JPWO2016063889A1 - 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and method for producing the same, and aromatic polycarbonate resin and method for producing the same - Google Patents

Abstract

1,3-bis (3-methyl-4-hydroxyphenyl) -5,7, which is a novel bisphenol compound having an adamantane skeleton, which can be used as a raw material for various resins excellent in heat resistance, optical properties, and mechanical strength properties -Provision of dimethyladamantane compounds. It is another object of the present invention to provide a polycarbonate resin and a resin composition characterized by excellent heat resistance and high surface altitude. The above-described problem includes a 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane compound, a method for producing the compound, and a structural unit represented by the following formula (1). This is solved by a novel aromatic polycarbonate resin. [Chemical 1]

Description

The present invention relates to a novel 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane which is a raw material suitable for improving the heat resistance, optical properties, and mechanical strength properties of various resins. And a manufacturing method thereof.
The present invention also relates to a novel aromatic polycarbonate resin having high heat resistance and high surface hardness and a method for producing the same.

  Resins manufactured using bisphenols as raw materials are used in various applications taking advantage of heat resistance, optical properties, and mechanical strength properties. In particular, when used as an optical resin, Patent Document 1 describes that inconvenience such as coloring occurs due to the influence of a trace amount of impurities contained in the raw material bisphenols, and high-purity bisphenols are required.

  As bisphenols having an adamantane skeleton among the bisphenols, 1,3-bis (4-hydroxyphenyl)-synthesized in Patent Document 2 by reacting 1,3-dibromo-5,7-dimethyladamantane with phenol. 5,7-dimethyladamantane is described.

  In Patent Document 3, as a method for producing an aromatic dihydroxy compound, 1,3-adamantanediol and phenol are reacted in the presence of hydrochloric acid to synthesize 1,3-bis (4-hydroxyphenyl) adamantane, and silica gel chromatography. A method for the production of adamantane purified by chromatography is described.

  Further, Patent Document 4 discloses 1,3-bis (4-hydroxyphenyl) adamantanes and 1,3-bis (2-hydroxy) synthesized by reacting 1,3-adamantanediols and substituted phenols in the presence of an acid catalyst. Phenyl) adamantanes are described.

  Polycarbonate resins are widely used in various fields because they exhibit excellent electrical properties, flame retardancy, transparency, dimensional stability, mechanical properties, and are lightweight. In particular, bisphenol A-derived polycarbonate resin (BPA-PC) is inexpensive and has excellent transparency and impact strength. Therefore, it is used as an electrical and electronic part, automobile part, and building material as an alternative material for inorganic glass.

Generally, BPA-PC is used by improving the heat resistance and surface hardness by applying a hard coat to the surface of a molded body using a silicone or acrylic material, or by laminating a layer of an acrylic polymer material. . Patent Document 5 proposes that a thin layer made of a resin composition in which a specific filler is dispersed is formed on the surface of a BPA-PC molded body to improve surface strength.
However, in these methods, since layers made of different materials are bonded to each other, there is a problem that adhesion failure is likely to occur, and warpage is likely to occur due to a difference in water absorption and a difference in linear expansion coefficient. Moreover, from the viewpoint of recycling after use, there was also a drawback that it was difficult to separate and collect.

International Publication No. 2002-022536 US Pat. No. 3,594,427 JP 2000-95720 A JP 2003-306460 A Japanese Patent Laid-Open No. 2007-14450 JP 2011-089049 A JP 2012-068381 A Japanese Patent Laid-Open No. 05-093057

  First, as for the adamantane compound, although it is described that phenol is used in the synthesis method of 1,3-bis (4-hydroxyphenyl) adamantanes described in Patent Document 2, Use is not described. Patent Document 3 only describes production examples of 1,3-bis (4-hydroxyphenyl) adamantane, but does not describe examples of the use of substituted adamantanes or o-cresol. . In addition, only adamantane having no substituent has been reported as the adamantane skeleton portion of 1,3-bis (4-hydroxyphenyl) adamantanes in Examples of Patent Document 4.

  Furthermore, no trace impurities are described in the bisphenols having an adamantane skeleton described in these documents.

  An object of the present invention is to provide a 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane compound, which is a novel bisphenol compound having an adamantane skeleton, and bromine of the compound An object of the present invention is to provide a production method that can reduce the sulfur content and can be suitably used as a resin raw material.

Moreover, in order to solve the problem regarding the above polycarbonate resin, a polycarbonate resin including a special structure has been proposed. For example, in Patent Documents 6 and 7, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC) or 1,1 is used instead of bisphenol A (BPA) as a dihydroxy compound constituting polycarbonate. -Bis (3-methyl-4-hydroxyphenyl) -1-phenylethane (BPCAP), 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (BPCFL), 1,1-bis (3-methyl) It has been proposed that the polycarbonate resin itself has a function of modifying the surface hardness by using -4-hydroxyphenyl) cyclohexane (BPCZ) or the like.
However, all of these polycarbonate resins have a glass transition temperature of 160 ° C. or less, and problems remain in terms of heat resistance.

  Patent Document 8 proposes a high heat-resistant polycarbonate using 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane (BPDMA) as a dihydroxy compound. These polycarbonate resins have a glass transition temperature of 160 ° C. or higher, but their surface hardness is not satisfactory.

  The problem to be solved by the present invention is to provide a polycarbonate resin having high heat resistance and high surface hardness.

  First, regarding the problem of providing the above-mentioned novel adamantane compound, the present inventors have conducted extensive studies, and as a result, 1,3-bis which can be suitably used as a resin raw material with a small amount of bromine and sulfur. It has been found that (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane can be produced.

That is, the present invention is as follows.
[1]
1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane.
[2]
1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane having a bromine concentration as an impurity of 500 ppm or less and a sulfur concentration of 400 ppm or less.
[3]
1,3-bis (methyl-hydroxyphenyl) -5 having 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane as a main component and an isomer purity of 98% or more , 7-dimethyladamantane.
[4]
A method for producing 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, comprising reacting 1,3-dibromo-5,7-dimethyladamantane with o-cresol.
[5]
1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyl, characterized by reacting 1,3-dihydroxy-5,7-dimethyladamantane with o-cresol in the presence of an acid catalyst A method for producing adamantane.
[6]
After the reaction, a poor solvent was added and stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, and then the crude crystals were separated. The 1,3-bis (3-methyl) according to [4] or [5], wherein impurities are removed by washing a solution obtained by dissolving the separated crude crystals in an organic solvent with an alkaline aqueous solution. A process for producing -4-hydroxyphenyl) -5,7-dimethyladamantane.
[7]
After the reaction, a poor solvent was added and stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, and then the crude crystals were separated. The solution in which the separated crude crystals are dissolved in an organic solvent is washed with an alkaline aqueous solution, further dissolved in an organic solvent, and a poor solvent is added to precipitate crystals [4] or [4] 5]. The method for producing 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane according to [5].

Furthermore, regarding the problem of realizing the high heat resistance and high surface hardness of the polycarbonate resin, the present inventors have intensively studied, and as a result, found that the above-mentioned problem can be solved by the following polycarbonate resin. Reached.
The present invention is as follows.
[8]
An aromatic polycarbonate resin containing a structural unit derived from 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane represented by the following formula (1).

[9]
1,3-bis (methyl-hydroxyphenyl)-, the isomer purity of which is the main component of the 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and is 98% or more The aromatic polycarbonate resin according to [8], containing a structural unit derived from 5,7-dimethyladamantane.
[10]
Furthermore, the aromatic polycarbonate resin as described in [8] or [9] containing the structural unit represented by following General formula (2).

(In formula (2), R _{1 to} R ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C 1-20 alkyl group that may have a substituent, It represents any of an alkoxy group having 1 to 5 carbon atoms and an aryl group having 6 to 12 carbon atoms, where X is a single bond, a sulfur atom, a sulfonyl group, an alkylidene group having 2 to 10 carbon atoms, or an alkyl group having 5 to 12 carbon atoms. (Represents any one of a cycloalkylidene group, an arylalkylidene group having 7 to 15 carbon atoms, and a fluorenylidene group.)
[11]
The structural unit represented by the general formula (2) is 1,1′-biphenyl-4,4′-diol (BP), bis (4-hydroxyphenyl) methane (BPF), 1,1-bis (4- Hydroxyphenyl) ethane (BPE), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ) Ketone, 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-) Hydroxyphenyl) propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4 Hydroxyphenyl) cyclohexane (BPZ), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1 , 1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane (BPCAP), 9,9-bis (4-hydroxyphenyl) ) Fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [3- (o -Hydroxyphenyl) propyl] polydimethylsiloxane, and 4,4 '-[1,3-phenylene vinyl [10] The aromatic polycarbonate resin according to [10], which is at least one selected from the group consisting of (bis (1-methylethylidene)] bisphenol.
[12]
The viscosity-average molecular weight, 1.0 × ¹⁰ 4, characterized in that 8.0 a ^{× 10 4, [8] ~} [11] or an aromatic polycarbonate resin according to one of.
[13]
The novel aromatic polycarbonate resin according to any one of [8] to [12], wherein the content ratio of the structural unit represented by the formula (1) is 10 to 100 mol%.
[14]
Aromatic polycarbonate resin as described in any one of [8]-[13] whose glass transition temperature is 160 degreeC or more.
[15]
The aromatic polycarbonate resin according to any one of [8] to [14], wherein the pencil hardness is HB or more.
[16]
The film and sheet | seat using the aromatic polycarbonate as described in any one of [8]-[15].
[17]
The film and sheet according to [16], wherein the film and sheet are transparent conductive films.
[18]
In any one of [8] to [15], 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane represented by the following formula (3) is used as a raw material. The manufacturing method of aromatic polycarbonate resin of description.

