JP2006052166A - Aromatic ethers and method for producing aromatic ethers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method by which aromatic ethers having the objective structure can be produced from phenols and an oxirane compound as raw materials while suppressing the formation of by-products. <P>SOLUTION: The method for producing the aromatic ethers is characterized as follows. The phenols are reacted with the oxirane compound to synthesize the aromatic ethers. In the process, an anion exchange resin is used as a catalyst. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a corresponding aromatic ether from a phenol and an oxirane compound.

  Among aromatic ethers, glycol ethers such as β-phenoxyethanols are used for various applications because they have excellent characteristics. For example, since it has a high boiling point, it is used in a wide range of fields as a solvent excellent in terms of work environment. In addition, they are also used as emulsifiers, plasticizers, and adhesive compositions. It is also used as an important raw material for polymer chemicals such as polyester, polyurethane and (meth) acrylate. Furthermore, using the bactericidal action of the aromatic ethers, a wide range of uses such as antibacterial agents, preservatives, cosmetic compositions, personal care, fragrance retention agents, and pharmaceutical compositions are known. In addition, it has good resolution, depth of focus, and developability, and is used as a resist composition for creating integrated circuits that has excellent sensitivity resist cross-sectional shape and storage stability, and as a cationic electrodeposition coating composition. Is also known.

  Among such aromatic ethers, 2-phenoxyethanol has been used in various ways so far. Examples of such use results include paints, inks, dyes, hair dyes, agricultural chemicals, detergents as solvents; various emulsions, aqueous building materials, paints, emulsified cosmetics as emulsifiers; plasticizers; adhesive compositions ; As intermediate materials for various chemicals, synthetic intermediates and raw materials for fluorene derivatives, polyester, polyurethane, sterilizing reagents; as antibacterial and antiseptic agents, cosmetics, antibacterial hypoallergenic cosmetics, fragrances, fungicides, fungicides, disinfectants Agents, low-temperature stable preservatives, antiseptic pharmaceutical preparations; cosmetic compositions, topical skin preparations for sensitive skin, hair cosmetics; personal care, hair conditioning compositions such as shampoos and hair rinses, oral compositions, sunscreen compositions Examples thereof include perfume retention agents and cosmetic bactericides in the perfume field; antiseptic pharmaceutical preparations in the pharmaceutical field, and the like.

  The synthesis of the above aromatic ethers has a very slow reaction rate and many side reactions without a catalyst. For this reason, the aromatic ethers are produced using a catalyst.

  For example, as a method for producing β-phenoxyethanols contained in the aromatic ethers, a method of synthesizing using an alkali metal salt and a large amount of water has been conventionally known (Patent Document 1). However, the application of a large amount of water has the potential problem of not only reducing the use efficiency of the oxirane compound but also generating a large amount of industrial wastewater. In particular, since many phenols have a bactericidal action, when the wastewater contains unreacted phenols, it is difficult to treat the wastewater with activated sludge.

  For these reasons, as a method for producing the aromatic ether, a non-aqueous process is required instead of the aqueous process disclosed in Patent Document 1.

  As a method for producing the above aromatic ethers by a non-aqueous process, a reaction in the presence of a halogenated phosphonium salt or a catalyst comprising a tertiary phosphine and an alkyl halide (Patent Document 2), or a halogenated trialkylbenzylammonium compound. Known (Patent Document 3).

  By the way, if the catalyst remains in the aromatic ethers which are reaction products, the product (the aromatic ethers) may be adversely affected. Therefore, it is preferable to remove the catalyst after the production of the aromatic ethers.

  However, since the techniques disclosed in Patent Document 2 and Patent Document 3 use a homogeneous catalyst, it is difficult to recover the catalyst after the reaction product is generated.

  For example, in addition to the techniques disclosed in Patent Document 2 and Patent Document 3, homogeneous catalysts such as metal hydroxides and ammonium salts are known as general catalysts. When these aromatic ethers are synthesized using these catalysts, the catalysts form salts with phenols that are raw materials. In order to remove this salt, complicated steps such as acid neutralization and water washing are required. However, phenols are liberated by reaction with acid, resulting in an increase in phenols as raw materials.

  It is possible to reduce the amount of free phenols at the time of neutralization by carrying out an excessive addition reaction between phenols and oxirane compounds. This causes a problem that it is difficult to obtain a product with high purity.

  Further, as a method for synthesizing the above aromatic ethers having a phenolic hydroxyl group, for example, a method of adding an oxirane compound to polyhydric phenols in the presence of a transition metal ion catalyst such as an iron ion is known ( Patent Document 4).

  However, according to the study by the present inventors, in this method, quinones are formed because a trace amount of oxygen present in the reaction system is oxidized by the transition metal ion as a catalyst to oxidize polyhydric phenol (catechol) as a raw material. It turns out that it is easy to do. Such quinones form so-called quinhydrones with phenols. Since these quinhydrones cause coloring of the aromatic ethers to be produced, the burden on the purification step after the reaction step increases, and this is not an industrially advantageous method.

  In general, quinhydrone is a molecular compound consisting of hydroquinone, which is a polyhydric phenol, and p-benzoquinone, which is an oxidation product thereof. The quinhydrone here refers to polyhydric phenols and their oxidation products. It refers to molecular compounds composed of quinones.

Furthermore, Patent Document 5 discloses a method of adding ethylene oxide to polyhydric phenols using a halogenated quaternary ammonium compound and a halogenated quaternary phosphonium compound. However, according to the study by the present inventors, it is difficult to selectively synthesize aromatic ethers having a phenolic hydroxyl group by this method, and since the catalyst is a low molecule, the reaction crude after the reaction is completed. It was found that it was difficult to separate the catalyst from the liquid, and this was not an industrially advantageous method.
Japanese Examined Patent Publication No. 39-30272 Japanese Patent Publication No. 50-654 Japanese Patent Publication No.49-33183 Dutch Patent No. 6600188 Japanese Patent Publication No.54-1291

  The present invention has been made in view of the above circumstances, and its purpose is to produce aromatic ethers having the desired structure with high selectivity while suppressing the production of by-products from phenols and oxirane compounds as raw materials. It is to provide a method of obtaining.

  The present inventors have found a method of using an anion exchange resin as a catalyst as a method for producing aromatic ethers satisfactorily by reacting phenols with an oxirane compound.

  By using an anion exchange resin as a catalyst, the aromatic ethers can be produced in a high yield by increasing the reaction activity. Further, since the reaction can be carried out even under reaction conditions that substantially use no water, the loss of the oxirane compound is small and the aromatic ethers can be produced with little waste water.

  When the anion exchange resin is solid, the target compound (aromatic ethers) and the catalyst can be easily separated and can be used repeatedly. Further, since the catalyst can be easily separated, a neutralization step of the catalyst after the reaction is not required, and the increase of unreacted phenol salts and impurity salts does not occur. Furthermore, since it is not necessary to add an oxirane compound excessively because unreacted phenols can be reduced, there is little production of by-products and the production selectivity of aromatic ethers of the target structure is good.

  As the aromatic ethers produced by the method of the present invention, first, after the reaction with the oxirane compound, at least one hydroxyl group of the polyhydric phenol remains, that is, phenolic hydroxyl group. And aromatic ethers. In this case, polyhydric phenols are used as the raw material phenols.

  In the second aspect of the aromatic ether produced by the method of the present invention, a phenol or a polyhydric phenol is used as a raw material, and the oxirane is substantially left without leaving a phenolic hydroxyl group of the phenol. Those reacted with a compound can be mentioned.

  In the production of the aromatic ethers, a solvent is used in the reaction step between the phenol and the oxirane compound, and the solvent used in the crystallization step performed after the reaction step is the same as the solvent used in the reaction step. It is recommended that they be common. By adopting such a method, the aromatic ethers can be obtained economically advantageously.

  In addition, the above aromatic ethers (aromatic ethers having an alcoholic hydroxyl group), the metal content is suppressed to less than 100 ppm (mass basis, the same shall apply hereinafter), and the halogen element content In the present invention, the above is suppressed to less than 100 ppm.

  The aromatic ethers have excellent compatibilizing ability because of their lipophilicity consisting of an aromatic ring moiety and hydrophilicity derived from a hydroxyl group and / or an ether group as structural characteristics. Moreover, since it has a high boiling point and low volatility, it is excellent in terms of safety, and is useful for applications such as solvents, emulsifiers and cleaning agents. Furthermore, in addition to the properties of excellent compatibilizing ability and high boiling point, it has a bactericidal action, so it is useful as an antibacterial / preservative, a cosmetic composition, and a fragrance retention agent.

