JPH083298A - Production of polyester polycarbonate - Google Patents

Abstract

PURPOSE:To produce a polyester carbonate of excellent quality from inexpensive easily available starting materials by a simple process. CONSTITUTION:This process consists of polycondensing a complex of an aromatic carboxylic acid with a tert. amine with bischloro-formate of a bisphenol or a chloroformate-group-containing bisphenol polycarbonate oligomer in the presence of an alkali in an organic solvent. The polymer obtained by this process is heated to 150 deg.C or above to produce a polyester carbonate of excellent heat resistance.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an improved method for producing polyester carbonates. More specifically, the present invention relates to a method for efficiently producing a high-quality polyester carbonate using inexpensive and easily available raw materials and using a simple process.

[0002]

2. Description of the Related Art Polyester carbonate has the characteristics of both polycarbonate and polyester, and is particularly attracting attention as an engineering plastic having higher heat resistance than polycarbonate. For example, it is used as a material for electrical / electronic parts, mechanical parts, automobile parts, etc. Is expected to be used. As a method for producing such a polyester carbonate, various methods have been proposed so far. For example, as a method for producing polyester carbonate by interfacial polycondensation, (1) a method using terephthalic acid chloride or isophthalic acid chloride as an acid component (JP-A-57-170924), (2) bisphenol, phosgene and terephthalic acid. And isophthalic acid (JP-A-53-102399), and (3) a method using bischloroformate of bisphenol and terephthalic acid or isophthalic acid (JP-A-60-8803).
No. 2) has been proposed. However, none of these methods can be said to be a satisfactory method because they have drawbacks such as expensive raw materials, multistage manufacturing steps, and complexity.

Further, US Pat. No. 3,220,978 discloses a method of reacting a bishaloformate with a dicarboxylic acid in the presence of a tertiary amine.
According to this method, the amount of the tertiary amine is more than twice that of the bishaloformate, which is not economical. And, in that example, only pyridine was used as the tertiary amine, and the effect of the tertiary amine such as trialkylamine was not clear.

[0004]

DISCLOSURE OF THE INVENTION The present invention has improved the above-mentioned drawbacks of the conventional production method by interfacial polycondensation of polyester carbonates, uses inexpensive and easily available raw materials, and uses a simple process to improve quality. It is an object of the present invention to provide a method for efficiently producing an excellent polyester carbonate.

[0005]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventor has found that a complex obtained by reacting an aromatic carboxylic acid and a tertiary amine with bischlorobisphenol By subjecting a bisphenol polycarbonate oligomer containing a formate or a chloroformate group to polycondensation in an organic solvent in the presence of an alkali, and subjecting the polymer obtained by the interfacial polycondensation to a heat treatment at a certain temperature or higher. It has been found that a polyester carbonate excellent in quality such as heat resistance can be obtained and the object of the present invention can be achieved. The present invention has been completed based on such findings.

That is, the present invention provides a complex obtained by reacting an aromatic carboxylic acid with a tertiary amine,
The present invention provides a method for producing a polyester carbonate, which comprises polycondensing a bischloroformate of bisphenol or a bisphenol polycarbonate oligomer containing a chloroformate group in an organic solvent in the presence of an alkali. The present invention also provides the method for producing the polyester carbonate described above, which comprises subjecting the polymer obtained by the polycondensation to a heat treatment at a temperature of 150 ° C. or higher.

The present invention is characterized by using a complex obtained by reacting an aromatic carboxylic acid with a tertiary amine when carrying out a polycondensation reaction in producing a polyester carbonate. The aromatic carboxylic acid used for the formation of the complex is not particularly limited and various ones are available. For example, the general formula (II)
~ (V)

[0008]

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Examples thereof include compounds represented by R'in the general formula (V) may be the same as R of the bisphenol represented by the general formula (I), and has an alkylene group having 1 to 13 carbon atoms, an alkylidene group having 2 to 13 carbon atoms, and carbon. C5-C13 cycloalkylene group, C5-C13 cycloalkylidene group, C6
To 13 arylene groups, —O—, —S—, —SO ₂ —,
There may be mentioned —CO— or a single bond. Further, these aromatic carboxylic acids may have one or more appropriate substituents on the aromatic ring. As this substituent,
For example, halogen atom such as chlorine, bromine, fluorine, iodine, methyl group, ethyl group, propyl group, n-butyl group,
Examples thereof include alkyl groups having 1 to 8 carbon atoms such as isobutyl group, amyl group, isoamyl group, and hexyl group.

