KR102263143B1 - Novel dihydroxy compound - Google Patents

Abstract

An object of the present invention is to provide a novel dihydroxy compound having an indoline skeleton suitable as a raw material such as an aromatic polycarbonate oligomer or resin. The above problem can be solved by the dihydroxy compound represented by Formula 1 below.
[Formula 1]

Description

Novel dihydroxy compound

The present invention relates to novel dihydroxy compounds. Specifically, it relates to a dihydroxy compound having an indoline skeleton suitable as a raw material such as an aromatic polycarbonate oligomer or resin.

Conventionally, bisphenoxy alcohols (compounds in which the hydrogen atom of the hydroxy group of bisphenols is substituted with a hydroxyalkyl group) is a raw material for a thermoplastic synthetic resin such as polycarbonate resin, a raw material for a thermosetting resin such as an epoxy resin, a raw material for an antioxidant, and a heat-sensitive recording medium. It is used as a raw material, a photosensitive resist raw material, etc., and in recent years, the performance required for these bisphenoxy alcohols is becoming more and more advanced.

Moreover, as bisphenoxy alcohol, 3, 3-bis (4- (2-hydroxyethoxy) phenyl) -2-phenylphthalimidine which has an isoindoline skeleton is known (nonpatent literature 1). However, the compound is insufficient in heat resistance or optical properties, and further improvement is required.

Izvestiya Akademii Nauk Gruzinskoi SSR, Seriya Khimicheskaya, 1985, vol. 11, p.78-80

The present invention has been made in view of the above circumstances, 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 3,3-bis(4-(2-hydroxyethoxy)phenyl)-1-phenyl-1H-indol-2-ones having an indoline skeleton A compound in which a phenyl group is substituted for a hydroxyphenyl skeleton has higher heat resistance and higher refractive index than the conventional compound (3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylphthalimidine). Found and completed the present invention.

The present invention is as follows.

1. A dihydroxy compound represented by Formula 1 below.

(Wherein, R each independently represents an alkylene group having 2 to 6 carbon atoms, R ₁ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ₃ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or represents a halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 2, with the proviso that when m is 2, R ₁ may be the same or different, and when n is 2, R ₃ is They may be the same or different.)

Since the dihydroxy compound according to the present invention has high heat resistance and also has a high refractive index, excellent effects can be expected as a raw material for resins such as polycarbonate, polyester, epoxy resin, and acrylic resin for optical materials.

In addition, the polycarbonate using the dihydroxy compound of the present invention as a raw material monomer is expected to have high purity, high heat resistance and high refractive index, and particularly excellent effects can be expected in the polycarbonate for optical materials.

The present invention will be described in detail below.

The dihydroxy compound of the present invention is represented by Formula 1 below.

[Formula 1]

(Wherein, R each independently represents an alkylene group having 2 to 6 carbon atoms, R ₁ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ₃ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or represents a halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 2, with the proviso that when m is 2, R ₁ may be the same or different, and when n is 2, R ₃ is They may be the same or different.)

In the formula (1), each R is independently an alkylene group having 2 to 6 carbon atoms, and specifically as the alkylene group, for example, 1,2-ethylenediyl group, 1,2-propanediyl group, 1,3- A propanediyl group, a pentamethylene group, a hexamethylene group, etc. are mentioned, Preferably it is a C2-C4 linear or branched alkylene group, Especially preferably, it is a C2-C3 alkylene group. Here, when describing the hydroxyalkoxy group represented by "-OR-OH" in Formula 1, the bonding position of the hydroxy group bonded to the alkylene group R is the carbon atom (position 1) constituting the alkylene group R directly bonded to the ether group. does not bind to carbon atoms). When R is an alkylene group having 3 or more carbon atoms, the bonding position of the hydroxy group is preferably the 2-position or 3-position of the alkylene group "R", and among these, the 2-position is more preferable. Specific examples thereof include a 2-hydroxyethoxy group, a 2-hydroxypropoxy group, a 2-hydroxy-1-methylethoxy group, and a 3-hydroxypropoxy group.

R ₁ is each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, and when R ₁ is an alkyl group having 1 to 8 carbon atoms, the alkyl group preferably has 1 carbon atom It is a linear and branched alkyl group of - 4, and specifically, a methyl group, an ethyl group, n-propyl group, an isopropyl group, an isobutyl group, etc. are mentioned, for example. Such an alkyl group may have, for example, a substituent such as a phenyl group and an alkoxy group within a range that does not impair the effects of the present invention.

Further, when R ₁ is an alkoxy group having 1 to 8 carbon atoms, the alkoxy group is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms, specifically, for example, a methoxy group, an ethoxy group, n - A propoxy group, an isopropoxy group, etc. are mentioned. Such an alkoxy group may have a substituent, such as a phenyl group and an alkoxy group, in the range which does not impair the effect of this application, for example.

Further _{, when R 1} is a phenyl group, the phenyl group may have a substituent such as an alkyl group or an alkoxy group within the range not impairing the effects of the present application, but an unsubstituted phenyl group is preferable.

When R ₁ is a halogen atom, specific examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ₁ is preferably a methyl group or a phenyl group.