  The 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the present invention can be suitably used as a raw material for resins and the like.

  Furthermore, in the present invention, it is possible to provide a novel polycarbonate resin having high heat resistance and high surface hardness at a level that could not be achieved conventionally.

The GC / MS analysis result of the product (1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane) obtained in Example 2 is shown. The result of the 1H-NMR analysis of the product obtained in Example 2 is shown. The assignment of the 1H-NMR peak of the product obtained in Example 2 is shown. The result of the 13C-NMR analysis of the product obtained in Example 2 is shown. The result of DEPT45 degree-NMR analysis of the product obtained in Example 2 is shown. The attribution of the 13C-NMR peak of the product obtained in Example 2 is shown.

  Hereinafter, a mode for carrying out the present invention relating to a novel adamantane compound (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

  1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of this embodiment is represented by the following formula (3).

The isomers represented by the following formulas (4) and (5) in 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the formula (3) of the present embodiment Traces of body can be included. If these isomers increase, the physical properties of the resin produced from the bisphenol compound may be adversely affected, so that 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyl The isomer purity of adamantane is preferably 98% or more, and more preferably 99% or more.
That is, in this embodiment, 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane is 1,3-bis (3-methyl-4-hydroxyphenyl of formula (3) as a main component. ) -5,7-dimethyladamantane, and further includes isomers related to the positions of the methyl group and the phenolic hydroxyl group, which are substituents of the phenyl group, that is, the isomer of formula (4) or formula (5) You can leave.

  Further, the 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of this embodiment may contain bromine and sulfur as impurities. When the concentration of these impurities increases, the physical properties of a resin produced from the bisphenol compound may be adversely affected. Therefore, the bromine concentration in the bisphenol compound is preferably 500 ppm or less, more preferably 250 ppm or less, and even more preferably 200 ppm. Furthermore, the sulfur concentration is 400 ppm or less, preferably 100 ppm or less, more preferably 50 ppm or less, and still more preferably 25 ppm.

  1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of this embodiment is used as a raw material for various resins such as epoxy resins, photosensitive resins, cyanate resins, and polyester resins. A resin excellent in heat resistance, optical properties, and mechanical strength properties can be produced by using 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. can do.

  1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the present embodiment includes 1,3-dibromo-5,7-dimethyladamantane represented by the following formula (6): It can be produced by reacting o-cresol. (First manufacturing method)

  In addition, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane includes 1,3-dihydroxy-5,7-dimethyladamantane represented by the following formula (7) and o- It can also be produced by reacting cresol in the presence of an acid catalyst. (Second manufacturing method)

Hereinafter, the first manufacturing method of the present embodiment will be described.
For 1,3-dibromo-5,7-dimethyladamantane used as a raw material in the first production method, a known method described in JP-A No. 2002-145809 and JP-A No. 57-5000785 is used. Can be manufactured.

  In the first production method of the present embodiment, 1,3-bis (3-methyl-4-methyl-1,4-dibromo-5,7-dimethyladamantane is reacted with an excess amount of o-cresol. Hydroxyphenyl) -5,7-dimethyladamantane can be obtained with good yield. The amount of o-cresol used is preferably 4 to 30 times, more preferably 6 to 15 times, and more preferably 8 to 13 times in molar ratio to 1,3-dibromo-5,7-dimethyladamantane. More preferably it is.

  The reaction temperature in the first production method of the present embodiment is preferably in the range of 160 to 190 ° C, more preferably 170 to 190 ° C, and further preferably 180 to 185 ° C. When the reaction temperature is lower than 160 ° C., the reaction is slowed down, so that the reaction time becomes long, and many raw materials and reaction intermediates remain. Further, by setting the reaction temperature to 190 ° C. or lower, the reaction can be carried out at the boiling point of o-cresol or less, and it is not necessary to pressurize the reactor.

  Although a solvent may be used in the reaction of the first production method of the present embodiment, 1,3-dibromo-5,7-dimethyladamantane is easily subjected to solvolysis, and the reaction temperature is set high. For this, an inert high boiling point solvent is preferred. More preferably, no reaction solvent is used.

  Although the reaction time in a 1st manufacturing method is based also on reaction temperature, it is preferable that it is 1 to 15 hours, It is more preferable that it is 2 to 10 hours, It is still more preferable that it is 3 to 8 hours. If the reaction time is less than 1 hour, many raw materials and reaction intermediates remain.

  When the conversion of the raw material 1,3-dibromo-5,7-dimethyladamantane is less than 75% when the reaction is terminated, a large amount of organic bromine compounds such as raw materials and intermediates remain. It is difficult to remove impurities in a purification process described later. Therefore, the conversion of 1,3-dibromo-5,7-dimethyladamantane is preferably 75% or more. In order to increase the conversion rate of 1,3-dibromo-5,7-dimethyladamantane to 75% or more, for example, when the reaction temperature is 170 ° C., 8 to 8% of 1,3-dibromo-5,7-dimethyladamantane. Using 13 times mole of o-cresol, the reaction time may be 5 hours or more.

  In the first production method of the present embodiment, a crude solvent of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane is prepared by adding a poor solvent to the product after completion of the reaction. Can be deposited. As the poor solvent, a solvent having low solubility of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and miscible with o-cresol may be used. Aliphatic hydrocarbons such as are preferred, and heptane is more preferred. The amount of the poor solvent used is preferably 0.5 to 3 times the weight of o-cresol used in the reaction. The precipitated crude crystals are separated from the solvent and collected by a method such as filtration or centrifugation.

  In the first production method of the present embodiment, hydrogen bromide is by-produced by the reaction of 1,3-dibromo-5,7-dimethyladamantane and o-cresol. There arises a problem that it remains as a bromine-containing impurity in methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. Bromine-containing impurities are removed by dissolving crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane obtained after the reaction in an organic solvent and washing with an alkaline aqueous solution. In addition, the bromine concentration can be lowered. The remaining o-cresol can also be removed by washing with an alkaline aqueous solution. In addition, by washing with an alkaline aqueous solution, the red color-causing substance and o-cresol can be easily washed away to the aqueous phase side.

  Examples of the organic solvent used for dissolving the crude crystals include ethyl acetate, toluene, acetone, methanol, and the like, but ethyl acetate and acetone are more preferable, and ethyl acetate is more preferable.

  The alkaline aqueous solution used for the washing is not particularly limited, but an alkali metal hydroxide aqueous solution is preferable. Moreover, sodium hydroxide is used suitably for the alkali metal hydroxide used for alkali metal hydroxide aqueous solution. When sodium hydroxide is used, if the concentration of the sodium hydroxide aqueous solution is too high, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane is disodium phenolate salt or mono Since it is converted into sodium phenolate, disodium phenolate is distributed to the aqueous phase, and monosodium phenolate is not easily dissolved in the organic phase or the aqueous phase and precipitates as crystals. Resulting in reduced yield of 3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. The concentration of the aqueous sodium hydroxide solution used for washing the crude crystals is preferably 0.1 to 1.0% by weight. More preferably, it is 0.2-0.8 weight%, More preferably, it is 0.3-0.6 weight%.

  After the washing with the alkali metal hydroxide aqueous solution, washing with pure water is more desirable in order to prevent the alkali metal from being mixed.

  Although the concentration of the bromine-containing compound can be reduced by the above washing operation, it is desirable to further perform purification by recrystallization in consideration of the possibility that it cannot be completely removed. Recrystallization can be performed by heating and stirring in the minimum amount of organic solvent, adding the poor solvent, and stirring. The combination of the solvent and the poor solvent is not particularly limited. For example, when ethyl acetate is used as the solvent and heptane is used as the poor solvent, 1,3-bis (3 represented by the above formula (1) is used. -Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, 1.5 to 3 times the weight of ethyl acetate was added, and the mixture was heated and stirred to dissolve the crystals. 1,3-bis (3-methyl-4-hydroxyphenyl) is preferably added to 1 to 5 times, more preferably 2 to 4 times the amount of heptane with respect to the weight of ethyl acetate. ) -5,7-dimethyladamantane crystals can be precipitated with a high recovery rate. Even if the amount of heptane to be added is 5 times or more of the weight of ethyl acetate, the crystal recovery rate does not remarkably improve, but rather there is a problem that impurities increase. In addition, when the amount of heptane is less than 1 time, the crystal recovery of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane decreases, which is not preferable.

  Impurities are reduced by the above purification method, that is, by dissolving crude crystals in an organic solvent, washing with an aqueous alkali metal hydroxide solution, washing with pure water, and further recrystallization.

Hereinafter, the second manufacturing method of the present embodiment will be described.
In the second production method, 1,3-bis (3-methyl-4-hydroxyphenyl) is reacted by reacting 1,3-dihydroxy-5,7-dimethyladamantane with o-cresol in the presence of an acid catalyst. -5,7-dimethyladamantane is produced.

1,3-dihydroxy-5,7-dimethyladamantane used as a raw material in the second production method of the present embodiment is a method of oxidizing 1,3-dimethyladamantane in the presence of an imide compound and a cobalt compound, a ruthenium compound In the presence, it can be synthesized by methods such as oxidation with hypochlorites, oxidation of 1,3-dimethyladamantane with chromic acid, dihalogenation of 1,3-dimethyladamantane and hydrolysis. It is.
In this embodiment, 1,3-dihydroxy-5,7-dimethyladamantane synthesized by any of the above or other methods can also be used.

