JPH0135844B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a support for an olefin heavy catalyst. In particular, the present invention relates to a method for preparing a carrier suitable for producing a polyolefin having a spherical shape and good powder flowability.

Conventionally, in this type of technical field, many catalysts are known in which compounds of transition metals such as titanium or vanadium are supported on inorganic magnesium solids such as magnesium halides, magnesium oxides, and magnesium hydroxides. . However, in these known techniques, the obtained polymer particles generally have a small bulk specific gravity, a small average particle size, and a generally wide particle size distribution, so they have a large particulate powder portion, which makes productivity and slurry handling difficult. Improvements were strongly desired from this perspective. Furthermore, when molding these polymers, problems such as the generation of dust and a decrease in efficiency during molding occur, so the above-mentioned bulk specific gravity increases, average particle size increases, and the fine particulate powder portion decreases strongly. It was wanted.

The present invention improves the above-mentioned drawbacks and has the effect of making it possible to obtain a polymer having a high bulk specific gravity, a narrow particle size distribution, a spherical shape, and excellent powder flowability with no significant particulate portion of the polymer. The present invention provides a method for producing an outstanding catalyst support.

That is, the present invention dissolves a substance containing at least one component of magnesium dihalide (hereinafter abbreviated as magnesium halide), and contains alcohols, organic acid esters, An olefin polymerization catalyst consisting of a substance obtained by adding a saturated hydrocarbon (hereinafter referred to as an organic liquid compound) to at least one liquid medium selected from ketones and ethers, and then heating the mixture at a temperature of 40 to 200°C. Exists in a carrier for use. When olefin polymerization or copolymerization is carried out using a catalyst in which a solid catalyst component in which a titanium compound and/or vanadium compound is supported on the carrier of the present invention prepared in this manner is combined with an organometallic compound, This significantly increases the polymer yield and the polymer yield per transition metal, thereby eliminating the need for the step of removing catalyst residue from the resulting polymer, and the resulting polymer powder has a high bulk specific gravity and a narrow particle size distribution. Because the diameter is narrow, the particulate powder portion is small, and the shape is almost spherical, the powder fluidity is good, and it is not only easy to handle during polymerization operations, but also has few troubles during molding, making it extremely advantageous for polyolefins. can be manufactured.

The present invention will be explained in detail below.

In preparing the polyolefin polymerization catalyst carrier of the present invention, first, a substance containing at least one component of magnesium halide is dissolved in an organic liquid medium in which the substance can be dissolved.

The organic liquid medium used at this time to dissolve the substance containing at least one component of magnesium halide may be alcohols, esters, ethers, or ketones, but a preferred example is methanol. ,ethanol,
isopropanol, butanol, pentanol,
Alcohols such as hexanol, octanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, methyl formate, ethyl formate, methyl acetate, ethyl acetate, methyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, octyl butyrate, ethyl laurate, Esters such as octyl laurate, methyl benzoate, ethyl benzoate, octyl paraoxybenzoate, dibutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, dimethyl ether, diethyl ether, diisopropyl ether, Examples include ethers such as butyl ether, diamyl ether, terahydrofuran, dioxane, and anisole, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone, and cyclohexanone.

The substance containing magnesium halide as at least one component used in the present invention refers to magnesium halide or magnesium halide and another substance.
It is a reaction product with more than one kind of compound or a mixture thereof.

Magnesium halides include magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, with magnesium chloride being particularly preferred.

Various known magnesium halide-containing carriers are used as the reaction product of magnesium halide and one or more other compounds. Specific examples of these include magnesium halide and Si
(OR) Reaction product with _n X _4-n , Reaction product between magnesium halide and B(OR) _o X _3-o , Reaction product between magnesium halide and Al(OR) _o X _3-o , Halogen Reaction product of magnesium chloride and AlOX, reaction product of magnesium halide and compound having Al-O-C bond, reaction product of magnesium halide and aluminum chloride or aluminum chloride ether complex, magnesium halide and pentachloride Phosphorus, reaction product with phosphorus trichloride or phosphorus oxytrichloride, magnesium halide and dichloroethane,
Reaction products with organic halides such as trichlorobenzene, reaction products between magnesium halide and titanium oxyhalide, reaction products between magnesium halide and Si(OR) _n X _4-n and Al(OR) _o X _3-o reactant,
Magnesium halide, silicon tetrachloride and ROH
(In the formula,
R is a hydrocarbon residue having 1 to 20 carbon atoms, X is a halogen, and 0≦m≦4, 0<n≦3). of course,
Other known halogenated magnesium-containing carriers can also be used in the present invention.