R ₂ is each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen atom, R ₃ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or It is a halogen atom, and when R ₂ and R ₃ are an alkyl group having 1 to 8 carbon atoms, preferred groups and specific examples are the same as those _{of R 1 , and R 2} and R ₃ are an alkoxy group having 1 to 8 carbon atoms, a halogen atom _{Similarly to the case of R 1} , preferred groups and specific examples are the same as those of R 1 . R ₂ is preferably a hydrogen atom or a methyl group, and R ₃ is preferably a methyl group.

In addition, in the formula (1), m is 0, 1 or 2, preferably 0 or 1, particularly preferably 0, n is 0, 1 or 2, preferably 0 or 1, particularly preferably is 0.

In addition, in the above formula (1), the "-OR-OH" group and the phenyl group substituted with a phenyl group directly bonded to the carbon atom at position 3 of the indoline skeleton, and _{the substitution position of R 1} , first "-OR-OH" The " group is preferably substituted at the 4th or 2nd position with respect to the phenyl carbon atom directly bonded to the 3rd-position carbon atom of the indoline skeleton, and more preferably at the 4th position.

In addition, the phenyl group is preferably substituted at the o-position or the p-position with respect to the "-OR-OH" group, and the "-OR-OH" group is a phenyl carbon directly bonded to the carbon atom at the 3-position of the indoline skeleton. When substituted at the 4th position with respect to the atom, it is preferably substituted at the 3rd or 5th position, and when the "-OR-OH" group is substituted at the 2nd position, the 3rd or 5th position It is preferably substituted with a position.

In addition, in Formula 1, R ₁ is preferably substituted at the o-position or the p-position with respect to the “-OR-OH” group, and phenyl directly bonded to the carbon atom at the 3-position of the indoline skeleton. When the "-OR-OH" group is substituted at the 4th position and the phenyl group at the 3rd position with respect to the carbon atom, it is preferably substituted at the 5th position, the "-OR-OH" group at the 2nd position and the phenyl group at the 3rd When substituted at the position, it is preferably substituted at the 5th position, and when the "-OR-OH" group is substituted at the 2nd position and the phenyl group is substituted at the 5th position, it is preferably substituted at the 3rd position.

_{In addition, the substitution position of R 1} when m is 2 is the "-OR-OH" group at the 4th position and the phenyl group at the 3rd position with respect to the phenyl carbon atom directly bonded to the carbon atom at the 3rd position of the indoline skeleton. It is preferable that the position, R ₁ is substituted at the 5th and 6th positions, or the “-OR-OH” group is substituted with the 4th position, the phenyl group is substituted with the 3rd position, and R ₁ is substituted with the 2nd and 5th positions.

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

(Wherein, R ₁ , R ₂ , R ₃ , m, n are the same as those of Formula 1, and R ₄ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, with the proviso that each hydroxy The total number of carbon atoms of _{R 4} substituted with a oxy group is 4 or less.)

Preferred examples or specific examples of R ₁ , R ₂ , R ₃ , m, and n in Formula 3 are the same as those of Formula 1 above. Moreover, when R<_4> is a C1-C4 alkyl group, a methyl group, an ethyl group, n-propyl group, etc. are mentioned specifically, for example. R ₄ is preferably a hydrogen atom or a methyl group.

In the dihydroxy compound represented by Formula 3, when m is 1, _{the substitution position of R 1} is preferably the 5th position with respect to the phenyl carbon atom directly bonded to the 3rd position carbon atom of the indoline skeleton, , when m is 2, _{the substitution position of R 1} is preferably the 5th and 6th positions or the 2nd and 5th positions with respect to the phenyl carbon atom directly bonded to the carbon atom at the 3rd position of the indoline skeleton. Do.

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

3,3-bis(4-(2-hydroxy-2-methylethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxy-1-methylethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-5-methyl-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(5-ethyl-4-(2-hydroxyethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3,5-diphenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-5,6-dimethyl-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-2,5-dimethyl-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3-(4-methylphenyl)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3-(3-methylphenyl)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(2-(2-hydroxyethoxy)-5-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(2-(2-hydroxyethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1-(4-methylphenyl)-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1-(2-methylphenyl)-1H-indol-2-one

3,3-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1-(4-methoxyphenyl)-1H-indol-2-one

and the like.

The dihydroxy compound represented by the formula (1) of the present invention is not particularly limited in its preparation method, and is preferably an N-phenylisatin compound represented by the following formula (5) and a phenylphenol compound represented by the following formula (6). A bisphenol compound having an indoline skeleton represented by the following formula (7) is obtained by reacting these as a raw material in the presence of an acid catalyst, and the obtained bisphenol compound is reacted with any one of alkylene carbonates, alkylene oxides and halogenated alcohols. can be obtained by

(Wherein, R ₃ , n is the same as that of Formula 1.)

Preferred examples and specific examples of R ₃ , n are also the same as those of formula (1).

