JPH03203926A - Production of copolyester carbonate - Google Patents

Abstract

PURPOSE:To obtain a copolyester carbonate giving a molded article having excellent fluidity, hue and mechanical properties, etc., by subjecting an aliphatic dicarboxylic acid, etc., a carbonic acid diester and an aromatic organic dihydroxyl compound to melt polycondensation in the presence of a specific catalyst. CONSTITUTION:An aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, a carbonic acid diester and an aromatic organic dihydroxyl compound are subjected to melt polycondensation in the presence of a catalyst composed of an alkali metal compound or an alkaline earth metal compound in an amount of <=10<-4>mol, preferably 10<-7>-10<-5>mol to 1mol said aromatic dihydroxyl compound, or said alkali or alkaline earth metal compound and a nitrogen- containing basic compound preferably in an amount of 10<-5>-10<-2>mol and/or boric acid or a boric acid ester preferably in an amount of 10<-6>-10<-4>mol to efficiently produce a copolyester carbonate.

Description

Detailed Description of the Invention Technical Field of the Invention The present invention relates to a method for producing a copolyester carbonate.More specifically, the present invention relates to a method for producing a copolyester carbonate. The present invention relates to a method for producing a copolyester carbonate that can efficiently obtain a copolyester carbonate that maintains excellent mechanical properties, heat resistance, etc.

Technical background of the invention and its problems Copolyester carbonates can be applied to various uses because the molded products formed therefrom have excellent mechanical properties such as impact resistance and heat resistance. As a method for producing such a copolyester carbonate, for example, a method using melt polycondensation of an organic dicarboxylic acid, a diaryl carbonate, and an organic trihydroxy compound is known (
(See Japanese Patent Publication No. 38-26299).

However, by this method, it is not possible to obtain a copolyester carbonate that retains sufficient original mechanical properties and heat resistance and has a satisfactory color. That is, if this method is used to obtain a copolyester carbonate that retains sufficient original mechanical properties and heat resistance, there is a problem in that the hue of the resulting copolyester carbonate deteriorates.

On the other hand, a method of directly reacting organic dicarbonate esters (interfacial method) is also known. Even with this method, it is not possible to obtain a copolyester carbonate with a good hue. There is a problem in that it is difficult to obtain a copolymer that

The present inventors conducted extensive studies to solve the above problems, and found that aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acid esters, carbonic acid diesters, and aromatic organic dihydroxyl compounds, or aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acid esters, If acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonate, and aromatic organic dihydroxyl group compound are melt-polycondensed in the presence of a specific catalyst, the color is good and the fluidity is improved. At the same time, it is possible to efficiently obtain a copolyester carbonate that maintains excellent mechanical properties and heat resistance, etc. This method also allows for short chain lengths, which have been difficult to obtain using conventional interfacial methods. It was discovered that a copolymer containing an aliphatic group can be easily obtained, and the present invention was completed. The purpose of the present invention is to provide a method for producing a copolyester carbonate with high fluidity, which provides a molded product with a good hue and maintains excellent mechanical properties, heat resistance, etc. There is.

Summary of the invention First method for producing copolyester carbonate according to the present invention &Dai (a) For 1 mol of aromatic organic dihydroxy compound,
A gourd consisting of an alkali metal compound or an alkaline earth metal compound in an amount of 10-4 mol or less or (a) per mol of an aromatic organic dihydroxy group compound,
An aliphatic dicarboxylic acid in the presence of a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of not more than 10 −4 molar amount, and (b) a nitrogen-containing basic compound and/or (c) boric acid or a boric acid ester. It is characterized by subjecting an aliphatic dicarboxylic acid ester, a carbonic acid diester, and an aromatic organic dihydroxyl group compound to melt polycondensation.

Second method for producing copolyester carbonate according to the present invention Method (a) For 1 mol of aromatic organic dihydroxy compound,
10-4 per mole of catalyst or aromatic organic dihydroxyl group compound consisting of an alkali metal compound or alkaline earth metal compound in an amount of 10-4 or less.
Aliphatic dicarboxylic acid and/or in the presence of a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 4 molar or less and (b) a nitrogen-containing basic compound and/or (c) boric acid or a boric acid ester. An aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxy group compound, and a carbonic acid diester having 17 to 5 carbon atoms or a phenol having 10 to 40 carbon atoms is the aromatic organic dihydroxy group compound. 0.05 per mole
It is characterized in that melt polycondensation is carried out in a reaction system in which the components coexist in an amount within the range of 15 mol %.

Third method for producing copolyester carbonate according to the present invention 4 For 1 mole of aromatic organic dihydroxy compound, 10-
10- for 1 mole of a catalyst or aromatic organic dihydroxyl group compound consisting of an alkali metal compound or alkaline earth metal compound in an amount of 4 moles or less
In the presence of a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 4 molar or less and (b) a nitrogen-containing basic compound and/or (e) boric acid or a boric acid ester, an aliphatic dicarboxylic acid and/or Alternatively, an aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxyl group compound are combined, and a carbonic acid diester having 13 to 16 carbon atoms or a phenol having 10 to 25 carbon atoms is combined with the aromatic organic dihydroxyl group. 0.05 per mole of compound
It is characterized in that melt polycondensation is carried out in a reaction system in which the components coexist in an amount within the range of 15 mol %.

