JPH06192329A - Carrier for alpha-olefin polymerization catalyst and production - Google Patents

Abstract

PURPOSE:To obtain the subject carrier having spherical form with narrow particle size distribution and, accordingly, giving a solid catalyst having excellent fluidity and polymerization activity in fluidized bed reactor by reacting a solution of a Grignard compound with a halogenated hydrocarbon compound. CONSTITUTION:The objective carrier is produced by reacting a solution of a Grignard compound (preferably alkylmagnesium chloride such as methylmagnesium chloride) with a halogenated hydrocarbon compound (preferably a hydrocarbon compound containing Cl-C bond such as chloroform). This reaction is preferably carried out by dissolving the Grignard compound in a hydrocarbon solvent containing >=20vol.% of an ether having total carbon number of >=6 (e.g. dipropyl ether), slowly adding the halogenated hydrocarbon to the obtained solution at <=60 deg.C slowly raising the reaction temperature to <=50 deg.C under stirring and collecting the precipitated solid particles.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a catalyst carrier for .alpha.-olefin polymerization and a method for producing a solid catalyst for ethylene copolymerization.

[0002]

2. Description of the Related Art Up to now, α-olefin polymers using a Ziegler type catalyst have been produced by solution, bulk, slurry or gas phase polymerization methods.
In recent years, the activity of the catalyst has been remarkably improved, and a process that does not require a step of separating the catalyst residue from the produced polymer has become widespread. Particularly, the method of polymerizing an α-olefin in a fluidized bed polymerization reactor has an industrial value. Is high and attracts attention.

When a polymer is produced in a fluidized bed polymerization reactor, the temperature of the system is kept constant by preventing local accumulation of polymerization heat during the polymerization, and the produced polymer particles form a large lump and flow. It is important to prevent the state from being destroyed. For example, JP-A-57-59903, 59-8706, and 59-2.
2907, 59-22908, 59-64611, and
In 59-71309, 60-42404, 60-133011, 62-232405, 62-297304, etc., the particle size distribution is narrow and transition to magnesium chloride is close to spherical. It is disclosed that a granular catalyst carrying a metal component is polymerized while maintaining a fluid state by an upward flow of a monomer gas.

Further, Japanese Patent Publication No. 52-40350 and 52-45749
JP-A No. 60-53044, JP-A No. 59-30806, and the like, preliminarily prepared a prepolymer, by using this prepolymer in a fluidized bed polymerization reactor, transition metal It is disclosed that the amount of polymer produced per weight is improved and that abrupt heat generation, particle aggregation and particle disintegration are prevented in the solid catalyst portion immediately after introduction into the fluidized bed polymerization reactor. In the above catalyst carrier or prepolymer, in order to achieve the above object, the particle size distribution thereof is relatively narrow, the average particle size is a certain value or more, and the particle size is extremely small. It is desirable that the ratio of the particles is smaller and the shape of the particles is spherical.

Up to now, for example, JP-A-59-22907,
59-22908, 62-232405, 62-297304
The publication discloses a method for producing a spherical catalyst carrier or solid catalyst having a narrow particle size distribution while controlling the shape and particle size distribution by the reaction of an organomagnesium compound and an organic halide. However, there is known a method for producing a catalyst carrier and a solid catalyst having a narrow particle size distribution and a nearly spherical shape by using an organomagnesium halide, which can be produced relatively easily and inexpensively, by a reaction between the organomagnesium halide and the organohalide. Not not. Further, the conventional techniques are not always industrially satisfactory in the production of ethylene polymers in a fluidized bed polymerization reactor, and the physical properties of the obtained polymers are not always industrially satisfactory, and further improvement is desired.

[0006]

DISCLOSURE OF THE INVENTION The present invention discloses a catalyst carrier having a spherical shape and a narrow particle size distribution, which can be used for the polymerization or copolymerization of α-olefins, and a method for producing a solid catalyst for ethylene copolymerization. To do.

[0007]

[Means for Solving Problems] The present invention is
A method for producing a catalyst carrier for α-olefin polymerization, which comprises reacting a Grignard compound solution with a halogenated hydrocarbon compound, and second, the catalyst carrier from an electron donor and titanium, zirconium, hafnium and vanadium. Ethylene and α with 3 or more carbon atoms characterized by being contact-treated with at least one selected transition metal compound
-A method for producing a solid catalyst for copolymerization with an olefin.

The catalyst carrier for α-olefin polymerization of the present invention can be produced by the following method. A particulate solid is formed by reacting the Grignard compound solution with a halogenated hydrocarbon compound. More preferably, a spherical solid carrier as a carrier is obtained by adding a chlorinated hydrocarbon compound to a solution of a Grignard compound containing 20% by volume or more of an ether having a total carbon number of 6 or more and reacting at 60 ° C. or less.

