JPWO2006030852A1 - Process for producing aromatic ethers - Google Patents

Abstract

The method for producing an aromatic ether according to the present invention uses a phenol and an oxirane compound as raw materials, and uses a catalyst having an anion exchange group in reacting the phenol with the oxirane compound in the presence of the aromatic ether. It is characterized by. The present invention is suitable for large-scale synthesis, and even if the target compound and aromatic ethers which are by-products have been mixed from the beginning of the reaction, the by-products produced by the reaction of the target compound and raw materials A high-quality target compound can be efficiently produced with high selectivity while suppressing the production of.

Description

  The present invention relates to a method for producing aromatic ethers from phenols and oxirane compounds.

  Among aromatic ethers, glycol ethers such as 2-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, a wide range of uses such as antibacterial agents, antiseptics, cosmetic compositions, personal care, fragrance retention agents, pharmaceutical compositions, etc. are known by utilizing the bactericidal action of the aromatic ethers. In addition, it has good resolution, depth of focus, and developability, and is used as a resist composition for forming integrated circuits with excellent sensitivity resist pattern 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 as a solvent, an emulsifier, a chemical intermediate material, an antibacterial agent, an antiseptic, a composition component such as cosmetics, and personal care. There is a track record. For example, paints, inks, dyes, hair dyes, agricultural chemicals, cleaning agents, various emulsions, aqueous building materials, emulsified cosmetics, plasticizers, adhesive compositions; fluorene derivatives, polyesters, polyurethanes, and bactericidal reagents Body and raw materials; cosmetics, antibacterial hypoallergenic cosmetics, fragrances, fungicides, insecticides, disinfectants, low-temperature stable preservatives, antiseptic pharmaceutical preparations, skin preparations for sensitive skin, hair cosmetics, shampoos and hair rinse Conditioning composition for hair, oral composition, sunscreen composition, perfume retention agent and cosmetic disinfectant in perfumery field, antiseptic pharmaceutical preparation in pharmaceutical field, detergent composition for medical detergent and household detergent, etc .; soft Applications such as an agent composition can be mentioned.

  Aromatic ethers are synthesized from phenols and oxirane compounds, but without a catalyst, the reaction rate is very slow and there are many side reactions. For this reason, aromatic ethers are produced using a catalyst.

  For example, as a method for producing 2-phenoxyethanols contained in aromatic ethers, a method of synthesizing using an alkali metal salt and a large amount of water is known (Japanese Patent Publication No. 39-30272). However, when a large amount of water is used, not only the use efficiency of the oxirane compound is reduced, but a large amount of industrial wastewater is generated. In particular, since many phenols have a bactericidal action, when the wastewater contains unreacted phenols, the activated sludge treatment of the wastewater is difficult.

  For these reasons, as a method for producing aromatic ethers, a non-aqueous process is required instead of the aqueous process disclosed in Japanese Examined Patent Publication No. 39-30272.

  Non-aqueous processes for producing aromatic ethers include a halogenated phosphonium salt or a catalyst comprising a tertiary phosphine and an alkyl halide (Japanese Patent Publication No. 50-654), or a trialkylbenzylammonium halide. Is known (Japanese Patent Publication No. 49-33183).

  As a method for synthesizing 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 (Netherlands). (Japanese Patent No. 6600188).

  However, according to the study by the present inventors, in this method, since a trace amount of oxygen present in the reaction system is oxidized by a transition metal ion as a catalyst, polyhydric phenol (catechol) as a raw material is oxidized, quinones are easily generated. It has been found. 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. It refers to a molecular compound consisting of quinones that are products.

  In consideration of mass synthesis in an industrial process, it is preferable to recover and reuse unreacted raw materials after completion of the reaction. However, when recovering phenols that are raw materials, the target compounds and aromatic ethers that are by-products have to be mixed because of their similar physical properties. For example, when manufacturing sequentially using the same reaction instrument, the aromatic ether in the previous reaction adhering to the instrument may be mixed into the reaction system.