Depending on the method for producing the copolyester carbonate according to the present invention! , using a specific catalyst to melt polycondensate aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acid esters, diphenyl carbonates, and aromatic organic dihydroxyl compounds, resulting in very good hue. A copolymer having the following can be produced. It is not possible to produce a copolymer with such excellent hue as the one obtained by the production method of the present invention, at least by the conventionally known interfacial methods.

DETAILED DESCRIPTION OF THE INVENTION First, the method for producing the first copolyester carbonate according to the present invention will be specifically described.

In the first method for producing a copolyester carbonate according to the present invention, an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, an aromatic organic dihydroxy compound, and a carbonic acid diester are melt-polycondensed using a specific catalyst. to produce copolyester carbonate.

The aliphatic dicarboxylic acid +L used in the present invention can be represented, for example, by the following formula [rl].

HOOC-(cH2), -COOH[1] Above formula [I]
In, n is an integer from 2 to 30.

In the present invention, a copolyester carbonate can be obtained by the following reaction between the aliphatic dicarboxylic acid, carbonic acid diester, and aromatic organic dihydroxy compound in the presence of a specific catalyst.

0 → Copolyester carbonate Examples of such aliphatic dicarboxylic acids include 14-succinic acid, geltanic acid, adipic acid, pimelic acid, and sperinic acid.
Mention may be made of azelaic acid, sebacic acid, dodecandioic acid, and the like.

Further, the aliphatic dicarboxylic acid ester used in the present invention can be represented, for example, by the following formula [■].

However, in the above formula [n], n is an integer of 2 to 30, and R is an aryl alkyl group.

In the present invention, a copolyester carbonate can be obtained by the following reaction between the aliphatic dicarboxylic acid ester, the carbonic acid diester, and the aromatic organic dihydroxy compound in the presence of a specific catalyst.

→Copolyester carbonate Examples of such aliphatic dicarboxylic acid esters include:
Diphenyl ester, dimethyl ester and diethyl ester of aliphatic dicarboxylic acids can be mentioned.

In the present invention, each of the above aliphatic dicarboxylic acids and aliphatic dicarboxylic acid esters can be used alone or in combination. As the aliphatic dicarboxylic acid ester, as mentioned above, diesters are usually used, but in the present invention, not only substitute diesters but also monoesters can be used.

Among the aliphatic dicarboxylic acids and aliphatic dicarboxylic acid esters mentioned above, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, and diphenyl esters thereof are particularly preferred.

Specific examples of carbonic acid diesters used in the present invention include hexa-diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, Mention may be made of dibutyl carbonate and dicyclohexyl carbonate.

Among these, diphenyl carbonate is particularly preferred.

Further, these carbonic acid diesters may contain broad dicarboxylic acids or dicarboxylic acid esters. 6 as such dicarboxylic acid or dicarboxylic acid ester
There is no particular restriction on the number of carbon atoms, and specific examples include miterephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate.

Further, the aromatic organic dihydroxyl group compound used in the present invention can be represented, for example, by the following formula [ml].

In the above formula [ml R2R.

-5O- or -502-, R1 and R2 are hydrogen atoms or monovalent hydrocarbon groups, and R3 is a divalent hydrocarbon group. Further, the aromatic nucleus may have a monovalent hydrocarbon group.

Specific examples of such aromatic organic dihydroxy compounds include I-bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, and 2,2-bis(4-hydroxyphenyl)ethane.
-hydroxyphenyl)propane, 2,2-bis(4-
hydroxyphenyl)butane, 2.2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2.2-bis(4-hydroxy-1-methylphenyl)propane, 1.1-bis (4
-hydroxy-t-butylphenyl)propane and 2
．． Bis(hydroxyaryl) alkanes such as 2-bis(4-hydroxy-3-bromophenyl)propane 1.1-bis(4-hydroxyphenyl)cyclopentane and 1.1-bis(4-hydroxyphenyl)cyclohexane Bis(hydroxyaryl)cycloalkanes such as 4.4'-dihydroxydiphenyl ether and dihydroxyaryl ethers such as 4.4'-dihydroxy-3,3'-dimethylphenyl ether
-dihydroxydiphenyl sulfide and 4.4゛-
Dihydroxydiaryl sulfides such as dihydroxy-3,3°-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxide cucumbers such as 4.4°-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; Dihydroxydiarylsulfones such as 4.4°-dihydroxydiphenylsulfone and 4°4°-dihydroxy-3,3′-dimethyldiphenylsulfone can be mentioned.

Among these, 2,2-bis(4-hydroxyphenyl)propane is particularly preferred.

In the present invention, the carbonic acid diester as described above is usually used in an amount of 1.0 per mole of the aromatic organic dihydroxy compound.
It is used in an amount of 1-1.30 mol, preferably 102-1.20 mol.

In the present invention, the amount of aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester 6 is usually 1 to 50 mol%, preferably 5 to 50% by mole, based on the aromatic organic dihydroxy compound.
It is used in an amount of 40 mol%, particularly preferably 10 to 30 mol%.

Next, a method for producing the second copolyester carbonate according to the present invention will be explained.

In the second method for producing copolyester carbonate according to the present invention! When producing a copolyester carbonate by melt polycondensing an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxy group compound in the presence of a specific catalyst, the reaction system The number of carbon atoms is 17
-50 carbonic acid diester or phenol having 10 to 40 carbon atoms in an amount of 0.005 to 15 mol%, preferably 0.005 to 15 mol%, preferably 0.005 to 15 mol%, based on 1 mol of the aromatic organic dihydroxy compound. The melt polycondensation reaction is carried out in a system containing 5 to 7 mol%.