There are no particular limitations on the operation and conditions for dissolving a substance containing at least one component of magnesium halide, and the dissolution may be carried out at, for example, nitrogen temperature, or may be carried out with appropriate heating.

When using a reaction product of magnesium halide and another compound, these may be reacted in advance and then dissolved, or the reaction may be performed in an organic liquid medium in which the magnesium halide can be dissolved.

There is no particular restriction on the time when the oxide of a metal of group ~~ of the periodic table is incorporated into the organic liquid medium, and it may be present before dissolving the substance containing at least one component of magnesium halide, or during dissolution. Alternatively, it may be added after dissolution.

The oxides of groups 1 to 2 of the periodic table used in the present invention may be not only oxides of individual metals of groups 1 to 1 of the periodic table, but also double oxides of these metals, and of course may be mixtures thereof. Specific examples of these metal oxides include MgO, CaO,
ZnO, BaO, SiO ₂ , SnO ₂ , Al ₂ O ₃ , MgO・
Al ₂ O ₃ , SiO ₂・Al ₂ O, MgO・SiO ₂ , MgO・
Examples include CaO・Al ₂ O ₃ , Al ₂ O ₃・CaO, and especially SiO ₂ , Al ₂ O ₃ , SiO ₂・Al ₂ O ₃ ,
MgO.Al ₂ O ₃ is preferred.

The proportion of these metal oxides is 10g of a substance containing at least one component of magnesium halide.
The amount ranges from 0.1 to 500 g, preferably from 1 to 100 g, and more preferably from 2 to 50 g. The thus obtained substance containing magnesium halide as at least one component is dissolved, and an organic liquid compound in which magnesium halide is not dissolved is added to a liquid medium containing an oxide of a metal of Groups 1 to 10 of the periodic table. The concentration of the substance containing at least one component of magnesium halide in the liquid medium when adding the organic liquid compound is not particularly limited and can be used within a wide range, but usually 1.
A range of 30% to 30%, preferably 5 to 30% by weight is desirable.

The organic liquid compound used at this time is a saturated hydrocarbon that does not dissolve magnesium halide, and for example, pentane, hexane, heptane, octane, etc. are preferably used.

The amount of the organic liquid compound added is at least the amount necessary to precipitate a substance containing at least one component of magnesium halide. Usually, 50 g or more, for example 50 to 5000 g, preferably 500 to 5000 g, of an organic liquid compound in which magnesium halide is not dissolved is added to solution 1 containing a substance containing magnesium halide as at least one component. There are no particular restrictions on the addition rate or addition method.

Solid substances are precipitated by the addition of the organic liquid compound, and in the present invention, the mixed solution containing these solid precipitates is subsequently heat-treated at a temperature of 40 to 200°C, preferably 50 to 100°C. The heat treatment time is not particularly limited, but is usually 5 minutes or more.
It is desirable to set it as 20 hours, preferably 10 minutes to 10 hours. After the heat treatment, the solvent is removed to obtain the solid support of the present invention.

A titanium compound and/or a vanadium compound is supported on the carrier of the present invention thus prepared, and used in combination with an organometallic compound as a catalyst for polymerization or copolymerization of olefin.

A method for supporting the titanium compound and/or vanadium compound on the carrier of the present invention includes, for example, bringing the carrier of the present invention into contact with the titanium compound and/or vanadium compound under heating in the presence or absence of an inert solvent. This can be done by combining both, preferably in the absence of a solvent.
This is carried out by heating to 50-300°C, preferably 100-150°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example, processing times can range from 5 minutes to 10 hours.

