JPH06128371A - Polycarbonate polymer - Google Patents

Abstract

PURPOSE:To obtain the title polymer which is improved in fluidity without detriment to mechanical properties such as impact resistance, and desirably be used for optical components, machine parts, electrical and electronic components, etc., and comprises two specified kinds of carbonate structural units. CONSTITUTION:The polymer has a main chain comprising carbonate structural units of formula I wherein X<1> and Y<1> are each H, halogen, 1-8 C alkyl or 6-15 C alkyl; m and n are each 1-4; and A is an alkylidene group of formula II wherein j is 0-6; and k is 7-20 and carbonate structural units of formula III wherein X<2> and Y<2> are each H, halogen, 1-8 C alkyl, 6-15 C arylene, 7-15 C arylalkylidene, a bivalent group of O, S, SO2 or CO or a single bond and has the content of structural units of formula I of 0.5-80mol% based on all the carbonate structural units and a viscosity-average molecular weight of 10000-50000. This polymer is improved in fluidity without detriment to mechanical properties such as impact resistance.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polycarbonate polymer, and more specifically, to improve fluidity without impairing mechanical properties such as impact resistance, optical parts, mechanical parts, electric / electronic parts, The present invention relates to a polycarbonate polymer preferably used for automobile parts and the like.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
Polycarbonate composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is an engineering plastic excellent in heat resistance, impact resistance, transparency and the like, and is, for example, an optical component, a mechanical component, an electric / electronic component. It is used for automobile parts and various containers. However, conventional bisphenol A-based polycarbonates have low fluidity, and improvement in fluidity is desired from the viewpoint of improvement of molding cycle and precision molding. Conventionally, in order to improve fluidity, a method of lowering the molecular weight is generally adopted. However, with this method, although the molecular weight can be reduced to a certain extent, the impact resistance is significantly reduced, and there is a limit to that. As an improved technique, a technique in which the impact resistance is not significantly lowered even if the molecular weight is lowered is disclosed in, for example, JP-A-64-70528. This is a method in which cumylphenol is used as a terminal group sealant and the acetone-soluble matter is controlled. According to this method, the fluidity can be improved to some extent, but further improvement is desired. Also known is a method of introducing a compound containing a flexible long-chain fatty chain into the terminal or inside the molecule. That is, for example, in Japanese Examined Patent Publication No. 52-50078, an alkylphenol and an aliphatic acid halide are used as a compound containing a long fatty chain at the terminal. With this technology,
Since it can be introduced only at the terminal, there is a limit to introducing an effective amount. Further, JP-A-3-212424 discloses a technique of introducing an aliphatic dicarboxylic acid into the molecule. However, in this method, the reactivity of the aliphatic dicarboxylic acid is low, complicated operations such as pH control are required, and it is difficult to manufacture industrially.

The present invention overcomes the drawbacks of conventional polycarbonates, improves the fluidity without impairing mechanical properties such as impact resistance, and is a novel polycarbonate polymer that is easy to manufacture industrially. It is intended to provide a coalesce.

[0004]

Means for Solving the Problems As a result of intensive research conducted by the present inventors to develop a novel polycarbonate polymer having improved fluidity without impairing mechanical strength,
By using a bisphenol introduced with a specific fatty chain, it is possible to introduce an arbitrary amount of the fatty chain, a polycarbonate polymer having extremely excellent fluidity can be easily produced industrially with good reactivity. I found it. The present invention has been made based on such findings. That is, in the present invention, the main chain has the general formula (I)

[0005]

[Chemical 4]

[Wherein, X ¹ and Y ¹ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms, and m and n are integers of 1 to 4 respectively. Is. A is the general formula (II)

[0007]

[Chemical 5]

(Wherein j is an integer of 0 to 6 and k is 7
Is an integer of -20. ) Represents an alkylidene group. ] The carbonate structural unit I represented by
II)

[0009]

[Chemical 6]

[Wherein, X ² and Y ² each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms, and p and q are each an integer of 1 to 4] Is. B is an alkylidene group having 1 to 15 carbon atoms, an alkylene group having 1 to 15 carbon atoms, and 6 to 6 carbon atoms.
15 arylene group, arylalkylene group having 7 to 15 carbon atoms, -O -, - S -, - SO 2 -, - CO- or a single bond. ] The carbonate structural unit II represented by the following, the ratio of the carbonate structural unit I is 0.5 to 80 mol% with respect to all the carbonate structural units, and the viscosity average molecular weight is 10000 to 50000. A polycarbonate polymer is provided.

