JP2000247617A - Interlayer compound and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an interlayer compound intercalated with a secondary aliphatic, alicyclic or aromatic monoalcohol between the layers of a laminar compound having a basic composition consisting of vanadium, phosphorus and oxygen. SOLUTION: Vanadium oxide of hexad or below and over quadrivalent valance of vanadium, phosphorus pentaoxide and monoalcohol are reacted under reflux conditions to obtain the interlayer compound of the structure in which part or the whole of PHO existing in the vanadyl hydrogenphosphate 0.5 hydrate [(VO)(HOP)O3/0.5 H2P] laminar compound is replaced with phosphate POCxHx of the monoalcohol and part or the whole of H2O is replaced with the monoalcohol CxHyOH. The monoalcohol is preferably 1-12C primary aliphatic monoalcohol, 3-8C secondary aliphatic monoalcohol, 5-8C alicyclic monoalcohol or 7-12C aromatic monoalcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interlayer compound having a basic composition of vanadium, phosphorus and oxygen in which a monoalcohol is intercalated between layers, and a method for producing the same.

[0002]

2. Description of the Related Art Vanadyl phosphate, vanadyl hydrogen phosphate hemihydrate and the like are known as layered compounds having a basic composition of vanadium, phosphorus and oxygen. Here, vanadyl hydrogenphosphate hemihydrate _(VOHPO 4 · 0.5H ₂
O) is divanadyl pyrophosphate [(VO) ₂ P as a catalyst for producing maleic anhydride by a butane oxidation reaction
₂ O ₇ ] is widely known as a precursor.

[0003] It is known that by intercalating an organic compound between these layered compounds in the presence of an organic compound, a substance having an increased interlayer distance can be obtained. For example, a substance in which pyridine or pyrrole is intercalated between layers has been disclosed [Inorg. Chem. 21, 3820 (198
2) or Chem. Lett. 31 (1993)].

[0004] US Pat. No. 4,418,003 discloses a process for preparing a phosphorus vanadium catalyst suitable for the process for producing maleic anhydride from butane, in which P ₂ is present in an aliphatic alcohol having 1 to 8 carbon atoms. O ₅ were reacted to produce a mixed phosphoric acid ester, and with the vanadium compound is reacted with an inorganic acid in an aliphatic alcohol to produce an alcohol and vanadium esters of acidic and acidified to alcohol using these A method is disclosed that includes producing a vanadium phosphorus oxide catalyst that is in solution. The layer spacing of the obtained catalyst was 8.75 angstroms, and the layer spacing of vanadyl hydrogen phosphate hemihydrate was 5.4.
Broader than Angstroms, suggesting that methanol is intercalated between the layers.

[0005]

DISCLOSURE OF THE INVENTION The present invention relates to a method for preparing a secondary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen. A novel method for quickly and easily producing an intercalation compound in which monoalcohol is intercalated between layers of a novel intercalation compound and a layered compound having a basic composition of vanadium, phosphorus and oxygen. To provide.

[0006]

JP-A-8-259208 discloses an interlayer compound in which a diol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen, and a method for producing the same. It has been disclosed. But,
It does not intercalate monoalcohol,
As shown in the comparative example, in the production method of the present invention, isobutyl alcohol, which is a monoalcohol,
It is not possible to intercalate between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen.

[0007] WO 98/15353 discloses that
Layered compounds based on vanadium, phosphorus and oxygen
Intercalation of primary aliphatic monoalcohol between layers
Intercalation compounds and methods for producing the same are disclosed.
You. The method comprises V₂O₅, P ₂O₅And primary aliphatic molybdenum
It reacts alcohol. The method is first
Intercalates lower aliphatic monoalcohols
Yes, alicyclic monoalcohol or aromatic monoalcohol
Nothing is described about intercalating
Not in. In the comparative example, secondary alcohol, tertiary alcohol
Stated that alcohol cannot be intercalated
Have been. In addition, primary aliphatic monoalcohols
Requires very long reaction times to
(In Example 1, methanol is intercalated.
Takes 455 hours), and a primary branched aliphatic
Phosphoric acid concentrate to intercalate monoalcohol
The need to increase the reaction rate
Although hinted, the process involves primary branched aliphatic
X-ray showing that alcohol is intercalating
Due to the low intensity of the diffraction peaks, primary branched aliphatic
Intercalation with sufficient intercalation of alcohol
Compound cannot be manufactured.

The present inventors have conducted various studies to intercalate various monoalcohols between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen.
As a result, surprisingly, if vanadium is reacted with monoalcohol using vanadium oxide and phosphorus pentoxide in which the valence of the vanadium is less than pentavalent and is four or more, surprisingly,
The monoalcohol that could not be intercalated by the method described in 259208 can be intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen. / 153
No. 53 method could not be intercalated, secondary aliphatic monoalcohols other than primary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol also quickly and easily The present inventors have found that intercalation can be performed between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen, and have completed the present invention.

