JP4284407B2 - Method for producing organic group-substituted phosphate - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic group-substituted phosphate, a method for producing the same, and a phosphate obtained by firing the organic group-substituted phosphate.
[0002]
[Prior art]
The synthesis and application of phosphates having a layered structure have been studied for a long time and reported in various literatures. For example, Patent Document 1 discloses a layered tin phosphate compound in which silica, alumina, or zirconia is interposed as a pillar between layers. Patent Document 2 discloses bis (phosphate monohydrate) titanium (IV) dihydrate Ti (HPO)._Four) 2.2H₂An intercalation compound in which β-mercaptoethylamine (β-MEA) is intercalated with O is disclosed.
[0003]
A phosphate compound containing an organic group between layers of a phosphate having a layered structure is also known. For example, Patent Document 3 discloses a phosphate compound in which various organic compounds are intercalated between layers of zirconium phosphate having a layered structure.
[0004]
The phosphate compound containing the existing organic group as described above is manufactured by a method in which only an inorganic component is prepared and then an organic group is introduced. Non-Patent Documents 1 and 2 report that all of the phosphate compounds containing an organic group produced by the method have mesopores having a pore diameter exceeding 2 nm in the phosphate portion. In other words, those having micropores with a pore diameter of 2 nm or less in the phosphate portion are not known.
[0005]
If a phosphate compound containing organic groups having micropores with a pore size of 2 nm or less in the phosphate portion is developed, a catalyst, a separating agent, etc. for synthesizing high added value organic compounds such as fine chemicals It is very advantageous because it can be applied to.
[0006]
In developing a phosphate compound having an organic group and having micropores, it is necessary to review the conventional production method. In the conventional production method, phosphoric acid and a metal salt are mixed, and then HF is added to prepare a complete homogeneous solution (solution without precipitation), followed by hydrothermal treatment with an autoclave or the like. However, in this method, it is necessary to use HF having a low yield of about 40% and high toxicity.
[0007]
[Patent Document 1]
JP-A-8-165110
[0008]
[Patent Document 2]
JP 2001-064003 A
[0009]
[Patent Document 3]
Japanese Patent Laid-Open No. 10-251168
[0010]
[Non-Patent Document 1]
A. A. Clearfield et al., Journal of Chemical Society, J. Chem. Soc, Dalton Trans, United Kingdom, 2002, 2938
[0011]
[Non-Patent Document 2]
E. W. Stein et al., “Solid State Ionics”, Netherlands, 1996, 83, p. 113.
[0012]
[Problems to be solved by the invention]
In the present invention, an organic group-substituted phosphate having a micropore having a pore diameter of 2 nm or less in a phosphate portion can be obtained in a high yield from an organic group-substituted phosphoric acid and a metal halide without using harmful HF. The main purpose is to provide the resulting manufacturing method.
[0013]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventor has found that a specific production method can achieve the above object, and has completed the present invention.
[0014]
  That is, the present invention provides the following organic group-substituted phosphoric acidSaltyManufacturing methodTo the lawRelated.
1.After stirring a mixed solution of an organic group-substituted phosphoric acid and a metal halide containing a metal having a valence of 4 or more, a precipitate is obtained by adding an anionic surfactant and further stirring, and the resulting precipitate is hydrothermally treated. And a method for producing an organic group-substituted phosphate.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Organic group-substituted phosphate
The organic group-substituted phosphate of the present invention is an organic group-substituted phosphate having a layered structure and is characterized by having micropores of 2 nm or less in the phosphate portion. Such an organic group-substituted phosphate of the present invention has a smaller pore size and a larger specific surface area than existing organic group-substituted phosphates having mesopores with a pore diameter exceeding 2 nm in the phosphate portion. It is a feature.
[0016]
As an example of the organic group-substituted phosphate of the present invention, the structure of a phenyl group-substituted phosphate in which a phenyl group is introduced as an organic group is shown in FIG. The outline is as follows.