The polycarbonate polymer of the present invention is a polycarbonate polymer having a carbonate structural unit I represented by the general formula (I) and a carbonate structural unit II represented by the general formula (III) as a main chain. . In the polycarbonate polymer of the present invention, the ratio of the carbonate structural unit I represented by the general formula (I) is such that the structural units I and II
Of 0.5 to 80 mol%, preferably 1 to 50
Mol%. The viscosity average molecular weight is 100,000.
It is characterized in that it is 0 to 50,000, and has excellent fluidity without impairing mechanical strength.

The polycarbonate polymer of the present invention has the general formula (IV) as the raw material bisphenol.

[0013]

[Chemical 7]

(Wherein X ¹ , Y ¹ , m, n and A are the same as above) and the bisphenol (i) and the general formula (V)

[0015]

[Chemical 8]

The bisphenol (ii) represented by the formula (wherein X ² , Y ² , p, q and B are the same as above) is used. The bisphenol (i) represented by the general formula (IV) is the same as the corresponding phenols and the general formula (VI).

[0017]

[Chemical 9]

It can be produced by condensing with a ketone represented by the formula (wherein j and k are the same as above). Examples of the phenols include phenol; cresol; 2,6-dimethylphenol; 2,6-dichlorophenol; 2,6-dibromophenol; o-phenylphenol; 2,6-diphenylphenol. May be used alone or in combination of two or more.

Examples of the ketones represented by the general formula (VI) include 2-dodecanone, 2-tridecanone, 2-tetradecanone, 3-tetradecanone, 2-pentadecanone, 2-hexadecanone, 3-hexadecanone, 2-Heptadecanone, 2-octadecanone, 3-octadecanone, 2-undecanone, 3-undecanone and the like can be mentioned. These ketones are easily obtained by oxidizing the corresponding olefin.

Hydrogen chloride gas, concentrated hydrochloric acid, sulfuric acid, etc. are used as a catalyst in the condensation reaction of the above-mentioned phenols and ketones, and among these, hydrogen chloride gas is particularly preferable. At this time, it is advantageous to use mercaptoacetic acid, 3-mercaptopropionic acid, dodecylthiol, calcium chloride, boric acid, hydrogen sulfide or the like as the cocatalyst. Among these promoters, mercaptoacetic acid, 3-mercaptopropionic acid, and dodecylthiol are suitable. Regarding the usage ratio of the phenols and ketones, both components are used so that the phenol / ketone molar ratio is usually 2/1 to 10/1, preferably 3/1 to 6/1. The reaction temperature is usually 10 to 100 ° C., preferably 20 to
It is selected in the range of 60 ° C., and the reaction time is usually 0.5 to 200 hours, preferably about 1 to 100 hours. The method of purifying and recovering the target bisphenol (i) from the reaction-terminated liquid is not particularly limited, but the purified bisphenol (i) can be recovered by performing the following operation, for example. That is, the reaction completion liquid is heated to 50 to 90 ° C
After washing with hot water of about 1 to 10 times, preferably about 2 to 5 times with hot water of 60 to 90 ° C., cooling is performed to precipitate a solid, and then washing with warm hexane, then 10 to 25 mmH
g, 210 ° C. or less, preferably 15 to 20 mmHg, 2
The target bisphenol (i) is obtained by distilling off unreacted phenols by distillation under reduced pressure at a temperature of 00 ° C or lower.
Is obtained. If necessary, it may be recrystallized using a suitable solvent for further purification.