That is, the present invention relates to (1) a method in which a secondary aliphatic monoalcohol, an alicyclic monoalcohol or an aromatic monoalcohol is intercalated between layered compounds having a basic composition of vanadium, phosphorus and oxygen. Is an intercalation compound. In a preferred embodiment, (2) vanadyl hydrogen phosphate hemihydrate [(VO) (HOP) O _3.
0.5H ₂ O] A part or all of the POH present in the layered compound is a phosphate ester PO of a secondary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol.
A part or all of H ₂ O which has been replaced by C _x H _y and is present between the above-mentioned layers is a secondary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol C
_{x H} y above where having replaced by that structure _OH (1) intercalation compounds according, (3) secondary aliphatic above where the carbon number of the monoalcohol is 3-8 (1) or The intercalation compound according to (2), wherein (4) the secondary aliphatic monoalcohol is selected from 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol or 2-octanol. (1) The intercalation compound according to (2), (5) the intercalation compound according to (1) or (2), wherein the alicyclic monoalcohol has 5 to 8 carbon atoms, (6) alicyclic ring (1) wherein the group monoalcohol is selected from cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3-methylcyclopentanol or 3-ethylcyclopentanol; Or the intercalation compound according to (2), (7) the intercalation compound according to (1) or (2), wherein the aromatic monoalcohol has 7 to 12 carbon atoms, and (8) the aromatic monoalcohol, The interlayer distance of the intercalation compound according to the above (1) or (2), which is benzyl alcohol or 2-phenylethyl alcohol, and (9) the intercalation compound where the secondary aliphatic alcohol is intercalated, The interlayer distance of the interlayer compound according to any one of the above (1) to (4), which is 10 to 15 Å, and the interlayer distance of the interlayer compound where the alicyclic monoalcohol is intercalated, ,
The interlayer compound according to any one of (1), (2), (5) and (6) above, which has a thickness of 10 to 15 Å, and (11) an aromatic monoalcohol intercalated. The interlayer compound according to any one of (1), (2), (7) and (8) above, wherein the interlayer distance of the interlayer compound is 15 to 25 angstroms. The intercalation compound in which the secondary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol of the present invention is intercalated can be produced by the following method of the present invention. According to the method of the present invention, not only secondary aliphatic monoalcohols, alicyclic monoalcohols or aromatic monoalcohols, but also primary aliphatic monoalcohols can be intercalated very quickly and easily between layers. can do. That is, the method of the present invention comprises: (12) a vanadium oxide in which the valence of vanadium is less than 5 and more than 4,
This is a method of reacting phosphorus pentoxide and monoalcohol to produce an intercalation compound in which monoalcohol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen. As a preferred embodiment, (13) the method according to (12) above, wherein the vanadium valence of the vanadium oxide is 4.5.
4) The method according to the above (12) or (13), wherein the vanadium oxide is V ₄ O ₉ ; (15) Less than pentavalent tetravalent obtained by reducing a pentavalent vanadium compound in alcohol or aldehyde. After separating the above vanadium oxide, the oxide is mixed with a monoalcohol, and then the vanadium, which reacts by adding phosphorus pentoxide to the mixture, is a layered compound having a basic composition of phosphorus and oxygen. (16) A method for producing an intercalation compound in which a monoalcohol is intercalated between the layers, (16) 5 obtained by reducing a pentavalent vanadium compound in an alcohol or an aldehyde.
A layered compound having a basic composition of vanadium, phosphorus and oxygen, in which after separating a vanadium oxide having a valency of less than 4, the oxide is added to a reaction product of a monoalcohol and phosphorus pentoxide to carry out a reaction. (17) A method for producing an intercalation compound in which a monoalcohol is intercalated between the layers of (a), (17) a mixture obtained by reducing a pentavalent vanadium compound in a monoalcohol or an aldehyde, and further adding a monoalcohol and a pentoxide. (18) a method for producing an intercalation compound in which monoalcohol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen in which phosphorus is added, and (18) a pentavalent vanadium compound Is vanadium pentoxide (15)
(19) The method according to any one of (17) to (17), wherein the monoalcohol is a primary aliphatic monoalcohol having 1 to 12 carbon atoms, or a secondary aliphatic monoalcohol having 3 to 8 carbon atoms. The method according to any one of the above (12) to (18), which is selected from an alicyclic monoalcohol having 5 to 8 carbon atoms or an aromatic monoalcohol having 7 to 12 carbon atoms, (20 ) Primary aliphatic monoalcohol is methanol, ethanol, 1-propanol, 1-butanol,
Isobutanol, isopentanol, neopentanol, 2-methyl-1-butanol, 1-pentanol,
Selected from 1-hexanol or 1-octanol, wherein the secondary aliphatic monoalcohol is 2-propanol, 2-propanol,
Butanol, 2-pentanol, 2-hexanol, 2
An alicyclic monoalcohol selected from heptanol or 2-octanol, wherein the alicyclic monoalcohol is selected from cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3-methylcyclopentanol or 3-ethylcyclopentanol; (21) the method according to the above (19), wherein the alcohol is selected from benzyl alcohol or 2-phenylethyl alcohol, (21) vanadium,
The intercalation compound in which the monoalcohol is intercalated between the layers of the layered compound having a basic composition of phosphorus and oxygen is vanadyl hydrogen phosphate hemihydrate [(VO)
_{(HOP) O 3 · 0.5H 2} O] part of POH present in layered compound or all, has been replaced by a phosphate ester _POC x _{H y} monoalcohols, and present in the compounds _H 2 O Part or all of the monoalcohol C
_{x H} y (12) of the is where those having been replaced structure _OH can be mentioned a method according to any one of - (20).

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The vanadium oxide used in the method for producing an intercalation compound according to the present invention has a valence of vanadium of less than pentavalent and tetravalent or more, preferably 4.5.
And particularly preferably V ₄ O ₉ .

There is no particular limitation on the method for producing the vanadium oxide having a valence of less than 5 and a valence of 4 or more, preferably 4.5. For example, it can be obtained by a method in which a pentavalent vanadium compound is partially reduced to reduce the valency of vanadium to less than pentavalent to four or more, preferably to 4.5. The reduction can be performed in a gas phase or a liquid phase, and is preferably performed in a liquid phase. In the gas phase reduction, for example, hydrogen, butene, butadiene, sulfur dioxide or the like is used as the reducing agent, while in the liquid phase reduction, an organic medium is preferably used as the reducing agent. Examples of the organic medium include alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, and benzyl alcohol; aldehydes such as benzaldehyde, acetaldehyde and propionaldehyde; and hydrazines. And oxalic acid. Alcohols are preferably used, and isobutanol and benzyl alcohol are particularly preferable. 5
Examples of the vanadium compound having a valence include vanadium pentoxide, ammonium vanadate, and the like, and preferably vanadium pentoxide is used.

As the above-mentioned reduction method, for example, a pentavalent vanadium compound such as vanadium pentoxide is mixed in an alcohol such as isobutanol and / or benzyl alcohol, and the mixture is preferably refluxed under a reflux condition. There is a method in which reduction is carried out by heating for 80 hours, more preferably 1 to 10 hours, followed by filtration, washing with a low boiling point solvent such as acetone, methanol, ethanol or the like, followed by drying. The compound thus produced was confirmed to be V ₄ O ₉ from the diffraction pattern of X-ray diffraction (Cu-Kα against the cathode).

The vanadium obtained in this way has a valence of less than 5 and a valence of 4 or more, preferably 4.5, preferably V ₄ O _9, which is reacted with phosphorus pentoxide and a monoalcohol. Vanadium,
An intercalation compound in which a monoalcohol is intercalated between layers of a layered compound having a basic composition of phosphorus and oxygen can be produced.

The monoalcohol to be intercalated is preferably a primary aliphatic monoalcohol having 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, preferably a secondary aliphatic monoalcohol having 3 to 8 carbon atoms. It is selected from lower aliphatic monoalcohols, preferably alicyclic monoalcohols having 5 to 8 carbon atoms, or preferably aromatic monoalcohols having 7 to 12 carbon atoms. The primary aliphatic monoalcohol is preferably methanol, ethanol, 1-propanol, or 1-propanol.
Butanol, isobutanol, isopentanol, neopentanol, 2-methyl-1-butanol, 1-pentanol, 1-hexanol or 1-octanol and the like are used. As the secondary aliphatic monoalcohol, preferably, 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol or 2-
Octanol and the like are used. As the alicyclic monoalcohol, preferably, cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3-methylcyclopentanol or 3-ethylcyclopentanol is used, and an aromatic monoalcohol is used. Preferably, the alcohol is
Benzyl alcohol, 2-phenylethyl alcohol methanol and the like are used.

In the method of the present invention, the amount of the monoalcohol used is preferably 1000 mol, particularly preferably 100 mol, and the lower limit is preferably 3 mol, particularly preferably 5 mol, per mol of vanadium. Is a mole. Below the lower limit, the monoalcohol cannot be sufficiently intercalated. The upper limit of the amount of phosphorus pentoxide used is preferably 3 mol, particularly preferably 1.5 mol, and the lower limit is preferably 0.7 mol, particularly preferably 1 mol, in terms of the ratio of phosphorus atoms to vanadium atoms. It is. Below the lower limit, the monoalcohol cannot be sufficiently intercalated.

