JPH0881548A - Production of polyester-carbonate - Google Patents

Abstract

PURPOSE: To produce a polyester-carbonate of excellent quality from inexpensive easily available starting materials at good efficiency by a simple process. CONSTITUTION: This production process comprises reacting an aromatic carboxylic acid/tert. amine complex with a bischloroformate of a bisphenol or a chloroformate-group-containing bisphenol polycarbonate oligomer in an organic solvent, washing the obtained reaction mixture with an aqueous acid solution, and subjecting the washed product to interfacial polycondensation. The polymer obtained by this interfacial polycondensation is heated to 150 deg.C or above to produce a polyester-carbonate excellent in 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 by using inexpensive and easily available raw materials and by a simple process, with easy control of the molecular weight.

[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.

[0003]

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 whose molecular weight can be easily controlled.

[0004]

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 After reacting a bisphenol polycarbonate oligomer containing a formate or a chloroformate group in an organic solvent and washing the resulting reaction mixture with an acidic aqueous solution to remove the tertiary amine, the interface weight is then removed in the presence of an alkaline aqueous solution. By condensing and heat treating the polymer obtained by the interfacial polycondensation above a certain temperature,
It has been found that a polyester carbonate having an easily controlled molecular weight and excellent 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,
Bisphenol formate of bisphenol or a chloroformate group-containing bisphenol polycarbonate oligomer is reacted in an organic solvent, and after the reaction is completed,
The present invention provides a method for producing a polyester carbonate, which comprises washing the obtained reaction mixture with an acidic aqueous solution and then subjecting it to interfacial polycondensation in the presence of an alkaline aqueous solution. The present invention also provides a method for producing the polyester carbonate described above, which comprises subjecting the polymer obtained by the interfacial polycondensation to a heat treatment at a temperature of 150 ° C. or higher.

The first feature of the present invention is to use 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, general formulas (II) to (V)

[0007]

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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 acids include terephthalic acid, isophthalic acid, methylterephthalic acid, methylisophthalic acid, p-hydroxybenzoic acid, and 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. , 0.5 mol or more is preferable. If the amount used is less than 0.5 mol, the reaction is slow and the carboxyl groups may not react sufficiently. On the other hand, if the amount is too large, it is economically disadvantageous and the polymer may be decomposed, which is not preferable. From the viewpoints of reactivity of the carboxyl group, economy and degradability of the polymer, the more preferable amount of the tertiary amine used is in the range of 0.5 to 2 mol, particularly 0. 5
The range of ˜1 mol is preferred. Then, the reaction of the aromatic carboxylic acid and the tertiary amine is carried out without solvent or in an aqueous medium or an organic solvent, but with the bischloroformate of bisphenol or a chloroformate group-containing bisphenol polycarbonate oligomer in the subsequent step. Considering the reaction, it is preferably carried 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;
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.

Next, in the present invention, a bischloroformate and a chloroformate group of 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.

[0013]

[Chemical 3]

[In the formula, 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)

[0015]

[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)

[0017]

[Chemical 5]

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

[0019]

[Chemical 6]

A compound 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)

[0021]

[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; bis (3-chloro-4-hydroxyphenyl) sulfone and other dihydroxydiaryls, and bis (4 -Hydroxyphenyl) 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 bisphenols represented by the general formulas (XI) and (XII) or the compounds having a substituent on the aromatic ring thereof include, for example, dihydroxybenzenes such as hydroquinone, resorcinol and methylhydroquinone, 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 for preparing 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 process of the present invention, the bisphenol bischloroformate of bisphenol or the bisphenol polycarbonate oligomer containing a chloroformate group thus obtained is obtained by the reaction of the above aromatic carboxylic acid and a tertiary amine. The second feature is to react the complex with an organic solvent, and after the reaction is completed, the resulting reaction mixture is washed with an acidic aqueous solution. Examples of the organic solvent used in the above reaction include the same ones 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. it can. These organic solvents may be used alone or in combination of two or more.