On the other hand, as the bisphenol (ii) represented by the general formula (V), particularly 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A]
Is preferred. Examples of bisphenols other than bisphenol A include bis (4-hydroxyphenyl) methane; bis (4-hydroxyphenyl) phenylmethane; bis (4-hydroxyphenyl) naphthylmethane;
Bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane; Bis (3,5-dichloro-4-hydroxyphenyl) methane; Bis (3,5-dimethyl-4)
-Hydroxyphenyl) methane; 1,1-bis (4-hydroxyphenyl) ethane; 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane; 1-phenyl-
1,1-bis (4-hydroxyphenyl) ethane; 1,
2-Bis (4-hydroxyphenyl) ethane; 2-methyl-1,1-bis (4-hydroxyphenyl) propane; 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1-ethyl -1,1-bis (4-
Hydroxyphenyl) propane; 2,2-bis (3,5)
-Dichloro-4-hydroxyphenyl) propane; 2,
2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2-bis (3-chloro-4-hydroxyphenyl) propane; 2,2-bis (3-methyl-)
4-hydroxyphenyl) propane; 2,2-bis (3
-Fluoro-4-hydroxyphenyl) propane; 1,
1-bis (4-hydroxyphenyl) butane; 2,2-
Bis (4-hydroxyphenyl) butane; 1,4-bis (4-hydroxyphenyl) butane; 2,2-bis (4
-Hydroxyphenyl) pentane; 4-methyl-2,2
-Bis (4-hydroxyphenyl) pentane; 1,1-
Bis (4-hydroxyphenyl) cyclohexane; 1,
1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane; 2,2-bis (4-hydroxyphenyl) hexane; 4,4-bis (4-hydroxyphenyl) heptane; 2,2-bis (4 -Hydroxyphenyl) nonane; 1,10-bis (4-hydroxyphenyl) decane; 1,1-bis (4-hydroxyphenyl)
Dihydroxyarylalkanes such as cyclodecane,
Bis (4-hydroxyphenyl) sulfone; bis (3,3
5-dimethyl-4-hydroxyphenyl) sulfone; dihydroxyarylsulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ether; bis (3,5-dimethyl-)
4-hydroxyphenyl) ether and other dihydroxyaryl ethers, 4,4′-dihydroxybenzophenone; 3,3 ′, 5,5′-tetramethyl-4,4 ′
-Dihydroxy aryl ketones such as dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide; dihydroxyaryl such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide Sulfides, dihydroxyaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, 4,4 ′
And dihydroxydiphenyls such as dihydroxydiphenyl. In addition to the bisphenol (ii) represented by the general formula (V), dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 1,5-dihydroxynaphthalene; dihydroxynaphthalene such as 2,6-dihydroxynaphthalene, etc. Can also be used. These bisphenols may be used alone or in combination of two or more.

The polycarbonate polymer of the present invention is produced by a method commonly used in the production of ordinary polycarbonate, for example, an interfacial polycondensation method using phosgene or a phosgene derivative and a transesterification method (melting method). Of these, the interfacial polycondensation method is preferred. As an interfacial polycondensation method using phosgene or a phosgene derivative, for example, a polycarbonate oligomer of bisphenol (i) or a polycarbonate oligomer of bisphenol (ii) is previously synthesized from bisphenol and phosgene or a phosgene derivative, and the oligomer of these oligomers is not formed. A method of reacting an active organic solvent solution with an alkaline aqueous solution containing bisphenol (i) and (ii) in a predetermined ratio, and an alkaline aqueous solution containing bisphenol (i) and (ii) in a predetermined ratio. Examples thereof include a method in which phosgene or a phosgene derivative is added to a mixed solution with an inert organic solvent and the reaction is carried out. Of these, the former oligomer method is preferable. Examples of the phosgene or phosgene derivative include phosgene, triphosgene, bromophosgene, bis (2,4,6-trichlorophenyl) carbonate, bis (2,4-dichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate, and chloroformic acid. Trichloromethyl etc. are mentioned.

Next, the method for producing the polycarbonate polymer of the present invention by the oligomer method will be described.
First, the bisphenol (i) or (ii) is dissolved in an aqueous solution of an alkali metal hydroxide to prepare an alkaline aqueous solution of bisphenol. Then, phosgene or a phosgene derivative is introduced into the mixed solution of the alkaline aqueous solution and the inert organic solvent to synthesize the polycarbonate oligomer of bisphenol (i) or (ii). At this time, the alkali concentration of the alkaline aqueous solution is preferably in the range of 1 to 15% by weight, and the volume ratio of the organic phase to the aqueous phase is 5: 1 to 1: 1.
It is desirable to be in the range of 7, preferably 2: 1 to 1: 4. The reaction temperature is generally 0 to 50 ° C., preferably 5 to 40 ° C., and the reaction time is 15 minutes to 4 hours, preferably 30 minutes to 2 hours. The degree of polymerization of the polycarbonate oligomer thus obtained is usually 20 or less, preferably about 2 to 10.