As a method of producing an intercalation compound in which a monoalcohol is intercalated, for example, vanadium having a valence of less than 5 and a valence of 4 or more, obtained as described above,
Preferably, a 4.5-valent vanadium oxide, particularly preferably V ₄ O ₉ , is mixed with a monoalcohol, and then phosphorus pentoxide is added to the mixture (provided that the order of mixing the above three substances is mixed). The reaction is carried out under reflux conditions, followed by filtration, washing with a low-boiling solvent such as acetone, methanol, ethanol or the like, followed by drying, or the reaction product of a monoalcohol and phosphorus pentoxide. , Vanadium has a valence of less than 5 and a valence of 4 or more, preferably 4.5, more preferably V _4.
A method of adding O ₉ , performing a reaction under reflux conditions, filtering, washing with a low boiling point solvent such as acetone, methanol, ethanol and the like, followed by drying, for example. Also,
A pentavalent vanadium compound, such as vanadium pentoxide, is mixed in a monoalcohol, such as benzyl alcohol, and reduced under reflux conditions. After that, the mixture is further added with monoalcohol and phosphorus pentoxide to form a mixture under reflux conditions. It can also be produced by performing a reaction below. In the above case, the reaction time is preferably from 0.1 to 100 hours, particularly preferably from 1 to 60 hours. Below the lower limit, the monoalcohol cannot be intercalated, and above the upper limit, the production cost increases and the operation becomes complicated. The reaction temperature is preferably a reflux temperature.

According to the method of the present invention, it is possible to obtain an intercalation compound in which a monoalcohol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen according to the invention. The intercalation compound is vanadyl hydrogen phosphate hemihydrate [(VO) (HOP) O ₃
· 0.5H ₂ O] phosphoric acid ester part or all of the monoalcohol POH present in the layered compound _POC x _{H y}
And H ₂ present in the above compound
O part or all has the structure that are replaced by monoalcohols C _{x H} y _OH. Here, x and y are determined by the type of monoalcohol used in the production of the intercalation compound, and the monoalcohol used is as described above.

In particular, according to the method of the present invention, a secondary aliphatic monoalcohol, preferably having 3 carbon atoms, is interposed between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen.
~ 8 secondary aliphatic monoalcohols, more preferably 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol or 2-
Octanol, an alicyclic monoalcohol, preferably an alicyclic monoalcohol having 5 to 8 carbon atoms, more preferably cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3-methylcyclopentanol or 3-ethylcyclohexane Pentanol or an aromatic monoalcohol, preferably an aromatic monoalcohol having 7 to 12 carbon atoms, more preferably benzyl alcohol and 2-phenylethyl alcohol can be intercalated.

The interlayer distance of the interlayer compound obtained by the method of the present invention is determined by the type of the monoalcohol to be intercalated, and is at least 9.0 angstroms, preferably 9.0 to 25.0 angstroms. In particular, in an intercalation compound in which a secondary aliphatic alcohol is intercalated, preferably 1 is used.
0 to 15 Å, and in the intercalation compound in which the alicyclic monoalcohol is intercalated,
It is preferably 10 to 15 angstroms, and preferably 15 to 25 angstroms in the intercalation compound in which the aromatic monoalcohol is intercalated.

In the intercalation compound produced by the method of the present invention, the fact that the monoalcohol is intercalated between the layers can be confirmed by X-ray diffraction using vanadyl hydrogen phosphate as described in detail in the Examples below. Instead of the diffraction peak on the (001) plane of 0.5 pentahydrate, 2θ is 2 to 1
A diffraction peak indicating that the interlayer distance was widened between 0 ° was confirmed (see FIGS. 1 to 5).

The interlayer distance increases almost in proportion to the increase in the number of carbon atoms of the monoalcohol used (see FIG. 6, for example, which is noticeable in primary aliphatic monoalcohols) and the interlayer distance. Increases almost in proportion to the increase in the molecular size of the monoalcohol used (see FIG. 7),

In the infrared absorption spectrum of the intercalation compound of the present invention [intercalation compound in which monoalcohol (methanol, 2-propanol, 2-butanol, cyclopentanol, cyclohexanol or benzyl alcohol) is intercalated], phosphorus Absorbed and isolated CO attributed to POC not present in vanadyl hydrogen oxyhemihydrate
The presence of an absorption attributed to H (see FIGS. 8-13);

From the thermal analysis, it is confirmed that the weight loss on the low temperature side which is considered to be caused by the monoalcohol present and the weight loss on the high temperature side which is considered to be caused by the combustion of the monoalcohol having an ester bond (FIGS. 19), and that the structural formula estimated from the elemental analysis values substantially matches the weight loss by the thermal analysis described above.

The intercalation compound of the present invention can be used as a precursor of divanadyl pyrophosphate [(VO) ₂ P ₂ O ₇ ] as a catalyst for producing maleic anhydride by a butane oxidation reaction and has a wide interlayer spacing. Therefore, it can be used not only as an adsorbent and a separating agent utilizing the interlayer, but also for controlling the molecular weight of the polymer by reacting the monomer between the interlayers. For use as a catalyst, similarly to vanadyl hydrogen phosphate hemihydrate, it is prepared by calcination in nitrogen or air or in a butane oxidation reaction atmosphere. If the interlayer compound of the present invention is calcined after cross-linking the interlayer with a silane coupling agent or a polycation of aluminum, etc., it can be used as a porous material having a large space between layers, for example, as an adsorbent, a separating agent, or also as a catalyst. it can. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0025]

EXAMPLES In Examples and Comparative Examples, each measurement was carried out as follows. <X-ray diffraction> Cu-Kα ray was used as an X-ray source. The equipment used was RINT-140, manufactured by Rigaku Corporation.
0. <Infrared analysis> After the measurement sample was diluted to 1% by weight with KBr, it was press-formed into a disk and used. The measurement was performed by a transmission method. The equipment used was PerkinElmer m
odel 1600. <Thermal analysis> Measurement was performed at a temperature rising rate of 5 ° C / min in an air flow of 100 ml / min. The equipment used was
TG / DTA-200 manufactured by Seiko Electronic Industry Co., Ltd.

[0026]

Example 1 14.55 g (0.08 mol) of vanadium pentoxide was suspended in a mixed solvent of 90 ml (0.98 mol) of isobutanol and 60 ml (0.58 mol) of benzyl alcohol, and the suspension was refluxed (105 ° C.) under a reflux condition (105 ° C.). After heating for a period of time to reduce vanadium pentoxide, the mixture was cooled to room temperature. Next, the precipitate was separated by filtration, washed with 250 ml of acetone, and dried overnight at room temperature to obtain a black solid (V ₄ O ₉ ). 12.02 g of this black solid was suspended in 150 ml (1.45 mol) of benzyl alcohol, and toluene was added thereto.
A suspension of 13.53 g (0.095 mol) of phosphorus pentoxide in 40 ml was added at room temperature with stirring. After the addition, the suspension was heated at 105 ° C. for 3 hours with stirring to react, and then cooled to room temperature. Next, the precipitate was separated by filtration, washed with 250 ml of acetone, and dried at room temperature overnight.

The resulting light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ = 5.
3 °, and the interlayer distance of this intercalation compound was found to be 16.6 Å [FIG.
1)].

