TWI465481B - Aromatic polycarbonate polymers - Google Patents

Description

Aromatic polycarbonate polymer

The present invention relates to aromatic polycarbonate polymers, and more particularly to aromatic polycarbonate polymers having a high degree of flame retardancy.

Polycarbonate resin is excellent in strength, electrical properties, transparency, etc., and is widely used as a glass substitute material and engineering plastics in OA equipment and electricity. Various fields such as electronics, automotive, and construction. Among these, in the field of OA, the field of electronics and electronics, there is a field that requires a high degree of flame retardancy.

Although a polycarbonate resin has a high oxygen index among various thermoplastic resins, and is generally a self-extinguishing resin, it is proposed to add a halogen-based, sulfur-based, phosphorus-based or the like for the purpose of further improving flame retardancy. Various flame retardants. For example, in Patent Documents 1 and 2, a polycarbonate copolymer using a bromine-containing comonomer is disclosed, but a polycarbonate resin containing such a halogen may cause a harmful substance to be generated during firing. Further, for example, in Patent Document 3, a polycarbonate copolymer using a halogen-free comonomer is disclosed, but its flame retardancy is insufficient.

[Patent Document 1] JP-A-H05-279467

[Patent Document 2] JP-A-9-87377

[Patent Document 3] Japanese Patent Laid-Open No. Hei 5-117382

In the above-described circumstances, the present invention has an object to provide an aromatic polycarbonate polymer which is high in flame retardancy and which does not contain a halogen which generates a harmful substance when it is burned.

The inventors of the present invention have found that the above problems can be solved by repeating meticulous research and finding that an aromatic polycarbonate polymer composed of a specific repeating unit is found. The present invention is an invention based on this related knowledge.

That is, the present invention provides

An aromatic polycarbonate polymer characterized in that the main chain contains a repeating unit represented by the following general formula (I); (wherein R ¹ and R ² each independently represent an aryl group; and Y represents a single bond or a linking group represented by -C(CH ₃ ) ₂ -).

2. The aromatic polycarbonate polymer according to the above 1, wherein the repeating unit represented by the general formula (I) or the repeating unit represented by the general formula (I) and the following a repeating unit represented by the formula (II); (Wherein, X represents a single bond, -S -, - SO -, - SO 2 -, - O -, - CO - ﹑ - CR ³ R ⁴ -, or the following general formula (III), (IV) or The linking group represented by (V); R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms).

3. The aromatic polycarbonate polymer according to the above 1 or 2, wherein the molar ratio of the repeating unit represented by the above general formula (I) and the repeating unit represented by the above general formula (II) is 100. :0~1:99;

4. The aromatic polycarbonate polymer according to any one of the above 1 to 3, wherein the viscosity average molecular weight is 10,000 to 50,000;

5. The aromatic polycarbonate polymer according to any one of 1 to 4 above, wherein R ¹ and R ² are a phenyl group, and Y is a single bond;

The aromatic polycarbonate polymer according to any one of the above 1 to 4, wherein R ¹ and R ² are a phenyl group, and Y is a linking group represented by -C(CH ₃ ) ₂ -.

The aromatic polycarbonate polymer of the present invention is a halogen which does not contain a harmful substance when it is burned, and has high flame retardancy.

[Best Mode for Carrying Out the Invention]

The aromatic polycarbonate polymer of the present invention may contain a repeating unit represented by the above general formula (I) as a main chain as described above, or may be a main chain system represented by the above general formula (I). It is preferably constituted by a repeating unit or a repeating unit represented by the above general formula (I) and a repeating unit represented by the above general formula (II). The repeating unit represented by the above general formula (I) and the repeating unit represented by the above general formula (II) may be mixed with two or more kinds of repeating units. The production method is not particularly limited. For example, it may be added to a dilute phenol, phosgene or the like in an inert organic solvent such as dichloromethane in the presence of a catalyst or a molecular weight modifier. It is produced by the reaction of a carbonate precursor, and can also be produced by a transesterification reaction of a dihydric phenol with a carbonate precursor such as a carbonate compound.

