WO2014171511A1 - ポリオール-エーテル化合物及びその製造方法 - Google Patents
ポリオール-エーテル化合物及びその製造方法 Download PDFInfo
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- WO2014171511A1 WO2014171511A1 PCT/JP2014/060930 JP2014060930W WO2014171511A1 WO 2014171511 A1 WO2014171511 A1 WO 2014171511A1 JP 2014060930 W JP2014060930 W JP 2014060930W WO 2014171511 A1 WO2014171511 A1 WO 2014171511A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/28—Preparation of ethers by reactions not forming ether-oxygen bonds from acetals, e.g. by dealcoholysis
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/04—Saturated ethers
- C07C43/13—Saturated ethers containing hydroxy or O-metal groups
- C07C43/132—Saturated ethers containing hydroxy or O-metal groups both carbon chains being substituted by hydroxy or O-metal groups
Definitions
- the present invention relates to a polyol-ether compound and a method for producing the same.
- Patent Document 1 discloses a method for obtaining neopentyl glycol-trimethylolpropane ether from a condensation reaction with neopentylglycol by ring-opening of trimethylolpropane oxetane as a method for producing a polyol-ether compound. ing.
- Patent Document 2 (1) the aliphatic polyhydric alcohol is susceptible to hydrocracking reaction in the presence of a specific hydrogenation catalyst, and (2) the terminal primary is susceptible to hydrocracking. The fact that it is a hydroxyl group is described.
- di-trimethylolpropane is a byproduct from the trimethylolpropane production plant
- di-pentaerythritol is a byproduct from the pentaerythritol production plant. Therefore, there is 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.
- by-product polyol-ether compounds such as di-trimethylolpropane and di-pentaerythritol are polyol-ether compounds having a symmetrical structure such that trimethylolpropane and pentaerythritol are dimerized, respectively. Therefore, there is a demand for a method for producing a polyol-ether compound that can change the number and arrangement of hydroxyl groups, the polarity and symmetry of molecules, and the like according to various applications.
- Neopentyl glycol-trimethylol propane ether described in Patent Document 1 is an example of a polyol-ether compound having both three primary hydroxyl groups and an ether bond, and the hydroxyl groups are arranged asymmetrically with respect to the ether bond. Since the three hydroxyl groups possessed by this compound are distributed 1: 2 with respect to the ether bond, it can be used for the synthesis of a specifically branched useful polymer compound represented by, for example, a dendrimer. However, in order to synthesize more highly and specifically branched polymer compounds, polyols that have more hydroxyl groups and the hydroxyl groups are arranged asymmetrically with respect to the ether bond and have a higher distribution ratio. -Ether compounds are desired.
- 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 and a novel polyol-ether compound obtained by the production method.
- the present inventors have intensively studied on a method for efficiently producing a polyol-ether compound. 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 have reached the present invention. That is, the present invention is as follows. ⁇ 1> Process for producing a polyol-ether compound, wherein a polyol-ether compound represented by the following general formula (2) is obtained by hydrogenating and reducing a compound represented by the following general formula (1) in the presence of a hydrogenation catalyst .
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms; R 3 Represents a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxymethyl group.
- R 3 is a methyl group or an ethyl group.
- R 3 is a hydroxymethyl group.
- ⁇ 4> The production method according to any one of ⁇ 1> to ⁇ 3>, wherein R 1 and R 2 are both methyl groups.
- ⁇ 5> Any one of ⁇ 1> to ⁇ 4>, wherein the compound represented by the general formula (1) is hydroreduced in a reaction solvent containing at least one selected from the group consisting of an ether compound and a saturated hydrocarbon compound The manufacturing method as described in one.
- ⁇ 6> The production method according to any one of ⁇ 1> to ⁇ 5>, wherein the hydrogenation catalyst is a solid catalyst containing palladium.
- ⁇ 7> The production method according to any one of ⁇ 1> to ⁇ 6>, wherein the hydrogenation catalyst is a solid catalyst containing a zirconium compound or an apatite compound.
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms.
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms.
- the polyol-ether compound can be efficiently produced by the production method of the present invention. Also, an asymmetric novel polyol-ether compound can be obtained.
- a polyol represented by the following general formula (2) is obtained by hydrogenating and reducing a compound represented by the following general formula (1) in the presence of a hydrogenation catalyst.
- An ether compound is obtained.
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms
- R 3 represents a linear or branched alkyl group having 1 to 6 carbon atoms or a hydroxymethyl group.
- the compound represented by formula (1) may have a plurality of geometric isomers.
- R 1 and R 2 are different from each other, the compound represented by the formula (1) and the formula (2) has a plurality of optical isomers.
- the compound used as a raw material in the method for producing a polyol-ether compound of the present embodiment (hereinafter also simply referred to as “production method”) is a six-membered compound having a 1,3-dioxane skeleton represented by the above general formula (1). It is a ring acetal compound (hereinafter referred to as “compound (1)”).
- 3-Hydroxy-2,2-disubstituted-propionaldehyde and 2-hydroxymethyl-2-substituted-1,3-propanediol can be used in the production of compound (1) by dehydration cyclization.
- -2,2-disubstituted-propionaldehyde includes, 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, Examples include 3-hydroxy-2-propyl-2-pentyl-propionaldehyde and 3-hydroxy-2-methyl-2-hexyl-propionaldehyde.
- 2-hydroxymethyl-2-substituted-1,3-propanediol applicable in this case include, for example, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolethane), 2-hydroxymethyl-2-ethyl-1,3-propanediol (trimethylolpropane), 2-hydroxymethyl-2-propyl-1,3-propanediol, 2-hydroxymethyl-2-butyl-1,3-propanediol, 2-hydroxymethyl-2-pentyl-1,3-propanediol, 2-hydroxymethyl-2-hexyl-1,3-propanediol and pentaerythritol (2,2-bis-hydroxymethyl-propane-1,3-diol) Is mentioned.
- a hydroxymethyl group and a substituent corresponding to R 3 in the general formula (1) are bonded to the carbon atom at the 2-position of 1,3-propanediol.
- R 1 and R 2 in the general formula (1) each independently a methyl group, ethyl group, n-propyl group, 1-methylethyl group (isopropyl group), 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-dimethylbut
- R 1 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, or a 1-methylethyl group (isopropyl group). More preferably, R 1 and R 2 are both methyl groups.
