JPS603332B2 - Zirconium-containing phosphate compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel zirconium-containing phosphate compound, and more particularly to a zirconium phosphate ester and a method for producing the same.

It has long been known that zirconium compounds react with certain organic or inorganic phosphorus compounds to form inert solids, and this reaction can be used to extract and quantify zirconium compounds, or to develop catalysts. It has been proposed to produce zirconium compounds useful as fillers, fillers, and the like.

The most typical product obtained by the reaction of a zirconium compound and an inorganic phosphorus compound is zirconium phosphate. This material is well known as an inorganic ion exchanger, and a great deal of research has been conducted on it. For example, the present inventors published a new method for producing amorphous zirconium phosphate with a large specific surface area in Japanese Patent Publication No. 51-31799. proposed a new manufacturing method for crystalline zirconium phosphate, published in Japanese Patent Publication No. 45-1897.
This was proposed in Publication No. 4. Furthermore, as a new application of zirconium phosphate, it was proposed in Hakama Kosho 45-28566 and 49-6994 that it has excellent performance as a condensation catalyst for ketones. On the other hand, 2 to 8 methods are known for the reaction between a zirconium compound and an organic phosphorus compound.

In most of these known separations, zirconium tetrachloride and phosphate ester are reacted in a non-aqueous solvent, and a powder is separated and recovered. For example, R ship sian Jom
nal of Inorganic Chemist 141297 (1969) describes the reaction of zirconium tetrachloride and tributyl phosphate to obtain a powder containing a high chlorine content (8 to 9%), but there is also no analysis of the powder. The structure and properties are not clear. Also, for example, Russian Jom cape loofInorganic
In Chemistry 14 1780 (1969),
It has been reported that when zirconium oxynitrate and phosphate ester are reacted at the interface, a powder containing nitrate radicals that is insoluble in various organic solvents is obtained. The present inventors have also confirmed that powder cannot be obtained. Furthermore, J. l
norg. N ratio 1. Chem. 35 3938 (197
Regarding the quantitative determination of monobutyl phosphate and dibutyl phosphate in triptyl phosphate, 3) suggests that various forms of zirconium compounds quantitatively react with mono- and dibutyl phosphate; however, this reaction and The reaction products have not been disclosed at all. The inventors
We have been conducting research on the reaction between zirconium compounds and organic or inorganic phosphorus compounds for many years, and now we have discovered that a dialkyl ester phosphate reacts specifically with a zirconium oxyhalide, resulting in a new and useful zirconium-containing phosphate compound. The inventors discovered that the present invention could be produced, and completed the present invention.

The zirconium-containing phosphate compound provided by the present invention is
{P02(OR)2}2 of the formula fIZ (1), where R
represents an alkyl group, and is a substance having a structural unit represented by the following.

In the above formula (1), the alkyl group may be straight or branched, and has 8 or less carbon atoms, more preferably a lower alkyl group having 1 to 5 carbon atoms. For example, methyl, ethyl, n-
Or iso-propyl, n-, lso- or rt-butyl, n-pentyl and the like.

The substance of the present invention generally exists as a polymeric substance in which a plurality of structural units represented by the above formula (1), usually six or more, are condensed.

Therefore, a preferred group of substances of the present invention has the following formula ← Z {
P02(OR)2}2nan(1-a) In the formula, R has the above meaning, especially a lower alkyl group having 1 to 5 carbon atoms, and n is a number of 6 or more. is a zirconium phosphate ester that can be represented by .

The zirconium phosphate ester provided by the present invention can exist as either soluble or insoluble in organic solvents.

In general, those obtained by the production method described below, for example, by reacting in the presence of an organic solvent or a mixture of water and a water-immiscible organic solvent, include aliphatic hydrocarbons such as hexane and heptane;
Aromatic hydrocarbons such as benzene, toluene, and xylene, alcohols such as methyl alcohol, ethyl alcohol/impropyl alcohol, and n-butyl alcohol; ethers such as diethyl alcohol and tetrahydrofuran; esters such as ethyl acetate; methylene chloride, chloroform,
It may exist in a soluble form in organic solvents such as carbon tetrachloride, methylchloroform, chlorinated hydrocarbons such as trichloroethane, and the like. Further, those soluble in these organic solvents generally exist in a state where n in the formula (11a) is smaller than about 24. On the other hand, if the degree of polymerization increases or if a substance soluble in an organic solvent becomes a solid that is substantially insoluble in the organic solvent as described above by subjecting it to the post-treatment described below, it becomes extremely difficult to measure its molecular weight. Have difficulty.

Further, these solid substances that are immovable to organic solvents can exist in the form of fibers, spheres, and particles. The zirconium phosphate esters of the present invention generally do not exhibit a clear melting point;
It has the property of decomposing immediately without melting.

One feature of the zirconium phosphate ester of the present invention is that regardless of the number of structural units of formula (1), the ester residue (
R) has a characteristic decomposition point that is approximately constant depending on the type of R). That is, when the zirconium phosphate ester of the present invention is subjected to, for example, differential thermal analysis, it exhibits a sharp exothermic peak. The decomposition temperatures of typical zirconium phosphate esters of the present invention are shown in Table 1 below. In Table 1 and the following description, decomposition temperature means the temperature at which weight loss or exothermic peak begins in differential thermal analysis. Table 1 The zirconium phosphate esters of the present invention differ depending on the manufacturing method and/or purification method described below, but when observing the X-ray diffraction pattern, the interplanar spacing (d) is generally 10.
A sharp peak indicating crystallinity is observed within the range of ~20 angstroms, while a broad peak indicating amorphism is observed at d<10 angstroms.

From this, it is presumed that the zirconium phosphate ester of the present invention is usually not a completely crystalline substance but a polymeric substance having both crystalline regions and amorphous regions. Furthermore, in observation using a scanning electron microscope, it was observed that the shape did not show a constant shape even under a magnification of tens of thousands of times.
However, when the zirconium phosphate ester soluble in the organic solvent mentioned above is introduced into a specific solvent such as ethyl acetoacetate, a crystalline solid is precipitated, and when the ethyl acetoacetate is removed by evaporation, the crystalline zirconium phosphate is recovered. When this substance is subjected to X-ray diffraction in the same manner as above, d=10-20
The sharp peak between angstroms became stronger, and at the same time, the appearance of a sharp crystalline peak was observed above the broad peak of d<10 angstrom, which clearly indicates the progress of crystallization.

Therefore, it should be understood that it is not impossible to obtain the zirconium phosphate ester of the present invention in an almost completely crystallized state depending on the method of production and/or purification. Furthermore, according to the infrared absorption spectrum of the zirconium phosphate ester of the present invention, it is distinctive in that it has the following characteristic absorption band compared to known zirconium phosphates.

Approximately 2800-3000 skin-IC-day stretching vibration approximately 1370
〜1470ｽ-IC one day bending vibration about 1000 to 120 Lus-Stretching vibration based on IP-○ or P-01C The presence of the above characteristic absorption band indicates that the substance of the present invention This shows that it has the structural unit shown in the following, that is, it is a phosphate ester derivative in which the acid site of zirconium phosphate is substituted with an alkyl group.

Furthermore, the substance of the present invention having a small number of structural units represented by the above formula (1) is soluble in an organic solvent, and its molecular weight can be measured.

Although the molecular weight varies depending on the manufacturing conditions and subsequent treatment conditions, for example, the following molecular weights have been confirmed for zirconium phosphate diisopropyl ester and zirconium scale acid di-n-butyl ester. According to the above molecular weight measurement results, it is estimated that the zirconium phosphate ester of the present invention has a structure in which six of the structural units represented by the above formula (1) are the minimum units, and is grown in approximately multiples thereof.

Of course, it has been confirmed that zirconium phosphate dialkyl esters other than the above two also show the same tendency of increasing molecular weight as above. In addition, the measurement results of elemental analysis in the Examples described below show that the substance of the present invention has the formula (
The elemental analysis value of the halogen atom of the substance of the present invention soluble in the organic solvent is in good agreement with the calculated value calculated assuming that the substance has the structural unit shown in 1). This suggests that halogen atoms are present in a proportion of . From this, it is presumed that the substance of the present invention, especially one with a small molecular weight, has the following estimated structural formula in which a halogen atom is bonded to one end, although it is not certain. In the formula, R represents an alkyl group, x represents a halogen atom, especially a chlorine atom, and m is a number of 1 or more. According to the present invention, the zirconium phosphate ester of the present invention having the above-mentioned properties has the formula HP02
(OR2)2(0) In the formula, R has the above-mentioned meaning. It is produced by reacting a phosphoric acid dialkyl ester represented by the following with a zirconium oxyhalide.

