JP2016138071A - Method for producing bis hydroxyethyl ether of bisphenols - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing high-purity bis hydroxyethyl ether of bisphenols from bisphenols and ethylene carbonate, which produces bis(hydroxyethyl) ether of bisphenols having sufficient purity for use as a polymer raw material industrially suitably and economically advantageously without performing complicated reaction operations or purification operations.SOLUTION: There is provided a method for producing high-purity bis hydroxyethyl ether of bisphenols which comprises a step of reacting bisphenols and ethylene carbonate and then adding a phase transfer catalyst and a strong basic substance to the resulting reaction product and subsequently stirring at a temperature of 60 to 120°C.SELECTED DRAWING: None

Description

The present invention relates to a novel process for producing bisphenols bishydroxyethyl ether useful as various polymer raw materials.

Bisphenol bishydroxyethyl ether is known to be a useful material as a raw material and modifier for polyester resin, polycarbonate resin, epoxy resin, acrylic resin, urethane resin and the like.

The production method of bisphenols bishydroxyethyl ether includes a method of reacting bisphenols with ethylene oxide (Patent Document 1), a method of reacting with ethylene chlorohydrin (Patent Document 2), and a method of reacting ethylene carbonate (Patent Document 3). ) Is known. When ethylene oxide is used, ethylene oxide is a highly toxic gas with carcinogenicity and mutagenesis, and since it is a liquefied gas, it is necessary to use a pressure vessel, which is a problem in terms of safety and operability. There is. On the other hand, when ethylene chlorohydrin is used, it requires an alkali equivalent to or more than bisphenol as a catalyst, and a large amount of salt containing halogen atoms is generated, so a stainless steel reaction kettle cannot be used due to corrosion problems. In addition, there are equipment restrictions such as high concentration of alkali may damage the reaction vessel made of glass lining.

  On the other hand, when ethylene carbonate is used, there is an advantage that it has low toxicity, can be easily melted at a melting point of about 35 ° C., and can be easily handled as a liquid. However, when producing bisphenols bishydroxyethyl ether from bisphenols and ethylene carbonate, even when ethylene oxide and ethylene chlorohydrin are used, by-product bisphenol monohydroxyethyl ether (hereinafter referred to as “1 mol adduct”) Impurities such as compounds in which 3 mol or more of ethylene carbonate or ethylene oxide or ethylene chlorohydrin is added to bisphenols (hereinafter also referred to as “3 mol or more adduct”) About 1 to 20% by weight as a by-product with respect to the bisphenols bishydroxyethyl ether of the product, there is a problem that the purity and hue are lowered. In addition, when this bisphenol bishydroxyethyl ether is used as a raw material such as polyester resin, polycarbonate resin, epoxy resin, acrylic resin, urethane resin, the problem that the polymerizability deteriorates, the heat resistance and hue of the obtained resin deteriorate. There is a problem.

  In order to solve the above-mentioned problems, the present inventors have proposed a post-treatment method for reducing impurities such as 1 mol adduct and 3 mol or more adduct contained in bisphenol bishydroxyethyl ether (Patent Document 4). However, in order to purify the bisphenols bishydroxyethyl ether obtained by this method, it is necessary to form a separable three-phase system consisting of an organic solvent phase, an intermediate phase and an aqueous phase after the reaction. Application to a wide range of bisphenols bishydroxyethyl ether may be difficult, and after forming three phases, the intermediate phase and aqueous phase are discarded, so that bisphenols bishydroxyethyl ether is obtained in high yield. It has been found that problems may arise.

JP 50-105638 A US Pat. No. 2,331,265 JP-A-4-230331 JP2013-216582A

An object of the present invention is to produce a high purity bisphenol bishydroxyethyl ether from a bisphenol and ethylene carbonate. An object of the present invention is to provide a manufacturing method which is suitable for industrial implementation without any operation and which is economically advantageous.

In order to solve the above-mentioned problems, the present inventors have intensively studied the post-treatment method after the reaction between bisphenols and ethylene carbonate, and as a result, the present invention has been completed.

That is, the present invention provides the following [1] to [7].

[1]
In the method of producing bisphenols bishydroxyethyl ether by reacting bisphenols and ethylene carbonate, after reacting the bisphenols and ethylene carbonate, the reaction product obtained is mixed with water, a phase transfer catalyst and a strongly basic substance. The manufacturing method of bisphenols bishydroxyethyl ether including the process of adding and stirring.

[2]
[1] The method for producing bisphenols bishydroxyethyl ether according to [1], wherein the stirring described in [1] is performed at 60 to 120 ° C.

[3]
The method for producing a bisphenol bishydroxyethyl ether according to [1] or [2], wherein the concentration of the strongly basic substance in the aqueous phase containing the strongly basic substance is 3 to 30% by weight.

[4]
The method for producing a bisphenol bishydroxyethyl ether according to any one of [1] to [3], wherein the amount of the strongly basic substance used is 0.3 to 4 mol with respect to 1 mol of the bisphenol.

[5]
After carrying out the process according to any one of [1] to [4], a phase containing bisphenols bishydroxyethyl ether and an aqueous phase are separated, and water and a strong acid are added to the obtained phase containing bishydroxyethyl ether. The manufacturing method of bisphenol bishydroxyethyl ether as described in any one of [1]-[4] including the process of adding and mixing a sex substance.

[6]
In the method of producing bisphenols bishydroxyethyl ether by reacting bisphenols and ethylene carbonate, after reacting the bisphenols and ethylene carbonate, the reaction product obtained is mixed with water, a phase transfer catalyst and a strongly basic substance. In addition, when adding and stirring, the organic solvent separable from water is added, The manufacturing method of bisphenol bishydroxyethyl ether as described in any one of [1]-[5].

[7]
The method for producing a bisphenol bishydroxyethyl ether according to [6], wherein the concentration of bishydroxyethyl ether in the organic solvent separable from water is 3% by weight or more.

According to the present invention, in the process for producing bisphenols bishydroxyethyl ether from bisphenols and ethylene carbonate, the bisphenols bishydroxyethyl ether can be obtained with high purity and high yield by a method suitable for industrial implementation. Is possible. In addition, since the hue of the resulting bisphenol bishydroxyethyl ether can be improved, it is possible to significantly improve the appearance characteristics such as the hue of the resin using the bisphenol bishydroxyethyl ether of the present invention.