  According to the method of the present invention, an anion exchange resin is used as a catalyst in producing a corresponding aromatic ether by reacting a phenol with an oxirane compound, thereby increasing the reaction activity and suppressing the generation of by-products. Aromatic ethers having the target structure can be produced with good yield. In addition, by using a solvent in the reaction step of the phenols and the oxirane compound, and using the same solvent as the solvent used in the reaction step, the solvent used in the crystallization step performed after the reaction step Aromatic ethers having such a structure can be obtained economically advantageously.

  Hereinafter, the present invention will be described in detail. The aromatic ether of the present invention is a compound that can be synthesized by reacting a phenol and an oxirane compound described below, and has an alcoholic hydroxyl group and a phenolic hydroxyl group, or has no phenolic hydroxyl group and is alcoholic. Those having a hydroxyl group are included. Such aromatic ethers are not limited to the reaction of such phenols with oxirane compounds, but can be synthesized by known techniques such as the reaction of alkylene carbonates, halogenated alkanols or polyhydric alcohols with phenols. You can also.

  The raw material phenols used in the method of the present invention may be either solid or liquid, and there is no particular limitation on the form (packaging) and purity.

  The phenols mean aromatic compounds containing one or more phenolic hydroxyl groups in the molecule. An aromatic compound is a compound having an aromatic ring, and the aromatic ring includes a non-benzene aromatic ring such as a cyclopentadiene ring; a benzene ring; a condensed aromatic ring such as a naphthalene ring, an anthracene ring, and a pyrene ring; Heteroaromatic rings (pyrrole ring, pyridine ring, thiophene ring, furan ring) in which one or more carbon atoms of the aromatic ring, aromatic ring or condensed aromatic ring are replaced by hetero atoms such as oxygen atom, nitrogen atom, sulfur atom Etc.);

  Unitary phenols include: phenol; o, m or p-cresol, o, m or p-ethylphenol, o, m or p-butylphenol, o, m or p-octylphenol, 2,3-xylenol, Phenols with hydrocarbon substituents such as 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,4-di-tert-butylphenol; o, m or p-phenylphenol, p- (α -Cumyl) phenol having an aromatic substituent such as phenol and 4-phenoxyphenol or a substituent containing an aromatic ring; phenol having an aldehyde group such as o, m or p-hydroxybenzaldehyde; ether bond such as guaiacol and guetol Phenol having a substituent containing; p-hydroxyphenethyl Phenol having a substituent containing an alcoholic hydroxyl group such as alcohol; phenol having a substituent containing an ester bond such as methyl p-hydroxybenzoate, methyl p-hydroxyphenylacetate and heptylparaben; 2,4,6-trichloro Phenol having a halogen group such as phenol and 2-amino-4-chlorophenol; phenol having a nitro group such as o or p-nitrophenol; aminophenol, 2,4,6-tris (dimethylaminophenol, p-hydroxy Examples include phenol having a substituent containing a nitrogen atom such as phenylacetamide, α-naphthol, β-naphthol, etc. Among these, phenol and cresol are preferable.

  As polyhydric phenols, catechols (catechol, protocatechuic acid, chloroacetylpyrocatechin, adrenalone, adrenaline, apomorphine, urushiol, tiron, phenylfluorone, etc.), resorcinols (resorcinol, orcin, hexyl resorcin, etc.), hydroquinone Dihydric phenols (eg, 2,3,5-trimethylhydroquinone, 2-t-butylhydroquinone, homogentisic acid ester); pyrogallols (pyrogallol, 2,3,4-trihydroxybenzophenone, lauryl gallate, gallic acid) Esters, purpurogallin, etc.), phloroglucins (eg, phloroglucin), trihydric phenols such as oxyhydroquinones (eg, oxyhydroquinone); bis (3,5-dimethyl-4 Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (4-methyl-6-tert-butylphenol), 3,9-bis (1,1-dimethyl-2 ( β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl-2,4,8,10-tetraoxaspiro (5,5) undecane, aluminone, atranoline, erythrin, catechin, epi Catechin, isocartamine, curcumin, coclaurine, cyanidin, syringidine, stilbestrol, tannic acid ester Bisphenols such as stealth, bisphenol A, bisphenol S, bisphenol Z, bisphenol fluorene, biscresol fluorene, phenol red, phlorizine, hexestrol, hematoxylin, pelargonidin, morin, decanolic acid; 1,4-dihydroxynaphthalene, carbonyl J acid , (R) -1,1′-bi-2-naphthol, (S) -1,1′-bi-2-naphthol, Eriochrome Black T, α-binaphthol, β-binaphthol, γ-binaphthol, etc. 1,4-dihydroxyanthraquinone, leuco-1,4-diaminoanthraquinone, leuco-1,4-dihydroxyanthraquinone, anthrahydroquinone, alizarin, alizarin S, emodin, quinizarin, kermesic acid Stealth, acidic anthraquinone dyes (alizarin safilol B and the like), hydroxyanthracenes or hydroxyanthraquinones such as purpurin and purproxanthine; citrazic acid; 1,1,3-tris (2-methyl-4-hydroxy-5-t -Butylphenyl) butane; 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-hydroxybenzyl) benzene; polyphenols, novolac resins, resole resins, atromentin, anthraquinone dyes (built) Dyed purple), usnic acid, dehydrourushiol, echinochrome, orthoserine ester, cartamine, acid mordant dye (diamond black F, chrome fast nebble B, paratin fast blue, etc.), dihydrophenylalanine ester, dilohol acid Ester, delphinidin, vitamin P, fluorescein, polymeric phenols, such as Poriporu acid; and the like.

  Among these polyhydric phenols, catechols, resorcinols, and hydroquinones are preferable as aromatic ethers having a phenolic hydroxyl group, and catechol, resorcinol, and hydroquinone are more preferable. Further, bisphenols are preferable as raw materials for aromatic ethers in which no phenolic hydroxyl group substantially remains, and bisphenol A, bisphenol S, bisphenol fluorene, and biscresol fluorene are more preferable.

  The oxirane compound as one raw material refers to a compound having one or more epoxy groups (three-membered ethers) in the molecule. For example, ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, aliphatic alkylene oxides such as pentylene oxide; aromatic alkylene oxides such as styrene oxide; cyclohexene oxide; It is. These oxirane compounds may be used alone or in combination of two or more. Among the above oxirane compounds, aliphatic alkylene oxides having 2 to 4 carbon atoms, that is, ethylene oxide, propylene oxide, isobutylene oxide, and 2,3-butylene oxide are preferable.

  The structure of the aromatic ether according to the present invention is represented by the following general formula (1).

In the above general formula (1), Z is a hydrocarbon residue containing an aromatic ring, and specifically, carbonization including non-benzene aromatic rings, benzene rings, condensed aromatic rings and heteroaromatic rings described above for phenols. A hydrogen residue is shown. "OH" and "O-A-OH" are groups that replace a hydrogen atom on Z, n is an integer of 1 or more and not more than the maximum number of hydrogen atoms that can be substituted on Z, and m is 1 or more and n The following integers are shown. A is represented by the following general formula (2).

In the general formula (2), R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group, or an aryl group. When R ^{1 to} R ⁴ are an alkyl group and / or an aryl group, they may have various substituents. R ¹ (or R ² ) and R ³ (or R ⁴ ) may form a cyclic structure (for example, a 5-membered ring or a 6-membered ring).

  The hydroxyl group bonded to the aromatic ring of Z in the general formula (1) is a “phenolic hydroxyl group” as used herein, and the hydroxyl group bonded to A is an “alcoholic hydroxyl group” as used herein.

  Moreover, the structure of the said phenols is shown by following General formula (3).

In the general formula (3), Z and n have the same meaning as in the general formula (1). “OH” is a group that substitutes a hydrogen atom on Z.

  Among these phenols, Z is a phenyl group and n = 1 (phenol), Z is a methylphenyl group and n = 1 (cresol), Z is a phenyl group and n = 2 (catechol, resorcinol, Hydroquinone), Z is a hydrocarbon residue represented by the following general formulas (4) to (7) and n = 2 {bisphenol A [general formula (4)], bisphenol S [general formula (5)], bisphenol Fluorene [general formula (6)] and biscresol fluorene [general formula (7)]} are preferable.

  Furthermore, the structure of the oxirane compound is represented by the following general formula (8).

In the general formula (8), R ^{5 to} R ⁸ each independently represent a hydrogen atom, an alkyl group, or an aryl group. When R ^{5 to} R ⁸ are an alkyl group and / or an aryl group, they may have various substituents. R ⁵ (or R ⁶ ) and R ⁷ (or R ⁸ ) may form a cyclic structure (for example, a 5-membered ring or a 6-membered ring).