Examples of dialkyl ester phosphates represented by formula (0) used as starting materials include dimethyl ester phosphate, diethyl phosphate, di-n-propyle ester phosphate, diisopropyle ester phosphate, and di-n-butyl ester phosphate. , phosphoric acid diisobutyl ester, phosphoric acid di-rt-butyl ester, phosphoric acid di(2-ethylhexyl) ester, etc., and each of these can be used alone, or if necessary, two or more types can be used in combination. You may.

Note that the dialkyl phosphate does not necessarily need to be used in pure form, and a mixture with a monoalkyl phosphate and/or a trialkyl phosphate can also be used.

In particular, as will be described later, when it is desired to produce a fibrous zirconium phosphate ester, it may be advantageous to use a dialkyl phosphate and a monoalkyl phosphate in combination as starting materials. Furthermore, as the zirconium oxyhalide to be reacted with the dialkyl phosphate, zirconium oxychloride (CI2 of Z) is most suitable, but is not limited to this, and zirconium oxybromide, zirconium oxyiodide, etc. is also available.

The above-mentioned zirconium oxyhalide may also be in the form of zirconium oxyhalide at the time of being subjected to the reaction, for example, oxyhalogen obtained by hydrolyzing zirconium tetrahalide such as zirconium tetrachloride. The zirconium chloride-containing solution can be directly subjected to the reaction, or the zirconium oxyhalide can be produced in the reaction system.

The reaction can generally be carried out in an inert liquid medium, with the exception of those using only water. There are no particular restrictions on the liquid medium that can be used, as long as it at least partially dissolves each of the above two types of starting materials and is substantially inert to the reaction, and can be used in a wide range. Suitable liquid media include alcohols such as methyl alcohol and ethyl alcohol, water and chlorinated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride, methyl chloroform, trichloroethane, etc.). ), water-aliphatic hydrocarbons (e.g. hexane,
Heptane, octane, etc.), water-aromatic hydrocarbons (eg, benzene, toluene, xylene, etc.), water-alcohols (eg, n-butyl alcohol, n-octyl alcohol, etc.), and the like are generally suitable. When a mixture of water and other inert liquid medium as mentioned above is used, it is suitable for the purpose of obtaining a fibrous material, which will be described later. The reaction according to the present invention may be carried out in either a homogeneous reaction system or an interfacial reaction system, which can be freely selected depending on the shape of the product, etc., if desired.

In the case of a homogeneous reaction system, alcohols (e.g., methyl alcohol, ethyl alcohol, etc.) are one of the preferred solvents because they have the ability to simultaneously dissolve both dialkyl phosphate and zirconium oxychloride, and can be used alone or with alcohol. Can be used in combination with miscible organic solvents.

In addition, when using an interfacial reaction system, water in which zirconium oxychloride is dissolved, water in which dialkyl phosphate is soluble; Hydrocarbons (e.g. benzene, toluene, xylene, etc.), chlorinated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride, methylchloroform, trichloroethane, etc.),
Combinations with alcohols such as n-butyl alcohol, n-amyl alcohol, n-octyl alcohol, etc. are advantageously used. The reaction generally proceeds well at room temperature, without the need for specific cooling or heating, although temperatures between about 0° C. and the reflux temperature of the reaction mixture can also be used if desired.

Particularly advantageous is the reaction at room temperature. There is no strict limit to the amount of dialkyl ester phosphate and zirconium oxyhalide to be used in the reaction; For example, it is suitable to use an amount of about 2 to 1.5 mol, particularly a stoichiometric amount of about 2 mol.

The reaction time can vary widely depending on the reaction temperature, the molecular weight of the desired target substance, etc., and cannot be specified unconditionally, but is generally between one hour and several tens of days.

According to the method of the present invention, by appropriately selecting the conditions for the reaction between the dialkyl phosphate and the zirconium oxyhalide, the zirconium phosphate having the structural unit represented by the formula (1) can be prepared using an organic solvent. It was discovered that it can be recovered as a solid that is soluble in organic solvents, or in the form of fibers that are not removable in organic solvents, or as granular materials that are incompatible with organic solvents.

The manufacturing conditions for each form of zirconium phosphate ester will be further explained below.

{1' Production of zirconium phosphate ester soluble in organic solvents: The zirconium phosphate esters soluble in organic solvents as described above can be produced by using either the homogeneous reaction system or the interfacial reaction system described above.

At this time, the pH of the reaction system is preferably maintained at 2 or less, and the reaction temperature is preferably room temperature.

Under the above conditions, the dialkyl phosphate and the zirconium oxyhalide react, and a zirconium phosphate having six of the above structural units is easily produced in a short period of time (usually at the same time as mixing), but the subsequent reaction The speed will be significantly reduced. Therefore, when producing the substance of the present invention having more than 6 of the above-mentioned structural units, the reaction is further continued.
In other words, it needs to be aged at room temperature. In this way, it is possible to obtain a zirconium phosphate ester that is soluble in organic solvents and usually has 12 to 24 structural units of the formula (1). The aging time at room temperature varies considerably depending on the type of dialkyl phosphate used, the type of reaction medium, etc., but is generally in the range of several tens to several hundreds of hours.

In addition, as another method for increasing the molecular weight,
A zirconium phosphate ester having a certain composition that is soluble in an organic solvent is synthesized in advance by a homogeneous reaction in alcohol, and then the alcohol is removed by flashing, and the resulting glassy solid is mixed with a water-immiscible organic solvent ( For example, the structure of formula (1) is a method in which free halogen ions such as chlorine ions are completely removed by redissolving them in an aromatic hydrocarbon or chlorinated hydrocarbon system and repeatedly replacing the aqueous layer. Zirconium phosphate esters having 12 to 24 units and soluble in organic solvents can be obtained.

The produced zirconium phosphate ester can be recovered by a conventional method. For example, the zirconium phosphate ester of the present invention can be recovered by removing the reaction medium from the reaction mixture after the reaction is completed by freezing or evaporating it. It can be recovered as a clear glassy solid or a viscous material.

That is, as the reaction medium is removed from the reaction product, it becomes viscous depending on the rate of removal of the reaction medium, and when the reaction medium is completely removed, it becomes a glassy solid.

Therefore, by controlling the removal rate of the reaction medium as necessary, it is possible to recover glassy solids from substances having various degrees of fineness. The clay-like substance or glassy solid zirconium phosphate thus recovered can be used in combination with alcohols (e.g., methanol, ethanol, inpropyl alcohol, n-butyl alcohol, etc.), aliphatic hydrocarbons (e.g., n-hexane, n-butyl alcohol, etc.). -hebutane, n-octane, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, etc.), chlorinated hydrocarbons (e.g. methylene chloride, chloroform, carbon tetrachloride, methyl chloroform, trichloroethane, etc.), ethers (e.g. diethyl ether) , tetrahydrofuran, dioxane, etc.),
It is soluble in organic solvents such as esters (eg ethyl acetate, butyl acetate).

Further, the reaction mixture obtained in the above reaction can be purified as it is, or the above viscous substance or the above glassy solid can be purified by treating with acetoacetic acid ethyl ester.

For example, it can be purified by dissolving the above-mentioned viscous maple substance or glassy solid in ethyl acetoacetate and leaving the solution at room temperature or refluxing. '21 Production of fibrous zirconium phosphate ester: When producing fibrous zirconium phosphate ester, it is particularly suitable to use an interfacial reaction system.

A suitable reaction medium is a combination of water and an organic solvent that has a higher specific gravity than water and is substantially immiscible with water. There is no particular restriction as long as it is soluble in water and does not have a substantial adverse effect on the reaction system of the present invention. For example, hydrogen chloride such as methylene chloride, chloroform, carbon tetrachloride, methyl chloroform, etc. can be used, In particular, solvents with appropriate volatility, such as methylene chloride and chloroform, are preferably used for ease of post-treatment. The reaction takes place at the interface between the aqueous phase in which zirconium oxyhalide is mainly dissolved and the organic phase in which dialkyl phosphate is mainly dissolved.