Hereinafter, the present invention will be described together with embodiments thereof.

The present invention provides the following formula (1)

（式中、Ｒは芳香環を含む炭素数６〜６０の炭化水素基を表し、２つの水酸基は芳香環に直接付加しているものとする）
で表すビスフェノール類とエチレンカーボネートを反応することにより得られる、ビスフェノール類ビスヒドロキシエチルエーテルを含む反応生成物に、水、相間移動触媒及び強塩基性物質を添加し攪拌すること（以下、アルカリ水洗工程と称することもある）により、高純度のビスフェノール類ビスヒドロキシエチルエーテルを製造することを特徴とする。

(In the formula, R represents a hydrocarbon group having 6 to 60 carbon atoms including an aromatic ring, and two hydroxyl groups are directly added to the aromatic ring)
Water, a phase transfer catalyst and a strongly basic substance are added to the reaction product containing bisphenols bishydroxyethyl ether, which is obtained by reacting bisphenols represented by formula (II) with ethylene carbonate (hereinafter, alkaline water washing step). In other words, a high-purity bisphenol bishydroxyethyl ether is produced.

In the present invention, bisphenols bishydroxyethyl ether is obtained by reacting 2 mol of ethylene carbonate with 1 mol of bisphenols represented by the above formula (1). Specifically, the following formula (2)

（式中、Ｒは芳香環を含む炭素数６〜６０の炭化水素基を表す）に示される２つのフェノール性水酸基の両方に１モルずつヒドロキシエチル基が付加したものをいう。

(In the formula, R represents a hydrocarbon group having 6 to 60 carbon atoms including an aromatic ring), which is obtained by adding a hydroxyethyl group to each of two phenolic hydroxyl groups.

Examples of bisphenols represented by the above formula (1) include bisphenolpropanes synthesized from acetone, bisphenolethanes synthesized from acetaldehyde, bisphenolmethanes synthesized from formaldehyde, bisphenolbutanes synthesized from butanone, and cyclohexanone. Bisphenolcyclohexanes synthesized from bisphenolphenylethanes synthesized from acetophenone, bisphenoldiphenylmethanes synthesized from benzophenone, bisphenol-3,3,5-trimethylcyclohexanes synthesized from 3,3,5-trimethylcyclohexanone Bisphenolcyclododecanes synthesized from cyclododecanone, bisphenolfluorenes synthesized from fluorenone, binaphthe Lumpur acids and the like.

As the bisphenol propanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a 6 to 20 carbon atom. Examples thereof include bisphenolpropanes substituted with 0 to 4 positions by an aryl group, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms.
Specific compounds of bisphenolpropanes include, for example, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), bisphenol C (2,2-bis (3-methyl-4-hydroxyphenyl) propane), bisphenol G Examples include (2,2-bis (4-hydroxy-3-isopropylphenyl) propane) and bisphenol PH (2,2-bis (2-hydroxy-5-biphenylyl) propane).
Among these bisphenol propanes, an aromatic ring having a hydroxy group is substituted with 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol propanes are preferred.

As bisphenol ethanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a 6 to 20 carbon atom. Bisphenol ethanes substituted with 0 to 4 positions by an aryl group, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms can be mentioned. Specific examples of the compound include bisphenol E (1,1-bis (4-hydroxyphenyl) ethane).
Among these bisphenolethanes, an aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol ethanes are preferred.

As bisphenolmethanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a 6 to 20 carbon atom. Bisphenol methanes substituted with 0 to 4 positions with an aryl group, an aralkyl group with 7 to 20 carbon atoms, a cycloalkoxyl group with 5 to 20 carbon atoms, or an aryloxy group with 6 to 20 carbon atoms, and these Specific examples of the compound include bisphenol F (bis (4-hydroxyphenyl) methane).
Among these bisphenolmethanes, an aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol methanes are preferred.

As the bisphenol butanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carbon atom having 6 to 20 carbon atoms. Bisphenol butanes substituted with 0 to 4 positions by an aryl group, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and these Specific examples of the compound include bisphenol B (2,2-bis (4-hydroxyphenyl) butane).
Among these bisphenol butanes, an aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol butanes are preferred.

As the bisphenolcyclohexane, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a carbon atom having 6 to 20 carbon atoms. And bisphenolcyclohexanes substituted with 0 to 4 positions by an aryl group, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms. Specific examples of the compound include bisphenol Z (1,1-bis (4-hydroxyphenyl) cyclohexane).
Among these bisphenolcyclohexanes, an aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenolcyclohexanes are preferred.

As the bisphenol phenylethanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 6 to 20 carbon atoms. Bisphenol phenylethanes substituted with 0 to 4 positions with an aryl group of 7 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, a cycloalkoxyl group with 5 to 20 carbon atoms, or an aryloxy group with 6 to 20 carbon atoms, Examples of these specific compounds include bisphenol AP (1,1-bis (4-hydroxyphenyl) -1-phenylethane).
Among these bisphenol phenylethanes, an aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol phenylethanes are preferred.

As bisphenol diphenylmethanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a 6 to 20 carbon atom. Bisphenol diphenylmethanes substituted by 0 to 4 positions with an aryl group, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and Specific examples of the compound include bisphenol BP (bis (4-hydroxyphenyl) diphenylmethane).
Among these bisphenol diphenylmethanes, an aromatic ring having a hydroxy group is substituted with 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol diphenylmethanes are preferred.

As bisphenol-3,3,5-trimethylcyclohexane, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, or a cycloalkyl having 5 to 20 carbon atoms. Group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, cycloalkoxyl group having 5 to 20 carbon atoms, or aryloxy group having 6 to 20 carbon atoms, substituted with 0 to 4 positions -3,3,5-trimethylcyclohexanes, and examples of these specific compounds include bisphenol TMC (1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane). .
Among these bisphenol-3,3,5-trimethylcyclohexanes, the aromatic ring having a hydroxy group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol-3,3,5-trimethylcyclohexanes substituted at 1 to 4 sites in

As bisphenol cyclododecanes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or 6 to 20 carbon atoms. Bisphenol cyclododecanes substituted with 0 to 4 positions with an aryl group, a C 7-20 aralkyl group, a C 5-20 cycloalkoxyl group, or a C 6-20 aryloxy group, Examples of these specific compounds include 1,1-bis (4-hydroxyphenyl) cyclododecane and 1,1-bis (4-hydroxy-2-methylphenyl) cyclododecane.
Among these bisphenol cyclododecanes, the aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenol cyclododecanes are preferred.

