JP2015030677A - Polyol-ether compound production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently producing a polyol-ether compound.SOLUTION: A compound represented by the specified general formula (1) is subjected to hydrogenation reduction in the presence of a hydrogenation catalyst to obtain at least one polyol-ether compound selected from the group consisting of compounds represented by the specified general formula (4) and the like.

Description

  The present invention relates to a process for producing a polyol-ether compound.

  Various polyol-ether compounds having a plurality of hydroxyl groups and ether bonds in the molecule have been synthesized and widely used industrially. Among them, di-trimethylolpropane, di-pentaerythritol, etc. are produced as those having at least 3 primary hydroxyl groups and ether bonds, and these are important compounds whose demand has been increasing in recent years. is there.

  By the way, as a method for producing a polyol-ether compound, a reaction in which a spiro compound having two 1,3-dioxane skeletons in a molecule is reductively opened by a hydrogenation catalyst is known. A simple manufacturing method is disclosed. That is, in Example of Patent Document 1, hydrogenation reduction using a copper chromite catalyst was performed to 1,7-di-phenyl-4,4-dihydroxymethyl-2,6-dioxa-n from pentaerythritol-bis-benzaldehyde acetal. The method for preparing heptane (Example 14) is also obtained from pentaerythritol-bis-acetophenone ketal from 1,7-di-methyl-1,7-di-phenyl-4,4-dihydroxymethyl-2,6-dioxa A method for producing n-heptane (Example 15) is disclosed.

German patent 1196174

  Di-trimethylolpropane, which is a typical polyol-ether compound having three or more primary hydroxyl groups and an ether bond, is a byproduct from a trimethylolpropane production plant, and di-pentaerythritol is a byproduct from the pentaerythritol production plant. For this reason, there has been a demand for a method for producing a polyol-ether compound that cannot be produced alone and does not depend on the production amount of other compounds.

  Patent Document 1 discloses a method of hydrogenating and reducing a pentaerythritol-bis-acetal compound or a pentaerythritol-bis-ketal compound as a spiro compound having two 1,3-dioxane skeletons in the molecule. However, only a polyol-ether compound having two primary hydroxyl groups and an ether bond can be obtained by this method. That is, only a method for producing a polyol-ether compound having two hydroxyl groups by hydrogenating a spiro compound not containing a hydroxyl group is disclosed. Any mention or suggestion of a polyol-ether compound that has at least one primary hydroxyl group and two 1,3-dioxane skeletons in the molecule and hydrogenates a spiro compound having at least three primary hydroxyl groups and an ether bond. Not allowed at all.

  An object of the present invention is to solve the above-mentioned problems in the prior art and to provide a method for efficiently producing a polyol-ether compound.

This inventor repeated earnest research about the method of manufacturing a polyol-ether compound efficiently. As a result, the inventors have found a method for efficiently producing a polyol-ether compound by hydrogenating a specific cyclic acetal compound in the presence of a hydrogenation catalyst, and reached the present invention.
That is, the present invention is as follows.
[1]
By hydrogenating and reducing the compound represented by the following general formula (1) in the presence of a hydrogenation catalyst, the compound selected from the group consisting of the compounds represented by the following general formulas (2), (3) and (4) A process for producing a polyol-ether compound to obtain at least one polyol-ether compound.
(In Formula (1) to Formula (4), R ¹ , R ² , R ³ , and R ⁴ may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms.)
[2]
The production method according to [1], wherein R ¹ and R ² are methyl groups.
[3]
The production method according to [1] or [2], wherein R ³ and R ⁴ are methyl groups.
[4]
The production method according to any one of [1] to [3], wherein the compound represented by the general formula (1) is hydrogen-reduced in a system including an ether compound as a reaction solvent.
[5]
The process according to any one of [1] to [4], wherein the hydrogenation catalyst is a solid catalyst containing palladium.
[6]
The said hydrogenation catalyst is a manufacturing method as described in any one of [1]-[5] which is a solid catalyst containing a zirconium compound.

  By the production method of the present invention, a polyol-ether compound having both at least three primary hydroxyl groups and an ether bond can be efficiently produced.