  In the conventional production method, a side reaction occurs in which the mixed aromatic ether and the oxirane compound further react, and the yield and quality of the target compound deteriorate. Therefore, in the conventional production method, raw material compounds such as unreacted phenols could not be recovered and reused. This loss of the raw material compound becomes a problem particularly in mass synthesis.

  The present invention has been made in view of the above circumstances, and its purpose is to produce aromatic ethers using phenols and oxirane compounds as raw materials, and is suitable for mass synthesis. Even when aromatic ethers are mixed from the beginning of the reaction, high-quality target compounds can be efficiently selected while suppressing the production of by-products due to the reaction between the target compound and the raw material. It is to provide a method that can be manufactured automatically.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies especially on the catalyst, and found that all of the above problems can be overcome by using a catalyst having an anion exchange group. That is, in the conventional method using an alkali catalyst or the like, the difference in reaction selectivity between the phenolic hydroxyl group and the alcoholic hydroxyl group is small. Therefore, when unreacted phenols are recovered and used, an oxirane compound is added to the accompanying aromatic ethers. The amount of by-products added excessively increases. On the other hand, in the case of a catalyst having an anion exchange group, the reaction with the phenolic hydroxyl group proceeds with high selectivity, so that the target aromatic ether can be selectively and efficiently obtained.

  In addition, by using the catalyst, it is possible to increase the reaction activity and produce the aromatic ether as the target compound in a high yield. In addition, since the reaction can be carried out even under reaction conditions that do not substantially use water, it is possible to produce aromatic ethers with little loss of oxirane compounds and little waste water.

  The method for producing an aromatic ether according to the present invention uses a phenol and an oxirane compound as raw materials, and uses a catalyst having an anion exchange group in reacting the phenol with the oxirane compound in the presence of the aromatic ether. It is characterized by.

  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, which will be described later, 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.

  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, which includes a non-benzene aromatic ring such as a cyclopentadiene ring, a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, etc .; a non-benzene aromatic ring and a benzene ring Condensed with each other; heteroaromatic rings in which one or more carbon atoms of these non-benzene aromatic rings, aromatic rings or condensed aromatic rings are replaced by heteroatoms such as oxygen atoms, nitrogen atoms and sulfur atoms (Pyrrole ring, pyridine ring, thiophene ring, furan ring, etc.); those in which a saturated heterocycle in which a heteroaromatic ring is reduced and an aromatic ring are condensed are included.

  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 (dimethylamino) phenol, p- Phenol having a substituent containing a nitrogen atom such as hydroxyphenylacetamide; α-naphthol, β-naphthol; and the like. Of these, phenol and cresol are preferred.

  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, phlorizin, 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 purproxanthin; 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 nebule 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, aliphatic alkylene oxides such as ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and pentylene oxide; aromatic alkylene oxides such as styrene oxide; and cyclohexene oxide are preferable. is there. These oxirane compounds may be used alone or in combination of two or more. Preferably one type is used alone. 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 which is the target compound of 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 which substitute a hydrogen atom on Z, m is an integer of 1 or more and n or less, n is 1 or more and a hydrogen atom which can be substituted on Z N is an integer equal to or less than the maximum number, and n represents an integer of 0 or more and m or less. 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).

上記一般式（８）において、Ｒ⁵〜Ｒ⁸は各々独立して、水素原子、アルキル基、またはアリール基を示す。Ｒ⁵〜Ｒ⁸がアルキル基および／またはアリール基の場合には、各種置換基を有していてもよい。また、Ｒ⁵（あるいはＲ⁶）とＲ⁷（あるいはＲ⁸）が環状構造（例えば、５員環や６員環など）を形成していてもよい。
これらオキシラン化合物の中でも、Ｒ⁵〜Ｒ⁸が水素原子（エチレンオキサイド）、Ｒ⁵〜Ｒ⁸のいずれか１つがメチル基で他の３つが水素原子（プロピレンオキサイド）、Ｒ⁵およびＲ⁶がメチル基で、Ｒ⁷およびＲ⁸が水素（イソブチレンオキサイド）、Ｒ⁵およびＲ⁷がメチル基で、Ｒ⁶およびＲ⁸が水素（２，３−ブチレンオキサイド）であるものが好ましい。

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 hydrogen (2,3-butylene oxide).

