JP4858148B2 - Solid catalyst for producing oxetane compound and process for producing the same - Google Patents

Description

  The present invention relates to a solid catalyst for producing an oxetane compound and a method for producing the same. The oxetane compound is a compound useful as a raw material for a thermosetting resin, for example.

Conventionally, as a catalyst for producing an oxetane compound, for example, calcium hydroxyapatite or partially substituted calcium hydroxyapatite in which a part of calcium is substituted with an alkali metal or the like (for example, refer to Patent Document 1), heteropolyacid or a salt thereof (for example, Patent Document 2), crystalline aluminosilicate (for example, see Patent Document 3), crystalline or non-crystalline metal oxide (for example, see Patent Document 4), and the like have been known. However, although the synthesis example of the oxetane compound using these catalysts is disclosed, the selectivity of the oxetane compound was low in any catalyst. That is, it cannot be said that the catalyst for producing oxetane compounds sufficiently fulfills its function, and there is a problem as a catalyst for industrial production of oxetane compounds.
Japanese Patent Laid-Open No. 10-158255 JP 61-126080 A Japanese Patent Laid-Open No. 3-206087 Japanese Unexamined Patent Publication No. 3-200777

  The subject of this invention is related with the solid catalyst for oxetane compound manufacture which can manufacture an oxetane compound with high selectivity.

  This is solved by a solid catalyst for producing an oxetane compound, wherein the chemical adsorption amount of ammonia is 100 μmol / g or less at 50 ° C. and the chemical adsorption amount of carbon dioxide is 100 μmol / g or less.

  The object of the present invention is also solved by a method for producing the solid catalyst for producing the oxetane compound.

  INDUSTRIAL APPLICABILITY According to the present invention, an industrially suitable solid catalyst for producing an oxetane compound capable of producing an oxetane compound useful as a raw material for a thermosetting resin or the like with a high selectivity and a production method thereof can be provided.

  The solid catalyst for producing an oxetane compound according to the present invention is characterized in that, at 50 ° C., the chemisorption amount of ammonia is 100 μmol / g or less and the chemisorption amount of carbon dioxide is 100 μmol / g or less. .

The measurement of the amount of chemisorption of ammonia and carbon dioxide can be performed, for example, by the following procedure.
(1) The solid catalyst is kept at 50 ° C. with a heater or the like, gradually exposed to ammonia or carbon dioxide from a high vacuum state, and the amount of adsorption is measured. Including both physical adsorption).
(2) Next, the solid catalyst is placed in a high vacuum, and after only the physically adsorbed ammonia or carbon dioxide is completely removed, it is exposed again to ammonia or carbon dioxide as it is. Corresponding to the adsorption isotherm).
(3) A chemical adsorption isotherm is obtained by the difference between the total adsorption isotherm (first adsorption isotherm; including both chemical adsorption and physical adsorption) and the physical adsorption isotherm.
(4) Since the chemisorption isotherm is almost a straight line, by extrapolating this to P = 0 of the chemisorption isotherm, the amount of ammonia or carbon dioxide chemisorbed on the solid catalyst in a monomolecular layer ( Recognize the amount of chemisorption.

  When measuring the amount of chemical adsorption of ammonia and carbon dioxide, the solid catalyst is preliminarily adsorbed to the solid catalyst by heat treatment, vacuum evacuation treatment, or a combination thereof. It is desirable to perform a pretreatment for desorbing the substance. The pretreatment may be appropriately selected in consideration of the properties of the catalyst, and examples thereof include heat treatment, vacuum exhaust treatment, and a method combining them. Processing conditions such as heating temperature, degree of vacuum and time are not particularly limited as long as the properties of the solid catalyst are not impaired.

  The solid catalyst for producing an oxetane compound of the present invention is preferably a catalyst in which an alkali metal compound is supported on a carrier. Examples of the alkali metal include lithium, sodium, potassium, cesium and the like. In addition, these alkali metals may be carried alone or in combination of two or more. In addition, these alkali metals are supported on a carrier, for example, in the form of nitrate, carbonate, hydroxide, oxide, chloride, acetate, oxalate or the like, using the solid catalyst as an alkali metal supply source. Used in preparation.

  The amount of the alkali metal supported on the carrier is preferably 0.01 to 2 g, more preferably 0.02 to 0.2 g, relative to 1 g of the carrier.