The dihydric phenol used for the production of the repeating unit represented by the above general formula (I) is exemplified as the dihydric phenol used in the production of the aromatic polycarbonate polymer of the present invention (hereinafter, referred to as dihydric phenol A). And a dihydric phenol (hereinafter referred to as dihydric phenol B) used as a raw material of the repeating unit represented by the above general formula (II).

The dihydric phenol A is a dihydric phenol represented by the following general formula (A).

(wherein R ¹ and R ² each independently represent an aryl group; and Y represents a single bond or a linking group represented by -C(CH ₃ ) ₂ -).

Examples of the aryl group in the above general formula (I) and general formula (A) include a phenyl group, a tolyl group, a styryl group, a p-nitrophenyl group, a p-methoxyphenyl group, and a p-ethoxy group. Phenyl, biphenylyl, naphthyl, anthracenyl, tert-triphenyl, anthracenyl, etc., preferably a carbon number of 6 to 12, and a phenyl group is more preferable.

As the above dihydric phenol A, one type or two or more types derived from the above general formula (A) can be used.

The dihydric phenol A represented by the above general formula (A) is 3,3'-dibenzimid-4,4'-diphenol, 2,2-bis(3'-benzidine-4'-hydroxyl group Phenyl)propane is preferred.

The dihydric phenol B is a dihydric phenol represented by the following general formula (B).

(wherein X represents a single bond, -S-, -SO-, -SO ₂ -, -O-, -CO-, -CR ³ R ⁴ -, or the following general formula (III), (IV) or The linking group represented by (V) is preferably a linking group represented by -CR ³ R ⁴ -; and R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a carbon number of 6 to 12 The substituted or unsubstituted aryl group preferably represents a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms in the above general formula (II) and general formula (B) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. An alkyl group such as tert-butyl, n-pentyl, isopentyl, n-hexyl, isohexyl, cyclopentyl, cyclohexyl or the like.

The substituted or unsubstituted aryl group having 6 to 12 carbon atoms in the above general formula (II) and general formula (B) may, for example, be a phenyl group, a tolyl group, a styryl group, a p-nitrophenyl group or a p- Methoxyphenyl, p-ethoxyphenyl, biphenyl, naphthyl and the like.

As the above dihydric phenol B, one type or two or more types derived from the above general formula (B) can be used.

The dihydric phenol B represented by the above general formula (B) is preferably 2,2-bis(4'-hydroxyphenyl)propane (commonly known as bisphenol A).

The foregoing carbonate precursor is exemplified by phosgene used in the interfacial polycondensation of a general polycarbonate, and examples thereof include triphosgene, bromo phosgene, bis(2,4,6-trichlorophenyl) carbonate, and bis ( 2,4-dichlorophenyl)carbonate, bis(2-cyanophenyl)carbonate, trichloromethyl chloroformate, etc., or a diaryl carbonate compound or dialkyl carbonate used in the transesterification reaction An ester compound or an alkyl aryl carbonate compound. Specific examples of the diaryl carbonate compound include diphenyl carbonate, xylene carbonate, bis(chlorophenyl) carbonate, m-cresol carbonate, binaphthyl carbonate, and bis(diphenyl)carbonic acid. Ester, bisphenol A bisphenyl carbonate, etc.; specific examples of the dialkyl carbonate compound include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, bisphenol A Dimethyl carbonate or the like; specific examples of the alkyl aryl carbonate compound include methyl phenyl carbonate, ethyl phenyl carbonate, butyl phenyl carbonate, cyclohexyl phenyl carbonate, bisphenol A Methyl phenyl carbonate and the like.