Among these oxirane compounds, R ^{5 to} R ⁸ are hydrogen atoms (ethylene oxide), one of R ^{5 to} R ⁸ is a methyl group, the other three are hydrogen atoms (propylene oxide), and R ⁵ and R ⁶ are methyl. R ⁷ and R ⁸ are preferably hydrogen (isobutylene oxide), R ⁵ and R ⁷ are methyl groups, and R ⁶ and R ⁸ are preferably hydrogen (2,3-butylene oxide).

  The anion exchange resin used as a catalyst in the method of the present invention refers to a polymer compound having anion exchange ability. As the anion exchange resin, a resin that dissolves in a reaction solvent (described later) may be used, or a resin that does not dissolve and remains as a solid may be used. That is, the form of the anion exchange resin at the time of the reaction may be uniformly dissolved in the reaction solution, may form a slurry with the reaction solution, or may exist as a solid in the reaction solution. When present as a solid, it may be in the form of granules, particles, powder, a state supported on a support, or the like.

  From the viewpoint of separating and repeatedly using the catalyst after the reaction between the phenol and the oxirane compound, it is preferable to use an anion exchange resin that does not dissolve in the reaction solvent and exists as a solid.

  As said anion exchange resin, what has a principal chain and an anion exchange group essential, and also has a bridge | crosslinking part is preferable. Examples of the anion exchange group include groups having a tertiary amine, quaternary ammonium salt, tertiary phosphine, or quaternary phosphonium salt structure. Among them, a quaternary ammonium salt structure and a quaternary phosphonium salt structure are exemplified. A group having Furthermore, the anion exchange group preferably has a structure excellent in heat resistance, and specifically, it is recommended to have the following two structures.

  The first is that the anion exchange group has a cyclic structure. The form of the cyclic structure is preferably a 5-membered ring or a 6-membered ring, and more preferably a 5-membered ring. In particular, when it has a quaternary ammonium salt structure, it preferably has a piperidine skeleton or a pyridine skeleton. As the anion exchange resin containing an anion exchange group having such a cyclic quaternary ammonium salt structure, one synthesized by diallyldimethylammonium chloride is recommended from the viewpoint of easily forming such a resin.

  Secondly, there is a structure in which the anion exchange group is bonded to the main chain via an alkylene chain having 4 or more carbon atoms.

  The quaternary ammonium salt and quaternary phosphonium salt have an anion paired with a cationized hetero atom. The initial anion species of the anion exchange resin in the present invention is not particularly limited. For example, hydroxide ions; halide ions such as fluorine, chlorine, bromine and iodine; organic acid anions (such as carboxylic acid anions and phenoxy anions); inorganic acid anions; Inorganic acid anions include sulfate, sulfite, bisulfite, phosphate, borate, cyanide, carbonate, thiocyanate, nitrate, phosphate, hydrogenphosphate, meta Rate ions (for example, molybdate, tungstate, phosphotungstate, metavanadate, pyrovanadate, hydrogen pyrovanadate, niobate, tantalate, etc.) are included. Among the anionic species exemplified above, anions, hydroxide ions, and halide ions of various organic acids are preferable.

  As the anion exchange resin, either a low molecular anion exchange resin or a high molecular anion exchange resin can be used. In the case of a low molecular weight anion exchange resin, those having a molecular weight of 500 or more are desirable, and those having a molecular weight of 1000 or more are more desirable from the viewpoint that it is preferable that the catalyst be separated and used repeatedly after the reaction of the phenols and the oxirane compound.

  As a specific example of the anion exchange resin described above, for example, “Diaion TSA1200” manufactured by Mitsubishi Chemical Co., Ltd. can be cited as an anion exchange group having the second structure.

  Moreover, although heat resistance is comparatively low, "Diaion PA300 series", "Diaion PA400 series", "Diaion HPA25,75" made by Mitsubishi Chemical Corporation; "Dawex" made by DOW (SBR, SBR-P-) C, SAR, MSA-1, MSA-2, 22, Marathon A, Marathon ALB, Marathon A2, Monosphere 550A); “Duolite” (A113, A113LF, A113MB, A109D, A116, manufactured by Rohm and Haas) Commercially available anion exchange resins such as A116LF, A161TRSO4, A162LF, A368S, A378D, A375LF, A561, A568K, A7); can also be used.

  In the method of the present invention, a solvent may or may not be used when the phenol and oxirane compound are reacted. In the case of using a solvent, a water solvent, an organic solvent, and a mixed solvent thereof can be used. However, it is more preferable to use a solvent other than water because wastewater containing phenols is difficult to be treated with activated sludge.

  Incidentally, the catalyst used in the method of the present invention does not require water because the reaction between the phenol and the oxirane compound can proceed advantageously in the absence of water. The substantial absence of water here means a state where the content of water relative to the raw materials (phenols and oxirane compound) is less than 1% by mass, and more preferably less than 1000 ppm (mass basis).

  Specific examples of the solvent that can be used in the method of the present invention include alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, hexanol, and cyclohexanol; ethylene glycol monomethyl ether, C3-6 glycol ethers such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; C2-6 ethers such as tetrahydrofuran and dioxane; and the like. In addition, aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane; acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl isopropyl ketone, Ketones such as cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane; glycols such as ethylene glycol; pyridine; acetonitrile; dimethyl sulfoxide; dimethylformamide; ; Can also be used.

  In addition, the solvent preferably has a solubility parameter of 7.0 or more and 20.0 or less. In particular, when such a solvent is used in combination with the above catalyst in the reaction of polyhydric phenols with an oxirane compound, a part of the phenolic hydroxyl groups possessed by the polyhydric phenols may remain depending on the selection of reaction conditions. The reaction can proceed while the selectivity of the production of aromatic ethers having a phenolic hydroxyl group is very high. The reason is not clear, but when the solubility parameter of the solvent is within the above range, it is close to the solubility parameter with the main chain of the anion exchange resin as a catalyst, which contributes to the improvement of the reaction selectivity. It is considered a thing.

The “solubility parameter” (δ) referred to in the present invention is an index representing a measure of miscibility between liquids, and is the square root of the cohesive energy density in regular solution theory, and is represented by the following formula (9).
δ = (ΔE ^V / V) ^1/2 (9)
Here, V represents the molar volume (cm ³ / mol) of the solvent, and ΔE ^V represents the heat of evaporation of the solvent (cal / mol) at 25 ° C.

  Among the solvents that can be used in the method of the present invention, those having a solubility parameter within the above range include, for example, pentane (δ = 7.0), hexane (δ = 7.3), heptane (δ = 7. 4), cyclohexane (δ = 8.2), methyl isobutyl ketone (δ = 8.4), butyl acetate (δ = 8.5), o-xylene (δ = 8.8), p-xylene (δ = 8.8), toluene (δ = 8.9), tetrahydrofuran (δ = 9.1), ethyl acetate (δ = 9.1), benzene (δ = 9.2), methyl ethyl ketone (δ = 9.3) , Dichloromethane (δ = 9.7), 1,2-dichloroethane (δ = 9.8), cyclohexanone (δ = 9.9), acetone (δ = 9.9), 1,4-dioxane (δ = 10) 0.0), pyridine (δ = 10.7), ethylene glycol monomethyl ether (Δ = 11.4), 1-butanol (δ = 11.4), 2-propanol (δ = 11.5), acetonitrile (δ = 11.9), dimethyl sulfoxide (δ = 12.0), Examples include dimethylformamide (δ = 12.1), ethanol (δ = 12.7), methanol (δ = 14.5), ethylene glycol (δ = 14.6), ethylene carbonate (δ = 14.7) and the like. it can. The solubility parameter of such a solvent is disclosed in, for example, “A.F.M. Burton, Chemical Reviews, 1975, Vol. 75, No. 6, p731-753”.

In the method of the present invention, these exemplified solvents may be used alone or in combination of two or more. When two or more solvents are mixed, the solubility parameter of the mixed solvent only needs to be within the above range, and the solubility parameter of each solvent to be mixed is not particularly limited. The solubility parameter δ _mix of the mixed solvent is obtained by the following formula (10).
δ _mix = (x ₁ V ₁ δ ₁ + x ₂ V ₂ δ ₂ +... x _n V _n δ _n )
/ (X ₁ V ₁ + x ₂ V ₂ +... X _n V _n ) (10)
Here, n represents the type of solvent to be mixed, and x, V, and δ represent the molar fraction, molar volume, and solubility parameter of each solvent.