Hereinafter, an embodiment of the present invention (hereinafter simply referred to as “the present embodiment”) will be described. In addition, the following this embodiment is an illustration for demonstrating this invention, and this invention is not limited only to this this embodiment. In the method for producing a polyol-ether compound of the present embodiment, the compound represented by the following general formula (1) is hydroreduced in the presence of a hydrogenation catalyst to thereby produce the following general formulas (2), (3) and At least one polyol-ether compound selected from the group consisting of compounds represented by (4) is obtained.
Here, in the formulas (1), (2), (3) and (4), R ¹ , R ² , R ³ and R ⁴ may be the same or different and are each a straight chain having 1 to 6 carbon atoms. Or represents a branched alkyl group. The compounds of formulas (2) and (3) have multiple geometric isomers. Further, when R ¹ and R ² are different from each other, or R ³ and R ⁴ are different from each other, the compounds of formulas (1), (2), (3) and (4) have a plurality of optical isomers. Exists.

<Raw compound>
The compound used as a raw material in the method for producing the polyol-ether compound of the present embodiment (hereinafter also simply referred to as “production method”) is a spiro compound having two 1,3-dioxane skeletons represented by the above general formula (1). (Hereinafter referred to as “compound (1)”).
There is no restriction | limiting in particular in the synthesis | combination raw material of a compound (1) used for this embodiment, a manufacturing method, etc., The thing manufactured by the conventionally well-known method can be used. The simplest and most efficient method for producing the compound (1) is a method in which 3-hydroxy-2,2-disubstituted propionaldehyde and pentaerythritol are subjected to dehydration cyclization with an acid catalyst or the like. In addition, a production method by acetal exchange reaction of pentaerythritol and 3-hydroxy-2,2-disubstituted propionaldehyde with a lower alcohol acetal may be used.

As 3-hydroxy-2,2-disubstituted-propionaldehyde that can be employed when 3-hydroxy-2,2-disubstituted-propionaldehyde and pentaerythritol are subjected to dehydration cyclization to produce compound (1), For example,
3-hydroxy-2,2-dimethyl-propionaldehyde,
3-hydroxy-2,2-diethyl-propionaldehyde,
3-hydroxy-2-methyl-2-ethyl-propionaldehyde,
3-hydroxy-2-methyl-2-propyl-propionaldehyde,
3-hydroxy-2-methyl-2-butyl-propionaldehyde,
3-hydroxy-2-ethyl-2-butyl-propionaldehyde,
3-hydroxy-2-propyl-2-pentyl-propionaldehyde,
And 3-hydroxy-2-methyl-2-hexyl-propionaldehyde. The substituent bonded to the carbon atom at the 2-position of the propionaldehyde skeleton corresponds to R ¹ , R ² , R ³ and R ⁴ in the general formula (1).

If there is only one kind of 3-hydroxy-2,2-disubstituted propionaldehyde used here, the compound (1) becomes a compound of the following general formula (5).
Here, in formula (5), R ¹ , R ² , R ³ and R ⁴ are the same as in formula (1).

When a plurality of 3-hydroxy-2,2-disubstituted propionaldehydes are reacted with pentaerythritol simultaneously or sequentially, a mixture of a plurality of compounds (1) is obtained. These may be isolated into a single compound (1) using a conventionally known separation method, or may be used in a hydrogenation reaction as a mixture.
Furthermore, two or more compounds (1) synthesized alone may be mixed and used as a raw material, and the combination and mixing ratio in that case are not particularly limited.

Examples of R ¹ , R ² , R ³ and R ^{4 in the} general formula (1) include a methyl group, an ethyl group, an n-propyl group, a 1-methylethyl group (isopropyl group), an n-butyl group, 1 -Methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group (tert-butyl group), n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group (neopentyl group), n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl Group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethyl Butyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group And 1-ethyl-2-methylpropyl group.

Among the polyol-ether compounds of the present embodiment, combinations of R ¹ and R ² and combinations of R ³ and R ⁴ are shown in the following table as compounds represented by general formulas (2) to (4). The compound which is a thing is mentioned.
Moreover, the compounds of general formulas (2) to (4) may be referred to as compounds (2) to (4), respectively.
Of the compounds of the general formulas (2) to (4) represented by the above table, the combinations of R ¹ and R ^{2 and} the combinations of R ³ and R ⁴ are shown in the following table.
Of the compounds of the general formulas (2) to (4) represented by the above table, the combinations of R ¹ and R ^{2 and} the combinations of R ³ and R ⁴ are shown in the following table for particularly preferable ones. .

