JP2001163912A - Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, preparation method of olefin polymer and preparation method of solid catalyst component for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation method of an olefin polymer (especially an ethylene/α-olefin copolymer) which contains an extremely small amount of a low-molecular- weight and/or a low crystalline polymer and which has good particle properties and a preparation method of a solid catalyst component for the olefin polymerization. SOLUTION: The solid catalyst component for olefin polymerization is obtained by contacting (a) a support comprising a polymer particle having an average particle diameter of 1-300 μm and a carboxylic group with (b) a compound of a group IV transitional metal in the periodic table. The catalyst for olefin polymerization is obtained by contacting (A) the solid catalyst component for olefin polymerization with (B) an organic aluminum compound and/or an organic aluminumoxy compound. The preparation method of an olefin polymer uses the catalyst for olefin polymerization. The preparation method of the solid catalyst component for olefin polymerization comprises contacting (a) a support comprising a polymer particle having an average particle diameter of 1-300 μm and a carboxylic group with (b) a compound of a group IV transitional metal in the periodic table.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a solid catalyst component for olefin polymerization, a catalyst for olefin polymerization, a method for producing an olefin polymer, and a method for producing a solid catalyst component for olefin polymerization.

[0002]

2. Description of the Related Art As a catalyst for olefin polymerization, a Ziegler-Natta catalyst obtained by bringing a transition metal component and an organic metal component into contact with each other has been known. For example, as a catalyst exhibiting high activity in olefin polymerization, a large number of catalysts prepared by contacting a solid catalyst component using a titanium compound and a magnesium compound with an organoaluminum compound have been proposed.
When olefin polymerization or ethylene / α-olefin copolymerization is carried out, there is a problem that a large amount of low molecular weight and low crystalline components are produced. Low molecular weight, low crystalline component, when the resulting olefin polymer is processed into a film or sheet,
It is a factor that has an adverse effect on transparency, impact resistance, blocking properties, and the like, and it is desirable to produce an olefin polymer having a low molecular weight and a small amount of low crystalline components.

In such a catalyst, as a method for reducing low molecular weight and low crystalline components, in the case of polymerization of an α-olefin such as propylene, an electron donor such as an ester or ether is used as an internal donor in a solid catalyst component. Methods have been proposed for improving stereoregularity and reducing low molecular weight and low crystalline components. Further, a method has been proposed in which stereoregularity is improved by using an electron donor such as an ester, an ether, an amine, or an organosilicon compound as an external donor in addition to the solid catalyst component and the organoaluminum compound. Also in the ethylene / α-olefin copolymerization, a method of reducing low molecular weight and low crystallinity components by using an electron donor as an internal donor and / or an external donor, similarly to the α-olefin polymerization catalyst. Has been proposed. However, in a method using an electron donor as an internal donor and / or an external donor, when polymerization of an α-olefin such as propylene or copolymerization of ethylene / α-olefin is carried out, reduction of the production of low molecular weight and low crystalline components is required. In that respect, it was not always satisfactory.

[0004] In the case of olefin polymerization, a large amount of polymer adhered to the polymerization tank causes various problems in operation and causes a decrease in operation efficiency. Therefore, it is desirable that adhesion to the polymerization tank be as small as possible. . From the viewpoint of operation stability and operation efficiency, it is preferable that the polymer powder has a high bulk density, a narrow particle size distribution, and good fluidity.

In recent years, in the field of olefin polymerization catalysts, as a new catalyst, a solid catalyst component for olefin polymerization obtained by immobilizing a magnesium compound and a titanium compound on a support using a polymer having a functional group as a support. Is disclosed. For example, WO 94/20545 and U.S. Pat.
JP-A-09875 describes that an ethylene / unsaturated carboxylic acid copolymer is dissolved in an organic solvent, and then a poor solvent is added thereto to precipitate out the impurities in the copolymer. A method for producing an ethylene-based polymer using a catalyst comprising a solid catalyst component prepared by pulverizing and then contacting with an organomagnesium compound and a transition metal compound and an organoaluminum compound is disclosed.