  When the solubility parameter of the solvent used is below the lower limit, the solubility of the polyhydric phenols is small and the concentration is low, so the productivity of the aromatic ethers tends to be low. A more preferred lower limit is 8.0, and a more preferred lower limit is 8.5. On the other hand, when the solubility parameter exceeds the upper limit, the difference between the solubility parameter of the hydrocarbon residue of the catalyst increases, and the selectivity of the aromatic ether to be produced (aromatic phenols having a phenolic hydroxyl group) Yield) tends to decrease. A more preferred upper limit is 12.5, a still more preferred upper limit is 11.5, and a particularly preferred upper limit is 10.5. Among the above solvents, for example, butyl acetate (δ = 8.5), toluene (δ = 8.9), methyl ethyl ketone (δ = 9.3), 1,4-dioxane (δ = 10.0) and the like. Particularly preferred.

  The form of the reaction in the method of the present invention is not particularly limited. For example, the reaction may be performed in a batch system or a continuous system. In the case of the continuous system, the catalyst can be suspended in the reaction kettle, and the reaction can be advanced by passing the reaction raw material through the catalyst as a fixed bed. In the method of the present invention, the raw materials are preferably mixed uniformly during the reaction, but may be separated into two layers as long as they can be reacted.

  In carrying out the above reaction, the amount of raw material charged, the amount of catalyst, the amount of solvent, the reaction time and the reaction temperature are not particularly limited, and these conditions may be appropriately selected according to the structure of the target aromatic ether.

  For example, when producing aromatic ethers having a phenolic hydroxyl group using polyhydric phenols as phenols, it is desirable to employ the following conditions. The raw material charge amount is 0.1 to 2.0 in terms of molar ratio of the oxirane compound to the amount of the phenolic hydroxyl group to which the oxirane compound should be added among the phenolic hydroxyl groups of the polyhydric phenols. Is preferable, and it is more preferable to set it as 0.5-1.5 from a viewpoint of economical efficiency. More preferably, it is 0.9-1.2.

  On the other hand, in order to produce aromatic ethers reacted with an oxirane compound without leaving phenolic hydroxyl groups as much as possible by using unit price or polyvalent phenols as phenols, the following conditions may be adopted. Recommended. The amount of raw material charged is preferably at least 0.9 in terms of molar ratio of the oxirane compound to the amount of phenolic hydroxyl group contained in the polyhydric phenol. More preferably, it is 0.95 or more, More preferably, it is 1.0 or more. Further, the upper limit of the molar ratio of the amount of oxirane compound to the amount of phenolic hydroxyl group possessed by polyhydric phenols is preferably 5, more preferably 2, still more preferably 1.5. 2 is particularly preferred and 1.05 is most preferred.

  It is recommended that the catalyst amount, the solvent amount, the reaction time, and the reaction temperature be selected from the following ranges regardless of the structure of the target aromatic ether.

  The amount of the catalyst is preferably 1 to 70% by volume, more preferably 5 to 30% by volume with respect to the total volume of the reaction solution containing the catalyst.

  The amount of the solvent is preferably 0 to 5 and more preferably 0 to 2.5 by mass ratio with respect to the polyhydric phenols which are raw materials.

  The reaction temperature is preferably 50 to 150 ° C, more preferably 80 to 120 ° C. In consideration of productivity, the reaction time is preferably 1 to 24 hours, and more preferably 1 to 12 hours.

  Since the aromatic ethers produced by the method of the present invention have high purity, they can be used as products directly after the reaction, but if necessary, only the aromatic ethers are distilled, extracted, and crystallized after the reaction. It is also preferable to separate the product by a general method such as Moreover, you may isolate | separate only the phenols which are raw materials by methods, such as distillation, extraction, and crystallization. In addition, the phenols that are raw materials are converted using a catalyst so that the phenols are substantially absent in the system, and the products after the conversion of the phenols are separated by a general method as described above. It doesn't matter.

  Examples of the distillation method include, but are not limited to, vacuum distillation, steam distillation, molecular distillation, and extractive distillation. The crystallization method includes (1) cooling the reaction solution after completion of the reaction, (2) adding a poor solvent for the target product to the reaction solution, (3) distilling off the solvent in the reaction solution, 4) There is a method of gradually pressurizing the reaction solution, and these can be carried out alone or in combination.

  Among these, it is preferable that a solvent is used in the reaction step of the phenols and the oxirane compound, and the solvent used in the crystallization step after the reaction step is the same as the solvent used in the reaction step. In this case, the cost for solvent loss and solvent recovery is low, and the target compound can be obtained economically advantageously. Here, “common” means that different types of solvents are not added to the reaction solution obtained in the reaction step. For example, the reaction solution obtained in the reaction step is substantially subjected to the crystallization step as it is, or the same kind of solvent as that used in the reaction step is added to the reaction solution, and this is subjected to the crystallization step. This is true. In this case, all or part of the solvent used in the reaction step may be contained in the crystallization solution in the crystallization step.

  Furthermore, the crystallization process can consist of one or more crystallization stages. During the crystallization process, it is preferable not to be in an open atmosphere but to be sealed with an inert gas. In the open state, oxygen is absorbed in the crystallization mother liquor, the hue is deteriorated, and it is difficult to obtain a high-quality product. The crystallization mother liquor from which the crystallization product has been separated is circulated to the reaction step or the crystallization step as necessary from the viewpoint of efficient use of the raw material phenols. In this case, at least a part of the crystallization mother liquor obtained in the crystallization step can be used as the raw material mother liquor. Usually, a multi-stage crystallization step and a solid-liquid separation step of the crystallization product are employed, and according to this, a plurality of types of mother liquors (phenol solutions) are obtained. The mother liquor at the stage can be used as a raw material mother liquor for the reaction step or the crystallization step. In these steps, as described above, it is more efficient to use a common solvent for the reaction step and the crystallization step.

  In the crystallization step, it is recommended that the solubility parameter of the solvent during crystallization is 7.5 or more and 12.5 or less. If the crystallization solvent has such a solubility parameter, for example, it is necessary to prepare the solution so that aromatic ether crystals precipitate well by changing the state of the crystallization solution slightly. Is easy.

  If the solubility parameter of the crystallization solvent is below the lower limit, the solubility of the aromatic ether in the solvent tends to be small, and crystallization may be difficult or substantially impossible. A more preferred lower limit is 8.0, and a more preferred lower limit is 8.5. On the other hand, if the solubility parameter of the crystallization solvent exceeds the above upper limit, the solubility of the aromatic ethers in the solvent is large, so that the degree of change in the state of the crystallization solution necessary for precipitating the crystals is increased. In some cases, the crystallization efficiency tends to decrease. A more preferred upper limit value is 11.0, a still more preferred upper limit value is 10.0, and a particularly preferred upper limit value is 9.5.

  For example, when the solubility parameter of the solvent used in the reaction step is 7.5 or more and 12.5 or less, crystallization may be performed directly from the reaction solution, and the solubility parameter is 7.5 or more and 12.12. It may be carried out after adjusting the solution concentration by adding 5 or less solvent or removing part of the solvent by distillation or the like.

  On the other hand, when the solubility parameter of the solvent used in the reaction solution is less than 7.5 or more than 12.5, other solvents are added and mixed so that the solubility parameter is in the range of 7.5 to 12.5. Alternatively, crystallization may be performed by replacing the reaction solvent with a solvent having a solubility parameter of 7.5 to 12.5.

  However, as described above, since it is preferable to use a common solvent for the reaction step and a solvent for the crystallization step, a solvent having a solubility parameter of 7.5 to 12.5 is selected as the solvent for the reaction step. It is desirable to keep it.

  Furthermore, it is desirable to remove the catalyst used for the reaction from the reaction solution (crystallization solution) prior to the crystallization step. For example, when an anion exchange resin catalyst that can be dissolved in a reaction solvent is used, the target compound may be contained in the target compound when crystallization is performed. As a method for removing the catalyst, a suitable method may be appropriately selected from known methods such as adsorption, filtration, concentration, distillation, and washing according to the catalyst used. The residual amount of the catalyst is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass in the crude aromatic ether contained in the crystallization solution. It is below mass%. The “crude aromatic ethers” include impurities such as unreacted raw materials and by-products generated during the reaction, in addition to the aromatic ethers that are target compounds.

  Hereinafter, preferable crystallization conditions will be described by taking mono (hydroxyethyl) ethers of dihydroxybenzene contained in β-phenoxyethanol as examples. In the case of other aromatic ethers, the conditions may be changed according to the respective characteristics. For example, when determining the concentration of the crystallization solution and the crystallization temperature, a solubility curve (a curve indicating the relationship between the temperature and the solubility of the aromatic ether) is obtained for the aromatic ethers and the solvent to be used. It can be easily determined based on the solubility curve.