  The polyol-ether compound obtained by hydrogen reduction of the compound (1) has at least three or more primary hydroxyl groups and ether bonds in the molecule, and can be used as industrial raw materials such as resins, paints and adhesives.

<Hydrogenation catalyst>
As an effective component of the hydrogenation catalyst used in the present embodiment, a metal element having a catalytic hydrogenation ability (hereinafter referred to as “specific metal component”) may be mentioned. Examples of the specific metal component include nickel, cobalt, iron, ruthenium, rhodium, palladium, platinum, iridium, copper, silver, molybdenum, tungsten, chromium, and rhenium. The specific metal component may be in a metal state or a cation state as long as it exhibits hydrogenation ability.
Among these, since the metal state generally has a higher hydrogenation ability and is stable in a reducing atmosphere, it is preferably in the metal state. A specific metal component can be used in the state contained in the solid catalyst individually by 1 type or in combination of 2 or more types. When using 2 or more types of specific metal components, there is no restriction | limiting in particular about those combination, a mixing ratio, and a form, It can use in forms, such as a mixture of each metal, or an alloy or an intermetallic compound.
In this embodiment, the hydrogenation catalyst is preferably a solid catalyst containing at least one specific metal component selected from the group consisting of palladium, platinum, nickel and copper, and particularly preferably a solid containing palladium as the specific metal component. It is a catalyst.

  There is no restriction | limiting in particular in the raw material of these specific metal components, What is used as a raw material when preparing a catalyst by a conventionally well-known method is employable. Examples of such raw materials include hydroxides, oxides, fluorides, chlorides, bromides, iodides, sulfates, nitrates, acetates, ammine complexes, and carbonyl complexes of the respective metal elements. These are used singly or in combination of two or more.

  The hydrogenation catalyst of this embodiment can also use a specific metal component as a metal component alone or in combination with a metal that does not have catalytic hydrogenation ability. As an example of using a specific metal component alone, as an example of combining a catalyst such as palladium black and platinum black composed of metal fine powder of a specific metal component, a specific metal component and a metal having no catalytic hydrogenation ability, And a sponge catalyst prepared by forming an alloy from a specific metal component, aluminum, and a small amount of an additive, and then leaching all or part of the aluminum.

In order to further improve the activity, selectivity, physical properties, etc. of the catalyst, at least one element selected from an alkali metal element, an alkaline earth metal element and a halogen element is used as a specific additive component, and the above-mentioned specific metal It can also be used by adding to the catalyst together with the components.
The alkali metal element is selected from lithium, sodium, potassium, rubidium and cesium, the alkaline earth metal element is selected from magnesium, calcium, strontium and barium, and halogen elements are fluorine, chlorine, bromine and iodine. You can choose.
One or more elements selected from mercury, lead, bismuth, tin, tellurium and antimony may be added to the specific additive component as an auxiliary additive element.

  There is no restriction | limiting in particular in the raw material of these specific addition components, What was used as a raw material when preparing a catalyst by a conventionally well-known method is employable. Examples of such raw materials include hydroxides, oxides, fluorides, chlorides, bromides, iodides, sulfates, nitrates, acetates, and ammine complexes of the respective metal elements. These are used singly or in combination of two or more. Moreover, there is no restriction | limiting in particular also about the addition method of a specific addition component, and the ratio of a specific addition component and a specific metal component.

  In the hydrogenation catalyst of this embodiment, a nonmetallic substance can also be used in combination with a specific metal component. Examples of non-metallic substances mainly include elemental elements, carbides, nitrides, oxides, hydroxides, sulfates, carbonates, and phosphates (hereinafter referred to as “specific nonmetallic components”). . Specific examples thereof include, for example, graphite, diamond, activated carbon, silicon carbide, silicon nitride, aluminum nitride, boron nitride, boron oxide, aluminum oxide (alumina), silicon oxide (silica), titanium oxide, zirconium oxide, hafnium oxide, Lanthanum oxide, cerium oxide, yttrium oxide, niobium oxide, magnesium silicate, calcium silicate, magnesium aluminate, calcium aluminate, zinc oxide, chromium oxide, aluminosilicate, aluminosilicate, aluminophosphate, borophosphate, magnesium phosphate , Calcium phosphate, strontium phosphate, apatite hydroxide (calcium hydroxyphosphate), apatite chloride, apatite fluoride, calcium sulfate, barium sulfate and barium carbonate And the like. A specific nonmetallic component is used individually by 1 type or in combination of 2 or more types. There are no particular restrictions on the combination, mixing ratio, and form when two or more kinds are used in combination, and they can be used in the form of a mixture of individual compounds, a complex compound, or a double salt.