[0017]
In the phenyl group-substituted phosphate of FIG. 1, the phenyl group is bonded to the phosphorus atom in the phosphate, and the plane containing a metal element such as zirconium or tin forms a layered structure (sheet shape). L represents a surface interval and is about 1.47 nm. The phenyl groups facing each other are considered to be electrostatically bonded to each other. The sheet-like phenyl group-substituted phosphate portion has a micropore of 2 nm or less and has a porous structure. In other words, the phenyl group-substituted phosphate has a sheet-like regular structure, but microscopically, it has a lamellar structure including defects (missing) in the crystal structure, and these defects are involved in the formation of micropores. it seems to do.
[0018]
As described in the example of the phenyl group-substituted phosphate, the organic group-substituted phosphate of the present invention has a lamellar structure and microscopically has a lamellar structure including defects in the crystal structure. And it is thought that the defect of a crystal structure participates in formation of a micropore, and has a porous structure.
[0019]
The degree of porosity is represented by pore volume, specific surface area, and the like. The pore volume is usually 0.03 to 0.7 cm^Three/ G, preferably 0.04 to 0.5 cm^Three/ G, more preferably 0.05 to 0.1 cm^Three/ G or so. Specific surface area is usually 40-400m²/ G, preferably 100-400 cm^Three/ G or so. The specific surface area is a value measured by the BET method based on nitrogen adsorption.
[0020]
Since the organic group-substituted phosphate of the present invention has a small pore size, it is useful as a catalyst effective for the synthesis of fine chemicals, particularly as a shape-selective catalyst. Strictly speaking, depending on the type of reaction substrate, when used for the reaction of an aromatic compound, those having a pore diameter of about 0.5 to 1 nm exhibit excellent shape-selective reactivity.
[0021]
The surface spacing of the organic group-substituted phosphate of the present invention is usually 1.2 to 3 nm, preferably about 1.4 to 2.5 nm.
[0022]
The organic group-substituted phosphate of the present invention can be used in various fields by taking advantage of its porous properties. Examples thereof include use as an adsorbent for adsorbing various gases or compounds from the gas phase, liquid phase, etc., and use as a catalyst or catalyst support in oxidation reactions and the like. It can also be used as a solid electrolyte utilizing the ion exchange ability.
[0023]
Among them, the use as a catalyst or a catalyst carrier is particularly useful, and when a sulfonic acid group is introduced as an organic group, it is very useful as an acid catalyst. Moreover, it can apply as a various catalyst support | carrier by converting an organic group into a suitable functional group. For example, conversion to a functional group such as phosphorus or amine makes it useful as a simple substance carrying a transition metal.
[0024]
Method for producing organic group-substituted phosphate
The method for producing the organic group-substituted phosphate of the present invention is not particularly limited. For example, in the presence of an anionic surfactant, a metal halide containing an organic group-substituted phosphoric acid and a metal having a valence of 4 or more (hereinafter, The resulting precipitate can be suitably produced by hydrothermal treatment.
[0025]
Such a production method is preferable in that no harmful HF is used and the target organic group-substituted phosphate is obtained in high yield. Hereinafter, this manufacturing method will be described.
[0026]
Although it does not specifically limit as organic group substituted phosphoric acid, The thing with a strong phosphorus-carbon bond between phosphorus-organic groups with respect to a hydrolysis reaction is preferable. As the organic group, for example, phenyl group, methyl group, ethyl group, n-propyl group, t-butyl group, xylyl group, benzyl group, chlorophenyl group, bromophenyl group and the like are preferable.
[0027]
That is, as the organic group-substituted phosphoric acid, for example, phenyl phosphoric acid, methyl phosphoric acid, ethyl phosphoric acid, n-propyl phosphoric acid, t-butyl phosphoric acid, 3,4-xylyl phosphoric acid, benzyl phosphoric acid, chlorophenyl phosphoric acid, bromophenyl Phosphoric acid and the like are preferable. These organic group-substituted phosphoric acids can be used alone or in admixture of two or more. The purity of the organic group-substituted phosphoric acid to be used is not particularly limited, but is usually preferably 80% or more, more preferably 95% or more.
[0028]
The metal halide is not particularly limited as long as it has a metal having a valence number of 4 or more. Examples of such a metal include tin, zirconium, niobium, and titanium.
