examples of the diether compound having a fluorene ring represented by the general formula (i) include
9,9-bis (methoxymethyl) fluorene,
9,9-bis (ethoxymethyl) fluorene,
9-methoxy-9-ethoxymethylfluorene,
9,9-bis (methoxymethyl) -2,7-dimethylfluorene,
9,9-bis (methoxymethyl) -2,6-diisopropylfluorene,
9,9-bis (methoxymethyl) -3,6-diisobutylfluorene,
9,9-bis (methoxymethyl) -2-isobutyl-7-isopropylfluorene,
9,9-bis (methoxymethyl) -2,7-dichlorofluorene,
9,9-bis (methoxymethyl) -2-chloro-7-isopropylfluorene.

  Examples of the polyether compound include compounds represented by the following general formula.

(In the formula, n is an integer of 2 ≦ n ≦ 10, and R ^{1 to} R ²⁶ have at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron, and silicon. Arbitrary R ^{1 to} R ²⁶ , preferably R ^{1 to} R ²⁰ may be combined to form a ring other than a benzene ring, and atoms other than carbon are contained in the main chain. May be.)
Of these, 1,3-diether is preferably used.
2,2-diisobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isobutyl-1,3-dimethoxypropane,
2-isopropyl-2-isopentyl-1,3-dimethoxypropane,
2,2-dicyclohexyl-1,3-dimethoxypropane,
2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane,
2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane,
2-isopropyl-2-s-butyl-1,3-dimethoxypropane,
2,2-diphenyl-1,3-dimethoxypropane,
2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane and the like are preferably used.

Furthermore, as the electron donor (a), an acid halide having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, anisic acid chloride;
Acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide, toluic acid N, N-dimethylamide;
Nitriles such as acetonitrile, benzonitrile, trinitrile;
Other amines such as methylamine, ethylamine, dimethylamine, diethylamine;
Pyrrole such as pyrrole, methylpyrrole, dimethylpyrrole;
Pyrroline; pyrrolidine; indole; nitrogen-containing cyclic compounds such as piperidine, quinoline, isoquinoline;
Examples thereof also include cyclic oxygenates such as tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalane, tetrahydropyran, pyran, and dihydropyran.

  Among these, the electron donor (a) is preferably an acid anhydride, an alcohol, a polyvalent carboxylic acid, a polyether and a diether having a fluorene ring, and further an acid anhydride, an aliphatic alcohol containing an alkoxy group, an aromatic Group polycarboxylic acid esters, 1,3-diethers and diethers having a fluorene ring are preferred, and diethers having a fluorene ring are particularly preferred.

Electron donor (b)
Examples of the electron donor (b) used for the preparation of the solid titanium catalyst component include the same compounds as those exemplified as the electron donor (a).

  Among these, as the electron donor (b), acid anhydrides, alcohols, polyvalent carboxylic acids, polyethers and diethers having a fluorene ring are preferable, and acid anhydrides, aliphatic alcohols containing alkoxy groups, aromatics Group polycarboxylic acid esters, 1,3-diethers and diethers having a fluorene ring are preferred, and diethers having a fluorene ring are particularly preferred.

  The electron donor (a) and the electron donor (b) may be the same compound or different compounds.

Liquid state titanium compound Examples of the liquid state titanium compound used for the preparation of the solid titanium catalyst component include a tetravalent halogen-containing titanium compound represented by the following formula.

Ti (OR) _m X _4-m
(In the formula, R represents a hydrocarbon group, X represents a halogen atom, and 0 ≦ m <4.)
Specifically, as such a halogen-containing titanium compound,
Titanium tetrahalides such as TiCl ₄ , TiBr ₄ , 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 (Oiso-C 4 H 9) Br Trihalogenated alkoxytitanium such as ₃ ;
Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On—C ₄ H ₉ ) ₂ Cl ₂ , Ti
Dihalogenated alkoxytitanium such as (OC ₂ H ₅ ) ₂ Br ₂ ;
Monohalogenated alkoxytitanium such as Ti (OCH ₃ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Cl, Ti (On—C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br;
Tetra such as Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On—C ₄ H ₉ ) ₄ , Ti (Oiso-C ₄ H ₉ ) ₄ , Ti (O-2-ethylhexyl) ₄ An alkoxy titanium etc. can be mentioned. Among these, titanium tetrahalide is preferable, and titanium tetrachloride is particularly preferable.