As the molecular weight modifier, various types of users from polymerization of a usual polycarbonate can be used. Specifically, the monohydric phenol may, for example, be phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumenylphenol, p-nonylphenol, behenic acid. Alkylphenol, tetracosylphenol, hexadecylphenol, octadecylphenol, triacontanol, tridodecylphenol, tridecylphenol, and the like. Among these monohydric phenols, p-tert-butylphenol, p-cumenylphenol or the like is preferably used. These may be one type or may be a mixture of two or more types. Further, these molecular weight modifiers may be used in combination with other phenol compounds or the like insofar as the effects of the present invention are not impaired.

As the catalyst, a phase transfer catalyst such as a tertiary amine or a salt thereof, a quaternary ammonium salt, a quaternary phosphonium salt or the like can be preferably used. Examples of the tertiary amine include triethylamine, tributylamine, N,N-dimethylcyclohexylamine, pyridine, dimethylaniline, etc., and a tertiary amine salt, and examples thereof include tertiary amines. Hydrochloride, bromate, etc. The quaternary ammonium salt may, for example, be trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride or tetrabutylammonium chloride. Further, tetrabutylammonium bromide or the like; and a quaternary phosphonium salt may, for example, be tetrabutylphosphonium chloride or tetrabutylphosphonium bromide. These catalysts may be used singly or in combination of two or more. Among the above catalysts, a tertiary amine is preferred, and a triethylamine is particularly preferred.

The aforementioned inert organic solvent has various kinds. For example, dichloromethane (methylene dichloride); chloroform; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; ; 1,1,2-trichloroethane; 1,1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene . These organic solvents may be used alone or in combination of two or more. Among these, methylene chloride is particularly preferred.

For the above-mentioned diverging agent, for example, 1,1,1-tris(4-hydroxyphenyl)ethane; 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methyl group can be used. Ethyl]phenyl]ethylidene]bisphenol; α,α',α"-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene; 1-[α-methyl- Α-(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4"-hydroxyphenyl)ethyl]benzene; fluoroglycine, trimellitic acid, ruthenium double A compound having three or more functional groups such as (o-cresol).

In the aromatic polycarbonate polymer of the present invention, the molar ratio of the repeating unit represented by the above general formula (I) and the repeating unit represented by the above general formula (II) is from 100:0 to 1:99. Preferably, 100:0~2:98 is better. When the repeating unit represented by the above general formula (I) is less than the above range, it is less preferable from the viewpoint of flame retardancy.

The aromatic polycarbonate polymer according to the present invention preferably has a viscosity average molecular weight of 10,000 to 50,000, preferably 11,000 to 30,000, and particularly preferably 13,000 to 25,000, from the viewpoint of mechanical properties and moldability.

[Examples]

Hereinafter, the aromatic polycarbonate polymer of the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the invention.

Production Example 1 (Synthesis of 3,3'-dibenzimid-4,4'-diphenol)

4,4'-diphenol (98.9 g) and benzoic acid (135.7 g) were dissolved in benzene (493 ml) under argon atmosphere. Phosphorus chloride (145.6 ml) was added to the suspension at 80 ° C. Stir for 3 hours. After cooling, the white suspension solution was transferred to ice water and filtered. It was washed twice with ion-exchanged water (1 liter), and dried to give white crystals. To the white crystals (190 g), o-dichlorobenzene (2,850 ml) was added, and aluminum chloride (136.8 g) was added, followed by heating under reflux for 3 hours. After allowing to cool, water and an aqueous sodium hydroxide solution (2 mol/liter) were added to the suspension solution. The suspension solution was further neutralized with concentrated hydrochloric acid, and the precipitated crystals were filtered. After the crude crystals were washed twice with methanol (1 L), the crystals were purified by recrystallization from ethyl acetate.

Production Example 2 (Synthesis of 2,2-bis(3'-benzoguanidino-4'-hydroxyphenyl)propane)

Production Example 1 was carried out in the same manner as in Production Example 1 except that 4,4'-diphenol (98.9 g) was changed to 2,2-bis(4'-hydroxyphenyl)propane (121.1 g).

