WO2017170095A1

WO2017170095A1 - Novel dihydroxy compound

Info

Publication number: WO2017170095A1
Application number: PCT/JP2017/011626
Authority: WO
Inventors: 隼溝口; 緒旺路
Original assignee: 本州化学工業株式会社
Priority date: 2016-03-28
Filing date: 2017-03-23
Publication date: 2017-10-05
Also published as: CN108884038A; TWI770014B; TW201738207A; KR20180130517A; KR102350817B1; JPWO2017170095A1

Abstract

The present invention addresses the problem of providing a novel dihydroxy compound having an indoline skeleton that has high heat resistance and a high refractive index. Provided as a solution is a dihydroxy compound represented by general formula (1) (in the formula, R represents a C2-6 alkylene group, R₁ and R₂ each independently represent a C1-8 alkyl group or C1-8 alkoxy group, m represents an integer of 0-3, and n represents an integer of 0-2; however, when m is 2 or higher, R₁ may be the same or different, and when n is 2, R₂ may be the same or different).

Description

Novel dihydroxy compounds

The present invention relates to a novel dihydroxy compound. Specifically, the present invention relates to a dihydroxy compound having an indoline skeleton, which is suitable as a raw material for aromatic polycarbonate oligomers and resins.

Conventionally, bisphenoxy alcohols (compounds in which the hydrogen atom of the hydroxy group of bisphenol is substituted with a hydroxyalkyl group) are thermoplastic synthetic resin raw materials such as polycarbonate resins, thermosetting resin raw materials such as epoxy resins, and antioxidant raw materials. In recent years, the performance required for these bisphenoxy alcohols has become increasingly sophisticated.
As bisphenoxy alcohols, 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine having an isoindoline skeleton is known (Non-patent Document 1). However, the compound has insufficient heat resistance and optical characteristics, and further improvement is required.
As a method for producing bisphenoxy alcohols, there is known a method in which a bisphenol compound is reacted with an alkylene carbonate or an alkylene oxide. In this method, as a impurity, a monohydroxyalkoxy compound or a target product is produced. Bisphenoxy alcohols further react with alkylene carbonates and alkylene oxides to produce a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group, resulting in a low reaction selectivity. In addition, since there are raw materials and intermediates having an aromatic hydroxyl group, the resulting compound is colored and has poor thermal stability, so it must be repeatedly purified for use as an optical application, which is industrially disadvantageous. is there.

The present invention has been made against the background described above, and an object of the present invention is to provide a novel dihydroxy compound having an indoline skeleton having high heat resistance and high refractive index.

As a result of intensive studies for solving the above-mentioned problems, the present inventors have found that the dihydroxy compound of the present invention having an indoline skeleton is excellent in optical properties such as high heat resistance and high refractive index, and completed the present invention. did.

The present invention is as follows.
1. A dihydroxy compound represented by the following general formula (1).

(Wherein R represents an alkylene group having 2 to 6 carbon atoms, R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 0 to 2, provided that when m is 2 or more, R ₁ may be the same or different. When n is 2, R ₂ is the same But it may be different.)

Since the dihydroxy compound according to the present invention has high heat resistance and a high refractive index, an excellent effect as a polycarbonate raw material for optical materials can be expected. Moreover, the dihydroxy compound according to the present invention is a monohydroxyalkoxy compound (sometimes referred to as 1EO form) or a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group (sometimes referred to as multi-EO form). High purity without containing, and excellent optical properties such as thermal stability and product hue.
Furthermore, the polycarbonate using the dihydroxy compound of the present invention as a raw material monomer is a monohydroxyalkoxy compound (1EO form) in which the raw material monomer is an impurity, or a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group (multi-EO form). ), It is expected to have high purity, high heat resistance, and high refractive index, and in particular, an excellent effect is expected in polycarbonate for optical materials.

Hereinafter, the present invention will be described in detail.
The dihydroxy compound of the present invention is represented by the following general formula (1).

(Wherein R represents an alkylene group having 2 to 6 carbon atoms, R ₁ and R ₂ each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 0 to 2, provided that when m is 2 or more, R ₁ may be the same or different. When n is 2, R ₂ is the same But it may be different.)
In the above general formula (1), each R is independently an alkylene group having 2 to 6 carbon atoms. Specific examples of the alkylene group include 1,2-ethylenediyl group, 1,2- Examples thereof include a propanediyl group, a 1,3-propanediyl group, a pentamethylene group, and a hexamethylene group, preferably a linear or branched alkylene group having 2 to 4 carbon atoms, particularly preferably. An alkylene group having 2 or 3 carbon atoms; Here, the hydroxyalkoxy group represented by “—O—R—OH” in the general formula (1) will be described. The bonding position of the hydroxy group bonded to the alkylene group R is alkylene bonded directly to the ether group. It is not bonded to the carbon atom constituting the group R (the 1st carbon atom). When R is an alkylene group having 3 or more carbon atoms, the bonding position of the hydroxy group is preferably the 2- or 3-position of the alkylene group “R”, and more preferably the 2-position. Specific examples include 2-hydroxyethoxy group, 2-hydroxypropoxy group, 2-hydroxy-1-methylethoxy group, 3-hydroxypropoxy group and the like.
R ₁ and R ₂ are each independently an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and when R ₁ is an alkyl group having 1 to 8 carbon atoms, Is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an isobutyl group. Can be mentioned. Such an alkyl group may have a substituent such as a phenyl group or an alkoxy group, as long as the effects of the present invention are not impaired.
When R ₁ and R ₂ are alkoxy groups having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. Examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group and the like. Such an alkoxy group may have a substituent such as a phenyl group or an alkoxy group, for example, within a range not impairing the effects of the present application.
Preferred R ₁ and R ₂ are methyl groups.
Moreover, in the said General formula (1), m is 0, 1, 2, or 3, Preferably it is 0, 1 or 2, Especially preferably, it is 0 or 1. In the said General formula (1), n is 0, 1 or 2, Preferably it is 0 or 1, Especially preferably, it is 0.

