JPS6312097B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the reaction of a divalent phenolic compound, an aromatic dicarboxylic acid dichloramide, and a carbonyl halide in the presence of a basic inorganic compound in a reaction medium consisting of water and a water-immiscible solvent. Used as a raw material,
The present invention relates to a novel method for producing an aromatic polyester carbonate resin which has ester bonds and carbonate bonds in the polymer chain and has a high degree of alternating alignment of these bonds by subjecting them to a contact reaction. More specifically, an aromatic oligocarbonate having a phenolic hydroxyl group at the end is produced by reacting a divalent phenolic compound and a carbonyl halide in the presence of a basic inorganic compound in a reaction medium consisting of water and a water-miscible solvent. (hereinafter this reaction step is referred to as the first step)
A step of adding a required amount of a basic inorganic compound to the resulting reaction product liquid, and then adding an aromatic dicarboxylic acid dichloride to carry out an esterification reaction to obtain a high molecular weight polyester carbonate resin ( The present invention relates to a method for producing an aromatic polyester carbonate resin having excellent heat resistance, solvent resistance, moldability, mechanical properties, etc., which comprises a step (hereinafter referred to as the second step).

Conventionally proposed methods for producing aromatic polyester carbonate resins include (a) melt polycondensation, which involves transesterification polycondensation at high temperatures and high vacuum, and (b) solution polycondensation, which involves polycondensation in organic solvents at low temperatures. There are interfacial polycondensation methods in which polycondensation is carried out in the presence of a basic inorganic compound in a reaction medium consisting of water and a water-immiscible solvent.

Methods ○A and ○B have defects due to poor performance of the resin obtained and the polymerization method, whereas method ○C is considered to be relatively practical, but has a structure A regular arrangement of the components is not achieved and resins with satisfactory properties are difficult to obtain.
○ Improvements to the method (3) have also been proposed (for example, in Japanese Patent Application Laid-open No. 55-25427), but the method involves the production of dihydroxyterephthalic acid oligoester, its chloroformation, and the chloroformate and divalent phenol system. This method cannot necessarily be called an economical method because it requires three steps of reaction with a compound and requires complicated operations.

The present inventors first used the interfacial polycondensation method described in ○C.
The present invention was achieved by attempting a new interfacial polycondensation method that is completely different from the conventional method of reacting a dihydric phenolic compound with an aromatic dicarboxylic acid chloride. That is, one of the features of the present invention is that first, a divalent phenolic compound and a carbonyl halide are reacted to produce an aromatic oligocarbonate having a phenolic hydroxyl group at the end. Although this reaction is in principle a reaction for synthesizing aromatic polycarbonate, it is surprising that it could be controlled to produce aromatic oligocarbonate.

The present invention produces an aromatic polyester carbonate resin in which the constituent components forming the polymer are arranged in a regular manner and have a high level of balance in physical and chemical properties, using a simplified process and a simple synthesis device. It's a method. Specifically, this method involves reacting a divalent phenolic compound with a carbonyl halide in the presence of a basic inorganic compound in a reaction medium consisting of water and a water-immiscible solvent to form a hydroxyl group at the terminal. In producing an aromatic oligocarbonate having a basic inorganic compound of 2
0.6 to 1.6 per mole of phenolic compound
The carbonyl halide is used in an amount in the molar range, and the carbonyl halide is used per mole of the divalent phenolic compound,
A first step of carrying out the reaction using an amount in the range of 0.3 to 0.8 mol to obtain an aromatic oligocarbonate reaction product having a phenolic hydroxyl group at the end, which is mainly composed of oligocarbonate with a degree of polymerization of 1 to 3; The esterification polycondensation reaction is carried out by reacting aromatic dicarboxylic acid dichloride in the presence of a basic inorganic compound in an amount sufficient to neutralize at least the free phenolic hydroxyl groups remaining in the reaction product solution obtained in the first step. By this method, the composition molar ratio of divalent phenolic compound residue, aromatic dicarboxylic acid residue, and carbonic acid bond is 2:0.5:1.5 to 2:1.4:0.6. in range,
This is a method for obtaining an aromatic polyester carbonate resin in which these components have a high degree of alternating alignment. Because the resin obtained here has a high degree of alternating arrangement, it has both the original excellent performance of the well-known polycarbonate resin and polyarylate resin, and specifically has a high glass transition point, high heat distortion temperature, etc. It exhibits excellent properties such as excellent solvent resistance, hydrolysis resistance, and thermal stability, as well as excellent moldability and colorless transparency. In addition, in the method of the present invention, the produced polymer can be easily washed and solidified, and the burden of solvent recovery is extremely small, making the present invention an economically advantageous method with high practical value.