In the present invention, the Grignard compound is represented by the formula R ¹ MgX ¹ (wherein R ¹ represents a hydrocarbon group having 1 to 20 carbon atoms and X ¹ represents a halogen atom). Alkylmagnesium chloride in which X ¹ is a chlorine atom is preferably used, and specific examples thereof include methylmagnesium chloride, ethylmagnesium chloride, n-butylmagnesium chloride and n-hexylmagnesium chloride.

In general, the Grignard compound can be prepared as an ether solution or as a solution in a hydrocarbon solvent containing a minimal amount of ether. In particular, it is preferable that the total amount of ether having 6 or more carbon atoms is 20% by volume or more in the Grignard compound. Specific examples of the ether having 6 or more carbon atoms include dipropyl ether, diisopropyl ether, dibutyl ether,
Examples thereof include diisobutyl ether, diisoamyl ether and dihexyl ether.

In the present invention, an ether having a total carbon number of less than 6 may be mixed and used in addition to the above-mentioned ether having a total carbon number of 6 or more. It is preferably a capacity. Particularly in the case of tetrahydrofuran (having 4 carbon atoms) which is commonly used as a solvent for Grignard compounds, it is preferably 10% by volume or less, particularly 5% by volume or less. Further, the solution of the Grignard compound, hexane, heptane, octane, toluene, xylene, hydrocarbon solvents such as cyclohexane may be mixed with ether, but these hydrocarbon solvents are usually less than 80% by volume, preferably Is less than 60% by volume. When the content of ether having a total carbon number of 6 or more in the Grignard compound solution is less than 20% by volume, the shape of the obtained carrier solid tends to be non-uniform, the particle size distribution is narrow, and a spherical catalyst carrier can be used. Hard to get.

As the halogenated hydrocarbon compound to be reacted with the solution in which the Grignard compound of the present invention is dissolved,
Particularly preferred are saturated or unsaturated hydrocarbon compounds containing a chlorine-carbon bond. Specific examples thereof include chloroform, methylene chloride, methyl chloride, ethyl chloride, propyl chloride, isopropyl chloride, butyl chloride, sec-butyl chloride,
Examples include tert-butyl chloride, hexyl chloride, chlorobenzene, dichlorobenzene, trichlorobenzene and benzyl chloride. Besides the above compounds,
An ether compound containing a halogen / carbon bond can also be used, and specific examples thereof include bis-2-chloroethyl ether and 2-chloroethyl methyl ether.

In the present invention, a carrier is produced by reacting a Grignard compound solution with a halogenated hydrocarbon compound. The reaction method is not particularly limited, but a method of adding a halogenated hydrocarbon compound to a container charged with the Grignard compound solution can be used. The reaction temperature is preferably maintained at 60 ° C or lower, and particularly preferably 50 ° C or lower. In this reaction, the temperature, the time, the addition rate of the halogenated hydrocarbon compound, the stirring rate of the reaction solution and the like influence the shape, particle size and particle size distribution of the carrier particles formed. A preferred reaction method is to gradually add the halogenated hydrocarbon compound to the Grignard compound solution while maintaining the temperature at 60 ° C or lower, and then stir the reaction solution at a reaction temperature of 60 ° C, more preferably within a range not exceeding 50 ° C. While gradually raising the temperature, the solid particles are precipitated. By this method, the shape, particle size, and particle size distribution of particles can be controlled. The proportion of the halogenated hydrocarbon compound used for the reaction between the Grignard compound solution and the halogenated hydrocarbon compound is preferably 0.5 mol or more, and particularly preferably 1 mol or more per 1 mol of the Grignard compound.

In the present invention, during the reaction of the Grignard compound solution and the halogenated hydrocarbon compound, unless the Grignard compound is brought into contact with the Grignard compound to precipitate a solid at room temperature, the Grignard compound solution does not previously contain a halogen-metal bond. / Or an organometallic compound can be made to coexist. The metal component of this compound is selected from boron, aluminum and silicon. This compound preferably has an alkoxy group, for example, (1) when the metal is boron, the formula B (OR ² ) _n R ³ _{3 -n} ,
(2) When the metal is aluminum, the formula Al (OR ² ) _n R ³ _3-n , (3)
When the metal is silicon, a compound represented by the formula Si (OR ² ) _n R ³ _4-n can be mentioned. In the formula, R ² and R ³ represent a hydrocarbon group having 1 to 20 carbon atoms, and 0 ≦ n 2 ≦ (maximum valence of each metal). Specific examples of R ² and R ³ include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, hexyl, heptyl, isoamyl, octyl and phenyl groups.