[0029]
That is, examples of metal halides include tin tetrachloride pentahydrate, zirconium tetrachloride, titanium tetrachloride, niobium pentachloride, tin iodide, zirconium iodide, niobium iodide, titanium iodide, tin bromide. Zirconium bromide, niobium bromide, titanium bromide and the like are preferable. These metal halides can be used alone or in admixture of two or more. The purity of the metal halide to be used is not particularly limited, but is usually preferably 95% or more, and more preferably 98% or more.
[0030]
Although it does not specifically limit as an anionic surfactant, The alkali metal salt of the sulfonic acid which has a long-chain alkyl group is preferable. As carbon number of a long-chain alkyl group, 8-20 are preferable normally, and 12-18 are preferable. As the anionic surfactant, for example, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate and the like are preferable. These anionic surfactants can be used alone or in admixture of two or more.
[0031]
In the production process of the organic group-substituted phosphate, the phosphate portion tends to be positively charged, which may inhibit the formation of dense phosphate. Therefore, it is considered effective to stabilize the phosphate charge using an anionic surfactant as a counter anion.
[0032]
In the production method of the present invention, first, an organic group-substituted phosphoric acid and a metal halide are reacted in the presence of an anionic surfactant. As the reaction solvent, for example, water, alcohol, water-alcohol mixed solution or the like can be used. Examples of the alcohol include methanol and 2-propanol. In particular, when the metal component is titanium, the reaction solvent is preferably 2-propanol.
[0033]
The blending ratio of the raw materials is not particularly limited, but is organic group-substituted phosphoric acid: metal halide = (1-3): 1, preferably (2-2.1): 1 (molar ratio). Moreover, it is organic group substituted phosphoric acid: anionic surfactant = 1: (0.2-0.7), Preferably it is 1: (0.25-0.6) (molar ratio).
[0034]
The concentration (solvent amount) of each raw material is not particularly limited, and the concentration of the organic group-substituted phosphoric acid is about 0.3 to 0.7 mol / L, preferably 0.4 to 0.6 mol / L. The concentration of the metal halide is about 0.2 to 0.5 mol / L, preferably 0.3 to 0.4 mol / L.
[0035]
In the production method of the present invention, first, the mixed solution of the organic group-substituted phosphoric acid and the metal halide is sufficiently stirred (about 3 to 10 minutes), and then an anionic surfactant is added and further stirred (10 to 60). About a minute). Thereby, precipitation (gel) is obtained as a reaction product.
[0036]
In this way, organic group substitution phosphoric acid having a strong phosphorus-carbon bond to hydrolysis reaction can be reacted directly with metal halide, so that the organic group substitution has micropores instead of mesopores in the phosphate part. This is important for obtaining phosphate selectively.
[0037]
The precipitate is then hydrothermally treated. The hydrothermal treatment can be performed, for example, by storing a heat-resistant container containing a precipitate in an autoclave or the like. The temperature of the hydrothermal treatment is usually about 120 to 180 ° C, and particularly preferably 140 to 160 ° C. The treatment time can be adjusted according to the temperature, but is usually about 1 to 3 days, particularly preferably 1.5 to 2 days. The atmosphere of the hydrothermal treatment is not particularly limited, and may be an air atmosphere, an oxidizing atmosphere, or the like. The pressure condition is not particularly limited, and may be about the self-generated pressure generated in the sealed container.
[0038]
An organic group-substituted phosphate is obtained by hydrothermal treatment. In such an organic group-substituted phosphate, the surfactant is not sandwiched between layers, but is electrostatically adsorbed to the outside of the phosphate to stabilize the positive charge of the phosphate. Conceivable.
[0039]
The surfactant can be easily removed by washing with, for example, an ethanol solution of hydrochloric acid (preferably, a mixed solution of 50 g of dry ethanol and 3 mL of 1 mol / L hydrochloric acid). The removal conditions are not particularly limited, but it is preferable to wash at a temperature of 20 to 100 ° C. for 1 to 5 hours.
[0040]
Note that a drying step may be provided after hydrothermal treatment or after removal of the surfactant. Although a drying temperature and drying time are not specifically limited, For example, what is necessary is just to dry about 120 days at 120 degreeC.
