KR20170072866A - 1,3-bis(3-methyl-4-hydroxyphenyl)-5,7-dimethyl-adamantane and method for preparing same, and aromatic polycarbonate resin and method for preparing same - Google Patents

Abstract

1,3-bis (3-methyl-4-hydroxyphenyl) -5, which is a novel bisphenol compound having an adamantane skeleton, which can be used as a raw material for various resins having excellent heat resistance, optical characteristics, Providing 7-Dimethyladamantane Compounds. It is a further object of the present invention to provide a polycarbonate resin and a resin composition which are excellent in heat resistance and have a high surface height. The above object is achieved by a process for producing a 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane compound, a process for producing the same, and further comprising a constitutional unit represented by the following formula By weight of the aromatic polycarbonate resin.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, a process for producing the same, an aromatic polycarbonate resin, 4-HYDROXYPHENYL) -5,7-DIMETHYL-ADAMANTANE AND METHOD FOR PREPARING SAME, AND AROMATIC POLYCARBONATE RESIN AND METHOD FOR PREPARING SAME}

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 heat resistance, optical properties, 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 made from bisphenols as raw materials are used for various purposes by taking advantage of heat resistance, optical characteristics, and mechanical strength characteristics. Particularly, when used as an optical resin, a problem such as coloring is caused by the influence of trace impurities contained in bisphenols as raw materials is described in Patent Document 1, and a bisphenol of high purity is required.

As a bisphenol having an adamantane skeleton among its bisphenols, Patent Document 2 discloses 1,3-bis (4-hydroxyphenyl) -1,3-bis (4-hydroxyphenyl) Hydroxyphenyl) -5,7-dimethyladamantane are described.

Patent Document 3 discloses a process for producing an aromatic dihydroxy compound by reacting 1,3-adamantanediol and phenol in the presence of hydrochloric acid to synthesize 1,3-bis (4-hydroxyphenyl) adamantane And purification is carried out by silica gel chromatography.

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

In addition, polycarbonate resins are widely used in various fields because they exhibit excellent electrical properties, flame retardance, transparency, dimensional stability, and mechanical properties and are lightweight. Particularly, a polycarbonate resin (BPA-PC) derived from bisphenol A is inexpensive, excellent in transparency and impact strength, and is used as a substitute material for inorganic glass in electrical and electronic parts, automobile parts, and building materials.

In general, BPA-PC uses a silicone-based or acrylic-based material to hard coat the surface of a molded article or laminate an acrylic polymer material layer to improve heat resistance and surface hardness. 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 article to improve the surface strength.

However, in these methods, since the layers made of different materials are bonded to each other, adhesion failure is likely to occur, and there is a problem in that warpage tends to occur due to difference in absorption rate and difference in linear expansion coefficient. In addition, from the viewpoint of recycling after use, there is also a drawback that it is difficult to separate and collect.

International Publication No. 2002-022536 US Patent No. 3594427 Japanese Patent Application Laid-Open No. 2000-95720 Japanese Patent Application Laid-Open No. 2003-306460 Japanese Patent Application Laid-Open No. 2007-145015 Japanese Patent Application Laid-Open No. 2011-089049 Japanese Patent Application Laid-Open No. H06-068381 Japanese Patent Application Laid-Open No. H05-093057

First, with regard to the adamantane compound, the use of phenol is described in the synthesis of 1,3-bis (4-hydroxyphenyl) adamantane described in Patent Document 2, but the use of o-cresol The use thereof is not described. Patent Document 3 discloses a production example of 1,3-bis (4-hydroxyphenyl) adamantane, but does not describe an example of the use of substituted adamantane or o-cresol . In addition, in the examples of Patent Document 4, only adamantane having no substituent is reported in the adamantane skeleton of 1,3-bis (4-hydroxyphenyl) adamantane.

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

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

Further, in order to solve the above-mentioned problem concerning the polycarbonate resin, a polycarbonate resin having a special structure has been proposed. For example, in Patent Documents 6 and 7, 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC) is used instead of bisphenol A (BPA) as a dihydroxy compound constituting polycarbonate. (3-methyl-4-hydroxyphenyl) -1-phenylethane (BPCAP), 9,9-bis It has been proposed that the polycarbonate resin itself has a function of modifying the surface hardness by using 1-bis (3-methyl-4-hydroxyphenyl) cyclohexane (BPCZ) or the like.

However, all of these polycarbonate resins have a glass transition temperature of 160 占 폚 or less and have a problem in terms of heat resistance.

Further, 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 캜 or higher, but their surface hardness is not satisfactory.

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

As a result of intensive investigations, the inventors of the present invention have found that 1,3-bis (3 (meth) acrylate), which can be used as a resin raw material, -Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane can be prepared.

That is, the present invention is as follows.

[One]

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 of 500 ppm or less as an impurity and a sulfur concentration of 400 ppm or less.

[3]

Bis (methyl-hydroxyphenyl) -5 (meth) acrylate having an isomer purity of not less than 98% and having 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane as a main component , 7-dimethyladamantane.

[4]

Bis (3-methyl-4-hydroxyphenyl) -5,7-dimethylanthraquinone, which is characterized in that 1,3-dibromo-5,7-dimethyladamantane is reacted with o- Just a method of making a shot.

[5]

(3-methyl-4-hydroxyphenyl) -5, 5-dihydroxy-5,7-dimethyladamantane and o-cresol in the presence of an acid catalyst, 7-Dimethyladamantane.

[6]

After the reaction, a poor solvent was added and the mixture was stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, (3-methyl-4-hydroxynaphthoquinone) according to [4] or [5], wherein the solution obtained by dissolving the separated crude crystals in an organic solvent is washed with an alkaline aqueous solution to remove impurities. Hydroxyphenyl) -5,7-dimethyladamantane.

[7]

After the reaction, a poor solvent was added and the mixture was stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, [4] or [5], characterized in that a solution obtained by dissolving the separated crude crystals in an organic solvent is washed with an alkaline aqueous solution, again dissolved in an organic solvent, and a poor solvent is added to precipitate crystals Bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane.

As a result of intensive studies on the problems of realizing the high heat resistance and high surface hardness of the polycarbonate resin, the present inventors have found that the above problems can be solved by the following polycarbonate resin, Respectively.

The present invention is as follows.

[8]

An aromatic polycarbonate resin containing a constituent unit derived from 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane represented by the following formula (1).

[Chemical Formula 1]

[9]

1,3-bis (methyl-hydroxyphenyl) - 5,7-dimethyladamantane whose main component is 1,3-bis (3-methyl-4-hydroxyphenyl) The aromatic polycarbonate resin according to [8], which contains a constituent unit derived from 5,7-dimethyladamantane.

[10]

The aromatic polycarbonate resin according to [8] or [9], further comprising a structural unit represented by the following general formula (2).

(2)

(Wherein R ₁ to R ₄ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 1 to 5 carbon atoms A halogen atom, a sulfonyl group, an alkylidene group having 2 to 10 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, a cycloalkylidene group having 7 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, An alkylarylidene group or a fluorenylidene group of 1 to 10 carbon atoms.

[11]

Wherein the constituent unit represented by the general formula (2) is at least one selected from the group consisting of 1,1'-biphenyl-4,4'-diol (BP), bis (4-hydroxyphenyl) methane (BPF) 4-hydroxyphenyl) ethane (BPE), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, (4-hydroxyphenyl) propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) BPZ), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl- 4-hydroxyphenyl) ?,? - bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane,?,? - bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, and 4,4 '- [1,3-phenylenebis (1-methylethylidene)] bisphenol. Wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin.

[12]

The aromatic polycarbonate resin according to any one of [8] to [11], wherein the viscosity average molecular weight is 1.0 × 10 ⁴ to 8.0 × 10 ⁴ .

[13]

The novel aromatic polycarbonate resin according to any one of [8] to [12], wherein the content of the structural unit represented by the formula (1) is 10 to 100 mol%.

[14]

The aromatic polycarbonate resin according to any one of [8] to [13], wherein the glass transition temperature is 160 占 폚 or more.

[15]

The aromatic polycarbonate resin according to any one of [8] to [14], wherein the pencil hardness is at least HB.

[16]

A film and a sheet using the aromatic polycarbonate according to any one of [8] to [15].

[17]

The film and sheet according to [16], wherein the film and the sheet are transparent conductive films.

[18]

[8] to [15], wherein 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane represented by the following formula (3) ≪ / RTI > wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin.

(3)

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.

Further, in the present invention, it is possible to provide a novel polycarbonate resin having a high heat resistance and a high surface hardness, which has not been achieved conventionally.

1 shows the GC / MS analysis results of the product obtained in Example 2 (1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane).
Fig. 2 shows the results of < 1 > H-NMR analysis of the product obtained in Example 2. Fig.
3 shows the binding of a peak of 1H-NMR of the product obtained in Example 2. Fig.
Fig. 4 shows the results of 13 C-NMR analysis of the product obtained in Example 2. Fig.
Figure 5 shows the results of a DEPT 45 ° -NMR analysis of the product obtained in Example 2.
Fig. 6 shows the 13C-NMR peak attribution of the product obtained in Example 2. Fig.