Here, as the aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester and the aromatic organic dihydroxyl group compound, 14 are the first compounds according to the present invention as described above, respectively.
It is possible to use the compounds described in the description of the method for producing the copolyester carbonate.

Further, as diphenyl carbonates, aromatic carbonic acid diesters having 13 to 16 carbon atoms are usually used. Specific examples of such diphenyl carbonates include melon diphenyl carbonate, triphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, and m-cresyl carbonate.

Among these, diphenyl carbonate is particularly preferred.

Further, these diphenyl carbonates may also contain dicarboxylic acid or dicarboxylic acid ester. As such dicarboxylic acids or dicarboxylic acid esters, there is no particular restriction on the number of carbon atoms, and various types can be used.
Mention may be made of terephthalic acid, isophthalic acid, diphenyl terephthalate and diphenyl isophthalate.

In the second method for producing a copolyester carbonate according to the present invention, the amount is usually 1.01 to 1.30 mol, preferably 1.01 to 1.30 mol per mol of the above-mentioned diphenyl carbonate compound. 1.02~1.2
It is used in an amount of 0 mol.

In the second method for producing a copolyester carbonate according to the present invention, jL is usually 0.0. The melt polymerization is carried out in an amount of 0.05 to 15 mol %, preferably 0.5 to 7 mol %, more preferably 1 to 5 mol %.

As such a carbonic acid diester, a compound represented by the following formula is usually used.

A-0-C-0-B In the above formula, A is a group having 8 to 25 carbon atoms,
B is a group having 10 to 25 carbon atoms, and the sum of the numbers of carbon atoms of A and B is 49 or less.

In addition, as phenols having 10 to 40 carbon atoms,
The following compounds are used.

o-n-butylphenol, m-n-butylphenol, p-n-butylphenol, 0-isobutylphenol, m-isobutylphenol, p-isobutylphenol, o-t-butylphenol, m-t-butylphenol, p-t-butylphenol , o-n-pentylphenol, m-n-pentylphenol, p-n-pentylphenol, o-n-hexylphenol, m-n-hexylphenol, p-n-hexylphenol, 0-cyclohexylphenol, m- Cyclohexylphenol, p-cyclohexylphenol, o-n-nonylphenol m-n-nonylphenol, p-n-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-7-butylphenol, 2 .5-dicumylphenol, 3.5-dicumylphenol, trinuclear phenols having the above are preferred, and p-cumylphenol, p-phenylphenol, etc. are particularly preferred.

Specifically, the following compounds are used as the above-mentioned carbonic acid diesters.

In the formula, R1 is a hydrocarbon group having 3 to 36 carbon atoms.

Chroman induction machine For example, in the formula, R2 represents a hydrocarbon group having 1 to 19 carbon atoms,
R5 represents a hydrocarbon group having 3 to 19 carbon atoms, and the sum of the carbon atoms of R2 and R3 is 37 or less.

Furthermore, R7 and R5 may be the same group or different groups.

Monovalent phenols such as.

In these phenols, two aromatic rings are represented by R.
4 is a hydrocarbon group having 1 to 30 carbon atoms, R3 is a hydrocarbon group having 1 to 2 o carbon atoms, and R4 and R5
The sum of the number of carbon atoms is 3 or more and 36 or less. In addition, R
4, R2 and 檄 may be the same or different.

In the formula, R6 is a hydrocarbon group having 4 to 37 carbon atoms.

In the formula, R7 is a hydrocarbon group having 1 to 30 carbon atoms, R6 is a hydrocarbon group having 2 to 20 carbon atoms, and the total number of carbon atoms of R7 and R6 is 36 or less. Further, R7 and R8 may be the same or different.

More specifically, the following compounds are preferably used as carbonic acid diesters used in the present invention as described above.

Carbobutoxyphenyl phenyl carbonate, methyl phenyl butylphenyl carbonate, ethylphenyl butylphenyl carbonate, dibutyl diphenyl carbonate, biphenylphenyl carbonate, diphenyl carbonates cumylphenylphenyl carbonate, dicumylphenyl carbonate, naphthylphenylphenyl carbonate, dinaphthylphenyl carbonate, These include carbopropoxyphenylphenyl carbonate, carbohebutoxyphenylphenyl carbonate, carbomethoxy t-butylphenylphenyl carbonate, carboprotoxyphenylmethylphenylphenyl carbonate, chromanylphenyl carbonate, diphenyl carbonates, and the like.

When the amount of carbonic acid diester described above is in the range of 05 mol% to 15 mol% (J, 05 mol% to 15 mol%) per 1 mol of the aromatic organic dihydroxy compound, the hydroxyl terminals of the resulting copolyester carbonate are blocked. Therefore, it is possible to obtain a copolyester carbonate having a good hue, improved fluidity, and sufficiently excellent mechanical properties, heat resistance, and water resistance.Moreover, the polycondensation reaction rate is increased.

The entire amount of such carbonic acid diester salt may be added to the reaction system in advance, or a portion may be added to the reaction system in advance.
The remainder may be added as the reaction progresses. In addition, depending on the case, the entire amount may be added to the descendant reaction system after the polycondensation reaction of the aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonate, and aromatic organic dihydroxyl group compound has partially progressed. .

Next, a method for producing the third copolyester carbonate according to the present invention will be specifically explained.