  In the second production method of the present embodiment, 1,3-bis (3-methyl-4-methyl-1,4-dimethyladamantane is reacted with an excess amount of o-cresol. Hydroxyphenyl) -5,7-dimethyladamantane can be obtained with good yield. The amount of o-cresol used is preferably 2 to 20 times, more preferably 5 to 15 times, and more preferably 6 to 10 times in terms of a molar ratio to 1,3-dihydroxy-5,7-dimethyladamantane. More preferably it is.

  As the acid catalyst used for the reaction in the second production method, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, strong acidic cation exchange resin and the like are preferable. When an acid containing water such as hydrochloric acid or dilute sulfuric acid is used, the reaction proceeds slowly, and when concentrated sulfuric acid which is a non-aqueous acid is used, 1,3-bis (3-methyl-4- Hydroxyphenyl) -5,7-dimethyladamantane is sulfonated and tends to remain as a sulfur-containing impurity, making it difficult to remove.

  The acid catalyst is used in a molar ratio with respect to 1,3-dihydroxy-5-adamantane, usually preferably 0.1 to 3 times, more preferably 0.3 to 2 times. More preferably, it is 5 to 1.5 times.

  In the second production method of this embodiment, it is not necessary to use a solvent for the reaction.

  If the reaction temperature of the second production method of the present embodiment is too low, the reaction is slow, and many reaction intermediates and isomers remain, so the higher one is preferable, and the range of 90 to 190 ° C is preferable.

  Although the reaction time in the second production method depends on the reaction temperature, it is preferably 1 to 36 hours, more preferably 2 to 24 hours, and still more preferably 3 to 10 hours. If the reaction time is less than 1 hour, many raw materials and reaction intermediates remain.

  In the second production method of this embodiment, a crude solvent of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane is added by adding a poor solvent after the completion of the reaction and stirring. Crystals can be precipitated. As the poor solvent, warm water, toluene and the like can be used, but a mixed solvent such as n-heptane, n-hexane, water / methanol, water / ethanol and the like can be preferably used. In particular, n-heptane and n-hexane are used as preferred poor solvents.

  After the crude crystals are precipitated, solid-liquid separation is performed by a method such as filtration or centrifugation. By washing and filtering the crude crystals after solid-liquid separation with a poor solvent, excess o-cresol and acid catalyst can be washed away, and the subsequent purification process can be easily performed, which is more preferable. As the poor solvent used for washing, n-heptane, n-hexane, a mixed solvent such as water / methanol, water / ethanol, or the like can be preferably used.

  By dissolving the crude crystals obtained by the above operation in an organic solvent and washing with an alkaline aqueous solution, sulfur-containing impurities can be removed and the sulfur concentration can be made extremely low. The remaining o-cresol can also be removed by washing with an alkaline aqueous solution. In addition, by washing with an alkaline aqueous solution, the red color-causing substance and o-cresol can be easily washed away to the aqueous phase side.

  Examples of the organic solvent used for dissolving the crude crystals include solvents such as ethyl acetate, toluene, acetone, and methanol, but ethyl acetate and acetone are more preferable, and ethyl acetate is more preferable.

  The alkaline aqueous solution used for the washing is not particularly limited, but an alkali metal hydroxide aqueous solution is preferable. Moreover, sodium hydroxide can be used suitably for the alkali metal hydroxide used for alkali metal hydroxide aqueous solution. When sodium hydroxide is used, if the concentration of the sodium hydroxide aqueous solution is too high, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane is disodium phenolate salt or mono These are converted into sodium phenolate, disodium phenolate is distributed into the aqueous phase, and monosodium phenolate is not easily dissolved in the organic layer or aqueous phase and precipitates as crystals. , 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. The concentration of the sodium hydroxide aqueous solution is preferably 0.1 to 1.0% by weight. More preferably, it is 0.2-0.8 weight%, More preferably, it is 0.3-0.6 weight%.

  Further, after washing with a dilute aqueous solution of the alkali metal hydroxide, the organic solvent solution is washed with pure water to neutralize the contamination by alkali metal.

  After the water washing step, further normal recrystallization can be performed to obtain 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane with higher purity.

  Of the solvents used in the recrystallization operation, ethyl acetate, acetone, and methanol can be suitably used as good solvents. Moreover, solvents, such as aliphatic saturated hydrocarbons, such as hexane and a heptane, can be used suitably as a poor solvent.

  Hereinafter, the present invention relating to a novel polycarbonate resin will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples, and the gist of the present invention is described below. Any change can be made without departing from the scope.

In the present invention, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane (hereinafter also referred to as BPCDMA) represented by the following formula (3) is reacted with a carbonate-forming compound. It is related with the polycarbonate resin and resin composition which are obtained by making it.

<Dihydroxy compound: production method of BPCDMA>

  Although the manufacturing method of BPCDMA is not specifically limited, For example, it can manufacture with the above-mentioned 1st, 2nd manufacturing method.

That is, in this embodiment, BPCDMA synthesized by any of the methods described above or other than the above can be used.
<Other dihydroxy compounds>

As the dihydroxy compound constituting the polycarbonate resin and composition of the present invention, one or two or more compounds represented by the following general formula (8) may be used in combination with BPCDMA as required.

(In General Formula (8), R _{1 to} R ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C 1-20 alkyl group that may have a substituent. Represents any one of an alkoxy group having 1 to 5 carbon atoms and an aryl group having 6 to 12 carbon atoms, X is a single bond, a sulfur atom, a sulfonyl group, an alkylidene group having 2 to 10 carbon atoms, or 5 to 12 carbon atoms. A cycloalkylidene group, a C 7-15 arylalkylidene group, or a fluorenylidene group.) By using such a dihydroxy compound, the resulting polycarbonate resin is a structural unit represented by the general formula (2) It will have.

  Specific examples of the compound represented by the general formula (8) include 1,1′-biphenyl-4,4′-diol (BP), bis (4-hydroxyphenyl) methane (BPF), 1,1-bis (4 -Hydroxyphenyl) ethane (BPE), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy) Phenyl) ketone, 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4) -Hydroxyphenyl) propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- (4-hydroxyphenyl) cyclohexane (BPZ), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) ) Diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane (BPCAP), 9,9-bis ( 4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [ 3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, 4,4 ′-[1,3-pheny Lenbis (1-methylethylidene)] bisphenol and the like.

  Among these, 1,1′-biphenyl-4,4′-diol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4- Hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) Cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ether, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-me (Lu-4-hydroxyphenyl) fluorene is preferred, and 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxy) is preferred from the viewpoints of the distribution amount, price and purity. Phenyl) propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane (BPCAP), 1,1 '-Biphenyl-4,4'-diol (BP), 1,1-bis (4-hydroxyphenyl) ethane (BPE), and bis (4-hydroxyphenyl) methane (BPF) are more preferable.

The copolymerization ratio of BPCDMA and the dihydroxy compound represented by the general formula (8) can be set to an arbitrary ratio, but the content ratio of BPCDMA is particularly preferably 10 to 100 mol%, more preferably 30 to The range is 100 mol%.
As the polycarbonate resin, a blend resin may be used together with the copolymer resin or instead of the copolymer resin. For example, only BPCDMA represented by the above general formula (3) or a polymer mainly composed of BPCDMA and only the dihydroxy compound represented by the above general formula (8) or the dihydroxy compound represented by the general formula (8) are mainly used. You may employ | adopt the blend resin obtained by mixing with the polymer of the polycarbonate which is a component. In the blending process for producing the blended resin thus obtained, for example, when a polycarbonate of BPCDMA and a polycarbonate of the dihydroxy compound of the general formula (8) are mixed in a molten state, an interesterification reaction proceeds. A blend resin having hot water having the same composition as that of the copolymer resin can be obtained.
<Carbonate forming compound>

Examples of carbonate ester-forming compounds that can be used in the present invention include bisallyl carbonates such as phosgene, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p-chlorophenyl carbonate, and dinaphthyl carbonate. Can be mentioned. Of these, phosgene is preferred from the viewpoint of quality such as hue and stability of the resin obtained.
In the production of the polycarbonate of the present invention, only one type of carbonate ester-forming compound may be used, or two or more types may be used in combination.
<Production method of polycarbonate>

  The polycarbonate resin of the present invention can be produced by a known synthesis method such as various methods, an interfacial polymerization method, and a transesterification method used when producing a polycarbonate from bisphenol A and a carbonate ester-forming compound.

  In general, the interfacial polymerization method is performed near room temperature, whereas the transesterification method is performed at a temperature higher than the temperature at which the raw material mixture and the polycarbonate resin to be produced melt. Therefore, when the polycarbonate resin of the present application is polymerized by the transesterification method, for example, if BPCDMA is a polycarbonate resin of 100%, it is necessary to perform the reaction at 213 ° C. or higher, which is its glass transition temperature. However, when the polymerization reaction is performed for a long time at such a high temperature, the thermal degradation of the dihydroxy compound itself is likely to proceed, and the carbonate-forming compound such as diphenyl carbonate is likely to be distilled out of the reaction system. There was a problem. Therefore, it is preferable to employ the interfacial polymerization method.