The first step of the present invention to produce an aromatic oligocarbonate having a phenolic hydroxyl group at the end, which is mainly composed of an oligocarbonate having a degree of polymerization of 1 to 3, is performed using potassium hydroxide, sodium hydroxide, lithium hydroxide, and calcium hydroxide. ,sodium carbonate,
It is carried out in the presence of a basic inorganic compound such as trisodium phosphate. Normally, in this embodiment, a basic inorganic compound is added to water together with a divalent phenol compound, and an aqueous solution in which the divalent phenol compound is dissolved in the form of a phenol salt is used. However, in the present invention, a basic inorganic compound is used. One of the significant requirements is to select the amount in the range of 0.6 to 1.6 moles per mole of the divalent phenolic compound. However, by adopting these conditions, the divalent phenolic compounds are only partially neutralized, and as a result, the divalent phenolic compounds that do not form salts in the reaction system do not dissolve in the aqueous phase. Therefore, it is dispersed as a solid. It has been found that even in such a reaction system, the phenolic hydroxyl group and the carbonyl halide react easily, and the above-mentioned aromatic oligocarbonate having a degree of polymerization of 1 to 3 can be obtained with good selectivity and high yield. In order to obtain the oligocarbonate of the present invention, the above requirements are critical; if the upper limit is exceeded, a high molecular weight aromatic oligocarbonate with a degree of polymerization of 4 or more is produced, and at the same time, unreacted divalent phenol that does not participate in the reaction is produced. Many of the system compounds remain, and this has a negative effect on various properties of the product resin, especially moldability, solvent resistance, etc. On the other hand, when it is below the lower limit, unreacted carbonyl halide remains, resulting in a decrease in the yield of the desired aromatic oligocarbonate and impairing the properties of the product resin.

Another requirement for the first step of the present invention is that the carbonyl halide is used in an amount ranging from 0.3 to 0.8 mol per mol of the divalent phenolic compound. Below the lower limit, there will be a large amount of unreacted divalent phenolic compounds, and as a result, the reaction with the aromatic dicarboxylic acid dichloride in the second step will generate a resin that is insoluble in the reaction medium, and polymerization will be inhibited. ,
This will adversely affect the transparency and moldability of the obtained product. On the other hand, if the upper limit is exceeded, the degree of polymerization of the oligocarbonate will increase, and the alternating arrangement of the constituent components of the polymer obtained therefrom will decrease, making it impossible to obtain a resin having the properties aimed at by the present invention.

As the divalent phenol compound used in the method of the present invention, a bisphenol compound represented by formula (1) is used. A divalent phenol type compound represented by formula (2), Or a phenolphthalein type compound represented by formula (3) are used, and an appropriate one is selected from these groups. In the above general formula, X ₁ and X ₂ are hydrogen atoms,
a chlorine atom, a bromine atom or a lower alkyl group,
Z is a linear or branched alkylene group having 9 or less carbon atoms, or -O-, -S-, -CO-, and -SO ₂ -
It means a cross-linking group selected from the group shown below. Representative examples of compounds represented by these general formulas include 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)
Examples include ketones, hydroquinone, resorcinol, and phenolphthalein. The concentration of the divalent phenolic compound in the aqueous phase of the reaction medium used in the first step is 0.05 to 2 mol/l, preferably 0.1
It is best to use it in a range of ~1.0 mol/l.

As the carbonyl halide used in the method of the present invention, for example, phosgene or trichloromethyl chloroformate (Cl ₃ COCOCl) is used, but phosgene is usually used. Phosgene is supplied to the aqueous phase containing the divalent phenolic compound or to the aqueous phase and the water-immiscible solvent phase under stirring in gaseous or liquid form or as a solution in a water-immiscible solvent.