  From the viewpoint of industrial use, specific non-metallic components that are simple and inexpensive are preferred. Preferred as such a specific nonmetallic component are a zirconium compound, an aluminum compound and an apatite compound, more preferably a zirconium compound and an apatite compound. Among them, particularly preferred are zirconium oxide and hydroxyapatite (calcium hydroxyphosphate). Furthermore, what modified or ion-exchanged some or all of these specific nonmetallic components using the above-mentioned specific addition component can also be used.

  In addition, carbides, nitrides, oxides, and the like of specific metal components can be used as the specific nonmetallic component. However, when these are exposed to a hydrogen reduction atmosphere, a part is reduced to a metal. In such a case, a part is used as a specific metal component and the rest is used as a non-metal component. Examples of such cases include oxides such as nickel oxide, iron oxide, cobalt oxide, molybdenum oxide, tungsten oxide, and chromium oxide.

  As the hydrogenation catalyst of the present embodiment, a specific metal component may be used alone, or a specific metal component and a specific non-metal component may be used in combination. In some cases, a specific additive component is included in addition to these. But you can. There is no restriction | limiting in particular in the manufacturing method of the hydrogenation catalyst of this embodiment, A conventionally well-known method can be used. For example, a specific metal component raw material compound is impregnated on a specific nonmetallic component (supporting method), a specific metal component raw material compound and a specific nonmetallic component raw compound are dissolved together in an appropriate solvent. Examples thereof include a method of co-precipitation using an alkali compound or the like later (coprecipitation method), a method of mixing and homogenizing a raw material compound of a specific metal component and a specific nonmetal component in an appropriate ratio (kneading method), and the like.

  Depending on the composition of the hydrogenation catalyst or the convenience of the catalyst preparation method, the specific metal component can be prepared in a cation state and then reduced to a metal state. As a reduction method and a reducing agent for that purpose, conventionally known methods can be used, and there is no particular limitation. Examples of the reducing agent include hydrogen gas, carbon monoxide gas, reducing inorganic gases such as ammonia, hydrazine, phosphine and silane, lower oxygenated compounds such as methanol, formaldehyde and formic acid, sodium borohydride and hydrogenation. Examples include hydrides such as lithium aluminum. By reducing the specific metal component in the cation state in the gas phase or liquid phase in which these reducing agents are present, the specific metal component is converted into a metal state. The reduction treatment conditions at this time can be set to suitable conditions depending on the types and amounts of the specific metal component and the reducing agent. This reduction treatment operation may be performed separately using a catalytic reduction device before the hydroreduction in the production method of the present embodiment, or before the start of the reaction in the reactor used in the production method of the present embodiment or You may carry out simultaneously with reaction operation.

  Moreover, there is no restriction | limiting in particular also in the metal content and shape of the hydrogenation catalyst of this embodiment. The shape may be powder or molded, and there is no particular limitation on the shape and molding method when molded. For example, spherical products, tablet-molded products, extrusion-molded products, and shapes obtained by crushing them into appropriate sizes can be appropriately selected and used.

A particularly preferred specific metal component is palladium, and a catalyst using this is described in detail below.
In the case where the specific metal component is palladium, considering that palladium is a noble metal, it is economically desired that the amount used is small and palladium is effectively used. Therefore, it is preferable to use palladium dispersed in a catalyst carrier, and a specific nonmetallic component can be used as the catalyst carrier.

  As the palladium compound used as a raw material of palladium, a palladium compound soluble in water or an organic solvent is suitable. Examples of such palladium compounds include palladium chloride, tetrachloropalladium salt, tetraammine palladium salt, palladium nitrate and palladium acetate. Among these, palladium chloride is preferable because of its high solubility in water or an organic solvent and easy industrial use. Palladium chloride can be used by dissolving in an aqueous sodium chloride solution, dilute hydrochloric acid, aqueous ammonia, or the like.