In the third method for producing a copolyester carbonate according to the present invention, in the presence of a specific catalyst, an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxy compound are combined. When producing copolyester carbonate by melt polycondensation, the number of carbon atoms in the reaction system is 13.
~16 carbonic acid diesters or carbon atoms of 10 to 25
of phenols are present.

+ As aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acid esters and aromatic organic dihydroxyl group compounds
4 Compounds similar to the aliphatic dicarboxylic acid, aliphatic dicarboxylic acid ester, and aromatic organic dihydroxy group compound used in the first method for producing the copolyester carbonate according to the present invention as described above are used.

Further, as the diphenyl carbonates, compounds similar to the diphenyl carbonates used in the method for producing the second copolyester carbonate according to the present invention as described above are used.

When producing the copolyester carbonate according to the present invention, the amount of diphenyl carbonate as described above is usually 1.01 mol per 1 mol of the aromatic organic dihydroxyl group compound.
It is used in an amount of ~1.30 mol, preferably 1.02-1.20 mol.

In the third method for producing a copolyester carbonate according to the present invention, carbonate diesters having 13 to 16 carbon atoms or phenols having 10 to 25 carbon atoms are added to an aromatic organic dihydroxy compound, usually at 0%. .05 to 15 mol%, preferably 05 to 7 mol%, more preferably 1 to 7 mol%
Present in an amount of 5 mol%.

In such a method for producing a copolyester carbonate, as the carbonate diester having 13 to 16 carbon atoms, in addition to the carbonate diesters shown below, the diphenyl carbonates having 13 to 16 carbon atoms can also be used. . Therefore, carbonic acid diesters such as diphenyl carbonate, phenyltolyl carbonate, and ditolyl carbonate may be the same compound as diphenyl carbonate.

The amount of carbonic acid diester or phenol as mentioned above is 0.0 per mole of the aromatic organic dihydroxyl group compound.
When it is in the range of 5 mol% to 15 mol%, the hydroxyl group terminals of the obtained copolyester carbonate are blocked,
The color is good and the fluidity is improved.
A copolyester carbonate with sufficiently excellent mechanical properties, heat resistance, and water resistance can be obtained.

Such diester carbonate or phenol may be added in its entirety to the reaction system in advance, or a portion thereof may be added in advance to the reaction system, and the remainder may be added as the reaction progresses. Further, depending on the case, the entire amount may be added to the reaction system after the polycondensation reaction between the aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonates, and aromatic organic dihydroxy compound has partially proceeded.

In addition, in the method for producing a copolyester carbonate according to the present invention as described above, it is preferable to reduce the total chlorine content contained in the starting materials as described above, and in particular, to reduce the chlorine content in the starting materials. , 20 ppm or less,
By setting the amount to preferably 10 ppm or less, a particularly highly transparent copolymer can be obtained.

In addition, the chlorine content in this specification and +L refer to the chlorine content in salt fish that exists as acids such as hydrochloric acid or salts such as sodium chloride and potassium chloride, or in organic compounds such as phenyl chloroformate and methylene chloride. It can be measured by analysis such as ion chromatography.

The total chlorine content in the starting materials as above is 20pp.
m or less (playful example + f, these raw materials are p
The H value is in the range of 6.0 to 9.0, preferably 7.0 to 8.5, more preferably 7.0 to 8.0, and the temperature is 78 to 105°C, preferably 80 to 100°C. , and more preferably with warm water of 80 to 90°C.

It is effective to use a weakly basic solution when cleaning carbonic diesters and phenyl carbonates such as those mentioned above. Examples of such weakly basic aqueous solutions include sodium hydroxide, potassium hydroxide, lithium hydroxide,
Sodium carbonate, potassium carbonate, ammonium hydroxide,
An aqueous solution of sodium hydrogen carbonate, potassium hydrogen carbonate, or tetramethylammonium hydroxide is used, especially sodium hydrogen carbonate,
Particularly preferred are aqueous solutions of sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate.

Further, it is preferable to wash the carbonic acid diester and diphenyl carbonate with warm water as described above, and then further distill it before use.

In addition, in the present invention, the total sodium ion content contained in the above starting materials is preferably 1.0 ppm or less, and more preferably 0.0 ppm or less. It is particularly preferable that the content be 5 ppm or less. By adjusting the sodium content to the above level, a copolyester carbonate with no further coloring can be obtained.

The sodium ion content contained in the starting material is
It can be determined by atomic absorption spectrometry and inductively coupled plasma emission spectrometry.

In order to reduce the sodium ion content contained in the starting material to the above-mentioned value or less, purification methods such as distillation and adducting with recondensed phenol may be employed.
- In the first to third methods for producing copolyester carbonates according to the present invention, a copolyester carbonate is produced by melt polycondensing an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, a diester carbonate, and an aromatic organic dihydroxyl group compound. When manufacturing polyester carbonate,
Alternatively, a copolyester carbonate is produced by melt polycondensing an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydric acid group compound in the presence of the catalyst described below.

That is, the catalyst used in the present invention is (a)
For 1 mole of the above aromatic organic dihydroxy compound,
Catalyst (a) consisting of an alkali metal compound or alkaline earth metal compound in an amount of not more than 10-4 mol per mole of the aromatic organic dihydroxyl compound (a) A tent consisting of a metal compound and (b) a nitrogen-containing basic compound; (a) an alkali metal compound or an alkaline earth metal compound in an amount of 10-4 mol or less per 1 mol of the aromatic organic dihydroxy compound; , (c) a catalyst consisting of boric acid or a boric acid ester (a) an alkali metal compound or alkaline earth metal compound in an amount of not more than 10 −4 mol per 1 mol of the aromatic organic dihydroxy compound; There is a catalyst consisting of b) a nitrogen-containing basic compound and (c) boric acid or a boric acid ester.