Example 1 (1) Polycarbonate oligomer synthesis step

To a 5.6 mass% aqueous sodium hydroxide solution, sodium dithionite was added in an amount of 2000 ppm by mass relative to the bisphenol A (hereinafter, also abbreviated as BPA) dissolved therein, and bisphenol A was dissolved therein until the bisphenol A concentration became 13.5 mass. %, a sodium hydroxide aqueous solution of bisphenol A was prepared. This bisphenol A aqueous solution of sodium hydroxide 40 liter/hr and dichloromethane 15 liter/hr and phosgene 4.0 kg/hr were continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube length of 30 m. The tubular reactor has a sleeve portion through which cooling water is passed to keep the temperature of the reaction liquid below 40 °C.

The reaction liquid from the tubular reactor was continuously introduced into a 40-liter inner tank with a backing wing and a baffle-type tank reactor, and a sodium hydroxide aqueous solution of bisphenol A was further added thereto at 2.8 liter/hr, 25 The reaction was carried out after 0.07 L/hr of a mass% aqueous sodium hydroxide solution, 17 L/hr of water, and 0.64 L/hr of a 1% by mass aqueous solution of triethylamine.

The reaction liquid overflowed from the tank type reactor was continuously taken out, and the aqueous phase was separated and removed by standing, and a dichloromethane phase was taken. The polycarbonate oligomer obtained had a concentration of 321 g/liter and a chloroformate group concentration of 0.73 mol/liter.

(2) Polycarbonate polymerization step

Add 142 ml of oligomer solution and chloroform of 3,3'-dibenzimid-4,4'-diphenol to a 1-liter tank reactor equipped with a buffer plate, agitating stirring blades and a cooling jacket. Solution (dissolve 4.82 g of 3,3'-dibenyl-4,4'-diphenol in 62 ml of chloroform), 28.4 μl of triethylamine, and an aqueous solution of sodium hydroxide (dissolve 2.69 g of NaOH in water) 39.3 ml of an aqueous solution), a reaction of a polycarbonate oligomer with 3,3'-dibenzimid-4,4'-diphenol was carried out for 20 minutes.

To the polymerization solution, a solution of p-tert-butylphenol (PTBP) in dichloromethane (dissolving PTBP 866 mg in 40 ml of dichloromethane) and a sodium hydroxide aqueous solution of BPA (as opposed to NaOH 15.3 g) were added. Thereafter, the dissolved BPA was dissolved in 2000 parts by mass of sodium dithionite in an aqueous solution of 78.1 ml of water to dissolve BPA 7.87 g, and polymerization was carried out for 40 minutes.

After 200 ml of dichloromethane for dilution was added, it was separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and NaOH, and the organic phase was isolated. The obtained polycarbonate resin in a dichloromethane solution, this solution is sequentially used with 15% by volume of 0.03 mol / L. The NaOH aqueous solution was washed with 0.2 mol/liter of hydrochloric acid, and then washed with pure water until the conductivity in the washed aqueous phase became 0.05 μS/m or less. The polycarbonate copolymer obtained by washing is concentrated in a dichloromethane solution. The pulverization was carried out, and the obtained small sheet was dried at 100 ° C under reduced pressure to obtain an aromatic polycarbonate copolymer. The molar ratio of the repeating unit derived from 3,3'-dibenzimid-4,4'-diphenol and the repeating unit derived from BPA determined by ¹³ C-NMR and ¹ H-NMR was 8:92.

Example 2

In the polymerization step of the (2) polycarbonate of Example 1, except that 3,3'-dibenyl-4,4'-diphenol was changed to 9.24 g, the aqueous solution of BPA in sodium hydroxide was changed to The same procedure as in Example 1 was carried out except that 4.44 g of NaOH was dissolved in an aqueous solution of 65 ml of water to dissolve an aqueous solution of 5.11 g of BPA. The obtained polycarbonate was subjected to ¹³ C-NMR and ¹ H-NMR to obtain a repeating unit derived from 3,3'-dibenzimid-4,4'-diphenol and a molar unit derived from a repeating unit of BPA. The result is 13:87.

