JPH09328313A - Production of anhydrous magnesium halide and preparation of solid titanium catalyst component for olefin polymerization - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an anhydrous magnesium halide solution almost free from calcium from a magnesium halide hydrate containing calcium as an impurity, in addition, prepare a high-activity solid titanium catalyst component for olefin polymerization from the anhydrous magnesium halide solution. SOLUTION: The solution of anhydrous magnesium halide is prepared by adding a potassium compound to the solution to precipitate and remove calcium, when water is distilled off from a solution comprising a magnesium halide hydrate containing at least calcium as an impurity and an oxygen-containing organic solvent to form a solution containing anhydrous magnesium halide and an oxygen-containing organic solvent. The resultant anhydrous magnesium halide solution is brought into contact with a titanium compound in the liquid form to precipitate a solid titanium catalyst component whereby the solid titanium catalyst component for olefin polymerization is prepared.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an anhydrous magnesium halide solution containing few impurities, and a method for preparing a solid titanium catalyst component for olefin polymerization obtained from the anhydrous magnesium halide solution.

[0002]

BACKGROUND OF THE INVENTION Catalysts conventionally used to produce ethylene or α-olefin homopolymers,
Alternatively, a catalyst containing a titanium compound supported on magnesium halide is known as a catalyst used for producing an olefin copolymer such as an ethylene / α-olefin copolymer. As such an olefin polymerization catalyst, for example, a catalyst composed of a solid titanium catalyst component composed of magnesium, titanium, halogen and an electron donor and an organometallic compound catalyst component is known.

Many proposals have already been made for a method of producing a solid titanium catalyst component used as the catalyst component for olefin polymerization, and a liquid halogen-containing magnesium compound is contacted with a liquid titanium compound to form a solid product. The method of making it known is known.

In the method for preparing such a solid titanium catalyst component, the magnesium halide compound is
Industrial and / or reagent grade anhydrous magnesium chloride and the like have been used. However, since anhydrous magnesium chloride for industrial use and / or reagents has problems in price, supply stability, etc., it is called cheaply and stably available hydrous magnesium chloride, for example, bittern produced from seawater. If it can be replaced with hydrous magnesium chloride, its industrial value will be great.

However, anhydrous magnesium chloride obtained from bittern contains calcium as an impurity, and when a solid titanium catalyst component is prepared from an anhydrous magnesium chloride solution containing such calcium as a raw material, it does not contain impurities. There is a problem that certain calcium reduces the polymerization activity of the catalyst.

Under these circumstances, the present inventors have proposed a method for producing anhydrous magnesium halide containing no calcium as an impurity from hydrous magnesium halide containing at least calcium as an impurity, such as hydrous magnesium chloride. As a result of examination, when preparing a solution of anhydrous magnesium halide in an oxygen-containing organic solvent solution by distilling water away from the oxygen-containing organic solvent solution in which a water-containing magnesium halide containing at least calcium as an impurity is dissolved, At any stage of the step of preparing an oxygen-containing organic solvent solution in which is dissolved or the step of preparing an anhydrous magnesium halide-containing organic solvent solution, a potassium compound is added to add calcium (calcium compound) and a potassium compound. And contact By removing by precipitation with potassium calcium from oxygen-containing organic solvent solution (calcium compound) of halogenated magnesium (potassium compound), it found that anhydrous magnesium halide solution containing no calcium impurities is obtained. Furthermore, when a solid titanium catalyst component is prepared using the anhydrous magnesium halide solution obtained by such a method,
It has been found that a highly active catalyst is obtained.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and provides a method for producing an anhydrous magnesium halide solution containing almost no calcium from hydrous magnesium halide containing at least calcium as an impurity. It is intended to be provided. further,
The object of the present invention is to provide a method for preparing a solid titanium catalyst component using the anhydrous magnesium halide solution as a raw material.

[0008]

SUMMARY OF THE INVENTION A method for producing an anhydrous magnesium halide solution according to the present invention is to remove anhydrous magnesium halide by distilling water from an oxygen-containing organic solvent solution in which hydrous magnesium halide containing at least calcium as an impurity is dissolved. In preparing the oxygen-containing organic solvent solution, at any stage of the step of preparing the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved or the step of preparing the oxygen-containing organic solvent solution of anhydrous magnesium halide, A potassium compound is added to bring calcium (calcium compound) into contact with potassium (potassium compound), and calcium (calcium compound) is removed together with potassium (potassium compound) from the solution of anhydrous magnesium halide in an oxygen-containing organic solvent. It is characterized by doing.

Further, the method for producing an anhydrous magnesium halide solution according to the present invention, at any stage of the step of preparing an oxygen-containing organic solvent solution in which anhydrous magnesium halide containing at least calcium as an impurity is dissolved,
A potassium compound is added to bring calcium (calcium compound) into contact with potassium (potassium compound), and calcium (calcium compound) is removed together with potassium (potassium compound) from the solution of anhydrous magnesium halide in an oxygen-containing organic solvent. It is characterized by doing.

In the present invention, the hydrous magnesium halide is preferably hydrous magnesium chloride,
More preferably, it is hydrous magnesium chloride produced from seawater.