Hereinafter, a mode for carrying out the present invention relating to a novel adamantane compound (hereinafter simply referred to as " present embodiment ") will be described in detail. The following embodiments are illustrative of the present invention and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the present invention.

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

[Chemical Formula 4]

In the 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the formula (3) of the present embodiment, a compound represented by the following formula (4) A small amount of an isomer may be contained. As the amount of these isomers increases, the physical properties of the resin prepared from the bisphenol compound as a raw material may be adversely affected. Therefore, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane Is preferably 98% or more, and more preferably 99% or more.

Namely, in the present embodiment, 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane is used as the main component and 1,3-bis (3-methyl- (4) or (5), which is a substituent of the phenyl group and the position of the phenolic hydroxyl group, .

[Chemical Formula 5]

[Chemical Formula 6]

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

The 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the present embodiment can be obtained by, for example, an epoxy resin, a photosensitive resin, a cyanate resin, (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane can be used as a raw material for various resins and excellent heat resistance, optical characteristics, and mechanical strength characteristics can be obtained Resin can be produced.

The 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of the present embodiment is 1,3-dibromo-5,7 -Dimethyladamantane with o-cresol (first production method).

(7)

The 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane is 1,3-dihydroxy-5,7-dimethyl Can also be prepared by reacting adamantane and o-cresol in the presence of an acid catalyst (second production method).

[Chemical Formula 8]

Hereinafter, the first manufacturing method of the present embodiment will be described.

The 1,3-dibromo-5,7-dimethyladamantane used as a raw material in the first production method can be obtained by a known method described in JP-A-2002-145809, Method. ≪ / RTI >

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

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

Although a solvent can be used in the reaction of the first production method of the present embodiment, 1,3-dibromo-5,7-dimethyladamantane is susceptible to solvolysis, and the reaction temperature is set to be high Inert solvents which are inert and have a high boiling point are preferred. More preferably, no reaction solvent is used.

The reaction time in the first production method is preferably from 1 to 15 hours, more preferably from 2 to 10 hours, even more preferably from 3 to 8 hours, though it varies depending on the reaction temperature. When the reaction time is less than 1 hour, a lot of raw materials and reaction intermediates remain.

When the conversion rate of 1,3-dibromo-5,7-dimethyladamantane as raw material is less than 75% at the end of the reaction, a large amount of organic bromine compounds such as raw materials and intermediates remain, It becomes difficult to remove impurities in the process. Therefore, the conversion rate of 1,3-dibromo-5,7-dimethyladamantane is preferably 75% or more. In order to make the conversion rate of 1,3-dibromo-5,7-dimethyladamantane not less than 75%, for example, at a reaction temperature of 170 ° C, 1,3-dibromo-5,7- However, o-cresol having an 8 to 13-fold molar amount relative to the carbon may be used, and the reaction time may be 5 hours or more.

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

In the first production method of the present embodiment, the reaction of 1,3-dibromo-5,7-dimethyladamantane with o-cresol produces by-produced hydrogen bromide, so that 1,3-bis -4-hydroxyphenyl) -5,7-dimethyladamantane as a bromide impurity. The crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane obtained after the reaction were dissolved in an organic solvent and washed with an alkaline aqueous solution to remove the bromine impurity , The bromine concentration can be lowered. Further, the remaining o-cresol can be removed by washing with an alkaline aqueous solution. Further, by performing cleaning with an alkaline aqueous solution, the red coloring causing substance or o-cresol can be easily washed away to the water side.

Examples of the organic solvent used for dissolving the crude crystals include ethyl acetate, toluene, acetone, methanol and the like, with ethyl acetate and acetone being more preferred, and ethyl acetate being more preferred.

The alkaline aqueous solution used for the above washing is not particularly limited, but an aqueous alkali metal hydroxide solution is preferable. The alkali metal hydroxide to be used for the alkali metal hydroxide aqueous solution is preferably sodium hydroxide. When sodium hydroxide is used, when the concentration of aqueous sodium hydroxide solution is excessively high, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantanisodium phenolate salt Monosodium phenolate salt is dispersed in water and the monosodium phenolate salt is difficult to dissolve in both the organic phase and water phase, and thus crystals are precipitated as crystals. Therefore, all 1,3-bis (3-methyl -4-hydroxyphenyl) -5,7-dimethyladamantane. The concentration of the sodium hydroxide aqueous solution used for washing the crude crystals is preferably 0.1 to 1.0% by weight. More preferably from 0.2 to 0.8% by weight, and still more preferably from 0.3 to 0.6% by weight.

After the cleaning with the alkali metal hydroxide aqueous solution, it is more preferable to clean with pure water in order to prevent the incorporation of alkali metal.

By the above cleaning operation, the concentration of the bromine-containing compound can be reduced. However, in consideration of the possibility that the concentration of the bromine-containing compound can not be completely removed, it is preferable to carry out purification by recrystallization again. Recrystallization can be carried out by stirring and heating the minimum amount of organic solvent with heating and stirring to dissolve, adding a poor solvent, and stirring. The combination of a solvent and a poor solvent is not particularly limited. For example, when ethyl acetate is used as a solvent and heptane is used as a poor solvent, 1,3-bis (3 Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane was added ethyl acetate in an amount of 1.5 to 3 times the weight of the crude crystals, and the mixture was heated and stirred to dissolve the crystals, followed by the addition of ethyl acetate (3-methyl-4-hydroxyphenyl) -5,7-dihydroxyphenyl) heptane is preferably added in an amount of 1 to 5 times, more preferably 2 to 4 times, The crystals of dimethyladamantane can be precipitated at a high recovery rate. Even if the amount of heptane to be added is 5 times or more the weight of ethyl acetate, the recovery rate of the crystals is not remarkably improved, and the problem is that the impurities are rather increased. Further, in the case of heptane amount not more than 1 time, the recovery rate of crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane decreases, which is not preferable.

By the above purifying method, that is, the crude crystals are dissolved in an organic solvent, and the impurities are reduced by washing with an alkali metal hydroxide aqueous solution, pure washing and further recrystallization.

Hereinafter, the second manufacturing method of the present embodiment will be described.

In the second production method, 1,3-dihydroxy-5,7-dimethyladamantane and o-cresol are reacted in the presence of an acid catalyst to obtain 1,3-bis (3-methyl- 5,7-dimethyladamantane is prepared.

1,3-Dihydroxy-5,7-dimethyladamantane used as a raw material in the second production method of the present embodiment can be produced by 1,3-dimethyladamantane in the presence of an imide compound and a cobalt compound, A method in which 1,3-dimethyladamantane is oxidized with chromic acid, a method in which 1,3-dimethyladamantane is dihalogenated and hydrolyzed, and the like. It is possible to synthesize by the method.

In this embodiment, 1,3-dihydroxy-5,7-dimethyladamantane synthesized by any of the methods described above or other than the above can also be used.

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

As the acid catalyst used in the reaction in the second production method, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, strongly acidic cation-exchange resin and the like are preferable. In the case of using an acid including water such as hydrochloric acid and dilute sulfuric acid, the progress of the reaction becomes slow. When the non-aqueous sulfuric acid is used, 1,3-bis (3-methyl-4-hydroxyphenyl) , 7-dimethyladamantane are sulfonated and easily remain as sulfur doping impurities, making it difficult to remove them.

The amount of the acid catalyst to be used is preferably from 0.1 to 3 times, more preferably from 0.3 to 2 times, still more preferably from 0.5 to 1.5 times, in terms of a molar ratio to 1,3-dihydroxy-5-adamantane Do.

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

The reaction temperature in the second production method of the present embodiment is preferably in the range of 90 to 190 캜 because the reaction is delayed and the reaction intermediate and the isomer are left in excess.

The reaction time in the second production method varies depending on the reaction temperature, but is preferably 1 to 36 hours, more preferably 2 to 24 hours, and further preferably 3 to 10 hours. When the reaction time is less than 1 hour, a lot of raw materials and reaction intermediates remain.

In the second production method of the present embodiment, after the completion of the reaction, a poor solvent is added and stirring is performed to obtain 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane A crude crystal can be precipitated. As the poor solvent, hot water, toluene and the like can be used, but n-heptane, n-hexane, mixed solvent such as water / methanol, water / ethanol and the like can be suitably used. Particularly, n-heptane and n-hexane are used as preferred poor solvents.

After precipitating the crude crystals, solid-liquid separation is carried out by filtration, centrifugation or the like. The crude crystals after the solid-liquid separation are again washed with a poor solvent and subjected to filtration, whereby o-cresol and an acid catalyst in an excess amount can be washed away, and further purification steps can be easily performed. As a poor solvent to be used for cleaning, n-heptane, n-hexane, mixed solvent such as water / methanol, water / ethanol and the like can be suitably used.