  In the interfacial polymerization method, in the presence of a chlorinated organic solvent such as methylene chloride as an organic solvent inert to the reaction and an alkaline aqueous solution, the pH is usually maintained at 10 or more, and a dihydroxy compound and a molecular weight modifier (terminal terminator) ) If necessary, use an antioxidant to prevent oxidation of dihydroxy compounds, react with phosgene, and then add a polymerization catalyst such as tertiary amine or quaternary ammonium salt to perform interfacial polymerization. Thus, a resin solution of polycarbonate resin can be obtained. The timing of adding the molecular weight regulator is not particularly limited as long as it is between the time of phosgenation and the start of the polymerization reaction. The reaction temperature is 0 to 35 ° C., and the reaction time is several minutes to several hours.

  Here, examples of the molecular weight regulator (end terminator) include compounds having a monovalent phenolic hydroxyl group. Specifically, m-methylphenol, p-methylphenol, m-propylphenol, p- Examples include propylphenol, p-tert-butylphenol, and p-long chain alkyl-substituted phenol.

  As a polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, pyridine; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, triethylbenzylammonium chloride, etc. Can be mentioned.

In the polycarbonate resin of the present invention, an antioxidant, a pigment, a dyeing reinforcing agent, a filler, a mold release agent, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent and the like are appropriately added. It may be added.
<Physical properties of polycarbonate resin>

The surface hardness of the polycarbonate resin of the present invention can be evaluated by a pencil scratch test (based on JIS-K5600-5-4).
A 20 wt% resin solution is prepared by dissolving 5 g of a polycarbonate resin in 20 g of methylene chloride, and this resin solution is cast on a glass plate having a thickness of 20 mm to produce a film having a thickness of 200 μm.
Using a Mitsubishi pencil UNI, the polycarbonate film produced by the above method was measured 5 times in accordance with JIS-K5600-5-4.
The pencil hardness of the polycarbonate resin of the present invention evaluated by the above measurement method is preferably HB to 2H, more preferably H to 2H.
In particular, since 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane has a methyl group as a substituent of a phenol group, in a polycarbonate resin produced using this as a monomer, The above-mentioned relatively high range of pencil hardness can be easily realized.

The glass transition temperature (Tg) of the polycarbonate resin of the present invention is a value (Tg calculation by the tangential method) measured under a nitrogen stream using Shimadzu Corporation DCS-50.
The Tg of the polycarbonate resin of the present invention evaluated by the above measurement method is preferably 160 to 220 ° C, more preferably 175 to 220 ° C.
In particular, since 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane has an adamantane skeleton, the polycarbonate resin produced using this as a monomer has a relatively high range as described above. A glass transition temperature (Tg) can be easily realized.

  The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention was determined by measuring 0.2 g / deciliter of a methylene chloride solution of a polycarbonate resin at a temperature of 20 ° C. with an Ubbelohde capillary viscometer. [Η] Deciliter / gram was determined and calculated by the following mathematical formula (I).

η = 1.23 × 10 ⁻⁴ × Mv ^0.83 (I)

The Mv of the polycarbonate resin of the present invention evaluated by the above measuring method is preferably 1.0 × 10 ^{4 to} 8.0 × 10 ⁴ , more preferably 2.0 × 10 ^{4 to} 4.0 × 10 ⁴ . It is a range.
<Use of the present invention>

The polycarbonate resin that is a preferred embodiment of the present invention has high heat resistance and surface hardness at the same time, so it is used as a raw material for injection molded products, extrusion molded products, films, sheets, etc. that require high heat resistance and high surface hardness. I can do it. Injection molded products / extruded products / films / sheets using the polycarbonate resin of the present invention are optical lenses, headlamps, lighting covers, printers / copiers, medical equipment, automobile parts, cooking products, electrical / electronic parts, displays. It can be widely used as a member for a substrate, a transparent conductive film, a retardation film, a brightness enhancement film, a reflective sheet, a solar battery back sheet, and the like. In particular, since the polycarbonate resin of the present invention has both high surface hardness and high heat resistance, it is useful as a transparent conductive film for display panels mounted on electric and electronic equipment.
The surface hardness can be further improved by applying a known thermosetting / ultraviolet curable hard coat to the surface layer of an injection molded product, an extrusion molded product, a film, a sheet or the like made of the polycarbonate resin of the present invention.

  Hereinafter, the present invention will be described in more detail with reference to examples of novel adamantane compounds, but the present invention is not limited to these examples.

<Analysis method>
(1) GC-FID analysis Agilent capillary column DB-1 30m, inner diameter 0.53mm, film thickness 1.5μm was attached to a gas chromatograph HP-6890 made by Hewlett Packard, and the composition analysis of the product was performed with the FID detector. went.

(2) GC / MS Analysis Agilent capillary column DB-1MS 30 m, inner diameter 0.250 mm, and film thickness 0.25 μm were attached to a Shimadzu gas chromatograph mass spectrometer GCMS-QP2010 Ultra for analysis.

(3) NMR analysis The measurement data was dissolved in acetone-D6 to make a 10% solution, and measured using a JNM-AL400 type nuclear magnetic resonance apparatus manufactured by JEOL.

(4) Fluorescent X-ray analysis 3 g of a measurement sample was molded into a pellet shape with a 20 MPa, 20-second press, and the bromine concentration and sulfur concentration were measured by fluorescent X-ray measurement using a fluorescent X-ray analyzer ZSX100e manufactured by Rigaku Corporation. Quantitative analysis was performed.

(5) HPLC analysis The HPLC ELITE LaChrom L-2200 manufactured by Hitachi High-Technologies Corporation was equipped with a phenomenex column Synergi 4u Hydro-RP 80A, 250 x 4.60 mm, 4 micron, and the column was maintained at 35 ° C under constant temperature conditions at 1.0 mL / min. The gradient analysis was performed with acetonitrile and a solution in which 3 g of phosphoric acid was dissolved in 1 L of pure water at a flow rate of. 0.1 mL of a solution in which 0.05 g of a sample was dissolved in 20 mL of acetonitrile was injected, and the isomer composition of the product was measured at 220 nm using a UV detector.

<Production Example 1> Production of 1,3-dibromo-5,7-dimethyladamantane 238 kg of dichloromethane was added to a 1000 L glass lining (GL) kettle, and 60 kg of 1,3-dimethyladamantane was further charged. Further, 4.80 kg of ferric chloride was charged, cooled, and the liquid temperature was adjusted to 20 ± 3 ° C. Cooling was performed, and 141 kg of bromine was added dropwise over 9 hours while controlling in a range of 20 ± 5 ° C. After completion of the dropping, the mixture was further stirred for 6 hours and 30 minutes while adjusting the temperature to 20 ± 3 ° C., and then aged. After aging, the liquid temperature was cooled to 5 ° C., and 185 kg of water was added. Although an exotherm was observed up to 9 ° C, the mixture was stirred for 15 minutes while cooling so as not to exceed 10 ° C. After further standing for 30 minutes, the lower methylene chloride layer and the upper acidic aqueous phase were separated.
Next, the lower dichloromethane layer was put into a 1000 L GL kettle and cooled to 9 ° C. A mixture of 210.9 kg of 185 kg of water, 9.6 kg of sodium bicarbonate, and 16.3 kg of sodium thiosulfate was added dropwise over 25 minutes with stirring. The mixture was further stirred for 15 minutes while maintaining the temperature at 10 ° C or lower. Stirring was stopped and the mixture was allowed to stand for 30 minutes, and then the lower dichloromethane layer and the upper aqueous phase were separated. The obtained lower dichloromethane layer was put into a 1000 L GL kettle, 185 kg of water was added, stirred for 15 minutes at room temperature, and allowed to stand for 30 minutes to separate the lower dichloromethane layer and the upper aqueous phase. Again, the lower dichloromethane layer was put into a 1000 L GL kettle, 185 kg of water was added, stirred at room temperature for 15 minutes, allowed to stand for 30 minutes, and the lower dichloromethane layer and the upper aqueous phase were separated. This was washed with water.
Further, the obtained lower dichloromethane layer was put into a 1000 L GL kettle, heated and concentrated. Crystal precipitation was observed during concentration. When about 100 L of dichloromethane was recovered by distillation, the concentration was stopped. 512 kg of methanol was added, the temperature was raised to 66 ° C., and the mixture was stirred for 30 minutes under reflux to dissolve the precipitated crystals. The mixture was further cooled to 5 ° C. and allowed to stand overnight to precipitate crystals, and the crystals were subjected to solid-liquid separation using a centrifuge. To the obtained 73 kg of crystals, 50 kg of dichloromethane was added, and 400 L of methanol was further added, heated and stirred to dissolve again, and then cooled to 10 ° C. to precipitate crystals. Solid-liquid separation was performed by centrifugation, and the obtained crystal was dried to obtain 56 kg of 1,3-dibromo-5,7-dimethyladamantane. As a result of dissolving the obtained white crystals in ethanol and performing GC-FID analysis, 1,3-dibromo-5,7-dimethyladamantan calculated by excluding the solvent peak was 98.02 with respect to all components. It occupied area%.