This interfacial reaction can be carried out by pre-mixing the above two types of reaction media at an appropriate ratio, such as a volume ratio of water to organic solvent, in the range of 1:1 to 3:1, and adding oxyhalogen to the mixed solvent. This can be achieved by adding zirconium oxide and dialkyl phosphate in the above molar ratio, or by dissolving zirconium oxyhalide in water and dialkyl phosphate in an organic solvent in advance, and then mixing both solutions. Ru.

In this case, the concentration of zirconium oxyhalide in the aqueous solution is preferably relatively high, and is generally 0.1 to 0.6 molar liter.

Further, the concentration of dialkyl phosphate in the organic solvent is preferably about several molar liters. According to the present invention, when producing a fibrous zirconium phosphate ester, a dialkyl phosphate ester can be used alone;
In addition, it has been found that the use of phosphoric acid monoalkyl esters often results in more effective formation of fibrous solids, for reasons that are not clear.

Therefore, when the purpose is to produce fibrous solids, the combination of phosphoric acid monoalkyl esters is often a suitable means. In this case, the type of alkyl moiety of the phosphoric acid monoalkyl ester that can be used is preferably the same as the alkyl moiety of the dialkyl ester used, but is not limited thereto, and different alkyl groups, Preferably, it may be a lower alkyl group having 1 to 5 carbon atoms. In addition, when a phosphate monoalkyl ester is used in combination, the amount used is not particularly limited, but the amount is 5% by weight or less, usually 5 to 4% by weight, based on the commonly used phosphoric acid dialkyl ester. It is advantageous to use the range.

The above-mentioned interfacial reaction can be carried out in a controlled manner, thereby promoting the reaction between the zirconium oxyhalide and the dialkyl ester phosphate. Moreover, the reaction can be advantageously carried out under the above-mentioned temperature conditions, especially at room temperature. The interfacial reaction can be carried out usually for several hours to several days until a sufficient amount of the zirconium phosphate ester soluble in the organic solvent described above is produced, and then further ripening can be carried out if necessary.

This aging is carried out by leaving the reaction mixture obtained above as it is for several hours to several days. Room temperature is sufficient for the temperature during ripening, but depending on the case, cooling or flooding may be carried out continuously or intermittently or temporarily. If the purpose is to produce short fibrous zirconium phosphate esters, the presence of phosphate monoalkyl esters is completely unnecessary, and by strongly immersing them, they gradually rise to the surface of the water.
Zirconium phosphate ester fibers are formed in suspension. This fibrous material can be separated and recovered as short fiber solids by appropriate means during filtration. At this stage, a reaction mixture usually in the form of a colloid or slurry may be produced.

The reaction mixture is washed as it is, or the concentrate obtained by removing excess reaction medium from the reaction mixture by means such as furnace filtration or centrifugal D separation is washed in water, and the hydrogen halide released during the above reaction is dissolved in water. and raise the barrier of the reaction mixture or concentrate. Repeat this washing operation once or several times, and the unevenness of the washing liquid is in the range of 1.5 to 7.
Preferably, when the value falls within the range of 2 to 5, the reaction product obtained in the above reaction is further aged in the washing liquid or in a water-containing state separated from the washing liquid. Washing with water can normally be carried out using water, but if necessary, it may also be carried out using a weakly alkaline aqueous solution containing ammonium carbonate, ammonium hydroxide, or the like. Generally, the pH can be easily adjusted to the above range by repeatedly washing with ordinary water. Aging in this case can also be carried out under the same conditions as above. In addition, in the middle of this ripening stage, washing with water may be repeated once or more as necessary, and the ripening may be performed while being gently rubbed. Thus, depending on the type of starting materials, reaction and aging conditions, etc., various types of fibrous solids can be produced, ranging from relatively short fibrous solids on the order of hundreds of microns to thousands of microns to long fibrous solids on the order of several ribs to several arcs. A shaped fibrous zirconium phosphate ester is formed. This fibrous zirconium phosphate ester can be air-dried (naturally dried) after water is separated if necessary, and fibers may grow further during this storm-drying stage.

According to the results of experiments conducted by the present inventors, it has been found that when diethyl phosphate and dipropyle phosphate are used as the dialkyl phosphate, fibrous zirconium phosphate is particularly easy to form and is suitable. The fibrous zirconium phosphate ester thus obtained is
It is usually a white solid and is quite strong.

This fibrous solid also contains aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols such as methyl alcohol, ethyl alcohol, and inpropyl alcohol; and methylene chloride, chloroform, carbon tetrachloride, methyl chloroform, and trichloroethane. It is virtually insoluble in chlorinated hydrocarbons such as chlorinated hydrocarbons. Furthermore, when the zirconium phosphate ester fiber obtained as described above is treated in an acid or weak alkali aqueous solution at room temperature or under heating, the ester portion thereof is easily hydrolyzed, and the zirconium phosphate fiber or its alkali is easily hydrolyzed. It changes into metal or alkaline earth metal exchangers, quaternary ammonium salts, etc. This ease of hydrolysis is unique to the fiber, which is much more susceptible to hydrolysis than the above-mentioned organic solvent-soluble zirconium phosphate ester or the granular material described below. in this case,
No change in the shape of the fibers before and after hydrolysis with acid or alkali is observed with the naked eye or with a microscope magnified several times to several tens of times. This shows that zirconium phosphate fibers and ion-exchanged fibers made of certain metals can be produced by hydrolyzing zirconium phosphate fibers and ion-exchanging the hydrolyzate. In addition, when the fibers obtained as described above are heat-treated in a strong alkaline solution, for example, 6 to 1 ml of caustic soda, together with the organic components contained in the fibers,
The phosphorus component is eluted and transferred to the zirconia fiber.

These chemical changes are supported by chemical analysis of the obtained zirconia fibers. However, it was revealed that the morphology before and after alkali treatment did not change with the naked eye and by microscopic observation at several tens of times magnification. This suggests that the skeleton of the fiber obtained in the present invention is composed of dimensions -〇tenn and has a structural unit represented by the above formula (1).

{3' Production of granular zirconium phosphate esters: According to the invention, zirconium phosphate esters can be produced in the form of granular solids (spheres).

In order to obtain the zirconium phosphate ester as a granular solid, the zirconium oxyhalide and the dialkyl phosphate are reacted in a homogeneous reaction system or an interfacial reaction system as described above, and if necessary, the product is aged. A reaction mixture containing a zirconium phosphate ester soluble in an organic solvent or a concentrate from which a portion of the reaction medium has been removed or a glassy solid recovered from the reaction mixture as described above is added to a reaction mixture containing a zirconium phosphate ester soluble in an organic solvent, with a pH of 9 or less, preferably 8 or less. More preferably, it may be introduced and mixed into an aqueous liquid having a pH in the range of 6 to 8 or a pH of 2 or less. As a result, zirconium phosphate ester is precipitated in the aqueous liquid in the form of particles.

In order to obtain granules with as uniform a particle size as possible industrially,
- It is preferable to treat the above mixed system under rope azusa. The concentration conditions at this time can be varied widely depending on the state of the zirconium phosphate ester introduced into the aqueous liquid, the pH of the aqueous liquid, etc., or depending on the desired particle size. This is an easy decision. Furthermore, the temperature during the mixing process is not critical and can be varied over a wide range depending on the state of the zirconium phosphate ester introduced into the water spraying liquid, the pH of the aqueous liquid, the desired particle size, etc.; is sufficient at room temperature,
If necessary, it can be heated up to boiling temperature.

Examples of aqueous liquids that can be used include alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, and ammonia, and acids such as hydrochloric acid, sulfuric acid, and acetic acid to adjust the pH as necessary. It is most common to use a mixed solvent of water and a water-miscible organic solvent (for example, alcohol).

In addition, the pH of the aqueous liquid may change during the treatment of the above-mentioned mixed system, but in this case, a moderating agent such as ammonium hydroxide or ammonium carbonate may be added to maintain the above pH range. It is advantageous to do so.

The amount of such aqueous liquid used is not critical at all and can be varied as required, but it is generally preferred that it be at least 0.3 times the volume of the substance introduced into the aqueous medium;
Usually, a range of 1 to 100 times is practical.

The time of the mixing process is also not critical; as before, the state of the zirconium phosphate ester introduced into the aqueous liquid;
Although it can be varied widely depending on the pH of the aqueous liquid, the desired particle size, etc., it is generally advantageous to treat for at least about one hour, and usually for several to several tens of hours.

The resulting particulate zirconium phosphate ester can be separated from the aqueous liquid by conventional methods and washed and/or dried by conventional methods.