[0006]

It is described that the above catalyst exhibits high activity in olefin polymerization, particularly in ethylene / α-olefin copolymerization, but the ethylene / α-olefin copolymer obtained by the catalyst is described. Coalescence was unsatisfactory in reducing low molecular weight and / or low crystalline components. The solid catalyst component had a wide particle size distribution and contained fine powder, and the obtained ethylene / α-olefin copolymer was not satisfactory in terms of particle properties.
Under such circumstances, the problem to be solved by the present invention,
That is, the object of the present invention is to exhibit high activity by using together with an organometallic compound in olefin polymerization,
An olefin polymerization solid which has an extremely small amount of a low molecular weight and / or low crystalline polymer represented by the amount of a polymer soluble in xylene at 20 ° C. (CXS) and can produce an olefin polymer having good particle properties. Catalyst component, olefin polymerization catalyst using the same, 20 ° C. using the catalyst
The amount of the low molecular weight and / or low crystalline polymer represented by the amount of the polymer soluble in xylene (CXS) is very small, and the olefin polymer having good particle properties (among others, ethylene / α-olefin copolymer) ), And a method for producing the solid catalyst component for olefin polymerization.

[0007]

The present invention comprises contacting (a) a carrier composed of polymer particles having a carboxyl group having an average particle diameter of 1 to 300 μm, and (b) a transition metal compound of Group 4 of the periodic table. The present invention relates to a solid catalyst component for olefin polymerization obtained by the above. Further, the present invention provides (A)
The solid catalyst component for olefin polymerization, and (B) an olefin polymerization catalyst obtained by contacting an organoaluminum compound and / or an organoaluminum oxy compound, and an olefin polymer using the olefin polymerization catalyst According to the method of manufacturing. Furthermore, the present invention provides (a) an average particle diameter of 1 to 300 μm.
The present invention relates to a method for producing a solid catalyst component for olefin polymerization, wherein a carrier comprising polymer particles having m carboxyl groups and (b) a transition metal compound belonging to Group 4 of the periodic table are brought into contact. Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Average particle size is 1 to 300 μm
Carrier consisting of polymer particles having a carboxyl group of m The carrier used in the present invention has an average particle diameter of 1 to 300 μm
It is a carrier comprising polymer particles having m carboxyl groups. The polymer having a carboxyl group is preferably a copolymer containing an unsaturated monomer unit having a carboxyl group, or a polymer having a carboxyl group introduced by chemical or physical modification.

Examples of the unsaturated monomer having a carboxyl group include unsaturated carboxylic acids. Specifically, acrylic acid, methacrylic acid and the like can be mentioned, among which acrylic acid is preferable.

The copolymer containing an unsaturated monomer unit having a carboxyl group is more preferably a copolymer of an unsaturated monomer having a carboxyl group and ethylene, propylene or styrene. For example, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, propylene / acrylic acid copolymer, propylene / methacrylic acid copolymer, styrene / acrylic acid copolymer, styrene / methacrylic acid copolymer And the like.

Among them, copolymers containing ethylene units, propylene units or styrene units as main components are preferred. More preferably, it contains 49.9 to 0.1% by weight, particularly preferably 30 to 1% by weight, of an unsaturated monomer unit having a carboxyl group, and contains 50.1 to 99% of an ethylene unit, a propylene unit or a styrene unit. It is a copolymer containing 9.9% by weight, particularly preferably 70 to 99% by weight. Among them, preferred is a copolymer containing 20 to 5% by weight of an acrylic acid unit or a methacrylic acid unit and 80 to 95% by weight of an ethylene unit.

As a method for introducing a carboxyl group by chemically or physically modifying a polymer, any known method may be employed. The polymer used here is preferably a polymer containing an ethylene unit, a propylene unit or a styrene unit. More preferably, it is a homopolymer of ethylene, propylene or styrene or a copolymer containing ethylene units, propylene units or styrene units as a main component, and still more preferably ethylene units, propylene units or styrene units of 50.1 to 100. (Co) polymer containing 49.9 to 0% by weight of an α-olefin unit. Specific examples include polyethylene, ethylene / α-
Olefin copolymer, polypropylene, propylene / ethylene copolymer, propylene / butene-1 copolymer, polystyrene and the like.