As the N-phenylisatin compound represented by the above formula (5), specifically, for example,

1-phenyl-1H-indole-2,3-dione

1-(4-methylphenyl)-1H-indole-2,3-dione

1-(2-methylphenyl)-1H-indole-2,3-dione

1-(4-methoxyphenyl)-1H-indole-2,3-dione

and the like.

Also,

(Wherein, R ₁ , R ₂ , and m are the same as those of Formula 1.)

Preferred examples and specific examples of R ₁ , R ₂ , and m are also the same as those of Formula (1).

As a phenylphenol compound represented by such general formula (6), specifically, for example,

2-phenylphenol

6-methyl-2-phenylphenol

6-ethyl-2-phenylphenol

2,6-diphenylphenol

5,6-dimethyl-2-phenylphenol

3,6-dimethyl-2-phenylphenol

2-(4-methylphenyl)phenol

2-(3-methylphenyl)phenol

and the like.

Also,

(Wherein, R ₁ , R ₂ , R ₃ , m, and n are the same as those of Formula 1.)

Preferred examples and specific examples of R ₁ , R ₂ , R ₃ , m, and n are also the same as those of Formula (1).

As the bisphenol compound represented by the above formula (7), a bisphenol compound represented by the following formula (8) is preferable.

(Wherein, R ₁ , R ₂ , R ₃ , m, and n are the same as those of Formula 1.)

Preferred examples and specific examples of R ₁ , R ₂ , R ₃ , m, and n are also the same as those of Formula (1).

As the bisphenol compound represented by the above formula (8), specifically, for example,

3,3-bis(4-hydroxy-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-5-methyl-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(5-ethyl-4-hydroxy-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-3,5-diphenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-5,6-dimethyl-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-2,5-dimethyl-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-3-(4-methylphenyl)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-3-(3-methylphenyl)phenyl)-1-phenyl-1H-indol-2-one

3,3-bis(2-hydroxy-5-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(2-hydroxy-3-phenylphenyl)-1-phenyl-1H-indol-2-one

3,3-bis(4-hydroxy-3-phenylphenyl)-1-(4-methylphenyl)-1H-indol-2-one

3,3-bis(4-hydroxy-3-phenylphenyl)-1-(2-methylphenyl)-1H-indol-2-one

3,3-bis(4-hydroxy-3-phenylphenyl)-1-(4-methoxyphenyl)-1H-indol-2-one

and the like.

In addition, the alkylene carbonates are preferably represented by the following formula (10).

(Wherein, R ₄ is the same as that of Formula 3).

Preferred examples and specific examples of R ₄ are also the same as those of Formula (3).

Specific examples of the alkylene carbonates represented by the above formula (10) include,

ethylene carbonate

propylene carbonate

1,2-Butylene carbonate

and the like.

In addition, the alkylene oxides are preferably represented by the following formula (11).

(Wherein, R ₄ is the same as that of Formula 3).

Preferred examples and specific examples of R ₄ are also the same as those of Formula (3).

Specific examples of the alkylene oxides represented by the above formula (11) include,

ethylene oxide

propylene oxide

1,2-butylene oxide

and the like.

In addition, the halogenated alcohols are represented by the following formula (12).

(Wherein, R is the same as that of Formula 1, and X represents a halogen atom, provided that X is not substituted with a carbon atom substituted with a hydroxyl group.)

Preferred examples and specific examples of R are also the same as those of formula (1).

Specific examples of the halogenated alcohols represented by the above formula (12) include,

2-chloroethanol

2-bromoethanol

2-Chloro-1-methylethanol

2-Bromo-1-methylethanol

2-chloro-2-methylethanol

and the like.

The method for producing the dihydroxy compound of the present invention is not particularly limited, but as an example, the bisphenol compound represented by the above formula (7) is synthesized by a condensation reaction, and alkylene carbonates represented by the formula (10) are used to obtain the A method for producing the dihydroxy compound will be described in detail.

The condensation reaction is carried out by reacting the N-phenylisatin compound represented by the above formula (5) and the phenylphenol compound represented by the formula (6) in the presence of an acid catalyst. First, a reaction mixture obtained by reacting an N-phenylisatin compound with a phenylphenol compound in the presence of an acid catalyst is neutralized with an alkali, and then crystallized and filtered according to a known method to obtain a target product.

The molar ratio of the addition of the phenylphenol compound to the N-phenylisatin compound during the reaction is not particularly limited as long as it is greater than or equal to the theoretical value (2.0), but is usually 2.5 times molar amount or more, preferably 2.5 to 20 times molar amount, particularly preferably Preferably, it is used in the range of 3 to 10 times the molar amount.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, hydrogen chloride gas, 60 to 98% sulfuric acid, 85% phosphoric acid, organic acids such as p-toluenesulfonic acid, methanesulfonic acid, oxalic acid, formic acid, trichloroacetic acid or trifluoroacetic acid, heteropolyacids Solid acids, such as these, etc. are mentioned. Preferably it is hydrogen chloride gas. A suitable amount of the 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 in to the concentration of hydrogen chloride gas in the gas phase in the reaction vessel. It is preferable to set the concentration of hydrogen chloride in the reaction solution as the saturation concentration by setting it to 75-100% by volume. 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, and more preferably in the range of 20 to 30 parts by weight based on 100 parts by weight of the phenylphenol compound.