Thus, generally on the order of 0.05 to 3 microns,
Usually, zirconium phosphate ester particles having an average particle size of about 0.1 to 1.0 microns are obtained.

The granules thus obtained are usually insoluble in the aromatic hydrocarbons and chlorinated hydrocarbons mentioned above, although they are sometimes soluble in alcohol.

Regarding other properties of the resulting granules, such as hydrolyzability to acids, the hydrolyzability of organic groups is weaker than that of fibrous zirconium phosphate esters, and when treated with IN-sulfuric acid at room temperature or under heating, fibers In this case, most of the organic groups are hydrolyzed to produce zirconium phosphate fibers, whereas in the case of the present granules, only 20 to 30% of the organic groups can be decomposed and liberated.

Furthermore, the results of infrared absorption spectrum, X-ray diffraction, and thermal analysis hardly change depending on the shape of the obtained zirconium phosphate ester. As explained above, the zirconium phosphate ester of the present invention is obtained in the form of an organic solvent-soluble solid, a fibrous solid, a granular solid, and the like.

Therefore, many useful applications are possible by taking advantage of the unique properties of each form. In addition to being useful as a catalyst, zirconium phosphate esters that are soluble in organic solvents can make these inorganic surfaces lipophilic if used as a surface treatment agent for various inorganic powders and inorganic fibers.

Furthermore, after coating an inorganic surface, if the organic groups are removed by hydrolysis using an appropriate method, the result is the same as coating an inorganic surface with zirconium phosphate. This material can be used as an ion exchanger. Also,
It is also useful as a coupling agent for inorganic and organic substances.
Fibrous zirconium phosphate esters are also useful in their own right as catalysts and fillers. Furthermore, like the organic solvent-soluble zirconium phosphate ester, zirconium phosphate fibers obtained by hydrolyzing organic groups are useful as ion exchange fibers. Furthermore, granular zirconium phosphate esters can be used in the same manner as fibrous zirconium phosphate esters, and can also be used with good dispersion as additives and fillers for rubbers, plastics, and others. Next, the present invention will be further explained by examples.

In this specification, the measurement of molecular weight, analysis of phosphorus and zirconium, decomposition temperature, infrared absorption spectrum, and X-ray diffraction were performed as follows. {11 Measurement of molecular weight Using a Hitachi model 115 molecular weight measuring device, using Wako reagent special grade chloroform as the solvent, and using a constant temperature bath at a temperature of 3.
I went with 5.6 qo.

■ Phosphorus and zirconium analysis samples were gradually burned and melted in hot water with sodium carbonate.The phosphorus components were extracted with hot water and analyzed colorimetrically using the lymphanadomolybdic acid method, and for zirconium, the residual liquid was scorched to produce zirconia. Determined by gravimetric analysis.

Phosphorus and zirconium could also be easily analyzed by crab light X-ray analysis. '3l Decomposition temperature The decomposition start temperature was measured by measuring two samples 9 by differential thermal analysis, and was carried out in air at a heating rate of 20 qC'min.

'4} Infrared absorption spectrum Using Hitachi's EPI-G base type infrared spectrophotometer, K
It was measured by the B-Kameyodase method.

{5) X-ray diffraction Using Rotorflex 20L manufactured by Rigaku Denki, Cu-
Diffraction patterns were recorded using the diffractometer method using KQ radiation.

Example 1 Commercially available (manufactured by Tokyo Chemical Industry Co., Ltd.) phosphoric acid di-n-butyl ester (purity 95%) 8.2% was mixed with ethanol (99.5%)
Dilute with 100ml.

On the other hand, zirconium oxychloride (Z's CI2/Mother's Day 20
) Dissolve 6.4 liters in 100 ml of ethanol. Mix both solutions at room temperature and continue to stir for another hour. At this time, no precipitate is formed and a clear solution is obtained. Then, using a rotary evaporator, the temperature was heated to 50°C.
, remove the ethanol under reduced pressure. Gradually increases viscosity,
Approximately 9.7 hours of glassy solid was finally obtained. This product was dissolved in chloroform, water was added to transfer free chlorine ions to the aqueous layer, and the chloroform layer was removed by volatilization at 50° C. under reduced pressure using a rotary evaporator. As a result of chemical analysis and elemental analysis of the obtained glassy solid, the P04/Zr molar ratio of this product was 1.97.
and C34.1%; day 6.7%; PII. 9%; Zr1
7-8%; CIO. It was 96%.

When it was redissolved in chloroform and the molecular weight was measured by the method described above, it was found to be 3,172.

In addition, the decomposition start temperature determined by differential thermal analysis was 27200
It was hot. The infrared absorption spectrum of the above product is shown in FIG.

The infrared absorption spectrum indicates that the product is zirconium phosphate dibutyl ester. The X-ray diffraction pattern of this product is shown in FIG. 2, which suggests that this product has an amorphous region and a crystalline region. From the above analytical crystals, the above product has the following formula CI÷
It is believed to be a zirconium phosphate dibutyl ester represented by Zr〇{P〇2 (〇1n-C4day9)2}2 H,6day.

Furthermore, these include alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; ethers such as ethyl ether and tetrahydrofuran; esters such as ethyl acetate; chlorinated carbons such as carbon tetrachloride, chloroform, and methylene chloride. Dissolved in hydrogen and aliphatic hydrocarbons such as hexane and heptane.

Further, the reaction product was mixed with acetoacetic acid ethyl ester, and the crystallized product was separated. The results of X-ray diffraction of this crystalline material are shown in FIG. Example 2 Commercially available diisopropylester phosphate (50% each of mono and diester)
The mixture (containing 5 folds) was diluted with Treso, and the anion exchange resin Am was passed over to IR20 in rli.
Adsorbs and removes phosphate monoisopropyl ester.

Toluene was removed from the eluate under reduced pressure to obtain highly pure diisopropylester phosphate (99.9%). 3.6 hours of the obtained diisopropylesterate phosphate was mixed with 11 minutes of ethanol.
The solution was diluted with 100% of zirconium oxychloride and added to a solution of 3.2% of zirconium oxychloride dissolved in 100% of ethanol at room temperature.

After continuing the hawk worship for 1 hour after the addition, in the same manner as in Example 1,
The ethanol was removed under reduced pressure to yield a glassy solid. Further, in the same manner as in Example 1, the product was brought into contact with a chloroform-water mixed solvent and shaken to transfer free chloride ions to the water layer. A solid substance was obtained.

This material has a P04/Zr molar ratio of 2.06 and a C28.
9%; Day 5.6%: P13.9%: Zrl9.9%; C
II. It was 26%.

As a result of dissolving it in chloroform and measuring its molecular weight, a molecular weight of 2,638 was obtained.

The decomposition start temperature determined by differential thermal analysis was 200 qo. The infrared absorption spectrum of this product (Figure 4) shows that the product is zirconium phosphate diisopropylester. The X-ray diffraction diagram and solubility in organic solvents were almost the same as in Example 1, and the characteristic peaks of the X-ray diffraction diagram were as follows. From the above analysis results, the above product has the following formula CItZn〇{P〇2(〇・iS.

-C3day7)2}2 It is believed to be the zirconium phosphate diisopropylester shown in wo6day. Example 3 Commercially available phosphoric acid diethyl ester (a mixture containing 45:55 of mono and gestal, respectively) was diluted with ion-exchanged water, first with barium carbonate to pH 6-7, then with barium hydroxide until pH 9.8. , and add it little by little while stirring vigorously to generate barium salt of phosphate ester.

The produced salt is separated in a furnace, and the furnace liquid is concentrated and dried to obtain a barium salt rich in diethyl ester phosphate. This is reconstituted with water and methanol (50:50), and this operation is repeated three times. When the obtained plate crystals are dissolved in ion-exchanged water and dilute sulfuric acid is added, barium sulfate is precipitated. This is centrifuged and this operation is continued until barium sulfate no longer precipitates. The solvent was removed from the resulting clear solution under reduced pressure to obtain high purity (99.5%) phosphoric acid diethyl ester. 3.1 parts of the obtained phosphoric acid ester are diluted with 100 parts of ethanol and added under a box at room temperature to a solution of 3.2 parts of zirconium oxychloride dissolved in 100 parts of ethanol.