These titanium compounds may be used alone or in the form of a mixture. Or you may dilute and use for the above hydrocarbon solvents.
Next, the method for preparing the solid titanium catalyst component for olefin polymerization will be described more specifically. Here, an example in which a halogen-containing magnesium compound is used for the preparation of a liquid magnesium compound, an alcohol is used as a compound capable of solubilizing the halogen-containing magnesium compound, and a diether having a fluorene ring is used as the electron donor (a). Indicates.

  First, the halogen-containing magnesium compound and the alcohol are brought into contact with each other in the hydrocarbon solvent to prepare a uniform solution (magnesium compound solution) in which the halogen-containing magnesium compound is dissolved in a mixed solvent of alcohol and hydrocarbon. To do.

  In this case, the alcohol is used in an amount of 1 to 40 mol, preferably 1.5 to 20 mol, relative to 1 mol of the halogen-containing magnesium compound, and the hydrocarbon solvent is used relative to 1 mol of the halogen-containing magnesium compound. It is used in an amount of 1 to 30 mol, preferably 1.5 to 15 mol. The contact temperature is 65 to 300 ° C, preferably 100 to 200 ° C, and the contact time is 15 to 300 minutes, preferably 30 to 120 minutes.

Next, the magnesium compound solution is contacted with a diether compound having a fluorene ring to prepare a uniform solution (magnesium-diether compound solution).
At this time, the diether compound having a fluorene ring is used in an amount of 0.01 to 1.0 mol, preferably 0.1 to 0.5 mol, per 1 mol of the halogen-containing magnesium compound in the magnesium compound solution. . The contact temperature is -20 to 300 ° C, preferably 20 to 200 ° C, and the contact time is 5 to 240 minutes, preferably 10 to 120 minutes.

  Next, the magnesium-diether compound solution is brought into contact with the liquid titanium compound to prepare a mixed liquid (magnesium-titanium solution) containing the halogen-containing magnesium compound and the liquid titanium compound.

  In this case, the liquid titanium compound is used in an amount of 2 to 100 gram atoms, preferably 4 to 50 gram atoms, based on 1 gram atom of magnesium in the magnesium-diether compound solution. The contact temperature is −70 to 200 ° C., preferably −70 to 50 ° C., and the contact time is 5 to 300 minutes, preferably 30 to 180 minutes.

Next, the magnesium-titanium solution obtained as described above is heated to 20 to 300 ° C., preferably 50 to 150 ° C., so that the solid titanium catalyst component is obtained in a suspended state in a hydrocarbon solvent. It is done. At this time, the heating time is 10 to 360 minutes, preferably 30 to 300 minutes.

  After contacting the magnesium-diether compound solution and the liquid titanium compound, the magnesium-titanium solution and the electron donor (b) may be contacted. When contacting an electron donor (b), it is preferable to contact after heating a magnesium-titanium solution. As an electron donor (b) used here, the diether compound which has the fluorene ring used when preparing said magnesium-diether compound solution can be used.

At this time, the electron donor (b) is used in an amount of 0.01 to 5 mol, preferably 0.1 to 1 mol, per 1 mol of the magnesium compound.
The suspension is subjected to solid-liquid separation by filtration or the like, and after the solid portion (solid titanium catalyst component) is collected, the solid portion may be further brought into contact with the liquid titanium compound. The obtained solid titanium catalyst component is preferably washed with a hydrocarbon solvent.

  The solid titanium catalyst component obtained in this way can be suspended in a hydrocarbon solvent and used as a catalyst component for olefin polymerization. May be used.

Olefin polymerization catalyst The olefin polymerization catalyst according to the present invention comprises:
(A) the solid titanium catalyst component,
(B) formed from an organometallic compound catalyst component and (C) an electron donor.

(B) Organometallic compound catalyst component The organometallic compound catalyst component preferably contains a metal selected from Groups I to III of the Periodic Table, specifically, an organoaluminum compound, a Group I metal and aluminum. And a complex alkyl compound and an organometallic compound of a Group II metal.

As such an organoaluminum compound, for example, an organoaluminum compound represented by the following formula can be exemplified.
R ^a _n AlX _3-n
(In the formula, Ra represents ^a hydrocarbon group having 1 to 12 carbon atoms, X represents halogen or hydrogen, and n is 1 to 3).
In the above formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, and tolyl group.