In the reaction of the bisphenol bischloroformate or chlorophenolate group-containing bisphenol polycarbonate oligomer with 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 0 to 100 ° C, preferably 20 to 40 ° C. The reaction time varies depending on the situation, but is usually 1
The reaction may be performed for about 1 minute to 1 hour, preferably about 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.

In the present invention, the reaction mixture obtained after the above reaction is washed with an acidic aqueous solution. By washing the reaction mixture with this acidic aqueous solution, the tertiary amine used for forming the complex is removed, and the molecular weight of the polyester carbonate can be easily controlled. Here, there are various types of acids used in the acidic aqueous solution, and there is no particular limitation. Specific examples include hydrochloric acid, dilute sulfuric acid, phosphoric acid, etc. Among these, hydrochloric acid is preferable. When hydrochloric acid is suitable as the acidic aqueous solution, its concentration is usually adjusted to 0.005 to 1 N and used as an aqueous hydrochloric acid solution. The amount used is 0.1 to 10 times, preferably 0.5 to 2 times the weight of the organic phase of the reaction mixture, and the reaction mixture is washed.

The reaction mixture thus washed with an acidic aqueous solution is then subjected to interfacial polycondensation in the presence of an aqueous alkaline solution to produce polyester carbonate. In the above interfacial polycondensation reaction, a terminal stopper (monohydric phenol), dihydric phenol (bisphenol), catalyst and / or bischloroformate can be used, if necessary. Then, the interfacial polycondensation reaction is carried out in a mixed solution of an organic solvent and an aqueous alkali solution, and as the organic solvent used in the interfacial polycondensation, the bisphenol formate of bisphenol or the chloroformate group-containing bisphenol polycarbonate oligomer is used. The same ones as exemplified in the description of the inert organic solvent used in the production of can be mentioned. 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, it is usually used in a proportion of 0.8 to 1.2 equivalents to 1 equivalent of the chloroformate group, and preferably a substantially equivalent equivalent ratio to the chloroformate group. The alkali concentration of the alkaline aqueous solution is usually selected in the range of 1 to 15% by weight.

Examples of the terminal terminator used as necessary include, for example, on-butylphenol; mn-
Butylphenol; pn-butylphenol; o-isobutylphenol; m-isobutylphenol; p-
Isobutylphenol; ot-butylphenol; m
-T-butylphenol; pt-butylphenol;
nn-pentylphenol; mn-pentylphenol; pn-pentylphenol; nn-hexylphenol; mn-hexylphenol; pn-hexylphenol; o-cyclohexylphenol; m
-Cyclohexylphenol; p-cyclohexylphenol; o-phenylphenol; m-phenylphenol; p-phenylphenol; nn-nonylphenol; mn-nonylphenol; pn-nonylphenol; o-cumylphenol; m- Cumylphenol; p-cumylphenol; o-naphthylphenol;
m-naphthylphenol; p-naphthylphenol;
2,6-di-t-butylphenol; 2,5-di-t-
Butylphenol; 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; formula

[0033]

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Examples of the compound or chroman derivative represented by the formula:

[0035]

[Chemical 9]

Monohydric phenols such as compounds represented by Of these phenols, although not particularly limited in the present invention, p-tert-butylphenol; p
-Cumylphenol; p-phenylphenol and the like are preferable. Also, the formula

[0037]

[Chemical 10]

Compounds represented by the following can also be used. Further, as the dihydric phenol used as necessary, the same one as the above-mentioned bisphenol can be used.

Various kinds of catalysts can be used as the catalyst used as required. In particular,
Quaternary ammonium salts, quaternary phosphonium salts, tertiary amines, etc. For example, as quaternary ammonium salts,
Trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium chloride, tetrabutylammonium bromide and the like can be mentioned. Further, examples of the quaternary phosphonium salt include tetrabutylphosphonium chloride and tetrabutylphosphonium bromide, and examples of the tertiary amine include triethylamine, tributylamine, and the like.
Examples thereof include N, N-dimethylcyclohexylamine, pyridine and dimethylaniline.