Specific examples of a method for introducing a carboxyl group by chemically or physically modifying a polymer include, for example, a polymer containing a halogenated styrene unit (eg, a styrene / bromostyrene copolymer). ) Is treated with an organic alkali metal compound (for example, nBuLi) and then reacted with carbon monoxide to obtain, for example, a styrene / carboxylstyrene copolymer, or a polyolefin (for example, polypropylene) and an unsaturated monomer having a carboxyl group. And melt kneading in the presence of an organic peroxide to obtain, for example, acrylic acid-modified polypropylene. As the unsaturated monomer having a carboxyl group used in the latter case, the same monomer as described above is used, but acrylic acid or maleic anhydride is preferably used. When using an acid anhydride such as maleic anhydride, hydrolysis is preferably carried out after melt-kneading.

Specific examples of polymers into which carboxyl groups have been introduced by chemical or physical modification include:
Styrene / carboxylstyrene copolymer, acrylic acid-modified polyethylene, acrylic acid-modified polypropylene, acrylic acid-modified polystyrene, maleic acid-modified polyethylene, maleic acid-modified polypropylene, maleic acid-modified polystyrene, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, Maleic anhydride-modified polystyrene, maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, or maleic anhydride-modified polystyrene hydrolyzed.

As the polymer having a carboxyl group, a copolymer containing an unsaturated monomer unit having a carboxyl group is more preferable. The carrier made of these polymers may be used alone, or a mixture of a plurality of them may be used. Alternatively, the carrier may be used as a mixture with other polymers as long as the essence is not impaired.

The carrier used in the present invention is the above-mentioned polymer having a carboxyl group and has an average particle diameter of 1 to 1.
300 μm polymer particles. The average particle diameter is more preferably 3 to 200 μm, and still more preferably 5 to 200 μm.
80 μm polymer particles are used. As the carrier used in the present invention, the standard deviation of the particle size distribution is 0.1 to 50 μm
Is preferable, and the standard deviation is more preferably 1 to 30 μm, and still more preferably 3 to 20 μm.
μm. By preparing a catalyst using such polymer particles, that is, relatively uniform particles, the low molecular weight and / or low crystallinity component of the obtained olefin polymer is further reduced, and the particles of the olefin polymer particles obtained by polymerization are obtained. The properties are better. As the average particle diameter, a value measured with a particle size measuring device (for example, COULTER MULTIZIZER) in a state of slurry in water or alcohol is adopted. In the present invention, the average particle diameter and the standard deviation of the particle size distribution refer to values in a weight distribution.

The polymer particles used in the present invention are preferably spherical or nearly spherical, and more preferably spherical or oval spherical polymer particles.

Since such polymer particles are commercially available, they may be used, or they may be produced using a crudely produced polymer having a carboxyl group as a raw material by a dispersion technique. Such dispersion techniques are described, for example, in US Pat.
No. 49 and U.S. Pat. No. 3,432,483. Specifically, it can be produced by mixing and stirring a polar solvent and a surfactant which do not completely dissolve the polymer under high temperature conditions and the crude polymer. The temperature at this time is preferably a temperature not lower than the melting point of the polymer and not thermally decomposing, and the pressure is usually from normal pressure to normal pressure.
It is performed at 250 atm. As the polar solvent that does not completely dissolve the polymer, water or a mixed solvent containing water as a main component is particularly preferable. Examples of the surfactant include a block copolymer of ethylene oxide and propylene oxide. Those produced by this method are also commercially available.