Specific examples of such organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, and tri-2-ethylhexylaluminum;
Alkenyl aluminum such as isoprenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide;
Alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Examples thereof include alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride.

Moreover, the compound shown by a following formula can also be used as an organoaluminum compound.
R ^a _n AlY _3-n
(Wherein, R ^a is the same as above, Y is —OR ^b group, —OSiR ^c ₃ group, —OAlR ^d ₂ group, —NR ^e ₂ group, —SiR ^f ₃ group or —N (R ^g )) Represents an AlR ^h ₂ group, n is 1 to 2, R ^b , R ^c , R ^d and R ^h represent a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, and the like ^; Represents hydrogen, methyl group, ethyl group, isopropyl group, phenyl group, trimethylsilyl group, etc., and R ^f and R ^g represent methyl group, ethyl group, etc.)
As such an organoaluminum compound, specifically, the following compounds are used.

_{^{(I) R a n Al (}} OR b) compound represented by the _3-n, e.g., dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum methoxide;
_{^{(Ii) R a n Al (}} OSiR c) compound represented by the _3-n, e.g., _{Et 2 Al (OSiMe 3),} (iso-Bu) 2 Al (OSiMe 3), (iso-Bu) 2 Al (OSiEt 3 )Such;
_{^{(Iii) R a n Al (}} OAlR d 2) a compound represented by the _3-n, e.g., Et ₂ AlOAlEt _2, such as _{(iso-Bu) 2 AlOAl (} iso-Bu) 2;
_{^{(Iv) R a n Al (}} NR e 2) a compound represented by the _3-n, e.g., _{Me 2 AlNEt 2, Et 2 AlNHMe} , Me 2 AlNHEt, Et 2 AlN (Me 3 Si) 2, (iso-Bu) 2 AlN (Me ₃ Si) ₂ etc .;
_{^{(V) R a n Al (}} SiR f 3) a compound represented by _3-n, such as _{(iso-Bu) 2 AlSiMe 3} ;
(Vi) R ^a _n Al [N (R ^g) AlR ^h ₂ The compound represented by the _3-n, e.g., _{Et 2 AlN (Me) AlEt 2} , (iso-Bu) 2 AlN (Et) Al (iso-Bu ) ₂ etc. (however, Me: methyl group, Et: ethyl group, Bu: butyl group).

Further, compounds similar to these, for example, an organoaluminum compound in which two or more aluminums are bonded through an oxygen atom or a nitrogen atom can be exemplified. More specifically,
_{(C 2 H 5) 2 AlOAl} (C 2 H 5) 2,
(C ₄ H ₉ ) ₂ AlOAl (C ₄ H ₉ ) ₂ ,
Such as _{(C 2 H 5) 2 AlN} (C 2 H 5) Al (C 2 H 5) 2.

Furthermore, aluminoxane such as methylaluminoxane can be mentioned.
Among the above organoaluminum compounds,
Can be exemplified ^{_{R a 3 Al, R a n}} Al (OR b) 3-n, an organic aluminum compound represented by ^{_{R a n Al (OAlR d 2}} ) 3-n Preferred examples.

Examples of the complex alkylated product of a Group I metal and aluminum include compounds represented by the following general formula.
M ¹ AlR ^j ₄
(Wherein M ¹ represents Li, Na or K, and R ^j represents a hydrocarbon group having 1 to 15 carbon atoms)
Specific examples include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the organometallic compound of Group II metal include compounds represented by the following general formula.
R ^k R ^l M ²
(In the formula, R ^k and R ^l each represent a hydrocarbon group having 1 to 15 carbon atoms or a halogen, and may be the same or different from each other, except for the case where both are halogen. M ² is Mg, Zn or Cd is shown.)
Specific examples include diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, and butyl magnesium chloride.
Two or more of these compounds can be used in combination.

(C) Electron Donor As the electron donor (C), for example, an organosilicon compound represented by the following general formula can be used.

R _n Si (OR ′) _4-n
(Wherein R and R ′ may be the same as or different from each other, each represents a hydrocarbon group, and 0 <
n <4)
Specific examples of the organosilicon compound represented by such a general formula include the following compounds.

Trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenyl Methyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bism-tolyldimethoxysilane, bisp-tolyldimethoxysilane, bisp-tolyldiethoxysilane, bisethylphenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyl Dimethoxysilane, cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyl Trimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t -Butyltriethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, cyclohexyl Trimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, silica Butyl, trimethyl phenoxy silane, methyl tri Lilo carboxylate (Allyloxy) silane, vinyltris (beta-methoxyethoxy silane), vinyl triacetoxy silane, dimethyl tetraethoxy disiloxane,
Cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,
Dicyclopentyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis (2,3-dimethylcyclopentyl) dimethoxysilane, dicyclopentyldiethoxysilane, p-tolylmethyldimethoxysilane, di-t-butyldimethoxysilane,
Tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, cyclopentyldimethylethoxysilane, and the like.

  Of these, ethyltriethoxysilane, n-propyltriethoxysilane, t-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p- Tolyldimethoxysilane, p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tri Cyclopentylmethoxysilane, di-t-butyldimethoxysilane, cyclopentyldimethylmethoxysilane and the like are preferably used.

Furthermore, in the present invention, as the electron donor (C),
2,6-substituted piperidines, 2,5-substituted piperidines,
Substituted methylenediamines such as N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetraethylmethylenediamine,
Nitrogen-containing electron donors such as substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine,
Phosphorus-containing electrons such as phosphites such as triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite Donor,
Oxygen-containing electron donors such as 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans can also be used.

Two or more of these electron donors (C) can be used in combination.
The catalyst for olefin polymerization according to the present invention can contain other components useful for olefin polymerization in addition to the above components.

  In the olefin polymerization catalyst according to the present invention, olefin may be preliminarily polymerized. The prepolymerization catalyst comprises olefins and polyenes used in the main polymerization described later in the presence of a solid titanium catalyst component (A), an organometallic compound catalyst component (B) and, if necessary, an electron donor (C). It is obtained by preliminarily (co) polymerizing a compound or the like.

Olefin Polymerization Method In the olefin polymerization method (main polymerization) according to the present invention, olefin polymerization comprising the solid titanium catalyst component (A), the organometallic compound catalyst component (B) and the electron donor (C) as described above. The olefin is polymerized or copolymerized in the presence of an olefin polymerization catalyst or an olefin polymerization catalyst containing a prepolymer.

Specific examples of the olefin polymerized in the present invention include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3 -Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4 , 4-Dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eikosen. Two or more of these may be used in combination.

These can be polymerized alone or in combination.
Of these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and the like are preferably used.

In addition to the above α-olefin, if necessary,
Aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalene, substituted vinylnaphthalene, allylnaphthalene, substituted allylnaphthalene,
Alicyclic vinyl compounds such as vinylcyclopentane, substituted vinylcyclopentanes, vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, allyl norbornane,
Cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octa Cyclic olefins such as hydronaphthalene,
Silane unsaturated compounds such as allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1-hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-decene, and polyene A compound or the like can also be used.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.
When the polymerization takes a reaction form of slurry polymerization, a reaction inert hydrocarbon can be used as a solvent, or a liquid olefin can be used at the reaction temperature. Of these hydrocarbon solvents, it is preferable to use aliphatic hydrocarbons.

  In the polymerization method of the present invention, the solid titanium catalyst component (A) or the prepolymerized catalyst is usually about 0.001 to 100 mmol, preferably about 0.005, in terms of titanium atom per liter of polymerization volume. The amount used is 20 mmol.

  In the organometallic compound catalyst component (B), the metal atom in the catalyst component (B) is usually about 1 to 2000 mol with respect to 1 mol of titanium atom in the solid titanium catalyst component (A) in the polymerization system, Preferably it is used in such an amount that it is about 2 to 500 mol.

The electron donor (C) is generally used in an amount of about 0.001 to 10 mol, preferably 0.01 to 5 mol, relative to 1 mol of the metal atom in the catalyst component (B).
If hydrogen is used during the polymerization, the molecular weight of the resulting polymer can be adjusted, and a polymer having a high melt flow rate can be obtained. In the polymerization method according to the present invention, although it depends on the olefin used, the polymerization is usually carried out under the following conditions.

The polymerization temperature is usually about 20 to 300 ° C., preferably about 50 to 150 ° C., and the polymerization pressure is normal pressure to 100 kg / cm ² , preferably about ² to 50 kg / cm ² .
In the present invention, the polymerization can be carried out by any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be carried out in two or more stages by changing the reaction conditions.