- R 3 in the above general formula (1) is, for example, methyl group, ethyl group, n-propyl group, 1-methylethyl group (isopropyl group), n-butyl group, 1-methylpropyl group, 2-methylpropyl.
- R 3 is methyl group, ethyl group, n-propyl group, 1-methylethyl group (isopropyl group), n-butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1- A dimethylethyl group (tert-butyl group) or a hydroxymethyl group is preferred.
- R 3 is more preferably a methyl group, an ethyl group or a hydroxymethyl group.
- R 1 and R 2 and R 3 may be any combination of the above-described examples.
- the number of hydroxyl groups and the polarity of the molecule can be changed by appropriately selecting the substituent of the compound (1), and a desired polyol-ether suitable for industrial use.
- a desired polyol-ether suitable for industrial use There is an advantage that only a compound can be produced.
- two or more kinds of the compound (1) may be used to produce two or more kinds of polyol-ether compounds according to this embodiment.
- a metal element having a catalytic hydrogenation ability (hereinafter referred to as “specific metal component”) may be mentioned.
- 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.
- 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.
- raw materials for these specific metal components there are no particular limitations on the raw materials for these specific metal components, and those used as raw materials when preparing a catalyst by a conventionally known method can be employed.
- 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.
- a specific metal component can be used alone or in combination with another metal element having no catalytic hydrogenation ability as a metal component.
- a specific metal component alone include a catalyst such as palladium black and platinum black composed of metal fine powder of a specific metal component, and a combination of the specific metal component and another metal element that does not have catalytic hydrogenation ability.
- Examples include a sponge catalyst prepared by forming an alloy from a specific metal component, aluminum and a small amount of additives, and then leaching all or part of the aluminum.
- lithium, sodium, potassium, rubidium and cesium as alkali metal elements, magnesium, calcium, strontium and barium, halogen as alkaline earth metal elements Fluorine, chlorine, bromine and iodine as elements, and compounds of one or more elements selected from the group consisting of mercury, lead, bismuth, tin, tellurium and antimony as auxiliary additive elements (hereinafter referred to as “specific additive components”) ))
- specific additive components auxiliary additive elements
- raw materials for these specific additive components there are no particular limitations on the raw materials for these specific additive components, and those used as raw materials when preparing a catalyst by a conventionally known method can be employed.
- 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.
- a specific metallic component can be used in combination with a nonmetallic substance.
- 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 substances, a composite compound, or a double salt.
- a specific non-metallic component obtained simply and inexpensively is preferable.
- 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.
- particularly preferred are zirconium oxide and hydroxyapatite (calcium hydroxyphosphate).
- zirconium oxide and hydroxyapatite calcium hydroxyphosphate
- carbides, nitrides, oxides, and the like of specific metal components can be used as the specific nonmetallic component.
- some of them are reduced to metals, so in such cases, some become specific metal components and the rest become non-metallic components.
- Substances can also be used. Examples of such cases include oxides such as nickel oxide, iron oxide, cobalt oxide, molybdenum oxide, tungsten oxide, and chromium oxide.
- a specific metal component may be used alone, or a specific metal component and a specific non-metal component may be used in combination. Ingredients may be included.
- 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.
- the specific metal component can be prepared in a cation state and then reduced to a metal state.
- a reduction method and a reducing agent for that purpose conventionally known methods can be used, and there is no particular limitation.
- 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.
- 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.
- hydrides such as lithium aluminum.
- the specific metal component 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.
- the metal content and shape of the hydrogenation catalyst of this embodiment are not particularly limited.
- the shape may be powder or molded, and there is no particular limitation on the shape and molding method when molded.
- 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.
- 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 by dispersing it on the catalyst carrier.
- 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.
- 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.
- the palladium compound solution is added to the catalyst carrier, or the catalyst carrier is immersed in the palladium compound solution to immobilize palladium or the palladium compound on the catalyst carrier.
- 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 metallic palladium. It is 10% by mass, and more preferably 0.5 to 5% by mass.
- 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.
- 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.
- palladium may be supported on the support in the form of a cation rather than a metal.
- the supported cation palladium (for example, present in the state of a palladium compound) can be used after being reduced to metallic palladium.
- 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.
- one of the preferable ones is a zirconium compound, and the hydrogenation catalyst containing this is described in detail below.
- the zirconium compound used in this embodiment is preferably one or two kinds selected from the group consisting of zirconium oxide, zirconium hydroxide, zirconium carbonate, zirconate alkaline earth salt, 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.
- 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.
- 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.
- zirconium oxide As a specific non-metallic component, there are no particular restrictions on its physical properties and shape. Moreover, there is no restriction
- 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.
- M include calcium, strontium, aluminum, yttrium, lanthanum, and cerium.
- Z include phosphorus, arsenic, vanadium, and chromium.
- X include a hydroxyl group and a carbonate group.
- 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.
- an apatite compound has a nonstoichiometric composition, and the apatite compound of this embodiment also includes it.
- This non-stoichiometric composition is represented by the general formula of M 10-a (HZO 4 ) a (ZO 4 ) 6-a X 2-a , and 0 ⁇ a ⁇ 1.
- 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.
- an apatite compound has anion exchange properties, and an anion exchange can be easily performed even after the portion corresponding to the above X 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 is, for example, a method of synthesizing calcium hydroxide phosphate and bringing it into contact with a solution containing chloride or fluoride ions, or a negative metal 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 in which ions are brought into contact with the apatite compound at the time of supporting the specific metal component or the specific additive component on the apatite compound used as the carrier. 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.
- the BET specific surface area when these are used as a catalyst carrier is not particularly limited, and those having a general specific surface area of about 0.1 to 400 m 2 / g can be used, but 1 to 300 m 2 / g. Preferably 10 to 200 m 2 / g.
- the reaction may be performed in a solvent-free environment using only the compound (1) as a raw material, or a reaction solvent may be used.
- a reaction solvent the type and concentration are not particularly limited as long as they are inactive in the hydrogenation reduction.
- the reaction rate may be extremely lowered or the reaction may be stopped.
- 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.
- Preferred as the reaction solvent are saturated hydrocarbon compounds, ester compounds and ether compounds, and more preferred are saturated hydrocarbon compounds and ether compounds. These are used singly or in combination of two or more.