  Palladium or the palladium compound is immobilized on the catalyst support by adding a solution of the palladium compound to the catalyst support or by immersing the catalyst support in a solution of the palladium compound. Methods for immobilization are generally methods such as adsorption onto a support, crystallization by distilling off a solvent, and precipitation using a reducing substance and / or a basic substance that act with a palladium compound. Is used. The palladium content in the hydrogenation catalyst prepared by such a method is preferably 0.01 to 20% by mass, more preferably 0.1 to 20% by mass, based on the total amount of the hydrogenation catalyst, in terms of metal palladium. It is 10 mass%, More preferably, it is 0.5-5 mass%. When the content of palladium is 0.01% by mass or more, a sufficient hydrogenation rate is obtained, and the conversion rate of the compound (1) tends to be high. On the other hand, when the palladium content is 20% by mass or less, the dispersion efficiency in the palladium hydrogenation catalyst tends to be high, so that palladium can be used more effectively.

  Depending on the convenience of the palladium compound and the catalyst preparation method, palladium may be supported on the support in the form of a cation rather than a metal. In that case, the supported cation palladium (for example, present in the state of a palladium compound) can be used after being reduced to metallic palladium. For the reduction method and reducing agent for that purpose, conventionally known ones can be employed, and there is no particular limitation. Examples of the reducing agent include hydrogen gas, carbon monoxide gas, reducing inorganic gases such as ammonia and hydrazine, lower oxygenates such as methanol, formaldehyde and formic acid, carbonization such as ethylene, propylene, benzene and toluene. Hydrides such as hydrides, sodium borohydride and lithium aluminum hydride. Cationic palladium can be easily reduced to metallic palladium by contacting with a reducing agent in the gas phase or in the liquid phase. The reduction treatment conditions at this time can be set to suitable conditions depending on the type and amount of the reducing agent. This reduction treatment operation may be performed separately using a catalytic reduction device before the hydroreduction in the production method of the present embodiment, or before the start of the reaction in the reactor used in the production method of the present embodiment or You may carry out simultaneously with reaction operation.

As a specific nonmetallic component used together with the specific metal component of the present invention, one of the preferred non-metallic components is a zirconium compound, and a hydrogenation catalyst containing this is described in detail below.
The zirconium compound used in the present embodiment is preferably one or two kinds selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium carbonate, alkaline earth salt of zirconate, rare earth zirconate and zircon. It is a combination of the above.

  A particularly preferred zirconium compound is zirconium oxide, and the production method is not particularly limited. For example, what is known as a general method is a method in which an aqueous solution of a soluble zirconium salt is decomposed with a basic substance to form zirconium hydroxide or zirconium carbonate, and then thermally decomposed. There is no restriction | limiting in the raw material of a zirconium compound at this time, For example, a zirconium oxychloride, a zirconium oxynitrate, a zirconium chloride, a zirconium sulfate, a zirconium tetraalkoxide, a zirconium acetate, and a zirconium acetylacetonate are mentioned. These are used singly or in combination of two or more. Examples of basic substances used for decomposition include ammonia, alkylamines, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium hydroxide, potassium carbonate, and potassium hydrogen carbonate. , Magnesium hydroxide, calcium hydroxide, lanthanum hydroxide, yttrium hydroxide, and cerium hydroxide. These may be used alone or in combination of two or more.

  When zirconium oxide is used as the specific nonmetallic component, there are no particular limitations on the physical properties and shape thereof. Moreover, there is no restriction | limiting in particular also in the purity of a zirconium oxide, The thing of the purity of the general purpose to a high purity product level can be used suitably.

As a specific non-metallic component used together with the specific metal component of the present embodiment, another preferable one is an apatite compound, and a hydrogenation catalyst containing this is described in detail below.
The apatite compound used in the present embodiment has a composition of M ₁₀ (ZO ₄ ) ₆ X ₂ as described in the journal “Catalyst”, 27 (4), 237-243 (1985), for example. Examples include hexagonal compounds. Here, examples of M include calcium, strontium, aluminum, yttrium, lanthanum, and cerium. Examples of Z include phosphorus, arsenic, vanadium, and chromium. Examples of X include a hydroxyl group and a carbonate group. , Fluorine, chlorine, bromine and iodine. Any of M, Z and X may be composed of one or more of the above, within the limits of physical structure due to ionic radius and the like. Moreover, it is also known that an apatite compound has a nonstoichiometric composition, and the apatite compound of this embodiment also includes it. This non-stoichiometric composition is represented by a general formula of M _10-a (HZO ₄ ) _a (ZO ₄ ) _6-a X _2-a , and 0 <a ≦ 1.