Such polymer particles often have impurities such as a surfactant and impurities during polymerization attached thereto, and it is preferable to remove them from the viewpoint of polymerization activity. The carrier (a) used in the present invention has an average particle diameter of 1 to 30.
Carriers comprising particles obtained by washing polymer particles having a carboxyl group of 0 μm with an organic solvent are more preferred. More specifically, as the carrier (a) used in the present invention, a polymer particle having a carboxyl group having an average particle diameter of 1 to 300 μm is slurried with an organic solvent, and then filtered and dried. Is particularly preferably used. Unlike the polymer powder obtained by dissolving and reprecipitating the impurities to remove the impurities, the particles thus obtained retain the shape of the particles at the same time as the impurities are removed. When a carrier comprising such particles is used, the catalyst for olefin polymerization of the present invention is particularly preferred because it can produce an olefin polymer having a high activity, a low molecular weight and / or a low crystallinity polymer, and a good particle property. .

As the organic solvent used herein, an organic solvent which does not completely dissolve the polymer particles having a carboxyl group is used, and a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone, a nitrile solvent such as acetonitrile, Aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane and decane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; alicyclic hydrocarbon solvents such as cyclohexane and cyclopentane; Examples include halogenated hydrocarbon solvents such as dichloroethane and monochlorobenzene, and ether solvents such as diethyl ether and tetrahydrofuran. Among them, ketone solvents are preferable, and acetone is particularly economically advantageous and preferably used.

The washing with the organic solvent is preferably carried out under conditions that can maintain the shape without dissolving the polymer particles to be used, and the temperature is usually -30 to 120 ° C.
Up to 0, but preferably 0
-100 ° C, more preferably 20-80 ° C.

In practice, washing with an organic solvent usually involves slurrying polymer particles in an organic solvent, stirring for 1 minute to 10 hours, filtering, and drying. Dry at 5-60 ° C for 10
It is preferable to dry under reduced pressure for minutes to 10 hours.

(B) Transition metal compound Examples of the transition metal compound belonging to Group 4 of the periodic table used in the present invention include a titanium compound, a zirconium compound and a hafnium compound, and preferably a titanium compound. More preferably, the general formula Ti (O
R) _n X _4-n (wherein, Ti represents a titanium atom, O represents an oxygen atom, R represents an alkyl group having 1 to 4 carbon atoms, and X represents a chlorine atom, a bromine atom or an iodine atom. And n represents 0 or an integer of 1 to 3.).

Specific examples of the titanium compound represented by the general formula include titanium tetrachloride, titanium tetrabromide,
Titanium tetrahalogenated compounds such as titanium tetraiodide, methoxytitanium trichloride, ethoxytitanium trichloride, butoxytitanium trichloride, trihalogenated alkoxytitanium compounds such as ethoxytitanium tribromide, dimethoxytitanium dichloride, Dihalogenated dialkoxy titanium compounds such as diethoxy titanium dichloride, dibutoxy titanium dichloride, diphenoxy titanium dichloride, diethoxy titanium dibromide, trimethoxy titanium chloride, triethoxy titanium chloride, tributoxy titanium chloride, triphenoxy titanium chloride, tri Monohalogenated trialkoxy titanium compounds such as ethoxy titanium bromide, tetramethoxy titanium Down, tetraethoxy titanium,
Tetraalkoxy titanium compounds such as tetraphenoxytitanium. Preferred are titanium tetrahalide compounds, and particularly preferred is titanium tetrachloride.

(A) Solid catalyst component for olefin polymerization The solid catalyst component for olefin polymerization of the present invention comprises (a) a carrier comprising carboxyl group-containing polymer particles having an average particle diameter of 1 to 300 μm, and (b) It is obtained by bringing a transition metal compound of Group 4 of the periodic table into contact. The solid catalyst component for olefin polymerization of the present invention is used as a component to be brought into contact for the production thereof, as the first, second or first component of the periodic table.
No organometallic compounds of Group 3 metals are used. This makes it possible to produce an olefin polymer having an extremely low molecular weight and / or low crystallinity polymer production amount. The contact preparation time is not particularly limited, but is usually 5 minutes to 24 hours.