The crude crystals obtained by the above operation are dissolved in an organic solvent and washed with an alkaline aqueous solution, whereby the sulfur impurity is removed and the sulfur concentration can be very low. Further, the remaining o-cresol can be removed by washing with an alkaline aqueous solution. Further, by performing cleaning with an alkaline aqueous solution, the substance causing coloring of the red color system or o-cresol can be easily washed away to the water side.

Examples of the organic solvent used for dissolving the crude crystals include a solvent such as ethyl acetate, toluene, acetone, and methanol, with ethyl acetate and acetone being more preferred, and ethyl acetate being more preferred.

The alkaline aqueous solution used for the above washing is not particularly limited, but an aqueous alkali metal hydroxide solution is preferable. The alkali metal hydroxide to be used in the alkali metal hydroxide aqueous solution may be suitably sodium hydroxide. When sodium hydroxide is used, when the concentration of aqueous sodium hydroxide solution is excessively high, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantanisodium phenolate salt Mono sodium phenolate salt, the sodium phenolate salt is distributed as an aqueous phase, and the monosodium phenolate salt is difficult to dissolve in both an organic phase and an aqueous phase and precipitates as crystals. Therefore, these phenolate salts are all 1,3 -Bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. The concentration of the aqueous sodium hydroxide solution is preferably 0.1 to 1.0% by weight. More preferably from 0.2 to 0.8% by weight, and still more preferably from 0.3 to 0.6% by weight.

Furthermore, after the alkali metal hydroxide is washed with a dilute aqueous solution or the like, the organic solvent solution may be washed with pure water to neutralize the alkali metal hydroxide, thereby suppressing contamination with the alkali metal.

After the water washing step, a normal recrystallization operation is carried out again to obtain 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane of higher purity.

As the solvent in the recrystallization operation, ethyl acetate, acetone, and methanol may be suitably used as the good solvent. Further, as the poor solvent, a solvent such as aliphatic saturated hydrocarbons such as hexane, heptane and the like can be suitably used.

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 can be arbitrarily changed within the range not to be used.

The present invention relates to a process for producing 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane (hereinafter also referred to as BPCDMA) represented by the following formula (3) To a polycarbonate resin and a resin composition.

[Chemical Formula 9]

≪ Dihydroxy compound: Production method of BPCDMA >

The production method of BPCDMA is not particularly limited, but can be produced, for example, by the first and second production methods described above.

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

≪ Other dihydroxy compound >

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

[Chemical formula 10]

(Wherein R ₁ to R ₄ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 1 to 5 carbon atoms A halogen atom, a sulfonyl group, an alkylidene group having 2 to 10 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, An arylalkylidene group or a fluorenylidene group of 1 to 15 carbon atoms.) By using such a dihydroxy compound, the obtained polycarbonate resin has a structural unit represented by the general formula (2).

Specific examples of the compound represented by the general formula (8) include 1,1'-biphenyl-4,4'-diol (BP), bis (4-hydroxyphenyl) methane (BPF) (4-hydroxyphenyl) ethane (BPE), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) propane (BPC) (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) diphenyl (4-hydroxyphenyl) Methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl-4-hydroxyphenyl) (4-hydroxyphenyl Bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane, [alpha], [omega] -bis [ (3-hydroxyphenyl) propyl] polydimethylsiloxane, 4,4 '- [1,3-phenylenebis (1-methylethylidene)] bisphenol and the like.

Of these, 1,1'-biphenyl-4,4'-diol, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1- (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) ether, 9,9- (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) fluorene are preferable from the viewpoints of flow rate, ) Propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclohexane (BPZ), 1,1- , 1'-biphenyl-4,4'-diol (BP), 1 , 1-bis (4-hydroxyphenyl) ethane (BPE) and bis (4-hydroxyphenyl) methane (BPF).

The copolymerization ratio of BPCDMA and the dihydroxy compound represented by the general formula (8) can be any ratio, but it is particularly preferable that the content ratio of BPCDMA is 10 to 100 mol%, more preferably 30 to 100 mol% Mol%.

As the polycarbonate resin, a blended resin may be used together with or in place of the copolymer resin. For example, only BPCDMA represented by the above general formula (3), or a polymer containing BPCDMA as a main component and a dihydroxy compound represented by the general formula (8) or dihydroxy compound represented by the general formula (8) A blend resin obtained by mixing a polymer of a polycarbonate containing a compound as a main component may be employed. When the polycarbonate of BPCDMA and the polycarbonate of the dihydroxy compound of the general formula (8) are mixed in a molten state in the blending process for producing the blended resin thus obtained, for example, And a blend resin containing the same composition as the copolymer resin can be obtained.

≪ Carbonic acid ester forming compound >

Examples of the carbonic ester forming compound usable in the present invention include bisallyl compounds such as phosgene, diphenyl carbonate, di-p-tolylcarbonate, phenyl-p-tolylcarbonate, di-p- chlorophenyl carbonate and dinaphthyl carbonate Carbonates. Among them, phosgene is preferable from the viewpoint of quality such as hue and stability of the obtained resin.

In the production of the polycarbonate of the present invention, the above carbonic ester-forming compound may be used singly or two or more of them may be used in combination.

≪ Process for producing polycarbonate >

The polycarbonate resin of the present invention can be produced by a known synthesis method such as various methods used in production of polycarbonate from bisphenol A and carbonic acid ester forming compound, interface polymerization method, ester exchange method and the like.

Generally, the interfacial polymerization is carried out at room temperature, whereas the ester exchange method is carried out at a temperature higher than the temperature at which the raw material mixture and the resulting polycarbonate resin are melted. Accordingly, when the polycarbonate resin of the present invention is polymerized by transesterification, for example, if the polycarbonate resin is 100% BPCDMA, it is necessary to conduct the reaction at a glass transition temperature of 213 ° C or higher. However, if the polymerization reaction is carried out at such a high temperature for a long period of time, thermal dehydrogenation of the dihydroxy compound itself tends to proceed, and a carbonate ester-forming compound such as diphenyl carbonate tends to be removed from the reaction system. Therefore, it is preferable to employ an interface polymerization method.

In the interfacial polymerization method, a dihydroxy compound and a molecular weight regulator (terminal terminator) are usually used in the presence of a chlorine-based organic solvent such as methylene chloride as an organic solvent inert to the reaction and an aqueous alkali solution, , An antioxidant for preventing the oxidation of the dihydroxy compound is used as needed and reacted with phosgene and then a polymerization catalyst such as a tertiary amine or a quaternary ammonium salt is added and subjected to interfacial polycondensation to form a polycarbonate resin Can be obtained. The timing of adding the molecular weight modifier is not particularly limited as long as it is from the time of phosgenation to the start of the polymerization reaction. The reaction temperature is 0 to 35 ° C, and the reaction time is several minutes to several hours.

As the molecular weight modifier (terminal terminator), a compound having a monovalent phenolic hydroxyl group can be exemplified. Specific examples thereof include m-methylphenol, p-methylphenol, m-propylphenol, tert-butylphenol, p-long-chain alkyl-substituted phenol, and the like.

As the polymerization catalyst, tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine and pyridine; And quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride and triethylbenzylammonium chloride.

Antioxidants, pigments, dyeing enhancers, fillers, release agents, ultraviolet absorbers, lubricants, nucleating agents, plasticizers, flow improvers, antistatic agents and the like may be added to the polycarbonate resin of the present invention.

<Physical Properties of Polycarbonate Resin>

The surface hardness of the polycarbonate resin of the present invention can be evaluated by a pencil scratch test (in accordance with JIS-K5600-5-4).

5 g of a polycarbonate resin was dissolved in 20 g of methylene chloride to prepare a 20 wt% resin solution, and this resin solution was cast on a glass plate having a thickness of 20 mm to prepare a film having a thickness of 200 m.

Using a Mitsubishi pencil made by UNI, the polycarbonate film produced by the above method was measured five times in accordance with JIS-K5600-5-4, and when the occurrence of scratches was two times or less, the evaluation was made acceptable.

The pencil hardness of the polycarbonate resin of the present invention, which is evaluated by the above measuring method, is preferably HB to 2H, more preferably H to 2H.

Particularly, since 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane has a methyl group as a substituent of a phenol group, in the polycarbonate resin prepared using the monomer as a monomer, A comparatively 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 measured by a tangential method (Tg calculation) using a DCS-50 manufactured by Shimadzu Corporation.

The Tg of the polycarbonate resin of the present invention, which is evaluated by the above measuring method, is preferably 160 to 220 占 폚, more preferably 175 to 220 占 폚.

Particularly, since 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane has an adamantane skeleton, in the polycarbonate resin prepared by using it as a monomer, A glass transition temperature (Tg) in a high range can be easily realized.

The viscosity average molecular weight (Mv) of the polycarbonate resin of the present invention was measured at a temperature of 20 占 폚 by using a urethane resin capillary viscometer with a methylene chloride solution of a polycarbonate resin of 0.2 grams / deciliter and a Hoggins constant of 0.45 The intrinsic viscosity [eta] deciliter / gram was calculated and calculated by the following equation (I).