In the present invention, as a method for distilling water from the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved, an inert gas is added to the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved. Examples thereof include a venting method and a method of azeotropically distilling off the oxygen-containing organic solvent and water in the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved.

The method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention is to prepare a solid titanium catalyst component by bringing the anhydrous magnesium halide solution obtained by the above method into contact with a titanium compound in a liquid state. It is characterized by precipitation.

Further, in the method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention, a hydrocarbon solvent may be added to the anhydrous magnesium halide solution obtained by the above method, and further, an oxygen-containing organic solvent. It may be a solution obtained by adding an electron donor other than the above.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The method for producing an anhydrous magnesium halide solution and the method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention will be specifically described below.

First, a method for producing an anhydrous magnesium halide solution according to the present invention will be described. In the present invention,
First, a hydrous magnesium halide containing at least calcium (calcium compound) as an impurity and an oxygen-containing organic solvent are in a molar ratio of 1: 2 to 1: 100, preferably 1 :.
The mixture is mixed at a ratio of 2 to 1:30 to prepare an oxygen-containing organic solvent solution in which hydrous magnesium halide is dissolved.

As the hydrated magnesium halide, hydrated magnesium chloride, hydrated magnesium bromide and hydrated magnesium iodide are used. Among these, hydrated magnesium chloride is preferably used, and is particularly produced from seawater called bittern. Hydrous magnesium chloride is preferably used.

The hydrous magnesium halide means a magnesium halide containing water,
Moisture is not limited to water of crystallization, water of adsorption and the like. For example, when the hydrous magnesium halide is hydrous magnesium chloride, the hydrous magnesium chloride includes magnesium chloride hexahydrate, magnesium chloride hexahydrate with some crystal water lost, and magnesium chloride hexahydrate. A mixture of anhydrous magnesium chloride and a mixture of magnesium chloride hexahydrate with water other than water of crystallization are included.

Examples of the oxygen-containing organic solvent include ethers, ketones, alcohols, organic epoxy compounds and organic phosphoric acid compounds. Examples of ethers include tetrahydrofuran, anisole, diphenyl ether, isopropyl ether, acyl ether and the like.

Examples of ketones include methyl ethyl ketone and methyl isobutyl ketone. As alcohol, ethanol, ethylene glycol, 2-
Aliphatic alcohols such as methylpentanol, 2-ethylbutanol, n-heptanol, n-octanol, 2-ethylhexanol, decanol, dodecanol, tetradecyl alcohol, undecenol, oleyl alcohol, stearyl alcohol; cyclohexanol, methylcyclohexanol, etc. Alicyclic alcohols; benzyl alcohol, methylbenzyl alcohol, isopropylbenzyl alcohol, α-methylbenzyl alcohol,
Aromatic alcohols such as α, α-dimethylbenzyl alcohol; aliphatic alcohols containing an alkoxy group such as n-butyl cellosolve and 1-butoxy-2-propanol. Examples of the organic epoxy compound include ethylene oxide, propylene oxide, butadiene oxide, and epoxychloropropane. Examples of the organic phosphoric acid compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, and trimethyl phosphite.

Of these, aliphatic alcohols are preferable, and 2-ethylhexanol is particularly preferable. In the present invention, the oxygen-containing organic solvent may be used alone or in combination of plural kinds. Next, water is distilled off from the oxygen-containing organic solvent solution in which the water-containing magnesium halide is dissolved to prepare an oxygen-containing organic solvent solution of anhydrous magnesium halide, but in the present invention, the water-containing magnesium halide is dissolved. At any stage of the step of preparing an oxygen-containing organic solvent solution or the step of preparing an anhydrous magnesium halide-containing organic solvent solution, a potassium compound is added to separate calcium (calcium compound) and potassium (potassium compound). Contact.

Specifically, the potassium compound may dissolve the hydrous magnesium halide and the potassium compound in the oxygen-containing organic solvent almost at the same time, and water may be removed from the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved. It may be added before distilling off, or may be added during the distilling of water from the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved, or the oxygen-containing organic solution in which the hydrous magnesium halide is dissolved. Water may be distilled off from the solvent solution to prepare an oxygen-containing organic solvent solution of anhydrous magnesium halide, which is then added.

The addition of the potassium compound may be carried out in plural times. The potassium compound is finally 0.01 to 100 times mol, preferably 0.05 to 30 times mol, and more preferably 0.1 to 100 times mol with respect to calcium (calcium compound) contained as an impurity in the hydrous magnesium halide. It is added in an amount such that the molar ratio is 20 times.

As the potassium compound, potassium carbonate,
Examples thereof include potassium bicarbonate, potassium acetate, acidic potassium sulfate, potassium chloride, potassium dihydrogen phosphate, potassium ethoxide, potassium hydrogen sulfate and the like.

The method for distilling water from the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved is not particularly limited as long as it is a method capable of distilling water from the solution. For example, hydrous magnesium halide is used. A method of distilling water to the exhaust side by aerating an inert gas in the dissolved oxygen-containing organic solvent solution, heating the oxygen-containing organic solvent solution in which the hydrous magnesium halide is dissolved and heating the oxygen-containing organic solvent and water. There is a method of distilling off azeotropically.