In preparing the solid catalyst component (A) by bringing the components into contact with each other, it is preferable to bring the components into contact with each other in a slurry state in the presence of a solvent, such as pentane, hexane, heptane, octane and decane. Aliphatic hydrocarbons, benzene, toluene, aromatic hydrocarbons such as xylene, cyclohexane, alicyclic hydrocarbons such as cyclopentane, 1,2-dichloroethane, halogenated hydrocarbons such as monochlorobenzene, diethyl ether, dibutyl ether, Ether compounds such as diisoamyl ether and tetrahydrofuran can be used. It is preferably an aliphatic hydrocarbon or an aromatic hydrocarbon, and more preferably hexane, heptane, octane, toluene or xylene.

The preparation of the solid catalyst component (A) is preferably carried out under an inert gas such as nitrogen or argon. Also,
The preparation temperature is preferably carried out under conditions where the polymer particles to be used can maintain the shape, and is usually -30 to 120 ° C.
Up to 0, but preferably 0
-100 ° C, more preferably 20-80 ° C.

With respect to the ratio of each component in the preparation of the solid catalyst component (A), the molar ratio of (b) the transition metal compound to the carboxyl group in the polymer carrier is usually 0.1%.
It is 100 times, preferably 0.1 to 10 times.

The obtained solid catalyst component (A) is preferably stored in a cool and dark place under an inert gas such as nitrogen or argon.

(B) Organoaluminum Compound and / or Organoaluminum Oxy Compound The olefin polymerization catalyst of the present invention comprises (A) the solid catalyst component for olefin polymerization described above, and (B) an organoaluminum compound and / or an organoaluminum compound. It is obtained by contacting an oxy compound.

The organoaluminum compound used in the present invention has at least one Al—C bond in the molecule. For example, the compound represented by the general formula R ⁴ _n AlZ _3-n ( _where
l represents an aluminum atom, and R ⁴ represents 1 to 1 carbon atoms.
Represents an alkyl group of 0, and Z represents a halogen atom or a hydrogen atom. n is a number satisfying 0 <n ≦ 3. ). Specific examples of such organoaluminum compounds include trimethylaluminum, triethylaluminum, trinormalpropylaluminum, trinormalbutylaluminum, triisobutylaluminum, tri-tert-butylaluminum, triisopropylaluminum, tripentylaluminum,
Trinormal hexyl aluminum, tri (2-methylpentyl) aluminum, trinormal octyl aluminum, diethyl aluminum hydride, diisobutyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isobutyl aluminum sesquichloride, dimethyl aluminum chloride, diethyl aluminum chloride, Dinormal propyl aluminum chloride,
Di-n-butylaluminum chloride, diisobutylaluminum chloride, di-tert-butylaluminum chloride, diisopropylaluminum chloride, dipentylaluminum chloride, methylaluminumdichloride, ethylaluminumdichloride, isobutylaluminumdichloride, tert
-Butyl aluminum dichloride, isopropyl aluminum dichloride, pentyl aluminum dichloride and the like. Of these organoaluminum compounds, diethylaluminum chloride, triethylaluminum, and triisobutylaluminum are more preferably used.

As the organoaluminum oxy compound, a known compound (aluminoxane) can be used. For example, a compound obtained by reacting one kind of trialkylaluminum with water, or a compound obtained by reacting two or more kinds of trialkylaluminum with water And the like obtained by the condensation of Specific examples include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane, isobutylaluminoxane or methylisobutylaluminoxane is preferably used.

As the component (B) used in the olefin polymerization catalyst of the present invention, the above-mentioned general formula R ⁴ _n AlZ _3-n (where Al represents an aluminum atom and R ⁴ has 1 to 1 carbon atoms) And Z represents a halogen atom or a hydrogen atom, and n is a number satisfying 0 <n ≦ 3.)

[Production of Olefin Polymer] In the production of an olefin polymer in the present invention, a method of supplying each catalyst component to a polymerization tank is, for example, a method in which water is contained in an inert gas such as nitrogen or argon without moisture. And a method of supplying in the presence of a monomer. (A) The solid catalyst component for olefin polymerization and (B) the organoaluminum compound and / or the organoaluminum oxy compound may be supplied individually or may be supplied in advance in contact with each other.