^{η = 1.23 × 10 -4 × Mv} 0 .83 (I)

The Mv of the polycarbonate resin of the present invention, which is evaluated by the above measuring method, is preferably in the range of 1.0 x 10 ⁴ to 8.0 x 10 ⁴ , more preferably 2.0 x 10 ⁴ to 4.0 x 10 ⁴ .

&Lt; Use of the present invention &

The polycarbonate resin, which is a preferred embodiment of the present invention, has both high heat resistance and surface hardness, and thus can be used as raw materials for injection molded articles, extrusion molded articles, films, sheets and the like which require high heat resistance and high surface hardness. The injection molded article, extruded molded article, film or sheet using the polycarbonate resin of the present invention can be used for optical lenses, head lamps, lighting covers, printers and copiers, medical devices, automobile parts, cooking utensils, A transparent conductive film, a retardation film, a brightness enhancement film, a reflection sheet, a solar cell back sheet, and the like. In particular, the polycarbonate resin of the present invention is useful as a transparent conductive film for a display panel mounted on an electric / electronic apparatus since it has both high surface hardness and high heat resistance.

Further, the surface hardness can be further improved by applying known thermosetting and ultraviolet hardening hard coats to the surface layer of an injection molded article, an extrusion molded article, a film or a sheet by the polycarbonate resin of the present invention.

Example

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

<Analysis method>

(1) GC-FID analysis

An Agilent capillary column DB-1 30 m, an inner diameter 0.53 mm, and a film thickness 1.5 탆 were attached to a gas chromatograph HP-6890 manufactured by Hewlett Packard, and the composition of the product was analyzed with an FID detector.

(2) GC / MS analysis

Analytical analysis was carried out by attaching it to a gas chromatograph mass spectrometer GCMS-QP2010 Ultra manufactured by Shimadzu Corporation with an Agilent capillary column DB-1MS 30 m, an inner diameter 0.250 mm and a film thickness 0.25 μm.

(3) NMR analysis

The measurement data was dissolved in acetone-D6 to make a 10% solution, and the measurement was carried out using a JNM-AL400 type nuclear magnetic resonance apparatus manufactured by JEOL.

(4) Fluorescence X-ray analysis

3 g of the sample to be measured was molded into pellets with a 20 MPa, 20 sec press machine, and quantitative analysis of bromine concentration and sulfur concentration was performed by fluorescence X-ray measurement using a fluorescence X-ray spectrometer ZSX100e manufactured by National Institute of Advanced Industrial Science and Technology.

(5) HPLC analysis

Synergi 4u Hydro-RP 80A, 250 x 4.60 mm, 4 micron was attached to a HPLC ELITE LaChrom L-2200 manufactured by Hitachi Hi-Technology Co., Ltd., and the column was immersed in a 1 L Was dissolved in 3 g of phosphoric acid and analyzed by gradient using acetonitrile. 0.1 mL of a solution prepared by dissolving 0.05 g of the sample in 20 mL of acetonitrile was injected and the isomer composition of the product was measured by a UV detector at 220 nm.

PREPARATION EXAMPLE 1 Preparation of 1,3-dibromo-5,7-dimethyladamantane

238 kg of dichloromethane was charged into a 1000 L glass lining (GL) furnace, and 60 kg of 1,3-dimethyladamantane was added again. 4.80 kg of ferric chloride was further added, cooling was carried out, and the temperature was adjusted to 20 ± 3 ° C. Cooling was carried out, and 141 kg of bromine was added dropwise over 9 hours while controlling the temperature to 20 ± 5 ° C. After completion of the dropwise addition, agitation was carried out again for 6 hours and 30 minutes while adjusting the temperature to 20 ± 3 ° C again. After aging, the solution was cooled to 5 DEG C and 185 kg of water was added. An exotherm was observed up to 9 캜, but stirring was carried out for 15 minutes while cooling to prevent the temperature from exceeding 10 캜. After standing for another 30 minutes, the methylene chloride layer as the lower layer and the acidic aqueous phase as the upper layer were separated.

Subsequently, the dichloromethane layer in the lower layer was charged into a 1000 L GL furnace and cooled to 9 캜. 210.9 kg of a mixed solution of 185 kg of water, 9.6 kg of a sodium bicarbonate and 16.3 kg of sodium thiosulfate was added dropwise over 25 minutes while stirring. Stirring was further carried out for 15 minutes while maintaining the temperature below 10 ° C. After the stirring was stopped and the mixture was allowed to stand for 30 minutes, the lower layer of dichloromethane and the upper layer of water phase were separated. The obtained lower layer of dichloromethane was put into a 1000 L GL furnace, and 185 kg of water was added. After stirring at room temperature for 15 minutes, the mixture was allowed to stand for 30 minutes, and the lower layer of dichloromethane layer and the upper layer of water phase were separated. The dichloromethane layer of the lower layer was again charged into a 1000 L GL furnace and 185 kg of water was added and stirred at room temperature for 15 minutes and then allowed to stand for 30 minutes to separate the lower layer of dichloromethane layer from the upper layer of water phase, And was washed.

Again, the obtained lower layer of dichloromethane was put into a 1000 L GL kiln, heated and concentrated. Precipitation of crystals was observed during concentration. When about 100 L of dichloromethane was distilled and collected, the concentration was stopped. Methanol (512 kg) was added, the temperature was raised to 66 ° C, and the mixture was stirred at reflux for 30 minutes to dissolve the precipitated crystals. Cooled to 5 DEG C again, allowed to stand overnight, crystals were precipitated, and crystals were separated by solid-liquid separation using a centrifuge. To 73 kg of the obtained crystals, 50 kg of dichloromethane was added, and 400 L of methanol was further added. The mixture was heated and stirred to dissolve again, and then cooled to 10 캜 to precipitate crystals. In the centrifugal separation, solid-liquid separation was carried out, and the obtained crystals were dried to obtain 56 kg of 1,3-dibromo-5,7-dimethyladamantane. The obtained white crystals were dissolved in ethanol and subjected to GC-FID analysis. As a result, 1,3-dibromo-5,7-dimethyladamantane calculated excluding the peak of the solvent was 98.02% by area Respectively.

Example 1 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production process

40.40 g (0.125 mol) of 1,3-dibromo-5,7-dimethyladamantane was added to a 500-mL separable flask, and 108.68 g (1.01 mol) of o-cresol was added thereto. While stirring at room temperature, nitrogen was blown for several minutes, and nitrogen in the system was replaced. The blowing of nitrogen was stopped and heating was started. The temperature reached 170 占 폚 at about 20 minutes, and then the stirring was continued for 5 hours at a set temperature of the temperature controller of 170 占 폚. After 5 hours, heating was stopped and cooling by natural cooling was started. At this point, the color of the reaction solution was a pale pink transparent liquid. At the time of cooling to 99 DEG C, 105.6 g of heptane was added, and natural cooling was continued again while stirring. At the time of cooling to 39 deg. C, the precipitated solid and liquid were separated by suction filtration. The solid was further added with 104.1 g of heptane, rinsed, and again subjected to solid-liquid separation by suction filtration. The collected agricultural and rinsing liquids were all 291.7 g, and the composition was analyzed by GC-FID and HPLC. The crystals recovered by suction filtration were dried in a drier 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 lost. Composition analysis of crude crystals was carried out by GC-FID and HPLC.

To the crude crystals obtained, 22.66 g of ethyl acetate was added and the mixture was stirred at room temperature to dissolve immediately. 150 mL of toluene was further added, and the mixture was stirred to obtain a homogeneous solution. Transferred to a 1 L separating funnel, 300 mL of a 0.5 wt% aqueous solution of sodium hydroxide was added, and stirred for 10 minutes. It was politicized and separated the following awards. The pH of the water phase was approximately 8 on the test paper. 300 ml of pure water was added to the separating funnel, and the mixture was stirred for 10 minutes. It was politicized and separated the following awards. The pH of the water phase was about 7 on the test paper. The organic solvent solution of the light liquid of the separating funnel was transferred to a 500 mL eggplant flask and concentrated by an evaporator. Crystals were precipitated. When almost no solvent was removed, the concentration was stopped, 40.63 g of ethyl acetate was further added, and the mixture was heated and stirred in a water bath at 70 캜 to completely dissolve the crystals. 80.1 g of heptane was added to a 500 mL beaker. An organic solvent solution dissolved in 500 mL of a beaker was added, and stirring was continued at room temperature for about 10 minutes to precipitate crystals. Liquid separation was carried out by suction filtration, and rinsing was carried out again with 79.8 g of heptane. The collected agricultural and rinsing liquids were all 196.3 g, and the composition was analyzed by GC-FID and HPLC. The solid recovered by suction filtration was dried in a drier 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 lost. The composition of the crystals was analyzed by GC-FID and HPLC.

The results are shown in Table 1. The results are shown in Table 1 below.