After the addition, stirring was continued for 1 hour, and the ether/tar was removed under reduced pressure in the same manner as in Example 1 to obtain 3.6 hours of a glassy solid. The glassy solid was brought into contact with a chloroform-water mixed solvent and shaken, free chlorine ions were transferred to the water layer, and the chloroform layer was heated to 50°C and chloroform was removed under reduced pressure.
A purified glassy solid was collected. This one is P04/Z
r molar ratio is 2.0, C22.7%; day 4.8%; P1
5.2%; Z22.8%; CII. It was 43%.

As a result of dissolving it in chloroform and measuring its molecular weight, a molecular weight of 2,410 was obtained. The decomposition start temperature determined by differential thermal analysis was 25. The solubility in organic solvents was the same as in Example 1. The infrared absorption spectrum (FIG. 5) of this product showed that the product was zirconium phosphate diethyl ester, and the characteristic peaks of the x-ray diffraction pattern of this product were as follows.

From the above facts, the above product has the following formula CIMoZn○{P
02(OC2&)2}2 It is believed to be a zirconium phosphate diethyl ester represented by Chi6.

Example 4 Commercially available dimethyl phosphate (a mixture containing 42.4:57.6 of mono and gestal, respectively) was diluted with ion-exchanged water, and axes 6-7 were first treated with barium carbonate and then with barium hydroxide. Add a little bit at a time while stirring vigorously until the bait reaches 9.8 to generate barium salt of phosphate ester.

The produced salt is separated in a furnace, and the furnace liquid is concentrated and dried to obtain a barium salt rich in dimethyl phosphate. This is reconstituted with water and methanol (50:50), and this operation is repeated three times. When the obtained plate crystals are dissolved in ion-exchanged water and dilute sulfuric acid is added, barium sulfate is precipitated. This is centrifuged and this operation is continued until barium sulfate no longer precipitates. The solvent was removed from the resulting clear solution under reduced pressure to obtain dimethyl phosphate with high purity (99.4%). 2.5 parts of the obtained dimethyl phosphate was diluted with 100 parts of ethanol, and this was added to a solution in which 3.2 parts of zirconium oxychloride was dissolved in 100 M of ethanol at room temperature.

After the addition, distillation was continued for 30 minutes, and the ethanol/al was removed under reduced pressure in the same machine as in Example 1, yielding 3.3 hours of a glassy solid. The glassy solid is brought into contact with a mixed solvent of chloroform and water.
The mixture was shaken to transfer free chlorine ions to the aqueous layer, and the chloroform layer was removed under reduced pressure of 50 mm to recover a glassy solid. This one has a P04/Zr molar ratio of 2.07, CI 3.1%; day 3.6%; P17.7
%:Zr25.1:CII. It was 66%. In addition, the infrared absorption spectrum (Figure 6) of this product shows that it is zirconium phosphate dimethyl ester, and the X-ray diffraction pattern shows the diffraction characteristic of polymers having amorphous and crystalline regions. The characteristic peaks were as follows.

This product was dissolved in alcohol, aromatic hydrocarbon, ether, ester, chlorinated hydrocarbon, and aliphatic hydrocarbon as in Example 1, but the ester part was slightly dissolved in reaction products having two or more carbon atoms. However, economic changes were significant. Therefore, it was not possible to measure the molecular weight by redissolving it in chloroform. The decomposition initiation temperature determined by differential thermal analysis was 24 mm. Based on the above facts, the above product has the following formula CIfZr.

It is believed to be zirconium phosphate dimethyl ester, represented by {P〇2(〇CH3)2}2. Example 5 Commercially available phosphoric acid-n-dibutyl ester (a mixture of about 45:55 of mono and gester, respectively) was diluted with toluene and treated with IR2, an anion exchange resin.
00qo to adsorb and remove phosphate monobutyl ester.

Toluene is removed from the eluate under reduced pressure. The obtained di-n-butyl phosphate is added to carbon tetrachloride, and the remaining monobutyl phosphate is extracted and removed with water. The solvent from the carbon tetrachloride layer was removed under reduced pressure to obtain highly pure phosphoric acid di-n-butyl ester (99.7%). 8.2 ml of the phosphoric acid di-n-butyl ester obtained is diluted with 100 ml of methanol previously purified by dry distillation.

On the other hand, 6.4 liters of zirconium oxychloride was added to 1 ton of methanol.
Dissolve in 00 secretion. Hereinafter, the same treatment as in Example 1 was carried out,
The obtained glassy solid was washed with water to obtain a solid of 9.6 mm. The P04/Zr molar ratio of this product was 1.93, and the C8
3.5%, 6.4% per day, PII. 9%: Zr18.2%
;CII. It was 01%.

Further, the molecular weight was 3262, the decomposition start temperature determined by differential thermal analysis was 273 qo, and it was completely dissolved in each of the organic solvents shown in Example 1. The infrared absorption spectrum and X-ray diffraction diagram were the same as in Example 1. Example 6 In Example 2, methanol was used instead of ethanol to obtain 4.2 hours of a glassy solid.

This product has a P04/Zr molar ratio of 2.0 and a C28.8
%; Day 5.6%: P13.8%; Zrl9.6%; CI
I. It was 3%. Moreover, the molecular weight was 2,690, and the decomposition start temperature was 20,400. The infrared absorption spectrum, X-ray diffraction results, and solubility in organic solvents of this product were the same as in the case of using ethanol (Example 2). Example 7 8.2 ml of the high purity di-n-butyl phosphoric acid ester (99.7%) obtained in Example 5 is diluted in 100 methylene chloride.

On the other hand, zirconium oxychloride is 6.4 liters of water 100'
dissolve in The former is added to the latter, and the mixture is kept at room temperature for 3 hours to react at the interface. At this time, a thin film is formed at the interface, but no precipitation occurs. Next, the methylene chloride layer was taken out and the methylene chloride was diffused under reduced pressure to obtain 9.5 g of a glassy solid. P04/Z of the obtained solid product
r molar ratio is 2.04, its composition is C34.9%; day 6
．． 7%: P12.1%: Zr17.4%: CII. 04
%Met.

The molecular weight determined by redissolving it in chloroform was 3225, and the rest was the same as in Example 1. Example 8 3.6 ml of the high purity diisopropylesterate phosphate obtained in Example 2 is diluted with 100 g of methylene chloride.

Meanwhile, 3.2 g of zirconium oxychloride was dissolved in 100 g of water. The former was added to the latter, and the mixture was kept at room temperature for 3 hours to react at the interface. At this time, no precipitation was observed. The methylene chloride layer was taken out and the methylene chloride was diffused under reduced pressure to obtain a glassy solid of 3.8 mm.The P04/Zr molar ratio of this was 2.0 and C29.0%;
Day 5.9%; P13.4%; Zrl 9.8%: CII.
It was 2%.

Further, the molecular weight was 2,654, and the decomposition start temperature was 20,600. The results of infrared absorption spectrum, X-ray diffraction, and dissolution in organic solvent were the same as in Example 2. Example 9 Diethyl ester phosphate obtained in Example 3 (purity 99.5
%) 3.1 diluted with 100 ml of carbon tetrachloride.

Meanwhile, 3.2 g of zirconium oxychloride was dissolved in 100 g of water. The former is added to the latter at room temperature under a sieve. After the addition, stirring was continued for 2 hours, and in the same manner as in Example 1, carbon tetrachloride was removed by flashing under reduced pressure to obtain 3.5 hours of a glassy solid. This product had a PQ/Zr molar ratio of 1.94 and a molecular weight of 2,388.

The decomposition start temperature was 25,600, and the solubility in organic solvents was the same as in Example 1. Example 10 An interfacial reaction was carried out in exactly the same manner as in Example 7, except that carbon tetrachloride was used as the solvent instead of methylene chloride.

The composition and properties of the obtained product were also similar to those in Example 7.

Example 11 8.2 ml of the high purity di-n-butyl phosphoric acid ester (99.7%) obtained in Example 5 is diluted in 100 ml of toluene.

On the other hand, zirconium oxychloride is 6.4 liters of water 100'
dissolve in The former is added to the latter and the pseudo-azusa is continued at room temperature for 3 hours to react at the interface. Next, the toluene layer was separated, and the toluene was thinly removed under reduced pressure to obtain a glassy solid. The composition and properties of the obtained solid were similar to those in Example 7.

Example 12 3.6 ml of the high purity phosphoric acid diisopropyl ester (99.0%) obtained in Example 2 is diluted with 100 ml of m-xylene.