As the bisphenol fluorenes, for example, an aromatic ring having a hydroxy group is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a 6 to 20 carbon atom. Bisphenol fluorenes substituted with 0 to 4 positions by an aryl group, an aralkyl group having 7 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms, and these Specific examples of the compound include 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, and 9,9-bis (3-ethyl-4-hydroxyphenyl). ) Fluorene, 9,9-bis (2-hydroxy-4-methylphenyl) fluorene, 9,9-bis (2-hydride) Xyl-4-ethylphenyl) fluorene, 9,9-bis (2-hydroxy-4-phenylphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9,9-bis Examples include (3-phenyl-4-hydroxyphenyl) fluorene and 9,9-bis (6-hydroxy-2-naphthyl) fluorene.
Among these bisphenol fluorenes, an aromatic ring having a hydroxy group is substituted at 1 to 4 positions by an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Bisphenolfluorenes are preferred.

Further, 2,2′-bis (2-hydroxy) -9,9′-spirobifluorene, 2,7-hydroxyfluorene, 1,1′-bi-2-naphthol, halogenated derivatives thereof, and the like can be given. .

  Among the bisphenols used in the present invention listed above, bisphenol C (2,2-bis (3-methyl-4-hydroxyphenyl) propane) and bisphenol G (2,2-bis (4-hydroxy-) are preferred. 3-isopropylphenyl) propane), bisphenol PH (2,2-bis (2-hydroxy-5-biphenylyl) propane), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1- Bis (4-hydroxy-2-methylphenyl) cyclododecane, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9, 9-bis (2-hydroxy-4-methylphenyl) fluorene, 9,9-bis (2-hydroxy-4- Tilphenyl) fluorene, 9,9-bis (2-hydroxy-4-phenylphenyl) fluorene, 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-phenyl-) 4-hydroxyphenyl) fluorene, 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 2,2′-bis (2-hydroxy) -9,9′-spirobifluorene.

In the present invention, the reaction product containing the bisphenols bishydroxyethyl ether bisphenols represented by the above formula (2) by reacting the bisphenols represented by the above formula (1) with ethylene carbonate (hereinafter referred to as reaction products). The reaction conditions for obtaining the reaction product are not particularly limited as long as the object of the present invention is achieved, and can be carried out by a known method. For example, with respect to 1 mol / 1 times by weight of the bisphenol represented by the above formula (1), usually 2 to 3 times mol, preferably 2 to 2.5 times mol of ethylene carbonate is reacted. If the amount of ethylene carbonate used is more than 3 moles per mole of bisphenols, adducts of 3 moles or more will increase, and if it is less than 2 moles per mole of bisphenols, 1 mole adducts and unreacted bisphenols will increase. To do.

When the bisphenol represented by the above formula (1) is reacted with ethylene carbonate, the reaction is usually performed in the presence of a basic compound. Examples of basic compounds used in this reaction include carbonates such as potassium carbonate, sodium carbonate, lithium carbonate and cesium carbonate, bicarbonates such as potassium bicarbonate, sodium bicarbonate, lithium bicarbonate and cesium bicarbonate, hydroxide Examples thereof include hydroxide salts such as sodium, potassium hydroxide and lithium hydroxide, and organic bases such as triethylamine and triphenylphosphine, preferably potassium carbonate, sodium carbonate and triphenylphosphine. The amount of these basic compounds used is usually 0.01 to 5 times by weight, preferably 0.01 to 3 times by weight with respect to the bisphenols represented by the above formula (1).

When the bisphenol represented by the above formula (1) is reacted with ethylene carbonate, it may be in the presence of a solvent or in the absence of a solvent. When using a solvent, it is used for the purpose of dissolving the bisphenols represented by the above formula (1) and for the purpose of lowering the viscosity of the reaction product. The solvent that can be used may be any solvent that does not react with ethylene carbonate. For example, ketones such as acetone, methyl ethyl ketone, butyl methyl ketone, aromatic hydrocarbons such as toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, etc. Halogenated aromatic hydrocarbons, aliphatic hydrocarbons such as pentane, hexane, heptane, halogenated aliphatic hydrocarbon solvents such as dichloromethane, 1,2-dichloroethane, diethyl ether, di-iso-propyl ether, methyl-tarsha Ethers such as Li-butyl ether, cyclopentyl methyl ether and diphenyl ether; esters such as ethyl acetate and butyl acetate; aliphatic nitriles such as acetonitrile; dimethylformamide and dimethylacetamide Earth and sulfoxides such as dimethyl sulfoxide. Aromatic hydrocarbons, ketones or ethers are preferred. These organic solvents may be used alone or as a mixture of two or more if necessary. The amount used is not particularly limited, but is usually 0.1 to 5 times, preferably 0.5 to 3 times the weight of the bisphenol represented by the formula (1). is there.

The reaction between the bisphenols represented by the above formula (1) and ethylene carbonate is carried out by adding the bisphenols represented by the above formula (1), ethylene carbonate, a basic compound and an organic solvent as required to the reaction vessel, Usually, 30-150 degreeC, Preferably it implements at 80-150 degreeC.

In addition to the desired bisphenols bishydroxyethyl ether represented by the above formula (2), the reaction product obtained by the above-described method includes the catalyst used in the reaction and its residue, unreacted bisphenols, 1 Mole adducts, 3 mol or more adducts, and other impurities are included. Subsequently, the step of adding and stirring water, a phase transfer catalyst and a strongly basic substance to the reaction product (alkali washing step) will be described in detail.