&Lt; Identification of the product of Example 1 >

The GC / MS analysis results of the product obtained in Example 1 are shown in Fig. The molecular weight of the product from the mass spectrum is considered to be 376.

The NMR measurement results of the product obtained in Example 1 are shown below.

(2H, d, J = 2.2 Hz), 7.04 (2H, dd, J = 8.0, 2.2 Hz), 6.74 (2H, s) (2H, s), 0.95 (6H, s), 2.19 (6H, s), 1.59

13C-NMR (ACETONE-D6) ?: 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

2 shows a chart of &lt; 1 &gt; H-NMR, and Fig. 3 shows the attribution of 1 H-NMR peak. FIG. 4 shows a chart of 13 C-NMR, FIG. 5 shows a chart of DEPT 45 ° -NMR, and FIG. 6 shows the attribution of the peak of 13 C-NMR. Judging comprehensively from these measurement results, it was confirmed that the product obtained in Example 1 was 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane.

Example 2 Preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the First Production Process

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , 7-dimethyladamantane, and purification by alkaline washing and recrystallization to obtain a purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane &Lt; / RTI &gt; Table 1 shows the items under the conditions different from those in Example 1 in the input amount, the reaction condition, and the purification condition. The results of the analysis of the crystals and the filtrate are summarized in Table 1.

Example 3 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , 7-dimethyladamantane, and purification by alkaline washing and recrystallization to obtain a purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane &Lt; / RTI &gt; Table 1 shows the items under the conditions different from those in Example 1 in the input amount, the reaction condition, and the purification condition. The results of the analysis of the crystals and the filtrate are summarized in Table 1.

Example 4 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production method

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , 7-dimethyladamantane, and purification by alkaline washing and recrystallization to obtain a purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane &Lt; / RTI &gt; Table 1 shows the items under the conditions different from those in Example 1 in the input amount, the reaction condition, and the purification condition. The results of the analysis of the crystals and the filtrate are summarized in Table 1.

Example 5 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the first production process

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , And 7-dimethyladamantane were synthesized to obtain crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane. The obtained crude crystals were analyzed without alkali washing and recrystallization. Table 1 shows the items under the conditions different from those in Example 1 in terms of the amount and the reaction conditions. Table 1 summarizes the results of analysis of crude crystals and filtrate. Further, when the bromine concentration and the sulfur concentration were analyzed by fluorescent X-ray, the bromine concentration was 531 ppm and the sulfur concentration was 29 ppm.

Example 6 Preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the First Production Process

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , 7-dimethyladamantane, and purification by alkaline washing and recrystallization to obtain a purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane &Lt; / RTI &gt; Table 1 shows the items under the conditions different from those in Example 1 in the input amount, the reaction condition, and the purification condition. The results of the analysis of the crystals and the filtrate are summarized in Table 1.

Example 7 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the First Production Process

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , 7-dimethyladamantane, and purification by alkaline washing and recrystallization to obtain a purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane &Lt; / RTI &gt; Table 1 shows the items under the conditions different from those in Example 1 in the input amount, the reaction condition, and the purification condition. The results of the analysis of the crystals and the filtrate are summarized in Table 1.

Example 8 Preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the First Production Process

Bis (3-methyl-4-hydroxyphenyl) -5 (3-methyl-4-hydroxyphenyl) -5,6-dihydroxy-5,7-dimethyladamantane was obtained in the same manner as in Example 1, , 7-dimethyladamantane, and purification by alkaline washing and recrystallization to obtain a purified crystal of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane &Lt; / RTI &gt; Table 1 shows the items under the conditions different from those in Example 1 in the input amount, the reaction condition, and the purification condition. The results of the analysis of the crystals and the filtrate are summarized in Table 1.

[Table 1]

The compounds shown in Table 1 as the compound (4), the compound (1), the isomer (2) and the isomer (3) are shown below.

Compound (4): 1,3-dibromo-5,7-dimethyladamantane

Compound (1): 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane

Isomer (2): A compound represented by the following formula (4)

Isomer (3): A compound represented by the following formula (5)

(11)

[Chemical Formula 12]

PREPARATION EXAMPLE 2 Preparation of 1,3-dihydroxy-5,7-dimethyladamantane

25 kg of 1,3-dibromo-5,7-dimethyladamantane was added to a 500 L GL furnace, and 150 kg of pure water and 0.2 kg of diethylamine as a secondary amine were added. After heating, the liquid temperature was raised to 140 캜, and the internal pressure rose to 0.35 MPa. The reaction was allowed to proceed at 140 占 폚 for 5 hours. After 5 hours, cooling was started, and when it was cooled to 70 deg. C, crystals precipitated. Cooled to 35 deg. C again, and filtered to conduct solid-liquid separation. The crystals were dried to obtain 15 kg of crude crystals. Approximately half of the crude crystals were charged into a 500 L GL furnace, and 390 L of acetone was added, the temperature was raised to 50 캜 and stirring was performed for 1 hour to dissolve the crystals. 180 L of acetone was distilled, collected and concentrated, cooled to 10 캜, and stirred at 10 캜 for 1 hour to precipitate crystals. The solid-liquid separation was carried out by filtration, and the crystals were dried. The remaining half of the crude crystals were recrystallized by the same procedure to obtain 10 kg of white crystals of 1,3-dihydroxy-5,7-dimethyladamantane. The obtained white crystals were dissolved in ethanol, and analyzed by GC-FID. As a result, the peak was 99.75% by area, excluding the peak of the solvent. The bromine concentration was analyzed by fluorescent X-ray analysis and found to be 2.96 ppm.

Example 9 Preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the second production process

Nitrogen was poured into a 2 L separable flask, and nitrogen substitution was carried out. 104.68 g of 1,3-dihydroxy-5,7-dimethyladamantane was added, and 460.67 g of o-cresol was added again. The mixture was stirred while heating, and the temperature was raised to 80 캜. When the temperature reached 80 占 폚, dropping of methanesulfonic acid was started. 53.59 g was added dropwise over 10 minutes. As a result, the temperature was raised to 90 占 폚 by heat generation. The reaction was continued at 90 DEG C for 4 hours. After 4 hours, 400 mL of warm water at 65 to 70 DEG C was added, and then 800 mL of heptane at room temperature was added to lower the liquid temperature to 65 DEG C. [ After cooling for 30 minutes, the mixture was cooled to 60 DEG C, and a pale pink solid precipitated. The precipitated solid was filtered under reduced pressure, rinsed again with 400 mL of heptane at room temperature, and rinsed 4 times with 800 mL of hot water again. The light pink solid was dissolved in 600 mL of ethyl acetate, and 300 mL of toluene was again added. 800 mL of a 0.5% sodium hydroxide aqueous solution was added, stirred, and then allowed to stand. As a result, the aqueous phase below was changed to pink, and the organic phase was changed to colorless. The organic phase was recovered, and the solvent was distilled and recovered in an amount of about 500 mL, and concentration was carried out. 800 mL of heptane was added to 2 L of the beaker, the concentrated organic solvent solution was poured again, and stirring was continued for several minutes, whereby white crystals were precipitated. The crystals were separated by solid-liquid separation by filtration under reduced pressure, and rinsed with 800 mL of heptane again. The crystals were dried in a drier at 90 DEG 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 crystals were dissolved in ethanol and analyzed by GC-FID, and found to be 99.64% by area, excluding the peak of the solvent. As a result of analyzing the bromine concentration and the sulfur concentration by fluorescent X-ray, it was not detected. The isomer ratio of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and its isomers was analyzed by HPLC. Table 2 summarizes the reaction conditions and the analysis results of the purified crystals.

Example 10 Production of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the second production process

Nitrogen was poured into a 500 mL flask, and nitrogen substitution was carried out. Then, 13.75 g of 1,3-dihydroxy-5,7-dimethyladamantane was added thereto, and 60.56 g of o-cresol was further added. The mixture was stirred while heating, and the temperature was raised to 85 캜. When the temperature reached 85 占 폚, 13.32 g of p-toluenesulfonic acid was added, and the temperature was raised to 90 占 폚 by heat generation. The reaction was continued at 90 DEG C for 7 hours. After 7 hours, 100 mL of warm water at 60 DEG C was added, and the liquid temperature was lowered to 73 DEG C, and a pale pink solid precipitated. The precipitated solid was filtered under reduced pressure, and rinsed 4 times with 100 mL of hot water at 60 캜. It was confirmed that the washing solution of the fourth rinse was neutral with a pH test paper. The pale pink solid was dissolved in 150 mL of ethyl acetate, and 100 mL of toluene was added again to dissolve the solid completely. Washed with 50 mL of pure water, and the water phase was discarded. And then washed again with 50 mL of pure water twice. After adding 50 mL of a 0.5% sodium hydroxide aqueous solution, stirring was performed, and the mixture was allowed to stand, the following aqueous phase was changed to pink and the organic phase was changed to colorless. The organic phase was recovered, and about 30 mL of the solvent was distilled and collected, and concentration was carried out. To the 200 mL beaker, 50 mL of ethyl acetate and 100 mL of hexane were added. The concentrated organic solvent solution was poured again, and stirring was continued for several minutes. White crystals were precipitated. After standing at 23 DEG C for 15 minutes again, the crystals were separated by solid-liquid separation by filtration under reduced pressure, and rinsed with 100 mL of hexane again. The crystals were dried in a dryer at 80 캜 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 crystals were dissolved in ethanol and subjected to GC-FID analysis. As a result, 98.52% by area was excluded from the peaks of the solvent. As a result of analyzing the bromine concentration and the sulfur concentration by fluorescent X-ray, it was not detected. The isomer ratio of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and its isomers was analyzed by HPLC. Table 2 summarizes the reaction conditions and the analysis results of the purified crystals.