Aromatic ethers produced from the phenols and oxirane compounds include 2-phenoxyethanols. These 2-phenoxyethanols are compounds which have 2-phenoxyethanol as a basic skeleton and may have a general substituent. General substituents are not particularly limited, and examples thereof include C _1-6 alkyl, cycloalkyl, aryl, heteroaryl, C _1-6 alkoxy, C _1-6 acyloxy, amino, C _1-6 alkylamino, di ( C _1-6 alkyl) amino, C _1-6 acylamino, carbamoylamino, C _1-6 alkoxycarbonyl, C _1-6 alkylthio, arylthio, heteroarylthio, carboxy, hydroxy, hydroxyimino, and halogen atoms Can be mentioned.

  The catalyst having an anion exchange group used in the method of the present invention promotes the reaction with high selectivity with respect to a compound having a more acidic hydroxyl group. In other words, the aromatic ethers which are the target compounds of the method of the present invention are produced by reacting one or more phenolic hydroxyl groups contained in the phenols which are the raw material compounds with the oxirane compounds. Although a hydroxyl group is generated, the acidity of the alcoholic hydroxyl group is lower than that of the phenolic hydroxyl group. In the conventional catalyst, such a difference in acidity cannot be sufficiently reflected in the reactivity, and if there are many target compounds in the reaction system, the reaction between the alcoholic hydroxyl group of the target compound and the oxirane compound can be prevented. Promote. On the other hand, the catalyst of the present invention can selectively catalyze a raw material compound having higher acidity, and thus can efficiently catalyze the main reaction.

  Examples of the anion exchange group capable of exhibiting such an action include groups having structures of tertiary amine, quaternary ammonium salt, tertiary phosphine, or quaternary phosphonium salt. Among them, quaternary ammonium salt structure and 4 Groups having a secondary phosphonium salt structure are preferred. Furthermore, the anion exchange group preferably has a structure excellent in heat resistance, and specifically, it is recommended to have the following two structures.

  First, the anion exchange group has a cyclic structure. The form of the cyclic structure is preferably a 5-membered ring or 6-membered ring, and more preferably a 5-membered ring. In particular, when it has a quaternary ammonium salt structure, those having a pyrrolidine skeleton, a piperidine skeleton or a pyridine skeleton are preferred. As such an anion exchange resin containing an anion exchange group having a cyclic quaternary ammonium salt structure, those synthesized from vinylpyridine or diallyldimethylammonium chloride are recommended from the viewpoint of easily forming such a resin. Moreover, as an anion exchange resin which has a quaternary ammonium salt structure, what is described in Unexamined-Japanese-Patent No. 2001-354777 and Unexamined-Japanese-Patent No. 2002-105138 can be illustrated.

  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 catalyst of the present invention may have either one of the first and second structures or may have both.

  In addition, the quaternary ammonium salt or quaternary phosphonium salt generally has an anion that is paired with a cationized hetero atom, and the ionic species is not particularly limited. For example, a hydroxide ion; Halide ions such as fluoride ions, chloride ions, bromide ions, iodide ions; organic acid anions (such as carboxylate anions and phenoxy anions); inorganic acid anions; and the like. 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 catalyst used in the present invention, a catalyst that does not substantially dissolve in the reaction system is suitable. This is because it can be easily separated by filtration after the completion of the reaction and can be used repeatedly. On the other hand, conventional catalysts (for example, those described in Japanese Patent Publication Nos. 50-654 and 49-33183) are dissolved in the reaction system. As a result, it cannot be completely removed even after the completion of the reaction, and it may be mixed into the target aromatic ether and adversely affect the product (the aromatic ether). Some conventional catalysts form salts with unreacted starting phenols. In that case, a neutralization step and a washing step are required after the reaction to remove the salt. Although there is a method of suppressing the formation of the salt by using an oxirane compound in excess, there is a risk of causing an increase in impurities added excessively by the oxirane compound. On the other hand, a salt that does not substantially dissolve does not form such a salt.