- reaction solvent examples 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.
- n-octane iso-octane, n-nonane and iso-nonane and isomers thereof
- n-decane n-pentadecane
- cyclohexane methylcyclohexane, dimethylcyclohexane and isomers thereof and decalin
- ether compounds such as dimethyl ether and die Ether, di-n-propyl ether, diiso-propyl ether, di-n-butyl ether, diiso-but
- the saturated hydrocarbon compound as the reaction solvent includes linear, branched, and cyclic alkanes.
- the hydrogenation reduction reaction system in the present embodiment is formed from a liquid phase containing compound (1) or a reaction solvent thereof, a gas phase containing hydrogen gas, and a solid phase of a hydrogenation catalyst.
- a reaction is performed.
- the type of the reaction vessel in the hydroreduction of the present embodiment any conventionally known type such as a tube type, a tank type, and a kettle type can be used.
- the supply method of a raw material composition may be either a distribution method or a batch method.
- the hydrogenation catalyst any conventionally known system such as a fixed bed, a fluidized bed and a suspended bed can be adopted, and there is no particular limitation.
- 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.
- the reaction temperature in the hydrogenation reduction of this embodiment is preferably 50 to 350 ° C., more preferably 100 to 300 ° C., and further preferably 150 to 280 ° C.
- the reaction temperature is 50 ° C. or higher, a higher hydrogenation rate tends to be easily obtained.
- 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.
- 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.
- the reaction pressure is 30 MPa or less, the cost of the reaction equipment is further reduced. There is a tendency to be economically favorable.
- the hydrogen gas used for the hydroreduction of the present embodiment does not have to be purified with a particularly high purity, and may be a quality usually used for an industrial hydrogenation reaction. Moreover, since the hydrogenation reaction is promoted depending on the hydrogen partial pressure, the purity of the hydrogen gas used is preferably higher. However, hydrogen gas may be mixed with a gas inert to the reaction such as helium, argon, nitrogen and methane.
- the ratio of hydrogen gas to compound (1) in the reaction system is the molar ratio of hydrogen gas to compound (1) in the case of batch reaction, and the molar conversion of hydrogen gas to compound (1) in the case of flow reaction. Expressed as a speed ratio, it is preferably 0.1 to 300, more preferably 0.5 to 100.
- polyol-ether compound of this embodiment will be described in detail.
- a polyol-ether compound having three primary hydroxyl groups and an ether bond in the molecule, and the hydroxyl groups are arranged asymmetrically with respect to the ether bond neopentyl glycol-trimethylolpropane ether described in Patent Document 1 is known. It has been.
- the three hydroxyl groups of this compound are distributed 1: 2 with respect to the ether bond.
- a polyol-ether compound having a higher primary hydroxyl group and a hydroxyl group arranged asymmetrically with respect to the ether bond and having a higher distribution ratio is useful, for example, in a specifically branched form represented by dendrimers. Although it is expected to be used for industrial purposes such as the synthesis of complex polymer compounds, it is not known.
- the compound represented by the following general formula (A) is hydroreduced by the above production method, thereby having four primary hydroxyl groups, and the hydroxyl groups are converted into ether bonds.
- a polyol-ether compound having an asymmetrical arrangement and a distribution ratio of 1: 3 can be easily and efficiently produced.
- Examples of the asymmetric novel polyol-ether compound that can be produced according to this embodiment include those represented by the following general formula (B).
- R 1 and R 2 may be the same or different and each represents a linear or branched alkyl group having 1 to 6 carbon atoms.
- R 1 and R 2 have the same meanings as those in the general formula (A).
- R 1 and R 2 in the general formula (B) are each independently a methyl group, ethyl Group, n-propyl group, 1-methylethyl group (isopropyl group), 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,
- R 1 and R 2 are each independently a methyl group, ethyl group, n-propyl group, 1-methylethyl group (isopropyl group), 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 And a 1,2-dimethylpropyl group or a 2,2-dimethylpropyl group (neopentyl group). More preferably, R 1 and R 2 are both methyl groups.
- the polyol-ether compound represented by the general formula (B) is a novel substance.
- the polyol-ether compound thus obtained is a compound having at least three or more primary hydroxyl groups and an ether bond in the molecule and having an asymmetric structure as seen from the ether bond, such as a resin, paint, adhesive, etc. It can be used as an industrial raw material.
- the isolated compound (B) was identified by 1 H-NMR measurement and 13 C-NMR measurement. The measurement conditions are shown below. Apparatus: ECA500, product name 1 H-NMR manufactured by JEOL Ltd. Nuclide: 1 H Measurement frequency: 500 MHz Measurement sample: 5% CD 3 OD solution 13 C-NMR Nuclide: 13 C Measurement frequency: 125 MHz Measurement sample: 5% CD 3 OD solution Further, the molecular weight of the compound (B) was measured by GC-MS measurement (chemical ionization method [CI +], high-resolution mass spectrometry [millimeter]). The measurement conditions are shown below.
- Apparatus Agilent 7890A Agilent product name and ACCU-TOF-GCV (JMS-T100GCV) JEOL Ltd.
- product name GC measurement column HP-5 Product name manufactured by Agilent Technologies MS measurement conditions: chemical ionization method, Ionization voltage 200 eV, Ionization current 300 ⁇ A, detector voltage 1700V
- 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 ).
- ZrO 2 zirconium oxide
- This is stored in a magnetic crucible, and subjected to a baking treatment at 400 ° C.
- carrier A powdered zirconium oxide
- apatite compound used as a carrier for the metal component was prepared by the following method. 78.7 g of calcium nitrate tetrahydrate was dissolved in 300.5 g of ion-exchanged water, and 260 mL of 28% aqueous ammonia was added thereto. Further, 26.4 g of diammonium hydrogen phosphate was dissolved in 500.6 g of ion-exchanged water, and 150 mL of 28% ammonia water and 150 mL of ion-exchanged water were added thereto.
- the diammonium hydrogen phosphate-ammonia solution was added little by little, gradually becoming cloudy to obtain a white precipitate.
- the mixture was stirred for about 2 hours and allowed to stand.