Example 1 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane according to the first production method 1,3-dibromo-5,7 in a 500 mL separable flask -Dimethyladamantane 40.40g (0.125mol) was prepared, and o-cresol 108.68g (1.01mol) was prepared. While stirring at room temperature, nitrogen was blown for several minutes to perform nitrogen substitution in the system. Nitrogen blowing was stopped and heating was started. In about 20 minutes, the temperature reached 170 ° C., and then the temperature controller was set at 170 ° C. and stirring was continued for 5 hours. After 5 hours, heating was stopped and cooling by natural cooling was started. At this time, the color of the reaction liquid was a light pink transparent liquid. When it was cooled to 99 ° C., 105.6 g of heptane was added, and natural cooling was further continued while stirring. When cooled to 39 ° C., the precipitated solid and liquid were separated by suction filtration. The solid was further rinsed by adding 104.1 g of heptane, and further solid-liquid separated by suction filtration. The collected filtrate and rinse solution were 291.7 g in total, and composition analysis was performed by GC-FID and HPLC. Crystals recovered by suction filtration were dried in a dryer at 100 ° C. for 16 hours to obtain 22.83 g of crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. It was. The composition of the crude crystals was analyzed by GC-FID and HPLC.
Of the obtained crude crystals, 150 mL of ethyl acetate was added to 22.66 g, and dissolved immediately after stirring at room temperature. When 150 mL of toluene was further added and stirred, a uniform solution was obtained. The mixture was transferred to a 1 L separatory funnel, 300 mL of a 0.5 wt% aqueous sodium hydroxide solution was added, and the mixture was stirred for 10 minutes. Allow to settle and separate the lower aqueous phase. The pH of the aqueous phase was approximately 8 on the test paper. 300 mL of pure water was added to the separatory funnel and stirred for 10 minutes. Allow to settle and separate the lower aqueous phase. The pH of the aqueous phase was approximately 7 on the test paper. The light organic solvent solution in the separatory funnel was transferred to a 500 mL eggplant flask and concentrated with an evaporator. When crystals were precipitated and almost no solvent was used, concentration was stopped, 40.63 g of ethyl acetate was added again, and the mixture was heated and stirred on a water bath at 70 ° C. to completely dissolve the crystals. 80.1 g of heptane was added to a 500 mL beaker. An organic solvent solution dissolved in a 500 mL beaker was added, and stirring was continued at room temperature for about 10 minutes to precipitate crystals. Solid-liquid separation was performed by suction filtration, followed by rinsing with 79.8 g of heptane. The collected filtrate and rinse solution were 196.3 g in total, and composition analysis was performed by GC-FID and HPLC. The solid collected by suction filtration was dried in a dryer at 100 ° C. for 16 hours to obtain 13.66 g of purified crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. It was. The composition of the crystals was analyzed by GC-FID and HPLC.
Table 1 summarizes the charged amount, reaction conditions, purification conditions, and analysis results of crystals and filtrate.

<Identification of the product of Example 1>
FIG. 1 shows the GC / MS analysis result of the product obtained in Example 1. From the mass spectrum, the molecular weight of the product was considered to be 376.
The NMR measurement results of the product obtained in Example 1 are shown below.
1H-NMR (400 MHz) (ACENETE-D6) δ: 7.89 (2H, s), 7.15 (2H, d, J = 2.2 Hz), 7.04 (2H, dd, J = 8.0) 2.2 Hz), 6.74 (2H, d, J = 8.0 Hz), 2.19 (6H, s), 1.79 (2H, s), 1.56-1.48 (8H, m). ), 1.21 (2H, s), 0.95 (6H, s)
13C-NMR (ACETONE-D6) δ: 153.92, 142.04, 128.22, 124.11, 123.83, 115.01, 50.72, 49.71, 49.21, 38.89, 32.96, 30.98, 16.46
FIG. 2 shows a 1H-NMR chart, and FIG. 3 shows assignment of 1H-NMR peaks. FIG. 4 shows a 13C-NMR chart, FIG. 5 shows a DEPT 45 ° -NMR chart, and FIG. 6 shows 13C-NMR peak assignments. Judging comprehensively from these measurement results, it can be confirmed that the product obtained in Example 1 is 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. It was.

<Example 2> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method In the same procedure as in Example 1, 1,3-dibromo- Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by reaction of 5,7-dimethyladamantane and o-cresol, and purification by alkali washing and recrystallization, A purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. Table 1 shows the items that were different from Example 1 in the charged amount, reaction conditions, and purification conditions. Table 1 summarizes the analysis results of the crystals and the filtrate.

Example 3 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method In the same procedure as in Example 1, 1,3-dibromo- Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by reaction of 5,7-dimethyladamantane and o-cresol, and purification by alkali washing and recrystallization, A purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. Table 1 shows the items that were different from Example 1 in the charged amount, reaction conditions, and purification conditions. Table 1 summarizes the analysis results of the crystals and the filtrate.

<Example 4> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method In the same procedure as in Example 1, 1,3-dibromo- Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by reaction of 5,7-dimethyladamantane and o-cresol, and purification by alkali washing and recrystallization, A purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. Table 1 shows the items that were different from Example 1 in the charged amount, reaction conditions, and purification conditions. Table 1 summarizes the analysis results of the crystals and the filtrate.

<Example 5> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method In the same procedure as in Example 1, 1,3-dibromo- 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was synthesized by the reaction of 5,7-dimethyladamantane and o-cresol, and 1,3-bis (3-methyl- Crude crystals of 4-hydroxyphenyl) -5,7-dimethyladamantane were obtained. The obtained crude crystals were analyzed without alkali washing and recrystallization. Table 1 shows the items different from those in Example 1 in the charged amount and reaction conditions. The analysis results of the crude crystals and the filtrate are summarized in Table 1. As a result of analyzing the bromine concentration and sulfur concentration by fluorescent X-ray, the bromine concentration was 531 ppm and the sulfur concentration was 29 ppm.

<Example 6> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane according to the first production method In the same procedure as in Example 1, 1,3-dibromo- Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by reaction of 5,7-dimethyladamantane and o-cresol, and purification by alkali washing and recrystallization, A purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. Table 1 shows the items that were different from Example 1 in the charged amount, reaction conditions, and purification conditions. Table 1 summarizes the analysis results of the crystals and the filtrate.

<Example 7> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method In the same procedure as in Example 1, 1,3-dibromo- Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by reaction of 5,7-dimethyladamantane and o-cresol, and purification by alkali washing and recrystallization, A purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. Table 1 shows the items that were different from Example 1 in the charged amount, reaction conditions, and purification conditions. Table 1 summarizes the analysis results of the crystals and the filtrate.

Example 8 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method In the same procedure as in Example 1, 1,3-dibromo- Synthesis of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by reaction of 5,7-dimethyladamantane and o-cresol, and purification by alkali washing and recrystallization, A purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. Table 1 shows the items that were different from Example 1 in the charged amount, reaction conditions, and purification conditions. Table 1 summarizes the analysis results of the crystals and the filtrate.

The compounds shown in Table 1 as compound (4), compound (1), isomer (2) and isomer (3) are the compounds shown below.
Compound (4): 1,3-dibromo-5,7-dimethyladamantane Compound (1): 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane isomer ( 2): Compound / isomer represented by the following formula (4) (3): Compound represented by the following formula (5)

<Production Example 2> Production of 1,3-dihydroxy-5,7-dimethyladamantane A 500 L GL kettle was charged with 25 kg of 1,3-dibromo-5,7-dimethyladamantane, and further with 150 kg of pure water and a secondary amine. 0.2 kg of some diethylamine was added. The liquid temperature was raised to 140 ° C., and the internal pressure increased to 0.35 MPa. The reaction was continued at 140 ° C. for 5 hours. After 5 hours, cooling was started, and when cooled to 70 ° C., crystals were deposited. Furthermore, it cooled to 35 degreeC, filtered, and solid-liquid separation was performed. The crystals were dried to obtain 15 kg of crude crystals. About half of the crude crystals were charged into a 500 L GL kettle, 390 L of acetone was added, the temperature was raised to 50 ° C., and the mixture was stirred for 1 hour to dissolve the crystals. 180 L of acetone was recovered by distillation and concentrated, cooled to 10 ° C., and stirred for 1 hour at 10 ° C. to precipitate crystals. Solid-liquid separation was performed by filtration, and the crystals were dried. The remaining half of the crude crystals were recrystallized by the same operation, and white crystals of 1,3-dihydroxy-5,7-dimethyladamantane were combined to obtain 10 kg. The obtained white crystals were dissolved in ethanol and analyzed by GC-FID. The result was 99.75 area% excluding the solvent peak. The result of analyzing the bromine concentration by fluorescent X-ray was 2.96 ppm.

<Example 9> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the second production method Nitrogen was passed through a 2 L separable flask to perform nitrogen substitution. , 104.68 g of 1,3-dihydroxy-5,7-dimethyladamantane was added, and 460.67 g of o-cresol was added. Stirring was performed while heating, and the temperature was raised to 80 ° C. When the temperature reached 80 ° C., dropwise addition of methanesulfonic acid was started. As a result of dropwise addition of 53.59 g over 10 minutes, the temperature was raised to 90 ° C. due to heat generation. The reaction was continued at 90 ° C. for 4 hours. After 4 hours, 400 mL of hot water at 65 to 70 ° C. was added, followed by addition of 800 mL of room temperature heptane, and the liquid temperature dropped to 65 ° C. When allowed to cool for 30 minutes, the temperature dropped to 60 ° C., and a light pink solid precipitated. The precipitated solid was filtered under reduced pressure, further rinsed with 400 mL of heptane at room temperature, and further rinsed 4 times with 800 mL of warm water. The light pink solid was dissolved in 600 mL of ethyl acetate, and 300 mL of toluene was further added. When 800 mL of a 0.5% aqueous sodium hydroxide solution was added and stirred, and then allowed to stand, the lower aqueous phase changed to pink and the upper organic phase changed to colorless. Liquid separation was performed, the organic phase was recovered, and about 500 mL of the solvent was recovered by distillation and concentrated. When 800 mL of heptane was added to a 2 L beaker, the concentrated organic solvent solution was poured, and stirring was continued for several minutes, white crystals were precipitated. The crystals were separated into solid and liquid by filtration under reduced pressure, and further rinsed with 800 mL of heptane. The crystals were dried in a dryer at 90 ° C. for 9 hours to obtain 94.7 g of purified crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. The obtained purified crystal was dissolved in ethanol and analyzed by GC-FID. As a result, it was 99.64 area% excluding the solvent peak. As a result of analyzing the bromine concentration and the sulfur concentration by fluorescent X-ray, neither was detected. The isomer ratio of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and its isomer was analyzed by HPLC. Table 2 summarizes the reaction conditions and analysis results of the purified crystals.