[0028]

Example 2 Vanadium pentoxide was reduced as in Example 1 to obtain a black solid. Separately, a suspension of 13.53 g (0.095 mol) of phosphorus pentoxide in 40 ml of toluene was added to 150 ml (1.45 mol) of benzyl alcohol with stirring at room temperature, and stirring was continued for 30 minutes at room temperature to continue the addition. All of the phosphorus oxide was dissolved. Next, 12.02 g of the above black solid was added thereto, and the mixture was heated and reacted at 105 ° C. for 3 hours while stirring, and then cooled to room temperature. Then, the precipitate was filtered off, washed with 250 ml of acetone,
Dry at room temperature overnight.

The resulting light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ = 5.
3 °, and the interlayer distance of this intercalation compound was found to be 16.6 Å [FIG.
2)].

[0030]

Example 3 7.28 g (0.04 mol) of vanadium pentoxide was suspended in a mixed solvent of 45 ml (0.49 mmol) of isobutanol and 30 ml (0.29 mol) of benzyl alcohol, and the suspension was refluxed (105 ° C.) under a reflux condition (105 ° C.). After heating for a period of time to reduce vanadium pentoxide, the mixture was cooled to room temperature.
Then, 5.65 g of phosphorus pentoxide in 15 ml of toluene
(0.04 mol) was added to the above-mentioned suspension after the reduction with stirring at room temperature. Thereafter, another 15 ml (0.15 mol) of benzyl alcohol was added with stirring at room temperature. After the addition, the suspension was heated at 105 ° C. for 3 hours with stirring to react, and then cooled to room temperature. Next, the precipitate was separated by filtration, washed with 125 ml of acetone, and dried at room temperature overnight.

The resulting black-gray solid vanadium had a valence of 4. The X-ray diffraction pattern was the same as in Example 1 or 2, and the interlayer distance of this interlayer compound was found to be 16.6 Å.

[0032]

Example 4 Vanadium pentoxide was reduced as in Example 1 to obtain a black solid. Thereafter, the reaction was carried out in the same manner as in Example 1 except that the reaction was carried out by refluxing for 72 hours using methanol instead of benzyl alcohol.

The resulting light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ = 9.
7 °, and the interlayer distance of this interlayer compound was found to be 9.1 Å (CH ₃ O in FIG. 2).
H).

[0034]

Example 5 A reaction was carried out in the same manner as in Example 4 except that 1-propanol was used in place of methanol to reflux and react for 18 hours. The obtained light blue solid vanadium had a valence of 4. From X-ray diffraction, diffraction peak is 2θ
= 7.4 °, and the interlayer distance of this interlayer compound is 11.9.
Angstrom (C ₃ H in FIG. 2).
₇ OH).

[0035]

Example 6 A reaction was carried out in the same manner as in Example 4 except that the reaction was carried out by refluxing for 3 hours using 1-butanol instead of methanol.

The resulting light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ = 5.
It exists at 4 °, and the interlayer distance of this interlayer compound was found to be 16.4 Å (C ₄ H ₉ O in FIG. 2).
H).

[0037]

Example 7 A reaction was carried out in the same manner as in Example 4 except that 1-hexanol was used in place of methanol and refluxed for 3 hours to carry out the reaction. The obtained light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ =
It exists at 5.0 °, and the interlayer distance of this interlayer compound was found to be 17.7 Å (C ₆ H in FIG. 2).
₁₃ OH).

[0038]

Example 8 A reaction was carried out in the same manner as in Example 4 except that the reaction was carried out for 3 hours using 1-octanol instead of methanol. The obtained light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ = 3.7 °.
It was found that the interlayer distance of this intercalation compound was 23.7 Å (C ₈ H ₁₇ O in FIG. 2).
H).

[0039]

Example 9 The procedure of Example 4 was repeated except that the reaction was carried out by refluxing for 24 hours using isobutanol instead of methanol. The obtained light blue solid vanadium had a valence of 4. From X-ray diffraction, the diffraction peak was 2θ =
Exists at 6.3 °, and the interlayer distance of this interlayer compound is 14.1
It was found to be a long strong (Fig. 3).

[0040]

Example 10 Vanadium pentoxide was reduced as in Example 1 to obtain a black solid. Thereafter, the reaction was carried out in the same manner as in Example 1 except that 2-propanol was used in place of benzyl alcohol and the mixture was refluxed at 81 ° C. for 53 hours to cause a reaction. The obtained light blue solid vanadium had a valence of 4. X-ray diffraction showed that a diffraction peak was present at 2θ = 7.6 °, and the interlayer distance of this interlayer compound was 11.6 Å (2-C ₃ H ₇ O in FIG. 4).
H).

[0041]

Example 11 A reaction was carried out in the same manner as in Example 10 except that 2-butanol was used instead of 2-propanol and the mixture was refluxed at 92 ° C. and reacted. The valence of the obtained gray solid vanadium was tetravalent. X-ray diffraction showed that a diffraction peak was present at 2θ = 6.4 °, and that the interlayer distance of this interlayer compound was 13.7 Å (2-C ₄ H ₉ OH in FIG. 4).

[0042]

Example 12 Vanadium pentoxide was reduced in the same manner as in Example 1 to obtain a black solid. Thereafter, cyclohexanol was used in place of benzyl alcohol at 115 ° C.
The procedure was performed in the same manner as in Example 1 except that the reaction was carried out by refluxing for 5 hours. The obtained light blue solid vanadium has a valence of 4.
Value. From X-ray diffraction, the diffraction peak was 2θ = 7.0.
°, and the interlayer distance of this interlayer compound was found to be 12.7 Å (Cyhex in FIG. 5).
OH).

[0043]

Example 13 The procedure was carried out in the same manner as in Example 12, except that cyclopentanol was used in place of cyclohexanol and the mixture was refluxed at 111 ° C. for 28 hours to react. The obtained light blue solid vanadium had a valence of 4. X-ray diffraction showed that a diffraction peak existed at 2θ = 7.2 °, and the interlayer distance of this interlayer compound was 12.3 Å (CypenOH in FIG. 5).

[0044]

Comparative Example 1 14.55 g (0.08 mol) of vanadium pentoxide was suspended in a mixed solvent of 90 ml (0.98 mol) of isobutanol and 60 ml (0.58 mol) of benzyl alcohol, and the suspension was refluxed (105 ° C.) under a reflux condition (105 ° C.). After heating for a period of time to reduce vanadium pentoxide, the mixture was cooled to room temperature. Then, 15.8 g (0.16 mmol) of 99% H ₃ PO ₄ was added to the suspension after reduction over 30 minutes with stirring. After the addition, the suspension was heated under reflux conditions (105 ° C.) for 3 hours to react, and then cooled to room temperature. Then, the precipitate was filtered off, washed with 250 ml of acetone,
Dry at room temperature overnight.

The valence of the obtained light blue solid vanadium was tetravalent. From X-ray diffraction, the precipitate was VOH
PO ₄ .0.5H ₂ O, diffraction peak 2θ = 15.8
° and the interlayer distance was found to be 5.4 Å (VOHPO ₄ .0.5H ₂ O in FIG. 2).