In the above general formula (1), the “—O—R—OH” group substituted for the phenyl group directly bonded to the 3-position carbon atom of the indoline skeleton and the substitution position of R ₁ are first described as “ The —O—R—OH ”group is preferably substituted at the 4-position or 2-position with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, more preferably at the 4-position. preferable.
R ₁ is preferably substituted at the o-position or the p-position with respect to the “—O—R—OH” group, and is a phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton. On the other hand, when the “—O—R—OH” group is substituted at the 4-position, it is preferably substituted at the 3-position or the 5-position, and the “—O—R—OH” group is substituted at the 2-position. When it is, it is preferable to substitute at the 3-position or 5-position.
In addition, when m is 2, the substitution position of R ₁ is the 4-position of the “—O—R—OH” group with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, or R ₁ is substituted on 3-position and 5-position "-O-R-OH" group is 4-position, it is preferred _{that R 1} is substituted on the 2- and 5-positions.
Furthermore, when m is 3, the substitution position of R ₁ is the 4-position of the “—O—R—OH” group with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, R ₁ is preferably substituted at the 2-position, 3-position and 5-position.

Therefore, the dihydroxy compound represented by the general formula (1) is preferably represented by the following general formula (3).

Wherein R ₂ and n are the same as those in formula (1), and R ₃ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. And each R ₄ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, provided that the total number of carbon atoms of R ₄ substituted for each hydroxyethoxy group is 4 or less.)
In the general formula (3), preferred examples and specific examples relating to R ₂ and n are the same as those in the general formula (1).
In the general formula (3), when R ₃ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, preferred examples and specific examples thereof are represented by the general formula (1 ) Is the same as when R ₁ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. R ₃ is more preferably a hydrogen atom or a methyl group. As a preferred combination, at least one of R ₃ at the 3-position and the 5-position is preferably a hydrogen atom with respect to the phenyl carbon atom directly bonded to the 3-position carbon atom of the indoline skeleton, R ₃ in the 2nd and 5th positions is preferably a hydrogen atom with respect to a phenyl carbon atom directly bonded to the 3rd carbon atom of the indoline skeleton, and in particular, all R ₃ are preferably hydrogen atoms. .
In the general formula (3), when R ₄ is an alkyl group having 1 to 4 carbon atoms, specific examples include a methyl group, an ethyl group, an n-propyl group, and the like.
R ₄ is particularly preferably a hydrogen atom or a methyl group.

Specific examples of the dihydroxy compound represented by the general formula (1) of the present invention include 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indole-2- on

3,3-bis (4- (2-hydroxy-2-methylethoxy) phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxy-1-methylethoxy) Phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -3-methylphenyl) -1-phenyl-1H-indole-2-one 3,3- Bis (3-ethyl-4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) -3,5-dimethylphenyl) -1-phenyl-1H-indole-2-one 3,3-bis (4- (2-hydroxyethoxy) -2,5-dimethylphenyl) -1-phenyl-1H-indole-2-one 3,3 Bis (4- (2-hydroxyethoxy) -2,3,5-trimethylphenyl) -1-phenyl-1H-indol-2-one 3,3-bis (2- (2-hydroxyethoxy) phenyl) -1 -Phenyl-1H-indol-2-one 3,3-bis (2- (2-hydroxyethoxy) -3-methylphenyl) -1-phenyl-1H-indol-2-one 3,3-bis (4- (2-Hydroxyethoxy) phenyl) -1- (4-methylphenyl) -1H-indol-2-one 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1- (2-methylphenyl) -1H-indole-2-one 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1- (4-methoxyphenyl) -1H-indole-2-one and the like.

The production method of the dihydroxy compound represented by the general formula (1) of the present invention is not particularly limited. Preferably, the N-phenylisatin compound represented by the following general formula (5) and the following general formula It can be obtained by using a phenoxy alcohol compound represented by the formula (6) as a raw material and reacting them in the presence of an acid catalyst.
The raw material N-phenylisatin compound of the above production method is represented by the following general formula (5).

(In the formula, R ₂ and n are the same as those in the general formula (1).)
Preferred examples and specific examples of R ₂ and n are the same as those in the general formula (1).
Specific examples of the N-phenylisatin compound represented by the general formula (5) include 1-phenyl-1H-indole-2,3-dione 1- (4-methylphenyl)- Examples thereof include 1H-indole-2,3-dione 1- (2-methylphenyl) -1H-indole-2,3-dione 1- (4-methoxyphenyl) -1H-indole-2,3-dione.

Moreover, the raw material phenoxy alcohol compound of the above-mentioned manufacturing method is represented by the following general formula (6).