Next, if desired, an inert organic solvent is added to the organic phase containing the polycarbonate oligomer thus obtained, and this and an aqueous alkaline solution containing bisphenols (i) and (ii) in a predetermined ratio are added. Contacting is performed, and the interfacial polycondensation is carried out at a temperature of usually 0 to 50 ° C., preferably 5 to 40 ° C. for about 10 minutes to 6 hours. At this time, the alkali concentration of the alkaline aqueous solution is 1 to 15% by weight.
And the volume ratio of the organic phase to the aqueous phase is 7: 1 to
It is desirable to be in the range of 1: 2, preferably 4: 1 to 1: 1. The bisphenol / oligomer ratio is such that the molar ratio of bisphenol / oligomer chloroformate group is usually 0.4 to 0.55, preferably 0.45 to 0.5.
Selected to be 5. The ratio of alkali metal hydroxide to oligomer is such that the alkali metal hydroxide / oligomer chloroformate group molar ratio is usually 1.0 to 2.
0, preferably 1.2 to 1.7. Furthermore, in this reaction, a terminal stopper or a catalyst can be used if desired. The amount of the terminator used is usually such that the molar ratio of the terminator / oligomer chloroformate group is 0.
It is chosen to be 02 to 0.20, preferably 0.04 to 0.17. On the other hand, the amount of catalyst used is such that the catalyst / oligomer chloroformate group molar ratio is usually from 1.0 × 10 ⁻³ to 10 10.
It is selected to be 0 × 10 ⁻³ , preferably 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻³ .

Examples of the alkali metal hydroxide used in the production of the polycarbonate polymer include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Of these, sodium hydroxide and potassium hydroxide are preferred.
There are various types of inert organic solvents. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane; 1,1,1,2-tetrachloroethane;
1,1,2,2-tetrachloroethane; chlorinated hydrocarbons such as pentachloroethane and chlorobenzene, and acetophenone. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferable.

Various types of end terminators can be used. Specific examples of the monohydric phenol include phenol, p-cresol, pt-butylphenol, p-cumylphenol, tribromophenol, nonylphenol and pt-octylphenol. As the catalyst, various kinds can be used. Specifically, it is a quaternary ammonium salt, a quaternary phosphonium salt, a tertiary amine, or the like. Examples of the quaternary ammonium salt include trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, Examples thereof include tetrabutylammonium chloride and tetrabutylammonium bromide. Examples of the quaternary phosphonium salt include tetrabutylphosphonium chloride and tetrabutylphosphonium bromide, and examples of the tertiary amine include triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine and dimethylaniline. And so on.

The polymer thus produced can be recovered as a polycarbonate polymer of the present invention by carrying out a recovery operation according to a usual method. The polycarbonate polymer of the present invention is a novel polycarbonate polymer having a carbonate structural unit I represented by the general formula (I) and a carbonate structural unit II represented by the general formula (III) as a main chain. In the polycarbonate polymer of the present invention, the ratio of the carbonate structural unit I represented by the general formula (I) is such that
It is 0.5 to 80 mol%, preferably 1 to 50 mol%.
And, the viscosity average molecular weight is from 10,000 to 50,000.
And has excellent fluidity without impairing mechanical strength.