Titanium compound and/or used in the present invention
Alternatively, the amount of the vanadium compound may be used in excess, but it can usually be used in an amount of 0.001 to 50 times the weight of magnesium halide. Preferably, excess titanium compound and/or vanadium compound is removed by washing with a solvent after the mixing and heating treatment. After completion of the reaction, the means for removing unreacted titanium compounds and/or vanadium compounds is not particularly limited, and may include washing the Ziegler catalyst several times with a solvent inert to the catalyst and evaporating the washings under reduced pressure to obtain a solid powder. is usually done.

In addition, the amount of the titanium compound and/or vanadium compound to be supported is such that the titanium and/or vanadium content contained in the produced solid is 0.5 to 20.
It is most preferable to adjust the amount within a range of 1 to 10% by weight, and in order to obtain well-balanced activity per titanium and/or vanadium and activity per solid, a range of 1 to 10% by weight is particularly desirable.

Examples of the titanium compound and/or vanadium compound used in the present invention include halides, alkoxy halides, alkoxides, and halogenated oxides of titanium and/or vanadium. Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula Ti(OR) _o X _4-o (where R is 1 carbon number) ~20 alkyl, aryl or aralkyl groups;
X represents a halogen atom. n is 0≦n≦4), titanium tetrachloride,
Titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxy Trichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxytitanium Examples include cymonochlorotitanium and tetraphenoxytitanium. Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides, such as titanium tetrachloride and titanium tetrabromide, with hydrogen, aluminum, titanium, or organometallic compounds of metals in the ~groups of the periodic table. It will be done. In addition, the general formula _Ti (OR) _n
A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by the formula 0<m<4) with an organometallic compound of a group metal of the periodic table can be mentioned. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, and tetraethoxyvanadium; Examples include trivalent vanadium compounds such as trivalent vanadium compounds, vanadium trichloride, and vanadium triethoxide.

As the organometallic compound in the present invention, organometallic compounds of groups 1 to 10 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R ₃ Al,
R ₂ AlX, RAlX ₂ , R ₂ AlOR, RAl(OR)X and
Organoaluminum compound _of R ₃ Al _{2 2} Zn (however, R is an alkyl group having 1 to 20 carbon atoms and may be the same or different), and is represented by an organic zinc compound of triethylaluminum,
triisopropylaluminium, triisobutylaluminum, trisec-butylaluminum,
Examples include tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound and/or vanadium compound.

Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization, and the polymerization reaction is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. Polymerization conditions for olefin include temperature of 20 to 120°C, preferably 50 to 100°C.
℃, and the pressure is normal pressure to 70℃/cm ² , preferably 2 to 60Kg/cm ² . Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization concentration can be carried out without any problem.

The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1 and octene-1, and ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- Suitable for use in copolymerization of butene, etc.

Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.

Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.

Example 1 (a) Preparation of solid carrier 10 g of commercially available anhydrous magnesium chloride and 5 g of aluminum ethoxide were placed in a stainless steel pot with an internal volume of 400 ml containing 25 stainless steel balls having a diameter of 1/2 inch, and the mixture was placed in a nitrogen atmosphere. Ball milling was performed at room temperature for 16 hours to obtain a reaction product. A 3-necked flask equipped with a stirrer and a reflux condenser was replaced with nitrogen.
In this three-necked flask, 15 g of the above reaction product and SiO ₂ (Fuji Davison,
#952) 10g, then 350ml of tetrahydrofuran, heated at 80℃ for 2 hours,
200 ml of tetrahydrofuran were removed by distillation. Next, 500 ml of hexane was added at 60° C. to precipitate a solid material. Subsequently, the mixed solution containing the precipitate was heat-treated at 80° C. for 1 hour while stirring. After the heat treatment, the supernatant liquid was removed, and then drying was performed at 100° C. for 2 hours under reduced pressure to obtain a solid carrier.

(b) Production of solid catalyst component 2 g of the solid support and 0.5 ml of titanium tetrachloride
was added to 40 ml of hexane, and 1
A time reaction was performed. Next, the supernatant liquid was removed, and washing was repeated with hexane until titanium tetrachloride was no longer detected in the washing liquid to obtain a solid catalyst component. Each gram of solid catalyst component contained 40 mg of titanium.