Example 11 Preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane by the second production process

In a 50 L GL furnace, 99 kg of 1,3-dihydroxy-5,7-dimethyladamantane was added and again 17.67 kg of o-cresol was added. The mixture was stirred while heating, and the temperature was raised to 76 캜. When the temperature reached 76 占 폚, dropping of concentrated sulfuric acid started. 2.01 kg was dropwise added over 15 minutes, and as a result, the temperature was raised to 90 占 폚 by heat generation. The reaction was continued at 90 DEG C for 8.5 hours. After 8.5 hours, 20.4 kg of water was added and the temperature dropped to 48 占 폚. Cooling was performed again, and the temperature was lowered to 4 캜 to precipitate a solid. The precipitated solid was filtrated under reduced pressure, and rinsed again with 12.0 kg of hot water at 50 ° C. The resulting pale pink solid was dispersed in 30.0 kg of hot water at 50 占 폚. 200 mL of a 1 mol / L sodium hydroxide aqueous solution was added to the hot water in which crystals were dispersed, and the hot water was neutralized. The solid dispersion was filtrated under reduced pressure, subjected to solid-liquid separation, and further rinsed with hot water at 50 캜. The resulting solid was added to 49.17 kg of toluene and dissolved by heating. And completely dissolved at the time point of 88 ° C. Cooling was performed, cooling was carried out to 4 캜, and stirring was further carried out for 1 hour to precipitate white crystals. Liquid separation by filtration under reduced pressure, rinsing with 3 L of hexane again, and drying overnight with a hot air drier at 60 캜 to obtain 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7- 5.1 kg of purified crystals were obtained. The purified crystals obtained were analyzed by GC-FID and found to be 99.03 area%, excluding the peak of the solvent. As a result of analyzing the bromine concentration and the sulfur concentration by the fluorescent X-ray, bromine was not detected, and the sulfur concentration was 394 ppm. By HPLC analysis, the ratio of isomers of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane and its isomers was analyzed. Table 2 summarizes the reaction conditions and the analysis results of the purified crystals.

[Table 2]

In the above Table 2, the compound (5) is the compound shown below.

Compound (5): 1,3-Dihydroxy-5,7-dimethyladamantane

The compounds of the compound (1), the isomer (2) and the isomer (3) are the same as those shown in Table 1.

As described above, according to the above-described embodiment, the compound (1), that is, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, While realizing, it was confirmed that it can be manufactured. That is, in Examples 1 to 11, about 99% by weight or more of 1,3-bis (methyl-hydroxyphenyl) -5,7-dimethyladamantane to be produced is 1,3- Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, and the production amount of the isomers (2) and the isomers (3) can be suppressed to less than 1% by weight in total.

In addition, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane selectively prepared in the above-mentioned embodiment is present in the para position with the phenolic hydroxy group, And is particularly suitable as a monomer used in the production of an aromatic polycarbonate resin. On the other hand, the isomer (2) or the isomer (3) is not suitable for producing an aromatic polycarbonate resin in that 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 the phenol group, aromatic polycarbonate having a moderately high glass transition point The resin can be easily produced.

Further, in the compound (1) produced by the above-described embodiment, that is, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, In particular, impurities of bromine can be suppressed to an extremely small amount, so that unnecessary coloring can be prevented. In addition, in the case of adamantane containing a large amount of sulfur as an impurity, there is a possibility that the aqueous phase of the reaction solution of the polymerization reaction for producing a polycarbonate resin to be performed later and the organic phase are difficult to be easily separated. Therefore, dimethyladamantane containing a large amount of sulfur impurities is not always suitable for the production of polycarbonate resin as will be described later in detail. However, in the case of the dimethyladamantane of the compound (1) produced by the above-mentioned example, the concentration of sulfur as the impurity was suppressed to 400 ppm or less, which was a good result.

Hereinafter, the present invention will be described based on examples of polycarbonate resin. However, the present invention is not limited to the examples, and various numerical values and materials in the examples are examples.

&Lt; Synthesis Example 1 &

Preparation of 1,3-dihydroxy-5,7-dimethyladamantane

25 kg of 1,3-dibromo-5,7-dimethyladamantane was added to a 500 L GL furnace, and 150 kg of pure water and 0.2 kg of diethylamine as a secondary amine were added. When the inside of the GL furnace was heated and the liquid temperature was raised to 140 캜, the internal pressure rose to 0.35 MPa. The reaction was allowed to proceed at 140 占 폚 for 5 hours. After 5 hours, cooling was started, and after cooling to 70 캜, crystals precipitated. Cooled to 35 DEG C again, filtered, and subjected to solid-liquid separation. When the crystals were dried, 15 kg of crude crystals were obtained. Approximately half of the crude crystals were charged into a 500 L GL furnace, and 390 L of acetone was added, the temperature was raised to 50 캜 and stirring was performed for 1 hour to dissolve the crystals. 180 L of acetone was distilled, collected and concentrated, cooled to 10 캜, and stirred at 10 캜 for 1 hour to precipitate crystals. The solid-liquid separation was carried out by filtration, and the crystals were dried. The remaining half of the crude crystals were recrystallized by the same procedure to obtain 10 kg of white crystals of 1,3-dihydroxy-5,7-dimethyladamantane.

&Lt; Synthesis Example 2 &

Preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane

Nitrogen was poured into a 2 L separable flask, and nitrogen substitution was carried out. 104.68 g of 1,3-dihydroxy-5,7-dimethyladamantane was added, and 460.67 g of o-cresol was added again. The mixture was stirred while heating in a flask, and the temperature was raised to 80 캜. When the temperature reached 80 占 폚, dropping of methanesulfonic acid was started. 53.59 g was added dropwise over 10 minutes. As a result, the temperature was raised to 90 占 폚 by heat generation. The reaction was continued at 90 DEG C for 4 hours. After 4 hours, 400 mL of hot water at 65-70 DEG C was added to the reaction solution, and then 800 mL of heptane at room temperature was added to lower the liquid temperature to 65 DEG C. [ The reaction solution was cooled to 60 캜 by natural cooling for 30 minutes, and a pale pink solid precipitated. The precipitated solid was filtered under reduced pressure, rinsed with 400 mL of heptane at room temperature, and rinsed 4 times with 800 mL of hot water again. The light pink solid was dissolved in 600 mL of ethyl acetate, and 300 mL of toluene was again added. 800 mL of a 0.5% sodium hydroxide aqueous solution was added, stirred, and then allowed to stand. As a result, the aqueous phase below was changed to pink, and the organic phase was changed to colorless. The organic phase was recovered, and the solvent was distilled and recovered in an amount of about 500 mL, and concentration was carried out. 800 mL of heptane was added to 2 L of the beaker, the concentrated organic solvent solution was poured again, and stirring was continued for several minutes, whereby white crystals were precipitated. The crystals were separated by solid-liquid separation by filtration under reduced pressure, and rinsed with 800 mL of heptane again. The crystals were dried in a drier at 90 DEG 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.

&Lt; Synthesis Example 3 &

Preparation of 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane

Nitrogen was poured into a 300L GL furnace, and nitrogen substitution was carried out. 14.99 kg of 1,3-dihydroxy-5,7-dimethyladamantane was added, and 57.34 kg of phenol was added again. The mixture was stirred while heating, and the temperature was raised to 80 캜. When the temperature reached 80 占 폚, dropping of methanesulfonic acid was started. 7.34 kg was dropwise added over 30 minutes, and as a result, the temperature was raised to 100 占 폚 by heat generation. The reaction was continued at 100 DEG C for 6 hours. After a lapse of 6 hours, cooling was started and the temperature was cooled to 60 占 폚. 54 L of a 1: 1 mixed solvent of water and methanol was added to the reaction solution, and the mixture was subjected to natural cooling while stirring to precipitate a solid. While stirring, the reaction solution was allowed to stand for 16 hours. The precipitated solid was subjected to solid-liquid separation using a centrifugal filter, and rinsed with 26 L of a mixed solvent of water and methanol 1: 1. The obtained white solid was dissolved in 90 kg of ethyl acetate, and the solution was transferred to a 200 L GL kiln by a pump. Again 43 kg of toluene was added. 50 L of a 0.5% sodium hydroxide aqueous solution was added, stirred, and then allowed to stand. Separation was carried out, and the water phase was discarded. To the organic phase, 50 L of a 0.5% sodium hydroxide aqueous solution was added again, stirred, and allowed to stand. Separation was carried out, and the water phase was discarded. The pH of the second aqueous phase was confirmed to be approximately 8 with a pH test paper. 50 L of pure water was further added, stirred, and allowed to stand. Separation was carried out, and the water phase was discarded. The organic phase was recovered in a 200 L stainless steel bucket. The washed 200 L GL kiln was passed through a filter and transferred. The reaction mixture was concentrated by heating under reduced pressure, and the solvent was concentrated by evaporation until a small amount of crystals precipitated. Ethyl acetate was added again, and the mixture was heated and stirred to dissolve again. About 100 L of solution was obtained in the whole amount. 150 L of heptane was added to a 300 L vessel. To the solution, an ethyl acetate solution was added with stirring to precipitate white crystals. The mixture was allowed to stand in a freezer at -20 캜 for 16 hours to precipitate crystals. The crystals were separated by solid-liquid separation by filtration under reduced pressure, and rinsed again with 30 L of heptane. The crystals were dried for 3 days in a dryer at 80 ° C 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.