(In the formula, R, R ₁ and m are the same as those in the general formula (1).)
Preferred examples and specific examples relating to R, R ₁ and m are also the same as those in the general formula (1).
As such a phenoxy alcohol compound represented by the general formula (6), a compound represented by the general formula (7) is preferable.

(In the formula, R ₃ and R ₄ are the same as those in the general formula (3).)
Preferred examples and specific examples relating to R ₃ and R ₄ are also the same as those in the general formula (3).
Specific examples of the compound represented by the general formula (7) include 2-phenoxyethanol 2-phenoxypropanol 1-phenoxy-2-propanol 2- (2-methylphenoxy) ethanol 2- (2 -Ethylphenoxy) ethanol 2- (2,6-dimethylphenoxy) ethanol 2- (2,5-dimethylphenoxy) ethanol 2- (2,3,6-trimethylphenoxy) ethanol and the like.

Although the manufacturing method of the dihydroxy compound of this invention is not specifically limited, As an example of the preferable manufacturing method for obtaining the more preferable dihydroxy compound (1EO body and 3EO body are not included) of this invention, it represents with General formula (5). The dihydroxy compound represented by the general formula (1) having an indoline skeleton is produced by reacting the N-phenylisatin compound produced with the phenoxy alcohol compound represented by the general formula (6) or (7). The method of performing will be described in detail.
The condensation reaction is carried out by reacting the above N-phenylisatin compound with a phenoxy alcohol compound, usually in the presence of an acid catalyst. First, an N-phenylisatin compound and a phenoxyalcohol compound are reacted in the presence of an acid catalyst, and the resulting reaction mixture is neutralized with an alkali, and then crystallized and filtered according to a known method to produce primary crystals. An analysis filtrate is obtained.
In the reaction, the charged molar ratio of the phenoxy alcohol compound to the N-phenylisatin compound is not particularly limited as long as it is the theoretical value (2.0) or more, but preferably 3.0 times the molar amount or more, More preferably, it is used in the range of 3.5 to 20 times the molar amount, particularly preferably in the range of 4.0 to 15 times the molar amount. Examples of the acid catalyst include hydrochloric acid, hydrogen chloride gas, 60-98% sulfuric acid, 85% phosphoric acid and other inorganic acids, p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid, etc. Organic acids, heteropolyacids, ion exchange resins, activated clays, and solid acids such as silica-alumina. Hydrogen chloride gas is preferred. The amount of such an acid catalyst used varies depending on the reaction conditions. For example, in the case of hydrogen chloride gas, after replacing the air in the reaction system with an inert gas such as nitrogen gas, hydrogen chloride gas is blown, The hydrogen chloride gas concentration in the gas phase in the reaction vessel is preferably 75 to 100% by volume, and the hydrogen chloride concentration in the reaction solution is preferably saturated. In the case of 35% hydrochloric acid, it is used in the range of 5 to 70 parts by weight, preferably in the range of 10 to 40 parts by weight, more preferably in the range of 20 to 30 parts by weight with respect to 100 parts by weight of the phenoxy alcohol compound. Here, when sulfuric acid is used as the acid catalyst, there is a concern that the hue of the compound deteriorates because sulfuric acid remains in the target compound, and when a heteropolyacid is used as the acid catalyst, the reaction temperature is increased. Since it is necessary, it is not efficient such as a reduction in reaction selectivity.
In the reaction, a co-catalyst may be used together with the acid catalyst as necessary. For example, when hydrogen chloride gas is used as a catalyst, the reaction rate can be accelerated by using thiols as a co-catalyst. Examples of such thiols include alkyl mercaptans and mercaptocarboxylic acids, preferably alkyl mercaptans having 1 to 12 carbon atoms and mercaptocarboxylic acids having 1 to 12 carbon atoms, such as methyl mercaptan. And alkali metal salts such as ethyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, and sodium salts thereof, thioacetic acid, thioglycolic acid, β-mercaptopropionic acid, and the like.
Moreover, these can be used individually or in combination of 2 or more types.
The amount of thiols used as a co-catalyst is usually in the range of 0.5 to 20 mol%, preferably in the range of 2 to 10 mol%, relative to the starting N-phenylisatin compound.