Specific examples of the organoaluminum compound (2) above include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-
Alkyl aluminum dialkoxide or dialkyl aluminum such as trialkyl aluminum such as hexyl aluminum, methyl aluminum -t-butoxide, ethyl aluminum -t-butoxide, ethyl aluminum isopropoxide, isobutyl aluminum -t-butoxide, isobutyl aluminum isopropoxide. Alcoxides can be mentioned. The above-mentioned aluminum alkoxide compound can be easily prepared by reacting a desired molar ratio of trialkylaluminum with an alcohol.

The α-olefin polymerization catalyst carrier of the present invention is treated with a transition metal compound, or
By treatment with a suitable conventionally known electron donor and transition metal compound, a polymer of ethylene with high activity, ethylene having a relatively narrow composition distribution and α having 3 or more carbon atoms can be obtained.
-Used in the production of solid catalysts which give copolymers with olefins or highly stereoregular polymers of α-olefins. In particular, it is possible to produce a solid catalyst that can be suitably used in a gas phase polymerization method. This solid catalyst is used for the polymerization of α-olefin in the form of a suitable organoaluminum compound or a combination of an organoaluminum compound and an electron donor.

The solid catalyst for copolymerization of ethylene and the α-olefin having 3 or more carbon atoms of the present invention can be produced, for example, according to the following method. In the first method, the catalyst carrier obtained by the above method is continuously contact-treated with an electron donor and at least one transition metal compound selected from titanium, zirconium, hafnium and vanadium. The order of contact treatment of the electron donor and the transition metal compound with the carrier is not particularly limited, but a method in which the carrier and the electron donor are first contacted and then the transition metal compound is subsequently contacted is preferable.

The electron donor used in the present invention includes organic acid esters, inorganic acid esters, acid halides, ethers,
Acid amides, N, N-dialkyl acid amides, amines, nitriles, acid anhydrides, silicate compounds, ketones, alcohols, aldehydes, carboxylic acids, isocyanates and the like can be used. A silicate compound is particularly preferable.

Specific examples of organic acid esters include methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate and dichloro. Ethyl acetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, toluic acid Methyl, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadicate, diisopropyl tetrahydrophthalate, phthalate Diethyl phthalate, diisobutyl phthalate,
Examples thereof include di-n-butyl phthalate, di-2-ethylhexyl phthalate, diheptyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide and ethylene carbonate.

Specific examples of acid halides include acetyl chloride, toluic acid chloride, anisic acid chloride and the like. Specific examples of ethers include diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, anisole, diphenyl ether epoxy-p-menthane and the like. Specific examples of the acid amides include acetic acid amide, benzoic acid amide,
Examples thereof include toluic acid amide. Specific examples of N, N-dialkyl amides include dimethylformamide and dimethylacetamide.

Specific examples of amines include methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline and tetramethylenediamine. Specific examples of nitriles include acetonitrile,
Examples thereof include benzonitrile and tolunitrile. Specific examples of the acid anhydride include acetic anhydride, phthalic anhydride, benzoic anhydride and the like.

Specific examples of the silicate compound include tetramethoxysilane, tetraethoxysilane and tetra-n-
Propoxysilane, tetra-n-butoxysilane, tetra-isopentoxysilane, tetra-n-hexoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-butoxysilane, methyltriisopentoxysilane, methyltri-n -Hexoxysilane,
Ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltriisopentoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane,
Isopentyl triethoxysilane, isopentyl tri-
n-butoxysilane, dimethyldiethoxysilane, dimethyldi-n-butoxysilane, dimethyldiisopentoxysilane, diethyldiethoxysilane, diethyldiisopentoxysilane, diisobutyldiisopentoxysilane,
Di-n-butyldiethoxysilane, diisobutyldiisopentoxysilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisobutoxysilane, triethylisopropoxysilane, tri-n-propylethoxysilane, tri-n-butylethoxysilane, Triisopentylethoxysilane, phenyltriethoxysilane, phenyltriisobutoxysilane, phenyltriisopentoxysilane, diphenyldiethoxysilane, diphenyldiisopentoxysilane, diphenyldioctoxysilane, triphenylmethoxysilane, triphenylethoxy Silane, triphenylisopentoxysilane, benzyltriethoxysilane, benzyltributoxysilane, dibenzyldiethoxysilane, cyclopentyltrimethoxysilane, 2- Chill cyclopentanol trimethoxysilane, 2,3-dimethyl cyclopentene trimethoxysilane, cyclopentene triethoxysilane, tri cyclopentylethoxy silane.