Here, specific examples of the alkali metal compounds include sodium hexahydroxide, potassium hydroxide, lithium hydroxide,
Sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate,
Sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, phosphoric acid Mention may be made of disodium hydrogen and dipotassium hydrogen phosphate, dilithium hydrogen phosphate, and the disodium, dipotassium and dilithium salts of bisphenol A, the sodium, potassium and lithium salts of phenol.

Further, specific examples of alkaline earth metal compounds include calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, Mention may be made of barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate and strontium stearate.

The alkali metal compound or alkaline earth metal compound (a) as described above is 10-4 mol or less, preferably 10-δ to 1 mol of the aromatic organic dihydroxy compound.
It is used in a proportion of 10-5 mol, particularly preferably 10-7 to 10-5 mol.

Amount of alkali metal compound or alkaline earth metal compound c: 1 per mole of the above aromatic organic dihydroxy compound
When the amount is 0-8 to 10-S mol, a polymer with high polymerization activity can be formed, and a copolyester carbonate with excellent color fluidity, mechanical properties, heat resistance, and water resistance can be obtained.

A specific example of the nitrogen-containing basic compound is takatetramethylammonium hydroxide (Me.

N0H), tetraethylammonium hydroxide (E
t4NOH), tetrabutylammonium hydroxide (Bu, N0H), trimethylbenzylammonium hydroxide group, aryl group, aryl group, etc. Tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, etc. In the formula, R is alkyl such as methyl and ethyl, phenyl,
Primary amines represented by NH2 (wherein R is the same as above), or ammonia, tetramethylammonium borohydride (Me4NBH4), tetrabutylammonium Niborohydride (Bu.

Examples include basic salts such as NBH4), tetrabutylammonium tetraphenylborate (Bu4NBPh4), and tetramethylammonium tetraphenylborate (M 84N B P h4).

Among these, tetraalkylammonium hydroxides are particularly preferred.

Nitrogen-containing basic compound +3 as described above is used in a ratio of 10-8 to 10-1 mol, preferably 10-5 to 10-2 mol, per 1 mol of the aromatic organic dihydroxy compound.

When the amount of the nitrogen-containing basic compound is 10-8 to 10-1 mol per 1 mol of the aromatic organic dihydroxy compound, the transesterification reaction\polymerization reaction will proceed at a sufficient rate, and the color and fluidity will be improved. A copolyester carbonate with excellent properties such as properties, mechanical properties, heat resistance, and water resistance can be obtained.

(c) As boric acid or boric acid ester, boric acid or 2B (OR) , (OH)3-n (in the formula, R is
methyl group, alkyl group such as ethyl group, aryl group such as phenyl group, etc., where n is 1°2 or 3)
The boric acid ester shown is used.

Specific examples of such borate esters include trimethyl borate, triethyl borate, tributyl borate,
Mention may be made of trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate and trinaphthyl borate.

The above boric acid or boric acid ester is usually 10-δ to 10-1 mole of the aromatic organic dihydroxy compound.
It is used in amounts of 1 mol, preferably lo-7 to 10-2 mol, particularly preferably 10-8 to 10-4 mol.

When the amount of boric acid or boric acid ester is 10-8 to 10-1 mol per 1 mol of the aromatic organic dihydroxyl compound, the molecular weight after heat aging is less likely to decrease, and furthermore, the hue and fluidity are improved. , a copolyester carbonate with excellent heat resistance and water resistance is obtained.

In the present invention, in particular, a catalyst comprising the above (a) alkali metal compound or alkaline earth metal compound and (b) a nitrogen-containing basic compound, or the above (a) alkali metal compound or alkaline earth metal compound and ( It is preferable to use a catalyst comprising b), a nitrogen-containing basic compound, and (c) boric acid or a boric acid ester.

The above-mentioned catalyst consisting of (a) an alkali metal compound or an alkaline earth metal compound and (b) a nitrogen-containing basic compound has high polymerization activity and can produce a high molecular weight copolyester carbonate. The resulting copolyester carbonate has excellent flow properties, mechanical properties, heat resistance and water resistance, as well as improved hue.

In addition, the above (a) alkali metal compound or alkaline earth metal compound, (b) nitrogen-containing basic compound, and (c
) Catalytic method consisting of boric acid or boric acid ester It is possible to produce copolyester carbonates with higher polymerization activity and high molecular weight, and the resulting copolyester carbonates have excellent fluidity, mechanical properties, and heat resistance. It has excellent durability and water resistance, and the hue has been further improved.

In the present invention, a polycondensation reaction between an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, a carbonic acid diester, and an aromatic organic dihydroxyl group compound, or a polycondensation reaction between an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester and a diphenyl carbonate The polycondensation reaction with the aromatic organic dihydroxy compound can be carried out under the same conditions as the polycondensation reaction conditions in the conventionally known method for producing copolyester carbonates.

Specifically, the temperature of the first stage reaction plate is 80 to 250°C, preferably 100 to 230°C, more preferably 120 to 1
at a temperature of 90°C for 0 to 5 hours, preferably 0 to 4 hours,
More preferably, it is carried out for 0.25 to 3 hours at normal pressure. Next, the reaction temperature is raised while reducing the pressure of the reaction system to further carry out the reaction, and finally the reaction temperature is reduced to 24 cm under reduced pressure of 1ffi■Hg or less.
Polycondensation reaction of aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester, diester carbonate, and aromatic organic dihydric acid group compound or aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester and diphenyl at a temperature of 0 to 320°C Performs a polycondensation reaction between carbonates and aromatic organic dihydroxyl compounds.