  When carrying out the alkali washing step, after completion of the reaction, water, a phase transfer catalyst, a strongly basic substance, and if necessary an organic solvent separable from water are added to the obtained reaction product. Addition of water, a phase transfer catalyst, a strongly basic substance, and an organic solvent separable from water as necessary may be performed simultaneously, or any one of them may be added later. When an organic solvent that does not dissolve in water arbitrarily is added, it is preferable to add a phase transfer catalyst and a strongly basic substance after adding an organic solvent that is separable from water, because it is difficult to precipitate crystals and the operation is easy.

Examples of strongly basic substances used in the alkali washing step are those having a pKb of less than 1, and examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, calcium hydroxide and barium hydroxide. And alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide are particularly preferable. These strong basic substances may be used alone or as a mixture of two or more if necessary.

For example, the amount of the strongly basic substance used in the alkali washing step is usually 0.3 to 4 mol, preferably 0.4 to 2.5, per 1 mol of the bisphenol represented by the above formula (1) used in the reaction. Use mol. By making the amount of the strongly basic substance used 0.3 mol or more, the decomposition of impurities is promoted and it is easy to obtain bisphenols of higher purity bishydroxyethyl ether bisphenol. Can be reduced.

The strongly basic substance and water used in the alkali washing step may be prepared by adding water and a strongly basic substance to individual reaction products, and may be used as an aqueous solution at the time of stirring, or an aqueous solution in which water and a strongly basic substance are mixed in advance. May be used as As the amount of water used in the alkali washing step, for example, the concentration of the strongly basic substance in the aqueous phase produced from the water and the strongly basic substance added to the reaction product is usually 1 to 50% by weight, preferably It is used so as to be 3 to 30% by weight. By setting the concentration of strongly basic substances in the aqueous phase to 1% by weight or more, the effect of decomposing impurities is enhanced. By setting the concentration to 50% by weight or less, decomposition of bisphenols bishydroxyethyl ether can be suppressed, and wastewater treatment can be performed. This is preferable because it can reduce the burden.

Examples of the phase transfer catalyst used in the alkali washing step include quaternary ammonium salts, quaternary phosphonium salts, pyridinium salts, and crown ethers. As quaternary ammonium salts, for example, a linear or branched alkyl group having 1 to 18 carbon atoms, phenyl whose alkyl moiety is a linear or branched alkyl group having 1 to 6 carbon atoms And quaternary ammonium salts substituted with a group selected from the group consisting of an alkyl group and a phenyl group, such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetrabutyl. Ammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tributylmethylammonium chloride, tributylbenzylammonium chloride, tetrapentylammonium chloride, tetrapentylammonium bromide, tetrahexylan Nium chloride, benzyldimethyloctylammonium chloride, methyltrihexylammonium chloride, benzyldimethyloctadecanylammonium chloride, methyltridecanylammonium chloride, benzyltripropylammonium chloride, benzyltriethylammonium chloride, phenyltriethylammonium chloride, tetraethylammonium chloride, Examples include tetraethylammonium bromide, tetramethylammonium chloride, tetramethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, and cetyltributylammonium bromide.
As quaternary phosphonium salts, for example, a linear or branched alkyl group having 1 to 18 carbon atoms, phenyl whose alkyl part is a linear or branched alkyl group having 1 to 6 carbon atoms Examples thereof include phosphonium salts substituted with a group selected from the group consisting of an alkyl group and a phenyl group. Specific examples include tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, cetyltributylphosphonium bromide, and tetraphenylphosphonium bromide. . Examples of pyridinium salts include pyridinium salts substituted with a linear or branched alkyl group having 1 to 18 carbon atoms, specifically 1-dodecanylpyridinium chloride. Specific examples of the crown ethers include 15-crown-5, 18-crown-6, benzo-18-crown-6, dibenzo-18-crown-6, and dibenzo-24-crown-8.

Among the phase transfer catalysts used in the present invention listed above, quaternary ammonium salts and quaternary phosphonium salts are preferable, and tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium fluoride, tetra Butylammonium iodide, tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate, tributylmethylammonium chloride, tributylbenzylammonium chloride, tetrapentylammonium chloride, tetrapentylammonium bromide, tetrahexylammonium chloride, benzyldimethyloctylammonium chloride, methyl Trihexylammonium chloride, benzyltripropylammonium chloride, benzyltriethyl Nmo chloride, phenyl triethyl ammonium chloride, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide and tetraphenylphosphonium bromide.
These phase transfer catalysts may be used alone or in combination of two or more as required.

As a usage-amount of the phase transfer catalyst used for this invention, it is 0.001-2 mol normally with respect to 1 mol of bisphenol represented by the said Formula (1) of the raw material used for reaction, Preferably it is 0.01-1 mol. is there. When the amount of the phase transfer catalyst used is 0.001 mol or more, decomposition of impurities is promoted, and when the amount is 2 mol or less, the color of the bisphenol bishydroxyethyl ether obtained can be improved.

When carrying out the alkaline water washing step, it is preferable to add an organic solvent separable from water because the solution viscosity is lowered and the decomposition rate of impurities is improved. The organic solvent separable from water means that it does not react with the target bisphenols bishydroxyethyl ether, strong basic substance and phase transfer catalyst, and by adding the organic solvent, water, phase transfer catalyst and strong base It represents an organic solvent that can be separated by forming a phase different from the aqueous phase containing the active substance.

Examples of organic solvents that can be separated from water include aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, and aliphatic hydrocarbons such as pentane, hexane, and heptane. Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, ethers such as diethyl ether, di-iso-propyl ether, methyl tertiary butyl ether, cyclopentyl methyl ether, diphenyl ether, ethyl acetate, n-acetate -Esters such as butyl, intermediates such as butanol, pentanol, hexanol and heptanol, higher alcohols, aliphatic intermediates such as methyl isobutyl ketone, and higher ketones. Of these, aromatic hydrocarbons, halogenated aromatic hydrocarbons, and ethers, particularly toluene, xylene, chlorobenzene, dichlorobenzene, and cyclopentylmethyl ether are preferable. In addition, when using an organic solvent when obtaining a reaction product, you may use the organic solvent as it is. These organic solvents may be used alone or as a mixture of two or more if necessary.