In the present invention, an olefin homopolymer may be produced, or a random copolymer or a block copolymer may be produced from two or more olefins.
When the olefin polymerization method is carried out using the olefin polymerization catalyst as described above, it can be produced with extremely high polymerization activity. When an olefin having 3 or more carbon atoms is polymerized, an olefin polymer having high stereoregularity can be obtained. Can be manufactured.

When, for example, propylene is polymerized by the olefin polymerization method according to the present invention as described above, isotactic stereospecificity (stereoregularity). I. However, a highly stereoregular polypropylene of 94.5 to 98.5% can be produced.

  The melt flow rate (MFR, ASTM D1238E) of the olefin polymer obtained in the present invention is usually 5000 g / 10 min or less, preferably 0.01-3000 g / 10 min, more preferably 0.02-2000 g / 10 min, especially Preferably it exists in the range of 0.05-1000 g / 10min.

  The intrinsic viscosity [η] measured in decalin at 135 ° C. is usually in the range of 0.05 to 20 dl / g, preferably 0.1 to 15 dl / g, particularly preferably 0.2 to 13 dl / g.

  Furthermore, the olefin polymer obtained in the present invention is blended with a heat stabilizer, a weather stabilizer, an antistatic agent, an antiblocking agent, a lubricant, a nucleating agent, a pigment, a dye, an inorganic or organic filler, if necessary. You can also.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.

[Preparation of solid titanium catalyst component (A)]
Anhydrous magnesium chloride (47.7 g), purified toluene (235 ml) and 2-ethylhexyl alcohol (195.3 g) were heated under reflux at 120 ° C. for 3 hours to obtain a homogeneous solution. Bis (methoxymethyl) fluorene (19.1 g) was added, and the mixture was further stirred and mixed at 120 ° C. for 1 hour to completely dissolve 9,9-bis (methoxymethyl) fluorene.

  After cooling the homogeneous solution thus obtained to room temperature, 30 ml of this homogeneous solution was charged dropwise into 80 ml of titanium tetrachloride maintained at −20 ° C. over 20 minutes. After the completion of charging, the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and then kept at the same temperature for 2 hours with stirring.

After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 110 ml of titanium tetrachloride, and then the temperature was raised again to 110 ° C. with stirring and the reaction was continued for 2 hours. Went.
After completion of the reaction, the solid part was again collected by hot filtration, washed with decane at 110 ° C., and further thoroughly washed at room temperature with hexane until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component (A) prepared by the above operation was stored as a decane slurry, but a part thereof was dried for the purpose of examining the catalyst composition.
The solid titanium catalyst component (A) thus obtained has a crystallite size of 26 kg, a pore volume with a radius of 0.1 μm or less is 0.002 cm ³ / g, and a radius of 0.1 to 7 .5μ
The volume of the pores of m was 0.560 cm ³ / g, and the average catalyst particle size measured by the light transmission precipitation method was 11.2 μm. The solid titanium catalyst component (A) is composed of 4.7% by weight of titanium, 54% by weight of chlorine, 15% by weight of magnesium, and 16.2% by weight of 9,9-bis (methoxymethyl) fluorene. Contained.

[polymerization]
An autoclave having an internal volume of 1 liter was charged with 400 ml of purified n-heptane, and at 60 ° C. in a propylene atmosphere, 0.4 mmol of triethylaluminum, 0.04 mmol of cyclohexylmethyldimethoxysilane and the solid titanium catalyst component (A) were added. 0.004 mmol was charged in terms of titanium atoms.

Further, 75 ml of hydrogen was introduced at 60 ° C., the temperature was raised to 70 ° C., and this was maintained for 1 hour to carry out propylene polymerization. The pressure during the polymerization was kept at 5 kg / cm ² -G.
After completion of the polymerization, the slurry containing the produced solid was filtered to separate it into a white powder and a liquid phase part.