(c) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow rate controller, and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water through the jacket.

The above solid catalyst component was fed to an autoclave adjusted to 80°C at a rate of 50 mg/hr and triethylaluminum at a rate of 5 mmol/hr, and the butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was set to 0.28. Furthermore, hydrogen is added to 15% of the total pressure.
Polymerization was carried out by supplying each gas while adjusting the following, and by circulating the gas in the system using a blower to maintain the total pressure at 10 kg/cm ² ·G. The produced ethylene copolymer had a bulk specific gravity of 0.38, a melt index (MI) of 0.88, and a density of 0.9210.

Also, the catalytic activity is 300000g copolymer/gTi
The activity was extremely high.

After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.

The obtained polymer particles were approximately spherical, with a large average particle size of 880μ, and a small amount of fine powder with a particle size of 200μ or less at 0.1%.

Comparative Example 1 Example 1 except that the heat treatment was not performed when preparing the solid carrier in Example 1.
A solid support and a solid catalyst component (amount of titanium supported: 40 mg/g) were produced in the same manner as described above.

Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 using the solid catalyst component.

The resulting copolymer had a bulk specific gravity of 0.22, a melt index of 0.85, and a density of 0.9205, and had an extremely high catalytic activity of 290,000 g copolymer/g Ti.

However, the obtained polymer particles were amorphous, had a small bulk specific gravity of 0.22, had a small average particle size of 350 μm, and had a significantly large proportion of fine powder with a particle size of 200 μm or less at 10.5%.

Example 2 10 g of anhydrous magnesium chloride, 3 g of aluminum triethoxide and 2 g of tetraethoxysilane
of the reactants and 10 g of silicon dioxide in ethyl acetate.
Add to 350ml and heat at 100℃ for 1 hour, then heat to 60℃
500 ml of hexane was added to precipitate a solid material. Subsequently, stir the above mixture.
Heat treatment was performed at 100°C for 1 hour. Next, the supernatant liquid was removed, and then drying was performed at 100° C. for 2 hours under reduced pressure to obtain a solid carrier.

The solid catalyst component (amount of titanium supported:
40 mg/g) and copolymerized ethylene and butene-1 in the same manner as in Example 1.

The resulting copolymer had a bulk specific gravity of 0.37, a melt index of 0.90, and a density of 0.9220, and had an extremely high catalytic activity of 240,000 g copolymer/g Ti.

The obtained polymer particles are almost spherical, with a large average particle size of 780μ, and 0.2% of the particles are fine powder with a particle size of 200μ or less.
There were very few.

Example 3 When preparing the solid carrier in Example 1,
A solid support was prepared in the same manner as in Example 1 except that 500 ml of pentane was used instead of 500 ml of hexane, and the solid catalyst component (titanium supported amount: 40 mg/ g) was produced. When ethylene and butene-1 were copolymerized using the solid catalyst component in the same manner as in Example 1, the resulting copolymer had a bulk density of 0.37, a melt index of 0.87, and a density of 0.9207. The activity was extremely high at 270,000 g copolymer/g Ti.

The obtained polymer particles are almost spherical and have a large average particle size of 790μ, and the fine powder with a particle size of 200μ or less is
It was as low as 0.1%.

Example 4 Tetrahydrofuran containing 10g of alumina
10 g of anhydrous magnesium chloride and 5 g of magnesium ethoxide were added to 350 ml, and after heating at 100° C. for 1 hour, 200 ml of tetrahydrofuran was distilled off. Thereafter, 500 ml of hexane was added at 60° C. to precipitate a solid material.
Subsequently, the above mixture was heated at 100°C for 1 hour while stirring.
Heat treatment was carried out for a period of time. Next, after removing the supernatant liquid, drying was performed at 100° C. for 2 hours under reduced pressure to obtain a solid carrier.

Example 1 except that the above solid support was used.
Solid catalyst component (titanium loading: 40
mg/g) and copolymerized ethylene and butene-1 in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.39, a melt index of 0.85, a density of 0.9215, and a catalytic activity of
The activity was extremely high at 230,000g copolymer/gTi.