<Example 10> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the second production method Nitrogen was passed through a 500 mL flask to perform nitrogen substitution. , 3-Dihydroxy-5,7-dimethyladamantane (13.75 g) was added, and 60.56 g of o-cresol was added. Stirring was performed while heating, and the temperature was raised to 85 ° C. When the temperature reached 85 ° C., 13.32 g of p-toluenesulfonic acid was added. As a result, the temperature was raised to 90 ° C. due to heat generation. The reaction was continued at 90 ° C. for 7 hours. Seven hours later, 100 mL of hot water at 60 ° C. was added, the liquid temperature dropped to 73 ° C., and a light pink solid precipitated. The precipitated solid was filtered under reduced pressure, and further rinsed 4 times with 100 mL of hot water at 60 ° C. The fourth rinse was confirmed to be neutral with pH test paper. The light pink solid was dissolved in 150 mL of ethyl acetate, and further 100 mL of toluene was added, and the solid was completely dissolved. It was washed with 50 mL of pure water and the aqueous phase was discarded. Washing with 50 mL of pure water was further performed twice. When 50 mL of 0.5% aqueous sodium hydroxide solution was added and stirred and allowed to stand, the lower aqueous phase turned pink and the upper organic phase turned colorless. Liquid separation was performed, the organic phase was recovered, and about 30 mL of solvent was distilled and recovered, followed by concentration. To a 200 mL beaker, 50 mL of ethyl acetate and 100 mL of hexane were added, and the concentrated organic solvent solution was poured. When stirring was continued for several minutes, white crystals were precipitated. After further standing at 23 ° C. for 15 minutes, the crystals were subjected to solid-liquid separation by filtration under reduced pressure, and further rinsed with 100 mL of hexane. The crystals were dried in a dryer at 80 ° C. for 9 hours to obtain 14.7 g of purified crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. The obtained purified crystal was dissolved in ethanol and subjected to GC-FID analysis. As a result, it was 98.52 area% excluding the solvent peak. As a result of analyzing the bromine concentration and the sulfur concentration by fluorescent X-ray, neither was detected. The isomer ratio of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and its isomer was analyzed by HPLC. Table 2 summarizes the reaction conditions and analysis results of the purified crystals.

<Example 11> Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane according to the second production method Into a 50 L GL kettle, 1,3-dihydroxy-5,7 -3.99 kg of dimethyladamantane was charged, and 17.67 kg of o-cresol was further added. Stirring was performed while heating, and the temperature was raised to 76 ° C. When the temperature reached 76 ° C., dripping of concentrated sulfuric acid was started. As a result of dropping over 2.01 kg over 15 minutes, the temperature was raised to 90 ° C. due to heat generation. The reaction was continued at 90 ° C. for 8.5 hours. After 8.5 hours, when 20.4 kg of water was added, the liquid temperature dropped to 48 ° C. Furthermore, cooling was performed and the temperature was lowered to 4 ° C., and a solid was precipitated. The precipitated solid was filtered under reduced pressure, and further rinsed with 12.0 kg of warm water at 50 ° C. The obtained light pink solid was dispersed in 30.0 kg of hot water at 50 ° C. 200 mL of a 1 mol / L sodium hydroxide aqueous solution was added to warm water in which crystals were dispersed to neutralize the warm water. The solid dispersion was filtered under reduced pressure to perform solid-liquid separation, and further rinsed with hot water at 50 ° C. The obtained solid was added to 49.17 kg of toluene and dissolved by heating. It dissolved completely at 88 ° C. The mixture was cooled, cooled to 4 ° C., and further stirred for 1 hour to precipitate white crystals. Solid-liquid separation by vacuum filtration, rinsing with 3 L of hexane, and drying overnight with a 60 ° C. hot air dryer, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7 -5.1 kg of purified crystals of dimethyladamantane were obtained. As a result of analyzing the obtained purified crystal by GC-FID, it was 99.03 area% excluding the solvent peak. As a result of analyzing the bromine concentration and sulfur concentration by fluorescent X-ray, bromine was not detected, and the sulfur concentration was 394 ppm. By HPLC analysis, the isomer ratio of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and its isomer was analyzed. Table 2 summarizes the reaction conditions and analysis results of the purified crystals.

In Table 2 above, compound (5) is the following compound.
Compound (5): 1,3-dihydroxy-5,7-dimethyladamantane The compound (1), isomer (2), and isomer (3) are the same as those shown in Table 1. .
As described above, according to the above-mentioned Examples, the compound (1), that is, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, has high isomer selectivity. It was confirmed that it could be manufactured while realizing it. That is, in Examples 1 to 11, approximately 99% by weight or more of 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane produced was 1,3-bis (3- Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, and it was possible to reduce the total amount of isomer (2) and isomer (3) to less than 1% by weight.
And 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane selectively produced in the above-mentioned examples is aromatic because the phenolic hydroxy group exists in the para position. It is particularly suitable as a monomer used in the production of polycarbonate resin. On the other hand, the isomer (2) or isomer (3) is not suitable for producing an aromatic polycarbonate resin because the phenolic hydroxy group is present at the meta position or the ortho position.
In addition, since 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane has a methyl group as a substituent of a phenol group, an aromatic polycarbonate having a reasonably high glass transition point It has the advantage that the resin can be easily manufactured.
Furthermore, in the compound (1) produced according to the above-mentioned example, that is, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, bromine and sulfur, particularly impurities of bromine Therefore, unnecessary coloring can be prevented. In addition, in adamantane containing a large amount of sulfur as an impurity, there is a possibility that the aqueous phase and the organic phase of the reaction liquid for the polymerization reaction for producing a polycarbonate resin to be performed later cannot be easily separated. Therefore, dimethyladamantane containing a large amount of sulfur impurities is not necessarily suitable for the production of polycarbonate resin, as will be described in detail later. However, in the dimethyladamantane of the compound (1) produced according to the above examples, the concentration of sulfur as an impurity was suppressed to 400 ppm or less, which was a favorable result.

  Hereinafter, although this invention is demonstrated based on the Example of polycarbonate resin, this invention is not limited to an Example, The various numerical value and material in an Example are illustrations.

<Synthesis Example 1>
Production of 1,3-dihydroxy-5,7-dimethyladamantane 500 kg of GL kettle was charged with 25 kg of 1,3-dibromo-5,7-dimethyladamantane, and 150 kg of pure water and 0.2 kg of diethylamine, a secondary amine. Was added. When the inside of the GL kettle was heated and the liquid temperature was raised to 140 ° C., the internal pressure increased to 0.35 MPa. The reaction was continued at 140 ° C. for 5 hours. After 5 hours, cooling was started, and when cooled to 70 ° C., crystals were deposited. Furthermore, it cooled to 35 degreeC, filtered, and solid-liquid separation was performed. When the crystals were dried, 15 kg of crude crystals were obtained. About half of the crude crystals were charged into a 500 L GL kettle, 390 L of acetone was added, the temperature was raised to 50 ° C., and the mixture was stirred for 1 hour to dissolve the crystals. 180 L of acetone was recovered by distillation and concentrated, cooled to 10 ° C., and stirred for 1 hour at 10 ° C. to precipitate crystals. Solid-liquid separation was performed by filtration, and the crystals were dried. The remaining half of the crude crystals were recrystallized by the same operation, and white crystals of 1,3-dihydroxy-5,7-dimethyladamantane were combined to obtain 10 kg.

<Synthesis Example 2>
Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane Nitrogen was passed through a 2 L separable flask to perform nitrogen substitution, and 1,3-dihydroxy-5,7- 104.68 g of dimethyladamantane was charged, and 460.67 g of o-cresol was further added. Stirring was performed while heating the flask, and the temperature was raised to 80 ° C. When the temperature reached 80 ° C., dropwise addition of methanesulfonic acid was started. As a result of dropwise addition of 53.59 g over 10 minutes, the temperature was raised to 90 ° C. due to heat generation. The reaction was continued at 90 ° C. for 4 hours. After 4 hours, 400 mL of hot water at 65 to 70 ° C. was added to the reaction solution, and then 800 mL of heptane at room temperature was added, and the temperature of the solution dropped to 65 ° C. When the reaction solution was allowed to cool for 30 minutes, the temperature was lowered to 60 ° C., and a light pink solid was deposited. The precipitated solid was filtered under reduced pressure, rinsed with 400 mL of heptane at room temperature, and further rinsed 4 times with 800 mL of hot water. The light pink solid was dissolved in 600 mL of ethyl acetate, and 300 mL of toluene was further added. When 800 mL of a 0.5% aqueous sodium hydroxide solution was added and stirred, and then allowed to stand, the lower aqueous phase changed to pink and the upper organic phase changed to colorless. Liquid separation was performed, the organic phase was recovered, and about 500 mL of the solvent was recovered by distillation and concentrated. When 800 mL of heptane was added to a 2 L beaker, the concentrated organic solvent solution was poured, and stirring was continued for several minutes, white crystals were precipitated. The crystals were separated into solid and liquid by filtration under reduced pressure, and further rinsed with 800 mL of heptane. The crystals were dried in a dryer at 90 ° C. for 9 hours to obtain 94.7 g of purified crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. This monomer is hereinafter referred to as BPCDMA.