[0046]

Comparative Example 2 Vanadium pentoxide was reduced in the same manner as in Example 1 to obtain a black solid. 12.02 g of this black solid was suspended in 150 ml (1.45 mol) of benzyl alcohol,
To this was added 15.8 g of 99% H ₃ PO ₄ with stirring at room temperature over 30 minutes. After the addition, the suspension was heated under reflux conditions (105 ° C.) for 3 hours to react, and then cooled to room temperature. Next, the precipitate was separated by filtration, washed with 250 ml of acetone, and dried at room temperature overnight.

The valence of vanadium in the obtained light blue solid was tetravalent. X-ray diffraction, the pattern is the same as Comparative Example 1, precipitate the VOHPO ₄ · 0.5
Although a diffraction peak unique to H ₂ O was observed, no diffraction peak was observed in a region where 2θ was 10 ° or less, indicating that benzyl alcohol was not intercalated between the layers.

[0048]

Comparative Example 3 The same procedure as in Comparative Example 2 was carried out except that 2-propanol was used instead of benzyl alcohol, and the reflux heating time was changed to 10 hours. The results were the same as in Comparative Example 2, and it was found that 2-propanol was not intercalated between the layers.

[0049]

Comparative Example 4 The same procedure as in Comparative Example 2 was carried out except that 2-butanol was used instead of benzyl alcohol, and the reflux heating time was changed to 5 hours. The results were the same as in Comparative Example 2, and it was found that 2-butanol was not intercalated between the layers.

[0050]

Comparative Example 5 The same procedure as in Comparative Example 2 was carried out except that cyclohexanol was used instead of benzyl alcohol, and the reflux heating time was changed to 10 hours. The results were the same as in Comparative Example 2, and it was found that cyclohexanol was not intercalated between the layers.

[0051]

Comparative Example 6 The same procedure as in Comparative Example 2 was carried out except that cyclopentanol was used instead of benzyl alcohol, and the reflux heating time was changed to 10 hours. The results were the same as in Comparative Example 2, and it was found that cyclopentanol was not intercalated between the layers.

[0052]

Comparative Example 7 8.858 g (0.049 mol) of vanadium pentoxide,
8.35 g (0.059 mol) of phosphorus pentoxide and 200 ml of methanol were reacted by heating under reflux conditions (64 ° C.) for 72 hours, and then cooled to room temperature. Next, the precipitate was separated by filtration, washed with 250 ml of acetone, and dried at room temperature overnight.

From X-ray diffraction, it was found that V ₂ O ₅ was almost present in the precipitate, and almost no intercalation compound in which methanol was intercalated between the layers was formed.

[0054]

Comparative Example 8 The same procedure was performed as in Comparative Example 7, except that cyclohexanol was used instead of methanol.

[0055] from the X-ray _diffraction, VOHPO 4 · 0.5H ₂
The presence of O was confirmed. However, the diffraction intensity was very weak, and a very broad peak indicating the presence of an amorphous phase was observed at around 2θ = 10 to 30 °. Therefore, the precipitate was an amorphous layer, and cyclohexanol was intercalated. It was found that no intercalation compound was formed at all.

Further, the heating time was extended to 400 hours, but no intercalation compound in which cyclohexanol was intercalated was formed.

The interlayer compound of the present invention shown in Examples 1 to 13 wherein the monoalcohol was intercalated between the layers was the layered compound VOHPO ₄ .0.5H ₂ O of Comparative Example 1.
The interlayer distance was remarkably widened as compared with. Comparative Example 2
Starting from No. 6, benzyl alcohol, 2-phosphoric acid was prepared using phosphoric acid (H ₃ PO ₄ ) according to the method described in JP-A-8-259208
It was found that heating propanol, 2-butanol, cyclohexanol or cyclopentanol with V ₄ O ₉ did not allow these alcohols to intercalate between the layers. Comparative Example 7 was carried out in the same manner as Example 1 described in WO 98/15353, and the reaction time was 455.
This is shortened from the time to 72 hours as in the case of the fourth embodiment of the present invention. According to the method described in this publication, it was found that an interlayer compound in which methanol was intercalated between layers in a short time could hardly be obtained. That is, according to the method described in this publication, it was found that intercalating the monoalcohol between the layers required a significantly longer reaction time than the method of the present invention. Comparative Example 8 was published in International Patent Application Publication No.
The reaction was carried out using cyclohexanol in the same manner as in Example 1 described in JP-A-98 / 15353, and the reaction time was 72 hours, which was the same as that of Comparative Example 7, and 40 hours, which was almost the same as Example 1 described in the above-mentioned publication.
It is 0 hours. According to the method described in this publication, cyclohexanol could not be intercalated between the layers even if the reaction time was extremely short or the reaction time was significantly increased.

In Examples 1 to 3, the manufacturing procedure was changed. In each case, it was found that benzyl alcohol (aromatic monoalcohol) could be intercalated between the layers. Examples 4, 5, 6, 7 and 8 show methanol, 1-propanol, 1-
Butanol, 1-hexanol and 1-octanol (primary aliphatic monoalcohol) are used. It was found that the interlayer distance increased in proportion to the increase in the number of carbon atoms in the monoalcohol (FIG. 6). Example 9 uses isobutanol (a primary branched aliphatic monoalcohol). Example 6 using 1-butanol
A compound having a somewhat smaller interlayer distance than that of was obtained. Examples 10 or 11 were 2-propanol or 2-propanol, respectively.
Butanol (secondary aliphatic monoalcohol) is used. As compared with Examples 5 or 6 using 1-propanol or 1-butanol, compounds having a somewhat smaller interlayer distance were obtained. Example 12 or 13 uses cyclohexanol or cyclopentanol (alicyclic monoalcohol), respectively. In each case, a compound having a smaller interlayer distance was obtained as compared with the case where the primary aliphatic monoalcohol having the same carbon number was used.

Next, the structure of the interlayer compound of the present invention was examined. FIG. 6 shows the relationship between the number of carbon atoms of the primary aliphatic monoalcohol, the secondary aliphatic monoalcohol and the alicyclic monoalcohol, and the interlayer distance of the intercalated compound in which these alcohols are intercalated. is there. VO
As compared with the interlayer distance of 5.4 Å (in the case of carbon number 0) of HPO ₄ .0.5H ₂ O, the interlayer distance in the interlayer compound of the present invention is all larger. In addition, it can be seen that as the number of carbon atoms of the primary aliphatic monoalcohol, secondary aliphatic monoalcohol or alicyclic monoalcohol increases, the interlayer distance increases in proportion to each type of monoalcohol. . This is thought to be due to the intercalation of each monoalcohol between the layers.

In the primary aliphatic monoalcohol, the interlayer distance increases by about 2.1 to 2.2 angstroms every time the carbon number of the alcohol increases by one. Considering that the CC bond distance is about 1.4 angstroms,
In the intercalation compound of the present invention, it is presumed that alcohols are present in two layers between the layers. On the other hand, the VOH shown in FIG.
As can be seen from a comparison between the X-ray diffraction pattern of PO ₄ .0.5H ₂ O and the X-ray diffraction pattern of the intercalation compound intercalated with each primary aliphatic monoalcohol, (11)
The diffraction lines of (0), (220) and (040) are all observed at almost the same position, and it is considered that the two-dimensional structure of the layer surface is the same. This is the same for the secondary aliphatic monoalcohol, alicyclic monoalcohol and aromatic monoalcohol.