In the reaction, a cocatalyst may be used along with the acid catalyst as needed. 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 or mercaptocarboxylic acids having 1 to 12 carbon atoms, for example, methyl mercaptan , ethyl mercaptan, n-octyl mercaptan, n-lauryl mercaptan, and alkali metal salts such as sodium salts thereof, thioacetic acid and β-mercaptopropionic acid. In addition, these can be used individually or in combination of 2 or more types.

The amount of thiol used as a co-catalyst is usually in the range of 1 to 30 mol%, preferably in the range of 2 to 10 mol%, based on the N-phenylisatin compound as a raw material.

In addition, the reaction solvent during the reaction has a low melting point of the raw materials N-phenylisatin compound and phenylphenol compound, and there is no need to use a solvent if there is no problem in operability, but for reasons such as improvement of operability or reaction rate in industrial production You may use it. The reaction solvent is not particularly limited as long as it does not flow out of 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, and aliphatic such as isobutyl alcohol aliphatic hydrocarbons such as alcohol, hexane, heptane and cyclohexane; and carboxylate esters such as ethyl acetate and butyl acetate; and mixtures thereof. Of these, aliphatic alcohols are preferably used.

Further, in order to lower the freezing point of the phenylphenol compound and promote the reaction of the acid catalyst, a small amount of water may be added as needed. In particular, when the acid catalyst is hydrogen chloride gas, water is preferable from the viewpoint of accelerating absorption of the hydrogen chloride gas as the catalyst. When adding water, the amount is preferably in the range of 0.5 to 5.0 parts by weight based on 100 parts by weight of the phenylphenol compound.

The reaction temperature varies depending on the conditions such as the catalyst used, but is usually in the range of 10 to 60°C, preferably 25 to 50°C. 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 is within the above range. When the reaction is conducted under these conditions, the reaction is usually completed in about 1 to 30 hours.

The endpoint of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. It is preferable to make the time point when unreacted N-phenyl isatin compound disappear|disappear|disappears and the increase of the target substance no longer confirmed as an end point.

The reaction yield for the phenylphenol compound is usually about 75 to 95 mol%.

After completion of the reaction, an alkali solution such as aqueous ammonia or aqueous sodium hydroxide solution is added to the obtained reaction mixture to neutralize the acid catalyst to obtain a reaction mixture solution containing the bisphenol compound represented by the general formula (7) of the present invention.

A method for separating and purifying the target substance from the reaction completion mixture may be a known method. For example, the neutralized reaction-finished liquid mixture is cooled as it is or once heated to make a uniform solution, or cooled after addition of a crystallization solvent such as methanol to precipitate crystals, and the precipitated crystals are separated by filtration to prepare ) or a high-purity target can be obtained.

Thus, the obtained bisphenol compound is good also as a high-purity product by further refine|purifying as needed. In particular, when using as a raw material dihydroxyphenol of polycarbonate, it is preferable to set it as a high-purity product. For example, the obtained crystals of the target product are again dissolved in a suitable solvent, for example, an aromatic solvent such as toluene, an aliphatic ketone solvent such as methyl ethyl ketone, etc. and cooled, or a crystallization solvent such as methanol or water is added. Cool again, crystallize, filter, fractionate, and dry. Alternatively, instead of the above crystallization operation, after completion of the reaction, the reaction solvent or the like is concentrated from the reaction mixture under reduced pressure, and the residue is purified by column chromatography or the like to obtain a high-purity product of the target product.

As an example of a production method other than the above preferred method for preparing the dihydroxy compound represented by the above formula (1) of the present invention, it is obtained by reacting an N-phenylisatin compound represented by the following formula (5) with phenylphenoxyalcohol in the presence of an acid catalyst. method can be found.

Next, hydroxyalkylation to prepare a dihydroxy compound of Formula 1 using alkylene carbonates will be described.

Hydroxyalkylation is usually carried out in the presence of a base catalyst. Examples of the base catalyst include alkali catalysts such as sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate, and quaternary ammonium halides such as tetra-n-butylammonium bromide, tetraethylammonium chloride and tetramethylammonium chloride, In addition, these base catalysts can be used individually or in combination of 2 or more types. The amount of the base catalyst used varies depending on the reaction conditions, but is usually used in the range of 0.005 to 0.5 moles, preferably 0.01 to 0.4 moles, based on 1 mole of the bisphenol compound.

The amount of the alkylene carbonates to be used relative to the bisphenol compound in the reaction is usually in the range of 2 to 10 moles, preferably in the range of 2.5 to 5 moles, per 1 mole of the bisphenol compound. The reaction temperature is usually in the range of 100 to 150 °C, preferably 120 to 130 °C.

In addition, the reaction is usually carried out using a reaction solvent. Examples of the reaction solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic alcohols such as 1-butanol, 2-butanol and ethylene glycol, ketones such as acetone and methyl isobutyl ketone, tetrahydrofuran, dioxane, 1,2- ethers such as diethoxyethane, aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, and mixtures thereof.