&Lt; Synthesis Example 4 &

According to the production method described as Example 11 (preparation of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane according to 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.

&Lt; Example 12 >

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 in 400 ml of a 5% by mass aqueous solution of sodium hydroxide. Then, 350 ml of methylene chloride was added thereto, and 17.0 g (0.172 mol) of phosgene was blown in over 20 minutes while being maintained at 15 캜 while stirring. After the completion of the blowing of the phosgene, 0.460 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 2.71 × 10 ⁴ , a glass transition temperature of 213 ° C. and a pencil hardness of 2H.

&Lt; Example 13 >

(0.098 mole) of BPCDMA obtained in Synthesis Example 2 and 9.58 g (0.042 mole) of 2,2-bis (4-hydroxyphenyl) propane (manufactured by Shin Nittsu Chemical Co., Ltd.) were added to 400 ml of a 5 mass% aqueous sodium hydroxide solution , 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 22.2 g (0.224 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of phosgene, 0.617 g of p-tert-butylphenol from DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous solution of sodium hydroxide and 100 ml of methylene chloride were added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 2.72 × 10 ⁴ , a glass transition temperature of 195 ° C. and a pencil hardness of H.

&Lt; Example 14 >

(0.073 mole) of BPCDMA obtained in Synthesis Example 2, 16.56 g (0.073 mole) of BPA, 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved in 400 ml of a 5 mass% aqueous sodium hydroxide solution Respectively. To this, 300 ml of methylene chloride was added, and 23.7 g (0.239 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of the phosgene, 0.648 g of p-tert-butylphenol of DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 x 10 &lt; ⁴ &gt;, a glass transition temperature of 180 DEG C, and a pencil hardness of F. [

&Lt; Example 15 >

(0.050 mole) of BPCDMA obtained in Synthesis Example 2, 26.81 g (0.118 mole) of BPA, 0.3 g of a hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved in 450 ml of a 5 mass% aqueous sodium hydroxide solution Respectively. Then, 300 ml of methylene chloride was added thereto, and 27.9 g (0.282 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the introduction of phosgene, 0.760 g of p-tert-butylphenol from DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 2.69 × 10 ⁴ , a glass transition temperature of 164 ° C. and a pencil hardness of HB.

&Lt; Example 16 >

(0.073 mole) of BPCDMA obtained in Synthesis Example 2 and 18.69 g (0.073 mole) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane Hereinafter abbreviated as BPC), 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride. Then, 300 ml of methylene chloride was added thereto, and 24.3 g (0.245 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of the phosgene, 0.645 g of p-tert-butylphenol, manufactured by DIC Co., Ltd., was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 161 ° C. and a pencil hardness of 2H.

&Lt; Example 17 >

(0.073 mole) of BPCDMA obtained in Synthesis Example 2 and 19.56 g (0.073 mole) of 1,1-bis (4-hydroxyphenyl) -cyclohexane (manufactured by Honshu Chemical Industry Co., Ltd.) in 450 ml of an aqueous sodium hydroxide solution of 5 mass% Hereinafter abbreviated as BPZ), 0.3 g of hydrosulfite, and 0.03 g of triethylbenzylammonium chloride. Then, 300 ml of methylene chloride was added thereto, and 23.4 g (0.236 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of phosgene, 0.585 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 2.62 × 10 ⁴ , a glass transition temperature of 187 ° C., and a pencil hardness of 2H.

&Lt; Example 18 >

(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- Phenyl ethane (abbreviated as BPCAP, hereinafter abbreviated as Honshu Chemical Industry Co., Ltd.), 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 300 ml of methylene chloride was added thereto, and 27.6 g (0.279 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of phosgene, 0.713 g of p-tert-butylphenol made by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 2.60 × 10 ⁴ , a glass transition temperature of 176 ° C., and a pencil hardness of 2H.

&Lt; Example 19 >

52.45 g (0.139 mole) of BPCDMA obtained in Synthesis Example 2, 8.6 g (0.046 mole) of 4,4-biphenol (abbreviated as BP hereinafter, manufactured by Honsyu Chemical Industry Co., Ltd.) was added to 650 ml of an aqueous sodium hydroxide solution of 5% , 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 300 ml of methylene chloride was added thereto, and 30.1 g (0.304 mol) of phosgene was blown in over 20 minutes while the mixture was kept at 15 캜 with stirring. After the completion of the blowing of the phosgene, 0.805 g of p-tert-butylphenol made by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 3.27 × 10 ⁴ , a glass transition temperature of 209 ° C. and a pencil hardness of H.

&Lt; Example 20 >

(0.093 mole) of BPCDMA obtained in Synthesis Example 2 and 19.90 g (0.093 mole) of 1,1-bis (4-hydroxyphenyl) ethane (manufactured by Honsyu Chemical Co., Ltd.) were added to 550 ml of a 5 mass% aqueous sodium hydroxide solution , Hereinafter abbreviated as BPE), 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 300 ml of methylene chloride was added thereto, and 29.6 g (0.299 mol) of phosgene was blown in over 20 minutes while being maintained at 15 캜 with stirring. After the completion of the introduction of phosgene, 0.912 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The mixture was dropped into one warm water, the solvent was evaporated and removed, and the solid product was pulverized to obtain a white powdery precipitate. The resulting 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 2.84 × 10 ⁴ , a glass transition temperature of 168 ° C. and a pencil hardness of F.

&Lt; Example 21 >

(0.093 mole) of BPCDMA obtained in Synthesis Example 2 and 18.69 g (0.093 mole) of bis (4-hydroxyphenyl) methane (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter referred to as BPF) were added to 550 ml of a 5 mass% aqueous sodium hydroxide solution 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved. Then, 300 ml of methylene chloride was added thereto, and 30.1 g (0.304 mol) of phosgene was blown in over 20 minutes while the mixture was kept at 15 캜 with stirring. After the completion of the introduction of phosgene, 0.676 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 3.51 × 10 ⁴ , a glass transition temperature of 167 ° C., and a pencil hardness of F.

&Lt; Example 22 >

40.0 g (0.106 mol) of BPCDMA-2, 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved in 400 ml of a 5% by mass aqueous solution of sodium hydroxide. Then, 350 ml of methylene chloride was added thereto, and 17.0 g (0.172 mol) of phosgene was blown in over 20 minutes while being maintained at 15 캜 while stirring. After completion of the phosgene blowing, 0.460 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, , 1 ml of triethylamine was added, and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to polymerize. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The mixture was dropped into one warm water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a white powdery precipitate. The resulting 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 x 10 ⁴ , a glass transition temperature of 200 캜, and a pencil hardness of 2H.

&Lt; Comparative Example 1 &

38.3 g (0.168 mol) of BPA and 0.3 g of hydrosulfite were dissolved in 450 ml of a 5% by mass aqueous solution of sodium hydroxide. To this, 300 ml of methylene chloride was added and 21.6 g (0.218 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the introduction of phosgene, 0.770 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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.

&Lt; Comparative Example 2 &

37.38 g (0.146 mole) of BPC, 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved in 400 ml of a 5 mass% aqueous solution of sodium hydroxide. To this, 300 ml of methylene chloride was added and 21.7 g (0.219 mole) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of the phosgene, 0.645 g of p-tert-butylphenol, manufactured by DIC Co., Ltd., was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting precipitate was filtered and dried at 110 DEG 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 캜 and a pencil hardness of 2H.