On the other hand, zirconium oxychloride is 3.2 liters of water 100'
'This dissolves. The former is added to the latter, and the mixture is continuously pounded at room temperature for 3 hours to react at the interface. At this time, no precipitation was observed. Next, the xylene layer was separated, and the xylene was removed by scattering under reduced pressure to obtain a glassy solid material of 4.1 mm.
The composition and properties of the obtained solid were the same as in Example 8. That is, the P04/Zr molar ratio is 2.01 and C28.9
%: Day 5.9%; P13.4%; Zrl9.7%; CI
I. It was 3%. Moreover, the molecular weight was 25 molecules, and the decomposition start temperature, infrared absorption spectrum, X-ray diffraction pattern, and solubility in organic solvents were all the same as in Example 2. Example 13 A glassy solid obtained in the same manner as in Example 1 is redissolved in 50 methylene chloride.

Add 50ml of water to this and shake and mix for about 5 minutes using a shaker to bring both liquid phases into sufficient contact. Let stand to separate the water layer, add 50 ml of water again, shake, mix, and let stand in the same manner to separate the water layer. This water washing was repeated until the pH of the aqueous layer became 3.3. Then, separate the methylene chloride layer,
Methylene chloride was removed by volatilization under reduced pressure to obtain a colorless and transparent polymer. This product has a P04/Zr molar ratio of 1.96, a molecular weight of 9,400, and can be woven into a fibrous yarn, an infrared absorption spectrum similar to that of Example 1, and a decomposition initiation temperature of 275°C.
Met.

This result is considered to indicate that only the molecular weight of the product increased without changing its unit structure. That is, the product has the following formula CIfZr〇{PQ(〇1n-C4day9)2
}2 Chi:. It is estimated that the period is 8 days.

Example 14 Stiffness of glassy solid material 5 obtained in the same manner as in Example 2 The same water washing operation as in Example 13 was repeated to obtain a polymer.

This product has a P04/Zr molar ratio of 1.95 and a molecular weight of 78.
It was 60. The infrared absorption spectrum, X-ray diffraction diagram, decomposition start temperature, and solubility in organic solvents were the same as in Example 2, and the notable difference from Example 2 was an increase in molecular weight. The product has the following formula CItZr〇{PQ(〇-iS.-C3day7
) 2} It is estimated that the period of time is 8 days. Example
15 The glassy solid material 5 obtained in the same manner as in Example 3 was dried, and the same water washing operation as in Example 13 was repeated to obtain a polymer.

This product has a P04/Zr molar ratio of 2.03 and a molecular weight of 72.
It was 10. The infrared absorption spectrum, X-ray diffraction diagram, decomposition start temperature, and solubility in organic solvents are the same as in Example 3,
The notable difference from Example 3 was the increase in molecular weight. The product has the following formula CI÷Zr○{PQ(OC2 ratio)2}2
It is estimated that it lasts 8 days. Example 16 Commercially available di-n-butyl phosphate (95%)8.
Dilute 2 ml of methylene chloride in 100' of methylene chloride.

On the other hand, zirconium oxychloride is 6.4 liters of water 100'
dissolve in Mix both at room temperature and stir. Under these conditions, both the aqueous layer and the methylene chloride layer were transparent, and as described in Example 7, it is presumed that zirconium phosphate butyl ester soluble in an organic solvent was formed in the methylene chloride layer. As the fly worship continued even more intensely, as time passed, floating substances began to form on the water surface (methylene chloride has a higher specific gravity than water, so it exists in the lower layer), and after 1 to 2 days, a considerable amount was formed. The solid product has a white foamy appearance.

Observation using a scanning electron microscope revealed that the obtained foam was a fibrous material with a size of several hundred microns to several thousand microns. This material was insoluble in solvents such as chlorinated hydrocarbons, alcohols and aromatic hydrocarbons. Its infrared absorption spectrum was similar to that of the product of Example 1 (FIG. 1), indicating that it was zirconium phosphate butyl ester. The decomposition onset temperature determined by differential thermal analysis is 27
The temperature was 8°C. Example 17 Commercially available phosphoric acid methyl ester (58% mono and gestal
:42) diluted 180 ml of methylene chloride 150 ml of methylene chloride.

Meanwhile, 160 g of zirconium oxychloride is dissolved in 667 g of water. Add the former into the latter at once and mix at room temperature for about 1
I worship time intensely. A white colloidal substance forms upon addition. At this time, the water layer and the methylene chloride layer are not separated, and the white colloidal slurry produced exists in a uniformly dispersed state. This was then passed through a furnace, but the first time it took about 8 hours. The resulting cake contains methylene chloride. Add water for 1 night, stir for 30 minutes (pH 1.3), and leave overnight to ripen. Approximately 1 additional hour was required for each second furnace. This operation was repeated four times, but as the number of times per furnace increased, the furnace speed decreased. The pH of the final furnace solution was 3.95. The resulting cake appeared to still contain methylene chloride. When this product was air-dried for several days, cotton-like long fibers as long as one arc were formed on the powder. An electron micrograph of this product (magnification: 22.Kalon) is shown in FIG.

Furthermore, the infrared absorption spectrum is extremely similar to that shown in Figure 6, indicating that this is zirconium phosphate dimethyl ester. P04/Z of the obtained fiber
r molar ratio is 2.01, CI 3.8%:day 3.7%:P
17.8%; Zr 25.0%.

The results of X-ray diffraction showed a pattern peculiar to polymers consisting of amorphous regions and crystalline regions, similar to FIG. 2 of Example 1. Furthermore, the decomposition temperature of the produced fiber was determined to be 25,000 by differential thermal analysis.

As a result of treatment in caustic soda at 120° C. for 4 hours, the morphology of the fibers did not change at all, but the phosphorus component and organic components completely disappeared, and the obtained fibers were found to be zirconia fibers. Example 18 50 parts of commercially available phosphoric acid diethyl ester (a mixture of mono and gestal, the ratio is 45:55) was mixed with 1 part of methylene chloride.
Dilute to 50'.

Meanwhile, 32 parts of zirconium oxychloride is dissolved in 350 parts of water. Add the former into the latter at once and leave it at room temperature for about 1
I worshiped him intensely for a long time. A white colloidal substance forms upon addition. At this time, the water layer and the methylene chloride layer are not separated, and the white colloidal slurry produced exists in a uniformly dispersed state. Next, the mixture was separated into furnaces, and the first furnace separation took about 5 hours. 500 g of water was added to the resulting cake, stirred for about 3 minutes (pH 1.4), and left overnight to ripen. The second oven week took about 6 hours. As a result of repeating this operation four times, the final reactor liquid value was 3.6.
When the resulting cake was air-dried for several days, flocculent fibers extending over a dozen micrometers were formed on the powder.

The infrared absorption spectrum and decomposition start temperature of the produced fiber were the same as those of Example 3, and it was estimated that it was a zirconium phosphate ethyl ester fiber. This thing's P04/Z
r molar ratio is 1.95, C22.8%: day 4.9%:P
15.2%; Zr 22.8%. The X-ray diffraction results showed that the crystals were imperfectly oriented and had crystalline portions and amorphous portions as in Example 17. Example 1
9. Dilute 54 parts of commercially available isopropylester phosphate (a mixture of mono and ester in the ratio 46:54) with 150 parts of methylene chloride.

Meanwhile, 32% of zirconium oxychloride is dissolved in 350% of water. The former was added to the latter at once, and the mixture was heated vigorously at room temperature for about 1 hour. As in the case of Example 17,
A white colloidal substance is formed upon addition, and methylene chloride and water do not undergo phase separation. Next, the mixture was separated into furnaces, and the first furnace separation took about 4 hours. The obtained cake contained a considerable amount of methylene chloride, and 500 g of water was added thereto, heated for about 30 minutes (FH 1.2), and left overnight to ripen. The second furnace filtration took about 6 hours. As a result of repeating this operation four times, the p mark of the final furnace liquid was 3.87.
When the resulting cake was air-dried for several days, fluff-like fibers with hairs that grew about 1 skin thick were formed all over the powder. As a result of microscopic observation of this fiber, the shape of the fiber was almost the same as that of the zirconium phosphate methylester fiber of Example 17. The infrared absorption spectrum of the produced fiber is extremely similar to the infrared absorption spectrum of the zirconium diisopropyl phosphate obtained in Example 2 (Figure 4). It is estimated that it consists of propyl ester. The P04/Zr molar ratio of this product was 1.95, C29.6%; day 5.6%; P13.0%:Zrl9.
It was 6%. The X-ray diffraction pattern shows that the fiber has a crystalline part and an amorphous part, similar to Examples 2, 6, and 8. Electron micrograph of this item (18x magnification)
is shown in Figure 8. The fiber obtained above was treated in carp-caustic soda at 120 qo for 4 hours in the same manner as in Example 17. As a result, the phosphorus component and organic component completely disappeared, but the fiber form was retained.