Specific examples of the ketones include methyl ethyl ketone, acetylacetone, methyl isobutyl ketone,
Examples include acetophenone and benzophenone. Specific examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, octanol, dodecanol, and benzyl alcohol. Particularly preferred electron donors are phthalic acid diesters, silicate compounds, acetylacetone, dimethylformamide and tetrahydrofuran. Two or more of these electron donors may be used in combination. Further, the carrier may be contact-treated by using the electron donor stepwise twice or more.

The conditions for the case where the carrier is first contacted with an electron donor and then with a transition metal compound to produce a catalyst are shown below. The contact treatment between the catalyst carrier and the electron donor is usually carried out in an inert organic solvent, usually at a treatment temperature of 10 to 100 ° C, preferably 20 to 60 ° C, particularly preferably 25 to 45 ° C, and a treatment time of It is usually carried out for 1 minute to 10 hours, preferably 10 minutes to 3 hours. The amount of the electron donor used is usually 0.5 to 1 g of the carrier.
100 mM, preferably 2-50 mM, particularly preferably 5-30 mM
Is preferred. When the amount of the electron donor used exceeds 100 mM, the polymerization activity of the catalyst is lowered and the shape tends to be deteriorated. If it is less than 0.5 mM, it becomes difficult to obtain a copolymer having a narrow composition distribution.

In the subsequent contact treatment with the transition metal compound, the solid is separated from the organic solvent by filtration after the contact treatment with the catalyst carrier and the electron donor, and the washing with the organic solvent is repeated to remove the unsupported electron donor. Alternatively, it can be continuously carried out without separation or washing. Preferably, the transition metal compound is subsequently subjected to a contact treatment without separation and washing.

The transition metal compound has the formula MX ² _p (O
R ⁴ ) _pq R ⁵ _pqr (where M is titanium, zirconium,
Indicates hafnium or vanadium, X ² is a halogen atom, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 20 carbon atoms, p is the maximum valence of the metal, and 0 <q <p, 0 <q + r <p. ), A transition metal halide, a hydrocarbyl oxyhalide, a hydrocarbyloxy halide, a hydrocarbyloxyhydrocarbyl halide, a hydrocarbyl halide, a hydrocarbyloxyhydrocarbyl halide and the like. In the above formula
R'includes a cycloalkadiene with π coordination,
Further, a transition metal compound, which is usually called metallocene, having two cycloalkadiene ligands independently / or by bridging can be employed.

A titanium compound can be preferably used as the transition metal compound. Specific examples thereof include methoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxychlorotitanium, ethoxytrichlorotitanium,
Diethoxydichlorotitanium, propoxytrichlorotitanium, dipropoxydichlorotitanium, butoxytrichlorotitanium, dibutoxydichlorotitanium, phenoxytrichlorotitanium, diphenoxydichlorotitanium, methoxytribromotitanium, phenoxytribromotitanium, methoxytriiodotitanium. , Phenoxytriiodotitanium, tetrachlorotitanium, tetrabromotitanium, tetraiodotitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium and the like. Two or more kinds of these titanium compounds may be used in combination. Among them, tetrachlortitanium, methoxytrichlortitanium,
Dimethoxydichlorotitanium, ethoxytrichlorotitanium, diethoxydichlorotitanium, propoxytrichlorotitanium, dipropoxydichlorotitanium, butoxytrichlorotitanium and dibutoxydichlorotitanium are particularly preferably used.

The contact treatment temperature with the transition metal compound is usually 10 to 100 ° C., preferably 20 to 60 ° C., and particularly preferably 25.
It is preferable that the treatment is performed at ˜45 ° C. for 10 minutes to 10 hours. After the contact treatment, it is preferable to obtain a solid catalyst by repeating filtration separation of the solid from the organic solvent and washing with the organic solvent. The amount of the transition metal compound used is preferably determined according to the amount of the electron donor used in the treatment of the electron donor of the carrier. That is, the molar ratio of electron donor / transition metal compound is preferably 1/20 to 2, particularly 1/5.
~ 1 is preferred. If the molar ratio is smaller than 1/20, the composition distribution of the copolymer is narrow, and if it is larger than 2, the polymerization activity of the catalyst tends to decrease.

In the present invention, if a copolymer of ethylene and α-olefin is produced by the catalyst obtained by the first method in which the carrier is continuously contact-treated with a specific amount of electron donor and transition metal compound, It is possible to suppress the production of adhesive components having a high α-olefin content, and to obtain a copolymer having a narrow composition distribution. Further, according to the method for producing a catalyst of the present invention, the transition metal component which is not involved in the activity on the carrier is removed as much as possible, thus the polymerization activity per transition metal component is increased and the deashing step of the polymer can be omitted. Furthermore, the residual amount of the transition metal compound in the waste liquid can be reduced, thus facilitating the treatment of the waste liquid.