The yield of the white powder polymer after drying is 90.5 g, the extraction residual ratio (II) with boiling heptane is 98.74%, the MFR is 3.5 g / 10 min, and the apparent bulk density is It was 0.41 g / cm ³ . On the other hand, 0.2 g of a solvent-soluble polymer was obtained by concentrating the liquid phase part. Therefore, the activity was 22,700 g-PP / mmol-Ti, 21,700 g-PP / g-catalyst, and the extraction residual ratio (tI.I.) with boiling heptane in the whole polymer was 98.5%. It was.
[Reference Example 1]

[Preparation of solid titanium catalyst component (B)]
95.3 g of anhydrous magnesium chloride, 485 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 140 ° C. for 3 hours to obtain a homogeneous solution, and 22.2 g of phthalic anhydride was added to this solution, and the temperature was further increased to 130 ° C. The mixture was stirred and mixed for 1 hour, and phthalic anhydride was dissolved in this homogeneous solution.

  After cooling the homogeneous solution thus obtained to room temperature, 30 ml of this homogeneous solution was charged dropwise into 80 ml of titanium tetrachloride maintained at −20 ° C. over 20 minutes. After the completion of charging, the temperature of the mixture was raised to 110 ° C. over 4 hours, and when it reached 110 ° C., 1.91 g of 9,9-bis (methoxymethyl) fluorene previously dissolved in toluene was added. From this, the mixture was kept under stirring at the same temperature for 2 hours.

  After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and this solid part was resuspended in 110 ml of titanium tetrachloride, and then heated again to 110 ° C. with stirring and heated for 2 hours. Reaction was performed.

After completion of the reaction, the solid part was again collected by hot filtration, and washed thoroughly with 110 ° C. decane and hexane until no free titanium compound was detected in the washing solution.
The solid titanium catalyst component (B) prepared by the above operation was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition.

The microcrystal size of the solid titanium catalyst component (B) thus obtained is 46 mm, the volume of pores having a radius of 0.1 μm or less is 0.128 cm ³ / g, and the radius is 0.1 to 7 The pore volume of 0.5 μm was 0.431 cm ³ / g, and the average catalyst particle size measured by the light transmission precipitation method was 12.1 μm. The solid titanium catalyst component (B) is composed of 2.5% by weight of titanium, 60% by weight of chlorine, 18% by weight of magnesium and 8.6% by weight of 9,9-bis (methoxymethyl) fluorene. Contained.

[polymerization]
In Example 1, propylene was polymerized in the same manner as in Example 1 except that the solid titanium catalyst component (B) was used instead of the solid titanium catalyst component (A).

The yield of the white powder polymer after drying was 89.3 g, the extraction residual ratio (II) with boiling heptane was 98.33%, the MFR was 5.1 g / 10 min, and the apparent bulk density was It was 0.38 g / cm ³ . On the other hand, 1.0 g of a solvent-soluble polymer was obtained by concentrating the liquid phase part. Therefore, the activity was 22,600 g-PP / mmol-Ti, 11,800 g-PP / g-catalyst, and the extraction residual ratio (tI.I.) with boiling heptane in the whole polymer was 97.3%. It was.

[Comparative Example 1]
[Preparation of solid titanium catalyst component (C)]
An anhydrous magnesium chloride (95.3 g), decane (485 ml) and 2-ethylhexyl alcohol (390.6 g) were heated at 140 ° C. for 2 hours to obtain a homogeneous solution, and then this solution was treated with 2-isopropyl-2-isobutyl having the following structure. 1,4.6 ml of 1,3-dimethoxypropane was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour.

  After cooling the homogeneous solution thus obtained to room temperature, 30 ml of this homogeneous solution was charged dropwise into 80 ml of titanium tetrachloride maintained at −20 ° C. over 20 minutes. After completion of the charging, 7.5 ml of methylhydropolysiloxane was further added, and then the temperature of the mixed solution was raised to 110 ° C. over 4 hours, and then kept at the same temperature for 2 hours with stirring.

After completion of the reaction for 2 hours, the solid part was collected by hot filtration, and the solid part was resuspended in 110 ml of titanium tetrachloride, and then the temperature was raised again to 110 ° C. with stirring and the reaction was continued for 2 hours. Went.
After completion of the reaction, the solid part was again collected by hot filtration, washed with decane at 110 ° C., and further thoroughly washed at room temperature with hexane until no free titanium compound was detected in the washing solution.