[0041]
The organic group-substituted phosphate thus obtained has micropores having a pore diameter of 2 nm or less in the phosphate portion. The abundance of the organic group in the phosphate portion can be easily confirmed by measuring the weight loss using, for example, a thermal analysis measuring device (TG-DTA).
[0042]
In the production method of the present invention, an organic group-substituted phosphate having a dense structure and having micropores can be produced in a yield of 95% or more under normal conditions and 97% or more under optimum conditions.
[0043]
In the production method of the present invention, it is considered effective not to use HF that causes hydrolysis of organic groups in order to form micropores without forming mesopores. It is also useful in that there is no toxicity due to HF.
[0044]
By the way, in the conventional method for producing an organic group-substituted phosphate, a homogeneous aqueous solution composed of phosphoric acid, metal chloride and HF is hydrothermally treated to first synthesize phosphate, and then reactive with the phosphate. A high organic group (for example, epoxide) was reacted to introduce an organic group. Accordingly, mesopores are first formed by phosphate formation under highly acidic conditions with HF, and then the phosphate portion is liberated during the introduction of the organic group, and further, mesopores are formed. It is considered that an organic group-substituted phosphate having only pores was not obtained.
[0045]
Phosphate
By subjecting the organic group-substituted phosphate of the present invention to baking treatment, a phosphate having mesopores (pore diameter exceeding 2 nm) can be obtained.
[0046]
Although a calcination temperature is not specifically limited, Usually, about 200-400 degreeC and especially about 350-400 degreeC are preferable. The firing time can be appropriately adjusted according to the firing temperature, but is usually 2 to 10 hours, and particularly preferably 4 to 6 hours. The firing atmosphere is not particularly limited, but may be an air atmosphere, an oxidizing atmosphere, or the like.
[0047]
The obtained phosphate has a mesoporous structure. The diameter of the mesopores is usually 2 to 14 nm, but is about 2 to 12 nm when the pore diameters are uniform, and the diameter peak is in the range of about 5 to 7 nm.
[0048]
As the degree of porosity of phosphate, the pore volume is usually 0.05 to 0.5 cm.^Three/ G, preferably 0.1 to 0.3 cm^Three/ G. Specific surface area is usually 100-500m²/ G, preferably 100 to 300 m²/ G.
[0049]
The phosphate has a layered structure lost by firing. The mesopores are considered to be generated as pores reflecting the interplanar spacing when the organic group disappears and the layered structure is lost by firing. The generated pores are relatively well aligned, and the phosphate itself has an amorphous structure.
[0050]
The phosphate can be used in various fields by taking advantage of its porous properties. For example, it is useful as an adsorbent that adsorbs various gases or compounds from the gas phase, liquid phase, and the like. It is also useful as a catalyst and catalyst support in oxidation reactions and the like. It is also useful as a solid electrolyte utilizing the ion exchange ability.
[0051]
【Example】
The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples.
[0052]
Example 1
An aqueous solution obtained by dissolving 3.33 g (20 mmol) of phenylphosphoric acid (95%) in 40 g of water was added to 3.58 g (10 mmol) of an aqueous solution of tin tetrachloride pentahydrate (weight of water: 30 g). Added over a minute with vigorous stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added and stirred for about 30 minutes to obtain a gel.
[0053]
The gel was transferred to a Teflon (registered trademark) beaker, placed in a stainless steel autoclave, and allowed to react at 150 ° C. for 2 days in an air atmosphere. After the reaction, the solid was thoroughly washed with distilled water and dried at 120 ° C. for 1 day.
[0054]
Here, although the obtained solid is a complex of surfactant and phosphate, 1 g of the solid is added to a mixed solution of 50 g of dry ethanol and 3 mL of 1 mol / L hydrochloric acid, and the mixture is stirred at 60 ° C. for 2 hours. This removed the surfactant.
[0055]
Next, the solid was separated by filtration, washed with ethanol, and dried at 120 ° C. for 1 day to obtain phenyl group-substituted tin phosphate.
[0056]
It was found from the X-ray diffraction pattern that the obtained phenyl group-substituted tin phosphate had a layered structure with a surface spacing of 1.45 nm. In X-ray diffraction, the following two theta values (plane spacing values) were observed. 6.08 (1.42 nm), 12.02 (0.74 nm), 17.88 (0.5 nm), 21.32 (0.42 nm), 35.84 (0.25 nm).