The solid catalyst for copolymerization of ethylene with an α-olefin having 3 or more carbon atoms of the present invention comprises, as a second method,
It is obtained by catalytically treating the support with a mixture of at least one transition metal compound selected from titanium, zirconium, hafnium and vanadium and an electron donor. In this method, as the electron donor and the transition metal compound, those described in the first method can be adopted.

The contact treatment between the carrier and the above mixture is usually carried out.
It can be carried out in an inert organic solvent, and the carrier or the organic solvent slurry is contacted with the mixture or the organic solvent solution of the mixture. The treatment temperature is usually 10 to 100 ° C., preferably 20 to 60 ° C., particularly preferably 25 to 45 ° C., and the treatment time is preferably 10 minutes to 10 hours. The ratio of both components in the mixture of the transition metal compound and the electron donor is
It is important because it greatly affects the performance of the catalyst solid. The electron donor / transition metal compound molar ratio is preferably 1/20 to 2, and particularly preferably 1/5 to 1. If this molar ratio is less than 1/20, a copolymer having a narrow composition distribution cannot be obtained, and if it is more than 2, the polymerization activity of the catalyst tends to decrease. The amount of the mixture used for the carrier is usually 0.5 electron donor / g carrier.
˜100 mM, preferably 2 to 50 mM, particularly preferably 5 to 30 mM. If the amount of the electron donor used exceeds 100 mM, the shape of the catalyst tends to deteriorate. If it is less than 0.5 mM, the polymerization activity tends to decrease. After the contact treatment, the solid can be separated by filtration from the organic solvent and washed with the organic solvent repeatedly, or the solid can be used as a catalyst for the copolymerization of ethylene and α-olefin without washing.

The solid catalyst for copolymerization of ethylene and the α-olefin having 3 or more carbon atoms of the present invention is, as a third method,
It is obtained by first treating the carrier with an electron donor and then with a mixture of an electron donor and at least one transition metal compound selected from titanium, zirconium, hafnium and vanadium. In this method, as the electron donor and the transition metal compound, those described in the first method can be adopted. The contact treatment condition with the first electron donor and the contact treatment condition with the following mixture are:
Those described in the first and second methods can be adopted.

In the present invention, in the presence of the solid catalyst obtained by the above production method and the organoaluminum compound,
It is possible to copolymerize ethylene with an α-olefin having 3 or more carbon atoms. In the copolymerization of ethylene, a small amount of non-cyclic or cyclic non-conjugated diolefin can be terpolymerized. Examples of the organoaluminum compound used together with the catalyst solid include trialkylaluminum, dialkylaluminum halide, dialkylaluminum hydride and alkylalumoxane (usually 2
To 20 parts by weight) and the like. Specific examples thereof include trimethyl aluminum, triethyl aluminum, tributyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, diethyl aluminum chloride, diethyl aluminum hydride, isoprenyl aluminum,
Methylalumoxane may be mentioned.

The α-olefin having 3 or more carbon atoms to be copolymerized with ethylene of the present invention includes, for example, propylene and butene.
-1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, cyclopentene and cyclohexene. Non-conjugated diolefins include, for example, non-conjugated linear or dicyclopentadiene such as 1,5-hexadiene, 5-
Examples include cyclic unsaturated compounds such as ethylidene-2-norbornene and vinylcyclohexene.

Polymerization or copolymerization of ethylene and α-olefin having 3 or more carbon atoms in the present invention is carried out by a stirring type or fluidized bed type gas phase method, a slurry method in an inert hydrocarbon solvent, a high temperature high pressure tubular method, a high temperature method. It can be adopted in any polymerization method of the solution method. Particularly, in the present invention using a solid catalyst having an excellent carrier shape, that is, a catalyst shape, a fluidized bed type gas phase method can be preferably adopted. In the slurry method, the stirring type or fluidized bed type gas phase method, the polymerization temperature is usually 5 to 100 ° C. and the polymerization time is 20 to
It can be carried out for 300 minutes under the conditions that the atomic ratio (Al / M) of the transition metal in the solid catalyst to the organoaluminum compound is 1 to 10000 and the polymerization pressure is atmospheric pressure to 130 kg / cm ² . The high-temperature high-pressure tubular method is usually a polymerization temperature of 100 to 300 ° C, a polymerization time of 5 to 600 seconds, an atomic ratio (Al / M) of the transition metal in the solid catalyst to the organoaluminum compound (Al / M) of 5 to 200, and a polymerization pressure of
It can be performed under the condition of 130 kg / cm ² or more.