  As the catalyst used in the present invention, a catalyst in which the anion exchange group is bonded to a polymer directly or via a crosslinking site, that is, an anion exchange resin is also suitable. As such an 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.

  In addition, the anion exchange resin may be one that dissolves in the raw material phenol itself or the reaction solvent, or one that remains in a solid state without being dissolved, but for the reasons described above. Those that do not dissolve are preferred. In the case where it exists as a solid without being dissolved, it can be in the form of granules, particles, powder, or a state supported on a support.

  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) A116LF, A161TRSO4, A162LF, A368S, A378D, A375LF, A561, A568K, A7); Rohm and Haas “Amberlite” (RA400, etc.); Reilly “Reillex HPQ547719” Fat can also be used.

  In the method of the present invention, a solvent may or may not be used when the phenols and the 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. Moreover, since it is not necessary to remove the solvent and purification is easy, an embodiment without using a solvent is preferable.

  Incidentally, the catalyst used in the method of the present invention can advantageously proceed with the reaction between the phenol and the oxirane compound in the absence of water, and therefore does not require 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-C6 glycol ethers, such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; C2-C6 ethers, such as tetrahydrofuran and dioxane, etc. are mentioned. 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; Etc. can also be used.

  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 may be performed in 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, more preferably 1.5, Particularly preferred is 1.05 and most preferred is 1.05.

  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.

  When using a solvent, it is preferable that the quantity shall be 0-5 by mass ratio with respect to the polyhydric phenols which are raw materials, More preferably, it is 0-2.5.

  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.

  After the completion of the reaction, it is preferable to purify the produced aromatic ether. The method is not particularly limited, and general methods such as distillation, extraction, and crystallization can be used. However, since the aromatic ethers produced by the method of the present invention have a high purity, the product can be used as it is after the above reaction. In addition, the raw material phenols are converted using a catalyst so that the phenols are substantially absent in the system, and the products after the phenols are converted are separated by a general method as described above. It doesn't matter.

  The method of the present invention is characterized in that the target compound can be efficiently synthesized even when the target compound or an aromatic ether similar to the target compound is mixed into the starting phenols and oxirane compound. Here, as a case where aromatic ethers are mixed in the raw material, there may be a case where the target compound remains in a continuous mass synthesis process, but in particular, there is a case where unreacted phenols are collected and recycled. Conceivable. That is, if the aromatic ethers which are the target compounds are separated by the method as described above, and the phenols remaining unreacted are recovered and used as all or part of the raw materials, the production efficiency can be improved. it can. However, in this case, aromatic ethers are mixed due to the similarity of physical properties.

  In the prior art, a reaction in which an oxirane compound is excessively added to a mixed aromatic ether occurs, and the by-product tends to increase. For example, an oxirane compound may be further added to the alcoholic hydroxyl group of a compound obtained by adding one oxirane compound to a phenolic hydroxyl group. On the other hand, in the method of the present invention, by using the catalyst described above, the reaction between the raw material phenols and the oxirane compound can be promoted preferentially, and side reactions can be suppressed. From this, since the raw material phenols can be more effectively utilized by recycling the recovered phenols containing the aromatic ethers to the reaction system, the target aromatic ethers can be produced economically and advantageously.

  In the present invention, the ratio of the aromatic ether in the reaction raw material solution is not particularly limited, but it is preferably contained so as not to impair the productivity, and the upper limit is 50% by mass with respect to the total reaction solution. Preferably, it is 30% by mass or less.