[0028]

EXAMPLES Further, the present invention will be described with reference to Examples and Comparative Examples.
explain in detail. In the present invention, the ketone was synthesized by oxidizing the α-olefin with linearene [made by Idemitsu Petrochemical Co., Ltd.] by the Wacker method. For the Wacker method, see Synthesis p369, 1984 (Jiro Tsuji).
(Author). Example 1 (Synthesis of 2-dodecanone) In a 1 liter flask, Pd
Cl ₂ 53 g, placed CuCl29.7G, water 30cc and N, N'-dimethylformamide (DMF) 210cc, the flow of oxygen, followed by stirring at room temperature. 1 hour later, with vigorous stirring at room temperature, 1-dodecene (Linearene 12) 50.5 g water 10
A cc-DMF70cc solution was added dropwise. The stirring was stopped 2 hours after the dropping and the mixture was left for 24 hours. The reaction product is 3N-H
It was poured into 1 liter of Cl and extracted with ether. The extract was washed with saturated aqueous sodium carbonate solution and brine, and dried over anhydrous magnesium sulfate. Distillation under reduced pressure gave 2-dodecanone. Ketones were similarly synthesized by changing the starting α-olefin. Table 1 shows α-olefins and ketones produced.

[0029]

[Table 1]

Example 2-1 [Synthesis of 2,2-bis (4-hydroxylphenyl) dodecane] 200 g (1.09 mol) of 2-dodecanone, 6.07 g (0.03 mol) of dodecylthiol, 410 g of phenol
(4.36 mol) in a 2 liter, 3-necked flask,
With stirring, HCl gas was blown in at a rate of 80 ml / hour for 2 hours. Furthermore, it stirred at 25 degreeC for 5 hours. A part of the sample was taken, and after confirming that 2-dodecanone was almost completely consumed by gas chromatography, 500 ml of water was added, and the mixture was heated and stirred at 80 ° C. for 30 minutes. After removing water, 500 ml of water was further added, and the same operation was repeated 4 times. A precipitate was obtained by continuing stirring while cooling. Then, the precipitate is washed with warm hexane and cooled, and then 10 to 20 mmH
The mixture was heated to 180 ° C in g and the phenol was distilled off. The residue was taken out to obtain 2,2-bis (4-hydroxylphenyl) dodecane.

Example 2-2 [Synthesis of 2,2-bis (4-hydroxylphenyl) tetradecane] Example 2 except that 2-tetradecanone was used instead of 2-dodecanone in Example 2-1. −
The same procedure as in 1 was performed.

Example 2-3 [Synthesis of 2,2-bis (4-hydroxylphenyl) hexadecane] Example 2 was repeated except that 2-hexadecanone was used in place of 2-dodecanone in Example 2-1. −
The same procedure as in 1 was performed.

Example 2-4 [Synthesis of 2,2-bis (4-hydroxylphenyl) octadecane] Example 2 was repeated except that 2-octadecanone was used in place of 2-dodecanone in Example 2-1. −
The same procedure as in 1 was performed.

Example 2-5 [Synthesis of 3,3-bis (4-hydroxylphenyl) octadecane] In Example 2-1, 3-octadecanone (manufactured by Lancaster) was used instead of 2-dodecanone. Was carried out in the same manner as in Example 2-1.

Example 2-6 [Synthesis of 2,2-bis (4-hydroxylphenyl) nonane] In Example 2-1, 2-nonanone (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of 2-dodecanone. Example 2-1, except that was used. Table 2 shows the analysis results of the obtained bisphenols.

[0036]

[Table 2]

The mass analysis and elemental analysis were performed as follows. 1) Mass spectrometry JEOL JMS-AX505H was used and measured by the direct introduction method (ionization method, fast atom bombardment (FAB)).
Law). 2) Elemental analysis Gas chromatograph-atomic emission detector [GC-AED,
Elemental analysis was carried out using relative sensitivity of C, H, and O using bisphenol A as a standard by using Hewlett Packard 5921A].

Example 3-1 [Production of Polycarbonate Oligomer A] 2,200 g of 2,2-bis (4-hydroxylphenyl) dodecane was dissolved in 8 liters of methylene chloride in a vessel equipped with a stirrer and having an inner volume of 50 liters, and 2 14 liters of a 0.0 N aqueous sodium hydroxide solution was added and stirred, and phosgene was blown into this at a flow rate of 0.2 mol / min for 70 minutes, and then an aqueous phase and an organic phase were separated. Thus, a methylene chloride solution of polycarbonate oligomer A having a concentration of 328 g / liter was obtained. The chloroformate group concentration in this solution was 0.67N.