<Synthesis Example 3>
Production of 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane A nitrogen flow was performed by flowing nitrogen into a 300 L GL kettle, and 1,3-dihydroxy-5,7-dimethyladamantane was 14.99 kg. Was added, and 57.34 kg of phenol was further added. Stirring was performed while heating, and the temperature was raised to 80 ° C. When the temperature reached 80 ° C., dropwise addition of methanesulfonic acid was started. As a result of dropping over 7.34 kg over 30 minutes, the temperature was raised to 100 ° C. due to heat generation. The reaction was continued for 6 hours at 100 ° C. Cooling was started after 6 hours, and the mixture was cooled to 60 ° C. 54 L of a water / methanol 1: 1 mixed solvent was added to the reaction solution, and the mixture was naturally cooled while stirring to precipitate a solid. The reaction solution was allowed to stand for 16 hours while stirring. The precipitated solid was subjected to solid-liquid separation with a centrifugal filter, and further rinsed with 26 L of water / methanol 1: 1 mixed solvent. The obtained white solid was dissolved in 90 kg of ethyl acetate, and the solution was transferred to a 200 L GL kettle by a pump. An additional 43 kg of toluene was added. After adding 50 L of 0.5% aqueous sodium hydroxide solution and stirring, the mixture was allowed to stand. Liquid separation was performed and the aqueous phase was discarded. To the organic phase, 50 L of a 0.5% aqueous sodium hydroxide solution was added again, and the mixture was stirred and allowed to stand. Liquid separation was performed and the aqueous phase was discarded. The pH of the second aqueous phase was confirmed to be approximately 8 using pH test paper. Further, 50 L of pure water was added and stirred, and then allowed to stand. Liquid separation was performed and the aqueous phase was discarded. The organic phase was collected in a 200 L stainless steel bucket. The filter was passed through a 200 L GL kettle that had been washed. Concentration was carried out under reduced pressure, and the solvent was distilled off until a small amount of crystals was precipitated. Further, ethyl acetate was added, heated and stirred, and dissolved again. The total amount was about 100 L. 150 L heptane was added to a 300 L vessel. Into it, an ethyl acetate solution was added with stirring to precipitate white crystals. Furthermore, it was left to stand in a freezer at −20 ° C. for 16 hours to precipitate crystals. The crystals were separated into solid and liquid by filtration under reduced pressure, and further rinsed with 30 L of heptane. The crystals were dried at 80 ° C. for 3 days to obtain 17.15 kg of purified crystals of 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane.
This monomer is hereinafter referred to as BPDMA.

<Synthesis Example 4>
According to the production method described as Example 11 (production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the second production method), 1,3-bis ( 3-Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was obtained. In this 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, bromine was not detected and the sulfur concentration was 394 ppm.
This monomer is hereinafter referred to as BPCDMA-2.

<Example 12>
In 400 ml of 5% by mass aqueous sodium hydroxide solution, 40.0 g (0.106 mol) of BPCDMA obtained in Synthesis Example 2, 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. . Then, 17.0 g (0.172 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 350 ml of methylene chloride and stirring. After completion of phosgene blowing, 0.460 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and 100 ml of 5% by weight aqueous sodium hydroxide and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was added dropwise to warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.71 × 10 ⁴ , a glass transition temperature of 213 ° C., and a pencil hardness of 2H.
<Example 13>
In 400 ml of 5% by weight aqueous sodium hydroxide solution, 36.85 g (0.098 mol) of BPCDMA obtained in Synthesis Example 2, 9.58 g (0.042 mol) of 2,2-bis (4-hydroxyphenyl) ) Propane (manufactured by Nippon Steel Chemical Co., Ltd., hereinafter abbreviated as BPA), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. To this, 300 ml of methylene chloride was added and stirred, and 22.2 g (0.224 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. After the completion of phosgene blowing, 0.617 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.72 × 10 ⁴ , a glass transition temperature of 195 ° C., and a pencil hardness of H.
<Example 14>
In 400 ml of 5% by mass aqueous sodium hydroxide solution, 27.30 g (0.073 mol) of BPCDMA obtained in Synthesis Example 2, 16.56 g (0.073 mol) of BPA, 0.3 g of hydrosulfite, 0.03 g of triethylbenzylammonium chloride was dissolved. Then, 23.7 g (0.239 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.648 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5 mass% sodium hydroxide solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 2.76 × 10 ⁴ , a glass transition temperature of 180 ° C., and a pencil hardness of F.
<Example 15>
In 450 ml of 5% by weight aqueous sodium hydroxide solution, 18.95 g (0.050 mol) of BPCDMA obtained in Synthesis Example 2, 26.81 g (0.118 mol) of BPA, 0.3 g of hydrosulfite, 0.03 g of triethylbenzylammonium chloride was dissolved. Then, 27.9 g (0.282 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.760 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5 mass% sodium hydroxide solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.69 × 10 ⁴ , a glass transition temperature of 164 ° C., and a pencil hardness of HB.
<Example 16>
In 400 ml of 5% by weight aqueous sodium hydroxide solution, 27.30 g (0.073 mol) of BPCDMA obtained in Synthesis Example 2, 18.69 g (0.073 mol) of 2,2-bis (3-methyl- 4-hydroxyphenyl) propane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as BPC), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 24.3 g (0.245 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After the completion of the phosgene blowing, 0.645 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.75 × 10 ⁴ , a glass transition temperature of 161 ° C., and a pencil hardness of 2H.
<Example 17>
27.30 g (0.073 mol) of BPCDMA obtained in Synthesis Example 2 and 19.56 g (0.073 mol) of 1,1-bis (4-hydroxyphenyl) in 450 ml of 5% by weight aqueous sodium hydroxide solution ) -Cyclohexane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as BPZ), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 23.4 g (0.236 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.585 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was added dropwise to warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.62 × 10 ⁴ , a glass transition temperature of 187 ° C., and a pencil hardness of 2H.
<Example 18>
In 550 ml of 5% by weight aqueous sodium hydroxide solution, 32.0 g (0.085 mol) of BPCDMA obtained in Synthesis Example 2 and 27.0 g (0.085 mol) of 1,1-bis (3-methyl- 4-hydroxyphenyl) -1-phenylethane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as BPCAP), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 27.6 g (0.279 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of phosgene blowing, 0.713 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.60 × 10 ⁴ , a glass transition temperature of 176 ° C., and a pencil hardness of 2H.
<Example 19>
In 650 ml of a 5% by weight aqueous sodium hydroxide solution, 52.45 g (0.139 mol) of BPCDMA obtained in Synthesis Example 2 and 8.6 g (0.046 mol) of 4,4-biphenol (Honshu Chemical Co., Ltd.) Made by company, hereinafter abbreviated as BP), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 30.1 g (0.304 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After the completion of the phosgene blowing, 0.805 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and 100 ml of 5% by mass aqueous sodium hydroxide and 100 ml of methylene chloride were further added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 3.27 × 10 ⁴ , a glass transition temperature of 209 ° C., and a pencil hardness of H.
<Example 20>
In 550 ml of 5% by weight aqueous sodium hydroxide solution, 34.97 g (0.093 mol) of BPCDMA obtained in Synthesis Example 2, 19.90 g (0.093 mol) of 1,1-bis (4-hydroxyphenyl) ) Ethane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter abbreviated as BPE), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 29.6 g (0.299 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.912 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight aqueous sodium hydroxide and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water maintained at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery anti-precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.84 × 10 ⁴ , a glass transition temperature of 168 ° C., and a pencil hardness of F.
<Example 21>
In 550 ml of 5% by weight aqueous sodium hydroxide solution, 34.97 g (0.093 mol) of BPCDMA obtained in Synthesis Example 2, 18.69 g (0.093 mol) of bis (4-hydroxyphenyl) methane (Honshu) Chemical Industry Co., Ltd. (hereinafter abbreviated as BPF), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 30.1 g (0.304 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.676 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight aqueous sodium hydroxide and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 3.51 × 10 ⁴ , a glass transition temperature of 167 ° C., and a pencil hardness of F.
<Example 22>
In 400 ml of 5% by weight aqueous sodium hydroxide solution, 40.0 g (0.106 mol) of BPCDMA-2, 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 17.0 g (0.172 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 350 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.460 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were further added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added, and the mixture was stirred at 20 ° C. to 25 ° C. for about 1 hour for polymerization. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was added dropwise to warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 2.00 × 10 ⁴ , a glass transition temperature of 200 ° C., and a pencil hardness of 2H.