- it was filtered, washed with ion exchange water, dried at 110 ° C. for 10 hours, and then baked at 500 ° C. for 3 hours in air using an electric furnace. Then, it grind
- the BET specific surface area of the carrier B was 60.7 m 2 / g.
- a catalyst containing palladium as a specific metal component was prepared by the following method. A 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. The adsorbed metal component was instantaneously reduced by pouring formaldehyde-sodium hydroxide aqueous solution there. 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”).
- A1 catalyst 1.0 mass% palladium-supported zirconium oxide catalyst
- a catalyst containing palladium as a specific metal component was prepared by the following method. A 0.32 mass% palladium acetate-acetone solution was added to 5.0 g of carrier B and adsorbed, and then acetone was evaporated and dried to carry palladium acetate on carrier B. This was stored in a magnetic crucible, and baked at 400 ° C. for 3 hours in air using an electric furnace. The calcined product was reduced at 110 ° C. under a hydrogen gas stream to prepare a 1.0 mass% palladium-supported apatite catalyst (hereinafter referred to as “B1 catalyst”).
- B1 catalyst 1.0 mass% palladium-supported apatite catalyst
- B1 catalyst 3.0g was added to the 5.9 mass% sodium chloride aqueous solution, and it stirred for 2 hours, and performed the ion exchange process. Thereafter, the catalyst is filtered and washed with ion-exchanged water, and dried, and then a 1.0 mass% palladium-supported catalyst (hereinafter referred to as “B2 catalyst”) of a hydroxide apatite carrier partially ion-exchanged with chloride. ) was prepared. As a result of elemental analysis by ICP emission analysis, this catalyst contained chlorine corresponding to about 5% of the total hydroxyl groups.
- the hydrogen reduction reaction was carried out by the following method. ⁇ Example 1> In a 100 mL SUS reactor, 0.60 g of A1 catalyst, 2.0 g of compound HTPA, and 24.0 g of diisopropyl ether were placed, and the inside of the reactor was replaced with nitrogen gas. Thereafter, 8.5 MPa of hydrogen gas was charged into the reactor, and the temperature was raised to 210 ° C., which is the reaction temperature, and reacted for 6 hours. Thereafter, the reactor was cooled and the contents of the reactor were collected and analyzed by gas chromatography.
- 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 instead of 24.0 g of diisopropyl ether, the reaction temperature was changed from 210 ° C. to 230 ° C., and the reaction time was changed from 6 hours to 9 hours. Went. As a result, the conversion rate of compound HTPA was 82.7%, and the selectivity to compound NTPE was 79.8%.
- Example 3 The reaction was performed in the same manner as in Example 2 except that 1.00 g of B1 catalyst was used instead of 0.60 g of A1 catalyst. As a result, the conversion rate of compound HTPA was 82.6%, and the selectivity to compound NTPE was 72.7%.
- Example 4 The reaction was conducted in the same manner as in Example 2 except that 1.02 g of B2 catalyst was used instead of 0.60 g of A1 catalyst. As a result, the conversion rate of compound HTPA was 84.7%, and the selectivity to compound NTPE was 76.8%.
- Example 5 The reaction was conducted in the same manner as in Example 2 except that 24.0 g of n-hexane was used instead of 24.0 g of 1,4-dioxane. As a result, the conversion rate of compound HTPA was 86.9%, and the selectivity to compound NTPE was 63.2%.
- Example 6 The reaction was conducted in the same manner as in Example 2 except that 1.8 g of compound HTEA was used instead of 2.0 g of compound HTPA. As a result, the conversion of compound HTEA was 95.5%, and the product was selected as 2- (3-hydroxy-2,2-dimethyl-propoxymethyl) -2-methyl-propane-1,3-diol. The rate was 79.4%.
- the reaction scheme in Example 6 is shown below.
- Example 7 The reaction was performed in the same manner as in Example 2 except that 1.8 g of compound HPEA was used instead of 2.0 g of compound HTPA, and the reaction time was changed from 9 hours to 12 hours. As a result, the conversion rate of the compound HPEA was 87.8%, and the product 3- (3-hydroxy-2,2-bis-hydroxymethyl-propoxy) -2,2-dimethyl-propan-1-ol ( Hereinafter, the selectivity to “compound NPEE”) was 68.8%.
- the reaction scheme in Example 7 is shown below.
- the compound NPEE was isolated by the above chromatographic method, and the same structure was confirmed by NMR analysis.
- Compound NPEE Further, the molecular weight of the compound NPEE was measured by GC-MS analysis (chemical ionization method [CI +], high-resolution mass spectrometry [Millimass]). In chemical ionization mass spectrometry, molecules are ionized and subjected to mass analysis with almost no fragmentation, so that molecular weight information can be obtained, and at the same time, high-resolution mass analysis can be verified as a composition formula.
- the composition formula of the compound NPEE was determined to be C 10 H 22 O 5 . Moreover, it was 101 degreeC when melting
- a catalyst containing platinum as a specific metal component was prepared by the following method.
- a 0.90 mass% potassium chloroplatinate 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 to reduce the adsorbed metal component.
- the catalyst was washed with ion-exchanged water and dried to prepare a 1.0 mass% platinum-supported zirconium oxide catalyst (hereinafter referred to as “D1 catalyst”).
- Example 8 The reaction was conducted in the same manner as in Example 2 except that 2.42 g of D1 catalyst was used instead of 0.60 g of A1 catalyst. As a result, the conversion of compound HTPA was 48.0%, and the selectivity to compound NTPE was 50.5%.
- Example 9 The reaction was carried out in the same manner as in Example 1 except that a commercially available 5 mass% palladium-supported alumina catalyst (manufactured by Wako Pure Chemical Industries, Ltd., product code: 163-13871) was used as the hydrogenation catalyst. As a result, the conversion rate of compound HTPA was 75.8%, and the selectivity to compound NTPE was 61.5%.
- Example 10 In a 600 mL SUS reactor, 9.2 g of A1 catalyst, 61.3 g of compound HTPA, and 321 g of 1,4-dioxane were placed, and the inside of the reactor was replaced with nitrogen gas. Thereafter, 8.5 MPa of hydrogen gas was charged into the reactor, and the reaction temperature was raised to 230 ° C., which was a reaction time, for 6 hours. Thereafter, the reactor was cooled and the contents of the reactor were collected and analyzed by gas chromatography. As a result, the conversion rate of compound HTPA was 97.7%, and the selectivity to compound NTPE was 85.5%.