The amount of the reaction solvent used is preferably in the range of 50 to 300 parts by weight, more preferably in the range of 100 to 200 parts by weight, based on 100 parts by weight of the bisphenol compound.

The hydroxyalkylation method is not particularly limited and a known method can be used. For example, the reaction raw material, catalyst, reaction solvent, etc. may be placed in a reaction vessel at once and the temperature may be raised to the reaction temperature. The liquid mixture of a solvent and a catalyst may be heated up to predetermined temperature, and alkylene carbonates may be dripped there.

After completion of the reaction, the target substance can be taken out as crude crystals or a high-purity product by a known purification method from the reaction-completed liquid mixture. For example, after completion of the reaction, water is added to the reaction mixture to decompose excess alkylene carbonate with water. When an alkali catalyst is used, an acid may be added to neutralize it. Next, after adding a solvent that is separated from water as needed, the oil layer is washed with water, and the catalyst or neutralized salt is removed. Thereafter, the desired product can be obtained by concentrating and cooling the oil layer as necessary, or by concentrating the oil layer and dissolving it by adding a solvent, followed by cooling, crystallization, and filtration. Recrystallization makes it possible to obtain a higher purity target.

Next, the use of the dihydroxy compound of the present invention will be described.

First, a polycarbonate using the dihydroxy compound represented by Formula 1 as a raw material will be described.

The polycarbonate is represented by the following formula (2).

(Wherein, R each independently represents an alkylene group having 2 to 6 carbon atoms, R ₁ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ₃ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or represents a halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 2, with the proviso that when m is 2, R ₁ may be the same or different, and when n is 2, R ₃ is They may be the same or different.)

In the formula (2), _{preferred examples and specific examples of the substituents represented by R, R 1} , R ₂ , and R ₃ , and the definition of the number of substitutions and preferred substitution positions represented by m and n are the same as those of the formula (1). .

Accordingly, in the polycarbonate including the repeating unit represented by Chemical Formula 2, the polycarbonate including the repeating unit is represented by the following Chemical Formula 13.

(Wherein, R ₁ , R ₂ , R ₃ , m, and n are the same as those of Formula 2, and R ₄ is the same as those of Formula 3.)

Preferred examples and specific examples of R ₁ , R ₂ , R ₃ , m and n are the same as those of Formula 1, and _{preferred examples and specific examples of R 4} are the same as those of Formula 3.

The polycarbonate including the repeating unit represented by the formula (2) is not particularly limited in its preparation method, and any conventionally known method may be used. Specifically, interfacial polymerization method, melt transesterification method, solid-state polymerization method, ring-opening polymerization method of a cyclic carbonate compound, pyridine method, etc. are mentioned. Among them, interfacial polymerization using a dihydroxy compound and a carbonate precursor as raw materials. Method and melt transesterification are preferable, and in particular, it is preferable to prepare the dihydroxy compound represented by the formula (1) and carbonate esters such as diphenyl carbonate by melt transesterification in the presence of a transesterification catalyst.

The dihydroxy compound used as a raw material of the aromatic polycarbonate containing the repeating unit represented by the formula (2) is, for example, other than the dihydroxy compound represented by the formula (1) in the range that does not interfere with the effects of the present invention. Other dihydroxy compounds, such as bisphenol A, can also be used as a copolymerization raw material.

In the case of using the raw material for copolymerization, the ratio of the raw material for copolymerization of a dihydroxy compound other than the dihydroxy compound represented by Formula 1, which is mainly used among the total dihydroxy compounds, is not particularly limited as long as the effect of the present invention is not hindered. , 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%.

A melt transesterification method for preparing a polycarbonate including a repeating unit represented by Formula 2 by melt polycondensation will be described in more detail. Here, as a melt transesterification method, a conventionally well-known method can be used.

For example, the raw material dihydroxy compound is 3,3-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one, and the raw material diester carbonate is The reaction to obtain the aromatic polycarbonate in the case of diphenyl carbonate is shown in the following scheme.

The melt transesterification reaction is carried out by stirring a dihydroxy compound and a diester carbonate in the presence of a catalyst while heating the diester carbonate in an inert gas atmosphere at normal pressure or reduced pressure, and distilling the resulting phenol.

Specific examples of the diester carbonate reacted with the dihydroxy compound include diaryl carbonate such as diphenyl carbonate, ditolyl carbonate, and bis(m-cresyl) carbonate, dimethyl carbonate, diethyl carbonate, and dicyclohexyl carbonate. and alkylaryl carbonates such as dialkyl carbonate such as carbonate, methylphenyl carbonate, ethylphenyl carbonate and cyclohexylphenyl carbonate, dialkenyl carbonate such as divinyl carbonate, diisopropenyl carbonate and dipropenyl carbonate. Diaryl carbonate is preferred, and diphenyl carbonate is particularly preferred.

In general, by adjusting the mixing ratio of the dihydroxy compound and the diester carbonate and the degree of reduced pressure during the transesterification reaction, an aromatic polycarbonate in which the desired molecular weight and the amount of terminal hydroxyl groups are adjusted can be obtained.