The polycondensation reaction described above may be carried out in a continuous manner,
Alternatively, it may be carried out in a batch manner. Further, the reaction apparatus used in carrying out the above polycondensation reaction (may be of a tank type, a tube type, or a base type).

When a copolyester carbonate is produced by melt polycondensing an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, a diester carbonate, and an aromatic organic dihydroxyl group compound as described above, all of the copolyester carbonate obtained is Among the terminals, the hydroxyl group terminal is usually 30
% or less, preferably 20% or less, more preferably 10% or less
~20%, and the intrinsic viscosity measured in methylene chloride at 20°C is usually 0.3 to 1.0 dl/g.
A copolyester carbonate is obtained within the range of .

Furthermore, the copolyester carbonate obtained by the present invention has good hue and improved fluidity.

In addition, aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonates and aromatic organic When a copolyester carbonate is produced by melt polycondensation with a dihydroxyl group compound, hydroxyl group ends account for 30% or less, preferably 20% or less, more preferably 10 to 20% of all the ends of the copolyester carbonate obtained.
% and whose intrinsic viscosity [V], measured in methylene chloride at 20 DEG C., is usually from 0.3 to 1.0 dl/g. Furthermore, the copolyester carbonate obtained by the present invention has a good hue and improved fluidity.

In addition, aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acid esters, diphenyl carbonates, and aromatic compounds can be prepared in the presence of carbonic acid diesters having 13 to 16 carbon atoms or phenols having 10 to 25 carbon atoms in the reaction system. When a copolyester carbonate is produced by melt polycondensation with an organic dihydroxy compound, the proportion of hydroxyl terminals in the total terminals of the copolyester carbonate usually obtained is 30% or less, preferably 20% or less, more preferably 10 to 20%.
% and whose intrinsic viscosity [V], measured in methylene chloride at 20° C., is usually from 0.3 to 1.0 dl/g. Further, cobolyester carbonate obtained according to the present invention) 14
The color is good and the fluidity is improved.

Effects of the Invention In the first method for producing a copolyester carbonate according to the present invention, 14 aliphatic dicarboxylic acids and/or aliphatic dicarboxylic acid esters, diester carbonates, and aromatic organic dihydroxyl group compounds are melted using a specific catalyst. Polycarbonate is produced by polycondensation, so the color is good and
Moreover, a copolyester carbonate having improved fluidity and maintaining excellent mechanical properties, heat resistance, and water resistance (hydrolysis resistance) can be obtained.

In addition, in the second method for producing a copolyester carbonate according to the present invention, an aliphatic dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxy group compound are mixed using a specific catalyst. In addition to melt polycondensation in the reaction system, a specific amount of carbonic acid diester having 17 to 50 carbon atoms is present in the reaction system, resulting in good color, improved fluidity, and excellent mechanical properties. Characteristics, heat resistance, water resistance (hydrolysis resistance)
A copolyester carbonate having the following properties is obtained.

Saraban-Third copolyester carho according to the present invention*-
), an aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxyl group compound are melt-polycondensed using a specific catalyst. The presence of a specific amount of carbonic acid diester having 13 to 16 carbon atoms provides good color and improved fluidity, as well as excellent mechanical properties, heat resistance, and water resistance (hydrolysis resistance). )
A copolyester carbonate having the following properties is obtained.

Moreover, according to the method for producing the first to third copolyester carbonates according to the present invention, it is possible to easily obtain a copolymer containing an aliphatic group with a short chain length, which is difficult to obtain by the conventional interfacial method. be able to.

Although the present invention has been explained above using examples, the present invention is not limited to these examples.

Examples The physical properties of the polycarbonate obtained in the following examples are as follows: Resin composition measured as follows. , GX-270) to measure the terminal structure and proportion. Intrinsic viscosity (IV):
Nine hues (YI), measured using an Ubbelohde viscometer at 20 °C in j chloride + syn (0,5 dl/g): 2
．． The Lab value of the thick press sheet was determined by Nippon Denshoku Kogyo Co.
1or and Co1or DifferenceM
Measured by transmission method using eter ND-1001DP.
Have you calculated yellowness index (YI)? 1.53a+ 178.82b YI= Melt index (MI): JIS K7210
300℃, weight 1.2 according to the method specified in
Measured in kg (g/10 min).

Press sheet creation conditions: 120°C, 400mHg.

After drying the pellet for 12 hours and heating it at 280℃ for 10 molecules,
Pressed at 280°C for 5 minutes at 1ookg/cm2 and cold pressed at room temperature for 5 minutes.