  The solid catalyst for producing an oxetane compound of the present invention is preferably one in which a phosphorus compound is supported on a carrier in addition to the alkali metal. The support of phosphorus on the carrier is used, for example, when preparing the solid catalyst using phosphoric acid (including an aqueous solution thereof) or an alkali metal salt thereof (including an aqueous solution thereof) as a phosphorus supply source.

  The amount of the phosphorus supported on the carrier is preferably 0.001 to 1 g, more preferably 0.005 to 2 g, relative to 1 g of the carrier.

  The carrier of the solid catalyst for producing the oxetane compound of the present invention is not particularly limited as long as it does not inhibit the reaction. For example, at least one carrier comprising silica, alumina, silica alumina, zirconia, zeolite and activated carbon is preferably used. used.

  The solid catalyst for producing the oxetane compound of the present invention is produced, for example, by adding an alkali metal source, water, a carrier and, if necessary, a phosphorus source, evaporating water to dryness, and calcining. The firing temperature at that time is preferably 200 to 1000 ° C., more preferably 400 to 800 ° C., and the pressure is not particularly limited. Also, the firing atmosphere is not particularly limited, but is preferably performed in the presence of oxygen (for example, in air).

  The shape of the solid catalyst may be either a powder or a molded body, and can be appropriately selected according to the reaction method and the shape of the reactor. For example, a spherical shape, a cylindrical shape, a granular shape, etc. are suitable for a molded body. Used for.

  Next, although an Example and a comparative example are given and this invention is demonstrated concretely, the scope of the present invention is not limited to these. In addition, the chemical adsorption amount of ammonia and carbon dioxide was measured using a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C type (manufactured by Yuasa Ionics). In the Reference Example, trimethylolpropane and 3-ethyl-3-hydroxymethyloxetane (oxetane compound) were analyzed by gas chromatography, and the selectivity (mol%) of the oxetane compound was generated relative to the converted trimethylolpropane. It calculated | required by the ratio (mol ratio) of 3-ethyl-3-hydroxymethyl oxetane.

Example 1 (Catalyst A; Production of cesium-phosphorus-oxygen / silica (Cs-PO / SiO ₂ ))
To a glass flask, 5.2 g of cesium nitrate and 20 g of ion exchange water were added and stirred to obtain an aqueous cesium nitrate solution. Next, after adding the above cesium nitrate aqueous solution to 16 g of amorphous silica (particle size: 10 to 20 mesh), phosphoric acid aqueous solution (prepared by adding 10 g of ion-exchanged water to 2.5 g of 85% phosphoric acid aqueous solution) Was added. The resulting aqueous solution was evaporated to dryness and then calcined in air at 600 ° C. for 2 hours to obtain Catalyst A.

Example 2 (Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst A)
1.5 g of catalyst A was put into a glass sample cell and heated at 380 ° C. for 2 hours at 4 Pa or less (pretreatment). Next, in order to perform the chemical adsorption amount measurement of ammonia, the pretreated catalyst A is installed in a high-performance, fully automatic gas adsorption amount measuring device Autosorb-1-C type (manufactured by Yuasa Ionics Co., Ltd.) as a sample cell. did.
The solid catalyst is kept at 50 ° C. with a heater, and ammonia gas is gradually introduced from the vacuum state into the sample cell, and the adsorption amount (that is, the chemical adsorption amount and the total adsorption point) is 20 points from the absolute pressure 5.3 kPa to 5.3 kPa at 106.7 kPa. Measure the total adsorption amount) (measurement temperature: 50 ° C, thermal equilibrium time: 60 minutes, pressure tolerance: 4, adsorption equilibrium time: 2 minutes), and determine the total adsorption isotherm (chemical adsorption and physical adsorption) Including both).
Then, the ammonia that was physically adsorbed was removed by evacuating in a high vacuum, and the adsorbed amount (that is, the physical adsorbed amount) was measured at a total of 20 points from absolute pressure 5.3 kPa to 106.7 kPa at intervals of 5.3 kPa. Created a line. A chemical adsorption isotherm was created from the difference between the total adsorption amount and the physical adsorption amount, and extrapolated to P = 0. As a result, the ammonia chemisorption amount of catalyst A was 6 μmol / g.
Further, the amount of chemical adsorption of carbon dioxide was measured by changing the adsorption gas from ammonia gas to carbon dioxide. As a result, the amount of carbon dioxide chemisorption was 1 μmol / g or less.