  Here, mono (hydroxyethyl) ethers of dihydroxybenzene are substances having a structure in which one of the phenolic hydroxyl groups of dihydroxybenzenes is converted to a hydroxyethoxy group. Dihydroxybenzenes include catechol, resorcin, hydroquinone, and substituted products in which one or more hydrogen atoms on these benzene rings are substituted with a hydrocarbon residue (such as an alkyl group) or a halogen atom.

  The concentration of the crystallization solution is 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more of the crude dihydroxybenzene mono (hydroxyethyl) ether with respect to the total amount of the solution. Recommended. Below the lower limit, productivity [yield of monohydroxyethyl ether of dihydroxybenzene extracted from the reaction solution] is low, and it is necessary to recover a large amount of solvent, leading to an increase in cost. It is not preferable.

  On the other hand, the upper limit of the concentration of the crystallization solution is 40% by mass, more preferably 30% by mass, and still more preferably 20% by mass. When the above upper limit is exceeded, solid-liquid stirring at the time of crystal precipitation becomes difficult, and there is a risk of hindrance in industrial implementation. Further, as will be described later, it is preferable to precipitate crystals while stirring the crystallization solution. However, when the concentration of mono (hydroxyethyl) ethers of dihydroxybenzene exceeds the above range, mono (hydroxyethyl) ether of dihydroxybenzene It becomes difficult to stir solid-liquid after the crystals of a kind are precipitated, a good slurry cannot be obtained, and purification tends to be inadequate or it is difficult to take out the crystals.

  Prior to the precipitation of crystals, the crystallization solution is heated after preparation, and if an insoluble component exists, it is also preferable to perform a separation operation to remove it. As the separation method, various known methods such as filtration such as vacuum filtration and pressure filtration; and centrifugal separation can be employed. The filter cloth and filter used in the case of filtration are not particularly limited, and a filter having an opening that can remove insolubles may be selected.

  The preferred temperature for crystallization varies depending on the crystallization solvent to be used, but is usually set to a temperature of −50 ° C. or higher and the boiling point of the crystallization solvent or lower. The temperature at the time of crystallization here means the temperature from the start to the end of the crystallization process. For example, as a crystallization method, a method in which a crystallization solution is heated and then cooled to precipitate a crystal can be used (described later). Even in this case, the crystallization solution is heated and the solution is cooled. It is recommended that the temperature of the crystallization solution at the point of time when the crystallization process is completed is within the above range.

  If the temperature at the time of crystallization is below the above range, there will be a great disadvantage in terms of cost.On the other hand, if the temperature at the time of crystallization exceeds the above range, the evaporation of the solvent used will become remarkable, and Changes in solvent concentration can be problematic. As a more preferred embodiment, crystallization is carried out under the condition of −50 to 100 ° C. using a solvent having a boiling point of 100 ° C. or higher, and if such a condition is adopted, the crystallization is performed. This is advantageous in terms of temperature control.

  Depending on the solvent, mono (hydroxyethyl) ethers of dihydroxybenzene may be difficult to dissolve at room temperature and may become a suspension (slurry). In this case, the slurry is once heated to form a solution and then crystallized. What is necessary is just to select the temperature at the time of heating within the suitable range in the above-mentioned crystal precipitation.

  The pressure at the time of crystallization is generally normal pressure. However, for example, when a low boiling point solvent is used, it is also preferable to perform crystallization under pressurized conditions.

  As described above, as the crystallization method, mono (hydroxyethyl) ethers of raw material dihydroxybenzene are completely dissolved in a solvent to form a solution, (I) a method of gradually lowering the temperature of the solution; A method of gradually volatilizing; (III) a method of gradually adding the solution to a poor solvent of mono (hydroxyethyl) ethers of dihydroxybenzene; (IV) a method of gradually pressurizing the solution; Thus, when the state of the crystallization solution is changed in order to precipitate mono (hydroxyethyl) ether crystals of dihydroxybenzene, it is preferable to carry out the stirring of the system.

  Among the above crystallization methods, a method of gradually lowering the temperature of the solution after mono (hydroxyethyl) ethers of the raw material dihydroxybenzene are completely dissolved in the solvent is preferable. In this case, the temperature for complete dissolution is preferably 80 to 100 ° C. If the temperature at the initial stage of crystallization is within such a range, the subsequent cooling is easy. The rate at which the crystallization solution thus obtained is cooled is preferably 40 ° C./hour or less, more preferably 30 ° C./hour or less, still more preferably 20 ° C./hour. It is as follows. If the cooling rate exceeds the above upper limit, the purification will be insufficient, the crystals of mono (hydroxyethyl) ethers of dihydroxybenzene will become finer, and the filtration rate tends to be slower when taking out the crystals from the crystallization solvent. is there.

  As described above, dihydroxybenzene mono (hydroxyethyl) ether crystals are precipitated by changing the state of the crystallization solution, such as by lowering the temperature of the crystallization solution. Even if the degree is relatively large, if the crystal precipitation is not good, it is also preferable to add a mono (hydroxyethyl) ether of dihydroxybenzene to the crystallization solution to promote the crystal precipitation.

  By such an operation, crystals of mono (hydroxyethyl) ethers of dihydroxybenzene are precipitated in the crystallization solvent. If the concentration of the crystallization solution before the crystallization is within the above range, the crystallization including the precipitated crystals is performed. The solvent (slurry) does not become a viscous paste or the like, and stirring of the slurry does not become difficult. Further, separation of crystals from the slurry can be easily performed.

  After the crystals are sufficiently precipitated, a separation operation for taking out the crystals from the slurry is performed. As a separation method, known methods such as filtration such as reduced pressure filtration and pressure filtration; centrifugation; and the like can be carried out, and the conditions at that time are not particularly limited. The filter cloth and filter used for the filtration are not particularly limited, and a filter having a degree of opening that can sufficiently collect crystals can be used.

  After taking out the crystals, drying is performed with a drier or the like to obtain mono (hydroxyethyl) ethers of dihydroxybenzene.

  Moreover, it is also preferable to make the crude product taken out from the reaction solution by the above crystallization method or the like into a purified product with higher purity by a known purification method. Incidentally, the crystallization method using the solvent having the above solubility parameter can be used not only for removing the aromatic ether from the reaction solution but also for purifying the aromatic ether after removal from the reaction solution. It is.

  Unreacted polyhydric phenols in the aromatic ethers are easily oxidized at a high temperature, and are easily converted into quinones (benzoquinones and the like) to produce the quinhydrones that cause coloring of purified products. In addition, quinones have sublimability and are difficult to remove by distillation purification. Furthermore, since the above-mentioned aromatic ethers are solid at room temperature, it is necessary to always keep each part of the distillation apparatus warm at the time of distillation purification in order to keep the aromatic ethers in a liquid state. Was needed.

  However, if the crystallization method uses a solvent having a solubility parameter within the above range as a crystallization solvent, oxidation of unreacted polyphenols (generation of quinones) in the purification process can be suppressed, and the quinone Even if the product is produced, it can be sufficiently removed in this crystallization step. Therefore, the purified aromatic ethers have high purity with suppressed coloring. Further, in the crystallization method, the amount of energy required in the purification process can be greatly reduced as compared with the conventional method that employs the distillation method.

  In addition, when the crystallization method is employed in the purification step of the aromatic ethers, the raw material aromatic ethers (corresponding to the “crude aromatic ethers”) used in the purification step are target compounds. It is preferable that 40 mass% or more and 98 mass% or less of aromatic ethers are contained. Below the lower limit, the purification yield of the target compound, aromatic ethers, tends to decrease. A more preferred lower limit is 50% by mass, and a still more preferred lower limit is 60% by mass. On the other hand, when the above upper limit is exceeded, the effect of purifying the aromatic ether as the target compound tends to decrease. A more preferable upper limit value is 95% by mass, and a further preferable upper limit value is 90% by mass. Prior to the crystallization step, other purification may be performed so that the amount of the aromatic ether in the raw material aromatic ether falls within the above range. Other purification methods include various known methods such as concentration, distillation, and washing.

  As described above, the produced aromatic ethers can be used as long as there is no problem in use depending on the application, and in that range, after the completion of the reaction, the product remains containing unreacted raw materials and other impurities. Can be used as

  As described above, alkali metal salts, metal hydroxides, ammonium halide salts, phosphonium halide salts, and the like are known as conventionally used catalysts for producing the aromatic ethers. However, when these known catalysts are used for the production of the aromatic ethers according to the present invention, even if a catalyst removal step is provided, a trace amount of metal (for example, alkali metal in the above alkali metal salt, metal water in the above) Aromatic ethers in which the metal is an oxide) or halogen (for example, in the above-mentioned ammonium halide salt and phosphonium halide salt, these halogens, specifically, F, Cl, Br, I) are products. It is unavoidable to be mixed in.