Hereinafter, a potassium compound was added to an oxygen-containing organic solvent solution in which hydrous magnesium halide was dissolved,
The method of distilling water from this solution by aeration with an inert gas to the exhaust side will be described more specifically.

An oxygen-containing magnesium halide containing oxygen is obtained by passing an inert gas through an oxygen-containing organic solvent solution in which water-containing magnesium halide is dissolved (hereinafter referred to as "water-containing mixed solution"), and distilling water off to the exhaust side. When obtaining an organic solvent solution,
It is preferable to heat the water-containing mixed liquid and to stir the water-containing mixed liquid.

The pressure during heating of the water-containing mixed liquid may be any of normal pressure, reduced pressure or increased pressure. The heating temperature is preferably a temperature close to the boiling point according to the pressure and the composition of the water-containing mixed solution, specifically, 100 to 200 ° C.,
It is preferably in the range of 130 to 170 ° C. Further, the heating temperature and / or pressure may be changed in the heating process.

Nitrogen gas, helium gas, argon gas or the like is used as the inert gas to be passed through the water-containing mixed liquid.
Of these, nitrogen gas is preferable because it is the most economical.

The amount of nitrogen gas aerated in the water-containing mixed solution varies depending on the temperature and pressure during heating, but is 1 to 1000 N-liter / hr per mol of magnesium halide,
The range of 1 to 300 N-liter / hr is preferable.

The water content in the oxygen-containing organic solvent solution of anhydrous magnesium halide after nitrogen gas is bubbled through the water-containing mixed solution is 0.4% by weight or less, preferably 0.2% by weight or less. The water content in the solution can be measured by the Karl Fischer method. In the present invention,
The oxygen-containing organic solvent solution of anhydrous magnesium halide thus obtained may be further heated to distill off part of the oxygen-containing organic solvent. The heating temperature is usually 170 ° C or higher, preferably 180 ° C or higher. The oxygen-containing organic solvent solution of anhydrous magnesium halide obtained by distilling off the oxygen-containing organic solvent has a molar ratio of anhydrous magnesium halide and oxygen-containing organic solvent of 1: 2 to 1:10, preferably It is 1: 2-1: 5. When the molar ratio of the anhydrous magnesium halide to the oxygen-containing organic solvent in the anhydrous magnesium halide-containing organic solvent solution is within the above range, the solid titanium catalyst component can be efficiently obtained.

Thus, when water is distilled off from the hydrous magnesium halide in the presence of the potassium compound, the sodium compound is deposited, but at the same time, the calcium compound is deposited together with the potassium compound. If the potassium compound is not present, the sodium compound is deposited but the calcium compound is not deposited.

By removing the precipitated calcium compound together with the sodium compound and the potassium compound from the solution of anhydrous magnesium halide in the oxygen-containing organic solvent, a solution of calcium-free anhydrous magnesium halide in the oxygen-containing organic solvent (anhydrous magnesium halide). A solution) is obtained.

The method for removing the calcium compound and the like from the solution of anhydrous magnesium halide in the oxygen-containing organic solvent is not particularly limited as long as it can remove the calcium compound and the like from the solution, but removal by filtration is preferable. In the case of performing filtration, there is no limitation on the filter material, and commonly used Teflon, SUS, cellulose, etc. are used as the filter material. Also, the opening of the filter medium is 1 to
100 μm, preferably 5 to 50 μm is desirable. The temperature at the time of filtration is 20 to 150 ° C., preferably 50 to 130
C is desirable. The filtration method may be any of atmospheric filtration, pressure filtration and vacuum filtration.

The anhydrous magnesium halide solution can be obtained by distilling off the oxygen-containing organic solvent from the thus-obtained anhydrous magnesium halide solution by a method such as distillation.

In the present invention, similarly to the above, one of the steps of preparing an oxygen-containing organic solvent solution in which anhydrous magnesium halide containing at least calcium as an impurity is used as a starting material and the anhydrous magnesium halide is dissolved. At a stage, a potassium compound is added to bring calcium (calcium compound) and potassium (potassium compound) into contact with each other, and calcium (calcium compound) is precipitated together with potassium (potassium compound) from this anhydrous magnesium halide-containing organic solvent solution. It can also be removed.

The method for producing the anhydrous magnesium halide solution according to the present invention has been described above. Next, the method for preparing the solid titanium catalyst component for olefin polymerization according to the present invention will be described. In the following method for preparing the titanium catalyst component, the case where the anhydrous magnesium halide is anhydrous magnesium chloride will be described as an example.

In the method for preparing a solid titanium catalyst component for olefin polymerization according to the present invention, an oxygen-containing organic solvent solution of anhydrous magnesium chloride containing a small amount of impurities such as calcium (anhydrous magnesium chloride solution) obtained by the above method is used. A solid titanium catalyst component for olefin polymerization is prepared by contacting with a liquid titanium compound. In this case, the anhydrous magnesium chloride solution may be brought into contact with the titanium compound in the liquid state as it is, or after the oxygen-containing organic solvent is partially distilled from the anhydrous magnesium chloride solution, it may be brought into contact with the titanium compound in the liquid state. Good.