Examples of such aromatic carboxylic acid include terephthalic acid, isophthalic acid, methylterephthalic acid, methylisophthalic acid, p-hydroxybenzoic acid, m
-Hydroxybenzoic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenylether-4,
4'-dicarboxylic acid, diphenylthioether-4,
4'-dicarboxylic acid, diphenyl sulfone-4,4'-
Dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 2,2'-diphenylpropane-4,4'-dicarboxylic acid and the like can be mentioned. Among these, terephthalic acid and isophthalic acid are preferable from the viewpoint of solubility and economy. These aromatic carboxylic acids may be used alone or in combination of two or more.

On the other hand, the tertiary amine used for forming the complex is a compound represented by the general formula (VI) NR " ₃ ... (VI). In the general formula (VI), R" Is an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, etc.), cycloalkyl group having 5 to 20 carbon atoms (For example, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc.), a C6-C20 aryl group (for example, a phenyl group, a naphthyl group, etc.), a C7-C20 alkylaryl group or an aralkyl group (for example, tolyl group). Group, benzyl group, etc.). A plurality of R ″ s may be the same or different from each other, and may be bonded to each other to form a ring.
Examples of the tertiary amine include triethylamine,
Examples include trimethylamine, tributylamine, N, N-dimethylcyclohexylamine, N-methylpiperidine, dimethylaniline and the like. These tertiary amines may be used alone or in combination of two or more.

In the present invention, the complex is obtained by reacting the aromatic carboxylic acid with a tertiary amine. In the reaction, the amount of the tertiary amine used is 1 mol of the aromatic carboxylic acid. , 0.01-2
The reaction is carried out in a molar ratio of preferably 0.5 to 1 mol. If the amount used is less than 0.01 mol, the reaction is slow and the carboxyl groups may not react sufficiently. On the other hand, if the amount exceeds 2 moles, it is economically disadvantageous and the polymer may be decomposed, which is not preferable. Then, the reaction between the aromatic carboxylic acid and the tertiary amine is carried out in an aqueous medium or in an organic solvent, but in consideration of the reaction with a bisphenol formate of bisphenol or a chloroformate group-containing bisphenol polycarbonate oligomer in the subsequent step. Then, it is preferable to carry out in an organic solvent. Here, as the organic solvent, those used in ordinary polycarbonate production can be used. For example, dichloromethane (methylene chloride); chloroform; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane;
Chlorinated hydrocarbons such as 1,1,2-tetrachloroethane; 1,1,2,2-tetrachloroethane; 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.

Next, in the present invention, a bischloroformate and a chloroformate group-containing bisphenol used for reacting with the complex obtained by the reaction of the aromatic carboxylic acid and the tertiary amine as described above. The bisphenol polycarbonate oligomer has the general formula (VII) or (VIII), respectively.

[0014]

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[Wherein A represents an aromatic residue and n represents an integer of 1 to 50]. ] It has a structure represented by. In the above general formulas (VII) and (VIII), the aromatic residue represented by A is, for example, the general formula (IX)

[0016]

[Chemical 4]

[In the formula, R is the same as above. ] The group represented by these is mentioned. The bischloroformate of bisphenol represented by the general formula (VII) and the general formula (VIII)
The chloroformate group-containing bisphenol polycarbonate oligomer represented by the general formula (X) HO-A-OH (X) [wherein A is the same as above. ] The bisphenol represented by these can be manufactured as a starting material. Examples of the bisphenol represented by the general formula (X) include, for example, the general formula (I)

[0018]

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[In the formula, R is the same as above. ] Or a compound represented by the general formula (XI) or (XII)

[0020]

[Chemical 6]

