JP2001163913A - 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 solid catalyst component for olefin polymerization which shows a high activity when used in combination with an organometallic compound in the polymerization of olefins and which can prepare an olefin polymer which contains an extremely small amount of a low-molecular-weight and/or a low crystalline polymer which is indicated as the amount of the polymer soluble in xylene at 20 deg.C, CXS, and a catalyst for olefin polymerization using the same and a preparation method of an olefin polymer using the catalyst. SOLUTION: The solid catalyst component for olefin polymerization is obtained by contacting (a) a polymer support having a carboxylic group with (b) a compound of a group IV transitional metal in the periodic table and (c) a phenol compound. 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.

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.

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.

[0005]

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. Under such circumstances, the problem to be solved by the present invention, that is, an object of the present invention, is to use an amount of a polymer (CX) which exhibits high activity and is soluble in xylene at 20 ° C. by using it together with an organometallic compound in olefin polymerization.
S) A solid catalyst component for olefin polymerization capable of producing an olefin polymer having an extremely small amount of the low molecular weight and / or low crystalline polymer represented by S), an olefin polymerization catalyst using the same, and an olefin using the catalyst An object of the present invention is to provide a method for producing a polymer (among others, an ethylene / α-olefin copolymer) and a method for producing the solid catalyst component for olefin polymerization.

[0006]

The present invention provides an olefin obtained by contacting (a) a polymer carrier having a carboxyl group, (b) a transition metal compound belonging to Group 4 of the periodic table, and (c) a phenol compound. It relates to a solid catalyst component for polymerization. The present invention also relates to (A) the solid catalyst component for olefin polymerization, and (B) a catalyst for olefin polymerization obtained by contacting an organoaluminum compound and / or an organoaluminum oxy compound. The present invention relates to a method for producing an olefin polymer using a polymerization catalyst. Further, the present invention provides (a) a polymer carrier having a carboxyl group,
(B) a transition metal compound of Group 4 of the periodic table, and (c)
The present invention relates to a method for producing a solid catalyst component for olefin polymerization in which a phenol compound is brought into contact. Hereinafter, the present invention will be described in detail.

[0007]

DETAILED DESCRIPTION OF THE INVENTION (a) Polymer Carrier Having Carboxyl Group The carrier used in the present invention is a polymer carrier having a carboxyl group. 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.

More preferably, the copolymer containing an unsaturated monomer unit having a carboxyl group is 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.

[0010] 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 are preferred. Polymer particles having an average particle size of preferably 3 to 200 μm, more preferably 5 to 80 μm are used. The carrier used in the present invention has a standard deviation of particle size distribution of 0.1 to 50.
μm polymer particles are preferable, and the standard deviation is more preferably 1 to 30 μm, and still more preferably 3 to 30 μm.
20 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 by 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. As the carrier (a) used in the present invention, a carrier composed of particles obtained by washing polymer particles having a carboxyl group with an organic solvent is more preferable. More specifically, as the carrier (a) used in the present invention, a carrier composed of particles obtained by slurrying polymer particles having a carboxyl group with an organic solvent, followed by filtration and drying 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 here, an organic solvent that 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 an organic solvent is preferably carried out under such a condition that the polymer particles used do not dissolve and the shape can be maintained, 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 a titanium compound is preferable. 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.

(C) Phenol compound As the phenol compound used in the present invention, unsubstituted or substituted phenols can be used, but a phenol compound having a substituent at least at the 2-position is preferable, and at least 2,6 A phenol compound having a substituent at the position is particularly preferably used. Here, the substituent is preferably a halogen atom, or an alkyl group, an aralkyl group, an aryl group, a silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a silyloxy group which may be substituted with a halogen atom.