- a polyol-ether compound can be efficiently produced by reducing the compound (1), which is a cyclic acetal compound, with a hydrogenation catalyst. Also, an asymmetric novel polyol-ether compound can be obtained.
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Abstract
Description
すなわち、本発明は、下記のとおりである。
<1>
水素化触媒の存在下に下記一般式(1)で表される化合物を水素化還元することにより、下記一般式(2)で表されるポリオール-エーテル化合物を得る、ポリオール-エーテル化合物の製造方法。
<2>
前記R3がメチル基又はエチル基である<1>に記載の製造方法。
<3>
前記R3がヒドロキシメチル基である<1>に記載の製造方法。
<4>
前記R1及び前記R2がいずれもメチル基である<1>~<3>のいずれか1つに記載の製造方法。
<5>
エーテル化合物及び飽和炭化水素化合物からなる群より選ばれる少なくとも1種を含む反応溶媒中で、前記一般式(1)で表される化合物を水素化還元する、<1>~<4>のいずれか1つに記載の製造方法。
<6>
前記水素化触媒はパラジウムを含む固体触媒である、<1>~<5>のいずれか1つに記載の製造方法。
<7>
前記水素化触媒はジルコニウム化合物又はアパタイト化合物を含む固体触媒である、<1>~<6>のいずれか1つに記載の製造方法。
<8>
下記一般式(3)で表されるポリオール-エーテル化合物。
<9>
前記R1及び前記R2がいずれもメチル基である<8>に記載のポリオール-エーテル化合物。
本実施形態のポリオール-エーテル化合物の製造方法(以下、単に「製造法」ともいう。)に原料として用いる化合物は、上記一般式(1)で表される1,3-ジオキサン骨格を有する六員環アセタール化合物(以下、「化合物(1)」という。)である。
3-ヒドロキシ-2,2-ジメチル-プロピオンアルデヒド、
3-ヒドロキシ-2,2-ジエチル-プロピオンアルデヒド、
3-ヒドロキシ-2-メチル-2-エチル-プロピオンアルデヒド、
3-ヒドロキシ-2-メチル-2-プロピル-プロピオンアルデヒド、
3-ヒドロキシ-2-メチル-2-ブチル-プロピオンアルデヒド、
3-ヒドロキシ-2-エチル-2-ブチル-プロピオンアルデヒド、
3-ヒドロキシ-2-プロピル-2-ペンチル-プロピオンアルデヒド、及び
3-ヒドロキシ-2-メチル-2-ヘキシル-プロピオンアルデヒド
が挙げられる。プロピオンアルデヒド骨格の2位の炭素原子に結合した置換基が一般式(1)におけるR1及びR2に該当する。
2-ヒドロキシメチル-2-メチル-1,3-プロパンジオール(トリメチロールエタン)、
2-ヒドロキシメチル-2-エチル-1,3-プロパンジオール(トリメチロールプロパン)、
2-ヒドロキシメチル-2-プロピル-1,3-プロパンジオール、
2-ヒドロキシメチル-2-ブチル-1,3-プロパンジオール、
2-ヒドロキシメチル-2-ペンチル-1,3-プロパンジオール、
2-ヒドロキシメチル-2-ヘキシル-1,3-プロパンジオール、及び
ペンタエリスリトール(2,2-ビス-ヒドロキシメチル-プロパン-1,3-ジオール)
が挙げられる。1,3-プロパンジオールの2位の炭素原子には、ヒドロキシメチル基及び上記一般式(1)におけるR3に該当する置換基が結合している。
また、化合物(1)を2種以上用い、本実施形態により2種以上のポリオール-エーテル化合物を製造してもよい。その場合に用いられる2種以上の化合物(1)の組み合わせ及び比率について特に制限はない。
I.特定金属成分
本実施形態において用いられる水素化触媒の有効成分としては、接触水素化能を有する金属元素(以下、「特定金属成分」という。)が挙げられる。特定金属成分としては、例えば、ニッケル、コバルト、鉄、ルテニウム、ロジウム、パラジウム、白金、イリジウム、銅、銀、モリブデン、タングステン、クロム及びレニウムが挙げられる。特定金属成分は、水素化能を示すのであれば、金属の状態であっても、陽イオンの状態であってもよい。
これらの中では、一般的には、金属状態の方が、水素化能が強く、還元雰囲気下で安定であるため、金属の状態であることが好ましい。特定金属成分は、1種を単独で又は2種以上を組み合わせて、固体触媒に含有された状態で用いることができる。特定金属成分を2種以上用いる場合、それらの組み合わせ、混合比率及び形態について特に制限はなく、個々の金属の混合物、あるいは、合金又は金属間化合物のような形態で用いることができる。
本実施形態において、水素化触媒は、パラジウム、白金、ニッケル及び銅からなる群より選ばれる少なくとも1種の特定金属成分を含む固体触媒であると好ましく、特に好ましくはパラジウムを特定金属成分として含む固体触媒である。
また、触媒の活性、選択性及び物性等を一層向上させるために、アルカリ金属元素としてリチウム、ナトリウム、カリウム、ルビジウム及びセシウム、アルカリ土類金属元素としてマグネシウム、カルシウム、ストロンチウム及びバリウム、ハロゲン元素としてフッ素、塩素、臭素及びヨウ素、補助添加元素として水銀、鉛、ビスマス、錫、テルル及びアンチモンからなる群より選ばれる1種又は2種以上の元素の化合物(以下、「特定添加成分」という。)を、前述の特定金属成分と共に触媒に添加して用いることもできる。