The mixing ratio of the dihydroxy compound to obtain the polycarbonate and the diester carbonate is usually 0.5 to 1.5 mole times, preferably 0.6 to 1.2 mole times, of the diester carbonate per 1 mole of the dihydroxy compound.

In order to increase the reaction rate in the melt transesterification reaction, a transesterification catalyst is used if necessary.

There is no restriction|limiting in particular as a transesterification catalyst, For example, alkali metal compounds, such as inorganic alkali metal compounds, such as a hydroxide of lithium, sodium, cesium, carbonate, hydrogen carbonate compound, and an organic alkali metal compound, such as alcoholate and organic carboxylate. ; Hydroxides such as beryllium and magnesium, inorganic alkaline earth metal compounds such as carbonates, and alkaline earth metal compounds such as organic alkaline earth metal compounds such as alcoholates and organic carboxylates; Tetramethylboron, tetraethylboron, butyltriphenylboron Basic boron compounds such as sodium salts, calcium salts and magnesium salts; trivalent phosphorus compounds such as triethylphosphine and tri-n-propylphosphine, or basic phosphorus such as quaternary phosphonium salts derived from these compounds Compounds; Basic ammonium compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide, or amine compounds such as 4-aminopyridine, 2-dimethylaminoimidazole and aminoquinoline. Transesterification catalysts may be used. Among them, alkali metal compounds are preferable, and especially cesium compounds such as cesium carbonate and cesium hydroxide are preferable.

The amount of the catalyst used is used in a range in which the catalyst residue does not cause a problem in the quality of the produced polycarbonate, and since the appropriate amount is different depending on the type of catalyst, it cannot be said uniformly, but roughly, for example, represented by the formula (1) It is normally 0.05-100 micromoles with respect to 1 mole of dihydroxy compound, Preferably it is 0.08-50 micromoles, More preferably, it is 0.1-20 micromoles, More preferably, it is 0.1-5 micromoles. The catalyst may be added as it is, or may be added by dissolving in a solvent. As the solvent, it is preferable not to affect the reaction of, for example, water or phenol.

The reaction conditions for the melt transesterification reaction are 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. When the reaction temperature is too low, the transesterification reaction does not proceed, and when the reaction temperature is high, side reactions such as decomposition reaction proceed, which is not preferable. The reaction is preferably carried out under reduced pressure, and the reaction pressure is preferably such that at the reaction temperature, diester carbonate as a raw material does not flow out of the system and phenol as a by-product flows out. Under these reaction conditions, the reaction is usually completed in about 0.5 to 10 hours.

The polycarbonate containing the repeating unit represented by the above formula (2) is obtained by subjecting the reaction product containing the polycarbonate obtained in this way to a drying step after performing a treatment to reduce separation of low molecular weight components if necessary.

The reaction product containing polycarbonate obtained by the above reaction step is usually a transparent viscous material in a molten state near the reaction temperature, and a solid material near the room temperature.

The separation reduction treatment of low molecular weight components that may be performed as needed is, for example, as described in Japanese Unexamined Patent Application Publication No. 7-192310, after dissolving polycarbonate in a suitable good solvent, polycarbonate in a poor solvent such as methanol By precipitating and drying the above-mentioned aromatic polycarbonate in the form of particles, powder, flakes, etc. in which low molecular weight components are reduced, it is possible to obtain the aromatic polycarbonate.

In addition, as a more preferable method for obtaining a high molecular weight polycarbonate, as described in Japanese Patent Application Laid-Open No. 3-223330 and WO00/18822, prepolymerization is performed in the reaction (first step) to obtain a polycarbonate oligomer, and the A high molecular weight polycarbonate can be obtained by solid-state polymerization or swelling solid-state polymerization of a polycarbonate oligomer in presence of a catalyst (2nd process).

The prepolymerization in the first step is performed by melt transesterification, and dihydroxy compound and diphenyl carbonate are distilled out in the presence of a catalyst while phenol is distilled at a temperature of 120 to 360° C., preferably 150 to 280° C., particularly Preferably, in 180-270 degreeC, a polycarbonate oligomer is obtained by making it react for 0.5 to 10 hours. The polycarbonate oligomer obtained in the first step is preferably made into a solid such as flakes, powder, or particles according to a known method from the viewpoint of operability in the second step.

In the second step, the above-mentioned transesterification catalyst, such as a quaternary phosphonium salt, is further added as appropriate to the polycarbonate oligomer obtained in the first step under reduced pressure, an inert gas is introduced, and the glass transition of polycarbonate is stirred under stirring. A high molecular weight polycarbonate is obtained by reacting while flowing out residual phenol in a solid state in which the crystallized oligomer during solid-state polymerization does not melt or in a swollen solid state above temperature.

Reaction of a 1st process and reaction of a 2nd process may be performed respectively, and may be performed continuously.

Here, the polycarbonate oligomer usually has a weight average molecular weight of, for example, about 500 to 15000. Moreover, with high molecular weight polycarbonate, a weight average molecular weight is about 15000-100000 normally, for example. However, the polycarbonate using the dihydroxy compound of the present invention as a raw material is not limited to such molecular weight.