Compounds represented by the following can be used. The bisphenol may have one or more appropriate substituents on the aromatic ring. In R of the general formula (I), the alkylene group having 1 to 13 carbon atoms or the alkylidene group having 2 to 13 carbon atoms is, for example,
Methylene group, ethylene group, propylene group, butylene group,
Examples of the cycloalkylene group having 5 to 13 carbon atoms or the cycloalkylidene group having 5 to 13 carbon atoms such as a pentylylene group, a hexylene group, an ethylidene group, and an isopropylidene group are, for example, a cyclopentylene group, a cyclohexylene group, and a cyclopentylene group. Examples of the arylene group having 6 to 13 carbon atoms such as a lidene group and a cyclohexylidene group include:
Naphthylmethylene group, naphthylethylidene group, formula (XIII)
Or (XIV)

[0022]

[Chemical 7]

Examples include groups represented by: further,
One or more substituents that may be introduced into the aromatic ring of the bisphenol include, for example, halogen atoms such as chlorine, bromine, fluorine and iodine, methyl group, ethyl group, propyl group, n-butyl group, isobutyl group. , An amyl group, an isoamyl group, a hexyl group and the like, and an alkyl group having 1 to 8 carbon atoms.

Examples of the bisphenol represented by the above general formula (I) or the compound having a substituent on the aromatic ring thereof include 2,2-bis (4-hydroxyphenyl) propane [common name: bisphenol A]; 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-
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;
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) -3,3,5-trimethylcyclohexane; dihydroxydiarylalkanes such as 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane Kind,
1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxyphenyl) cyclodecane and other dihydroxydiarylcycloalkanes , Bis (4-hydroxyphenyl) sulfone; bis (3,5-dimethyl-4-hydroxyphenyl) sulfone; dihydroxydiaryl sulfones such as bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxy) Phenyl) ether; dihydroxydiaryl ethers such as bis (3,5-dimethyl-4-hydroxyphenyl) ether, 4,4′-dihydroxybenzophenone; 3,
Dihydroxydiarylketones such as 3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide; bis (3-methyl-4-hydroxyphenyl) sulfide;
Dihydroxydiarylsulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide,
Dihydroxydiaryl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl,
Examples thereof include dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene.

The bisphenol represented by the general formulas (XI) and (XII) or the compound having a substituent on the aromatic ring thereof includes, for example, dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, and 1,5-
Dihydroxynaphthalene; and dihydroxynaphthalene such as 2,6-dihydroxynaphthalene. Among these bisphenols, the compounds represented by the above general formula (I) are preferable from the viewpoints of solubility and toughness of the produced polymer.
Bis (4-hydroxyphenyl) propane (common name: bisphenol A) is suitable. These bisphenols may be used alone or in combination of two or more.

In the method of the present invention, the method for producing the chloroformate group-containing bisphenol polycarbonate oligomer is not particularly limited, and various known methods can be used. For example, it can be preferably produced by the following method. First, an alkaline aqueous solution containing the bisphenol is prepared, an inert organic solvent is added to the alkaline aqueous solution, and in the coexistence of the alkaline aqueous solution containing the bisphenol and the inert organic solvent while stirring,
By reacting phosgene or a phosgene derivative,
A chloroformate group-containing bisphenol polycarbonate oligomer is obtained. The bischloroformate of bisphenol can be easily obtained by adjusting the amounts of bisphenol and phosgene or phosgene derivative used in the above method. here,
Examples of phosgene or phosgene derivatives include phosgene, triphosgene, bromophosgene, bis (2,4,6).
-Trichlorophenyl) carbonate, bis (2,4-
Examples thereof include dichlorophenyl) carbonate, bis (2-cyanophenyl) carbonate, bis (2-nitrophenyl) carbonate, and trichloromethyl chloroformate.