Example 3-2 [Synthesis of Polycarbonate Oligomer B] 60 kg of bisphenol A was dissolved in 400 liters of a 5 wt% sodium hydroxide aqueous solution to prepare an aqueous sodium hydroxide solution of bisphenol A. Then, this sodium hydroxide aqueous solution of bisphenol A kept at room temperature was introduced at a flow rate of 138 liters / hour and methylene chloride at a flow rate of 69 liters / hour through an orifice plate into a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. Then, phosgene was co-currently flown thereinto and blown at a flow rate of 10.7 kg / hour to continuously react for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the discharge temperature of the reaction solution at 25 ° C. The pH of the discharged liquid is 10
Adjusted to show ~ 11. The reaction solution thus obtained was allowed to stand to separate the aqueous phase, the methylene chloride phase (220 liters) was collected, 170 liters of methylene chloride was further added thereto, and the mixture was sufficiently stirred. Polycarbonate oligomer B (concentration 317 g
/ Liter). The degree of polymerization of Polycarbonate Oligomer B obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7N.

Example 4-1 [Manufacture of Polycarbonate A] 2,2-bis (4-hydroxylphenyl) was added to 10 liters of polycarbonate oligomer B (11.6 mol of bisphenol A unit) in a container with an internal volume of 50 liters equipped with a stirrer. Dodecane 312g (0.88
Mol) was dissolved. An aqueous sodium hydroxide solution (NaOH: 53 g, 1 liter of water) and 2.5 cc of triethylamine were added thereto, and the reaction was carried out at 300 rpm for 60 minutes.
Thereafter, 616 g of bisphenol A dissolved in an aqueous sodium hydroxide solution (NaOH: 360 g, 5 liters of water) and 73 g of p-tert-butylphenol were mixed with the above reaction system, and 8 liters of methylene chloride were added to the mixture, and 6
The reaction was carried out for 0 minutes at 450 rpm. After the reaction, 5 liters of methylene chloride and 5 liters of water were added, the organic phase and the aqueous phase were separated, and the organic phase was washed and separated in order of alkali (0.01N-NaOH), acid (0.1N-HCl) and water. . A flake-shaped polymer was obtained by removing methylene chloride. The resulting polymer was extruded at 280 ° C and pelletized. The obtained pellets were injection-molded at 280 ° C to obtain an injection-molded product. Then, in FIG. 1 the IR spectrum of the polymer, also, ¹ H
-NMR spectrum is shown in FIG.

Example 4-2 [Production of Polycarbonate B] In Example 4-1
312 g of 2,2-bis (4-hydroxylphenyl) dodecane
Was carried out in the same manner as in Example 4-1, except that 336 g of 2,2-bis (4-hydroxylphenyl) tetradecane was used instead of.

Example 4-3 [Production of Polycarbonate C] In Example 4-1
312 g of 2,2-bis (4-hydroxylphenyl) dodecane
Was carried out in the same manner as in Example 4-1, except that 361 g of 2,2-bis (4-hydroxylphenyl) hexadecane was used instead of.

Example 4-4 [Production of Polycarbonate D] In Example 4-1
312 g of 2,2-bis (4-hydroxylphenyl) dodecane
Was carried out in the same manner as in Example 4-1, except that 385 g of 2,2-bis (4-hydroxylphenyl) octadecane was used instead of.

Example 4-5 [Production of Polycarbonate E] In Example 4-1
312 g of 2,2-bis (4-hydroxylphenyl) dodecane
Was carried out in the same manner as in Example 4-1 except that 385 g of 3,3-bis (4-hydroxylphenyl) octadecane was used instead of.

Example 4-6 [Production of Polycarbonate F] In Example 4-1
312 g of 2,2-bis (4-hydroxylphenyl) dodecane
To 935 g of sodium hydroxide aqueous solution (NaOH: 5
(3 g, 1 liter of water) The procedure of Example 4-1 was repeated, except that 160 g of NaOH was used.

Example 4-7 [Production of Polycarbonate G] In a container having an internal volume of 50 liters equipped with a stirrer, 10 liters of polycarbonate oligomer A and 630 g of bisphenol A were dissolved in an aqueous sodium hydroxide solution (NaOH: 370 g, 5 liters of water). And 73 g of p-tert-butylphenol are mixed, 8 liters of methylene chloride is added, and 450 rp for 60 minutes
Reacted at m. Then, it carried out like Example 4-1 and obtained a flake-like polymer and obtained pellets.