The polycarbonate obtained as described above is a high molecular weight polycarbonate, so it is excellent in transparency, heat resistance, mechanical properties, impact resistance, fluidity, etc., optical lenses used for optical discs, smartphones, etc., optical films used for flat panel displays, etc. It can be expected to be used in various fields such as automobile field, electric/electronic field, and various containers as an optical use of the engineering plastics.

In addition, the polycarbonate oligomer can be used as a raw material for producing high molecular weight polycarbonate by various polymerization methods, as well as a surface modifier, a flame retardant, a UV absorber, a flow modifier, a plasticizer, a polymer modifier such as a compatibilizer for resin alloy, etc. , can be widely used as an additive.

In addition, for other uses, the dihydroxy compound of the present invention uses a terminal hydroxyl group, and in addition to polycarbonate, epoxy resins, oxetane resins, acrylic resins, polyesters, polyarylates, polyetheretherketones, polysulfones, furnaces It can also be expected to be used as a raw material for resins such as rock rock and resol, as a raw material for other photosensitive compositions, as a resist additive, as a developer, and as an antioxidant.

In particular, use as an acrylic monomer such as diacrylate obtained by reacting the dihydroxy compound of the present invention with acrylic acid or the like, as a raw material for an acrylic resin, and use as an optical hard coating material using these can be expected.

Example

The present invention will be specifically described below by way of Examples, but the present invention is not limited to these Examples.

In addition, the softening point in an Example, refractive index, and purity were measured by the following method.

[Analysis method]

1. Measurement of softening point

Device: manufactured by Shimadzu Corporation 　DSC-60 DIFFERENTIAL SCANNING CALORIMETER

Temperature rise condition: 10℃/min　(30℃→200℃)

Atmospheric gas: nitrogen gas (flow: 50 ml/min)

How to measure :

The first measurement was performed under the above-mentioned temperature rising condition, and the melting point was measured from the endothermic peak thereof.

Thereafter, the same material was cooled to room temperature, and measurement was performed a second time under the same conditions, and the endothermic peak thereof was taken as the softening point.

2. Measurement of refractive index

Apparatus: Refractometer RA-500N manufactured by Kyoto Electronics Industry Co., Ltd.

How to measure :

THF solutions (THF refractive index 1.40) of concentrations of 10, 15, and 30% were prepared, and the refractive index of the measurement compound was calculated by extrapolation from the refractive index of the solution.

3. Purity Determination

Equipment: manufactured by Shimadzu Corporation 　CLASS-LC10

Pump: LC-10ATvp

Column oven: CTO-10Avp

Detector: SPD-10Avp

Column: Shim-pack　CLC-ODS　6 mm inside diameter, 150 mm length

Oven temperature: 50℃

Flow rate: 1.0 ml/min

Mobile phase: (A) acetonitrile, (B) 0.2 vol% aqueous acetic acid solution

Gradient conditions: (A) Volume % (time from the start of analysis)

60%(0min)→60%(20min)→100%(40min)→100%(50min)

Sample injection amount: 20 μl

Detection wavelength: 280 nm

<Reference Example 1>

Preparation of 3,3-bis(4-hydroxy-3-phenylphenyl)-1-phenyl-1H-indol-2-one

680.4 g (4.00 mol) of 2-phenylphenol and 223 g (1.00 mol) of 1-phenyl-1H-indole-2,3-dione were placed in a 4-neck flask equipped with a thermometer, stirrer and cooling tube, and the reaction vessel was purged with nitrogen. After that, hydrogen chloride gas was blown in at 40°C to replace the inside of the system. Thereafter, 22.3 g of a 15% sodium methyl mercaptan aqueous solution (0.05 mol as sodium methyl mercaptan) was added, and the mixture was stirred at 40°C for 19 hours. After completion of the reaction, 409.4 g of a 16% aqueous sodium hydroxide solution (1.64 mol as sodium hydroxide) was added for neutralization. After heating up the obtained solution to 78 degreeC, 612.0 g of methanol was added and it cooled to 35 degreeC. The precipitated crystals were separated by filtration to obtain 691.7 g of white crystals.

To the obtained white crystals, 2026.2 g of toluene and 675.4 g of methyl ethyl ketone were added and dissolved, and then 675.4 g of water was added, stirred at 80° C., and after standing still, washing with water to extract the aqueous layer was repeated twice. The oil layer was heated to 107°C, the solvent 919.3 g was removed by distillation, and then cooled to 25°C, and the precipitated crystals were separated by filtration. The obtained crystal was dried under reduced pressure to obtain 417.6 g of 3,3-bis(4-hydroxy-3-phenylphenyl)-1-phenyl-1H-indol-2-one.