本実施形態の水素化触媒において、特定金属成分に非金属物質を組み合わせて用いることもできる。非金属物質としては、例えば、主に、元素単体、炭化物、窒化物、酸化物、水酸化物、硫酸塩、炭酸塩及びリン酸塩が挙げられる(以下、「特定非金属成分」という。)。その具体例としては、例えば、グラファイト、ダイアモンド、活性炭、炭化ケイ素、窒化ケイ素、窒化アルミニウム、窒化ホウ素、酸化ホウ素、酸化アルミニウム(アルミナ)、酸化ケイ素(シリカ)、酸化チタン、酸化ジルコニウム、酸化ハフニウム、酸化ランタン、酸化セリウム、酸化イットリウム、酸化ニオブ、ケイ酸マグネシウム、ケイ酸カルシウム、アルミン酸マグネシウム、アルミン酸カルシウム、酸化亜鉛、酸化クロム、アルミノシリケート、アルミノシリコホスフェート、アルミノホスフェート、ボロホスフェート、リン酸マグネシウム、リン酸カルシウム、リン酸ストロンチウム、水酸化アパタイト(ヒドロキシリン酸カルシウム)、塩化アパタイト、フッ化アパタイト、硫酸カルシウム、硫酸バリウム及び炭酸バリウムが挙げられる。特定非金属成分は1種を単独で又は2種以上を組み合わせて用いられる。2種以上を組み合わせて用いる場合の組み合わせや混合比率、形態については特に制限はなく、個々の物質の混合物、複合化合物、又は複塩のような形態で用いることができる。
本実施形態の水素化触媒として、特定金属成分を単独で用いてもよく、特定金属成分と特定非金属成分とを組み合わせて用いてもよく、場合によっては、これらに加えて特定添加成分を含んでもよい。本実施形態の水素化触媒の製造法は特に制限はなく、従来公知の方法を用いることができる。その例として、特定金属成分の原料化合物を、特定非金属成分上に含浸する方法(担持法)、特定金属成分の原料化合物と特定非金属成分の原料化合物とを適当な溶媒に共に溶解させた後にアルカリ化合物などを用いて同時に析出させる方法(共沈法)、特定金属成分の原料化合物と特定非金属成分を適当な比率で混合均一化する方法(混練法)などが挙げられる。
特定金属成分がパラジウムである場合、パラジウムが貴金属であることを考慮すると、その使用量は少なく、かつパラジウムが有効に利用されることが経済的に望まれる。そのため、パラジウムを触媒担体に分散させて担持して用いることが好ましい。
本実施形態に用いられるジルコニウム化合物は、好ましくは、酸化ジルコニウム、水酸化ジルコニウム、炭酸ジルコニウム、ジルコン酸アルカリ土類塩、ジルコン酸希土類塩及びジルコンからなる群より選ばれる1種を単独で又は2種以上を組み合わせたものである。
本実施形態に用いられるアパタイト化合物としては、例えば、学術誌「触媒」,27(4),237-243(1985)に記載されているようなM10(ZO4)6X2の組成を有する六方晶系化合物が挙げられる。ここで、Mとしては、例えばカルシウム、ストロンチウム、アルミニウム、イットリウム、ランタン及びセリウムが挙げられ、Zとしては、例えば、リン、ヒ素、バナジウム及びクロムが挙げられ、Xとしては、例えば、水酸基、炭酸基、フッ素、塩素、臭素及びヨウ素が挙げられる。イオン半径などによる物理的な構造上の制約の範囲内において、M、Z及びXのいずれも、上記のうちの1種又は2種以上から構成されていてよい。また、アパタイト化合物は、非量論組成を有することも知られており、本実施形態のアパタイト化合物はそれも包含する。この非量論組成は、M10-a(HZO4)a(ZO4)6-aX2-aの一般式で表され、0<a≦1である。
また、これらを触媒担体として用いる時のBET比表面積にも特に制限はなく、0.1~400m2/g程度の一般的な比表面積のものを用いることができるが、1~300m2/gのものが好ましく、10~200m2/gのものがより好ましい。
これらの中で、n-ペンタン、iso-ペンタン、n-ヘキサン、iso-ヘキサン、2,2-ジメチル-ブタン、n-ヘプタン、iso-ヘプタン、ジメチルエーテル、ジエチルエーテル、ジn-プロピルエーテル、ジiso-プロピルエーテル、ジn-ブチルエーテル、ジiso-ブチルエーテル、ジsec-ブチルエーテル、メチルプロピルエーテル、テトラヒドロフラン、メチルテトラヒドロフラン、テトラヒドロピラン、メチルテトラヒドロピラン及び1,4-ジオキサンからなる群より選ばれる少なくとも1種が好ましく、ジiso-プロピルエーテル、1,4-ジオキサン及びノルマルヘキサンからなる群より選ばれる少なくとも1種がより好ましい。
分子内に3つの一級水酸基とエーテル結合とを併せ持ち、且つ水酸基がエーテル結合に対して非対称に配置されたポリオール-エーテル化合物としては、特許文献1に記載のネオペンチルグリコール-トリメチロールプロパンエーテルが知られている。この化合物が有する3つの水酸基はエーテル結合に対して1:2に分配されている。
これらの中では、R1及びR2がそれぞれ独立して、メチル基、エチル基、n-プロピル基、1-メチルエチル基(イソプロピル基)、n-ブチル基、1-メチルプロピル基、2-メチルプロピル基、1,1-ジメチルエチル基(tert-ブチル基)、n-ペンチル基、1-メチルブチル基、2-メチルブチル基、3-メチルブチル基、1-エチルプロピル基、1,1-ジメチルプロピル基、1,2-ジメチルプロピル基又は2,2-ジメチルプロピル基(ネオペンチル基)であると好ましい。R1及びR2が共にメチル基であるとより好ましい。
上記一般式(B)で表されるポリオール-エーテル化合物は新規物質である。
原料アセタール(化合物(1))の転化率(%)=
100×[1-(反応液に残存する原料のモル数)/(仕込原料のモル数)]
各生成ポリオール-エーテル化合物の選択率(%)=
100×(目的とする生成物のモル数)/[(仕込原料のモル数)-(反応液に残存する原料のモル数)]
ただし、化合物(1)に異性体が存在する場合、それらの異性体を合算した値を用いた。
ガスクロマトグラフの測定には以下の機器を用いた。
装置:GC-2010 島津製作所製製品名
カラム:DB-1 アジレント・テクノロジー社製製品名
装置:ECA500 日本電子株式会社製製品名
1H-NMR
核種:1H
測定周波数:500MHz
測定試料:5%CD3OD溶液
13C-NMR
核種:13C
測定周波数:125MHz
測定試料:5%CD3OD溶液
さらに化合物(B)の分子量をGC-MS測定(化学イオン化法[CI+]、高分解能質量分析[ミリマス])により行った。測定条件を下記に示す。