First, if necessary, an electron donor [electron donor (a)] other than a hydrocarbon solvent and / or the oxygen-containing organic solvent is added to the anhydrous magnesium chloride solution obtained as described above. A magnesium compound solution is prepared.

The hydrocarbon solvent used here is
Aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, and aromatic carbonization such as benzene, toluene and xylene. Examples thereof include hydrogen, halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and mixtures thereof.

The electron donor (a) is used in an amount of 0.01 to 1.0 mol, preferably 0.1 to 0.5 mol, per 1 mol of the magnesium compound. Contact temperature is -2
The temperature is 0 to 300 ° C., preferably 20 to 200 ° C., and the contact time is 5 to 240 minutes, preferably 10 to 120 minutes. The electron donor (a) may be used alone or in combination of two or more kinds.

Examples of the electron donor (a) include alcohols, esters, ethers, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, acid amides and acid anhydrides as described below. , Oxygen-containing electron donors such as alkoxysilanes; ammonia, amines,
Nitrogen-containing electron donors such as nitriles, pyridines and isocyanates can be mentioned.

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

At this time, the titanium compound in the liquid state is
It is used in an amount of 2 to 100 g atom, preferably 4 to 50 g atom, per 1 g atom of magnesium in the magnesium compound solution. The contact temperature is -70 to 200 ° C, preferably -70 to 50 ° C, and the contact time is 5 to 300 minutes, preferably 30 to 180 minutes.

As the titanium compound in the liquid state,
For example, a tetravalent halogen-containing titanium compound represented by the following formula
Can be mentioned. Ti (OR)_nX_4-n (Wherein, R represents a hydrocarbon group, X represents a halogen atom)
However, 0 ≦ n ≦ 4. ) Such halogen-containing titanium
Specifically, TiCl 2_Four, TiBr_Four, T
iI_FourTetrahalogenated titanium such as; Ti (OCH_Three)
Cl_Three, Ti (OC_TwoH_Five) Cl_Three, Ti (On-C_FourH₉)
Cl_Three, Ti (OC_TwoH_Five) Br_Three, Ti (Oiso-C_FourH₉)
Br_ThreeTrihalogenated alkoxy titanium such as; Ti
(OCH_Three)_TwoCl_Two, Ti (OC_TwoH_Five)_TwoCl_Two, Ti
(On-C_FourH₉)_TwoCl _Two, Ti (OC_TwoH_Five)_TwoBr_TwoSuch as
Dihalogenated alkoxy titanium; Ti (OCH_Three)_ThreeC
l, Ti (OC_TwoH_Five)_ThreeCl, Ti (On-C_FourH₉)_ThreeC
l, Ti (OC_TwoH_Five)_ThreeMonohalogenated al such as Br
Coxy titanium; Ti (OCH_Three)_Four, Ti (OC
_TwoH_Five)_Four, Ti (On-C_FourH₉)_Four, Ti (Oiso-C
_FourH₉)_FourSuch as tetraalkoxy titanium
Can be.

These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be diluted with the above-mentioned hydrocarbon solvent before use. Then, the magnesium-titanium catalyst obtained as described above is added to 20-
By heating to 300 ° C., preferably 50 to 150 ° C., the solid titanium catalyst component is obtained in a state of being suspended in a hydrocarbon solvent. At this time, the heating time is 10 to 360.
Minutes, preferably 30 to 300 minutes.

In the present invention, the magnesium-titanium solution obtained as described above may be further contacted with the electron donor (a). Also, the electron donor (a) to be contacted
May be used alone or in combination of two or more.

In this case, the electron donor (a) is used in an amount of 0.01-5 mol, preferably 0.1-1 mol, per 1 mol of the magnesium compound. In the present invention, the suspension may be subjected to solid-liquid separation by filtration or the like to collect a solid part (solid titanium catalyst component), and then the solid part may be brought into contact with the liquid titanium compound.

The solid titanium catalyst component thus obtained can be suspended in a hydrocarbon solvent and used as a catalyst component for olefin polymerization, but after solid-liquid separation from this suspension by filtration or the like. It may be dried.

The obtained solid titanium catalyst component is usually 10 to 30% by weight of magnesium and 0.5 to 10 of titanium.
% By weight, 50 to 70% by weight of halogen, 0 to hydrocarbons
It contains 10% by weight and the electron donor (a) in a ratio of 0 to 50% by weight.

Specific examples of the electron donor (a) used in the present invention include the following compounds. As alcohols, methanol, ethanol, propanol, trichloromethanol, trichloroethanol,
Examples include trichlorohexanol.

Examples of the esters include methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate and methacrylic acid. Methyl, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl Ethyl benzoate, methyl anisate, ethyl anisate, ethyl ethoxybenzoate, γ-butyrolactone, δ-valerolactone,
Coumarin, phthalide, ethyl carbonate, etc., with 2 to 18 carbon atoms
Organic acid esters of methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, i-propyl orthotitanate, n-butyl orthotitanate, i-butyl orthotitanate, n-amyl orthotitanate, Orthotitanic acid
Orthotitanate such as 2-ethylhexyl, n-octyl orthotitanate, phenyl orthotitanate and cyclohexyl orthotitanate; methyl polytitanate,
Ethyl polytitanate, n-propyl polytitanate, i-propyl polytitanate, n-butyl polytitanate, i-butyl polytitanate, n-amyl polytitanate, 2-ethylhexyl polytitanate, n-octyl polytitanate, phenyl polytitanate and Examples thereof include polytitanate such as cyclohexyl polytitanate; vanadate obtained by replacing titanium of the titanate with vanadium, niobium or zirconium, metal acid esters such as niobate and zirconate.