The obtained polymer particles were approximately spherical, had a large average particle size of 780μ, and had a small amount of fine powder with a particle size of 200μ or less at 0.2% or less.

Example 5 In Example 2, instead of 500ml of hexane,
A carrier was synthesized in the same manner as in Example 2, except that 500 ml of heptane was used, and a solid catalyst component (titanium supported amount: 40 mg/g) was produced in the same manner.

When copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1 using the solid catalyst component, the resulting copolymer had a bulk specific gravity of 0.40, a melt index of 0.88, and a density of 0.9212. The catalyst activity was extremely high at 280,000 g copolymer/g Ti.

The obtained polymer particles were approximately spherical and had a large average particle size of 900μ, and the amount of fine powder with a particle size of 200μ or less was as low as 0.1%.

Example 6 Commercially available anhydrous magnesium chloride 10 was placed in a 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls.
g, and 5 g of aluminum triethoxide were added thereto, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere to obtain a reaction product. A 3-neck flask equipped with a stirrer and a reflux condenser was purged with nitrogen, and 15 g of the above reaction product and 10 g of SiO ₂ (Fuji Davison, #952) calcined at 600°C were placed in the 3-neck flask.
Next, 450 ml of acetone was added, and after heating at 80°C for 2 hours, 250 ml of acetone was removed by distillation. Next, 500 ml of hexane was added at 60° C. to precipitate a solid material. Subsequently, the mixed solution containing the precipitate was heat-treated at 80° C. for 1 hour while stirring. After the heat treatment, the supernatant liquid was removed, and then drying was performed at 100° C. for 2 hours under reduced pressure to obtain a solid carrier.

2 g of the solid support and 0.5 ml of titanium tetrachloride were added to 400 ml of hexane, and the mixture was reacted for 1 hour under reflux of hexane. Next, after removing the supernatant liquid,
Washing with hexane was repeated until titanium tetrachloride was no longer detected in the washing solution, to obtain a solid catalyst component containing 38 mg of titanium per gram of solid catalyst component. Using this solid catalyst component, ethylene and butene-1 were copolymerized in the same manner as in Example 1.

The resulting copolymer has a bulk specific gravity of 0.38, a melt index of 0.92, and a density of 0.9225, and its catalytic activity is
296,000g copolymer/gTi was extremely highly active.

The obtained polymer particles are almost granular, with a large average particle size of 860μ, and 0.1% of the particles are fine powder with a particle size of 200μ or less.
There were very few.

Example 7 Using the same solid catalyst component and equipment as in Example 1, the solid catalyst component was supplied at a rate of 50 mg/hr and triethylaluminum at a rate of 5 mmol/hr, and propylene was supplied to an autoclave adjusted to 80°C. Polymerization was carried out by circulating the gas in the system using a blower to maintain the total pressure at 10 kg/cm ² ·G. The propylene polymer produced had excellent particle properties with a bulk specific gravity of 0.43, and an extremely high catalytic activity of 115,000 g polymer/g Ti.

[Brief explanation of drawings]

FIG. 1 is a flowchart showing a method for producing a carrier for an olefin polymerization catalyst and a method for producing an olefin polymerization catalyst containing the same according to the present invention.

Claims (1)

[Scope of Claims] 1. A substance selected from alcohols, organic acid esters, ketones, and ethers that dissolves a substance containing at least one component of magnesium dihalide and contains an oxide of a metal of Groups 1 to 1 of the periodic table. 1. A method for producing an olefin polymerization catalyst carrier, which comprises adding a saturated hydrocarbon to at least one kind of liquid medium, and then heat-treating the mixture at a temperature of 40 to 200°C. 2 The oxides of metals from groups ~ of the periodic table are MgO,
CaO, ZnO, BaO, _SiO2 , _SnO2 , _{Al2O3 ,}
MgO・Al ₂ O ₃ , SiO ₂・Al ₃ O ₃ , MgO・SiO ₂ ,
The manufacturing method according to _claim 1, wherein the oxide is at least one type of oxide selected from the group consisting of MgO.CaO.Al ₂ O ₃ and Al ₃ O 3.CaO.