The amount of (B) the organoaluminum compound and / or the organoaluminum oxy compound is usually
(A) The molar amount of aluminum atoms per mole of transition metal atom in the solid catalyst component for olefin polymerization is from 1 to 1
It can be selected over a wide range, such as 0000 moles. Preferably, it is in the range of 1 to 3000 mol per mol of transition metal atom.

In the production of the olefin polymer according to the present invention, a known electron donor, hydrogen and the like may be allowed to coexist. As such an electron donor, preferably, Si-OR
An organic compound having a bond (here, R represents a hydrocarbon group having 1 to 20 carbon atoms) can be used.

Specific examples of the organic compound having a Si-OR bond include tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxysilane, diethoxydiethylsilane, ethoxytriethylsilane, tetraisopropoxysilane, and diisopropoxy. Diisopropylsilane, tetrapropoxysilane, dipropoxydipropylsilane, tetrabutoxysilane, dibutoxydibutylsilane, dicyclopentoxydiethylsilane, diethoxydiphenylsilane, cyclohexyloxytrimethylsilane, phenoxytrimethylsilane,
Tetraphenoxysilane, triethoxyphenylsilane, hexamethyldisilohexane, hexaethyldisilohexane, hexapropyldisiloxane, octaethyltrisiloxane, dimethylpolysiloxane, diphenylpolysiloxane, methylhydropolysiloxane, phenylhydropolysiloxane, etc. Examples can be given.

The solid catalyst component for olefin polymerization of the present invention may be used after pre-polymerization. The pre-polymerization is carried out, for example, by bringing the above-mentioned organoaluminum compound and olefin into contact. Examples of the olefin include ethylene, propylene, and butene-1. Preliminary polymerization may be either homopolymerization or copolymerization.

When the solid catalyst component for olefin polymerization of the present invention is preliminarily polymerized, it is preferable to slurry the catalyst component for olefin polymerization, but the solvent used in this case may be butane, pentane, hexane or heptane. And aromatic hydrocarbons such as toluene and xylene.

In the prepolymerization, the organoaluminum compound has an Al / Ti molar ratio of 0.1 to 100, especially 1 to 100.
It is preferable to use them in such a ratio as to be 10. The pre-polymerization temperature is preferably -30 to 80C, particularly preferably -10C to 50C. Prepolymerization amount is 1 g of solid catalyst component for olefin polymerization.
It is preferable to carry out in the range of 0.1 to 100 g, particularly 0.5 to 50 g per unit.

In the present invention, the (A) olefin polymerization solid catalyst component pre-polymerized or not pre-polymerized as described above may be used together with (B) the organoaluminum compound and / or the organoaluminum oxy compound together with the olefin polymer. For the production of

In the present invention, the olefins used for the polymerization may be any of olefins having 2 to 20 carbon atoms, diolefins and the like.
More than one olefin can be used. Specific examples of these include ethylene, propylene, butene-
1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 5-methyl-2-
Examples thereof include pentene-1, vinylcyclohexene and the like, but the present invention is not limited to the above compounds. Specific examples of the olefin constituting the copolymer composed of an olefin and another olefin include ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and octene-1, and propylene and butene-1. However, the present invention should not be limited to the above compounds.

The olefin polymer which can be produced by the present invention is preferably a copolymer of ethylene and an α-olefin, more preferably an ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / Hexene-1 copolymer or ethylene / octene-1 copolymer.

In the present invention, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the olefin polymer.

The polymerization can be carried out usually at a temperature ranging from -30 to 300 ° C, preferably from 20 to 2 ° C.
50 ° C., more preferably a temperature below the temperature at which the polymer melts.
0-100 ° C.

The polymerization pressure is not particularly limited, but is preferably from normal pressure to about 150 atm from the viewpoint of industrial and economical use. The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can range from 5 minutes to 40 hours.

As the polymerization process, any of a continuous system and a batch system can be applied. Slurry polymerization using an inert hydrocarbon solvent such as propane, pentane, hexane, heptane, and octane, solvent polymerization, liquid phase polymerization using no solvent, or gas phase polymerization can also be applied. The catalyst for olefin polymerization of the present invention is particularly suitable for slurry polymerization or gas phase polymerization.