  In addition, the aromatic ether contained in the reaction raw material does not specifically limit the manufacturing method, and does not necessarily need to be obtained by the method of the present invention. However, from the viewpoint of production efficiency, it is preferably obtained by the method of the present invention. Further, the aromatic ethers contained in the raw material do not need to be produced from the same phenols and oxirane compounds as in the method of the present invention. However, from the same viewpoint of production efficiency, it is preferable that the phenols and oxirane compounds used in the method of the present invention are produced from the same raw material.

  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 are methods such as gradually pressurizing the reaction solution, and these can be carried out alone or in combination.

  It is also 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 the reaction solvent is used, the catalyst 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.

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

  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 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 aromatic ethers, it is a cause of deterioration of physical properties, and from the viewpoint of consideration for the environment, reduction in the amount of such metals and halogens is required. 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 substantially contain metals and halogens. No products can be manufactured. Specifically, the metal and / or halogen content is suppressed to 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 suppressed to 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 ratio 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, in 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 or storage of aromatic ethers, there may be mentioned a crude product after completion of the reaction and a purified product with a diluent or a 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 also 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, about pH 6 to 7). In this case, for example, 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 or 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.

  As described above, since the aromatic ethers obtained by the method of the present invention are extremely high quality, various uses are conceivable. For example, the aromatic ethers according to the present invention have excellent compatibilizing ability because they exhibit lipophilicity consisting of an aromatic ring moiety and hydrophilicity derived from a hydroxyl group and / or an ether group as their 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 excellent compatibilizing ability and high boiling point, it has a bactericidal action, so it is useful as an antibacterial / preservative, a cosmetic composition, a fragrance retention agent, and the like.

  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 are included in the technical scope of the present invention without departing from the spirit of the preceding and following descriptions.

Example 1
As a catalyst having an anion exchange group, Diaion TSA1200 (a heat-resistant anion exchange resin manufactured by Mitsubishi Chemical, OH type water-containing body, 40.5 mL) was used. However, since this anion exchange resin contains water, the operation of washing with 2-phenoxyethanol (300 mL) as the target compound and then filtering was repeated twice (hereinafter referred to as “washed catalyst A”). In the following experimental examples, the same amount of the washed catalyst A was used.

Next, phenol (201.5 g, about 2.1 mol) and the washed catalyst A were charged into a 500 mL autoclave equipped with a gas supply pipe, a stirrer, and a drain line, and sealed. Dissolved oxygen in the liquid was removed by a degassing operation, and the gas phase portion was replaced with nitrogen, and then nitrogen was further added to pressurize (1.5 kg / cm ² ). Next, the temperature was raised to 100 ° C., and ethylene oxide (98.8 g, about 2.2 mol, hereinafter referred to as “EO”) was added through a gas supply pipe over 2 hours. Thereafter, the reaction was carried out for 2 hours while maintaining the internal temperature at 100 ± 2 ° C. In addition, the ratio of the said 2-phenoxyethanol with respect to the sum total of 2-phenoxyethanol contained in the phenol used as a raw material, ethylene oxide, and the washing | cleaning catalyst A was 11.2%.

  This reaction solution was analyzed by gas chromatography. The analysis conditions are as follows.

Apparatus: Shimadzu Corporation GC-15A
Column: J & W, DB-1 (φ0.53 mm × 30 m)
Carrier gas: Helium Temperature conditions: 70 ° C for 5 minutes → 15 ° C / min to 300 ° C
→ 300 ° C for 5 minutes As a result of gas chromatography, the conversion rate of the raw material phenol (reaction rate of the raw material phenol) was 93.7%, the selectivity of phenol EO1 adduct (2-phenoxyethanol) (reacted phenol Among them, the ratio of those converted to EO1 adducts) was 97.5%, and the selectivity of phenol EO2 adduct (compound in which EO was further added to the hydroxyl group of 2-phenoxyethanol) was 2.3%. .

  In this way, when an anion exchange resin is used as a catalyst in the reaction of a phenol with an oxirane compound to synthesize an aromatic ether, the aromatic ether that is the target compound is mixed from the beginning of the reaction. However, it was revealed that the production of the EO2 adduct was suppressed and the EO1 adduct could be efficiently synthesized.