This material was found to be zirconia fiber. Example 20 An interfacial reaction was carried out in exactly the same manner as in Example 19, except that carbon tetrachloride was used instead of methylene chloride.

As in Example 17, a white colloidal material is formed upon addition, and carbon tetrachloride and water do not undergo phase separation. Next, the furnace was separated, and the first furnace separation took about 6 hours. The resulting cake contains a significant amount of carbon tetrachloride;
Add 500ml of water to this and stir for about 3 minutes (pH.
1), It was left to mature overnight. The second furnace took about 9 hours. As a result of repeating this operation four times, the final furnace liquid P
H was 3.16. When the resulting cake was air-dried for several days, cotton-like fibers were formed on the powder.

Although the production of this fiber was smaller than in Example 18, it was estimated from the infrared absorption spectrum analysis of the produced fiber that the produced fiber was zirconium phosphate propyl ester.
The P04/Zr molar ratio of this product was 1.99, and the C29.
3%; Day 5.5%: P13.2%; Z and 19.5%;
Almost no chlorine was detected. Furthermore, the X-ray diffraction pattern and decomposition start temperature were the same as in Example 19. Visual observation and microscopic observation of this product showed that it had exactly the same shape as Example 19 (FIG. 9). Further, when treated in carp-caustic soda at 120 oo for 4 hours, the fibers changed to zirconia fibers while maintaining the fiber shape, as in Examples 17 and 19. Example 21 The organic solvent-soluble glass solid obtained in Example 1 was placed in an aqueous solution adjusted to pH 9 with ammonium hydroxide and stirred.

Glassy solids are initially water repellent, but unlike their immersion in water, they disperse very well in alkaline aqueous solutions.
As the solids dispersed, the axis of the solution decreased a little (
FH7.8). After keeping the fly azusa at room temperature for ten to several tens of hours, it is separated from the oven, and the resulting granular solids are thoroughly washed with water. Then, it is dried at a temperature of 110 oo. The obtained granules were found to be composed of zirconium phosphate butyl ester because their infrared absorption spectra (Fig. 1) were very similar.

Further, when this product was observed with a scanning electron microscope, it was found to be a super-spherical powder with stripes and particles on the order of about 0.2 to 0.5 microns. Note that all of the zirconium phosphate esters before the alkali treatment were irregular in shape, and no spherical particles were observed. The P04/Zr molar ratio of the spherical zirconium phosphate butyl ester obtained here is 1.8.
8, the composition is C33.5%: day 6.6%; PII. 8%;
The Zr content was 18.4%. The decomposition initiation temperature determined by differential ripening analysis was 276°C. This product was insoluble in various solvents. Example 22 The glassy solid obtained in Example 2 is dissolved in methylene chloride.

Add this to 2.5% ammonia water (pH 8.0),
Create a methylene chloride-water interface. When the mixture is allowed to stand at room temperature for 3 to 5 hours, a fine powder solid substance begins to form, and the precipitation is continued for about 10 hours to several days to complete the precipitation of the granular solid substance. This solid material is repeatedly separated in a furnace and washed with water, and then dried at a temperature of 110°C. Since the infrared absorption spectrum of the obtained granules was the same as that shown in FIG. 4, it was shown that the particles were composed of diisopropyl ester zirconium phosphate. Furthermore, observation of this material using a scanning electron microscope (magnification: 2000 M) revealed that it was a perfectly spherical particle with a particle size on the order of 0.3 to 0.5 microns. (Figure 10). Of course, the solid material before the alkali aqueous solution treatment did not have a specific shape. The P04/Zr molar ratio of the obtained spherical powder was 1.81, and the composition was C, 27.8%;
; P, 11.9%; Zr, 19.4%.

Further, the decomposition start temperature of this product was 0 at 20, and it was insoluble in organic solvents. Example 23 High purity phosphoric acid di-n-butyl ester (99.7%) obtained in Example 58.
Dilute 2 liters with 100 ml of ethanol.

On the other hand, 6.4 liters of zirconium oxychloride was added to 1 ton of ethanol.
00 Dissolve in the skin. Mix both at room temperature,
Allow time to react. After the reaction, when the ethanol solution containing the reaction product is poured into water, it becomes cloudy and solidifies. The granular solid material is dried in an oven of 8 U at a temperature of 11 mm. Since the infrared absorption spectrum of the obtained granules was the same as that shown in FIG. 1, it was found that they were zirconium phosphate dibutyl ester.

As a result of observing this material with a scanning electron microscope, it was found that a considerable portion of the particles were spherical, and the particle sizes were widely distributed (0.3 to 2
(on the order of microns). Moreover, the composition and decomposition start temperature of this product were the same as in Example 21. Furthermore, this product was either insoluble or only swollen in various organic solvents. Example 24 Commercially available di-n-butyl phosphate ester (95%) 8.2
Dilute the solution with 100% ethanol.

On the other hand, 6.4 hours of zirconium oxychloride was added to 10 minutes of ethanol.
0 dissolve in me. Both solutions were mixed at room temperature under takahai, and takahai was continued for about 6 hours. The obtained solution was poured into an acidic aqueous solution of hydrochloric acid (pHO.6) and kept at room temperature for 2 hours.

In this case, a precipitate formed simultaneously with the addition. The obtained granular precipitate was thoroughly washed with water and dried at 110°C. The infrared absorption spectrum of this product was similar to that of Example 23, indicating that the precipitate was zirconium phosphate dibutyl ester.

Also, a scanning electron micrograph of this item (magnification: 1000)
0 times), this material was found to be perfectly spherical with a particle size on the order of 0.5 to 1.5 microns (11th
figure). The P04/Zr molar ratio of the obtained spherical powder was 1.
83, its composition is C34.2%: day 6.8%; PII
．． 2qo: Zr was 18.0%.

The decomposition start temperature determined by differential thermal analysis was 275q0. Example 25 Highly purified jetyl ester phosphate obtained in Example 33.
Dilute the mixture with 100% ethanol.

On the other hand, 3.2 liters of zirconium oxychloride was added to 1 ton of ethanol.
Dissolve in '00'. Both solutions were strained under a rope at room temperature and stirred for an additional 3 hours. The obtained alcoholic solution was poured into an acidic aqueous solution of hydrochloric acid (volume 0.8) and allowed to stand at room temperature for 2 hours.

In this case, a precipitate formed upon addition. Further, the pH of the toplight solution was 0.8. The obtained precipitate was thoroughly washed with water and dried at 110°C. Analysis of the infrared absorption spectrum of this product showed that it was ethyl zirconium phosphate. Further, scanning electron micrographs of this material revealed that it was a perfectly spherical body with a particle size on the order of 0.4 to 1.6 microns. Other physical properties were the same as in Example 3. Example 26 The organic solvent-soluble glassy solid obtained in Example 2 is dissolved in 50 methylene chloride.

This was poured into 50ml of 2.5% ammonia water (pH 8.2) and left for 4 hours. The generated precipitate was thoroughly washed with water and dried at a temperature of 11,000. This product was a spherical body with a particle size on the order of 0.2 to 0.6 microns, as seen from a scanning electron microscope photograph, and other physical properties were almost the same as in Example 22. Example 27 Glassy solid soluble in organic solvent obtained in Example 9 3.5
Dissolve the liquid in 50% carbon tetrachloride.

This was injected into 50 doses of 2.5% ammonia water (solution 7.8), and the animals were fed for two hours. The generated precipitate was thoroughly washed with water and dried at a temperature of 11,000. A scanning electron micrograph of this material shows that this material is a spherical body with particles on the order of 0.2 to 0.8 microns, and other physical properties of this material are almost the same as those in Example 25. Example 28 The toluene layer obtained in Example 11 was separated and poured into 50 bottles of 25% ammonia water (pH 8.4) and allowed to stand for 4 hours.

The resulting precipitate was separated in a furnace, washed with water, and dried at a temperature of 11.0 mm. From the scanning exposure photomicrograph of this product, it was found that this product is a spherical body with a particle size on the order of 0.1 to 0.8 microns, and that the composition and other properties of this product are the same as in Example 21. confirmed. Example 29 3.6 ml of the high purity diisopropylester phosphate obtained in Example 2 is diluted with 100 methylene chloride.