As the reaction conditions for the interfacial polycondensation of the reaction mixture washed with the above acidic aqueous solution, the reaction temperature is usually selected in the range of 0 to 100 ° C, preferably 20 to 40 ° C. If the reaction temperature is lower than 0 ° C, the reaction becomes slow, which is not preferable. If it exceeds 100 ° C, the polymer may be decomposed. The reaction time varies depending on the situation, but it is usually 1 minute to 10 hours, preferably 5 minutes to 5 hours. The polymer thus produced by the interfacial polycondensation can be isolated from the reaction solution according to a usual method.

The polymer thus obtained usually contains an anhydride group (-OCO-OOC-). Therefore, in the present invention, the polymer has a temperature of 150 ° C or higher, preferably 150 to 350 ° C. A method in which heat treatment is performed at a temperature and 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,
Insufficient decarboxylation makes it 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%, 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 contain 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 each production condition. 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.

[0046]

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 Chloroformate-terminated bisphenol A polycarbonate oligomer 12.2 g (chloroformate group 0.0
A solution of 0.76 g of terephthalic acid and 0.76 g of isophthalic acid and 2.5 ml of triethylamine dissolved in 20 ml of methylene chloride was added to 34 ml of a methylene chloride solution containing 255 equivalents, and the mixture was stirred at 20 ° C. for 5 minutes. And allowed to react. After the reaction,
The reaction mixture was washed with 50 ml of 0.1 N hydrochloric acid.
Then add sodium carbonate to the washed methylene chloride solution.
20 ml of an aqueous sodium carbonate solution containing 2.0 g, 0.1 g of p-tert-butylphenol and 5 μl of triethylamine were added, and the mixture was stirred at 20 ° C. for 1 hour to be reacted. Then, 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 12.0 g of polymer (yield 9
4%). The obtained polymer was hot pressed at 300 ° C. to form a film, and the physical properties were measured. As a result, the glass transition temperature was 164 ° C., and the Mv (viscosity average molecular weight) was 28,100.

Example 2 Instead of 0.76 g of terephthalic acid and 0.76 g of isophthalic acid in Example 1, diphenylsulfone-4,
Example 1 except that 3.75 g of 4'-dicarboxylic acid was used.
It carried out similarly to. As a result, the glass transition temperature is 177.
At C, the Mv (viscosity average molecular weight) was 24,600.

Example 3 Terephthalic acid was added to 20 ml of a methylene chloride solution containing 4.24 g of bisphenol A.bischloroformate.
0.78 g and 0.78 g of isophthalic acid and triethylamine
Complex with 2.5 ml methylene chloride 2
The solution dissolved in 0 ml was added, and stirred at 20 ° C. for 5 minutes to cause a reaction. After the reaction was completed, the reaction mixture was adjusted to 0.1N.
It was washed with 30 ml of hydrochloric acid. Then, 20 ml of an aqueous sodium carbonate solution containing 2.0 g of sodium carbonate, 0.1 g of p-tert-butylphenol and 5 μl of triethylamine were added to the washed methylene chloride solution, and the mixture was reacted at 20 ° C. for 1 hour with stirring. afterwards,
100 ml of methylene chloride was added to the reaction solution for dilution, washed with water and 0.1N hydrochloric acid, and then methylene chloride was distilled off to obtain 5.2 g of a polymer (yield 97%). The obtained polymer was hot pressed at 300 ° C. to form a film, and the physical properties were measured. As a result, the glass transition temperature is 1
At 78 ° C., Mv (viscosity average molecular weight) was 38,100.

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

[0050]

EFFECTS OF THE INVENTION According to the present invention, a polyester carbonate having an easily controlled molecular weight and excellent heat resistance can be efficiently obtained by using a raw material which is inexpensive and easily available. 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 are reacted in an organic solvent, and after the reaction is completed. A method for producing a polyester carbonate, which comprises washing the obtained reaction mixture with an acidic aqueous solution and then subjecting it to interfacial polycondensation in the presence of an alkaline aqueous solution. 2. A polymer obtained by interfacial polycondensation,
The method for producing a polyester carbonate according to claim 1, wherein the heat treatment is performed at a temperature of 150 ° C. or higher. 3. The method for producing a polyester carbonate according to claim 1, wherein the aqueous alkali solution is an aqueous solution of 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.