  Among these, those in which M is calcium and Z is phosphorus are preferable. There is no restriction | limiting in particular in the manufacturing method of the apatite compound which has calcium and phosphorus, A conventionally well-known method can be used. As such a method, for example, a method in which an appropriate phosphate and calcium salt are mixed well in a stoichiometric ratio and then heated (solid phase method), a calcium cation-containing solution and a phosphate anion are contained. A method in which a solution is mixed under basic conditions to obtain a precipitate (precipitation method), and a slightly water-soluble calcium phosphate is used as a starting material, which is hydrolyzed under basic conditions and converted to apatite (hydrolysis method) ), A method of hydrothermally treating poorly water-soluble calcium phosphate in a sealed pressure vessel (hydrothermal synthesis method), and a suitable method is appropriately employed.

  Moreover, it is known that an apatite compound has anion exchange properties, and an anion exchange can be easily performed even after the portion corresponding to X described above is synthesized as an apatite compound. Calcium phosphate apatite having one or more of anions such as carbonate group, bicarbonate group, hydroxyl group, chloride and fluoride, part or all of which is exchanged with an anion different from the one used in the synthesis. Are also included in the apatite compound of this embodiment. Such an apatite compound includes, for example, a method of synthesizing calcium phosphate and bringing a solution containing chloride or fluoride ions into contact therewith, an anion contained as a part of a raw material of a specific metal component or a specific additive component. At least a part of the anions may be exchanged by a method of bringing the apatite compound used as the carrier into contact with the apatite compound during the supporting treatment of the specific metal component or the specific additive component. There are no particular limitations on the exchange raw material, concentration, treatment conditions, and the like in the ion exchange treatment at this time, and a suitable method is used as appropriate.

  When specific nonmetallic components typified by zirconium compounds and apatite compounds are used as catalyst carriers, there are no particular limitations on the physical properties such as the shape, particle size, and porosity of these carriers, and methods for loading metal components. . A shape, carrier physical properties, loading method and the like suitable for the reaction method and conditions can be appropriately selected and used.

<Hydrogenation reaction>
About the solvent used for the hydrogenation reduction of this embodiment, it may react in a solvent-free environment using only the compound (1) which is a raw material, and may use a reaction solvent. In the case of using a reaction solvent, the type and concentration are not particularly limited as long as they are inactive in the hydrogenation reduction. However, when a reaction solvent that interacts more strongly with the specific metal component in the hydrogenation catalyst than the compound (1) is used, the reaction rate may be extremely lowered or the reaction may be stopped. From such a viewpoint, for example, a compound containing phosphorus, nitrogen, and sulfur is preferably not used as a reaction solvent, but may be used as long as it does not significantly affect the reaction rate. Preferable as the reaction solvent are a saturated hydrocarbon compound, an ester compound and an ether compound, which are used alone or in combination of two or more.

Examples of the reaction solvent include saturated hydrocarbon compounds such as n-pentane, iso-pentane, n-hexane, iso-hexane, 2,2-dimethyl-butane, n-heptane, iso-heptane, 2,2,4. As trimethylpentane, n-octane, iso-octane, n-nonane and iso-nonane and isomers thereof, n-decane, n-pentadecane, cyclohexane, methylcyclohexane, dimethylcyclohexane and isomers thereof, decalin, ester compounds, Methyl acetate, ethyl acetate, butyl acetate, methyl propionate, n-methyl butyrate, n-ethyl butyrate, n-butyl butyrate, i-methyl butyrate, cyclohexyl n-butyrate, cyclohexyl i-butyrate and methyl valerate and isomers thereof , Ether compounds such as dimethyl ether, diethyl ether , Di n-propyl ether, diiso-propyl ether, di n-butyl ether, diiso-butyl ether, disec-butyl ether, methyl propyl ether, ethyl propyl ether, methyl butyl ether, methyl pentyl ether, ethyl butyl ether, propyl butyl ether, methyl Cyclopentyl ether, methyl cyclohexyl ether, ethyl cyclopentyl ether, ethyl cyclohexyl ether, propyl cyclopentyl ether, propyl cyclohexyl ether, butyl cyclopentyl ether, butyl cyclohexyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, die Lenglycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, methyltetrahydropyran, 1,4-dioxane and dimethyl-1,4-dioxane and isomers thereof Kind.
Among these reaction solvents, ether compounds are preferred, and particularly preferred are diethyl ether, di-n-propyl ether, diiso-propyl ether, di-n-butyl ether, diiso-butyl ether, methylcyclopentyl ether, methylcyclohexyl ether, ethylene glycol. Dimethyl ether, propylene glycol dimethyl ether, and 1,4-dioxane.
The concentration of the compound (1) in the raw material solution composed of the compound (1) and the reaction solvent is preferably in the range of 1 to 60% by weight. If it is 1% by weight or more, the reaction efficiency tends to be good and the economy is excellent, and if it is less than 60% by weight, the intermolecular side reaction of the compound (1) tends to occur and the selectivity does not tend to decrease.