In the case of using an organic solvent that can be separated from water, the amount of use is, for example, 40 weight times or less (1 weight times of bisphenols bishydroxyethyl ether contained in the reaction product) The concentration of ether is 2.5% by weight or more), preferably 32 times by weight or less (the concentration of bisphenols bishydroxyethyl ether in the non-aqueous phase is 3% by weight or more). It is preferable that the amount of the organic solvent used be 40 times by weight or less because decomposition of impurities is promoted and economic efficiency is improved. The lower limit of the amount of the organic solvent used is not particularly limited, but an amount that makes the non-aqueous phase uniform is good.

To the reaction product, water, a phase transfer catalyst, a strongly basic substance, and if necessary an organic solvent separable from water are added, followed by stirring. The temperature during stirring is usually 0 to 150 ° C, preferably 60 to 120 ° C. By setting the stirring temperature to 0 ° C. or higher, decomposition of impurities is promoted, and by setting the stirring temperature to 150 ° C. or lower, coloring of bisphenols bishydroxyethyl ether obtained is suppressed, which is preferable. The stirring time can be appropriately determined by a method such as analyzing the residual amount of impurities in the reaction product by, for example, high performance liquid chromatography and confirming disappearance, but it is usually performed for 1 hour or longer.

  If an organic solvent that can be separated from water in the alkaline washing step is not used during the alkaline washing step described above, an organic solvent that can be separated from water is added and further stirred. The usable organic solvent that can be separated from water, the amount used, and the stirring conditions are the same as those in the alkaline water washing step.

After completion of the alkaline water washing step described above, the stirring is stopped and the mixture is allowed to stand to separate into an organic phase containing a bisphenol bishydroxyethyl ether (hereinafter sometimes referred to as a non-aqueous phase) and an aqueous phase. Thereafter, the aqueous phase is removed. Depending on the type of bisphenol bishydroxyethyl ether, water, and the amount of organic solvent used, it may be separated into three phases, but when separated into three phases, in the present invention, it is between the non-aqueous phase and the aqueous phase. This phase (intermediate phase) is a non-aqueous phase and is not removed and the subsequent step is performed.

The bisphenol bishydroxyethyl ether may be taken out as crystals by crystallization of the non-aqueous phase thus obtained under the conditions described later, but further adding water and a strongly acidic substance to the non-aqueous phase and mixing them By performing (hereinafter sometimes referred to as an acid washing step), the hue of the resulting bisphenol bishydroxyethyl ether is further improved, which is preferable. Hereinafter, the acid cleaning step will be described in detail.

Although it does not specifically limit in the range which can solve the subject of this invention as a temperature at the time of an acid washing process, Usually, 0-100 degreeC, Preferably it implements at 20-95 degreeC. When the temperature is 0 ° C. or higher, the effect of improving the hue of the bisphenol bishydroxyethyl ether is enhanced, and when the temperature is 100 ° C. or lower, the decomposition of the bisphenol bishydroxyethyl ether is preferably suppressed. The acid washing step is usually carried out for 5 minutes or longer.

Examples of strongly acidic substances used in the acid washing step include inorganic strong acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid and nitric acid, and halogenated acetic acids such as chloroacetic acid, dichloroacetic acid, trichloroacetic acid and trifluoroacetic acid. Examples include acids having a pKa of less than 3, such as organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and toluenesulfonic acid. Preferably, pKa such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid is used. It is an inorganic strong acid of less than 1, and hydrochloric acid and sulfuric acid are particularly preferable. These strongly acidic substance media may be used alone or as a mixture of two or more if necessary.

The amount of the strongly acidic substance used in the acid washing step is usually 0.001 to 10 times by weight, preferably 0.005 to 1 weight by weight, based on 1 weight by weight of the bisphenol represented by the above formula (1) used in the reaction. Is double.

The strongly acidic substance and water used in the acid washing step may be separately added with water and a strongly acidic substance, and may be used as an aqueous solution at the time of stirring, or may be used as an aqueous solution in which water and a strong acidic substance are mixed in advance. The amount of water used in the acid washing step is usually 0.01 to 30% by weight, preferably 0.5 to 10%, as the concentration of the strongly acidic substance in the aqueous phase containing the strongly acidic substance after being added to the reaction product. Use so that it may become weight%. By setting the concentration of the strongly acidic substance aqueous solution to 0.01% by weight or more, the hue improving effect of bisphenols bishydroxyethyl ether is enhanced, and by setting the concentration to 30% by weight or less, the decomposition of bisphenols bishydroxyethyl ether is suppressed. In addition, it is preferable because it is economical. The acid washing step is usually carried out for 5 minutes or longer.

After the completion of the acid washing step, the stirring is stopped and the mixture is allowed to stand to separate into an organic phase containing bisphenol bishydroxyethyl ether (hereinafter sometimes referred to as a non-aqueous phase) and an aqueous phase. Thereafter, the aqueous phase is removed.

The bishydroxyethyl ether of the desired bisphenol can be recovered from the organic phase containing the bisphenol bishydroxyethyl ether obtained by the above operation by a normal crystallization operation. The crystallization operation may be performed using the organic solvent that does not arbitrarily dissolve with water used in the above step as the crystallization solvent, or after concentrating part or all of the organic solvent that does not arbitrarily dissolve with water, Other solvents may be added for crystallization.

Examples of the crystallization solvent include alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and butyl methyl ketone, aromatic hydrocarbons such as toluene, xylene and mesitylene, chlorobenzene and dichlorobenzene. Halogenated aromatic hydrocarbons, aliphatic hydrocarbons such as pentane, hexane and heptane, halogenated aliphatic hydrocarbon solvents such as dichloromethane and 1,2-dichloroethane, diethyl ether, di-iso-propyl ether, methyl-tertiary -Ethers such as butyl ether and diphenyl ether, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile, and water. Aromatic hydrocarbons, ketones, nitriles or ethers are preferred. Crystallization solvents can be used alone or in combination of two or more. The amount of the crystallization solvent used is usually 0.5 times or more, preferably 1 to 20 times, and more preferably 1 to 10 times the weight of the bisphenol bishydroxyethyl ether.