Further, for the purpose of improving the polymerization activity, maintaining the shape of the produced polymer, facilitating the introduction of the catalyst into the polymerization reactor, preventing the catalyst from adhering to the polymerization reactor, and improving the fluidity in the fluidized bed reactor. For example, ethylene or a certain amount of ethylene and another olefin can be preliminarily polymerized, and then the prepolymer can be used as a catalyst in the main polymerization. Prepolymerization is, for example, in a slurry method in an inert hydrocarbon solvent, usually, the polymerization temperature 5 ~ 80 ℃, preferably 10 ~ 80 ℃, polymerization time
It is carried out for 5 to 60 minutes under the condition that 1 to 100 g of the polymer is obtained per 1 mg atom of the transition metal in the catalyst solid. By using the solid catalyst of the present invention, a prepolymer having an average particle size of 100 μm or more and 10% by weight or less of particles having a particle size of less than 80 μm can be obtained. The average particle size of the prepolymer is relatively large,
Further, since the proportion of fine particles is small, it is not necessary to perform an operation such as classification. When the prepolymer was continuously polymerized in excess of 100 g per 1 mg atom of transition metal in the solid catalyst, the particle size of the prepolymer became too large, and the main polymerization in the subsequent fluidized bed polymerization reactor Moreover, it is difficult to supply to the reactor. When the prepolymerization is insufficient and contains less than 1 g of the prepolymer, the particle size of the prepolymer is small, it is difficult to control the fluidized state in the fluidized bed polymerization reactor, and the aggregation of the polymer also occurs. It is easy to happen.

[0037]

The catalyst carrier for α-olefin polymerization in the present invention has a spherical shape and a narrow particle size distribution, and the solid catalyst obtained from this catalyst carrier has particularly good fluidity in a fluidized bed reactor. Thus, stable polymerization can be carried out without adhesion and clogging of the polymer to the reactor, and the polymerization activity is high and the deashing step is not required. Further, in the copolymerization of ethylene with an α-olefin having 3 or more carbon atoms using the solid catalyst of the present invention, a polymer having a narrow composition distribution and a small amount of an adhesive component formed and excellent mechanical properties can be obtained.

[0038]

EXAMPLES Examples of the present invention will be described below. In the examples, “polymerization activity” means the transition metal in the solid catalyst component.
Yield (g) of polymer produced per 1 mmol of ethylene pressure 1 kg / cm ² for 1 hour. The transition metal content of the solid catalyst component was measured by a colorimetric method. The comonomer content of the copolymer was measured by NMR. The melting point of the copolymer is the temperature of the maximum absorption peak in the high temperature part by DSC measurement. The measurement condition is that the sample is heated up to 160 ° C at 10 ° C / min in advance.
Thaw, hold for 10 minutes, then cool to 0 ° C at 5 ° C / min and again at 10 ° C / min. The composition distribution of the copolymer is
Regarding the relationship between the melting point and the comonomer content, those having a constant content and a smaller melting point were evaluated as narrow. The "MI" of a copolymer means 1 under a load of 2.16 kg according to ASTM D1238.
It is the melt index of the polymer measured at 90 ° C. As the evaluation of the adhesive component, the weight percentage of the copolymer dissolved in o-dichlorobenzene at 30 ° C. or lower is shown.

Example 1 Synthesis of Carrier Solid-1 Toluene 262 was placed in a 1 L glass reactor pre-filled with nitrogen equipped with a mechanical stirring system and double jacket.
26 ml of triethylaluminum and 26 ml of
While maintaining at 0 ° C, 12 mmol of tert-butyl alcohol was added. To this mixture, a solution of diisoamyl ether containing 60 mmol of n-butylmagnesium chloride 4
0.2 ml was added. 66 mmol of tert-butyl chloride
The temperature was raised to 40 ° C. in 5 minutes and the mixture was added dropwise. Furthermore, 40 ℃
The reaction was carried out for 5 hours while maintaining The formed carrier solid was separated by filtration, and once with 50 ml of toluene and further with 50 ml of n-heptane.
After washing twice, it was dried under reduced pressure at 40 ° C. for 2 hours. The obtained carrier solid was spherical particles having a relatively narrow distribution with a particle size (radius) of 30 to 40 μm.