In the reaction, as the reaction solvent, the starting N-phenylisatin compound and the phenoxyalcohol compound have a low melting point, and if there is no problem in operability, it is not necessary to use a solvent. It may be used for reasons such as improving the reaction rate. The reaction solvent is not particularly limited as long as it does not distill from the reactor at the reaction temperature and is inert to the reaction. For example, aromatic hydrocarbons such as toluene and xylene, methanol, n-propyl alcohol, isobutyl alcohol, etc. And aliphatic alcohols such as hexane, heptane and cyclohexane, carboxylic acid esters such as ethyl acetate and butyl acetate, and mixtures thereof. Of these, aliphatic alcohols are preferably used.
Moreover, in order to lower the freezing point of the phenoxy alcohol compound and promote the reaction of the acid catalyst, a small amount of water may be added as necessary. In particular, when the acid catalyst is hydrogen chloride gas, water is preferable for promoting the absorption of hydrogen chloride gas by the catalyst. When water is added, the addition amount is preferably in the range of 0.5 to 15.0 parts by weight with respect to 100 parts by weight of the phenoxy alcohol compound.
Although the reaction temperature varies depending on the conditions of the catalyst used, for example, when hydrogen chloride gas is used as the catalyst, the range of 20 to 70 ° C. is preferable, and the range of 30 to 60 ° C. is more preferable. The reaction pressure is usually carried out under normal pressure, but depending on the boiling point of the organic solvent that may be used, the reaction may be carried out under pressure or reduced pressure so that the reaction temperature falls within the above range. If the reaction is carried out under such conditions, the reaction is usually completed in about 1 to 30 hours.
The end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. The end point of the reaction is preferably the point at which the unreacted N-phenylisatin compound disappears and no increase in the desired product is observed.
The reaction yield based on the phenoxy alcohol compound is usually about 75 to 95 mol%. After completion of the reaction, the resulting reaction mixture is added with an alkaline solution such as aqueous ammonia or aqueous sodium hydroxide solution to neutralize the acid catalyst, and contains the dihydroxy compound represented by the general formula (1) according to the present invention. A reaction mixture is obtained.
If necessary, after removing the unreacted raw material phenoxyalcohol compound by distillation from the neutralized reaction mixture, water washing treatment is performed to add water and an insoluble organic solvent to the water and sufficiently stir to separate the oil layer. Do. As the organic solvent used at this time, it is necessary to dissolve the dihydroxy compound of the general formula (1) and to have a low solubility in water. As the organic solvent having this property, an aromatic hydrocarbon such as toluene or xylene, an aliphatic hydrocarbon such as cyclohexane or n-heptane, an aliphatic ketone such as methyl isobutyl ketone, or an alcohol solvent such as butanol is employed. be able to.
The organic solvent layer obtained after the neutralization and washing with water is partially removed by distillation, if necessary, and then the organic solvent layer is heated as it is or once to a uniform solution, cooled, or appropriately When crystals are precipitated by adding a crystallization solvent or a poor solvent and cooling, a crude or high-purity target product can be obtained by filtering the crystals.
The target product obtained above can be further purified by recrystallization using a solvent. Organic solvents used at this time include aromatic hydrocarbon solvents such as toluene, xylene and mesitylene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester solvents such as ethyl acetate and butyl acetate, and alcohols such as butanol. A solvent is mentioned, These can be used individually or in mixture of 2 or more types.
Instead of the above crystallization operation, after completion of the reaction, the reaction solvent and the like are concentrated under reduced pressure, and the residue is purified by column chromatography or the like to obtain a high purity product.

Here, as impurities which the dihydroxy compound represented by the general formula (1) may contain, a 1EO body (monohydroxyalkoxy body) represented by the following general formula (8), and the following general formula (9) And a multi-EO body represented by the formula (a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group). However, for example, a method of reacting the N-phenylisatin compound represented by the general formula (5) with the phenoxy alcohol compound represented by the general formula (6) or the general formula (7), which is the above-described production method. By adopting, the 1EO body represented by the following general formula (8), the multi-EO body represented by the following general formula (9) and the 3EO body represented by the following general formula (10) do not contain impurities. It is possible to produce a dihydroxy compound represented by the formula (1).
The above 1EO body is represented by the following general formula (8).

(In the formula, R, R ₁ , R ₂ , m and n are the same as those in the general formula (1).)
Preferred examples and specific examples relating to R, R ₁ , R ₂ , m, and n are the same as those in the general formula (1).
The above multi-EO body is represented by the following general formula (9).

(In the formula, R, R ₁ , R ₂ , m, and n are the same as those in the general formula (1), and k each independently represents an integer of 1 to 5, provided that k is 1 at the same time. except for.)
Preferred examples and specific examples relating to R, R ₁ , R ₂ , m, and n are the same as those in the general formula (1).
The 3EO body which is a compound more likely to be contained in the multi-EO body represented by the general formula (9) is represented by the following general formula (10).

(In the formula, R, R ₁ , R ₂ , m and n are the same as those in the general formula (1).)
Preferred examples and specific examples relating to R, R ₁ , R ₂ , m, and n are the same as those in the general formula (1).

The purity of the dihydroxy compound represented by the general formula (1) of the present invention and the amount of impurities contained are not particularly limited, but the following range calculated from area% by high performance liquid chromatography is preferred. The purity of the dihydroxy compound represented by the general formula (1) of the present invention is preferably 97.5% or more, more preferably 98.0% or more, still more preferably 98.5% or more, and particularly preferably 99.0. % Or more. The content of 1EO is preferably 0.5% or less, more preferably 0.3% or less, still more preferably 0.1% or less, and particularly preferably substantially free (below the detection limit). The content of the multi-EO body is preferably 1.5% or less, more preferably 1.0% or less, further preferably 0.5% or less, particularly preferably 0.1% or less, and most preferably substantially contained. No (below detection limit). Among the multi-EO bodies, the content of 3EO bodies is preferably 1.5% or less, more preferably 1.0% or less, still more preferably 0.5% or less, particularly preferably 0.1% or less, and most preferably It is not substantially contained (below the detection limit).

Next, the use of the dihydroxy compound of the present invention will be described.
First, a polycarbonate using the dihydroxy compound represented by the general formula (1) as a raw material will be described.
The polycarbonate is represented by the following general formula (2).

In the above general formula (2), in the formula, preferred examples and specific examples of the substituents represented by R, R ₁ and R ₂ , the definition of the number of substitutions represented by m and n, and preferred substitution positions are represented by the general formula (1). ) Is the same as that.
Therefore, the polycarbonate containing a preferable repeating unit in the polycarbonate containing the repeating unit represented by the general formula (2) is represented by the following general formula (11).