The solid titanium catalyst component (C) prepared by the above operation was stored as a decane slurry, and a part thereof was dried for the purpose of examining the catalyst composition.
The microcrystal size of the solid titanium catalyst component (C) thus obtained is 153 mm, the volume of pores having a radius of 0.1 μm or less is 0.179 cm ³ / g, and the radius is 0.1 to 7 The pore volume of 0.5 μm was 0.383 cm ³ / g, and the average catalyst particle size measured by the light transmission sedimentation method was 13.6 μm. The solid titanium catalyst component (C) was composed of 19.0% by weight of titanium, 53% by weight of chlorine, 6% by weight of magnesium, and 5.8 of 2-isopropyl-2-isobutyl-1,3-dimethoxypropane. It contained in the ratio of weight%.

[polymerization]
In Example 1, instead of the solid titanium catalyst component (A), the solid titanium catalyst component (C
The polymerization of propylene was carried out in the same manner as in Example 1 except that.

After completion of the polymerization, the slurry containing the produced solid was filtered to separate it into a white powder and a liquid phase part.
The yield of the white powder polymer after drying was 3.2 g, the extraction residual ratio (II) with boiling heptane was 96.23%, the melt flow rate (MFR) was 7.8 g / 10 min, The apparent bulk density was 0.26 g / cm ³ . On the other hand, 0.1 g of a solvent-soluble polymer was obtained by concentrating the liquid phase part. Therefore, the activity was 800 g-PP / mmol-Ti, 3,300 g-PP / g-catalyst, and the extraction residual ratio (tI.I.) by boiling heptane in the whole polymer was 93.3%.

  The above results are shown in Tables 1 and 2.

Claims (6)

(A) A solid titanium catalyst component produced by contacting a liquid magnesium compound and a liquid titanium compound in the presence of a diether compound having a fluorene ring represented by the following general formula (i) : A solid titanium catalyst component having a crystallite size in the range of 10 to 40 mm calculated from a peak of (110) plane by X-ray diffraction of magnesium halide forming the catalyst component ;

(In the formula, R ^a and R ^b may be the same or different from each other and each represents an alkyl group having 1 to 6 carbon atoms, and X and Y may be the same or different from each other, and Represents an alkyl group of 1 to 6 or a halogen atom, m is 0 ≦ m ≦ 4, and n is 0 ≦ n ≦ 4.
(B) An olefin polymerization catalyst comprising an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table, and (C) an electron donor. (A) A solid titanium catalyst produced by contacting a liquid magnesium compound with a liquid titanium compound in the presence of a diether compound having a fluorene ring represented by the general formula (i) according to claim 1 A solid titanium catalyst component having a crystallite size in the range of 10 to 40 mm calculated from a peak of (110) plane by X-ray diffraction of magnesium halide forming the catalyst component ,
(B) an organometallic compound catalyst component containing a metal selected from Group I to Group III of the Periodic Table, and (C) an olefin polymerization catalyst, wherein an olefin is prepolymerized on an electron donor . (A) A liquid magnesium compound is brought into contact with a diether compound having a fluorene ring represented by the general formula (i) according to claim 1, and then the solution obtained above, a liquid titanium compound, The solid titanium catalyst component produced by contacting the catalyst, and the crystallite size calculated from the peak of the (110) plane by X-ray diffraction of the magnesium halide forming the catalyst component is in the range of 10 to 40 mm Solid titanium catalyst component ,
(B) An olefin polymerization catalyst comprising an organometallic compound catalyst component containing a metal selected from Groups I to III of the periodic table, and (C) an electron donor. (A) A liquid magnesium compound is brought into contact with a diether compound having a fluorene ring represented by the general formula (i) according to claim 1, and then the solution obtained above, a liquid titanium compound, The solid titanium catalyst component produced by contacting the catalyst, and the crystallite size calculated from the peak of the (110) plane by X-ray diffraction of the magnesium halide forming the catalyst component is in the range of 10 to 40 mm Solid titanium catalyst component ,
(B) an organometallic compound catalyst component containing a metal selected from Group I to Group III of the Periodic Table, and (C) an olefin polymerization catalyst, wherein an olefin is prepolymerized on an electron donor .   The liquid magnesium compound is prepared by contacting a magnesium compound with a compound capable of dissolving the magnesium compound selected from the group consisting of alcohol, ester and ether in a hydrocarbon solvent. The olefin polymerization catalyst according to claim 1.   An olefin polymerization method comprising polymerizing or copolymerizing an olefin in the presence of the olefin polymerization catalyst according to any one of claims 1 to 5.