The precipitated crystals are collected by filtration or the like, washed as necessary, and dried to obtain the desired bisphenol bishydroxyethyl ether. A recrystallization operation can be performed by adding a solvent again to the crystals recovered in the bisphenols bishydroxyethyl ether thus obtained. Furthermore, if necessary, usual purification operations such as adsorption and steam distillation can be repeated.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Analysis conditions>
Hereinafter, the content and purity of each component described in the Examples and Comparative Examples were determined by an internal standard method (LC-IS method) in which each sample was analyzed by high performance liquid chromatography under the following conditions and anisole was used as an internal standard. .
High performance liquid chromatograph: LC-2010 manufactured by Shimadzu Corporation
Developing solution: A solution Water B solution Acetonitrile A solution / B solution 50/50 → (25 minutes) → 0/100 → 15 minutes Hold column: Reversed phase column (WATERS XBRIDGE PHENYL (3.5 μm, 4.6 mmφ × 150 mm) )
Column temperature: 40 ° C
Flow rate 1.0mL / min
Analysis wavelength: 254 nm

Unless otherwise specified,% described in Examples and Comparative Examples below represents the content of each component analyzed as described above in the reaction product / product. D. Indicates that it was below the detection limit. In addition, about a yield, it is a solid yield with respect to the bisphenol which is a raw material.

<Example 1>
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene 60 g, ethylene carbonate 32.0 g, potassium carbonate 3.0 g and 30 g of toluene was added, and the mixture was heated and stirred at 115 ° C. for 16 hours to obtain a reaction product containing 82.4% of bishydroxyethyl ether of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. To this reaction product was added 420 g of toluene, 120 g of a 12.0% by weight aqueous sodium hydroxide solution and 0.9 g of tetrabutylammonium bromide, and the mixture was stirred at 85 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. To the organic solvent phase was added 120 g of 5.3 wt% hydrochloric acid, and the mixture was stirred for 15 minutes at 85 ° C. and allowed to stand. The organic solvent phase was separated, and the aqueous layer containing hydrochloric acid was removed. Next, 90 g of water was added to the organic solvent phase, and the mixture was allowed to stand after stirring at 85 ° C. for 15 minutes, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 300 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 66.2 g (yield: 89.5%) of 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene crystals. The obtained crystals were white and the purity was 96.1%.

<Example 2>
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 180 g of 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 89.3 g of ethylene carbonate, 3. 9 g and 180 g of chlorobenzene were added, and the mixture was heated and stirred at 115 ° C. for 42 hours to obtain a reaction product containing 84.0% of bishydroxyethyl ether of 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene. . To this reaction product was added 3240 g of chlorobenzene, 180 g of a 30 wt% aqueous potassium hydroxide solution and 0.7 g of tetramethylammonium bromide, and the mixture was stirred at 60 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. To the solvent phase was added 360 g of 10% by weight sulfuric acid, and the mixture was stirred at 60 ° C. for 15 minutes and allowed to stand. The organic solvent phase was separated and the aqueous layer containing sulfuric acid was removed. Next, 360 g of water was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 85 ° C. and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 1600 g of chlorobenzene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 203.1 g (yield 92.7%) of 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene crystals. The obtained crystals were white and the purity was 99.1%.

<Example 3>
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene 150 g, ethylene carbonate 56.2 g, potassium carbonate 3.2 g and 150 g of toluene was added, and the mixture was heated and stirred at 115 ° C. for 20 hours to obtain a reaction product containing 93.0% of bishydroxyethyl ether of 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene. To this reaction product, 1050 g of toluene, 850 g of 3% by weight potassium hydroxide aqueous solution and 15 g of tetramethylammonium chloride were added, stirred at 85 ° C. for 1 hour, allowed to stand, and then the organic solvent phase was separated and separated. To the phase was added 600 g of 0.5 wt% hydrochloric acid, and the mixture was stirred for 15 minutes at 85 ° C. and allowed to stand. The organic solvent phase was separated and the aqueous layer containing hydrochloric acid was removed. Next, 300 g of water was added to the organic solvent phase, and the mixture was allowed to stand after stirring at 85 ° C. for 15 minutes, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 750 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 161.0 g (yield 91.3%) of 9,9-bis (4- (2-hydroxyethoxy) -3-phenylphenyl) fluorene crystals. The obtained crystals were white and the purity was 98.8%.

<Example 4>
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 15 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane, 13.6 g of ethylene carbonate, 0.7 g of potassium carbonate and 22.5 g of orthodichlorobenzene was added, and the mixture was heated and stirred at 115 ° C. for 20 hours to obtain a reaction product containing 76.4% of 2,2-bis (4-hydroxy-3-methylphenyl) propane bishydroxyethyl ether. . To this reaction product was added 62.5 g of orthodichlorobenzene, 9 g of 15% by weight potassium hydroxide aqueous solution and 0.1 g of benzyltriethylammonium chloride, and the mixture was stirred at 95 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. Thereafter, 9 g of 1 wt% sulfuric acid was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 95 ° C. and allowed to stand. The organic solvent phase was separated, and the aqueous layer containing sulfuric acid was removed. Next, 15 g of water was added to the organic solvent phase, the mixture was stirred at 95 ° C. for 15 minutes and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, orthodichlorobenzene was completely concentrated from the organic solvent phase, and then dried to give 17.2 g of a viscous liquid of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane (yield) 84.7%) was obtained. The obtained liquid was colorless and the purity was 96.8%.

<Example 5>
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 15 g of 2,2-bis (4-hydroxy-3-methylphenyl) cyclohexane, 10.2 g of ethylene carbonate, 0.6 g of potassium carbonate and 22.5 g of toluene was added, and the mixture was heated and stirred at 115 ° C. for 20 hours to obtain a reaction product containing 78.4% of 2,2-bis (4-hydroxy-3-methylphenyl) cyclohexane bishydroxyethyl ether. To this reaction product was added 150 g of toluene, 24 g of a 5 wt% aqueous sodium hydroxide solution and 0.9 g of tetrabutylammonium iodide, and the mixture was stirred at 70 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. 30 g of 0.5 wt% hydrochloric acid was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 70 ° C. and allowed to stand. The organic solvent phase was separated and the aqueous layer containing hydrochloric acid was removed. Next, 30 g of water was added to the organic solvent phase, and the mixture was allowed to stand after stirring at 70 ° C. for 15 minutes, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 67.5 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 16.7 g (yield: 85.6%) of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) cyclohexane crystals. The obtained crystals were white and the purity was 97.0%.