  In the use of the above aromatic ethers, reduction of the amount of such metals and halogens is required from the viewpoint of deterioration of physical properties and from the viewpoint of environmental considerations. The upper limit of the allowable amount of metal contamination is 100 ppm, preferably 50 ppm, more preferably 30 ppm, still more preferably 10 ppm, and particularly preferably 1 ppm. Further, the upper limit value of the mixing of halogen is 100 ppm, preferably 50 ppm, more preferably 30 ppm, still more preferably 10 ppm, and particularly preferably 1 ppm. When the mixed amount of metal or halogen exceeds these upper limit values, various physical properties are lowered when aromatic ethers are used.

  In contrast, in the method of the present invention, since an anion exchange resin is used as a catalyst, the crude product and the purified product after the completion of the reaction have a low content of impurities such as metals and halogens and are substantially free of metals and halogens. Products that do not contain can also be manufactured. Specifically, the metal and / or halogen content is less than 100 ppm, preferably less than 50 ppm, more preferably less than 30 ppm, even more preferably less than 10 ppm, and particularly preferably less than 1 ppm.

  The metal content referred to in this specification is a value measured by inductively coupled plasma emission spectrometry, and the halogen content is a value measured by fluorescent X-ray analysis.

  Specifically, when measuring the metal content, an inductively coupled plasma emission analyzer “SPS4000” manufactured by Seiko Denshi Kogyo Co., Ltd. is used as an analyzer.

  In addition, for the measurement of the halogen content, a fluorescent X-ray analyzer “PW2404” manufactured by PHILPS is used as the analyzer, and a qualitative analysis program provided in the apparatus is used, and halogen elements (F, Cl, Br) are used. Quantification by comparison with a standard sample of I).

In addition, when the halogen content is lower than the detection limit of the fluorescent X-ray analyzer, the ion chromatography can be measured using “DX-500” manufactured by Dionex. In this ion chromatography, since detection is possible when the halogen is in an ionic state, measurement is performed after ionizing the halogen as necessary. The measurement conditions are as follows.
Detector: CD-20 (electric conductivity detector)
Column: AS4A-SC
Guard column: AG4A-SC
Eluent: 1.8 mmol / L Na ₂ CO ₃ , 1.7 mmol / L NaHCO ₃
Regenerating solution: 25 mmol / L H ₂ SO ₄ .

  In the method of the present invention, since an anion exchange resin is used as a catalyst, the content of impurities is small and the target compound can be produced efficiently. Furthermore, since the catalyst can be easily separated, the product can be purified efficiently. The amount of unreacted phenols can be 500 ppm or less (mass basis, the same shall apply hereinafter), preferably 100 ppm or less, more preferably 30 ppm or less with respect to the aromatic ethers. In addition, the proportion of impurities in which the oxirane compound is excessively added to the phenolic hydroxyl group of the aromatic ether can be 10% by mass or less, preferably 5% by mass or less, more preferably 2% by mass or less. .

  In addition, according to the method of the present invention, even when the target compound is an aromatic ether having a phenolic hydroxyl group, it can be produced with high selectivity. For example, when ethylene oxide, an oxirane compound, is reacted with catechol, which is a divalent phenol, 2- (2-hydroxyphenoxy) ethanol with one phenolic hydroxyl group remaining can be obtained with high selectivity. It is. This compound preferably has 6 mmol or more of phenolic hydroxyl group per gram. In addition, the suitable amount of this phenol hydroxyl group changes with raw material phenols and target aromatic ethers.

  The aromatic ethers thus obtained can be used alone or mixed with other components depending on the application. There is no particular limitation on the shape and state, and it can be handled in the form of a solid (eg, powder, flakes, granules, etc.), slurry, solution (eg, organic solvent solution), etc.

  Moreover, as a form of transport and storage of the aromatic ether, there may be mentioned a crude product after completion of the reaction, a purified product, and a diluent or stabilizer added thereto. For example, from the viewpoint of preventing the oxidation of phenolic hydroxyl groups, the gas phase is replaced with an inert gas (usually oxygen concentration: 0.01 vol% or less, preferably 0.001 vol% or less), and the light is shielded from light. Is preferred. Furthermore, it is more preferable that a radical scavenger (for example, about 10 to 100 ppm by mass of phosphorous acid or phosphorous acid diester) coexists. From the viewpoint of preventing hue deterioration, it is also recommended to use slightly acidic conditions (for example, pH = about 6 to 7). In this case, for example, an aliphatic carboxylic acid (formic acid, oxalic acid, citric acid, tartaric acid, glycolic acid, lactic acid, succinic acid, malic acid, glyceric acid, etc., more preferably low-volatile lactic acid, succinic acid, etc.) Organic acids can be added. The addition amount is preferably about 1 to 1000 ppm by mass, more preferably about 5 to 100 ppm by mass. The addition time of these additives (diluent, stabilizer) is not particularly limited. In other words, any time of the reaction process, the crystallization process, the production process, and the like may be used.

  Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention. In this example, “ppm” is based on mass.

Catalyst Synthesis Example Hereinafter, a method for preparing the anion exchange resin A used as a catalyst in this example will be described. First, 350 ml of toluene and 50 ml of liquid paraffin were charged into a 1 liter separable flask, sorbitan palmitate: 0.07 g, and ethyl cellulose: 0.21 g were added and dissolved to obtain a dispersion medium. In addition, an aqueous solution of diallyldimethylammonium chloride having a concentration of 65% by mass: 41.8 g, N, N, N ′, N′-tetraallyldipiperidylpropanium dichloride (TADPPC, crosslinking agent): 8.3 g, and water: 5.4 g was mixed and dissolved to obtain a monomer solution. Further, a solution in which 2,2′-azobis (2-amidinopropane) dihydrochloride as a polymerization initiator (“V-50” manufactured by Wako Pure Chemical Industries, Ltd.): 0.32 g and water: 3.5 g are mixed. Was added to the monomer solution. The crosslinking agent TADPPC is a compound obtained by adding allyl chloride to 1,3-di (4-piperidyl) propane and tetraallylating it.

  Next, the monomer solution was added to the dispersion medium with stirring, and reacted at 55 ° C. for 4 hours, at 60 ° C. for 16 hours, and further at 92 to 95 ° C. for 6 hours. Thereafter, the produced particles were separated by filtration, washed once with toluene: 600 ml, and further washed three times with methanol: 800 ml, and vacuum-dried to obtain 36.2 g of dry particles. The obtained particles were designated as anion exchange resin A (Cl type).

  An anion exchange resin A (OH type) was prepared as follows. The above-mentioned resin A (Cl type) is swollen with water and packed in a chromatographic column. The column is filled with 20N volume of 2N NaOH aqueous solution, 20 times volume of ion-exchanged water, 10 times volume. Of methanol were sequentially passed. Here, the liquid passing speed was SV2. Subsequently, methanol was removed by vacuum drying to obtain anion exchange resin A (OH type).

Experiment 1 <Production of Aromatic Ethers Reacted with Oxirane Compound without Substantially Remaining Hydroxyl Group of Raw Material Phenols>
Example 1
Addition reaction of ethylene oxide (EO) to phenol, which is a unit price phenol, was performed. A 500 ml autoclave equipped with a gas supply pipe and a stirrer was charged with 90 g of phenol, 239 g of ethylene glycol monomethyl ether as a solvent, and 15.5 g of anion exchange resin A (Cl-type dry product) as a catalyst, and sealed. . Subsequently, dissolved oxygen in the liquid was removed by a deaeration operation, and the gas phase portion was further replaced with nitrogen, and the pressure was increased to 1 kg / cm ² · G. Next, the internal temperature was raised to 100 ° C., and 48 g of EO was added over 30 minutes through the gas supply pipe. Furthermore, after reacting for 6.5 hours while maintaining the internal temperature at 90 to 100 ° C., the reaction solution and the anion exchange resin A were separated by filtration.

  The reaction solution was analyzed by gas chromatography (GC). The analysis conditions are described below. All GC analyzes in this example were performed according to the following conditions. “GC-15A” manufactured by Shimadzu Corporation was used for the GC device, “DB-1 (φ32 mm × 30 m)” manufactured by J & W was used for the column, and helium was used for the carrier. The temperature condition was such that the sample was held at 70 ° C. for 5 minutes after the sample injection, then heated to 300 ° C. at a rate of 15 ° C. per minute, and then held at 300 ° C. The composition in the measurement sample is indicated by the area ratio of the corresponding peak shown in the obtained GC chart.