Further, examples of the esters include polyvalent carboxylic acid esters having a skeleton represented by the following general formula.

[0053]

Embedded image

Wherein R ^a is a substituted or unsubstituted hydrocarbon group, R ^b , R ^e and R ^f are hydrogen atoms or substituted or unsubstituted hydrocarbon groups, and R ^c and R ^d are hydrogen atoms or substituted Or, it represents an unsubstituted hydrocarbon group, preferably at least one of which is a substituted or unsubstituted hydrocarbon group.
R ^c and R ^d may be connected to each other to form a cyclic structure. When the hydrocarbon groups R ^{a to} R ^f are substituted, the substituent includes a hetero atom such as N, O and S, and is, for example, C
-O-C, COOR, COOH, OH, SO 3 H, -C
It has a group such as -NC- and NH ₂ . Specific examples of such polycarboxylic acid ester include aliphatic polycarboxylic acid ester, alicyclic polycarboxylic acid ester, aromatic polycarboxylic acid ester, and heterocyclic polycarboxylic acid ester.

Specific preferred examples include n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahdrphthalate, diethyl phthalate, diisobutyl phthalate, diphthalate phthalate. n-butyl, di2-phthalate
Examples thereof include ethylhexyl and dibutyl 3,4-furandicarboxylate.

Examples of ethers include ethers having 2 to 20 carbon atoms such as methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole and diphenyl ether.

Further, examples of the ethers include polyether compounds represented by the following formula.

[0058]

Embedded image

(Where n is an integer of 2 ≦ n ≦ 10,
R ^{1 to} R ²⁶ are substituents having at least one element selected from carbon, hydrogen, oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon, and any R ^{1 to} R ²⁶
Preferably, R ^{1 to} R ²⁰ may together form a ring other than a benzene ring, and the main chain may contain an atom other than carbon. ) Among such polyether compounds, 1,3-diethers are preferable, and 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2 , 2-Dicyclohexyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) 1,3-dimethoxypropane, 2-isopropyl-2-cyclohexyl-
1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-
1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2-isopropyl-2-cyclopentyl-1,3-
Dimethoxypropane is preferred.

The phenols may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol and naphthol having 6 to 6 carbon atoms.
There are 20 phenols.

As the ketones, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone,
Examples include ketones having 3 to 15 carbon atoms such as benzophenone and benzoquinone.

Examples of the aldehydes include aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde and naphthaldehyde.

Examples of the organic acid halides include acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride and anisic acid chloride.

Examples of the acid amides include acid amides such as acetic acid N, N-dimethylamide, benzoic acid N, N-diethylamide and toluic acid N, N-dimethylamide. Examples of the acid anhydrides include acetic anhydride, phthalic anhydride, benzoic anhydride and the like.

Examples of amines include trimethylamine, triethylamine, tributylamine, tribenzylamine and tetramethylethylenediamine.

Examples of pyridines include pyridine, methylpyridine, ethylpyridine and dimethylpyridine. The solid titanium catalyst component obtained as described above is used as an olefin polymerization catalyst in combination with, for example, an organometallic compound of Group I to Group III metal of the periodic table.

Examples of the organometallic compounds of metals of groups I to III of the periodic table include organoaluminum compounds, complex alkyl compounds of group I metals and aluminum, organometallic compounds of group II metals and the like.

Examples of such organoaluminum compounds include compounds represented by the following formula. R ^g _n AlX _3-n (wherein, R ^g represents a hydrocarbon group having 1 to 12 carbon atoms, X
Is halogen or hydrogen, and n is 1 to 3. ) Specifically, the following compounds may be mentioned.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkyl aluminum such as ethylhexyl aluminum; alkenyl aluminum such as isoprenyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diisopropyl aluminum chloride, diisobutyl aluminum chloride, dialkyl aluminum halide such as dimethyl aluminum bromide; methyl aluminum sesquichloride, ethyl aluminum sesquichloride , Isopropyl aluminum sesquichloride, butyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Examples of complex alkylated products of Group I metal and aluminum include compounds represented by the following general formula. M ⁱ AlR ^h ₄ (wherein M ⁱ is Li, Na or K, and R ^h is a carbon number of 1 to
15 hydrocarbon groups) Specifically, LiAl (C ₂ H ₅ ) ₄ , LiAl (C
₇ H ₁₅ ) _{4 and the} like.

Examples of the organometallic compound of Group II metal include compounds represented by the following general formula. R ^j R ^k M ² (In the formula, R ^j and R ^k are a hydrocarbon group having 1 to 15 carbon atoms or halogen, and they may be the same or different from each other, but they are not halogen. ² is Mg,
Zn and Cd. ) Specifically, diethyl zinc, diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride and the like can be mentioned.