At this time, as the alkaline aqueous solution, one having a concentration of 1 to 15% by weight is usually preferably used.
The content of bisphenol in the alkaline aqueous solution is
Usually, it is selected in the range of 0.5 to 20% by weight. Furthermore, the amount of the inert organic solvent used is such that the volume ratio of the organic phase and the aqueous phase is 5/1.
It is desirable to select it to be ⅙, preferably 2/1 to ¼. The reaction temperature is generally selected in the range of 0 to 50 ° C., preferably 5 to 40 ° C., and the reaction time is 15 minutes to 4 hours, preferably about 30 minutes to 2 hours.
Further, the degree of polymerization of the oligomer is usually 50 or less from the viewpoint of easy handling of the oligomer solution, preferably 20 to 2 for the same reason, and more preferably 10 to 2 for the same reason. After the reaction, the aqueous phase and the organic phase of the polycarbonate oligomer are separated by an operation such as standing or centrifugation. The organic phase can be used as it is for the production of polyester carbonate without separating the polycarbonate oligomer.

Examples of the alkali used in the preparation of the aqueous alkali solution containing bisphenol include sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide. Among these, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is particularly preferable. On the other hand, there are various types of inert organic solvents. For example, dichloromethane (methylene chloride); trichloromethane; 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; and toluene and acetophenone. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferable.

In the method of the present invention, a bisphenol formate of bisphenol or a bisphenol polycarbonate oligomer containing a chloroformate group thus obtained is obtained by the reaction of the above aromatic carboxylic acid with a tertiary amine. Polycarbonate is produced by polycondensing the complex with an organic solvent in the presence of an alkali. Examples of the organic solvent used in this polycondensation include the same as those exemplified in the description of the inert organic solvent used in the production of the bischloroformate of bisphenol or the bisphenol polycarbonate oligomer containing a chloroformate group. You can These organic solvents may be used alone or in combination of two or more. Examples of the alkali include alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
Of these, alkali metal carbonates such as sodium carbonate and potassium carbonate are particularly preferable. These alkalis may be used alone or in combination of two or more. Further, usually, a chloroformate group 1
It is used in a ratio of 0.8 to 1.2 equivalents based on equivalents, preferably substantially equivalent equivalents based on chloroformate groups.

In the reaction between the bisphenol bischloroformate or chlorophenolate group-containing bisphenol polycarbonate oligomer and the complex, the complex is based on 100 parts by weight of bisphenol bischloroformate or chlorophenolate group-containing bisphenol polycarbonate oligomer. Usually, it is used in a proportion of 2 to 100 parts by weight, preferably 5 to 50 parts by weight. And the above reaction temperature is
Usually, it is selected in the range of 5 to 40 ° C, preferably 10 to 30 ° C. If the reaction temperature is lower than 5 ° C, the reaction becomes slow, which is not preferable. If it exceeds 40 ° C, the polymer may be decomposed. The reaction time varies depending on the situation, but it is usually 1 minute to 5 hours, preferably 5 to 30 minutes. The complex obtained by the reaction of the aromatic carboxylic acid and the tertiary amine may be added in advance during the production of the bischloroformate of bisphenol or the bisphenol polycarbonate oligomer containing a chloroformate group.

The polymer thus produced can be isolated from the reaction solution by a conventional method. The polymer obtained by the above method is usually an anhydride group (-
OCO-OOC-) is contained in the present invention, the polymer is used in the present invention at 150 ° C or higher, preferably 150 to
A method in which heat treatment is performed at a temperature in the range of 350 ° C., decarboxylation is performed to convert an anhydride group into an ester group, and a polyester carbonate having excellent heat resistance is modified is preferably used. When the heat treatment temperature is lower than 150 ° C., decarboxylation is insufficient and it is difficult to obtain a polyester carbonate having desired heat resistance. Further, the range of 350 ° C. or lower is preferable from the viewpoint that the coloring of the polyester carbonate is small.

The heat treatment time depends on the heat treatment temperature and cannot be determined unconditionally, but it is usually about 1 minute to 10 hours. As this heat treatment method,
For example, (1) a method of heating and modifying the powdery polymer as it is, (2) a method of heating and modifying the powdery polymer at the same time as molding, and (3) molding into a desired shape using a solution of the polymer. , Method of denaturation by heating,
(4) A method in which a polymer is dissolved or suspended in a high-boiling point inert solvent and heated to modify the polymer can be used. In the above methods (2) and (3), the foamed body can be obtained at the same time as the molding by the carbon dioxide generated during the modification.