Specific examples of phenol compounds include:
2-methylphenol, 2-ethylphenol, 2-n
-Butylphenol, 2-isobutylphenol, 2-
t-butylphenol, 2-n-propylphenol,
2-isopropylphenol, 2-phenylphenol, 2-fluorophenol, 2-chlorophenol,
2-substituted phenols such as 2-bromophenol, 2,
6-dimethylphenol, 2,6-diethylphenol, 2,6-di-n-butylphenol, 2,6-diisobutylphenol, 2,6-di-t-butylphenol, 2,6-di-n-propylphenol, 2,6 such as 2,6-diisopropylphenol, 2,6-diphenylphenol, 2,6-difluorophenol, 2,6-dichlorophenol and 2,6-dibromophenol
-Substituted phenol, 2,4,6-trimethylphenol, 2,6-di-t-butyl-4-methylphenol,
2,6, X-substituted phenols such as pentafluorophenol (X is one or more numbers selected from 3, 4 and 5). Preferably, 2-methylphenol, 2-ethylphenol, 2-n-butylphenol, 2-isobutylphenol, 2-t-butylphenol, 2-n-propylphenol, 2-isopropylphenol, 2-phenylphenol, 2,6 -Dimethylphenol, 2,6-diethylphenol, 2,
6-di-n-butylphenol, 2,6-diisobutylphenol, 2,6-di-t-butylphenol, 2,
6-di-n-propylphenol, 2,6-diisopropylphenol and 2,6-diphenylphenol. More preferably, the phenol compound is a 2-substituted phenol, a 2,6-substituted phenol, or a 2,6, X-substituted phenol wherein the substituent is a branched alkyl group, a cycloalkyl group or an aryl group (X is as defined above). ).

(A) Solid catalyst component for olefin polymerization The solid catalyst component for olefin polymerization of the present invention comprises (a) a polymer carrier having a carboxyl group, (b) a transition metal compound of Group 4 of the periodic table, and (C) It is obtained by contacting a phenol compound. The solid catalyst component for olefin polymerization of the present invention does not use an organometallic compound of a Group 1, 2 or 13 metal of the periodic table as a component to be brought into contact for its production. This makes it possible to produce an olefin polymer having an extremely low molecular weight and / or low crystallinity polymer production amount.

The order of contact of the above components is not limited, but after contacting (b) and (c), the product is contacted with (a) to obtain a solid catalyst component for olefin polymerization. preferable. Although each step may be performed successively, it is preferable to wash the product with a solvent for each step. The contact preparation time is not particularly limited, but is usually 5 minutes to 24 hours in each step.

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 performed 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 preparing the solid catalyst component (A), the molar ratio of the transition metal compound (b) to the carboxyl group (a) in the polymer carrier is usually 0.1.
It is 100 times, preferably 0.1 to 10 times.
The molar ratio of the phenol compound (c) to the transition metal compound (b) is usually 0.1 to 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 catalyst for olefin polymerization 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 and two or more kinds of trialkylaluminum and water are used. 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.

The component (B) used in the olefin polymerization catalyst of the present invention includes the above-mentioned general formula R ⁴ _n AlZ _3-n (wherein, 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 for supplying each catalyst component to a polymerization tank may be, 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 producing an olefin polymer in the present invention, a known electron donor, hydrogen, or 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 preliminary 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 also preferable to make the catalyst component for olefin polymerization into a slurry, but the solvent used in this case includes butane, pentane, hexane and heptane. And aromatic hydrocarbons such as toluene and xylene.

In the pre-polymerization, the organoaluminum compound is used in a molar ratio of Al / Ti 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 solid catalyst component for (A) olefin polymerization pre-polymerized or not pre-polymerized as described above is 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 in 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 of 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.