<Example 6>
In a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 40 g of 2,2-bis (4-hydroxy-3-methylphenyl) cyclododecane, 30.0 g of ethylene carbonate, 2.0 g of potassium carbonate And 40 g of cyclopentyl methyl ether were added, and the mixture was heated and stirred at 115 ° C. for 6 hours to obtain a reaction product containing 75.5% of bishydroxyethyl ether of 2,2-bis (4-hydroxy-3-methylphenyl) cyclododecane. . To this reaction product was added 480 g of cyclopentyl methyl ether, 60 g of a 9.7% by weight aqueous sodium hydroxide solution and 0.2 g of tetraphenylphosphonium bromide, and the mixture was stirred at 80 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. Thereafter, 0.9 g of hydrochloric acid (40 g) was added to the organic solvent phase, and the mixture was stirred at 80 ° C. for 15 minutes and allowed to stand. The organic solvent phase was separated, and the aqueous layer containing hydrochloric acid was removed. Next, 40 g of water was added to the organic solvent phase, the mixture was stirred at 80 ° C. for 15 minutes and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 200 g of cyclopentyl methyl ether was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 43.9 g (yield: 89.1%) of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) cyclododecane crystals. The obtained crystals were white and the purity was 97.4%.

<Example 7>
To a glass reactor equipped with a stirrer, nitrogen blowing tube, thermometer and cooling tube, 100 g of 2,2′-dihydroxy-9,9′-spirobifluorene, 57.8 g of ethylene carbonate, 6.2 g of triphenylphosphine and 100 g of xylene was added, and the mixture was heated and stirred at 135 ° C. for 6 hours to obtain a reaction product containing 83.3% of 2,2′-dihydroxy-9,9′-spirobifluorene bishydroxyethyl ether. To this reaction product, 500 g of cyclopentyl methyl ether, 200 g of a 12 wt% aqueous sodium hydroxide solution and 1.0 g of tetrabutylphosphonium bromide were added. After stirring for 1 hour at 80 ° C., the organic solvent phase was separated and separated. 200 g of 1.8 wt% hydrochloric acid was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 80 ° C. and allowed to stand. The organic solvent phase was separated, and the aqueous layer containing hydrochloric acid was removed. Next, 200 g of water was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 80 ° C. and allowed to stand to separate the organic solvent phase. Furthermore, the same operation was repeated twice. Thereafter, 300 g of cyclopentyl methyl ether was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 104.6 g (yield: 83.5%) of 2,2′-dihydroxyethoxy-9,9′-spirobifluorene crystals. The obtained crystals were white and the purity was 98.5%.

<Example 8>
The reaction was conducted in the same manner as in Example 4 to obtain a reaction product containing 77.1% of bishydroxyethyl ether of 2,2-bis (4-hydroxy-3-methylphenyl) propane. To this reaction product, 30 g of a 50 wt% aqueous potassium hydroxide solution and 0.1 g of benzyltriethylammonium chloride were added, stirred at 95 ° C. for 1 hour and allowed to stand, then 62.5 g of orthodichlorobenzene was added, and the mixture was stirred at 95 ° C. After standing still, the organic solvent phase was separated and separated. Next, 9 g of 1 wt% sulfuric acid was added to the organic solvent phase, and the mixture was allowed to stand after stirring at 95 ° C. for 15 minutes. The organic solvent phase was separated, and the aqueous layer containing sulfuric acid was removed. Next, 15 g of water was added to the organic solvent phase, the mixture was stirred at 95 ° C. for 15 minutes and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, orthodichlorobenzene was completely concentrated from the organic solvent phase and then dried to obtain 17.3 g of a viscous liquid of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane (yield) 85.8%). The resulting liquid was light yellow and the purity was 94.2%.

<Example 9>
The reaction was conducted in the same manner as in Example 3 to obtain a reaction product containing 92.7% of 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene bishydroxyethyl ether. To this reaction product was added 1050 g of toluene, 850 g of 3 wt% potassium hydroxide aqueous solution and 15 g of tetramethylammonium chloride, and the mixture was stirred at 85 ° C. for 1 hour and allowed to stand to separate the organic solvent phase, followed by acid washing step. Omitted, 300 g of water was added to the organic solvent phase, and the mixture was stirred at 85 ° C. for 15 minutes and allowed to stand to separate the organic solvent phase. Furthermore, the same operation was repeated twice. Thereafter, 750 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 162.0 g (yield 91.9%) of 9,9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene crystals. The obtained crystals were pale yellow and the purity was 98.4%.

<Comparative Example 1>
The reaction was conducted in the same manner as in Example 1 to obtain a reaction product containing 82.8% of bishydroxyethyl ether of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene. To this reaction product, 420 g of toluene and 120 g of a 12.0 wt% aqueous sodium hydroxide solution were added, and the mixture was stirred at 85 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. Then, 5.3 wt% was added to the organic solvent phase. % Hydrochloric acid (120 g) was added, and the mixture was stirred at 85 ° C. for 15 minutes and allowed to stand. The organic solvent phase was separated, and the aqueous layer containing hydrochloric acid was removed. Next, 90 g of water was added to the organic solvent phase, and the mixture was allowed to stand after stirring at 85 ° C. for 15 minutes, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 300 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 67.9 g (yield 91.8%) of 9,9-bis (4-hydroxyethoxy-3-methylphenyl) fluorene crystals. The obtained crystals were pale yellow and the purity was 84.4%.

<Comparative example 2>
The reaction was conducted in the same manner as in Example 2 to obtain a reaction product containing 84.1% of bishydroxyethyl ether of 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene. To this reaction product, 3240 g of chlorobenzene and 0.7 g of tetramethylammonium bromide were added, stirred at 60 ° C. for 1 hour and allowed to stand to separate the organic solvent phase, and 360 g of 10 wt% sulfuric acid was added to the organic solvent phase. In addition, the mixture was stirred at 60 ° C. for 15 minutes and allowed to stand, and the organic solvent phase was separated and the aqueous layer containing sulfuric acid was removed. Next, 360 g of water was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 60 ° C. and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 1600 g of chlorobenzene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 204.8 g (yield 93.5%) of 9,9-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) fluorene crystals. The obtained crystals were pale yellow and the purity was 87.9%.