Sodium content in the polymer: A polymer with a concentration of 2o was oxidized and the limit value of 0. Chlorine content in the polymer measured up to O5ppm: 50.1@ polymer with Schoriger
Ion chromatography (manufactured by Dionex: Ion Chromatograph 2)
Water resistance test measured to a limit value of 0, 05 ppm using 000i): The press sheet was immersed in hot water at 80°C for 24 hours, and the appearance change was observed and evaluated. In the reactor, dodecanoic acid diphenylic acid (dodecanoic acid and diphenyl carbonate was melt-reacted (230°C) using lithium hydroxide as a catalyst.
) was synthesized by recrystallization and purification.
．． O5ppm or less, chlorine content 0. (lppm or less)
4.6 g (0.02 mol) and 80 g (0.02 mol) of diphenyl carbonate (diphenyl carbonate manufactured by Bayer)
It was washed twice with hot water at pH 7.0 and purified by distillation with a yield of 90%, and the Na content was 0. O5ppm or less,
Chlorine content 0. O5ppm or less) 43.7g (0,
204 mol) and bisphenol A (manufactured by Japan GE Plastic ■, Na content 0.05 ppm or less, chlorine content 1.0 ppm) 45.6 g (0,200 mol)
) and boric acid H, BO, (special grade manufactured by Wako Reagent ■) 0.0
31 mg (0,025 x 10-4) was added under N2 atmosphere, heated at 180°C and stirred with a Ni stirring bar for 30 minutes, then tetramethylammonium hydroxide
Me4NOH 15% aqueous solution (manufactured by Toyo Gosei ■) 30.3
．． w (2,5X 10-4/bisulfonol A1mo
l) and sodium hydroxide NaOH (special grade manufactured by Wako Reagent ■) 0.008mg (0.01x 10”mol/
Bisphenol A (1 mol) was added, and further 180
℃, stirred for 30 minutes under N2 atmosphere to perform transesterification reaction, then heated to 210℃ and gradually heated to 200W+H.
The pressure was reduced to g for 1 hour, and then the temperature was raised to 240°C for 200 steps 1 (g for 20 minutes, gradually reduced to 150 mgg for 20 minutes, and further depressurized to 100 mgg for 20 minutes, 15a++e
After reducing the pressure to Hg and reacting for 0.5 hours, the temperature was raised to 270°C and finally the temperature was reduced to 0. Reduce pressure to 5gmHg, 20
When the time reaction was carried out as described above, IV 0. 5.4, Y
I 1. A copolyester carbonate of 90 and M116 was obtained. The results are shown in Table 1.

In a 100 ml glass reactor, dodecanionic acid (purified by recrystallizing and purifying a special grade reagent manufactured by Wako Tsumugi Pharmaceutical Co., Ltd. Na content: 0.5 ppm or less, chlorine content: 0.1 ppm or less) 4.
6g (0.02mol) and diphenyl carbonate (
Diphenyl carbonate manufactured by Bayer was heated at 80°C, p.
Washed twice with H7.0 hot water and distilled with a yield of 90%.
:, Na content.

0, O5ppm or less, chlorine content; o, osppm
(below) 52.2g (0,244mol), bisphenol A (manufactured by Japan GE Plastic ■, Na content 0.
O5ppm or less, chlorine content 1.0ppm) 45.6
g (0,200 mol) and boric acid H, BO, (special grade manufactured by Wako Reagent ■) 0.031-g (0,025X 10
-4 mol/1 mol of bisphenol A were heated to 180°C under N2 atmosphere and stirred with a Ni stirring bar for 30 minutes, followed by a 15% aqueous solution of tetramethylammonium hydroxide Me4NOH (manufactured by Toyo Gosei) 3
0.3.1@(2,5X 10-'mol/bisphenol A1mol) and sodium hydroxide NaOH (special grade manufactured by Wako Reagent ■) 0.08mg (0,LX 10-4
mol/bisphenol A 1 mol) and
Stirred at 250°C for 2 hours under N2 atmosphere, and 0. The esterification reaction was carried out while eliminating L, and then the temperature was lowered to 210°C. The pressure was gradually reduced to Zoo-ml (g) and the temperature was further raised to 240°C for 1 hour.

200-mHg for 20 minutes, gradually increasing to 150-mHg. , the pressure was reduced to HIZ for 20 minutes, the pressure was further reduced to roommHg for 20 minutes, the pressure was reduced to 15 In Hg and the reaction was allowed to proceed for 05 hours, the temperature was raised to 270°C, and the pressure was finally reduced to 0.5 gmHg for 20 hours. When the reaction was carried out as described above, IVo, 53, YI 2
．． A copolyester carbonate of 20, M116 was obtained and the results are shown in Table 1.

Example 3 In Example 1, instead of diphenyl dodecanoate E
, 7 diphenyl diphenyl 11.9g (0.04m
Table 1 shows the results of obtaining a copolyester carbonate in the same manner as in Example 1 except that ol) was used.

In Example 1, 6.8 g (0.02 mo) of diphenyl azelaate was used instead of diphenyl dodecanoate.
A copolyester carbonate was obtained in the same manner as in Example 1 except that 1) was used. The results are shown in Table 1.

Example 5 In Example 2, adipic acid (manufactured by Wako Tsumugi Pharmaceutical Co., Ltd., special grade reagent was recrystallized and used) instead of dodecanionic acid.
Table 1 shows the results of obtaining a copolyester carbonate in the same manner as in Example 2 except that 5.8 g (0.04 mol) was used.

In Example 2, the amount of sodium hydroxide used was 0.0.
08@ (0,IX 10-4mol/bisphenol A 1mol to 2.0mg (2,5X 10-4m
ol/bisphenol A 1 mol)
A copolyester carbonate was obtained in the same manner as in Example 2. The results are shown in Table 1.

Table 1 shows the results of determining the hue (yr) and melt index of homopolycarbonate (manufactured by Nippon GE Plastics Co., Ltd., Engineering vO054).