装置:Agilent 7890A アジレント社製製品名、及び
ACCU-TOF-GCV(JMS-T100GCV) 日本電子株式会社製製品名
GC測定カラム:HP-5 アジレント・テクノロジー社製製品名
MS測定条件:化学イオン化法、イオン化電圧200eV、
イオン化電流300μA、検出器電圧1700V
充填剤:和光純薬製、商品名「ワコーゲルC-200」
展開溶媒:メタノール-クロロホルム
<原料調製例1>
(2-(5-エチル-5-ヒドロキシメチル-[1,3]ジオキサン-2-イル)-2-メチル-プロパン-1-オールの調製)
2,2-ジメチル-3-ヒドロキシ-プロピオンアルデヒド(ヒドロキシピバルアルデヒド、三菱瓦斯化学株式会社製、純度99.8%)45.1gと、2-エチル-2―ヒドロキシメチル-プロパン-1,3-ジオール(トリメチロールプロパン、東京化成工業試薬)59.6g、と、ベンゼン706gと、粒状ナフィオン(商品名「NR-50」、シグマアルドリッチ社試薬)5.0gと、を2リットルの丸底フラスコに収容し、常圧下で生成する水をベンゼンと共沸させながらディーン・スターク・トラップを用いて系外へ抜き出して、水の留出が止まるまで反応させた。これを濾過した後に濃縮及び冷却することにより再結晶させて、2-(5-エチル-5-ヒドロキシメチル-[1,3]ジオキサン-2-イル)-2-メチル-プロパン-1-オール(以下、「化合物HTPA」と表記する。)の結晶を得た。下記にこの合成反応スキームを示す。
(2-(5-ヒドロキシメチル-5-メチル-[1,3]ジオキサン-2-イル)-2-メチル-プロパン-1-オールの調製)
2,2-ジメチル-3-ヒドロキシ-プロピオンアルデヒド45.1gに代えて2,2-ジメチル-3-ヒドロキシ-プロピオンアルデヒド(ヒドロキシピバルアルデヒド、三菱瓦斯化学株式会社製、純度99.8%)89.3gを用い、2-エチル-2―ヒドロキシメチル-プロパン-1,3-ジオール59.6gに代えて2-ヒドロキシメチル-2-メチル-プロパン-1,3―ジオール(トリメチロールエタン、東京化成工業試薬)106.0gを用いた以外は原料調製例1と同様にして、2-(5-ヒドロキシメチル-5-メチル-[1,3]ジオキサン-2-イル)-2-メチル-プロパン-1-オール(以下、「化合物HTEA」と表記する。)の結晶を得た。下記にこの合成反応スキームを示す。
(2-(5,5-ビス-ヒドロキシメチル-[1,3]ジオキサン-2-イル)-2-メチル-プロパン-1-オールの調製)
2,2-ジメチル-3-ヒドロキシ-プロピオンアルデヒド45.1gに代えて2,2-ジメチル-3-ヒドロキシ-プロピオンアルデヒド(ヒドロキシピバルアルデヒド、三菱瓦斯化学株式会社製、純度99.8%)27.3gを用い、2-エチル-2―ヒドロキシメチループロパン-1,3-ジオール59.6gに代えて2,2-ビス-ヒドロキシメチル-プロパン-1,3-ジオール(ペンタエリスリトール、東京化成工業試薬)54.0gを用い、ベンゼンに代えてベンゼン-1,4-ジオキサン混合溶液を用いた以外は原料調製例1と同様にして、2-(5,5-ビス-ヒドロキシメチル-[1,3]ジオキサン-2-イル)-2-メチル-プロパン-1-オール(以下、「化合物HPEA」と表記する。)の結晶を得た。下記にこの合成反応スキームを示す。
金属成分の担体として用いた酸化ジルコニウムを下記の方法で調製した。
酸化ジルコニウム(ZrO2)換算で25質量%の濃度のオキシ硝酸ジルコニウム水溶液505gに、撹拌しながら28%アンモニア水15.5gを滴下することにより白色沈殿物を得た。これを濾過し、イオン交換水で洗浄した後に、110℃で10時間乾燥して含水酸化ジルコニウムを得た。これを磁製坩堝に収容し、電気炉を用いて空気中で400℃、3時間の焼成処理を行った後、メノウ乳鉢で粉砕して粉末状酸化ジルコニウム(以下、「担体A」と表記する。)を得た。担体AのBET比表面積(窒素吸着法により測定。以下同様。)は102.7m2/gであった。
金属成分の担体として用いたアパタイト化合物を下記の方法で調製した。
硝酸カルシウム四水和物78.7gを300.5gのイオン交換水に溶解し、そこに28%アンモニア水260mLを添加した。また、リン酸水素二アンモニウム26.4gをイオン交換水500.6gに溶解し、そこに28%アンモニア水150mLとイオン交換水150mLとを添加した。硝酸カルシウム-アンモニア溶液を撹拌しながら、そこにリン酸水素二アンモニウム-アンモニア溶液を少しずつ添加したところ、徐々に白濁して白色沈殿物を得た。添加終了後、約2時間撹拌した後に静置した。次いで、静置後のものを濾過し、イオン交換水で洗浄した後に、110℃で10時間乾燥し、次に電気炉を用いて空気中で500℃、3時間の焼成処理を行った。その後、メノウ乳鉢で粉砕して粉末状水酸化アパタイト(以下、「担体B」と表記する。)を得た。担体BのBET比表面積は60.7m2/gであった。
パラジウムを特定金属成分とする触媒を下記の方法で調製した。
5.0gの担体Aに0.66質量%塩化パラジウム-0.44質量%塩化ナトリウム水溶液を添加し、担体A上に金属成分を吸着させた。そこにホルムアルデヒド-水酸化ナトリウム水溶液を注加して吸着した金属成分を瞬時に還元した。その後、イオン交換水により触媒を洗浄し、乾燥することにより1.0質量%パラジウム担持酸化ジルコニウム触媒(以下、「A1触媒」と表記する。)を調製した。
パラジウムを特定金属成分とする触媒を以下の方法で調製した。
5.0gの担体Bに0.32質量%酢酸パラジウム-アセトン溶液を添加し、吸着させた後に、アセトンを蒸発、乾固させて酢酸パラジウムを担体Bに担持した。これを磁製坩堝に収容し、電気炉を用いて空気中で400℃、3時間の焼成処理を行った。焼成処理後のものを水素ガス気流下、110℃で還元して、1.0質量%パラジウム担持アパタイト触媒(以下、「B1触媒」と表記する。)を調製した。