On the other hand, 3.2 g of zirconium oxychloride was dissolved in water, and the pH was adjusted to 1.6 with an aqueous ammonium carbonate solution.
Let the total amount be 100'. Add the latter solution to the former solution and shake at room temperature for about 15 minutes on a shaker. A white precipitate formed in the aqueous layer was filtered and washed through a filter with a pore size of 0.2 microns, and then dried at 10 mm. This material was confirmed to be zirconium phosphate isopropylester by infrared absorption spectrum analysis.

The composition and decomposition temperature of this product were almost the same as those in Example 22. A scanning electron micrograph (magnification: 1000) confirmed that this substance had a silk-like structure in which spherical bodies were connected (Fig. 12). It is presumed that this is because the above-mentioned processing conditions overlap with the production of spherules and fibers, resulting in a silk-like structure. Reference Example 1 This example is a specific example in which the zirconium diisopropyl phosphate fiber obtained in Example 19 is applied to an ion exchange membrane for electrolysis.

The structure of the membrane was obtained by mixing the zirconium phosphate fibers obtained in Example 19 by hydrolyzing the fibers with sulfuric acid and the polyvinyl chloride (PVC) powder (Sumirit PX-1A) in 10 t of tetrahydrofuran. After thoroughly dispersing and dispersing the flies, the mixture was supervised and left overnight at a mild temperature (approximately 35 qo) to scatter the solvent.

Electrical resistance (2) of the obtained zirconium phosphate-PVC film
yo, 0.50 state NaCI, 1000 cycles alternating current) is 8.60-me, and the rate (0.50 skin NaCI
/2. (calculated using the Nemst formula from the membrane potential between NaCl and NaCI) was 0.84. Reference Example 2 This example is a specific example in which the spherical zirconium dibutyl phosphate obtained in Example 24 is applied to an ion exchange membrane for electrolysis.

The membrane was produced by mixing the spherical zirconium phosphate di-n-butylester phosphorus obtained in Example 24 with a particle size of 0.5 to 1.5 microns and PVC powder (Sumirit PX-A) in about 5 days using tetrahydrofuran. After concentrating and dispersing the mixture, the mixture was allowed to settle down and left overnight at a slight temperature (approximately 35°C) to scatter the solvent.

Obtained zirconium phosphate di-n-butyl ester PV
The C membrane was soaked in 0.1N caustic soda for several days, followed by 1. Sail - Soaked in hydrochloric acid.

After thorough washing with water, it was dried at 80 qo. The electrical resistance and ring ratio of the obtained film were measured in the same manner as in Reference Example 1, and were found to be 1820 per block and 0.79, respectively.

Reference Example 3 This example is a specific example in which the zirconium phosphate obtained in Example 1 is applied as a catalyst component for the polymerization of isoprene.

A three-necked flask with an internal volume of 200 kg was used for the polymerization.

First, low mol (1 mol' of toluene solution) of aluminum diethyl chloride (manufactured by Nippon Alkyl Aluminum Co., Ltd.) was added to 100 g of dehydrated and purified toluene under an argon stream. Next, when 2 mol of the above-mentioned zirconium phosphate ester was added, the solution gradually turned brown, and when the solution was further heated, formation of brown fine particles was observed on the wall of the vessel. Then, use the magnetic stirrer for 20 minutes at room temperature.
After heating, 0.20 ol of dehydrated and purified isoprene (Tokyo Kasei, first grade product) was added to initiate polymerization. After feeding the flies at room temperature for 2 hours, the contents of the flask were poured into a large amount of methanol containing a small amount of hydrogen chloride to recover the produced polymer. During the polymerization, the viscosity of the solution increased slightly and no other significant changes were observed.
The produced polymer was a white powder, and the yield after vacuum drying at 50% was 13.6% (100%). The infrared spectrum of this polymer includes 810-1, 2685-1,
Characteristic absorption was observed in 1370-1 and 1385-1, respectively. These absorptions have already been reported, for example by M. STOL
K.A., J. VODEHNAL and IKOS
SLER, Joumaof Polymer Science
cePartA, Vo12, P3987-4001 (1
964) is consistent with that of known cyclized polyisoprenes. In addition, the above polymer was dissolved in cyclohexane, and U
When the V spectrum was measured, absorption was observed between 240 and 260.

From now on, for example, N. G. GAYLORD, B. M.A.
TYSKA, K. MACH and J. VODEHN
AL, Journal of Polymer Scie
ncePanA-1, VoL 4, P2493-251
1 (1966) shows that the product is cyclized polyisoprene. Furthermore, the cyclization rate of the produced polymer was 97% or more, the softening point was 100 to 110,000, and the molecular weight determined by vapor pressure method was 2,500.

The polymer did not dissolve in alcohols, polyhydric alcohols, ketones, dimethylformamide, and dimethyl sulfoxide, but it easily dissolved in aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, esters, and ethers. A homogeneous solution was obtained.

Incidentally, the cyclization rate was determined by the following method.

Synthetic rubber hand puck, P8 markings (November 30, 1968)
1,4-polyisoprene, 3,4-polyisoprene, and 1,2-polyisoprene were each analyzed according to "Quantitative analysis of bonding mode of polyisoprene" published by J.D.
1.4 polyisoprene + 3.4 polyisoprene + 1.2
The polyisoprene was calculated and the above A was subtracted from the product to determine the cyclization rate.

Cyclization rate (%) = 100-A

[Brief explanation of the drawing]

Figure 1 is an infrared absorption spectrum diagram of the product obtained in Example 1 before purification, Figure 2 is its X-ray diffraction diagram, and Figure 3 is the crystallization of the above product from acetoacetic acid ethyl ester. FIG. 4 is an infrared absorption spectrum diagram of the product obtained in Example 2, and FIG. 5 is an infrared absorption spectrum diagram of the product obtained in Example 3. , FIG. 6 is an infrared absorption spectrum diagram of the product obtained in Example 4, FIG. 7 is an electron micrograph (magnification: pine, seal) of the product obtained in Example 17, and FIG. is an electron micrograph (18x magnification) of the product obtained in Example 19, FIG. 9 is an electron micrograph of the product obtained in Example 20, and FIG. 10 is an electron micrograph of the product obtained in Example 22. Fig. 11 is a scanning electron micrograph (magnification: 1000 pm) of the product obtained in Example 24, and Fig. 12 is a scanning electron micrograph (magnification: 1000 pm) of the product obtained in Example 24. Scanning electron micrograph (1000 magnification) of the product obtained in Example 29. ticket! Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 71 Genka 8 Figure Sabata Zuko'o Figure 11 Figure Tsutomu 12

Claims (1)

[Scope of Claims] 1 Formula - [ZrO{PO_2(OR)_2}_2]-(I) In the formula, R represents an alkyl group. Surface spacing (d) is 1
A zirconium-containing phosphoric acid compound characterized by having a peak exhibiting crystallinity within a range of 0 to 20 angstroms. 2. The zirconium-containing phosphoric acid compound according to claim 1, which has a structural unit represented by the above formula (I) in which R is a lower alkyl group having 1 to 5 carbon atoms. 3 Claim 1 that is soluble in ether, ester, alcohol, aliphatic hydrocarbon or chlorinated hydrocarbon
The zirconium-containing phosphoric acid compound described in . 4 Formula HPO_2(OR)_2(II) In the formula, R represents an alkyl group, characterized in that a phosphoric acid dialkyl ester represented by the following is reacted with a zirconium oxyhalide, the formula-[
ZrO{PO_2(OR)_2}_2]-(I) in the formula,
A method for producing a zirconium-containing phosphoric acid compound having a structural unit represented by R has the same meaning as above. 5. The method according to claim 4, wherein the reaction is carried out in an inert liquid medium. 6. The method of claim 4, wherein the inert liquid medium is an alcohol or a mixture of water and a water-immiscible organic solvent. 7. The method of claim 4, wherein the reaction is carried out at a temperature between about 0° C. and the reflux temperature of the reaction mixture. 8. The method according to claim 4, wherein the reaction is carried out at room temperature. 9. The method according to claim 4, wherein the phosphoric acid ester represented by the above formula (II) is reacted in a ratio of about 2 moles or less to 1 mole of zirconium oxyhalide.