  As a result of GC analysis, the raw material phenol in the reaction solution was 70 ppm, the phenol EO1 adduct (β-phenoxyethanol) was 98.6%, and the phenol EO2 adduct was 1.4%. The phenol EO2 adduct means that two molecules of EO and the phenolic hydroxyl group react to form an ether.

Example 2
The EO addition reaction to phenol was carried out in the same manner as in Example 1 except that no solvent was used and the following points were changed. Phenol: 225.8 g, anion exchange resin A (Cl-type dry product): 10.0 g was charged in an autoclave, and EO: 110 g was fed at 100 ° C. over 2 hours. After further aging at 100 ° C. for 7 hours, the reaction solution and the anion exchange resin A were separated.

  The composition of the reaction solution by GC measurement was 90 ppm for raw material phenol, 95% for β-phenoxyethanol, and 4.9% for EO2 adduct of phenol.

Example 3
The EO addition reaction to bisphenol S (BPS), which is a polyhydric phenol, was carried out in the same manner as in Example 1 except that the following points were changed. BPS: 100 g, ethylene glycol monomethyl ether: 200 g as a solvent, and anion exchange resin A (Cl-type dry product): 13.6 g were charged into an autoclave and sealed. Next, the internal temperature was raised to 100 ° C., and 44 g of EO was added over 30 minutes. Further, after aging for 5.5 hours while maintaining the internal temperature at 100 ° C., the reaction solution and the anion exchange resin A were separated by filtration. When the separated reaction liquid was cooled, a white solid was precipitated.

  The analysis of the reaction solution was performed by liquid chromatography (LC) after adding dimethylformamide and dissolving it uniformly. Hereinafter, LC analysis conditions will be described. The LC device is manufactured by Hitachi, Ltd. (pump L-7100, UV detector L-7450H), the column is “Inert Sil ODS (φ4.6 mm × 25 cm)” manufactured by GL Sciences, and the carrier is 0.1% by mass phosphoric acid. / Methanol mixed solution (40/60 by volume) was used. The column temperature was 40 ° C. and the flow rate was 1 ml / min. The composition in the measurement sample is indicated by the area ratio of the corresponding peak shown in the obtained LC chart.

  As a result of LC analysis, the raw material BPS was converted to 100.0%, the BPS EO2 adduct was 95%, the BPS EO3 adduct was 4.1%, and the BPS EO1 adduct was not detected. . The EO1 adduct of BPS means that EO reacts with only one of the two hydroxyl groups of BPS to become ether. The EO2 adduct of BPS means that both of the two hydroxyl groups of BPS react with EO to become ether. The EO3 adduct of BPS means that one of the hydroxyl groups of BPS reacts with one molecule of EO, and the other hydroxyl group reacts with two molecules of EO to become an ether. Yes.

Example 4
Addition reaction of propylene oxide (PO) to phenol was performed. Phenol: 10.0 g, PO: 7.4 g, and anion exchange resin A (Cl-type dry product): 0.8 g as a catalyst were put into a 50 ml glass pressure vessel. Subsequently, the gas phase was purged with nitrogen, sealed, and heated in an oil bath at 100 ° C. while shaking. After reacting for 12 hours, the reaction solution and the anion exchange resin A were separated by filtration.

  The composition in the reaction solution by GC analysis was 10 ppm for the raw material phenol, 94.4% for the PO1 adduct of phenol, and 5.3% for the PO2 adduct of phenol. The phenol PO1 adduct means that one molecule of PO and the hydroxyl group of phenol react to form an ether. The phenol PO2 adduct means an ether formed by the reaction of two molecules of PO and the hydroxyl group of phenol.

Example 5
The addition reaction of PO to bisphenol A (BPA) was performed in the same manner as in Example 4 except that the following points were changed. BPA: 5.0 g, PO: 2.8 g, ethylene glycol monomethyl ether: 10.0 g as a solvent, and anion exchange resin A (OH type): 0.5 g as a catalyst were charged and heated at 100 ° C. After reacting for 6 hours, the reaction solution and anion exchange resin A were separated by filtration.

  The composition of the reaction mixture by GC analysis was 0.1% for BPA PO1 adduct, 99.0% for BPA PO2 adduct, and 0.8% for BPA 3PO adduct. The PO1 adduct of BPA means that one of the two hydroxyl groups of BPA reacts with PO to form ether. Further, the PO2 adduct of BPA means that both of the two hydroxyl groups of BPA react with PO to become ether. The PO3 adduct of BPA means that one of the hydroxyl groups of BPA reacts with one molecule of PO and the other hydroxyl group reacts with two molecules of PO to become an ether. Yes.

Example 6
The addition reaction of EO to BPA was carried out in the same manner as in Example 1 except that the following points were changed. That is, 100 g of BPA, 200 g of ethylene glycol monomethyl ether as a solvent, and 10.0 g of anion exchange resin A (Cl-type dry product) were charged into an autoclave and sealed. Next, after adding 44 g of EO and aging at 100 ° C. for 7 hours, the reaction solution and the anion exchange resin A were separated by filtration.

  The composition in the reaction solution by GC analysis was as follows: BPA EO1 adduct (BPA-1EO) 0.4%, BPA EO2 adduct (BPA-2EO) 97.7%, BPA 3PO adduct (BPA- 3EO) was 1.9%. Raw material BPA was not detected. The BPA EO1 adduct (BPA-1EO), the BPA EO2 adduct (BPA-2EO), and the BPA EO3 adduct (BPA-3EO) are the BPA PO1 adduct and BPA PO2 in Example 5, respectively. This means that the adduct, PO of BPA PO3 adduct, is replaced with EO.

Example 7
When the reaction solution of Example 6 was allowed to stand at room temperature, a white solid was precipitated. Furthermore, after cooling to -20 degreeC and leaving still for 3 hours, solid substance was isolate | separated by filtration and dried.

  The composition of the solid according to GC analysis was 0.1% for BPA-1EO, 98.3% for BPA-2EO, and 1.6% for BPA-3EO. Further, the recovery rate of BPA-2EO (yield relative to the theoretical yield of the oxirane compound adduct calculated from the amount of the raw material, the same applies hereinafter) was 80%.

Example 8
A catalyst reuse experiment was conducted. Experiments were conducted in the same manner as in Example 6 using the anion exchange resin A used and recovered in Example 6. However, the EO addition amount was changed to 39 g and the aging was changed to 9 hours. The composition in the reaction solution by GC analysis was 0.3% for BPA-1EO, 97.1% for BPA-2EO, and 2.6% for BPA-3EO, and BPA was not detected. This experiment revealed that the anion exchange resin catalyst can be reused.

Example 9
The reaction was conducted in the same manner as in Example 6 except that the solvent was changed to 200 g of methanol and the aging was changed to 9 hours. The composition in the reaction solution by GC analysis was 0.5% for BPA-1EO, 97.7% for BPA-2EO, and 1.9% for BPA-3EO, and BPA was not detected.

  Subsequently, the reaction solution was allowed to stand at 25 ° C. for 3 hours, and then the precipitated solid was collected and dried. The composition of the solid by GC analysis was 0.1% for BPA-1EO, 98.9% for BPA-2EO, and 1.0% for BPA-3EO. The recovery rate of BPA-2EO was 70%.

Example 10
The addition reaction of EO to bisphenolfluorene (BPF) was carried out in the same manner as in Example 1 except that the following points were changed. BPF: 100 g, ethylene glycol monomethyl ether: 200 g, anion exchange resin A (Cl-type dry product): 10.0 g were charged into an autoclave, and EO: 31 g was added. Next, it was made to react at 100 degreeC for 12 hours, and the reaction liquid and the anion exchange resin A were isolate | separated after that.

  The composition of the reaction solution by GC analysis was 97.1% for BPF-2EO and 2.7% for BPF-3EO. BPF and BPF-1EO were not detected.

Example 11
When the reaction solution obtained in Example 10 was allowed to stand at 25 ° C., a white solid was precipitated. This solid was collected and dried. The composition of the solid substance by GC analysis was 98.0% for BPF-2EO and 2.0% for BPF-3EO. The recovery rate of BPF-2EO was 60%.

Example 12
The EO addition reaction to biscresol fluorene (BCF), which is a polyhydric phenol, was carried out in the same manner as in Example 1 except that the following points were changed. BCF: 100 g, ethylene glycol monomethyl ether: 200 g as a solvent, and anion exchange resin A (Cl-type dry product): 10.0 g were charged into an autoclave and sealed. Next, 29.1 g of EO was added, and after aging at 100 ° C. for 10 hours, the reaction solution and the anion exchange resin A were separated by filtration.