According to FIG. 6, the secondary aliphatic monoalcohol (2-propanol or 2-butanol) has a smaller interlayer distance than the primary aliphatic monoalcohol having the same carbon number. It is closer to the interlayer distance of the primary aliphatic monoalcohol (ethanol or 1-propanol, respectively), which is one less in number. This suggests that the interlayer distance is governed by the number of carbon atoms in the longer chain of the branched aliphatic chain of the secondary aliphatic monoalcohol. In the alicyclic monoalcohol, the interlayer distance is smaller than that of the primary aliphatic monoalcohol having the same carbon number. This is because the molecular structure is considered to be even smaller because of the cyclic structure.

FIG. 7 shows the relationship between the molecular size of the primary aliphatic monoalcohol, the secondary aliphatic monoalcohol and the alicyclic monoalcohol, and the interlayer distance of the intercalated compound in which these alcohols are intercalated. The relationship was shown.
Here, the molecular size includes the hydrogen atom of the OH group in the alcohol molecule whose structure has been optimized by the semi-empirical molecular orbital method (program package MOPAC93) and the hydrogen atom located farthest from the hydrogen atom. Distance was used. Taking the relationship between the molecular size and the interlayer distance, it was found that all of these alcohols had one linear relationship between the molecular size and the interlayer distance. It is estimated that the interlayer distance of the interlayer compound depends on the molecular size of the intercalated monoalcohol.

Next, using the infrared absorption spectrum,
The structure analysis of the intercalation compound of the invention was performed. FIG. 8 shows VO
HPO₄・ 0.5H₂O and interlayer between layers produced in Example 4.
The infrared absorption spectrum of the compound (methanol) is shown in FIG.
Is the intercalation compound (benzyl alcohol) prepared in Example 1.
FIG. 10 shows the infrared absorption spectrum of Example 10;
Absorption of the intercalation compound (2-propanol) produced in
FIG. 11 shows the yield spectrum of the interlayer manufactured in Example 11.
Infrared absorption spectrum of compound (2-butanol), figure
12 shows the intercalation compound (cyclohexyl) produced in Example 12.
(Xanol), and FIG.
Represents the intercalation compound (cyclopentano) produced in Example 13.
) Was shown. Where VO
HPO₄・ 0.5H₂For the assignment of the absorption band of O
According to literature values [J. Catal., 99, 400 (1986) and J. Cata.
l., 141, 671 (1993)]. Examples 1, 4, 10, 11, 1
Assignment of the absorption band of the intercalation compound produced in 2 and 13
About VOHPO₄・ 0.5H₂O, methanol,
Benzyl alcohol, 2-propanol, 2-butanol
, Cyclohexanol, cyclopentanol and tri
Comparison with infrared absorption spectrum of alkyl phosphate
It was decided by doing. From the infrared absorption spectrum, the absorption attributed to POC (in the case of methanol: 810 cm
^-1, 1030 cm^-1For benzyl alcohol: 744cm
^-1, 1026 cm^-1For 2-propanol: 888cm
^-1, 1026 cm^-1In the case of 2-butanol: 886c
m^-1, 1015 cm^-1, For cyclohexanol: 894c
m^-1, 1024 cm^-1For cyclopentanol: 909c
m^-1, 1019 cm^-1) And absorption attributed to isolated COH (in the case of methanol: 35
31cm^-1, 3588 cm^{− 1}, For benzyl alcohol: 3
496 cm^-1For 2-propanol: 3534cm^-1, 36
02cm^-1, 3721cm^-1For 2-butanol: 3606cm
^-1, 3718cm ^-1For cyclohexanol: 3746cm
^-11For cyclopentanol: 3581cm^-1, 3711
 cm^-1) In Examples 1, 4, 10, 11, 12 and 1
VOHPO exists in the intercalation compound prepared in 3₄・
0.5H₂O was found not to be present.

FIG. 14 shows the results of a thermal analysis of the intercalation compound (benzyl alcohol) obtained in Example 1. About 5.7% by weight of the weight loss on the low temperature side is considered to be due to benzyl alcohol and water present between the layers, and about 34.
It is considered that 7% by weight is due to combustion of benzyl alcohol having an ester bond. The overall weight loss was about 40.4% by weight. Elemental analysis value of intercalation compound in which benzyl alcohol is intercalated manufactured in Example 1 (V: 19.1% by weight, P: 12.2)
% By weight, O: 32.7% by weight, H: 3.1% by weight, C:
When the structural formula was estimated from 32.9% by weight, VO (C ₆
H ₅ CH ₂ OP) _0.92 (HOP) _0.08 O _3.
0.12 (C ₆ H ₅ CH ₂ OH) · 0.38 (H ₂ O)
Becomes Benzyl alcohol and water [0.12 (C ₆ H ₅ CH ₂ OH) · 0.38 (H
₂ O)] and [VO (C ₆ H ₅ CH ₂ OP)
_0.92 (HOP) _0.08 O ₃ ], the theoretical value of the weight loss is 7.5% by weight, which is slightly different from the actually measured value of about 5.7% by weight. Since the pretreatment conditions for the thermal analysis and the thermal analysis are different, the amounts of benzyl alcohol or water physically adsorbed are different, and this is a difference caused by the difference, and it can be considered that both values are almost the same. This supports the above assumption that the low temperature side weight loss is due to benzyl alcohol and water present between the layers. Benzyl alcohol bound by ester bond is burned due to weight loss on the high temperature side and [VOPO ₄ ]
If so, the theoretical value of the amount of weight loss is 34.6% by weight, which substantially coincides with the actually measured value of about 34.7% by weight.
This supports the above assumption that the weight loss on the high temperature side is caused by the combustion of the ester-linked monoalcohol. The weight loss on the low temperature side was based on an endothermic reaction, while the weight loss on the high temperature side was based on an exothermic reaction. From the above, in the intercalation compound, benzyl alcohol is said to be intercalated between the layers in the form of phosphate ester and benzyl alcohol.

FIG. 15 shows the results of thermal analysis of the intercalation compound (methanol) obtained in Example 4. It is considered that about 9.0% by weight of the weight loss on the low temperature side is due to methanol existing between layers, and about 8.6% by weight of the weight loss on the high temperature side is due to the combustion of the ester-bonded methanol. It is considered to be caused. The overall weight loss was about 17.6% by weight. Elemental analysis value (V: 28.1% by weight, P: 1) of the intercalated compound in which methanol is intercalated, produced in Example 4.
When the structural formula is estimated from 7.4% by weight, O: 44.6% by weight, H: 6.5% by weight, and C: 2.0% by weight, VO is obtained.
_{(CH 3 OP) 0.50 (HOP} ) 0.50 O 3 · 0.
50 (CH ₃ OH). If methanol is desorbed due to weight loss on the low temperature side, the theoretical value of weight loss is 8.
6% by weight, which is almost the same as the actually measured value of about 9.0% by weight. This supports the above assumption that the low temperature side weight loss is due to methanol present between the layers. If methanol in an ester bond burns due to weight loss on the high temperature side, the theoretical value of the weight loss amount is 8.6% by weight, and the above measured value is about 8.6% by weight.
Matches. This supports the above assumption that the high-temperature side weight loss is due to the combustion of the ester-bound methanol. The weight loss on the low temperature side was based on an endothermic reaction, while the weight loss on the high temperature side was based on an exothermic reaction. From the above, it is considered that in the intercalation compound, methanol is intercalated between the layers in the form of a phosphate ester and in the form of methanol.