[0048]

The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited to the examples. In addition, the measurement value of each item in an Example was measured by the following method.

(1) Ti content in catalyst Using Optima 3000 manufactured by PerkinElmer,
It was measured by CP emission analysis.

(2) Content of α-Olefin Unit in Copolymer Determined from the characteristic absorption of ethylene and α-olefin using an infrared spectrometer (IR-810 manufactured by JASCO Corporation).
Expressed as the number of short-chain branches per 1000 carbons (SCB).

(3) Melt flow rate (MFR) Measured at 190 ° C. according to ASTM D1238.

(4) Melt flow rate ratio (MFRR) The MFRR is the ratio of the melt flow rate (MFR) measured at 190 ° C. according to ASTM D1238 to the case where the load at the time of measurement was changed to 21.60 kg. Expressed as MFRR = (the amount of outflow when the load is 21.60 kg) ÷
(Amount of outflow with a load of 2.160 kg)

(5) Low molecular weight and / or low crystallinity component: The weight% of the polymer soluble in cold xylene at 20 ° C. (CX
S) was evaluated. In general, the value of CXS tends to increase as the value of SCB increases.

Example 1 (1) Washing of Polymer Particles An ethylene / acrylic acid copolymer (trade name, manufactured by Sumitomo Seika Co., Ltd.) was placed in a 200 ml round bottom flask equipped with a stirrer and purged with nitrogen gas. Beads, acrylic acid unit content 7.0% by weight, average particle size 30 μm, standard deviation of particle size distribution 15.1 μm) 10 g, and acetone 100 ml
Was added and stirring was continued at room temperature for 10 minutes. After this operation, polymer particles were collected by filtration using a glass filter. The obtained white solid and 100 ml of acetone were added to a round-bottom flask, and the above operation was repeated. The recovered polymer particles were dried at 40 ° C. for 3 hours under reduced pressure. Polymer particles having approximately the same weight as the charged amount were recovered.

(2) Preparation of solid catalyst component 100 ml with a stirrer sufficiently replaced with nitrogen gas
Of the ethylene / acrylic acid copolymer washed in the above (1) and 60 ml of n-heptane were introduced into the round bottom flask. 1.1 ml of titanium tetrachloride was added dropwise, and 40
Stirred at C for 1 hour. After the reaction, the reaction solution was filtered, and 20 m
1 was washed three times with hexane, and dried under reduced pressure at room temperature for 2 hours to synthesize a solid catalyst component (I). The Ti content in the solid catalyst component (I) was 14.3 μmol / g.

(3) Copolymerization of ethylene / butene-1 A 400 ml stainless steel pressure-resistant reaction tube equipped with a stirrer sufficiently substituted with nitrogen gas was evacuated, and 20 g of butene-1 and 80 g of n-butane were introduced. , The temperature in the system to 70
Temperature. Then, 6.0 kg / c of hydrogen was added.
m ² , 10 kg / cm ^{2 of} ethylene were introduced, and the mixture was stirred for a while until a saturated state was reached (a state in which the gauge pressure of ethylene did not decrease from 10 kg / cm ² ). 0.1 mmol
/ Ml of trioctyl aluminum in heptane 2m
1) Then, a liquid in which 21.8 mg of the solid catalyst component (I) was suspended in 5 ml of n-heptane was pressure-fed into the system with argon to initiate polymerization. One hour later, ethanol was charged into the system to stop the polymerization, and then the unreacted gas was purged to recover the copolymer. The obtained copolymer under reduced pressure,
After drying at 60 ° C. for 4 hours, 7.6 g of ethylene / butene-
One copolymer was obtained. No fine powder was confirmed in the obtained copolymer, and the particle properties were good. The SCB of the obtained copolymer was 18.4 (/ 1000C), and the MFR was 0.4.
5 (g / 10 min), the MFRR is 39.6,
CXS was 4.3 wt%.