Example 2 Synthesis of carrier solid-2 A reactor similar to that of Example 1 was charged with 79 ml of toluene, 50 ml of diisoamyl ether and 36 mmol of triethylaluminum (concentration: 1 mmol / L heptane solution) and kept at 26 ° C. While adding 12 mmol of tert-butyl alcohol. To this toluene solution was added 102 ml of a diisoamyl ether solution containing 180 mmol of n-butylmagnesium chloride. The temperature was raised to 60 ° C., and a mixture of 66 mmol of tert-butyl chloride and 8.4 ml of toluene was added dropwise over 60 minutes. Furthermore, the reaction was carried out for 3 hours while maintaining the temperature at 60 ° C. The formed carrier solid was separated by filtration, and twice with 50 ml of toluene,
Further, after washing three times with 50 ml of n-heptane, it was dried under reduced pressure at 40 ° C. for 2 hours. The shape of the obtained carrier solid was spherical particles having a relatively narrow distribution with a particle diameter (radius) of 30 to 40 μm.

Example 3 Synthesis of Support Solid-3 A reactor similar to that used in Example 1 was charged with 79 ml of toluene, 50 ml of diisoamyl ether and 36 mmol of triethylaluminum (concentration: 1 mmol / L heptane solution) and kept at 26 ° C. While adding 36 mmol of tert-butyl alcohol. N-Butylmagnesium chloride was added to this mixture.
Diisopropyl ether solution containing 180 mmol 1
10 ml was added. The temperature was raised to 50 ° C., and a mixture of 198 mmol of tert-butyl chloride and 20 ml of toluene was added dropwise over 60 minutes. Furthermore, the reaction was carried out for 3 hours while maintaining the temperature at 50 ° C. The formed carrier solid was separated by filtration, twice with 50 ml of toluene, and
After washing 3 times with 50 ml of n-heptane, it was dried under reduced pressure at 40 ° C for 2 hours. The shape of the obtained carrier solid has a particle size (radius) of 30.
The particles were spherical with a distribution of ~ 35 µm. Example 4 In Example 3, instead of diisoamyl ether,
A carrier solid was synthesized in the same manner except that -butyl ether was used. The shape of the obtained carrier solid has a particle size (radius)
The particles were spherical with a distribution of 43 to 48 μm.

(Synthesis of Solid Catalyst) Example 5 5 g of the carrier solid obtained in Example 4 was slurried in 75 ml of toluene, and 75 mM of methyltriethoxysilane was added as an electron donor, and the mixture was added at 40 ° C. for 30 minutes. After stirring, 100 mM of tetrachlorotitanium was added and the mixture was stirred at 40 ° C. for 60 minutes. Then the solid was filtered off, washed 3 times with 50 ml toluene and once with 50 ml heptane and dried. The Ti content of the obtained spherical solid is 0.97%, the Al content is 0.61%.
, And the Mg content was 15.7%. Example 6 A solid catalyst was prepared according to Example 5, except that 80 ml of toluene was replaced with 50 mM of methyltriethoxysilane. The Ti content of the obtained spherical solid is 0.97%, the Al content is 0.41%.
, And the Mg content was 16.6%.

Example 7 A solid catalyst was prepared according to Example 5, except that 83 ml of toluene, 50 mM of methyltriethoxysilane and 75 mM of tetrachlorotitanium were used. The Ti content of the obtained spherical solid was 1.08%, the Al content was 0.77%, and the Mg content was 15.4%. Example 8 A solid catalyst was prepared according to Example 5, except that 98 ml of toluene, 5 mM of methyltriethoxysilane and 10 mM of tetrachlorotitanium were replaced. The Ti content of the obtained spherical solid was 0.72%, the Al content was 1.63%, and the Mg content was 16.1%.

Example 9 5 g of the carrier solid obtained in Example 4 was slurried in 80 ml of toluene, 100 mM of methyltriethoxysilane was added as an electron donor, and the mixture was stirred at 40 ° C. for 30 minutes.
The solid was separated by filtration, washed three times with 50 ml of toluene, and then 30 ml of toluene, 70 ml of a toluene solution containing 50 mM of methyltriethoxysilane and 100 mM of tetrachlorotitanium were added, and the mixture was stirred at 40 ° C. for 60 minutes. The solid is filtered off, washed 3 times with 50 ml toluene and then once with 50 ml heptane,
The solid was dried. The Ti content of the obtained spherical solid is 1.75%.
, Al content was 1.04%, and Mg content was 15.0%. Example 10 A solid catalyst was prepared according to Example 5 except that 70 ml of a toluene solution containing 5 mM of methyltriethoxysilane and 10 mM of tetrachlorotitanium was used as a mixed solution. The Ti content of the obtained spherical solid was 1.64%.