The water-immiscible solvent used here may be any organic solvent that does not completely dissolve in water when mixed with water and can form two layers by separating at least a portion of the water, and also phosgene. Alternatively, an organic solvent that dissolves the aromatic dicarboxylic acid dichloramide and is inert to these and dissolves the target aromatic polyester carbonate resin may be used. Typical examples include dichloromethane, 1,
2-dichloroethane, 1,1,2,2-tetrachloroethane, chloroform, 1,1,1-trichloroethane, carbon tetrachloride, monochlorobenzene,
Examples include chlorinated hydrocarbons such as dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and ether compounds such as diethyl ether; two or more of these organic solvents can be used in combination. You can also do it. If desired, these water-immiscible solvents can be mixed with water-compatible solvents such as ethers, ketones, esters, and nitriles other than those mentioned above, but the mixing ratio is as follows: Of course, the mixed solvent system must be within the range of being completely incompatible with water. The mixing ratio of this water-immiscible solvent and water is in the range of 50/1 to 1/40 (volume ratio), but considering the workability of the method of the present invention, the range is 5/1 to 1/5. preferable.

One of the specific embodiments of the first step of the present invention is to add a divalent phenol compound into a reaction system consisting of an aqueous phase containing a basic inorganic compound and a water-immiscible solvent phase, and stir the mixture. This is a method in which carbonyl halide is continuously introduced into this over a period of several minutes to several hours. The reaction temperature at this time is 0
The temperature is controlled within the range of ~40°C, preferably 5~30°C. In order to control the carbonylation reaction and increase the yield and selectivity of the desired aromatic oligocarbonate, a part of the basic inorganic compound is added to the aqueous phase, and the remainder is added dropwise as an aqueous solution along with the introduction of the carbonyl halide. method may be adopted. The time required to complete the carbonation reaction after the entire amount of carbonyl halide has been introduced depends on the reaction conditions, but usually 4 hours or less is sufficient. It is effective to add a reducing agent such as sodium hydrosulfite in the first step in order to prevent discoloration of the divalent phenol compound and, by extension, discoloration of the obtained aromatic polyester carbonate resin. Adopted. In order to promote the carbonation reaction in the first step and suppress the consumption of carbonyl halide in the carbonylation reaction, in other words, the hydrolysis of carbonyl halide, a known tertiary amine or quaternary amine is used as a carbonylation catalyst. Addition of grade ammonium salt is effective.

The aromatic oligocarbonate obtained in the first step is subjected to a second step of esterification in which the aromatic oligocarbonate is reacted with an aromatic dicarboxylic acid dichloride to form a polyester carbonate. The aromatic dicarboxylic acid dichloride used here includes terephthalic acid dichloride, 2-chloroterephthalic acid dichloride, 2,5-dichloroterephthalic acid dichloride, isophthalic acid dichloride, 4-chloroisophthalic acid dichloride, 5-chloroisophthalic acid dichloride, Examples include 2,3,5,6-tetrachloroterephthalic acid dichloride. These aromatic dicarboxylic acid dichlorides are usually prepared as a homogeneous solution dissolved in a water-immiscible solvent, and then added dropwise under stirring to the product solution after the reaction of the first step to cause a contact reaction. The aromatic dicarboxylic acid dichloride is used in an amount such that the total number of moles with the carbonyl halide is 1.0 to 1.5 per mole of the divalent phenol compound. The concentration of aromatic dicarboxylic acid dichloride in the water-immiscible solvent phase in the second step is preferably in the range of 0.1 to 4 mol/l, preferably 0.2 to 2 mol/l.

The second step is further carried out in the coexistence of a basic inorganic compound, where the basic inorganic compound is
It is used in an amount that is at least sufficient to neutralize free phenolic hydroxyl groups present in the reaction product liquid obtained in the step. In other words, the amount of the basic inorganic compound to be used may be selected within the range of 2 to 3 moles per mole of the above-mentioned aromatic dicarboxylic acid dichloride.

In order to promote the esterification polycondensation reaction in the second step and facilitate the increase in molecular weight, it is preferable to use a known tertiary amine or quaternary ammonium salt as a catalyst. Examples of the tertiary amine include trimethylamine, triethylamine, tributylamine, tripropylamine, trihexylamine, tridecylamine, N,N-dimethylcyclohexylamine, pyridine, quinoline, dimethylaniline, etc. Examples of the ammonium salts include trimethylbenzylammonium chloride and tetramethylammonium chloride. The amount of these catalysts used is 0.05 per mole of aromatic dicarboxylic acid dichloride.
Molar or less is sufficient, and tertiary amine and quaternary amine
Grade ammonium salts can also be used together.