  The reaction system for hydroreduction in this embodiment is formed from a liquid phase containing compound (1) or a reaction solvent and a reaction solvent, a gas phase of hydrogen gas, and a solid phase of a hydrogenation catalyst. There is no particular limitation as long as it is a reaction type. As the type of the reaction vessel in the hydroreduction of the present embodiment, a conventionally known type such as a tube type, a tank type, or a kettle type can be used. Moreover, the supply method of a raw material composition may be either a distribution method or a batch method. As the hydrogenation catalyst, conventionally known methods such as a fixed bed, a fluidized bed and a suspension bed can be adopted, and there is no particular limitation. In the case of the fixed bed flow system, the reaction can be performed even in a perfusion flow state and a bubbling flow state. The flow direction of the raw material liquid may be either a down flow that flows in the direction of gravity or an up flow that flows in the opposite direction, and the supply direction of the raw material gas may be either parallel flow or counter flow with respect to the raw material liquid. It may be.

  50-350 degreeC is preferable, as for the reaction temperature in the hydrogenation reduction of this embodiment, More preferably, it is 100-300 degreeC, More preferably, it is 150-280 degreeC. When the reaction temperature is 50 ° C. or higher, a higher hydrogenation rate tends to be easily obtained. When the reaction temperature is 350 ° C. or lower, side reactions involving decomposition of raw materials can be further suppressed, and the yield of the target product is further increased. Tend to be able to.

  The reaction pressure in the hydroreduction of this embodiment is preferably 0.1 to 30 MPa, more preferably 2 to 15 MPa. When the reaction pressure is 0.1 MPa or more, a higher hydrogenation rate is likely to be obtained, and the conversion rate of the compound (1) tends to be improved. When the reaction pressure is 30 MPa or less, the cost of reaction equipment is further reduced. Can be economically favorable.

  The hydrogen gas used in the hydrogenation reduction of the present embodiment does not have to be purified to a particularly high purity, and may be a quality that is usually used in an industrial hydrogenation reaction. Further, since the hydrogenation reaction is promoted depending on the hydrogen partial pressure, it is preferable that the purity of the hydrogen gas used is high. However, the hydrogen gas may be an inert gas such as helium, argon, nitrogen, and methane. You may mix. The ratio of the hydrogen gas to the compound (1) in the reaction system is the molar ratio of hydrogen gas to the compound (1) in the case of a flow reaction. Is preferably 0.1 to 300, and more preferably 0.5 to 100. When the molar ratio of hydrogen gas is 0.1 or more, the hydrogenation reaction tends to be further promoted, and when the molar ratio of hydrogen gas is 300 or less, the equipment cost for circulating and using excess hydrogen gas Tends to be kept lower.

  Hereinafter, the production method of the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples, and the gist of the present invention should not be changed.

The evaluation of the reaction results of the hydrogenation reduction was carried out by using the raw material (compound (1)), the raw material (compound (1)) in the reaction solution, and the produced polyol-ether compound (compounds (2) to (4)). It was calculated by gas chromatograph and evaluated based on the number of moles.

Conversion rate (%) of raw material acetal (compound (1)) =
100 × [1- (number of moles of raw material remaining in reaction liquid) / (number of moles of charged raw material)]

Selectivity of each produced polyol-ether compound (%) =
100 × (number of moles of target product) / [(number of moles of charged raw material) − (number of moles of raw material remaining in reaction liquid)]

However, when isomers exist in the compounds (2) and (3), a value obtained by adding the isomers was used.