(In the formula, R ₂ and n are the same as those in the general formula (1), and R ₃ and R ₄ are the same as those in the general formula (3).)
Preferred examples and specific examples relating to R ₂ and n are the same as those in the general formula (1), and preferred examples and specific examples relating to R ₃ and R ₄ are the same as those in the general formula (3).

The polycarbonate containing the repeating unit represented by the general formula (2) is not particularly limited as to its production method, and any conventionally known method can be used. Specific examples include an interfacial polymerization method, a melt transesterification method, a solid phase polymerization method, a ring-opening polymerization method of a cyclic carbonate compound, a pyridine method, etc. Among them, interfacial weight using a dihydroxy compound and a carbonate precursor as raw materials. A combined method and a melt transesterification method are preferable, and it is particularly preferable to produce a dihydroxy compound represented by the general formula (1) and a carbonate such as diphenyl carbonate by a melt transesterification reaction in the presence of a transesterification catalyst.

The dihydroxy compound used as a raw material of the polycarbonate containing the repeating unit represented by the general formula (2) is, for example, other than the dihydroxy compound represented by the general formula (1) as long as the effects of the present invention are not hindered. Other dihydroxy compounds such as bisphenol A can also be used as a copolymer raw material.
When the copolymer raw material is used, the ratio of the dihydroxy compound copolymer raw material other than the dihydroxy compound represented by the general formula (1) mainly used in all dihydroxy compounds is not particularly limited as long as the effect of the present invention is not hindered. However, it is preferably in the range of 0 to 20 mol%, more preferably in the range of 0 to 10 mol%, still more preferably in the range of 0 to 5 mol%, particularly preferably in the range of 0 to 2 mol%.
The melt transesterification method for producing a polycarbonate containing the repeating unit represented by the general formula (2) by melt polycondensation will be described in more detail. Here, a conventionally known method can be used as the melt transesterification method.
For example, in the case where the starting dihydroxy compound is 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one and the starting carbonic acid diester is diphenyl carbonate The reaction for obtaining the group polycarbonate is shown by the following reaction formula.

The melt transesterification reaction is performed by stirring the dihydroxy compound and the carbonic acid diester in the presence of a catalyst while heating the carbonic acid diester and an atmospheric pressure or a reduced pressure inert gas atmosphere to distill the produced phenol.
Specific examples of the carbonic acid diester to be reacted with the dihydroxy compound include, for example, diaryl carbonates such as diphenyl carbonate, ditolyl carbonate, and bis (m-cresyl) carbonate, dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and dicyclohexyl carbonate, and methyl. Examples thereof include alkylaryl carbonates such as phenyl carbonate, ethylphenyl carbonate and cyclohexyl phenyl carbonate, or dialkenyl carbonates such as divinyl carbonate, diisopropenyl carbonate and dipropenyl carbonate. Diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.

Usually, the aromatic polycarbonate which adjusted the desired molecular weight and the amount of terminal hydroxyl groups can be obtained by adjusting the mixing ratio of a dihydroxy compound and carbonic acid diester, and the pressure reduction degree at the time of transesterification.
Regarding the mixing ratio of the dihydroxy compound and the carbonic acid diester to obtain the polycarbonate, the carbonic acid diester is usually used in an amount of 0.5 to 1.5 moles, preferably 0.6 to 1.2 moles per mole of the dihydroxy compound.
In the transesterification reaction, a transesterification catalyst is used as necessary to increase the reaction rate. The transesterification catalyst is not particularly limited, and examples thereof include inorganic alkali metal compounds such as lithium, sodium and cesium hydroxides, carbonates and hydrogen carbonate compounds, and alkali alkali compounds such as alcoholates and organic carboxylates. Metal compounds: hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, alkaline earth metal compounds such as organic alkaline earth metal compounds such as alcoholates and organic carboxylates; tetramethylboron and tetraethyl Basic boron compounds such as sodium salts such as boron and butyltriphenylboron, calcium salts and magnesium salts; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine; or 4 derived from these compounds Basic phosphorus compounds such as quaternary phosphonium salts; Use a known transesterification catalyst such as basic ammonium compounds such as lamethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, or amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole, aminoquinoline, etc. Can do. Among these, alkali metal compounds are preferable, and cesium compounds such as cesium carbonate and cesium hydroxide are particularly preferable.
The amount of the catalyst used is within a range where the catalyst residue does not cause a problem in the quality of the produced polycarbonate, and since the preferred addition amount varies depending on the type of catalyst, it cannot be said unconditionally, for example, the general formula ( The amount is usually 0.05 to 100 μmol, preferably 0.08 to 50 μmol, more preferably 0.1 to 20 μmol, still more preferably 0.1 to 5 μmol with respect to 1 mol of the dihydroxy compound represented by 1). is there. The catalyst may be added as it is, or may be added after being dissolved in a solvent. As the solvent, for example, those which do not affect the reaction such as water and phenol are preferable.
As for the reaction conditions for the melt transesterification reaction, the temperature is usually in the range of 120 to 360 ° C, preferably in the range of 150 to 280 ° C, more preferably in the range of 180 to 270 ° C. If the reaction temperature is too low, the transesterification reaction does not proceed, and if the reaction temperature is high, side reactions such as a decomposition reaction proceed. The reaction is preferably carried out under reduced pressure, and the reaction pressure is preferably a pressure at which the diester carbonate as a raw material does not distill out of the system at the reaction temperature and phenol by-produced distills. Under such reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