Furthermore, during the polycondensation reaction in the second step, a molecular weight regulator is used to adjust the molecular weight of the target aromatic polyester carbonate resin to a desired level. Examples of molecular weight modifiers include monovalent phenols such as phenol, orthophenylphenol, paraphenylphenol, orthomethoxyphenol, metamethoxyphenol, cumylphenol, paratertiary butylphenol;
Examples include monobasic acid chlorides such as benzoic acid monochloride; monoamines such as aniline; The amount of molecular weight regulator used is per mole of the divalent phenol compound used in the first step.
It is appropriately selected within the range of 0.001 to 0.1 mol. There are no restrictions on the timing of adding the molecular weight regulator, and it may be added during the first step or the second step, or it can be added in portions during the second step.

One of the specific embodiments of the second step is to add an aqueous solution in which a basic inorganic compound and a molecular weight regulator are dissolved and a polycondensation promoting catalyst to the reaction product liquid containing the oligoester obtained in the first step. This is a method in which a water-immiscible solvent solution in which an aromatic dicarboxylic acid dichloride is dissolved is added dropwise while stirring. The dropwise addition of the aromatic dicarboxylic acid dichloride is selected within the range of several seconds to several hours, but the dropwise addition is usually completed in several tens of seconds to two hours. The reaction temperature is 0 to 75°C, preferably 5 to 50°C, and the time required to complete the esterification reaction and polycondensation reaction is within 5 hours after the completion of dropping the aromatic dicarboxylic acid dichloride, and usually about 3 hours. It is enough to choose.

In the second step of the present invention, the reaction product solution obtained in the first step is allowed to stand and the layers are separated, a water-immiscible solvent phase is taken out from the reaction product solution, and the water-immiscible solvent phase is concentrated.
Esterification can also be carried out using this solution as described above. Alternatively, it is also possible to carry out the method by isolating an oligoester having a degree of polymerization of 1 to 3 from the reaction product liquid obtained in the first step and esterifying this oligomer.

In order to obtain the desired aromatic polyester carbonate resin from the reaction product liquid after esterification in the second step of the present invention, the water-immiscible solvent phase is separated from the reactive liquid separated by standing. , washing, isolation, and solidification may be carried out according to commonly used methods. If the reaction product solution is difficult to separate into layers, known operations such as adjusting the PH of the solution, adding a salting agent, or centrifuging may be employed. Isolation and solidification can be accomplished by conventional methods, such as completely distilling off water-immiscible solvents under normal pressure or reduced pressure, or methods that dissolve in the water-immiscible solvent used in the reaction but produce Non-solvents that do not dissolve the polymer, such as methanol, ethanol, acetone,
A method of adding an organic solvent such as ethyl acetate, isopropyl ether, n-hexane, cyclohexane, methyl ethyl ketone, etc., or conversely, a method of adding a water-immiscible solvent solution containing the polymer in these non-solvents is used. .

This method using a non-solvent is an effective method because the amount of non-solvent used can be reduced by concentrating the water-immiscible solvent solution, which is a reactive liquid, to some extent. It is.

Next, the method of the present invention will be specifically explained using Examples.