[0057]
Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores.
[0058]
After completely removing the surfactant, the amount of organic groups present in the phosphate portion was examined by measuring the weight loss using a thermal analyzer (TG-DTA). The weight loss due to the disappearance of the phenyl group was 31.5% from the thermal analysis measurement, which almost coincided with the theoretical value (28.3%). The pore volume is 0.08cm^Three/ G and the specific surface area is 255 m.²/ G.
[0059]
Example 2
A solution obtained by dissolving 3.33 g (20 mmol) of phenylphosphoric acid (95%) in 40 g of water was vigorously added to 2.33 g (10 mmol) of an aqueous solution of zirconium tetrachloride (water weight: 30 g) over about 5 minutes. Added with stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0060]
The gel was treated in the same manner as in Example 1 to obtain a phenyl group-containing microporous layered zirconium phosphate.
[0061]
The interplanar spacing of the obtained phenyl group-containing microporous layered zirconium phosphate was 1.47 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen showed a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss due to the disappearance of the phenyl group was 32.7% based on the thermal analysis measurement, which almost coincided with the theoretical value (30.3%). The pore volume is 0.07cm^Three/ G and specific surface area of 232 m²/ G.
[0062]
Example 3
A solution obtained by dissolving 3.33 g (20 mmol) of phenylphosphoric acid (95%) in 40 g of water was vigorously added to 1.90 g (10 mmol) of an aqueous solution of titanium tetrachloride (water weight: 30 g) over about 5 minutes. Added with stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0063]
The gel was treated in the same manner as in Example 1 to obtain phenyl group-substituted titanium phosphate.
[0064]
The obtained phenyl group-substituted titanium phosphate was found to have a layered structure with a surface spacing of 1.43 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss due to the disappearance of the phenyl group was 33.8% from the thermal analysis measurement, which almost coincided with the theoretical value (33.9%). The pore volume is 0.08cm^Three/ G and the specific surface area is 252 m.²/ G.
[0065]
Example 4
A solution obtained by dissolving 3.33 g (20 mmol) of phenylphosphoric acid (95%) in 40 g of water was vigorously added to 2.70 g (10 mmol) of an aqueous solution of niobium pentachloride (water weight 30 g) over about 5 minutes. Added with stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0066]
The gel was treated in the same manner as in Example 1 to obtain phenyl group-substituted niobium phosphate.
[0067]
The obtained phenyl group-substituted niobium phosphate was found to have a layered structure with an interplanar spacing of 1.48 nm from an X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss due to the disappearance of the phenyl group was 30.5% based on the thermal analysis measurement, which almost coincided with the theoretical value (30.1%). The pore volume is 0.07cm^Three/ G and the specific surface area is 226 m.²/ G.
[0068]
Example 5
A solution prepared by dissolving 1.92 g (20 mmol) of methyl phosphoric acid (95%) in 40 g of water was added to 3.58 g (10 mmol) of an aqueous solution of tin tetrachloride pentahydrate (weight of water: 30 g). Added over a minute with vigorous stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0069]
The gel was treated in the same manner as in Example 1 to obtain methyl group-substituted tin phosphate.
[0070]
The obtained methyl group-substituted tin phosphate was found to have a layered structure with a surface spacing of 0.78 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The pore volume is 0.05cm^Three/ G and specific surface area of 312 m²/ G.
[0071]
Example 6
A solution prepared by dissolving 2.02 g (20 mmol) of ethyl phosphoric acid (95%) in 40 g of water was added to 3.58 g (10 mmol) of an aqueous solution of tin tetrachloride pentahydrate (weight of water: 30 g). Added over a minute with vigorous stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0072]
The gel was treated in the same manner as in Example 1 to obtain an ethyl group-substituted tin phosphate.
[0073]
The obtained ethyl group-substituted tin phosphate was found to have a layered structure with an interplanar spacing of 0.9 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss was 8.1%, which was almost the same as the theoretical value of 7.8%. The pore volume is 0.05cm^Three/ G, specific surface area of 305 m²/ G.