The solid titanium catalyst component obtained by the method of the present invention may be used for the polymerization of olefins together with the above-mentioned organometallic compound and the above-mentioned electron donor (a) and / or the following electron donor (b). Good.

Examples of the electron donor (b) include organic silicon compounds represented by the following general formula. R _n Si (OR ′) _4-n (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
Specifically, as such an organosilicon compound, ethyltriethoxysilane, n-propyltriethoxysilane,
t-Butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltributoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane, p-
Trilylmethyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, phenyltriethoxysilane, dicyclopentyldimethoxysilane, hexenyltrimethoxysilane, cyclopentyltriethoxysilane, tricyclopentyl Examples thereof include methoxysilane and cyclopentyldimethylmethoxysilane.

Further, as the electron donor (b), 2,6-substituted piperidines, 2,5-substituted piperidines, N, N, N ', N'-tetramethylmethylenediamine, N, N, N', Substituted methylenediamines such as N'-tetraethylmethylenediamine, nitrogen-containing electron donors such as 1,3-dibenzylimidazolidine, substituted imidazolidines such as 1,3-dibenzyl-2-phenylimidazolidine, triethylphosphite , Tri-n-propyl phosphite, triisopropyl phosphite, tri
n-butyl phosphite, triisobutyl phosphite,
Phosphorus-containing electron donors such as phosphites such as diethyl n-butyl phosphite and diethylphenyl phosphite, oxygen-containing electron donors such as 2,6-substituted tetrahydropyrans and 2,5-substituted tetrahydropyrans It can also be used.

The above electron donors (b) may be used alone or in combination of two or more. Although the method for preparing the solid titanium catalyst component for olefin polymerization according to the present invention has been described above, the present invention is not limited to the case where the hydrous magnesium halide is hydrous magnesium chloride,
The same applies to the case of hydrous magnesium bromide or hydrous magnesium iodide.

[0076]

According to the present invention, an anhydrous magnesium halide solution containing almost no calcium can be produced from hydrous magnesium halide containing at least calcium as an impurity. Further, the solid magnesium catalyst component for olefin polymerization can be prepared by using the anhydrous magnesium halide solution as a part of the raw material. The obtained solid titanium catalyst component has a catalytic activity equivalent to that of a conventional catalyst prepared by anhydrous magnesium halide for industrial and / or reagent use.

[0077]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the concentrations of calcium, sodium and potassium in the filtrate or solution were measured by atomic absorption spectrometry, and the concentration of magnesium was measured by plasma emission spectrometry.

[Production of anhydrous magnesium chloride solution]

[0079]

Example 1 Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Shigyo; water content 51.2% by weight, calcium content 0.109% by weight, sodium content 0.
It contains 131% by weight and does not contain potassium. In the following Examples and Comparative Examples, “magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Salt Industry)” is
It has the same composition as the magnesium chloride hexahydrate of this example. ) 40.6 g (0.2 mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169 g (1.3 mol) and potassium chloride (Wako Pure Chemical Industries, Ltd.) 0.126 g (included in the magnesium chloride hexahydrate). Calcium 1.
6 times mol) was put into a 500 ml glass container to prepare a mixed solution. Then, stirring is performed and nitrogen gas (dew point -60 ° C or less) containing substantially no water is added at 5 N-liter /
The mixture was heated at 150 ° C. for 7 hours and then at 170 ° C. for 2 hours while ventilating the mixture at a flow rate of hr. By this operation, the water content in the mixed solution was reduced to 0.0047% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined. The concentrations of calcium, sodium and potassium in the obtained filtrate are converted into the concentration in anhydrous magnesium chloride,
The calcium concentration was 0.023% by weight, the sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0080]

Example 2 Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Shigyo Co., Ltd.) 40.6 g (0.2
Mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169
g (1.3 mol) and potassium chloride (Wako Pure Chemical Special Grade)
The same operation as in Example 1 was carried out except that 0.41 g (5.1 mol of calcium contained in the above magnesium chloride hexahydrate) was placed in a 500 ml glass container. As a result, the water content in the mixed solution decreased to 0.0034% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.025% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0082]

Example 3 Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Shigyo Co., Ltd.) 40.6 g (0.2
Mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169
g (1.3 mol) and potassium chloride (Wako Pure Chemical Special Grade)
The same operation as in Example 1 was carried out except that 0.039 g (0.5 times the molar amount of calcium contained in the magnesium chloride hexahydrate) was placed in a 500 ml glass container. As a result, the water content in the mixed solution decreased to 0.0047% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.074% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0084]

Example 4 Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Shigyo Co., Ltd.) 40.6 g (0.2
Mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169
g (1.3 mol) and potassium acetate (Wako Pure Chemical Industries, Ltd.)
The same operation as in Example 1 was performed except that 0.163 g (1.5 times mol of calcium contained in the above magnesium chloride hexahydrate) was placed in a 500 ml glass container. As a result, the water content in the mixed solution decreased to 0.0047% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.030% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0086]

[Example 5] Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Shigyo Co., Ltd.) 40.6 g (0.2
Mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169
g (1.3 mol) and potassium carbonate (Wako Pure Chemical Special Grade)
The same operation as in Example 1 was performed except that 0.130 g (1.5 times mol of calcium contained in the magnesium chloride hexahydrate) was placed in a 500 ml glass container. As a result, the water content in the mixed solution decreased to 0.0047% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.035% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0088]