FIG. 16 shows the interlayer structure obtained in Example 10.
The results of thermal analysis of the compound (2-propanol) are shown.
You. About 19.6% by weight of the weight loss on the low temperature side
Attributed to 2-propanol present in
About 6.6% by weight of the weight loss on the hot side
It is attributed to the combustion of 2-propanol which has a ter bond.
Conceivable. Overall weight loss is about 26.2% by weight
Met. 2-propanol prepared in Example 10
Analysis values of intercalation compounds intercalated with
(V: 24.3% by weight, P: 15.9% by weight, O: 4
0.2% by weight, H: 3.5% by weight, C: 16.2% by weight
%), The VO (C₃H ₇OP)
_0.13(HOP)_0.87O₃・ 0.92 (C₃H₇
OH). 2-propanol due to weight loss on low temperature side
[0.92 (C₃H₇OH)] and [VO (C
₃H₇OP)_0.13(HOP)_0.87O₃]become
The theoretical value of the weight loss is 25.0% by weight,
Although slightly different from the above measured value of about 19.6% by weight,
It is the same as above, and the values are almost the same.
No. This is because the weight loss on the low temperature side exists between the two layers.
Support the above assumption that it is due to lopanol
It is Ester bond due to weight loss on high temperature side
Burning 2-propanol [VOPO₄]
If so, the theoretical value of the weight loss is 6.4% by weight.
This corresponds to the above measured value of about 6.6% by weight. this is,
Monoalcohol whose weight loss on the high temperature side is ester-bonded
Support for the above assumption that it is due to combustion of fuel
Things. The weight loss on the low temperature side is based on the endothermic reaction.
On the other hand, the weight loss on the high temperature side is based on the exothermic reaction.
It was a spider. From the above, the intercalation compound
Thus, 2-propanol is in the form of a phosphate ester and
Intercalated between layers in the form of propanol
It is said. Also, the detailed structure is currently unknown
However, the 2-propanol estimated above
Considering the structural formula of the callated intercalation compound,
In the intercalation compound, vanadyl hydrogen phosphate 0.5 water
Japanese [[VO) (HOP) O₃・ 0.5H₂O] Layering
H present in the compound₂All of O are replaced by 2-propanol
And more 2-propanol is introduced between the layers.
It is estimated to be tarcalating.

FIG. 17 shows the interlayer structure obtained in Example 11.
The results of thermal analysis of the compound (2-butanol) are shown.
You. Approximately 27% by weight of the weight loss at the low temperature side is between layers.
Is believed to be due to existing 2-butanol,
Approximately 6.2% by weight of the weight loss on the high temperature side is esterified.
Attributed to the combustion of 2-butanol
You. The overall weight loss was about 33.2% by weight.
Was. The 2-butanol produced in Example 11
Elemental analysis value (V: 2)
1.0% by weight, P: 13.7% by weight, O: 39.9% by weight
%, H: 4.8% by weight, C: 20.7% by weight)
By estimating the equation, VO (C₄H₉OP)_{0. 10}(HO
P)_0.90O₃・ 0.95 (C₄H₉OH).
2-butanol [0.95 (C
₄H₉OH)] and [VO (C ₄H₉OP)
_0.10(HOP)_0.90O₃]
The theoretical value of the decrease is 29.7% by weight, and the measured value
Slightly different from about 27% by weight, which is the same as above.
Therefore, it can be considered that both values are almost the same. This is low
Weight loss on warm side due to 2-butanol present between layers
Support the above assumption that
2-buta-ester linked by weight loss on high temperature side
Nol burns and [VOPO₄] If it becomes
The theoretical value of a small amount is 6.1% by weight, and the above measured value is approximately
6.2% by weight. This is because the weight loss on the hot side
Due to the burning of monoalcohols with ester bonds
This supports the above assumption that it is. Ma
In addition, the weight loss on the low temperature side is based on the endothermic reaction.
On the other hand, the weight loss on the high temperature side was based on an exothermic reaction.
From the above, in the intercalation compound, 2-butanol
Is in the form of phosphate esters and 2-butanol
It is said that the layers are intercalated. Also, 2-
Butanol intercalated intercalation compound
Also, the above 2-propanol is intercalated
Vanadyl hydrogen phosphate
H present in the hemihydrate layered compound₂O is 2-
Substituted with butanol, and more 2-butanol
Presumably intercalated between layers.

FIG. 18 shows the interlayer structure obtained in Example 12.
Of the thermal analysis of the compound (cyclohexanol)
Show. About 12.1% by weight of the weight loss on the low temperature side
Due to intervening cyclohexanol and water
About 9.8 times the weight loss on the high temperature side
Amount% is combustion of cyclohexanol with ester bond
It is thought to be caused by Overall weight loss is about 2
It was 1.9% by weight. The material produced in Example 12
Intercalation compounds in which rohexanol is intercalated
Elemental analysis value (V: 24.9% by weight, P: 16.1 weight)
%, O: 42.6% by weight, H: 2.9% by weight, C: 1
When the structural formula is estimated from 3.5% by weight, VO (C₆H
₁₁OP)_0.12(HOP)_0.88O₃・ 0.26
(C₆H ₁₁OH) .0.24 (H₂O). low temperature
Cyclohexanol and water [0.2
6 (C₆H₁₁OH) .0.24 (H₂O)]
[VO (C₆H₁₁OP)_0.12(HOP)
_0.88O₃], The theoretical value of the weight loss is 1
4.9% by weight, which is about 12.1% by weight of the actually measured value.
Although slightly different, this is the same as above, and both values are almost
It may be considered that they match. This is because the weight loss on the low temperature side
Due to cyclohexanol and water present between the layers
This supports the above assumption that High temperature side
-Linked cyclohexano due to weight loss of
Burns [VOPO₄] If it becomes
The theoretical value of the amount is 9.8% by weight, which is approximately 9.
8% by weight. This is due to the weight loss on the hot side.
Caused by burning of mono-alcohols with tell bonds
This supports the above assumption that Also low
The weight loss on the warm side is based on an endothermic reaction, while
The weight loss on the warm side was due to an exothermic reaction. More than
Therefore, in the intercalation compound, cyclohexanol
Is the phosphate ester form and the cyclohexanol form
Is said to intercalate between layers.