Reference Example 1 (Synthesis of 3-ethyl-3-hydroxymethyloxetane with catalyst A)
A Pyrex (registered trademark) glass vertical reaction tube having an inner diameter of 7 mm was filled with 1 ml of catalyst A, and 8 g of glass beads with a diameter of 2 mm were filled in the upper layer. Next, after the catalyst layer temperature was maintained at 350 ° C., a 5 mass% trimethylolpropane aqueous solution was supplied from above the reaction tube with a metering pump at a flow rate of 2.9 g / h while bubbling argon at 5 ml per minute. As a result of collecting and analyzing the reaction liquid for 1 to 5 hours (total 4 hours) from the start of the supply, the conversion of trimethylolpropane was 12.1 mol%, and the selectivity for 3-ethyl-3-hydroxymethyloxetane was 82.7. mol%.

Example 3 (Catalyst B; Production of sodium-phosphorus-oxygen / silica (Na-PO / SiO ₂ ))
A catalyst was produced in the same manner as in Example 1 except that cesium nitrate was changed to 2.3 g of sodium nitrate in Example 1 (Catalyst B).

Example 4 (Measurement of chemisorption amounts of ammonia and carbon dioxide of catalyst B)
In Example 2, the amount of chemical adsorption was measured in the same manner as in Example 2 except that the catalyst A was changed to the catalyst B. As a result, the chemisorption amount of ammonia was 11 μmol / g, and the chemisorption amount of carbon dioxide was 1 μmol / g or less.

Reference Example 2 (Synthesis of 3-ethyl-3-hydroxymethyloxetane with catalyst B)
In Reference Example 1, the reaction was performed in the same manner as Reference Example 1 except that Catalyst A was changed to Catalyst B. As a result, the conversion of trimethylolpropane was 11.4 mol%, and the selectivity for 3-ethyl-3-hydroxymethyloxetane was 50.6 mol%.

Example 5 (Catalyst C; sodium - production of oxygen / silica _{(Na-O / SiO 2)} )
A catalyst was produced in the same manner as in Example 1 except that phosphoric acid was not added (Catalyst C).

Example 5 (Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst C)
In Example 2, the amount of chemical adsorption was measured in the same manner as in Example 2 except that the catalyst A was changed to the catalyst C. As a result, the chemisorption amount of ammonia was 8 μmol / g, and the chemisorption amount of carbon dioxide was 15 μmol / g.

Reference Example 3 (Synthesis of 3-ethyl-3-hydroxymethyloxetane with catalyst C)
In Reference Example 1, the reaction was performed in the same manner as Reference Example 1 except that Catalyst A was changed to Catalyst C. As a result, the conversion of trimethylolpropane was 12.8 mol%, and the selectivity for 3-ethyl-3-hydroxymethyloxetane was 66.3 mol%.

Comparative Example 1 (Catalyst X; Production of Phosphorus -Oxygen / Silica (P / SiO ₂ ))
In Example 1, a catalyst was produced in the same manner as in Example 1 except that 10 g of ion-exchanged water was added without adding cesium nitrate (Catalyst X).

Comparative Example 2 (Measurement of chemisorption amount of ammonia and carbon dioxide of catalyst X)
In Example 2, the amount of chemical adsorption was measured in the same manner as in Example 2 except that the catalyst A was changed to the catalyst X. As a result, the chemisorption amount of ammonia was 278 μmol / g, and the chemisorption amount of carbon dioxide was 1 μmol / g or less.

Reference Example 4 (Synthesis of 3-ethyl-3-hydroxymethyloxetane with catalyst X)
In Reference Example 2, the reaction was performed in the same manner as Reference Example 2 except that the catalyst A was changed to the catalyst X. As a result, the conversion rate of trimethylolpropane was 25.7 mol%, but formation of 3-ethyl-3-hydroxymethyloxetane was not confirmed.