Example 3 (1) Polycarbonate oligomer synthesis step

To a concentration of 5.6 mass% sodium hydroxide aqueous solution, a sodium dithionite having a total amount of BPA and 3,3'-dibenzimid-4,4'-diphenol dissolved in a ratio of 0.2% by mass was added thereto. BPA: 3,3'-benzophenone-4,4,-diphenol = 75:25 (mole ratio) dissolved in BPA and 3,3'-dibenzimid-4,4'-diphenol total A monomer aqueous sodium hydroxide solution was prepared until the concentration reached 13.5% by mass. The sodium hydroxide aqueous solution of the above monomer was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube diameter of 30 m at a flow rate of 35 L/hr and dichloromethane at a flow rate of 35 L/hr while continuously passing at a flow rate of 4.0 kg/hr. Phosgene. The tubular reactor has a sleeve portion through which cooling water is passed to keep the temperature of the reaction liquid below 40 °C.

The reaction liquid sent from the tubular reactor was separated by standing to remove the aqueous phase, and a dichloromethane phase was taken. The polycarbonate oligomer solution obtained in this way has an oligomer concentration of 258 g/L, a chloroformate concentration of 0.73 mol/L, and 3,3'-dibenzimid-4,4'-diphenol. The content is 25 mol%.

(2) Polycarbonate polymerization step

174 ml of the above oligomer solution, 51 ml of dichloromethane, and 3,3'-dibenzimid-4,4 were placed in a tank reactor equipped with a buffer plate and a stirring type stirring blade. a solution of '-diphenol in chloroform (dissolving 10.4 g of 3,3'-dibenzimid-4,4'-diphenol in 62 ml of chloroform), adding 35.4 μl of triethylamine, aqueous sodium hydroxide solution (3.36 g of NaOH was dissolved in an aqueous solution of 49.2 ml of water), and a reaction of the polycarbonate oligomer with 3,3'-dibenzimid-4,4'-diphenol was carried out for 20 minutes.

To the polymerization solution, a solution of PTBP in dichloromethane (13.6 g of PTBP dissolved in 40 ml of dichloromethane) and an aqueous solution of sodium hydroxide with BPA (with a mass of 2,000 mg of NaOH 5.76 g and BPA after dissolution) The ppm of sodium dithionite was dissolved in 84.2 ml of water to dissolve BPA 6.97 g), and polymerization was carried out for 40 minutes.

After 200 ml of dichloromethane for dilution was added, it was separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and NaOH, and the organic phase was isolated. The obtained polycarbonate resin in a dichloromethane solution, this solution is sequentially used with 15% by volume of 0.03 mol / L. The NaOH aqueous solution was washed with 0.2 mol/L hydrochloric acid, and then washed with pure water until the conductivity in the washed aqueous phase became 0.05 μS/m or less. The polycarbonate copolymer obtained by washing is concentrated in a dichloromethane solution. The pulverization was carried out, and the obtained small sheet was dried at 100 ° C under reduced pressure to obtain an aromatic polycarbonate copolymer. The molar ratio of the repeating unit derived from 3,3'-dibenzimid-4,4'-diphenol and the repeating unit derived from BPA determined by ¹³ C-NMR and ¹ H-NMR was 30:70.

Example 4 (2) Polycarbonate polymerization step

In the polymerization step of the (2) polycarbonate of Example 1, except that 5.34 g of 2,2-bis(3'-benzimidazole-4'-hydroxyphenyl)propane was used, the 3,3'-di was substituted. The same procedure as in Example 1 was carried out except that benzamidine-4,4'-diphenol. The molar ratio of the repeating unit derived from 2,2-bis(3'-benzimid-4'-hydroxyphenyl)propane to the repeating unit derived from BPA as determined by ¹³ C-NMR and ¹ H-NMR was 8:92.