<Comparative Example 1>
34.3 g (0.168 mol) of BPA and 0.3 g of hydrosulfite were dissolved in 450 ml of a 5% by mass aqueous sodium hydroxide solution. Then, 21.6 g (0.218 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of phosgene blowing, 0.770 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 2.75 × 10 ⁴ , a glass transition temperature of 150 ° C., and a pencil hardness of 2B.
<Comparative example 2>
37.38 g (0.146 mol) of BPC, 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved in 400 ml of a 5% by mass aqueous sodium hydroxide solution. Then, 21.7 g (0.219 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After the completion of the phosgene blowing, 0.645 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 110 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 3.22 × 10 ⁴ , a glass transition temperature of 123 ° C., and a pencil hardness of 2H.
<Comparative Example 3>
In 450 ml of 5% by weight aqueous sodium hydroxide solution, 22.53 g (0.088 mol) BPC, 13.5 g (0.059 mol) BPA, 0.3 g hydrosulfite, 0.03 g triethylbenzylammonium The chloride was dissolved. Then, 21.7 g (0.219 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After the completion of the phosgene blowing, 0.645 g of p-tert-butylphenol made by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 110 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.66 × 10 ⁴ , a glass transition temperature of 131 ° C., and a pencil hardness of F.
<Comparative Example 4>
In 450 ml of 5% by weight aqueous sodium hydroxide solution, 43.22 g (0.146 mol) of 1,1-bis (3-methyl-4-hydroxyphenyl) -cyclohexane (Honshu Chemical Co., Ltd., hereinafter abbreviated as BPCZ) ), 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 21.8 g (0.220 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 300 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.753 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 1.81 × 10 ⁴ , a glass transition temperature of 138 ° C., and a pencil hardness of 2H.
<Comparative Example 5>
In 450 ml of 5% by weight aqueous sodium hydroxide solution, 60.00 g (0.203 mol) of BPCZ, 12.5 g (0.055 mol) of BPA, 0.3 g of hydrosulfite, 0.03 g of triethylbenzylammonium The chloride was dissolved. Then, 39.0 g (0.394 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 400 ml of methylene chloride and stirring. After completion of phosgene blowing, 1.11 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5 mass% sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.31 × 10 ⁴ , a glass transition temperature of 140 ° C., and a pencil hardness of H.
<Comparative Example 6>
5400 g (0.157 mol) of BPCAP, 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride were dissolved in 400 ml of a 5% by mass aqueous sodium hydroxide solution. To this, 350 ml of methylene chloride was added and stirred, and 23.0 g (0.232 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. After completion of the phosgene blowing, 0.730 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and 100 ml of 5% by weight aqueous sodium hydroxide and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 1.66 × 10 ⁴ , a glass transition temperature of 150 ° C., and a pencil hardness of 2H.
<Comparative Example 7>
42.80 g (0.200 mol) of BPE and 0.3 g of hydrosulfite were dissolved in 350 ml of 5% by mass aqueous sodium hydroxide solution. Then, 27.9 g (0.282 mol) of phosgene was blown in over 20 minutes while keeping the temperature at 15 ° C. while adding 250 ml of methylene chloride and stirring. After completion of phosgene blowing, 1.75 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by weight sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 110 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. This polycarbonate resin had a viscosity average molecular weight of 2.00 × 10 ⁴ , a glass transition temperature of 125 ° C., and a pencil hardness of 2B.
<Comparative Example 8>
3450 g (0.115 mol) of BPDMA obtained in Synthesis Example 3 and 0.3 g of hydrosulfite were dissolved in 450 ml of a 5% by mass aqueous sodium hydroxide solution. Then, 17.0 g (0.172 mol) of phosgene was blown in over 20 minutes while maintaining the temperature at 15 ° C. while adding 350 ml of methylene chloride and stirring. After completion of the phosgene blowing, 0.555 g of p-tert-butylphenol manufactured by DIC Corporation was added as a molecular weight regulator, and further 100 ml of 5% by mass sodium hydroxide aqueous solution and 100 ml of methylene chloride were added and stirred vigorously. After emulsifying the reaction solution, 1 ml of triethylamine was added and stirred at 20 ° C. to 25 ° C. for about 1 hour to proceed the polymerization reaction. After completion of the polymerization, the reaction solution is separated into an aqueous phase and an organic phase, the organic phase is neutralized with phosphoric acid, and washing with water is repeated until the conductivity of the washing solution (aqueous phase) is 10 μS / cm or less, and the resulting resin The solution was dropped into warm water kept at 50 ° C., and the solvent was removed by evaporation. At the same time, the solidified product was pulverized to obtain a white powdery precipitate. The obtained precipitate was filtered and dried at 120 ° C. for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 2.37 × 10 ⁴ , a glass transition temperature of 256 ° C., and a pencil hardness of B.

As described above, according to the above-described embodiment, by using BPCDMA as a monomer, that is, using 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane as a monomer, It was confirmed that an aromatic polycarbonate resin having a high transition point, excellent heat resistance, and high surface hardness can be produced.
On the other hand, in the comparative example bisphenol-derived polycarbonate resin produced using BPA or the like as the main monomer component, it can be said that the properties of heat resistance and surface hardness are inferior to those of the above-described polycarbonate resin.
In Example 22, although BPCDMA-2 having a relatively high sulfur concentration as an impurity was used, no particular problem occurred. More specifically, Example 12 using BPCDMA obtained in Synthesis Example 2 and containing almost no sulfur impurities, and about 394 ppm of sulfur impurities obtained in Synthesis Example 4 are included. Comparing the results of Example 22 using BPCDMA-2, the latter polymerization reaction using BPCDMA-2 tended to slightly separate the water phase and the organic phase of the reaction solution after polymerization. Therefore, a decrease in molecular weight, a decrease in yield, and an increase in terminal OH group were observed in the produced polycarbonate resin (in Example 12, the molecular weight of the PC resin was 27,100, the yield was 88%, the terminal OH group The proportion was 60 ppm, whereas in Example 22, the molecular weight of the PC resin was 20,000, the yield was 66%, and the proportion of terminal OH groups was 570 ppm.

The 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the present invention can be used as a raw material for various resins, and 1,3-bis (3-methyl-4 By using -hydroxyphenyl) -5,7-dimethyladamantane, a resin excellent in heat resistance, optical properties, and mechanical properties can be produced, and thus its industrial significance is great.

Claims (18)

  1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane.   1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane having a bromine concentration as an impurity of 500 ppm or less and a sulfur concentration of 400 ppm or less.   1,3-bis (methyl-hydroxyphenyl) -5 having 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane as a main component and an isomer purity of 98% or more , 7-dimethyladamantane.   A method for producing 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, comprising reacting 1,3-dibromo-5,7-dimethyladamantane with o-cresol.   1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyl, characterized by reacting 1,3-dihydroxy-5,7-dimethyladamantane with o-cresol in the presence of an acid catalyst A method for producing adamantane.   After the reaction, a poor solvent was added and stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, and then the crude crystals were separated. 6. The 1,3-bis (3-methyl-4 according to claim 4 or 5, wherein impurities are removed by washing a solution in which the separated crude crystals are dissolved in an organic solvent with an alkaline aqueous solution. -Hydroxyphenyl) -5,7-dimethyladamantane production method.   After the reaction, a poor solvent was added and stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, and then the crude crystals were separated. 6. A solution in which the separated crude crystals are dissolved in an organic solvent is washed with an alkaline aqueous solution, further dissolved in an organic solvent, and a poor solvent is added to precipitate crystals. A process for producing 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane as described in 1. above. An aromatic polycarbonate resin containing a structural unit derived from 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane represented by the following formula (1).
  1,3-bis (methyl-hydroxyphenyl)-, the isomer purity of which is the main component of the 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and is 98% or more The aromatic polycarbonate resin according to claim 8, comprising a structural unit derived from 5,7-dimethyladamantane. Furthermore, the aromatic polycarbonate resin of Claim 8 or 9 containing the structural unit represented by following General formula (2).

(In formula (2), R _{1 to} R ₄ are each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a C 1-20 alkyl group that may have a substituent, It represents any of an alkoxy group having 1 to 5 carbon atoms and an aryl group having 6 to 12 carbon atoms, where X is a single bond, a sulfur atom, a sulfonyl group, an alkylidene group having 2 to 10 carbon atoms, or an alkyl group having 5 to 12 carbon atoms. (Represents any one of a cycloalkylidene group, an arylalkylidene group having 7 to 15 carbon atoms, and a fluorenylidene group.)   The structural unit represented by the general formula (2) is 1,1′-biphenyl-4,4′-diol (BP), bis (4-hydroxyphenyl) methane (BPF), 1,1-bis (4- Hydroxyphenyl) ethane (BPE), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ) Ketone, 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-) Hydroxyphenyl) propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis ( -Hydroxyphenyl) cyclohexane (BPZ), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) -1-phenylethane (BPCAP), 9,9-bis (4-hydroxy) Phenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, α, ω-bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, α, ω-bis [3- ( o-hydroxyphenyl) propyl] polydimethylsiloxane and 4,4 ′-[1,3-phenyle] The aromatic polycarbonate resin according to claim 10, which is at least one selected from the group consisting of bis (1-methylethylidene)] bisphenol. The aromatic polycarbonate resin according to any one of claims 8 to 11, having a viscosity average molecular weight of 1.0 x 10 ^{4 to} 8.0 x 10 ⁴ .   The novel aromatic polycarbonate resin as described in any one of Claims 8-12 whose content rate of the structural unit represented by the said Formula (1) is 10-100 mol%.   The aromatic polycarbonate resin according to any one of claims 8 to 13, having a glass transition temperature of 160 ° C or higher.   The aromatic polycarbonate resin according to any one of claims 8 to 14, wherein the pencil hardness is HB or more.   The film and sheet | seat using the aromatic polycarbonate as described in any one of Claims 8-15.   The film and sheet according to claim 16, wherein the film and sheet are transparent conductive films. The manufacturing method of aromatic polycarbonate resin as described in any one of Claims 8-15 using the 1, 3- dihydroxy-5,7- dimethyladamantane represented by following formula (3) as a raw material.