Comparative Example 1 Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Shigyo Co., Ltd.) 40.6 g (0.2
Mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169
Example except that g (1.3 mol) and 0.089 g of sodium carbonate (Wako Pure Chemical Industries, Ltd.) (1.5 times mol of calcium contained in the magnesium chloride hexahydrate) were placed in a 500 ml glass container. The same operation as in 1 was performed.
As a result, the water content in the mixed solution decreased to 0.0047% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.205% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0090]

Comparative Example 2 Magnesium chloride hexahydrate containing calcium as impurities (manufactured by Naikai Shigyo Co., Ltd.) 40.6 g (0.2
Mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169
g (1.3 mol) and 0.301 g of sodium carbonate (Wako Pure Chemical Industries, Ltd.) (5.0 times mol of calcium contained in the magnesium chloride hexahydrate) in a 500 ml glass container. The same operation as in 1 was performed.
As a result, the water content in the mixed solution decreased to 0.0047% by weight. Next, the calcium compound and the like deposited by a 10 μm filter were removed by filtration, and the composition of the filtrate was examined.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.202% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[0092]

Comparative Example 3 A filtrate containing anhydrous magnesium chloride was obtained in the same manner as in Example 1 except that potassium chloride was not added.

When the concentrations of calcium, sodium and potassium in the obtained filtrate were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.250% by weight,
The sodium concentration was 0.008% by weight or less.

[Preparation of titanium catalyst component]

[0095]

[Example 6] [Preparation of raw material for catalyst component (A)] Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Salt Industry) 4
0.6 g (0.2 mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169 g (1.3 mol) and potassium chloride (Wako Pure Chemical Industries, Ltd.) 0.126 g (calcium contained in the magnesium chloride hexahydrate) 1.6 times the mole) to 50
It was put in a 0 ml glass container to obtain a mixed solution. Then, stirring is carried out, and nitrogen gas (dew point -60 ° C or less) containing substantially no water is aerated at a flow rate of 5 N-liter / hr into the mixed solution at 150 ° C for 7 hours, and then 1 hour.
Heated at 70 ° C. for 2 hours. By this operation, the water content in the mixed solution was reduced to 0.0047% by weight. Subsequently, the flow rate of nitrogen gas aerated to the solution was 30 N-liter / hr.
Then, the heating temperature was set to 185 ° C., part of 2-ethylhexanol was distilled off, and the mixture was prepared so that the molar ratio of magnesium chloride to 2-ethylhexanol was 1: 3. Next, the temperature of the solution was lowered to 110 ° C., 88 ml of n-decane (manufactured by San Techno Chemical) was added and sufficiently stirred, and then the calcium compound and the like precipitated by a 10 μm filter were removed by filtration under a nitrogen atmosphere. Phthalic anhydride (Wako Pure Chemical Industries special grade) 4.43 g was added to the solution, and the temperature was 130 ° C.
And heated for 1 hour to obtain a uniform solution.

When the concentrations of calcium, sodium and potassium in the obtained solution were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.023% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[Preparation of catalyst component (A)] The obtained homogeneous solution was cooled to room temperature, and 75 ml thereof was sampled at -20 ° C.
Titanium tetrachloride (Sumitomo Sitix) 200m cooled to room temperature
The entire amount was added dropwise to the mixture over 45 minutes. This mixture is
The temperature was raised to 110 ° C. over time, and when the temperature reached 110 ° C., 5 ml of diisobutyl phthalate (Wako Pure Chemical Industries, Ltd.) was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After completion of the reaction, a solid part was collected by hot filtration, and the solid part was separated by 200 m.
Resuspend in 1 liter of titanium tetrachloride and stir at 110 ° C for 2
Hold for hours. After completion of the reaction, the solid part was collected again by hot filtration and washed with n-decane at 110 ° C. and then with hexane at room temperature until free titanium was not detected in the washing liquid. The obtained solid portion is hereinafter referred to as catalyst component (A).
The catalyst component (A) was stored as a hexane slurry,
A portion was dried for analysis of catalyst composition. The composition of the catalyst component (A) was 2.6% by weight of titanium and 2% of magnesium.
0% by weight, chlorine 62% by weight, diisobutyl phthalate 1
2.5% by weight.

[Polymerization] 750 ml of dehydrated hexane was charged into an autoclave having an internal volume of 2 liters, and 0.75 mmol of triethylaluminum (manufactured by Toso Akzo) and cyclohexylmethyldimethoxysilane (in a propylene (manufactured by Ukishima Petrochemical) atmosphere at room temperature. Shin-Etsu Chemical) 0.07
5 mmol and 0.015 mmol of the catalyst component (A) in terms of titanium atom were charged. Hydrogen (manufactured by Nippon Oxygen,
After charging 200 ml of high-purity product, raise the temperature to 70 ° C and
Polymerization was carried out while feeding propylene to the autoclave for an hour. The pressure during the polymerization was kept at 7 kg / cm ² -G.