The reaction product containing polycarbonate obtained in this way is then subjected to a separation reduction treatment of low molecular weight components as necessary, and then subjected to a drying step, thereby being represented by the general formula (2). A polycarbonate containing repeating units is obtained.
The reaction-finished product containing polycarbonate obtained by the reaction step is usually a transparent viscous material in a molten state near the reaction temperature, and is a solid body near normal temperature.
The low molecular weight component separation and reduction treatment that may be performed as needed is, for example, as disclosed in JP-A-7-192310, in which polycarbonate is dissolved in an appropriate good solvent, and then the polycarbonate is dissolved in a poor solvent such as methanol. By precipitating and drying, the above-mentioned aromatic polycarbonate having a reduced molecular weight component, such as particles, powders, and flakes, can be obtained.
Further, as a more preferable method for obtaining a high molecular weight polycarbonate, prepolymerization is performed in the reaction as described in JP-A-3-223330 and WO00 / 18822 (first step) to obtain a polycarbonate oligomer. A high molecular weight polycarbonate can be obtained by solid phase polymerization or swelling solid phase polymerization in the presence of a catalyst (second step).

The prepolymerization in the first step is carried out by a melt transesterification reaction, and a dihydroxy compound and diphenyl carbonate are distilled at a temperature of 120 to 360 ° C., preferably 150 to 280 ° C., particularly preferably while distilling phenol in the presence of a catalyst. A polycarbonate oligomer is obtained by reacting at 180 to 270 ° C. for 0.5 to 10 hours. The polycarbonate oligomer obtained in the first step is preferably made into a solid body such as flakes, powders or particles according to a known method from the viewpoint of operability in the second step.
In the second step, the above-described transesterification catalyst, such as a quaternary phosphonium salt, is optionally added to the polycarbonate oligomer obtained in the first step as necessary under reduced pressure, and an inert gas is introduced. Then, by stirring and reacting while distilling the remaining phenol in a solid phase state or a swollen solid phase state in which the crystallized oligomer during solid phase polymerization is not melted or melted at a temperature above the glass transition temperature of the polycarbonate, A molecular weight polycarbonate is obtained.
The reaction in the first step and the reaction in the second step may be performed separately or continuously. Here, the polycarbonate oligomer usually has a weight average molecular weight of, for example, about 500 to 15,000. The high molecular weight polycarbonate usually has a weight average molecular weight of, for example, about 15000 to 100,000. However, the polycarbonate using the dihydroxy compound of the present invention as a raw material is not limited to such a molecular weight.
The polycarbonate obtained as described above is a high molecular weight polycarbonate, which is excellent in transparency, heat resistance, mechanical properties, impact resistance, fluidity, etc., and optical lenses and flat panel displays used in optical disks, smartphones, etc. It can be expected to be used in various fields such as optical applications such as optical films, and automotive plastics, electrical / electronics, and various containers as engineering plastics.
Polycarbonate oligomers can be used not only as raw materials for producing high molecular weight polycarbonate by various polymerization methods, but also as surface modifiers, flame retardants, ultraviolet absorbers, fluidity modifiers, plasticizers. Also, it can be widely used as additives such as polymer modifiers such as resin alloy solubilizers.
Furthermore, as other uses, the dihydroxy compound of the present invention uses an epoxy resin, an oxetane resin, an acrylic resin, a polyester, a polyarylate, a polyether ether ketone, a polysulfone, in addition to a polycarbonate, using a terminal hydroxy group. Use as a resin raw material such as novolak and resol, other photosensitive composition raw materials, resist additives, developers, and antioxidants can also be expected.
In particular, it can be expected to be used as an acrylic monomer or acrylic resin raw material such as diacrylate obtained by reacting the dihydroxy compound of the present invention with acrylic acid or the like, and as an optical hard coating material using them.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In addition, the softening point, refractive index, and purity in the examples were measured by the following methods.
[Analysis method]
1. Softening point measurement device: DSC-60 DIFFERENTIAL SCANNING CALORIMETER manufactured by Shimadzu Corporation
Temperature rising condition: 10 ℃ / min (30 ℃ → 200 ℃)
Atmospheric gas: Nitrogen gas (Flow rate: 50ml / min)
Measuring method:
The first measurement was performed under the above temperature rising conditions, and the melting point was measured from the endothermic peak.
Thereafter, the same sample was cooled to room temperature, the second measurement was performed under the same conditions, and the endothermic peak was taken as the softening point.
2. Refractive index measuring device: Refractometer RA-500N manufactured by Kyoto Electronics Industry Co., Ltd.
Measuring method:
A THF solution (THF refractive index of 1.40) having a concentration of 10, 15, or 30% was adjusted, and the refractive index of the measurement compound was calculated from the refractive index of the solution by extrapolation.
3. Purity measurement device: CLASS-LC10 manufactured by Shimadzu Corporation
Pump: LC-10ATvp
Column oven: CTO-10Avp
Detector: SPD-10Avp
Column: Shim-pack CLC-ODS inner diameter 6mm, length 150mm
Oven temperature: 50 ° C
Flow rate: 1.0ml / min
Mobile phase: (A) Methanol, (B) 0.2 vol% acetic acid water Gradient condition: (A) Volume% (time from the start of analysis)
60% (0min) → 60% (20min) → 100% (40min) → 100% (50min)
Sample injection volume: 20 μl
Detection wavelength: 280nm