The following equipment was used for the measurement of the gas chromatograph.
Apparatus: GC-2010 Shimadzu Corporation Column: DB-1 Agilent Technologies

<Carrier Preparation Example 1>
Zirconium oxide used as a carrier for the metal component was prepared by the following method.
A white precipitate was obtained by dropping 15.5 g of 28% aqueous ammonia with stirring into 505 g of an aqueous zirconium oxynitrate solution having a concentration of 25% by mass in terms of zirconium oxide (ZrO ₂ ). This was filtered, washed with ion-exchanged water, and then dried at 110 ° C. for 10 hours to obtain hydrous zirconium oxide. This is stored in a magnetic crucible, and subjected to a baking treatment at 400 ° C. for 3 hours in the air using an electric furnace, and then pulverized in an agate mortar and expressed as powdered zirconium oxide (hereinafter referred to as “carrier A”). .) The BET specific surface area of the carrier A (measured by a nitrogen adsorption method; the same applies hereinafter) was 102.7 m ² / g.

<Catalyst Preparation Example 1>
A catalyst containing palladium as a specific metal component was prepared by the following method.
0.66 mass% palladium chloride-0.44 mass% sodium chloride aqueous solution was added to 5.0 g of the carrier A, and the metal component was adsorbed on the carrier. A formaldehyde-sodium hydroxide aqueous solution was added thereto to instantaneously reduce the adsorbed metal component. Thereafter, the catalyst was washed with ion-exchanged water and dried to prepare a 1.0 mass% palladium-supported zirconium oxide catalyst (hereinafter referred to as “A1 catalyst”).

The hydrogen reduction reaction was carried out by the following method.
<Example 1>
In a 100 mL SUS reactor, 0.80 g of A1 catalyst, spiroglycol (Wako Pure Chemical Industries, 2- [9- (2-hydroxy-1,1-dimethyl-ethyl) -2, 4,8,10-tetraoxa-spiro [5.5] undec-3-yl] -2-methyl-propan-1-ol) and 24.1 g of diisopropyl ether as solvent. The inside was replaced with nitrogen gas. Thereafter, 8.5 MPa of hydrogen gas was charged into the reactor, the temperature was raised to 230 ° C., which is the reaction temperature, and the reaction was performed for 1.5 hours. Thereafter, the reactor was cooled and the contents of the reactor were collected and analyzed by gas chromatography.
As a result, the spiroglycol conversion was 48.8%, and the selectivity to the produced compound (2) and compound (4) was 22.5% and 23.7%, respectively, and the total selectivity of both Was 46.2%.
The reaction scheme in Example 1 is shown below.
In this reaction scheme, compound (2) and compound (3) are the same compound and cannot be distinguished from each other. The same applies to Example 2 below.

<Example 2>
The reaction was conducted in the same manner as in Example 1 except that 24.0 g of 1,4-dioxane was used in place of 24.1 g of diisopropyl ether, and the reaction time was changed from 1.5 hours to 6 hours. As a result, the spiroglycol conversion was 98.0%, and the selectivities to the produced compound (2) and compound (4) were 20.5% and 24.3%, respectively. Was 44.9%.

  According to the production method of the present invention, a polyol-ether compound can be produced efficiently by reducing the compound (1), which is a cyclic acetal compound, with a hydrogenation catalyst.

Claims (6)

By hydrogenating and reducing the compound represented by the following general formula (1) in the presence of a hydrogenation catalyst, the compound selected from the group consisting of the compounds represented by the following general formulas (2), (3) and (4) A process for producing a polyol-ether compound to obtain at least one polyol-ether compound.
(In Formula (1) to Formula (4), R ¹ , R ² , R ³ , and R ⁴ may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms.) The method according to claim ¹ , wherein R ¹ and R ² are methyl groups. The process according to claim 1 or 2, wherein R ³ and R ⁴ are methyl groups.   The process according to any one of claims 1 to 3, wherein the compound represented by the general formula (1) is hydrogen-reduced in a system containing an ether compound as a reaction solvent.   The manufacturing method according to claim 1, wherein the hydrogenation catalyst is a solid catalyst containing palladium.   The process according to any one of claims 1 to 5, wherein the hydrogenation catalyst is a solid catalyst containing a zirconium compound.