Example 5

In the polymerization step of the (2) polycarbonate of Example 2, except that 10.23 g of 2,2-bis(3'-benzimidazole-4'-hydroxyphenyl)propane was used, the 3,3'-di was substituted. The same procedure as in Example 2 was carried out except that benzamidine-4,4'-diphenol. Regarding the obtained aromatic polycarbonate copolymer, the repeating unit derived from 3,3'-dibenzimid-4,4'-diphenol was obtained by ¹³ C-NMR and ¹ H-NMR. The molar ratio of the repeating unit from BPA was 13:87.

Example 6 (1) Polycarbonate oligomer synthesis step

To a concentration of 5.6 mass% sodium hydroxide aqueous solution, a total amount of sodium dithionite was added in an amount of 0.2% by mass based on the amount of BPA and 2,2-bis(3'-benzimidazole-4'-hydroxyphenyl)propane dissolved later. , dissolved therein to BPA: 2,2-bis(3'-benzhydrazin-4'-hydroxyphenyl)propane = 75:25 (mole ratio) and BPA and 2,2-bis(3'-benzene A monomer aqueous solution of sodium hydroxide was prepared until the total concentration of formazan-4'-hydroxyphenyl group reached 13.5% by mass. The sodium hydroxide aqueous solution of the above monomer was continuously passed through a tubular reactor having an inner diameter of 6 mm and a tube diameter of 30 m at a flow rate of 35 L/hr and dichloromethane at a flow rate of 35 L/hr while continuously passing at a flow rate of 4.0 kg/hr. Phosgene. The tubular reactor has a sleeve portion through which cooling water is passed to keep the temperature of the reaction liquid below 40 °C.

The reaction liquid sent from the tubular reactor was separated by standing to remove the aqueous phase, and a dichloromethane phase was taken. The polycarbonate oligomer solution obtained in this manner has an oligomer concentration of 258 g/L, a chloroformate group concentration of 0.73 mol/L, and 2,2-bis(3'-benzidine-4'-hydroxyl group. The phenyl)propane content was 25 mol%.

(2) Polycarbonate polymerization step

174 ml of the above oligomer solution, 51 ml of dichloromethane, and 2,2-bis(3'-benzamide-) were placed in a tank reactor equipped with a buffer plate and a stirring type stirring blade of 1 liter. a solution of 4'-hydroxyphenyl)propane in chloroform (dissolving 11.11 g of 2,2-bis(3'-benzimidazole-4'-hydroxyphenyl)propane in 62 ml of chloroform), adding triethylamine 35.4 A microliter, aqueous solution of sodium hydroxide (dissolving 3.36 g of NaOH in 49.2 ml of water) for 20 minutes of polycarbonate oligomer and 2,2-bis(3'-benzidine-4'-hydroxyphenyl) The reaction of propane.

To the polymerization solution, a solution of PTBP in dichloromethane (13.6 g of PTBP dissolved in 40 ml of dichloromethane) and an aqueous solution of sodium hydroxide with BPA (with a mass of 2,000 mg of NaOH 5.76 g and BPA after dissolution) The ppm of sodium dithionite was dissolved in 84.2 ml of water to dissolve BPA 6.97 g), and polymerization was carried out for 40 minutes.

After 200 ml of dichloromethane for dilution was added, it was separated into an organic phase containing polycarbonate and an aqueous phase containing excess bisphenol A and NaOH, and the organic phase was isolated. The obtained polycarbonate resin in methylene chloride solution, the solution was sequentially used with 15% by volume of 0.03 mol/L. The NaOH aqueous solution was washed with 0.2 mol/L hydrochloric acid, and then washed with pure water until the conductivity in the washed aqueous phase became 0.05 μS/m or less. The polycarbonate copolymer obtained by washing is concentrated in a dichloromethane solution. The pulverization was carried out, and the obtained small sheet was dried at 100 ° C under reduced pressure to obtain a polycarbonate. The molar ratio of the repeating unit derived from 2,2-bis(3'-benzimid-4'-hydroxyphenyl)propane and the repeating unit derived from BPA obtained by ¹³ C-NMR and ¹ H-NMR was 30. :70.