After completion of the polymerization, the slurry containing the produced polymer was filtered to separate it into a white powdery polymer and a liquid phase. The yield of white powder polymer after drying was 420 g, which was 280
This corresponds to the activity of 00g-PP / mmol-Ti.

[0100]

[Example 7] [Preparation of raw material for catalyst component (B)] Magnesium chloride hexahydrate containing calcium as an impurity (manufactured by Naikai Salt Industry) 4
0.6 g (0.2 mol), 2-ethylhexanol (manufactured by Mitsubishi Chemical) 169 g (1.3 mol) and potassium chloride (Wako Pure Chemical Industries, Ltd.) 0.41 g (the above magnesium chloride 6)
(5.1 times the molar amount of calcium contained in the hydrate) 500
It was put in a ml glass container to prepare a mixed solution. Then, stirring is carried out and nitrogen gas (dew point -60 ° C or lower) containing substantially no water is aerated at a flow rate of 5 N-liter / hr into the above mixed solution at 150 ° C for 7 hours, then 17
Heated at 0 ° C. for 2 hours. By this operation, the water content in the mixed solution was reduced to 0.0034% by weight. Subsequently, the flow rate of nitrogen gas aerated to the solution was set to 30 N-liter / hr, the heating temperature was set to 185 ° C., and a part of 2-ethylhexanol was distilled off to obtain a molar ratio of magnesium chloride and 2-ethylhexanol. Was adjusted to be 1: 3. Next, the temperature of the solution was lowered to 110 ° C., 88 ml of n-decane (manufactured by San Techno Chemical) was added and sufficiently stirred, and then the calcium compound and the like precipitated by a 10 μm filter were removed by filtration under a nitrogen atmosphere. Phthalic anhydride (Wako Pure Chemical Industries special grade) 4.43 g was added to the solution, and the temperature was 130 ° C.
And heated for 1 hour to obtain a uniform solution.

When the concentrations of calcium, sodium and potassium in the obtained solution were converted into the concentrations in anhydrous magnesium chloride, the calcium concentration was 0.025% by weight,
The sodium concentration was 0.008% by weight or less, and potassium was not detected.

[Preparation of catalyst component (B)] The "catalyst component (A)" of Example 6 was prepared using the homogeneous solution thus obtained.
As a result of preparing a catalyst component in the same manner as in "Preparation", a catalyst component (B) containing 2.6% by weight of titanium, 19% by weight of magnesium, 61% by weight of chlorine and 12.8% by weight of diisobutyl phthalate was obtained.

[Polymerization] Example 6 using the catalyst component (B)
Polymerization of propylene is carried out in the same manner as in "Polymerization" of 4
15 g of white powder polymer was obtained. This is 27500g-
This corresponds to the activity of PP / mmol-Ti.

[0104]

Comparative Example 4 Example 6 except that potassium chloride was not added
The same operation as in [Preparation of raw material of catalyst component (A)] and [Preparation of catalyst component (A)] in (1) was performed to obtain a solid. The catalyst component is
Titanium 2.5% by weight, magnesium 20% by weight, chlorine 6
The amounts were 2% by weight and 12.4% by weight of diisobutyl phthalate.

"Polymerization" of Example 6 using the obtained solid
Polymerization of propylene was carried out in the same manner as described above. The yield of white powder polymer after drying was 306 g, which was 2040
This corresponds to the activity of 0 g-PP / mmol-Ti.

Claims (5)

[Claims] 1. When preparing an oxygen-containing organic solvent solution of anhydrous magnesium halide by distilling water away from the oxygen-containing organic solvent solution in which hydrous magnesium halide containing at least calcium as an impurity is dissolved, At any stage of the step of preparing an oxygen-containing organic solvent solution in which magnesium is dissolved or the step of preparing an oxygen-containing organic solvent solution of anhydrous magnesium halide,
A method for producing an anhydrous magnesium halide solution, which comprises contacting calcium and potassium and depositing and removing calcium together with potassium from an oxygen-containing organic solvent solution of anhydrous magnesium halide. 2. At any stage of the step of preparing an oxygen-containing organic solvent solution in which anhydrous magnesium halide containing at least calcium as an impurity is dissolved, calcium and potassium are brought into contact with each other to contain the anhydrous magnesium halide. A method for producing an anhydrous magnesium halide solution, which comprises depositing and removing calcium together with potassium from an oxygen-organic solvent solution. 3. An anhydrous magnesium halide solution obtained by the method according to claim 1 is brought into contact with a liquid titanium compound to precipitate a solid titanium catalyst component. A method for preparing a solid titanium catalyst component for olefin polymerization, which is characterized. 4. A solution obtained by adding a hydrocarbon solvent to the anhydrous magnesium halide solution obtained by the method according to any one of claims 1 to 2 is contacted with a titanium compound in a liquid state. A method for preparing a solid titanium catalyst component for olefin polymerization, which comprises depositing the solid titanium catalyst component. 5. A solution obtained by adding an electron donor other than a hydrocarbon solvent and the oxygen-containing organic solvent to the anhydrous magnesium halide solution obtained by the method according to any one of claims 1 and 2. And a titanium compound in a liquid state are brought into contact with each other to precipitate a solid titanium catalyst component, which is a method for preparing a solid titanium catalyst component for olefin polymerization.