In the polyester carbonate thus obtained, the content of the ester group is usually 1 to 80 mol%, preferably 3 to 75 mol%, and more preferably the total amount of the ester group and the carbonate group. Is in the range of 5 to 50 mol%. When the content of the ester group is less than 1 mol%, the properties as polyester carbonate cannot be sufficiently exhibited. On the other hand, if it exceeds 80 mol%, the properties originally possessed by polycarbonate are lost, which is not preferable.

The polyester carbonate obtained by the method of the present invention may include a heat stabilizer, an antioxidant such as a hindered phenol type, a phosphite type, or an amine type, a benzotriazole type, a benzophenone type, if desired. UV absorbers such as, light stabilizers such as hindered amine-based, external lubricants such as aliphatic carboxylic acid ester-based and paraffin-based, flame retardants, flame retardant aids, release agents, antistatic agents,
You may mix | blend various additives, such as a coloring agent, and also fillers, such as glass fiber, and various polymers. Blending and kneading of each additive component is a commonly used method, for example, ribbon blender, Henschel mixer, Banbury mixer,
It can be carried out by a method using a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder or the like. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C.

The production method of the present invention can include all of the above production conditions and various combinations of the various preferable conditions included in the production conditions. The polyester carbonate obtained by the method of the present invention or the polyester carbonate resin composition prepared as described above has various known molding methods, for example, injection molding, blow molding, extrusion molding, compression molding, calender molding,
A molded product having a desired shape can be obtained by applying rotational molding or the like. The molded product thus obtained has a heat resistance,
Excellent mechanical properties, good solvent resistance, dimensional stability,
Since it has transparency, it is suitable for use in, for example, electric / electronic parts, mechanical parts, automobile parts, and the like.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 7.48 g of chloroformate-terminated bisphenol A polycarbonate oligomer (chloroformate group 0.0
(34 equivalents) in 34 ml of methylene chloride solution, 1.5 g of sodium carbonate and 0.78 g of terephthalic acid.
Then, a complex of 0.78 g of isophthalic acid and 2.0 ml of triethylamine was added, and the mixture was reacted by stirring at 20 ° C. for 10 minutes. At this point, the raw material carboxylic acid is
Everything was reacting. After the reaction was completed, 200 ml of methylene chloride was added to the reaction solution to dilute it, and water and 0.1N were added.
After washing with hydrochloric acid, the methylene chloride was distilled off to remove the polymer 7.
5 g (yield 94%) was obtained. The polymer obtained is 300
The film was prepared by hot pressing at ℃ and the quality was measured. As a result, the glass transition temperature was 160 ° C, and the Mv
(Viscosity average molecular weight) was 24,100.

Example 2 The procedure of Example 1 was repeated, except that the reaction time was 30 minutes. As a result, the glass transition temperature was 162 ° C and the Mv (viscosity average molecular weight) was 26,100.

Example 3 7.48 g of chloroformate-terminated bisphenol A polycarbonate oligomer (chloroformate group of 0.0
To 78 ml of a methylene chloride solution containing 268 equivalents, 0.78 g of terephthalic acid, 0.78 g of isophthalic acid and 2.84 g of sodium carbonate are added, 0.1 ml of triethylamine is added with stirring, and the mixture is stirred at room temperature for 60 minutes. , Reacted. After completion of the reaction, 200 ml of methylene chloride was added to the reaction solution to dilute it, washed with water and 0.1N hydrochloric acid, and then methylene chloride was distilled off to obtain polymer 7.4.
g (yield 92%) was obtained. The polymer obtained is 300 ° C.
The film was prepared by hot pressing with a film, and the quality was measured. As a result, the glass transition temperature was 156 ° C. and the Mv (viscosity average molecular weight) was 26,700.