Comparative example 1

In the polymerization step of the (2) polycarbonate of Example 1, except that 3,3'-dibenzimid-4,4'-diphenol was changed to 4.35 g of 4,4'-diphenol, Example 1 was carried out in the same manner. The molar ratio of the repeating unit derived from 4,4'-diphenol and the repeating unit derived from BPA as determined by ¹³ C-NMR and ¹ H-NMR was 10:92.

Comparative example 2

The bisphenol A type polycarbonate resin (trade name: TARFLON FN1700A, manufactured by Idemitsu Kogyo Co., Ltd., molecular weight: 17,000) was used instead of the aromatic polycarbonate copolymer obtained in the examples.

Using the aromatic polycarbonate copolymer obtained in Examples 1 to 6 and the polycarbonates of Comparative Example 1 and Comparative Example 2, the measurement of the viscosity average molecular weight, the copolymerization amount, and the measurement of the thermogravimetric residue were carried out as follows. Measurement of the oxygen limited index. The results are shown in Table 1.

(Measurement of viscosity average molecular weight)

The viscosity of the methylene chloride solution at 20 ° C was measured using a Uber Lauder type viscometer to determine the ultimate viscosity [η], and the viscosity average molecular weight was calculated from [η] = 1.23 × 10 ^-5 Mv ^0.83 ( Mv).

(Measurement of the amount of copolymerization)

1H-NMR was measured using JNM-LA500, and the amount of copolymerization was calculated.

(Measurement of hot weight residue)

The copolymer which was dried at 100 ° C for 8 hours or more was heated at a temperature of 20 ° C / min using a thermal mass scale (manufactured by PerkinElmer, TGA 7), and the weight residue at 700 ° C was measured ( weight%).

(Measurement of oxygen limit index)

The polycarbonate was molded and measured in accordance with JIS K 7201 (length 80 mm, width 10 mm, thickness 4 mm).

The oxygen limit index refers to the minimum oxygen concentration required for the material to be tested to maintain combustion, expressed as the % of capacity in the air. The larger the value, the higher the flame retardancy of this material.

Dihydric phenol A-1: 3,3'-dibenylhydrazine-4,4'-diphenol dihydric phenol A-2: (2,2-bis(3'-benzidine-4'-hydroxybenzene) Propane

[Industrial availability]

As described above, the related aromatic polycarbonate polymer of the present invention has a unique structure and is particularly excellent in flame retardancy, so that it can be widely used in OA machines and electricity. Various fields such as electronics, automotive, and construction.

Claims (6)

An aromatic polycarbonate polymer characterized in that the main chain contains a repeating unit represented by the following general formula (I). (wherein R ¹ and R ² each independently represent an aryl group; and Y represents a single bond or a linking group represented by -C(CH ₃ ) ₂ -). An aromatic polycarbonate polymer according to claim 1, wherein the main chain is composed of a repeating unit represented by the above general formula (I) or a repeating unit represented by the above general formula (I) And a repeating unit represented by the following general formula (II), (wherein X represents a single bond, -S-, -SO-, -SO ₂ -, -O-, -CO-, -CR ³ R ⁴ -, or the following general formula (III), (IV) or (V) the linking group; R ³ and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms) An aromatic polycarbonate polymer according to claim 1 or 2, wherein the molar ratio of the repeating unit represented by the above general formula (I) and the repeating unit represented by the above general formula (II) is 100. :0~1:99. An aromatic polycarbonate polymer according to claim 1 or 2, wherein the viscosity average molecular weight is 10,000 to 50,000. An aromatic polycarbonate polymer according to claim 1 or 2 wherein R ¹ and R ² are a phenyl group and Y is a single bond. An aromatic polycarbonate polymer according to claim 1 or 2, wherein R ¹ and R ² are a phenyl group, and Y is a linking group represented by -C(CH ₃ ) ₂ -.