<Example 1>
Production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one In a four-necked flask equipped with a thermometer, stirrer and condenser, 2-phenoxyethanol 331 .2 g (2.40 mol) and 14.6-phenyl-1H-indole-2,3-dione (44.6 g, 0.20 mol) were charged, the reaction vessel was purged with nitrogen, and hydrogen chloride gas was blown at 40 ° C. The hydrogen chloride gas concentration in the gas phase was set to 95% or more. Thereafter, 4.2 g of a 15% aqueous solution of methyl mercaptan (0.009 mol as sodium methyl mercaptan) was added and stirred at 40 ° C. for 22 hours.
After completion of the reaction, the conversion of 1-phenyl-1H-indole-2,3-dione was 99.7%, 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indole- The reaction yield of 2-one (vs. 1-phenyl-1H-indole-2,3-dione) was 93.7%.
After completion of the reaction, 304.5 g of a 16% sodium hydroxide aqueous solution (1.22 mol as sodium hydroxide) was added to adjust the pH to 6. The resulting solution was heated to 150 ° C., unreacted 2-phenoxyethanol was removed by distillation under a reduced pressure of 2.4 kPa, and 268.3 g of toluene was added. 45.0 g of water was added to the obtained solution, and the mixture was stirred at 80 ° C. and then allowed to stand, and a water washing operation for removing the aqueous layer was performed twice. After washing with water, the obtained oil layer was heated to 160 ° C., the solvent was removed by distillation under a reduced pressure of 1.0 kPa, then cooled, 582.2 g of toluene was added at 110 ° C., and 72.3 g of methanol at 70 ° C. Was added. Thereafter, the mixture was cooled to 30 ° C., and the precipitated crystals were separated by filtration to obtain 61.4 g of crude crystals as white crystals.
After adding 226.5 g of 1-butanol to 55.5 g of the obtained crude crystals and dissolving at 110 ° C., 112.7 g of 1-butanol was removed by distillation under normal pressure, then cooled to 30 ° C. and precipitated. The crystals were filtered off. The obtained crystals were dried at 80 ° C. under reduced pressure to obtain 48.5 g of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -1-phenyl-1H-indol-2-one. .
Purity 99.2% (High performance liquid chromatography area%)
1EO body represented by the general formula (8) (below detection limit)
3EO body represented by general formula (10) (below detection limit)
Yield 55% (vs 1-phenyl-1H-indole-2,
3-dione)
Melting point 153 ° C (differential scanning calorimetry)
Softening temperature 73 ° C (differential scanning calorimetry)
Refractive index (n _D 20) 1.60
Proton nuclear magnetic resonance spectrum (400 MHz, solvent DMSO-D ₆ , standard TMS) Chemical shift (signal shape, number of protons): 3.7 ppm (m, 4H), 4.0 ppm (t, 4H), 4.9 ppm (t , 2H), 6.7 ppm (d, 1H), 6.9 ppm (d, 4H), 7.1 to 7.2 ppm (m, 5H), 7.3 ppm (t, 1H), 7.4 ppm (d, 1H), 7.5 ppm (m, 3H), 7.6 ppm (t, 2H).

<Comparative Example 1>
Production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine (Step 1)
A four-necked flask equipped with a thermometer, a stirrer, and a condenser tube was charged with 902.5 g (9.70 mol) of aniline, and after the reaction vessel was purged with nitrogen, 192.7 g of methanesulfonic acid was maintained at 85 to 95 ° C. Was dropped into the system. Thereafter, 385.4 g (1.21 mol) of phenolphthalein was added at 90 to 100 ° C., and after completion of the addition, the mixture was stirred for 21.5 hours while maintaining 147 to 153 ° C. After completion of the reaction, the mixture was cooled, 1480.6 g of toluene was added at 110 ° C., and 1480.6 g of water was added at 90 ° C., then cooled to 30 ° C. and the precipitated crystals were filtered off to obtain 481.6 g of crude crystals. Obtained.
To the crude crystals obtained above, 913.4 g of toluene and 228.4 g of methanol were added, stirred at 71 ° C. for 5 hours, cooled to 30 ° C., and the precipitated crystals were separated by filtration. The obtained crystals were dried under reduced pressure to obtain 347.2 g of 3,3-bis (4-hydroxyphenyl) -2-phenylphthalimidine.
Purity 99.6% (high performance liquid chromatography)
Yield 75% (vs. phenolphthalein)
Melting point 291.5 ° C (differential scanning calorimetry)
(Process 2)
30.0 g (0.076 mol) of 3,3-bis (4-hydroxyphenyl) -2-phenylphthalimidine obtained in Step 1 was added to a four-necked flask equipped with a thermometer, a stirrer and a condenser. 19.5 g (0.22 mol) of ethylene carbonate, 0.44 g of 48% potassium hydroxide aqueous solution (0.0038 mol as potassium hydroxide) and 45.0 g of 1-butanol were charged, and the reaction vessel was purged with nitrogen. Stir at ˜118 ° C. for 11 hours. After completion of the reaction, 2.7 g of water was added and stirred at 106 to 109 ° C. for 3 hours. Next, 2.2 g of 10% acetic acid was added to adjust the pH of the aqueous layer to 4-5. Methyl isobutyl ketone was added to the obtained oil layer, water was further added, the mixture was stirred at 80 to 85 ° C., and then the aqueous layer was removed twice. The obtained oil layer was heated to 125 ° C., and 50.0 g of a fraction was distilled by distillation. Acetone and water were added to the resulting solution, followed by cooling to 30 ° C., and the precipitated crystals were separated by filtration. The obtained crystals were dried to obtain 28.5 g of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine.
Purity 96.7% (High-performance liquid chromatography area%)
1EO body represented by the following general formula (12) (0.7%
)
3EO body represented by the following general formula (13) (1.6%
)
Yield 78% (vs. 3,3-bis (4-hydroxyphenyl) -2-phenylphthalimidine)
Melting point 155 ° C (differential scanning calorimetry)
Softening point 68 ° C (differential scanning calorimetry)
Refractive index (n _D 20) 1.60