B1触媒3.0gを5.9質量%塩化ナトリウム水溶液に添加し、2時間撹拌して、イオン交換処理を行った。その後にイオン交換水で触媒を濾過洗浄、乾燥することにより、部分的に塩化物にイオン交換された水酸化アパタイト担体の1.0質量%パラジウム担持触媒(以下、「B2触媒」と表記する。)を調製した。ICP発光分析により元素分析を行った結果、この触媒は全水酸基の約5%に相当する塩素を含んでいた。
<実施例1>
100mLのSUS製反応器内に、A1触媒0.60g、化合物HTPA 2.0g、及びジイソプロピルエーテル24.0gを収容し、反応器内を窒素ガスで置換した。その後、反応器内に水素ガスを8.5MPa充填し、反応温度である210℃へ昇温して6時間反応させた。その後に冷却して反応器の内容物を回収し、ガスクロマトグラフィーで分析した。
その結果、化合物HTPAの転化率は82.3%であり、生成物の2-エチル-2-(3-ヒドロキシ-2,2-ジメチル-プロポキシメチル)-プロパン-1,3-ジオール(以下、「化合物NTPE」と表記する。)への選択率は85.0%であった。
下記に実施例1における反応スキームを示す。
ジイソプロピルエーテル24.0gに代えて1,4-ジオキサン24.0gを用い、反応温度を210℃から230℃に、反応時間を6時間から9時間に代えた以外は実施例1と同様にして反応を行った。その結果、化合物HTPAの転化率は82.7%であり、化合物NTPEへの選択率は79.8%であった。
A1触媒0.60gに代えてB1触媒1.00gを用いた以外は実施例2と同様にして反応を行った。その結果、化合物HTPAの転化率は82.6%であり、化合物NTPEへの選択率は72.7%であった。
A1触媒0.60gに代えてB2触媒1.02gを用いた以外は実施例2と同様にして反応を行った。その結果、化合物HTPAの転化率は84.7%であり、化合物NTPEへの選択率は76.8%であった。
1,4-ジオキサン24.0gに代えてn-ヘキサン24.0gを用いた以外は実施例2と同様にして反応を行った。その結果、化合物HTPAの転化率は86.9%であり、化合物NTPEへの選択率は63.2%であった。
化合物HTPA 2.0gに代えて化合物HTEA 1.8gを用いた以外は実施例2と同様にして反応を行った。その結果、化合物HTEAの転化率は95.5%であり、生成物の2-(3-ヒドロキシ-2,2-ジメチル-プロポキシメチル)-2-メチル-プロパン-1,3-ジオールへの選択率は79.4%であった。
下記に実施例6における反応スキームを示す。
化合物HTPA 2.0gに代えて化合物HPEA 1.8gを用い、反応時間を9時間から12時間に代えた以外は実施例2と同様にして反応を行った。その結果、化合物HPEAの転化率は87.8%であり、生成物の3-(3-ヒドロキシ-2,2-ビス-ヒドロキシメチル-プロポキシ)-2,2-ジメチル-プロパン-1-オール(以下、「化合物NPEE」と表記する。)への選択率は68.8%であった。
下記に実施例7における反応スキームを示す。
(化合物NPEE)
また、化合物NPEEの融点を測定すると101℃であった。4価の類縁アルコールであるジトリメチロールプロパンの110℃及びペンタエリスリトールの260℃よりも低下しており、樹脂原料等としてのハンドリング性が改善していることが分かった。
白金を特定金属成分とする触媒を下記の方法で調製した。
5.0gの担体Aに0.90質量%塩化白金酸カリウム水溶液を添加し、担体A上に金属成分を吸着させた。そこにホルムアルデヒド-水酸化ナトリウム水溶液を注加して吸着した金属成分を還元した。その後、イオン交換水により触媒を洗浄し、乾燥することにより1.0質量%白金担持酸化ジルコニウム触媒(以下、「D1触媒」と表記する。)を調製した。
A1触媒0.60gに代えてD1触媒2.42gを用いた以外は実施例2と同様にして反応を行った。その結果、化合物HTPAの転化率は48.0%であり、化合物NTPEへの選択率は50.5%であった。
水素化触媒として市販の5質量%パラジウム担持アルミナ触媒(和光純薬工業社製、商品コード:163-13871)を用いた以外は実施例1と同様にして反応を行った。その結果、化合物HTPAの転化率は75.8%であり、化合物NTPEへの選択率は61.5%であった。
600mLのSUS製反応器内に、A1触媒9.2g、化合物HTPA 61.3g、及び1,4-ジオキサン321gを収容し、反応器内を窒素ガスで置換した。その後、反応器内に水素ガスを8.5MPa充填し、反応温度である230℃へ昇温して6時間反応させた。その後に冷却して反応器の内容物を回収し、ガスクロマトグラフィーで分析した。その結果、化合物HTPAの転化率は97.7%であり、化合物NTPEへの選択率は85.5%であった。
Claims (9)
- 前記R3がメチル基又はエチル基である、請求項1記載の製造方法。
- 前記R3がヒドロキシメチル基である、請求項1記載の製造方法。
- 前記R1及び前記R2がいずれもメチル基である、請求項1~3のいずれか1項に記載の製造方法。
- エーテル化合物及び飽和炭化水素化合物からなる群より選ばれる少なくとも1種を含む反応溶媒中で、前記一般式(1)で表される化合物を水素化還元する、請求項1~4のいずれか1項に記載の製造方法。
- 前記水素化触媒はパラジウムを含む固体触媒である、請求項1~5のいずれか1項に記載の製造方法。
- 前記水素化触媒はジルコニウム化合物又はアパタイト化合物を含む固体触媒である、請求項1~6のいずれか1項に記載の製造方法。
- 前記R1及び前記R2がいずれもメチル基である、請求項8記載のポリオール-エーテル化合物。
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WO2017204086A1 (ja) * | 2016-05-26 | 2017-11-30 | 三菱瓦斯化学株式会社 | 環状アセタール化合物の製造方法 |
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