[0050]

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, I
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 measurement obtained by changing the measurement load 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:% by weight of a cold xylene-soluble portion 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 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. 10 g of beads, an acrylic acid unit content of 7.0% by weight, an average particle diameter of 30 μm, a standard deviation of the particle size distribution of 8.3 μm), and 100 ml of acetone were 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 500 ml with a stirrer sufficiently replaced with nitrogen gas
Heptane 200 ml, 2-tert-
48.1 ml of butylphenol was added, and the temperature was raised while stirring until the temperature reached 40 ° C. A solution consisting of 17.6 ml of titanium tetrachloride and 80 ml of heptane was added dropwise over 70 minutes, and the temperature was raised to 60 ° C., followed by a reaction for 2 hours. After the reaction, 12
The solvent was evaporated at 0 ° C. to dryness. Hexane 2
Wash twice with 00 ml, at 120 ° C., 3
After drying for 0 minutes, the mixture was cooled to room temperature to obtain a solid component. 300 equipped with a stirrer sufficiently replaced with nitrogen gas
37.5 g of the solid component obtained above in a ml round bottom flask
(90 mmol of Ti atom) and 180 ml of heptane were added to form a slurry, and 18 g of the ethylene / acrylic acid copolymer washed in the above (1) and 10 ml of n-heptane were added. After stirring and reacting at 40 ° C. for 1 hour, the reaction solution was filtered, washed three times with 20 ml of hexane, and dried under reduced pressure at room temperature for 2 hours to synthesize a solid catalyst component (II).
The Ti content in the solid catalyst component (II) was 22.9 μmol /
g.

(3) Ethylene / butene-1 copolymerization A 400 ml pressure-resistant stainless steel 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 21.0 mg of the solid catalyst component (II) 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, 14.4 g of an ethylene / butene-1 copolymer was obtained. No fine powder was confirmed in the obtained copolymer, and the particle properties were good. The resulting copolymer had an SCB of 15.6 (/ 1000C) and an MFR of 0.1.
At 54 (g / 10 min), MFRR was 24.7 and CXS was below the detection limit.

[0059]

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 an extremely small amount of a low-molecular-weight and / or low-crystalline polymer represented by XS), an olefin polymerization catalyst using the same, and using the catalyst , 20 ° C
The present invention provides a method for producing an olefin polymer (especially an ethylene / α-olefin copolymer) having an extremely small amount of a low molecular weight and / or low crystalline polymer represented by the amount of a polymer soluble in xylene (CXS). Is done.

[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.

Continued on the front page (72) Inventor Seiki Kiuchi 5-1, Anesaki Beach, Ichihara-shi, Chiba F-term (reference) in Sumitomo Chemical Co., Ltd. 4J028 AA01A AB01A AC01A AC04A AC05A AC06A AC07A AC22A BA00A BA01B BB00A BB01B BC15B BC16B BC17B BC19 BC25B BC27B CB25A CB91C CB92C EB02 EB04 EB05 EB07 EB08 EB09 EB17 EC01 EC02 EC03 FA01 FA02 FA04

Claims (9)

[Claims] 1. A solid for olefin polymerization obtained by contacting (a) a polymer carrier having a carboxyl group, (b) a transition metal compound of Group 4 of the periodic table, and (c) a phenol compound. Catalyst component. 2. The method according to claim 1, wherein (c) the phenol compound is at least 2
The solid catalyst component for olefin polymerization according to claim 1, which is a phenol compound having a substituent at the 2-position. 3. 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. 3. The solid catalyst component for olefin polymerization according to 1 or 2. 4. The method according to claim 1, wherein the polymer having a carboxyl group is a copolymer of ethylene and acrylic acid.
The solid catalyst component for olefin polymerization according to the above. (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.) ~
5. The solid catalyst component for olefin polymerization according to any one of 4. 6. A catalyst obtained by contacting (A) the solid catalyst component for olefin polymerization according to any one of claims 1 to 5, and (B) an organoaluminum compound and / or an organoaluminum oxy compound. Olefin polymerization catalyst. 7. A process for producing an olefin polymer, comprising using the catalyst for olefin polymerization according to claim 6. 8. The method according to claim 7, wherein the olefin polymer is a copolymer of ethylene and an α-olefin. 9. A solid catalyst component for olefin polymerization characterized by contacting (a) a polymer carrier having a carboxyl group, (b) a transition metal compound of Group 4 of the periodic table, and (c) a phenol compound. Manufacturing method.