&Lt; Comparative Example 3 &

22.53 g (0.088 moles) of BPC, 13.5 g (0.059 moles) of BPA, 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved in 450 ml of a 5% by mass aqueous solution of sodium hydroxide. To this, 300 ml of methylene chloride was added and 21.7 g (0.219 mole) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of the phosgene, 0.645 g of p-tert-butylphenol, manufactured by DIC Co., Ltd., was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting precipitate was filtered and dried at 110 DEG C for 24 hours to obtain an aromatic polycarbonate resin powder. The polycarbonate resin had a viscosity average molecular weight of 2.66 x 10 &lt; ⁴ &gt;, a glass transition temperature of 131 DEG C, and a pencil hardness of F. [

&Lt; Comparative Example 4 &

(3-methyl-4-hydroxyphenyl) -cyclohexane (hereinafter abbreviated as BPCZ, manufactured by Honsyu Chemical Co., Ltd.) was added to 450 ml of a 5% by mass aqueous solution of sodium hydroxide, 0.3 g of hydrosulfite, 0.03 g of triethylbenzylammonium chloride was dissolved. Then, 300 ml of methylene chloride was added thereto, and 21.8 g (0.220 moles) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of phosgene, 0.753 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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.

&Lt; Comparative Example 5 &

60.00 g (0.203 mol) of BPCZ, 12.5 g (0.055 mol) of BPA, 0.3 g of hydrosulfite and 0.03 g of triethylbenzylammonium chloride were dissolved in 450 ml of a 5% by mass sodium hydroxide aqueous solution. Then, 400 ml of methylene chloride was added thereto, and 39.0 g (0.394 mol) of phosgene was blown in over 20 minutes while the mixture was kept at 15 캜 while stirring. After the completion of the introduction of phosgene, 1.11 g of p-tert-butylphenol of DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 2.31 × 10 ⁴ , a glass transition temperature of 140 ° C. and a pencil hardness of H.

&Lt; Comparative Example 6 >

50.0 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 solution of sodium hydroxide. To this, 350 ml of methylene chloride was added and 23.0 g (0.232 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of phosgene, 0.730 g of p-tert-butylphenol from DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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 x 10 ⁴ , a glass transition temperature of 150 캜, and a pencil hardness of 2H.

&Lt; Comparative Example 7 &

To 350 ml of an aqueous 5% by mass sodium hydroxide solution, 42.80 g (0.200 moles) of BPE and 0.3 g of hydrosulfite were dissolved. Then, 250 ml of methylene chloride was added thereto, and 27.9 g (0.282 mol) of phosgene was blown over the course of 20 minutes while maintaining the temperature at 15 캜 with stirring. After the completion of the blowing of phosgene, 1.75 g of p-tert-butylphenol manufactured by DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting precipitate was filtered and dried at 110 DEG 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 125 ° C. and a pencil hardness of 2B.

&Lt; Comparative Example 8 >

39.9 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 solution of sodium hydroxide. Then, 350 ml of methylene chloride was added thereto, and 17.0 g (0.172 mol) of phosgene was blown in over 20 minutes while being maintained at 15 캜 while stirring. After the completion of the blowing of phosgene, 0.555 g of p-tert-butylphenol from DIC Co., Ltd. was added as a molecular weight regulator, 100 ml of a 5 mass% aqueous sodium hydroxide solution and 100 ml of methylene chloride were further added, After the liquid was emulsified, 1 ml of triethylamine was added and the mixture was stirred at 20 캜 to 25 캜 for about 1 hour to carry out the polymerization reaction. After completion of the polymerization, the reaction solution was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and washing was repeated until the conductivity of the cleaning liquid (water phase) became 10 μS / cm or less. The solution was added dropwise to hot water, the solvent was removed by evaporation, and the solid product was pulverized to obtain a precipitate in the form of a white powder. The resulting 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.

[Table 3]

As described above, according to the above-described embodiment, BPCDMA, that is, 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane is used as a monomer as a monomer, It was confirmed that an aromatic polycarbonate resin having a high transition point and excellent heat resistance and a high surface hardness can be produced.

On the other hand, in the case of the bisphenol-derived polycarbonate resin prepared by using BPA or the like as a main monomer component, the properties of heat resistance and surface hardness are inferior to those of the polycarbonate resin of the above-described examples.

Further, in Example 22, although BPCDMA-2 having a relatively high sulfur concentration as an impurity was used, there was no particular problem. More specifically, Example 12 using BPCDMA containing almost no sulfur impurities and Comparative Example 22 using BPCDMA-2 containing about 394 ppm of sulfur impurity obtained in Synthesis Example 4 In comparison with the results, in the latter polymerization reaction using BPCDMA-2, the water phase of the reaction solution after polymerization tends to be slightly difficult to separate from the organic phase, so that the molecular weight of the produced polycarbonate resin, (In Example 12, the PC resin had a molecular weight of 27,100, a yield of 88% and a terminal OH group ratio of 60 ppm, whereas in Example 22, the PC resin had a molecular weight of 20,000 and a yield of 66 %, The terminal OH group ratio is 570 ppm).

Industrial availability

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- -Hydroxyphenyl) -5,7-dimethyladamantane can be used to produce a resin having excellent heat resistance, optical characteristics, and mechanical characteristics, and therefore its industrial significance is large.

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 of 500 ppm or less as an impurity and a sulfur concentration of 400 ppm or less.
Bis (methyl-hydroxyphenyl) -5 (meth) acrylate having an isomer purity of not less than 98% and having 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane as a main component , 7-dimethyladamantane.
Bis (3-methyl-4-hydroxyphenyl) -5,7-dimethylanthraquinone, which is characterized in that 1,3-dibromo-5,7-dimethyladamantane is reacted with o- Just a method of making a shot.
(3-methyl-4-hydroxyphenyl) -5, 5-dihydroxy-5,7-dimethyladamantane and o-cresol in the presence of an acid catalyst, 7-Dimethyladamantane.
The method according to claim 4 or 5,
After the reaction, a poor solvent was added and the mixture was stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, (3-methyl-4-hydroxyphenyl) -5,7-dimethylpyridine (hereinafter referred to as &quot; 3-methyl-4-hydroxyphenylsulfonyl chloride &quot;), which is obtained by washing a solution obtained by dissolving the separated crude crystals in an organic solvent with an alkaline aqueous solution (Preparation method of adamantane).
The method according to claim 4 or 5,
After the reaction, a poor solvent was added and the mixture was stirred to precipitate crude crystals of 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane, Bis (3-tert-butylpyridazinone) which is obtained by dissolving a separated crude crystal in an organic solvent is washed with an alkaline aqueous solution, again dissolved in an organic solvent, and a poor solvent is added, Methyl-4-hydroxyphenyl) -5,7-dimethyladamantane.
An aromatic polycarbonate resin containing a constituent unit derived from 1,3-bis (3-methyl-4-hydroxyphenyl) -5,7-dimethyladamantane represented by the following formula (1).
[Chemical Formula 1]

9. The method of claim 8,
1,3-bis (methyl-hydroxyphenyl) - 5,7-dimethyladamantane whose main component is 1,3-bis (3-methyl-4-hydroxyphenyl) And an aromatic polycarbonate resin containing a constituent unit derived from 5,7-dimethyladamantane.
10. The method according to claim 8 or 9,
An aromatic polycarbonate resin further comprising a structural unit represented by the following general formula (2).
(2)

(Wherein R ₁ to R ₄ each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkyl group having 1 to 5 carbon atoms A halogen atom, a sulfonyl group, an alkylidene group having 2 to 10 carbon atoms, a cycloalkylidene group having 5 to 12 carbon atoms, a cycloalkylidene group having 7 to 15 carbon atoms, an aryl group having 6 to 12 carbon atoms, An alkylarylidene group or a fluorenylidene group of 1 to 10 carbon atoms.
11. The method of claim 10,
Wherein the constituent unit represented by the general formula (2) is at least one selected from the group consisting of 1,1'-biphenyl-4,4'-diol (BP), bis (4-hydroxyphenyl) methane (BPF) 4-hydroxyphenyl) ethane (BPE), bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfoxide, bis Bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, (4-hydroxyphenyl) propane (BPC), 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) BPZ), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-methyl- 4-hydroxyphenyl) ?,? - bis [2- (p-hydroxyphenyl) ethyl] polydimethylsiloxane,?,? - bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane, and 4,4 '- [1,3-phenylenebis (1-methylethylidene)] bisphenol. Carbonate resin.
The method according to any one of claims 8 to 11,
An aromatic polycarbonate resin having a viscosity average molecular weight of 1.0 x 10 ⁴ to 8.0 x 10 ⁴ .
13. The method according to any one of claims 8 to 12,
The content of the structural unit represented by the formula (1) is 10 to 100 mol%.
14. The method according to any one of claims 8 to 13,
An aromatic polycarbonate resin having a glass transition temperature of 160 ° C or higher.
15. The method according to any one of claims 8 to 14,
An aromatic polycarbonate resin having a pencil hardness of not less than HB.
A film and a sheet using the aromatic polycarbonate according to any one of claims 8 to 15.
17. The method of claim 16,
Wherein the film and the sheet are transparent conductive films.
A process for producing an aromatic polycarbonate resin according to any one of claims 8 to 15, wherein 1,3-dihydroxy-5,7-dimethyladamantane represented by the following formula (3) is used as a raw material .
(3)

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