Example 1 Sodium hydroxide was added to a 1 liter reaction vessel equipped with a stirrer.
Prepare 2.15g (0.0538mol), sodium hydrosulfite 0.05g, and 35.5g (0.1555mol) of bisphenol A, and add 200ml of water and 125g of methylene chloride.
ml and stirred and dissolved at room temperature. More than half of the added amount of bisphenol A remained dispersed in the aqueous phase and methylene chloride phase without being completely dissolved. In this reaction vessel, add phosgene dissolved in 100 ml of methylene chloride while keeping the internal temperature at 18-20°C.
7.26 g (0.0734 mol) and 4.3 g (0.1075 mol) of sodium hydroxide dissolved in 100 ml of water were simultaneously added dropwise over 60 minutes with stirring. Bisphenol A, which was dispersed at the beginning of the reaction, begins to dissolve as the phosgene methylene chloride solution is added dropwise, and by the time approximately 2/3 of the total amount of the phosgene methylene chloride solution has been added dropwise, almost all of the bisphenol A has been dissolved in the reaction medium. Dissolved. After the entire amount of the phosgene methylene chloride solution was added dropwise, stirring was continued for an additional 3 hours to complete the synthesis of the dihydroxy carbonate oligoester in the first step. followed by 10.0 g (0.25 mol) of sodium hydroxide, 0.05 ml of triethylamine, dissolved in 80 ml of water;
Add 0.5g of paratertiary butylphenol,
Further, 16.85 g (0.083 mol) of terephthalic acid dichloride dissolved in 100 ml of methylene chloride was added dropwise over 30 minutes while stirring while maintaining the internal temperature at 21 to 23°C. After the entire amount of terephthalic acid dichloride was added dropwise, the reaction was continued for another 1.5 hours to complete the second step of esterification polycondensation reaction. After the reaction was completed, stirring was stopped and the mixture was allowed to stand still. After about 1 hour, the upper layer was an aqueous phase, and the lower layer was a methylene chloride phase, which were separated with slight turbidity. The entire amount of the lower methylene chloride phase was added dropwise to methanol 3 while stirring, and the precipitated white solid polymer was collected and dried. The weight of the obtained polymer was 47.14 g, corresponding to a yield of 96.1%. A thin film was prepared from a portion of the obtained polymer by a solvent (methylene chloride) film forming method and subjected to infrared spectroscopy.
Vysokomol.Ser., A 9 [5] 1012 pages (1967)
1740, and
Bisphenol A residues: terephthalic acid residues in the produced polymer from the absorbance ratio of characteristic absorption at 1770 nm:
Results of determining the composition ratio (molar ratio) of carbonic acid bonds 2:
It was 1:1. The resulting polymer was maintained at a concentration of 25°C.
Logarithmic viscosity (ηinh) in 1g/100ml methylene chloride is η _ioh = _lo t ₀ /t ₁ /C = 0.723 where C: Polymer concentration in methylene chloride solution (g/dl) to: Falling seconds of methylene chloride only Number (sec) t ₁ : Number of seconds (sec) for the methylene chloride polymer solution to fall. Using a compression molded piece obtained by heating and melting this polymer at 300°C for 10 minutes in a nitrogen gas atmosphere, Zakin JL, etal., J.Apply.Polymer Sci.,
The glass transition point (Tg) measured by the "Thermo mechanical analysis method" described in Vol. 10, p. 1455 (1966) is 176°C, ASTM D-648
The heat distortion temperature (HDT264psi) measured at 166°C.

The reaction in the first step was carried out in the same manner and under the same conditions, and the resulting liquid was separated. That is, as a result of GPC analysis (column packing product name: "shodex A802"; developer: methylene chloride) of a part of the methylene chloride phase separated by standing after the completion of the reaction in the first step, oligomers with a degree of polymerization of 1 to 2 were found. It was confirmed that bisphenol A oligocarbonate containing carbonate as a main component and having a phenolic hydroxyl group at the end was produced. Furthermore, the reaction product solution was acidified with phosphoric acid, and the precipitated unreacted bisphenol A was recovered, and its weight was measured to be 3.5 g.The amount of unreacted bisphenol A dissolved in the methylene chloride phase and remaining. When determined by the GPC internal standard method, it was 4.6g. As a result, bisphenol A in the first step
The reaction rate was found to be 77.2 mol%.

Example 2 The reaction in the first step was carried out in the same manner and under the same conditions as in Example 1, and 0.5 g of paratertiary butylphenol and triethylamine were added to the resulting reaction product liquid.
16.85 g (0.083 mol) of isophthalic acid dichloride dissolved in 100 ml of methylene chloride and 10.0 g (0.25 mol) of sodium hydroxide dissolved in 80 ml of water were added under stirring while maintaining the reaction temperature at 25-28°C. At the same time, the solution was added dropwise over a period of 30 minutes. After the entire amount of isophthaloyl dichloride was added dropwise, the reaction was continued for an additional 1.5 hours to complete the second step reaction. The obtained polymer has ηinh=0.688 Tg=
The temperature was 160°C and HDT (264psi) = 149°C.

Example 3 In the same manner as in Example 1, when bisphenol A oligocarbonate was synthesized in the first step, 0.05 ml of triethylamine was added as a catalyst to carry out the reaction. 10.1 g (0.2525 mol) of sodium hydroxide dissolved in 80 ml of water and 0.6 g of paratertiary butylphenol were added to the reaction product solution of the first step.
While keeping the reaction temperature at 20-23℃, add 16.85g (0.083mol) of terephthalic acid dichloride dissolved in 100ml of methylene chloride all at once (for about 20 seconds) while stirring.
The reaction was continued for 1.5 hours to complete the reaction. ηinh=0.635, Tg= of the obtained polymer
The temperature was 166°C, HDT (264psi) = 158°C.