  The reaction solution composition was analyzed by LC. The conditions for the LC analysis were the same as those in Example 3, except that a 0.1% by mass phosphoric acid / methanol mixed solution having a volume ratio of 35/65 was used. As a result of LC analysis, the raw material BCF was converted to 100.0%, BCF EO2 adduct was 96.3%, BCF EO3 adduct was 3.4%, and BCF EO1 adduct was detected. There wasn't. The EO1 adduct of BCF means that one of two hydroxyl groups of BCF reacts with EO to become ether. Moreover, the EO2 adduct of BCF means that both of the two hydroxyl groups of BCF react with EO to become ether. The EO3 adduct of BCF means that one of the hydroxyl groups of BCF reacts with one molecule of EO and the other hydroxyl group reacts with two molecules of EO to become an ether. Yes.

Example 13
Crystallization purification of the reaction solution obtained in Example 12 was performed. A crystallization solution composed of the above reaction solution was put into a separable flask equipped with a stirrer, a cooler and a thermometer, and heated to 95 ° C. with an oil bath. Next, the above crystallization solution was cooled from 95 ° C. to 40 ° C. at a rate of 5 ° C./hour while stirring at a rotation speed of 200 rpm. The crystallization solution was a fluid slurry as a whole. Further, the crystallization was completed by maintaining at 40 ° C. for 1 hour. The obtained slurry was filtered, and the collected matter was washed with 40 g of ethylene glycol monomethyl ether at room temperature and dried under reduced pressure at 60 ° C. to obtain a purified product. The purified product was subjected to LC analysis in the same manner as in Example 12. As a result, the composition of the purified product was 99.2% BCF 2EO adduct and 0.8% BCF 3EO adduct. The recovery rate of 2CF adduct of BCF was 60%.

Experiment 2 <Production of aromatic ethers having phenolic hydroxyl groups>
Example 14
Addition reaction of EO to catechol (CC) was performed. A 500 ml autoclave equipped with a gas supply pipe and a stirrer was charged with 100 g of CC, 200 g of ethylene glycol monomethyl ether as a solvent, and 14 g of anion exchange resin A (Cl-type dry product) as a catalyst, and sealed. Subsequently, dissolved oxygen in the liquid was removed by a deaeration operation, and the gas phase portion was further purged with nitrogen and pressurized. Next, the internal temperature was raised to 100 ° C., and 44 g of EO was added through a gas supply pipe over 30 minutes. Furthermore, the internal temperature was kept at 100 ° C., and aging was performed for 3 hours. After completion of the reaction, the reaction solution and the anion exchange resin A were separated by filtration.

  The composition analysis of the reaction solution was performed by GC. The raw material CC reacted 88%, and the ratio of the target product [EO1 adduct of CC = β- (2-hydroxyphenoxy) ethanol] (hereinafter referred to as “reaction selectivity”) in the product was 82%. It was.

Example 15
The reaction was carried out in the same manner as in Example 14 except that the solvent was changed to toluene. The reaction results are shown in Table 1. Furthermore, after completion | finish of reaction, the reaction liquid was subjected to pressure filtration, maintaining 100 degreeC, and resin A and the reaction liquid were isolate | separated. The obtained reaction liquid was allowed to stand at room temperature and allowed to cool, whereby a white solid was precipitated. As a result of GC analysis (calibration curve method), the composition of this solid was CC: 0.6% by mass, CC EO1 adduct: 96.8% by mass, CC EO2 adduct: 2.6% by mass The yield was 85 g. The EO2 adduct of CC means that both hydroxyl groups of CC react with EO to become ether.

  The sodium (metal) content in the obtained solid was measured by inductively coupled plasma emission spectrometry. “SPS4000” manufactured by Seiko Denshi Kogyo Co., Ltd. was used as the analyzer. As a result, the sodium content was less than 1 ppm based on the solid.

  Further, the content of halogen element in the obtained solid was measured by fluorescent X-ray analysis. “PW2404” manufactured by PHILIP was used as the analyzer, and quantification was performed by using a qualitative analysis program provided in the apparatus and comparing with a standard sample of a halogen element (F, Cl, Br, I). As a result, no halogen element was confirmed, and its content was less than 100 ppm.

Examples 16-18
The reaction was performed in the same manner as in Example 14 while changing various conditions. Reaction conditions and reaction results are shown in Table 1. However, in Examples 17 and 18, the addition time of EO was 3 hours.

Example 19
The anion exchange resin A used in Example 14 was recovered by separating from the reaction solution by filtration under reduced pressure. Next, the recovered anion exchange resin A was washed with 300 ml of methanol, vacuum dried and dried. Subsequently, the obtained recovered anion exchange resin A was used as a catalyst to carry out a reaction in the same manner as in Example 1, and a catalyst reuse experiment was conducted. As shown in Table 1, no significant decrease in activity was observed, indicating that the anion exchange resin catalyst can be reused.

Example 20
The addition reaction of PO to CC was performed. CC: 5.0 g, PO: 3.2 g, ethylene glycol monomethyl ether: 10.0 g as a solvent, and anion exchange resin A (Cl-type dry product): 0.8 g as a catalyst were put into a 50 ml glass pressure vessel. . Subsequently, the gas phase was purged with nitrogen, sealed, and heated in a 90 ° C. oil bath with shaking. After completion of the reaction, the reaction solution and the anion exchange resin A were separated by filtration.

  The composition analysis of the reaction solution was performed by GC. As a result, 89% of the raw material CC reacted in 12 hours of the reaction, and the target product occupying in the product [PO1 adduct of CC = α-methyl-β- (2-hydroxyphenoxy) ethanol, and β-methyl-β The selectivity for-(2-hydroxyphenoxy) ethanol] was 84%.

Examples 21-27
Various conditions were changed, and the reaction was performed in the same manner as in Example 20. Reaction conditions and reaction results are shown in Table 1. In Example 23, the anion exchange resin B is Diaion TSA1200 (a heat-resistant anion exchange resin manufactured by Mitsubishi Chemical Corporation, used in a chlorine ion-type dried product).

Comparative Examples 1-3
A typical example of the quaternary ammonium halide compound disclosed in Patent Document 5 is tetramethylammonium chloride. In the comparative example, this was used as a catalyst, and various reactions were performed in the same manner as in Example 20. Reaction conditions and reaction results are shown in Table 1. From these results, it was found that the reaction selectivity of the target product was lower than that of the anion exchange resin in various reactions. In addition, the anion exchange resin as a catalyst could be separated from the reaction solution by an easy operation of filtration, whereas the catalyst (tetramethylammonium chloride) used in the comparative example was separated from the reaction solution. Separation and recovery was very difficult.

  Abbreviations in Table 1 are as follows. CC: catechol, HQ: hydroquinone, RC: resorcin, EO: ethylene oxide, PO: propylene oxide, resin A: anion exchange resin A, resin B: anion exchange resin B, TMAC: tetramethylammonium chloride, EGMME: ethylene glycol monomethyl Ether, MIBK: methyl isobutyl ketone.

As for “reaction selectivity of the target product”, the target product is an aromatic ether having a phenolic hydroxyl group (β-phenoxyethanol), which is a compound obtained by adding one molecule of an oxirane compound to a polyhydric phenol. is there. The reaction selectivity is displayed as a GC area ratio relative to the total product. Furthermore, the time (reaction time) in the “reaction conditions” is indicated with 0 hour from the start of EO or PO addition.

Claims (11)

  A process for producing an aromatic ether, characterized in that an anion exchange resin is used as a catalyst in synthesizing an aromatic ether by reacting a phenol with an oxirane compound.   The production method according to claim 1, wherein polyphenols are used as the phenols and aromatic ethers having a phenolic hydroxyl group are synthesized.   The solvent used in the reaction step of the phenols and the oxirane compound, and the solvent used in the crystallization step performed after the reaction step is the same as the solvent used in the reaction step. Manufacturing method.   An aromatic ether produced by the method according to claim 1.   Aromatic ethers having an alcoholic hydroxyl group, characterized in that the metal content is suppressed to less than 100 ppm (mass basis, the same shall apply hereinafter), and the halogen element content is suppressed to less than 100 ppm. Aromatic ethers.   A solvent comprising the aromatic ether according to claim 4 or 5.   An emulsifier comprising the aromatic ether according to claim 4 or 5.   A cleaning agent comprising the aromatic ether according to claim 4 or 5.   An antibacterial / preservative containing the aromatic ether according to claim 4 or 5.   A cosmetic composition comprising the aromatic ether according to claim 4 or 5. A fragrance retention agent comprising the aromatic ether according to claim 4 or 5.