Purity 99.0% (high-speed liquid chromatography area%)

Yield 77% (vs. 1-phenyl-1H-indole-2,3-dione)

Melting point 180℃/218℃ (differential scanning calorimetry)

Proton nuclear magnetic resonance spectrum (400 MHz, solvent DMSO-D ₆ , standard TMS)

Chemical shift (signal shape, number of protons)

<Example 1>

Preparation of 3,3-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one

208.5 g (0.38) of 3,3-bis(4-hydroxy-3-phenylphenyl)-1-phenyl-1H-indol-2-one obtained in Reference Example 1 in a four-necked flask equipped with a thermometer, a stirrer and a cooling tube. mol), 97.6 g (1.11 mol) of ethylene carbonate, 1.23 g (0.004 mol) of tetra-n-butylammonium bromide, 2.23 g of 48% aqueous sodium hydroxide solution (0.03 mol as sodium hydroxide), 312.7 g of 1-butanol and 312.7 g of 1-butanol in a reaction vessel After nitrogen substitution, the mixture was stirred at 120° C. for 15 hours. After completion of the reaction, 121.3 g of water was added, followed by stirring at 95°C for 6 hours and at 105°C for 1 hour. Then, 1.0 g (0.22 mol) of acetic acid was added to adjust the pH of the aqueous layer to 5-6. Furthermore, after adding water to the oil layer and stirring at 80 degreeC, the water layer was extracted, and after adding 728.6 g of 1-butanol, 615.6 g of oil components were distilled out by distillation. The obtained solution was cooled to 25 degreeC, and the precipitated crystal|crystallization was separated by filtration. By drying the obtained crystal, 209.7 g of 3,3-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)-1-phenyl-1H-indol-2-one was obtained.

Purity 99.2% (high-speed liquid chromatography area%)

Yield 87% (versus bisphenol)

Melting point 185℃ (differential scanning calorimetry)

Softening Point 93℃ (Differential Scanning Calorimetry)

Refractive index (n _D 20) 1.63

Proton nuclear magnetic resonance spectrum (400 MHz, solvent DMSO-D ₆ , standard TMS)

Chemical shift (signal shape, number of protons)

<Comparative Example 1>

Preparation of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylphthalimidine

(Process 1)

After putting 902.5 g (9.70 mol) of aniline into a four-neck flask equipped with a thermometer, a stirrer, and a cooling tube, nitrogen purging the reaction vessel, and maintaining 85-95° C., 192.7 g of methanesulfonic acid was added dropwise into the system. Thereafter, 385.4 g (1.21 mol) of phenolphthalein was added at 90 to 100°C, and after the addition was completed, the mixture was stirred for 21.5 hours while maintaining 147 to 153°C. After completion of the reaction, after cooling and adding 1480.6 g of toluene at 110°C and 1480.6 g of water at 90°C, the mixture was cooled to 30°C and precipitated crystals were separated by filtration to obtain 481.6 g of crude crystals.

913.4 g of toluene and 228.4 g of methanol were added to the crude crystals obtained above, stirred at 71°C for 5 hours, cooled to 30°C, and the precipitated crystals were separated by filtration. 347.2 g of 3,3-bis(4-hydroxyphenyl)-2-phenylphthalimidine was obtained by drying the obtained crystal|crystallization under reduced pressure.

Purity 99.6% (high-speed liquid chromatography area%)

Yield 75% (vs. phenolphthalein)

Melting point 291.5℃ (differential scanning calorimetry)

(Process 2)

30.0 g (0.076 mol) of 3,3-bis (4-hydroxyphenyl) -2-phenylphthalimidine obtained in Step 1, 19.5 g (0.22 mol) of ethylene carbonate in a four-necked flask equipped with a thermometer, a stirrer, and a cooling tube ), 0.44 g of 48% potassium hydroxide aqueous solution (0.0038 mol as potassium hydroxide), and 45.0 g of 1-butanol were added, and the reaction vessel was purged with nitrogen, followed by stirring at 115 to 118° C. for 11 hours. After completion of the reaction, 2.7 g of water was added and stirred at 106-109°C for 3 hours. Then, 2.2 g of 10% acetic acid was added to adjust the pH of the aqueous layer to be 4-5. After adding methyl isobutyl ketone to the obtained oil layer, adding water and stirring at 80-85 degreeC, operation of extracting the water layer was performed twice. The obtained oil layer was heated to 125°C, and 50.0 g of the fraction was distilled off by distillation. After adding acetone and water to the obtained solution, it was cooled to 30°C, and the precipitated crystals were separated by filtration. By drying the obtained crystal, 28.5 g of 3,3-bis(4-(2-hydroxyethoxy)phenyl)-2-phenylphthalimidine was obtained.

Purity 96.7% (high-speed liquid chromatography area%)

Yield 78% (vs. 3,3-bis(4-hydroxyphenyl)-2-phenylphthalimidine)

Melting point 155℃ (differential scanning calorimetry)

Softening point 68℃ (differential scanning calorimetry)

Refractive index (n _D 20) 1.60

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

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

Claims (1)

A dihydroxy compound represented by Formula 1 below.
[Formula 1]

(Wherein, R each independently represents an alkylene group having 2 to 6 carbon atoms, R ₁ each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group or a halogen atom, R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a halogen atom, and R ₃ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, or represents a halogen atom, m represents an integer of 0 to 2, n represents an integer of 0 to 2, with the proviso that when m is 2, R ₁ may be the same or different, and when n is 2, R ₃ is They may be the same or different.)