3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine obtained in Step 2 of Comparative Example 1 is an 1EO compound represented by the following general formula (12), which is an impurity And a 3EO body represented by the following general formula (13).
The 1EO body in Comparative Example 1 is represented by the general formula (12).

The 3EO body in Comparative Example 1 is represented by the general formula (13).

The production method of Step 2 of Comparative Example 1 cannot avoid the production of 1EO body represented by the general formula (12) and 3EO body represented by the general formula (13), and these impurities are industrially used in the purification process. In Comparative Example 1, the purity of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine, which is the target product, is 96. It was 7% (high performance liquid chromatography area%), and a higher-purity target product could not be obtained.

Table 1 shows the melting point, softening point, and refractive index of the compound obtained in Example 1 and the compound obtained in Step 2 of Comparative Example 1.

Since the compound of Example 1 of the present invention has higher heat resistance (softening point temperature) and higher refractive index than the known compound of Step 2 of Comparative Example 1, it is used for optical materials. It is useful as a raw material for polycarbonate.

<Comparative example 2>
Study on production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine 1
A 4-necked flask equipped with a thermometer, stirrer, and condenser is charged with 331.6 g (2.40 mol) of 2-phenoxyethanol and 44.8 g (0.20 mol) of N-phenylphthalimide, and the reaction vessel is filled with nitrogen. After the replacement, hydrogen chloride gas was blown at 40 ° C., so that the hydrogen chloride gas concentration in the gas phase was 95% or more. Thereafter, 4.2 g of a 15% aqueous solution of methyl mercaptan (0.009 mol as sodium methyl mercaptan) was added and stirred at 40 ° C. for 22 hours.
In the reaction solution after 22 hours of reaction, formation of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine was not observed.

<Comparative Example 3>
Study on production of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine 2
In a four-necked flask equipped with a thermometer, stirrer and condenser, N-phenylphthalimide 9.6 g (0.043 mol), phosphotungstic acid 190 mg (5.6 × 10 ⁻⁵ mol), 2-phenoxyethanol 71 .3 g (0.52 mol) was added, and the reaction was carried out by stirring at a temperature of 130 to 135 ° C. for 22 hours under a reduced pressure of 2.0 to 3.0 kPa.
In the reaction solution after 22 hours of reaction, formation of 3,3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine was not observed.

The experimental results of Example 1 and Comparative Example 2 of the present invention show that 1-phenyl-1H-indole-2,3-dione reacts with 2-phenoxyethanol to produce 3,3-bis (4- (2-hydroxyethoxy) (Phenyl) -1-phenyl-1H-indol-2-one is produced (Example 1), whereas N-phenylphthalimide does not undergo a condensation reaction with 2-phenoxyethanol under the same reaction conditions. This shows that -bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine is not produced (Comparative Example 2). Further, the experimental result of Comparative Example 3 shows that in the condensation reaction of N-phenylphthalimide and 2-phenoxyethanol, even when phosphotungstic acid was used as a catalyst, the reaction did not proceed and 3,3-bis (4- (2 This shows that -hydroxyethoxy) phenyl) -2-phenylphthalimidine is not produced (Comparative Example 3).
That is, it is clear that the N-phenylisatin compound represented by the general formula (5) has extremely high reactivity with the phenoxy alcohol represented by the general formula (6) as compared with the N-phenylphthalimide compound. became.
The N-phenylisatin compound represented by the general formula (5) contains a conventionally known compound because the reaction with the phenoxy alcohol represented by the general formula (6) easily proceeds due to its unique chemical structure. It is represented by high-purity general formula (1) that does not contain impurities such as a hydroxyalkoxy compound (1EO form) or a compound in which the hydroxy group of the hydroxyalkoxy group is further substituted with a hydroxyalkoxy group (multi-EO form). It becomes possible to obtain a dihydroxy compound. Since the dihydroxy compound represented by the general formula (1) of the present invention is highly pure, it is excellent in optical properties such as thermal stability and product hue.
Furthermore, since the polycarbonate using the dihydroxy compound of the present invention as a raw material uses the dihydroxy compound represented by the general formula (1) having a high purity as a raw material monomer, it may have a high purity, a high heat resistance, and a high refractive index. Expected to be particularly effective in polycarbonate for optical materials.

Claims

A dihydroxy compound represented by the following general formula (1).

(Wherein R represents an alkylene group having 2 to 6 carbon atoms, R 1 and R 2 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, m represents an integer of 0 to 3, n represents an integer of 0 to 2, provided that when m is 2 or more, R 1 may be the same or different. When n is 2, R 2 is the same But it may be different.)