[0074]
Example 7
2.48 g (20 mmol) of n-propyl phosphoric acid (95%) dissolved in 40 g of water was dissolved in 3.58 g (10 mmol) of an aqueous solution of tin tetrachloride pentahydrate (weight of water: 30 g). Over about 5 minutes with vigorous stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0075]
The gel was treated in the same manner as in Example 1 to obtain n-propyl group-substituted tin phosphate.
[0076]
The obtained n-propyl group-substituted tin phosphate was found to have a layered structure with a surface spacing of 1.06 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss was 15.4%, almost the same as the theoretical value of 14.9%. The pore volume is 0.06cm^Three/ G and the specific surface area is 298 m.²/ G.
[0077]
Example 8
A solution obtained by dissolving 2.76 g (20 mmol) of t-butyl phosphate (95%) in 40 g of water was added to 3.58 g (10 mmol) of an aqueous solution of tin tetrachloride pentahydrate (weight of water: 30 g). Added over about 5 minutes with vigorous stirring. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0078]
The gel was treated in the same manner as in Example 1 to obtain t-butyl group-substituted tin phosphate.
[0079]
The obtained t-butyl group-substituted tin phosphate was found to have a layered structure with a surface spacing of 0.88 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss was 21.4%, almost the same as the theoretical value of 21%. The pore volume is 0.06cm^Three/ G and the specific surface area is 278 m.²/ G.
[0080]
Example 9
A solution prepared by dissolving 3.72 g (20 mmol) of 3,4-xylylphosphoric acid (95%) in 40 g of water was added to an aqueous solution of 3.58 g (10 mmol) of tin tetrachloride pentahydrate (weight of water: 30 g). ) With vigorous stirring over about 5 minutes. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0081]
The gel was treated in the same manner as in Example 1 to obtain 3,4-xylyl group-substituted tin phosphate.
[0082]
The obtained 3,4-xylyl group-substituted tin phosphate was found to have a layered structure with an interplanar spacing of 1.48 nm from the X-ray diffraction pattern. Further, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The weight loss was 38.5%, almost the same as the theoretical value 37.1%. The pore volume is 0.08cm^Three/ G and specific surface area of 325 m²/ G.
[0083]
Example 10
A solution prepared by dissolving 1.92 g (20 mmol) of methyl phosphoric acid (95%) in 40 g of water was vigorously stirred over 2.3 minutes in 2.33 g (10 mmol) of an aqueous solution of zirconium tetrachloride (water weight 30 g). Added while. Next, 1.52 g (5 mmol) of sodium dodecyl sulfate was added, and the mixture was further stirred for about 30 minutes to obtain a gel.
[0084]
The gel was treated in the same manner as in Example 1 to obtain methyl group-substituted zirconium phosphate.
[0085]
The obtained methyl group-substituted zirconium phosphate was found to have a layered structure with a surface spacing of 0.8 nm from the X-ray diffraction pattern. In addition, the adsorption / desorption isotherm of nitrogen shows a typical type I (IUPAC selection), and it was found that the phosphate portion has a lamellar structure having micropores. The pore volume is 0.05cm^Three/ G, specific surface area of 318 m²/ G.
[0086]
Example 11
The phenyl group-substituted tin phosphate obtained in Example 1 was calcined in air at 350 ° C. for 2 hours using an electric furnace.
[0087]
The layered structure of the obtained tin phosphate was broken. From the X-ray diffraction results, it was found to be amorphous.
[0088]
Tin phosphate had a pore diameter of 2 to 12 nm and a mesoporous state having a peak at 7 nm. Pore volume is 0.17cm^Three/ G, specific surface area is 235 m²/ G.
[Brief description of the drawings]
FIG. 1 is a diagram showing a layered structure and an interplanar spacing L of a phenyl group-substituted phosphate which is an example of the organic group-substituted phosphate of the present invention.

Claims (1)

After stirring a mixed solution of an organic group-substituted phosphoric acid and a metal halide containing a metal having a valence of 4 or more, a precipitate is obtained by adding an anionic surfactant and further stirring , and the resulting precipitate is hydrothermally treated. method for producing organic substituted phosphoric acid salt you characterized by.

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