Example 2
When 2-phenoxyethanol is synthesized using phenol and EO as raw materials, the remaining phenol is recovered and used as a part of the raw material, and 2-phenoxyethanol, which is the target compound, is further added to the reaction system. Were synthesized.

  Phenol (182.7 g, about 1.9 mol) and EO (89.8 g, about 2.0 mol) were used as raw materials, and 2-phenoxyethanol (30.0 g) was further added and reacted at 100 ± 2 ° C. for 3 hours. Except for the above, the same reaction as in Example 1 was performed. In this case, the ratio of 2-phenoxyethanol (total of those contained in the washed catalyst A and newly added) present in the reaction system from the beginning is based on the total of phenol, EO, and all 2-phenoxyethanol. About 19.1% by mass. The anion exchange resin was pretreated in the same manner as in Example 1 and the same amount was used.

  After completion of the reaction, the same gas chromatographic analysis as in Example 1 was conducted. As a result, the conversion rate of the starting phenol was 97.0%, the selectivity of phenol EO1 adduct was 97.3%, and phenol EO2 adduct. The selection rate was 2.6%. Therefore, according to the method of the present invention, even when 2-phenoxyethanol, which is the target compound, is present in the reaction system from the beginning, the product recovered as the raw material phenol is used while suppressing the production of EO2 adduct. -It has been demonstrated that phenoxyethanol can be synthesized efficiently.

Comparative Example 1
Assuming that the phenol recovered as the raw material is used, the reaction is performed by adding 2-phenoxyethanol, which is the target compound, to the reaction system from the beginning, using sodium hydroxide instead of an anion exchange resin as a catalyst. The experiment was conducted.

Phenol (172.8 g, approximately 1.8 mol), 2-phenoxyethanol (108.5 g) and sodium hydroxide (0.2635 g) were charged into a 500 mL autoclave similar to that in Example 1 and sealed. In this case, the proportion of 2-phenoxyethanol present from the beginning in the reaction system is about 29.6% by mass with respect to the total of phenol, EO, and 2-phenoxyethanol. Dissolved oxygen in the liquid was removed by a degassing operation, and the gas phase portion was replaced with nitrogen, and then nitrogen was further added to pressurize (1.5 kg / cm ² ). Next, the temperature was raised to 140 ° C., and EO (84.7 g, about 1.9 mol) was added through a gas supply pipe over 2 hours. Thereafter, the reaction was carried out for 1 hour while maintaining the internal temperature at 140 ± 5 ° C.

  The same gas chromatographic analysis as in Example 1 was performed immediately after the end of the EO addition. As a result, the raw material phenol conversion was 87.6%, the phenol EO1 adduct selectivity was 94.8%, and the phenol EO2 The selectivity for the adduct was 4.7%. Moreover, in the analysis after the completion of the reaction, although the raw material phenol conversion rate was 99.0% and the raw material was consumed, the phenol EO1 adduct selectivity was 94.2% and the phenol EO2 adduct selectivity. Was 5.2%.

Example 3
As in Example 2, the synthesis was performed by adding 2-phenoxyethanol, which is the target compound, from the beginning to the reaction system, assuming that the phenol recovered as the raw material was used. The same reaction as in Example 1 except that phenol (146.2 g, about 1.6 mol) and EO (71.9 g, about 1.6 mol) were used as raw materials, and 2-phenoxyethanol (90.1 g) was further added. Was done. In this case, the ratio of 2-phenoxyethanol (total of those contained in the washed catalyst A and newly added) present in the reaction system from the beginning is based on the total of phenol, EO, and all 2-phenoxyethanol. About 39.0% by mass.

  After completion of the reaction, the same gas chromatographic analysis as in Example 1 was conducted. As a result, the conversion rate of the starting phenol was 94.8%, the selectivity of phenol EO1 adduct was 97.2%, and phenol EO2 adduct. The selection rate was 2.7%.

Example 4
Aiming at industrial large-scale synthesis, the synthesis experiment was conducted with a larger capacity.