Example 4 In Example 1, terephthalic acid and isophthalic acid 0.7
The procedure of Example 1 was repeated, except that 3.85 g of diphenylsulfone-4,4′-dicarboxylic acid was used instead of 8 g. As a result, the glass transition temperature was 167 ° C. and the Mv
(Viscosity average molecular weight) was 18,900.

Comparative Example 1 7.48 g of a chloroformate-terminated bisphenol A polycarbonate oligomer (with a chloroformate group of 0.0
To 78 ml of a methylene chloride solution containing 268 equivalents), 0.78 g of terephthalic acid, 0.78 g of isophthalic acid and 1.58 g (0.02 mol) of pyridine were added, and the mixture was stirred at room temperature for 1 hour to cause reaction. Was not obtained. And, the complex of terephthalic acid or isophthalic acid and pyridine was not formed.

Comparative Example 2 Chloroformate-terminated bisphenol A polycarbonate oligomer 7.48 g (chloroformate group 0.0
To 78 ml of a methylene chloride solution containing 268 equivalents, 0.78 g of terephthalic acid, 0.78 g of isophthalic acid and 2.0 g of triethylamine (2.8 ml, 0.02 mol) were added, and the mixture was stirred at room temperature for 30 minutes to carry out the reaction. Let After completion of the reaction, 200 ml of methylene chloride was added to the reaction solution to dilute it, washed with water and 0.1N hydrochloric acid, and then methylene chloride was distilled off to obtain 5.95 g of a polymer (yield 74%). The obtained polymer was heated at 250 ° C. for 10 minutes, and then quality measurement was performed. As a result, the glass transition temperature is 1
At 53 ° C., Mv (viscosity average molecular weight) was 16,000.

Reference Example 1 The glass transition temperature of bisphenol A polycarbonate [Taflon A2500 manufactured by Idemitsu Petrochemical Co., Ltd.] was measured and found to be 148 ° C. Reference Example 2 Even if 4 times mole of pyridine was mixed with terephthalic acid or isophthalic acid, terephthalic acid or isophthalic acid was not dissolved.

The glass transition temperature and the viscosity average molecular weight were measured as follows. 1) Glass transition temperature It was measured by thermal analysis measurement [DSC: heating rate 20 ° C./min]. 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

[0044]

EFFECTS OF THE INVENTION According to the present invention, a polyester carbonate having excellent heat resistance can be efficiently obtained by using inexpensive and easily available raw materials and by a simple process. Therefore, the polyester carbonate obtained by the method of the present invention has excellent heat resistance and mechanical properties, and also has good solvent resistance, dimensional stability, transparency, etc. It is preferably used as a material for parts, machine parts, automobile parts, etc.

Claims (7)

[Claims] 1. A complex obtained by reacting an aromatic carboxylic acid with a tertiary amine, and a bischloroformate of bisphenol or a bisphenol polycarbonate oligomer containing a chloroformate group in an organic solvent in the presence of an alkali. A method for producing a polyester carbonate, characterized in that polycondensation is carried out. 2. A polymer obtained by polycondensation is
The method for producing a polyester carbonate according to claim 1, wherein the heat treatment is performed at a temperature of 0 ° C. or higher. 3. The method for producing a polyester carbonate according to claim 1, wherein the alkali is an alkali metal carbonate. 4. The method for producing a polyester carbonate according to claim 1, wherein the aromatic carboxylic acid is a dibasic acid. 5. The method for producing a polyester carbonate according to claim 4, wherein the dibasic acid is terephthalic acid and / or isophthalic acid. 6. A bisphenol formate of bisphenol or a bisphenol polycarbonate oligomer containing a chloroformate group is represented by the general formula (I): [In the formula, R is an alkylene group having 1 to 13 carbon atoms and 2 carbon atoms.
To C13 alkylidene group, C5 to C13 cycloalkylene group, C5 to C13 cycloalkylidene group, C6 to C13 arylene group, -O-, -S-, -SO
_2- , -CO- or a single bond is shown. ] The manufacturing method of the polyester carbonate of Claim 1 obtained from the bisphenol represented by these. 7. Bisphenol is 2,2-bis (4-
The method for producing a polyester carbonate according to claim 6, which is hydroxyphenyl) propane.