Comparative Example 3 (Ammonia and carbon dioxide chemisorption measurements of γ-alumina (NST-7; manufactured by JGC Universal))
In Example 2, the amount of chemical adsorption was measured in the same manner as in Example 2 except that the catalyst A was changed to γ-alumina (NST-7; manufactured by JGC Universal). As a result, the chemisorption amount of ammonia was 477 μmol / g, and the chemisorption amount of carbon dioxide was 104 μmol / g or less.

Reference Example 5 (Synthesis of 3-ethyl-3-hydroxymethyloxetane using γ-alumina (NST-7; manufactured by JGC Universal))
In Reference Example 2, the reaction was performed in the same manner as in Reference Example 2 except that the catalyst A was changed to γ-alumina (NST-7; manufactured by JGC Universal). As a result, the conversion rate of trimethylolpropane was 100 mol%, but formation of 3-ethyl-3-hydroxymethyloxetane was not confirmed.

Comparative Example 4 (Ammonia and carbon dioxide chemisorption measurements of zirconium oxide (XZ16052; manufactured by NORTON))
In Example 2, the amount of chemical adsorption was measured in the same manner as in Example 2 except that the catalyst A was changed to zirconium oxide (XZ16052; manufactured by NORTON). As a result, the chemisorption amount of ammonia was 376 μmol / g, and the chemisorption amount of carbon dioxide was 276 μmol / g.

Reference Example 6 (Synthesis of 3-ethyl-3-hydroxymethyloxetane with zirconium oxide (XZ16052; manufactured by NORTON))
In Reference Example 2, the reaction was performed in the same manner as in Reference Example 2 except that the catalyst A was changed to zirconium oxide (XZ16052; manufactured by NORTON). As a result, the conversion rate of trimethylolpropane was 100 mol%, but formation of 3-ethyl-3-hydroxymethyloxetane was not confirmed.

Comparative Example 5 (Ammonia and carbon dioxide chemisorption measurements of NaY-type zeolite (320NAA; manufactured by Tosoh Corporation))
In Example 2, the amount of chemical adsorption was measured in the same manner as in Example 2 except that the catalyst A was changed to NaY-type zeolite (320NAA; manufactured by Tosoh Corporation). As a result, the chemisorption amount of ammonia was 2596 μmol / g, and the chemisorption amount of carbon dioxide was 3 μmol / g.

Reference Example 7 (Synthesis of 3-ethyl-3-hydroxymethyloxetane with NaY-type zeolite (320NAA; manufactured by Tosoh Corporation))
In Reference Example 2, the reaction was performed in the same manner as in Reference Example 2 except that the catalyst A was changed to NaY-type zeolite (320NAA; manufactured by Tosoh Corporation). As a result, the conversion rate of trimethylolpropane was 100 mol%, but formation of 3-ethyl-3-hydroxymethyloxetane was not confirmed.

  INDUSTRIAL APPLICABILITY According to the present invention, an industrially suitable solid catalyst for producing an oxetane compound capable of producing an oxetane compound useful as a raw material for a thermosetting resin or the like with a high selectivity and a production method thereof can be provided.

Claims (6)

A catalyst in which an alkali metal compound is supported on a support used in a reaction for producing an oxetane compound by dehydrating trimethylolalkane, and at 50 ° C., the chemical adsorption amount of ammonia is 100 μmol / g or less, and A solid catalyst for producing an oxetane compound, wherein a chemical adsorption amount of carbon dioxide is 100 μmol / g or less. The solid catalyst for producing an oxetane compound according to claim 1, wherein the solid catalyst for producing an oxetane compound further comprises a phosphoric acid compound supported on a carrier. The solid catalyst for producing an oxetane compound according to claim 1 or 2 , wherein the carrier of the solid catalyst for producing an oxetane compound is at least one carrier comprising silica, alumina, silica alumina, zirconia, zeolite and activated carbon. The method for producing a solid catalyst for producing an oxetane compound according to claim 1 or 3 , wherein an alkali metal supply source, water and a carrier are added, water is evaporated to dryness, and then calcined. The method for producing a solid catalyst for producing an oxetane compound according to claim 2 or 3 , wherein an alkali metal supply source, water, a carrier and a phosphorus supply source are added, the water is evaporated to dryness, and then calcined. Oxetane compound 3-alkyl-3-hydroxymethyl-oxetane and is claims 1 to 3, wherein the oxetane compound for producing a solid catalyst.