  As a catalyst having an anion exchange group, Diaion TSA1200 (Mitsubishi Chemical heat-resistant anion exchange resin, OH type water-containing body, 810.0 mL) was used. In the same manner as in Example 1, the anion exchange resin was washed with 2-phenoxyethanol (about 6670 mL) as the target compound and then filtered, and the water was removed by repeating the operation twice. Hereinafter, this is called washed catalyst B.

Next, phenol (4021 g, about 42.7 mol) and the washed catalyst B were charged and sealed in a 10 L autoclave equipped with a gas supply pipe, a stirrer, and a liquid drain line. Dissolved oxygen in the liquid was removed by a degassing operation, and the gas phase portion was replaced with nitrogen, and then nitrogen was further added to pressurize (1.5 kg / cm ² ). Next, the temperature was raised to 100 ° C., and EO (1976 g, about 44.9 mol) was added through a gas supply pipe over 6 hours. Thereafter, the reaction was carried out for 2 hours while maintaining the internal temperature at 100 ± 2 ° C. In addition, the ratio of 2-phenoxyethanol (contained in the washed catalyst B) present in the reaction system from the beginning is about 12.6% by mass with respect to the total of phenol, EO, and 2-phenoxyethanol.

  This reaction solution was analyzed by gas chromatography. As a result, the conversion rate of the raw material phenol was 99.3%, the phenol EO1 adduct selectivity was 96.9%, and the phenol EO2 adduct selectivity was 2.9%. Thereafter, aging was performed until the residual phenol concentration reached 88 ppm.

  Next, after removing the anion exchange resin, the obtained filtrate (2012 g) was put into a 3 L glass distillation flask, and the top pressure was 2 kPa and the bottom temperature was 148 to 181 using an Oldershaw type distillation column having 10 stages. Distillation was performed at ° C. As the first fraction, 178 g of a fraction containing 99.9% phenol EO1 adduct and 643 ppm phenol was recovered. Thereafter, 1546 g of a 2-phenoxyethanol fraction was obtained (distillation yield: 76.8%). The obtained 2-phenoxyethanol was analyzed by an absorptiometer (manufactured by Shimadzu Corporation, UV-VISIVE SECTROPHOTOMETER “UV-1600”). As a result, the purity was 99.9% and the phenol content was 18 ppm.

  According to the method of the present invention, when an aromatic ether is synthesized by reacting a phenol with an oxirane compound, the aromatic ether is mixed into the raw material by using a catalyst having an anion exchange group as a catalyst. Even so, it is possible to efficiently produce aromatic ethers having the desired structure while suppressing the generation of side reactions. Therefore, when unreacted phenols are recovered and used as a raw material, even if aromatic ethers are mixed, the target compound can be efficiently produced, which is economical.

  Therefore, the production method according to the present invention is very useful industrially as being suitable for mass synthesis in the industrial process of aromatic ethers.

  This application is based on Japanese Patent Application No. 2004-269360 filed with the Japan Patent Office on September 16, 2004, and the contents of the basic application can be incorporated into the present specification by reference.

Claims (8)

A method for producing aromatic ethers, comprising:
Using phenols and oxirane compounds as raw materials,
A method comprising using a catalyst having an anion exchange group for reacting a phenol with an oxirane compound in the presence of an aromatic ether.   The method according to claim 1, wherein the catalyst is an anion exchange resin.   The method according to claim 1 or 2, wherein the aromatic ether present in the raw material and the aromatic ether as the target compound are compounds comprising a combination of the same phenol and oxirane compound.   The method according to claim 1, wherein the phenol is a unit price phenol.   The method according to claim 1, wherein the phenol is phenol or cresol.   The method according to any one of claims 1 to 5, wherein the oxirane compound is ethylene oxide, propylene oxide, isobutylene oxide or 2,3-butylene oxide.   The method according to claim 1, wherein the oxirane compound is ethylene oxide.   The method according to any one of claims 1 to 7, wherein 2-phenoxyethanols are produced.