FIG. 19 shows the interlayer structure obtained in Example 13.
Of the thermal analysis of the compound (cyclopentanol)
Show. About 9.8% by weight of the weight loss on the low temperature side is between layers
Due to cyclopentanol and water present in
Approximately 10.1 weight loss on the high temperature side
Amount% is combustion of cyclopentanol with ester bond
It is thought to be caused by Overall weight loss is about 1
It was 9.9% by weight. The material prepared in Example 13
Intercalation compounds with intercalated lopentanol
Elemental analysis value (V: 25.4% by weight, P: 15.7 weight)
%, O: 39.4% by weight, H: 2.8% by weight, C: 1
6.7% by weight), the VO (C₅H
₉OP)_0.16(HOP)_0.74O₃・ 0.3 (C
₅H₉OH) .0.2 (H₂O). Cold side weight
Cyclopentanol and water [0.3 (C₅H
₉OH) .0.2 (H₂O)] and [VO (C₅
H ₉OP)_0.16(HOP)_0.74O₃]To become and
Then the theoretical value of weight loss is 14.5% by weight,
The measured value is slightly different from the measured value of about 9.8% by weight.
It is considered the same, and the values are almost the same.
No. Ester bonded by weight loss on high temperature side
Lopentanol burns [VOPO₄]
If the theoretical value of the weight loss is 9.8% by weight,
This is almost the same as the measured value of about 10.1% by weight. Also, the low temperature side
Weight loss is based on an endothermic reaction, while
Weight loss was due to an exothermic reaction. Is that more
In the intercalation compound, cyclopentanol is phosphorus.
Interlayer in the form of acid ester and cyclopentanol
Is said to be intercalated.

From the above, it was found that the form of the monoalcohol in the intercalation compound of the present invention exists in two types, a phosphate ester and an alcohol. Further, the intercalation compound of the present invention is (VO) (HOP) O ₃ .0.5H
The _diphosphate ester whole or part of monoalcohols POH in O _POC x _{H y,} it has a structure in which all or part of 0.5H ₂ O is replaced by monoalcohol _C x _H y OH Do you get it.

[0071]

According to the present invention, a secondary aliphatic monoalcohol, an alicyclic monoalcohol or an aromatic monoalcohol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen. And a novel method for quickly and easily producing an intercalation compound in which a monoalcohol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen.

[Brief description of the drawings]

FIG. 1 shows an X-ray diffraction pattern of an intercalation compound obtained in Examples 1 and 2.

FIG. 2 shows X-ray diffraction patterns of the intercalation compounds obtained in Examples 4 to 8 and Comparative Example 1.

FIG. 3 shows an X-ray diffraction pattern of the intercalation compound obtained in Example 9.

FIG. 4 shows X-ray diffraction patterns of the intercalation compounds obtained in Examples 10 to 11.

FIG. 5 shows X-ray diffraction patterns of the intercalation compounds obtained in Examples 12 and 13.

FIG. 6 shows the relationship between the number of carbon atoms of the monoalcohol and the layer interval in the intercalation compound of the present invention.

FIG. 7 shows the relationship between the molecular size of monoalcohol and the layer interval in the intercalation compound of the present invention.

FIG. 8 shows infrared absorption spectra of VOHPO ₄ .0.5H ₂ O and the intercalation compound produced in Example 4.

FIG. 9 shows an infrared absorption spectrum of the intercalation compound produced in Example 1.

FIG. 10 shows an infrared absorption spectrum of the intercalation compound produced in Example 10.

FIG. 11 shows an infrared absorption spectrum of the intercalation compound produced in Example 11.

FIG. 12 shows an infrared absorption spectrum of the intercalation compound produced in Example 12.

FIG. 13 shows an infrared absorption spectrum of the intercalation compound produced in Example 13.

FIG. 14 is a view showing the relationship between the heating temperature and the weight loss of the intercalation compound produced in Example 1.

FIG. 15 is a graph showing the relationship between the heating temperature and the weight loss of the intercalation compound produced in Example 4.

FIG. 16 is a view showing the relationship between the heating temperature and the weight loss of the intercalation compound produced in Example 10.

FIG. 17 is a view showing the relationship between the heating temperature and the weight loss of the intercalation compound produced in Example 11.

FIG. 18 is a view showing the relationship between the heating temperature and the weight loss of the intercalation compound produced in Example 12.

FIG. 19 is a view showing the relationship between the heating temperature and the weight loss of the intercalation compound produced in Example 13.

Claims (9)

[Claims] 1. A secondary aliphatic monoalcohol between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen,
An intercalation compound in which an alicyclic monoalcohol or an aromatic monoalcohol is intercalated. 2. Vanadyl hydrogen phosphate hemihydrate [(V
O) (HOP) O ₃ .0.5H ₂ O] A part or all of the POH present in the layered compound is a phosphate POC of a secondary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol. _x H _y and part or all of H ₂ O present in the compound is replaced with a secondary aliphatic monoalcohol, alicyclic monoalcohol or aromatic monoalcohol C _x H _y OH. The intercalation compound according to claim 1, which has a structure as described above. 3. The secondary aliphatic monoalcohol is selected from secondary aliphatic monoalcohols having 3 to 8 carbon atoms, and the alicyclic monoalcohol is selected from alicyclic monoalcohols having 5 to 8 carbon atoms. 3. The intercalation compound according to claim 1, wherein the compound is selected from alcohols and the aromatic monoalcohol is selected from aromatic monoalcohols having 7 to 12 carbon atoms. 4. The method according to claim 1, wherein the secondary aliphatic monoalcohol is 2-propanol, 2-butanol, 2-pentanol or 2-propanol.
Hexanol, selected from 2-heptanol or 2-octanol, wherein the alicyclic monoalcohol is selected from cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3-methylcyclopentanol or 3-ethylcyclopentanol; 3. The intercalation compound according to claim 1, wherein the aromatic monoalcohol is selected from benzyl alcohol and 2-phenylethyl alcohol. 5. A method of reacting vanadium oxide, phosphorus pentoxide and monoalcohol having a valence of less than pentavalent and having a valence of four or more to form a monoalcohol between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen. A method for producing an intercalation compound in which is intercalated. 6. An interlayer compound in which a monoalcohol is intercalated between layers of a layered compound having a basic composition of vanadium, phosphorus and oxygen is formed of vanadyl hydrogen phosphate hemihydrate [(VO) ( _HOP) O 3 · 0.5H ₂
O] Some of POH present in layered compound or the whole has been replaced by phosphoric acid ester POC _x H _y monoalcohols, and present in the compound of H _{2 O} some or all monoalcohols C _x H _6. The method according to claim 5, wherein the method has a structure replaced with _y OH. 7. The method according to claim 5, wherein the vanadium oxide is V ₄ O ₉ . 8. The monoalcohol is a primary aliphatic monoalcohol having 1 to 12 carbon atoms, a secondary aliphatic monoalcohol having 3 to 8 carbon atoms, or an alicyclic monoalcohol having 5 to 8 carbon atoms. The method according to any one of claims 5 to 7, wherein the method is selected from alcohols and aromatic monoalcohols having 7 to 12 carbon atoms. 9. The method according to claim 9, wherein the primary aliphatic monoalcohol is methanol, ethanol, 1-propanol, 1-butanol, isobutanol, isopentanol, neopentanol, 2-methyl-1-butanol, 1-pentanol, An aliphatic ring selected from 1-hexanol or 1-octanol and the secondary aliphatic monoalcohol selected from 2-propanol, 2-butanol, 2-pentanol, 2-hexanol, 2-heptanol or 2-octanol; Group monoalcohol is cyclopentanol, cyclohexanol, 4-methylcyclohexanol, 3
9. The method according to claim 8, wherein the aromatic monoalcohol is selected from -methylcyclopentanol or 3-ethylcyclopentanol, and the aromatic monoalcohol is selected from benzyl alcohol or 2-phenylethyl alcohol.