(Preliminary Polymerization and Gas Phase Copolymerization of Ethylene and Butene-1) Example 11 800 ml of n-heptane was charged into a 2 L autoclave made of SUS filled with nitrogen gas, and tri-n-octylaluminum 7.
5 mM, 2.5 mM triethylaluminum and the catalytic solid synthesized in Example 5 (titanium content 2.5 mM) were added. Hydrogen gas of 1.5 kg / cm ² was injected under pressure, and then introduced up to 60 ° C. to initiate polymerization. Keep the temperature at 67-80 ° C during the polymerization and add 1 L / L of ethylene.
It was introduced at a min. and polymerization was carried out until 40 g of a prepolymer was produced per 1 mM of titanium. In advance, 500 g of low-density polyethylene pellets were put into a stirring gas-phase polymerization reactor having a diameter of 20 cm and a length of 50 cm, and while stirring the polyethylene pellets at 500 rpm, ethylene / triethylaluminum-containing ethylene /
A butene-1 / hydrogen (3/1 / 0.2 molar ratio) mixed gas at 45 ° C
It was raised at a flow rate of 20 cm / sec. The copolymerization is carried out by introducing 5 g of the prepolymer produced by the above-mentioned prepolymerization at a polymerization temperature of 75 to 85.
° C., polymerization pressure 21 kg / cm ^2, was performed 2hr atomic ratio 45 of the total Al / Ti. Polymerization activity 380g (TimM · hr · Ethylene pressure 1kg / cm ² ), MI 1.8, melting point 123.5 ℃, butene-1 content 3.53
A mol% copolymer was obtained.

Example 12 Using the catalyst solid synthesized in Example 6, a gas phase copolymerization of a prepolymer, ethylene and butene-1 was carried out in the same manner as in Example 11. Polymerization activity 800g (TimM ・ hr ・ Ethylene pressure 1kg / cm ² ), MI 2.9, melting point 124.6 ℃, butene-1 content 3.0
1 mol% of copolymer was obtained. Example 13 Using the catalyst solid synthesized in Example 7, vapor phase copolymerization of a prepolymer, ethylene and butene-1 was carried out in the same manner as in Example 11. Polymerization activity 800g (TimM ・ hr ・ Ethylene pressure 1kg / cm ² ), MI 2.5, melting point 122.6 ℃, butene-1 content 3.3
8 mol% of copolymer was obtained.

Example 14 Using the catalyst solid synthesized in Example 8, a gas phase copolymerization of a prepolymer, ethylene and butene-1 was carried out in the same manner as in Example 11. Polymerization activity 490g (TimM ・ hr ・ Ethylene pressure 1kg / cm ² ), MI 0.82, melting point 121.5 ℃, butene-1 content 4.
52 mol% of copolymer was obtained. Example 15 Using the catalyst solid synthesized in Example 9, vapor phase copolymerization of a prepolymer, ethylene and butene-1 was carried out in the same manner as in Example 11. Polymerization activity 480g (TimM ・ hr ・ Ethylene pressure 1kg / cm ² ), MI 1.3, melting point 122.6 ℃, butene-1 content 3.53
A mol% copolymer was obtained.

Example 16 Using the catalyst solid prepared in Example 10, a prepolymer, ethylene and butene-1 was subjected to vapor phase copolymerization in the same manner as in Example 11. Polymerization activity 480g (TimM ・ hr ・ Ethylene pressure 1kg / cm ² ), MI2.65, melting point 123.7 ℃, butene-1 content 4.15
A mol% copolymer was obtained.

Comparative Example 1 A solid catalyst was prepared in the same manner as in Example 5 except that methyltriethoxysilane was not used as the electron donor. The Ti content of the obtained spherical solid is 3.38%, the Al content is 2.23%,
The Mg content was 16.1%. In the same manner as in Example 11, vapor phase copolymerization of the prepolymer, ethylene and butene-1, was carried out. Polymerization activity 640g (TimM · hr · Ethylene pressure 1kg / cm ² )
A copolymer having an MI of 2.4, a melting point of 124.3 ° C and a butene-1 content of 4.41 mol% was obtained. At this butene-1 content, the copolymer had a high melting point and a wide composition distribution.

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for preparing a carrier solid and a solid catalyst of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Katsuo Yakumi 8-1 Goi Minamikaigan, Ichihara-shi, Chiba Ube Industries Ltd. Chiba Research Institute

Claims (2)

[Claims] 1. A method for producing a catalyst carrier for α-olefin polymerization, which comprises reacting a Grignard compound solution with a halogenated hydrocarbon compound. 2. An ethylene characterized in that the catalyst carrier for α-olefin polymerization according to claim 1 is catalytically treated with an electron donor and at least one transition metal compound selected from titanium, zirconium, hafnium and vanadium. And a method for producing a solid catalyst for copolymerization of an α-olefin having 3 or more carbon atoms.