Comparative Example 1 [Production of Polycarbonate H] In Example 4-1
312 g of 2,2-bis (4-hydroxylphenyl) dodecane
Was carried out in the same manner as in Example 4-1, except that 275 g of 2,2-bis (4-hydroxylphenyl) nonane was used instead of.

Comparative Example 2 [Production of Polycarbonate I] In Example 4-1
Example 4-except that 2,2-bis (4-hydroxylphenyl) dodecane was not used and only bisphenol A was used.
The same procedure as in 1 was performed.

Comparative Example 3 [Production of Polycarbonate J] In Comparative Example 2, p-
The procedure of Comparative Example 2 was repeated except that 109 g of lauric acid chloride was used instead of 73 g of tert-butylphenol.

Comparative Example 4 [Production of Polycarbonate K] In Comparative Example 2, p-
The procedure of Comparative Example 2 was repeated except that 92 g of p-cumylphenol was used instead of 73 g of tert-butylphenol. Table 3 shows the comonomer content and viscosity average molecular weight (Mv) of the polycarbonates A to K obtained in Examples 4-1 to 7 and Comparative Examples 1 to 4.

[0051]

[Table 3]

The comonomer content and the viscosity average molecular weight were measured as follows. 1) Comonomer content (mol%) The aromatic H of the bisphenol A residue found at 7.0 to 7.3 ppm by ¹ H-NMR and p-tert- at 1.33 ppm.
H and 0.82 of tert-butyl group of butylphenol residue
It was calculated from the intensity ratio of H of the methyl group of the long-chain alkyl of the comonomer residue found in ppm. 2) Viscosity average molecular weight (Mv) The viscosity of the methylene chloride solution at 20 ° C was measured with an Ubbelohde type viscosity tube, and the intrinsic viscosity [η] was calculated from this, and then calculated by the following formula. [Η] = 1.23 × 10 ^-5 Mv ^0.83

Further, Examples 4-1 to 7 and Comparative Examples 1 to 4
Table 4 shows the flow values of the polycarbonates A to K obtained in 1. and the Izod impact strength measured for each of the obtained molded articles.

[0054]

[Table 4]

The flow value and the Izod impact strength were measured as follows. 1) Flow value 280 ℃, under pressure of 160kg / cm ² 1mmφ × 1
The amount of resin flowing out of the 0 mm nozzle was measured. 2) Izod impact strength Based on JIS-K-7110.

[0056]

As described above, according to the present invention, fluidity is improved without impairing mechanical properties such as impact strength, and it is suitably used for optical parts, mechanical parts, electric / electronic parts, automobile parts and the like. The obtained polycarbonate polymer is easily obtained.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the polycarbonate polymer obtained in Example 4-1.

FIG. 2 is a ¹ H-NMR spectrum diagram of the polycarbonate polymer obtained in Example 4-1.

Claims (1)

[Claims] 1. The main chain has the general formula (I): [In the formula, X ¹ and Y ¹ are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or 6 to 15 carbon atoms.
Of the aryl group, and m and n are each an integer of 1 to 4. A is represented by the general formula (II): (In formula, j is an integer of 0-6 and k is an integer of 7-20.) The alkylidene group represented by these is shown. ] The carbonate structural unit I and the general formula (III) [In the formula, X ² and Y ² are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or 6 to 15 carbon atoms.
Is represented by an aryl group, and p and q are each an integer of 1 to 4. B is an alkylidene group having 1 to 15 carbon atoms, an alkylene group having 1 to 15 carbon atoms, an arylene group having 6 to 15 carbon atoms, an arylalkylene group having 7 to 15 carbon atoms, and -O.
-, - S -, - SO 2 -, - CO- or a single bond. ] The carbonate structural unit II represented by the following, the ratio of the carbonate structural unit I is 0.5 to 80 mol% with respect to all the carbonate structural units, and the viscosity average molecular weight is 10000 to 50000. A polycarbonate polymer characterized in that