Example 4 2.8g of sodium hydroxide in a reaction vessel with a stirrer
(0.07 mol) bisphenol A34.245g (0.15 mol),
Sodium hydrosulfite 0.05g, water 200g
ml, in a reaction vessel charged with 125 ml of methylene chloride, 9.3974 g (0.095 mol) of phosgene dissolved in 150 ml of methylene chloride and 5.6 g of sodium hydroxide dissolved in 100 ml of water were stirred while maintaining the reaction temperature at 18-20°C.
(0.14 mol) was added dropwise over 75 minutes, and
The reaction was continued for 2.5 hours to complete the first step reaction. Subsequently, 5.568 g (0.1392 mol) of sodium hydroxide dissolved in 100 ml of water, 0.5 g of paratertiary butylphenol, and 0.06 ml of triethylamine were added, and the mixture was dissolved in 100 ml of methylene chloride under stirring while maintaining the reaction temperature at 20-23°C. 11.775 g (0.058 mol) of terephthalic acid dichloride was added dropwise at once (during about 30 seconds). After the dropwise addition was completed, the reaction was continued for 1 hour, at which point 0.5 g of paratertiary butylphenol dissolved in 10 ml of methylene chloride was added again, and the reaction was continued for another 30 minutes to carry out the second step of esterification polycondensation reaction. finished.

The resulting polymer had a bisphenol A residue:terephthalic acid residue:carbonate bond ratio (molar ratio) of 2:
0.77:1.23, ηinh=0.574, Tg=162℃, HDT
(264 psi) = 150°C.

Example 5 Sodium hydroxide 4.72g (0.118 mol), bisphenol A 24.17g (0.6043 mol), sodium hydrosulfite 0.05g, water 450ml, methylene chloride
In a reaction vessel containing 300ml, set the reaction temperature to 12-15.
5.25 g of phosgene (0.0531
mol) was bubbled in gaseous form over a period of 30 minutes.
After finishing blowing into the phosgene, the reaction was continued for 2 hours to complete the first step reaction. After the reaction of the first step, 5.6 g (0.14 mol) of sodium hydroxide, 0.4 g of paratertiary butylphenol, and 0.137 g of trimethylbenzylammonium chloride dissolved in 150 ml of water were added, and the reaction temperature was increased to 23-25 ml.
10.76 g of terephthalic acid dichloride (0.053
mol) was added dropwise at once (during about 20 seconds). Thirty minutes after the completion of the dropwise addition, 0.03 ml of triethylamine was added, and the reaction was continued for an additional 1.5 hours to complete the second step of esterification polycondensation reaction. Obtained polymer ηinh=0.517, Tg=174℃, HDT (264psi)=163
It was warm at ℃.

Claims (1)

[Claims] 1. In a reaction medium consisting of water and a water-immiscible solvent, in the presence of a basic inorganic compound, a divalent phenolic compound and a carbonyl halide are reacted to produce an aromatic oligocarbonate having a hydroxyl group at the end. In doing so, 2 basic inorganic compounds
Use an amount in the range of 0.6 to 1.6 mol per 1 mol of the divalent phenolic compound, and use a carbonyl halide in an amount of 0.3 to 1.6 mol per 1 mol of the divalent phenolic compound.
carrying out the reaction using an amount in the range of 0.8 mol;
A first step of obtaining a reaction product mainly composed of an oligocarbonate having a polymerization degree of 1 to 3 and a terminal phenolic hydroxyl group, and at least free phenolic hydroxyl groups remaining in the reaction product liquid obtained in the first step. a second step in which an esterification reaction is carried out by reacting aromatic dicarboxylic acid dichloride in the presence of a basic inorganic compound in an amount sufficient to neutralize the divalent phenolic compound residue and the aromatic dicarboxylic acid. The composition molar ratio of residues and carbonic acid bonds is 2:
A method for producing an aromatic polyester carbonate resin having a ratio of 0.5:1.5 to 2:1.4:0.6 and having a high degree of alternating alignment of these composition components.