<Comparative Example 3>
The reaction was conducted in the same manner as in Example 3 to obtain a reaction product containing 93.1% of bishydroxyethyl ether of 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene. To this reaction product was added 1050 g of toluene, 850 g of 3 wt% potassium carbonate aqueous solution and 15 g of tetramethylammonium chloride, and the mixture was stirred for 1 hour at 85 ° C. and allowed to stand to separate and separate the organic solvent phase. 600 g of 0.5 wt% hydrochloric acid was added, and the mixture was stirred for 15 minutes at 85 ° C. and allowed to stand. The organic solvent phase was separated, and the aqueous layer containing hydrochloric acid was removed. Next, 300 g of water was added to the organic solvent phase, and the mixture was allowed to stand after stirring at 85 ° C. for 15 minutes, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 750 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 164.7 g (yield 93.4%) of 9,9-bis (4-hydroxyethoxy-3-phenylphenyl) fluorene crystals. The obtained crystals were light brown and the purity was 94.0%.

<Comparative example 4>
Reaction was carried out in the same manner as in Example 4 to obtain a reaction product containing 76.8% of bishydroxyethyl ether of 2,2-bis (4-hydroxy-3-methylphenyl) propane. To this reaction product was added 62.5 g of orthodichlorobenzene and 9 g of 1% by weight sulfuric acid, and the mixture was stirred for 1 hour at 95 ° C. and allowed to stand to separate the organic solvent phase, and then 15 g of water was added to the organic solvent phase. The mixture was allowed to stand after stirring at 95 ° C. for 15 minutes, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, orthodichlorobenzene was completely concentrated from the organic solvent phase and then dried to obtain 17.3 g of a viscous liquid of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) propane (yield) 85.8%). The resulting liquid was brown and the purity was 82.5%.

<Comparative Example 5>
Reaction was carried out in the same manner as in Example 5 to obtain a reaction product containing 78.9% of bishydroxyethyl ether of 2,2-bis (4-hydroxy-3-methylphenyl) cyclohexane. To this reaction product was added 150 g of toluene and 24 g of water, and the mixture was stirred at 70 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. Then, 30 g of water was added to the organic solvent phase, and the mixture was stirred at 70 ° C. for 15 minutes. The organic solvent phase was separated and separated. Furthermore, the same operation was repeated twice. Thereafter, 67.5 g of toluene was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 17.2 g (yield 88.4%) of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) cyclohexane crystals. The obtained crystals were pale yellow and the purity was 81.7%.

<Comparative Example 6>
The reaction was conducted in the same manner as in Example 6 to obtain a reaction product containing 76.4% of 2,2-bis (4-hydroxy-3-methylphenyl) cyclododecane bishydroxyethyl ether. To this reaction product was added 480 g of cyclopentyl methyl ether, 0.2 g of tetraphenylphosphonium bromide and 40 g of 0.9 wt% hydrochloric acid, and the mixture was stirred at 80 ° C. for 1 hour and allowed to stand to separate the organic solvent phase. 40 g of water was added to the organic solvent phase, and the mixture was stirred for 15 minutes at 80 ° C. and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 200 g of cyclopentyl methyl ether was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 44.6 g (yield 90.5%) of 2,2-bis (4- (2-hydroxyethoxy) -3-methylphenyl) cyclododecane crystals. The obtained crystals were pale yellow and the purity was 80.2%.

<Comparative Example 7>
The reaction was conducted in the same manner as in Example 7 to obtain a reaction product containing 84.5% of bishydroxyethyl ether of 2,2′-dihydroxy-9,9′-spirobifluorene. To this reaction product, 500 g of cyclopentyl methyl ether and 200 g of a 12.0% by weight aqueous sodium hydroxide solution were added. After stirring for 1 hour at 80 ° C., the organic solvent phase was separated and separated. 200 g was added, and the mixture was stirred for 15 minutes at 80 ° C. and allowed to stand, and the organic solvent phase was separated. Furthermore, the same operation was repeated twice. Thereafter, 300 g of cyclopentyl methyl ether was concentrated from the organic solvent phase, and then cooled to 25 ° C. to precipitate crystals. Next, the precipitated crystals were filtered and dried to obtain 107.0 g (yield 85.4%) of 2,2′-dihydroxyethoxy-9,9′-spirobifluorene crystals. The obtained crystals were pale yellow and the purity was 90.9%.

Claims (7)

In the method of producing bisphenols bishydroxyethyl ether by reacting bisphenols and ethylene carbonate, after reacting the bisphenols and ethylene carbonate, the reaction product obtained is mixed with water, a phase transfer catalyst and a strongly basic substance. The manufacturing method of bisphenols bishydroxyethyl ether including the process of adding and stirring. The manufacturing method of the bisphenol bishydroxyethyl ether of Claim 1 which implements stirring of Claim 1 at 60-120 degreeC. The method for producing a bisphenol bishydroxyethyl ether according to claim 1 or 2, wherein the concentration of the strongly basic substance in the aqueous phase containing the strongly basic substance is 3 to 30% by weight. The method for producing a bisphenol bishydroxyethyl ether according to any one of claims 1 to 3, wherein the amount of the strongly basic substance used is 0.3 to 4 mol with respect to 1 mol of the bisphenol. After carrying out the process according to any one of claims 1 to 4, a phase containing bisphenols bishydroxyethyl ether and an aqueous phase are separated, and water and a strongly acidic substance are added to the obtained phase containing bishydroxyethyl ether. The manufacturing method of the bisphenol bishydroxyethyl ether of any one of Claims 1-4 including the process of adding and mixing. In the method of producing bisphenols bishydroxyethyl ether by reacting bisphenols and ethylene carbonate, after reacting the bisphenols and ethylene carbonate, the reaction product obtained is mixed with water, a phase transfer catalyst and a strongly basic substance. The method for producing a bisphenol bishydroxyethyl ether according to any one of claims 1 to 5, wherein an organic solvent separable from water is further added when adding and stirring. The method for producing a bisphenol bishydroxyethyl ether according to claim 6, wherein the concentration of bishydroxyethyl ether in the organic solvent separable from water is 3% by weight or more.