[0057]

According to the present invention, when used together with an organometallic compound in the polymerization of olefins, the amount of the polymer having high activity and soluble in xylene at 20 ° C. (C
XS) A solid catalyst component for olefin polymerization capable of producing an olefin polymer having a very low particle weight and / or a low molecular weight and / or low crystallinity and having good particle properties, and an olefin polymerization catalyst using the same. And an olefin polymer having a very low molecular weight and / or low crystallinity expressed by the amount of a polymer soluble in xylene at 20 ° C. (CXS) using the catalyst and having a good particle property ( Among them, a method for producing ethylene / α-olefin copolymer) is provided.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Seiki Kiuchi 5-1, Anesaki Kaigan, Ichihara-shi, Chiba F-term (reference) in Sumitomo Chemical Co., Ltd. 4J028 AA01A AB00A AB01A AC01A AC04A AC05A AC06A AC07A AC24A AC25A BA00A BA00B BA01B BA02B BB00A BB00B BB01B BB02B BC15B BC16B BC17B BC18B BC25B CA02C CB09A CB91C CB92C DA01 DA02 DA03 EA01 EB02 EB04 EB05 EB07 EB08 EB09 EC01 EC03 FA02 FA04 FA06 GA02 GA07 GA21 GA24 4J100 AA02P AA03P AA03Q AA04P AA04Q AA07P AA15P AA16P AA16Q AA19P AA19Q AA20P AA21P AB02P AB09Q AJ02Q BA16H CA01 CA04 CA31 DA40 DA43 EA05 EA11 FA09 FA10 HA61 HC29 HC30 HC36 HC83 JA15

Claims (11)

[Claims] 1. A carrier obtained by contacting (a) a carrier composed of polymer particles having a carboxyl group having an average particle diameter of 1 to 300 μm and (b) a transition metal compound of Group 4 of the periodic table. Solid catalyst component for olefin polymerization. (2) A carrier comprising a carboxyl group-containing polymer particle having an average particle diameter of 1 to 300 μm is obtained by washing a carboxyl group-containing polymer particle having an average particle diameter of 1 to 300 μm with an organic solvent. The solid catalyst component for olefin polymerization according to claim 1, which is a carrier composed of particles. 3. A carrier comprising a carboxyl group-containing polymer particle having an average particle size of 1 to 300 μm, which is obtained by slurrying a carboxyl group-containing polymer particle having an average particle size of 1 to 300 μm with an organic solvent, followed by filtration. The solid catalyst component for olefin polymerization according to claim 1, which is a carrier comprising particles obtained by drying and drying. 4. The polymer particle having a carboxyl group having an average particle diameter of 1 to 300 μm is a polymer particle having a carboxyl group having a standard deviation of particle size distribution of 0.1 to 50 μm. The solid catalyst component for olefin polymerization according to the above. 5. The polymer having a carboxyl group is a copolymer containing an unsaturated monomer unit having a carboxyl group, or a polymer having a carboxyl group introduced by chemical or physical modification. 1-4
The solid catalyst component for olefin polymerization according to any one of the above. 6. The solid catalyst component for olefin polymerization according to claim 1, wherein the polymer having a carboxyl group is a copolymer of ethylene and acrylic acid. (B) The transition metal compound of Group 4 of the periodic table has a general formula: Ti (OR) _n X _4-n (wherein, Ti represents a titanium atom, O represents an oxygen atom, and R Represents an alkyl group having 1 to 4 carbon atoms, X represents a chlorine atom, a bromine atom or an iodine atom, and n represents 0 or an integer of 1 to 3.) ~
6. The solid catalyst component for olefin polymerization according to any one of 6. 8. A catalyst obtained by contacting (A) the solid catalyst component for olefin polymerization according to any one of claims 1 to 7 and (B) an organic aluminum compound and / or an organic aluminum oxy compound. Olefin polymerization catalyst. 9. A method for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to claim 8. 10. The olefin polymer according to claim 9, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.
The method for producing the olefin polymer according to the above. 11. An olefin polymerization comprising contacting (a) a carrier composed of polymer particles having a carboxyl group having an average particle diameter of 1 to 300 μm, and (b) a transition metal compound of Group 4 of the periodic table. Of producing a solid catalyst component for use.