Contents of procedural amendment amendment 1, indication of case 1999 Patent Application No. 340,289 1999 1
Patent application filed on February 29th (2) 2゜3゜Name of inventionRelationship with the case of a person amending the manufacturing method of copolyester carbonate Patent applicant name Title Japan GE Plastics Co., Ltd. 4゜Representative (postal code) 141) 3rd floor, Araku Building, 2-19-2 Nishigotanda, Tokyo Parts District [Telephone: 03-491-3181] 6° “Detailed Description of the Invention” column of the specification to be amended 7° Attachment to the contents of the amendment As per (1 except for matters stated in the column of subject of amendment) Specification No. 4
On page 8, line 12, [intrinsic viscosity (IV) J] is corrected to "intrinsic viscosity [η]".

2) On page 48, line 12 of the specification, ``(0.5 dl/g) J in methylene chloride will be corrected to ``(0.5 g/dl) J in methylene chloride.

3) On page 48, line 14 of the specification, "2■ thickness" will be corrected to "3■ thickness."

4) "rLab value" on page 48, line 14 of the specification.
Correct it to "X value, Y value, 2 values".

5) In lines 1 and 2 of page 49 of the specification, r
71. 53a+178. 82bYI= is corrected as .

6) In the fourth line of page 50 of the specification, "diphenylic acid (dodecanoic acid") will be corrected to "diphenyl (dodecanniic acid").

7) On page 51, line 12 of the specification, rlV O
, 54J will be corrected to ``[η], 0.54J.

8) On page 52, line 16 of the specification, "02" should be corrected to "rco□".

9) On page 53, line 5 of the specification, r[V 0.
53J is corrected to ``[ηko 0.53J.

1G) On page 53, line 11 of the specification, "diphenyl" will be amended to "diphenyl."

■) On page 53, line 17 of the specification, "diphenyl" will be corrected to "diphenyl J."

12) On page 54, line 17 of the specification, rlV
Correct the value 0.54J to [[η] 0.54J.

+3) Table 1 on page 55 of the specification will be amended as shown in the attached sheet.

Claims (12)

[Claims] (1) (a) A catalyst consisting of an alkali metal compound or an alkaline earth metal compound in an amount of 10^-^4 moles or less per 1 mole of the aromatic organic dihydroxyl compound, or (a) an aromatic organic dihydroxyl compound. 1 per mole of hydroxyl compound
0^-^Aliphatic in the presence of a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 4 or less, and (b) a nitrogen-containing basic compound and/or (c) boric acid or a boric acid ester. A method for producing a copolyester carbonate, which comprises melt polycondensing a dicarboxylic acid and/or an aliphatic dicarboxylic acid ester, a diester carbonate, and an aromatic organic dihydroxyl group compound. (2) The method according to claim 1, wherein the proportion of the alkali metal compound or alkaline earth metal compound is 10^-^8 to 10^-^5 mol per 1 mol of the aromatic organic dihydroxy compound. Method for manufacturing polyester carbonate. (3) Consisting of (a) an alkali metal compound or alkaline earth metal compound in an amount of 10^-^4 moles or less per 1 mole of the aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound. 1 per mole of catalyst or (a) aromatic organic dihydroxy compound
Claims using either a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 0^-^4 mol or less, (b) a nitrogen-containing basic compound, and (c) boric acid or a boric acid ester. A method for producing a copolyester carbonate according to item 1. (4) Claims 1 to 3, wherein the ratio of the aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester to the aromatic organic dihydroxy compound is 1 to 50 mol%.
A method for producing a copolyester carbonate according to any one of paragraphs. (5) (a) A catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 10^-^4 mol or less per mol of the aromatic organic dihydroxyl compound, or (a) an aromatic organic dihydroxyl group. For 1 mole of compound, 1
0^-^Aliphatic dicarbonate in the presence of a catalyst consisting of an alkali metal compound or alkaline earth metal compound of up to 4 molar amount and (b) a nitrogen-containing basic compound and/or (c) boric acid or boric acid ester. An acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxyl group compound are combined into a carbonate diester having 17 to 50 carbon atoms or a phenol having 10 to 40 carbon atoms. 0.05 per mole of organic dihydroxy compound
A method for producing a copolyester carbonate, which comprises carrying out melt polycondensation in a reaction system coexisting in an amount within the range of 15 mol %. (6) The method according to claim 5, wherein the proportion of the alkali metal compound or alkaline earth metal compound is 10^-^8 to 10^-^5 mol per mol of the aromatic organic dihydroxy compound. Method for manufacturing polyester carbonate. (7) Consisting of (a) an alkali metal compound or alkaline earth metal compound in an amount of 10^-^4 moles or less per 1 mole of the aromatic organic dihydroxy compound; and (b) a nitrogen-containing basic compound. 1 per mole of catalyst or (a) aromatic organic dihydroxy compound
Claims using either a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 0^-^4 mol or less, (b) a nitrogen-containing basic compound, and (c) boric acid or a boric acid ester. A method for producing a copolyester carbonate according to item 5. (8) Claims 5 to 7, wherein the ratio of the aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester to the aromatic organic dihydroxy compound is 1 to 50 mol%.
A method for producing a copolyester carbonate according to any one of paragraphs. (9) (a) A catalyst consisting of an alkali metal compound or an alkaline earth metal compound in an amount of 10^-^4 moles or less per 1 mole of the aromatic organic dihydroxyl group, or (a) an aromatic organic dihydroxyl group. For 1 mole of compound, 1
In the presence of a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 0^-^4 molar or less and (b) a nitrogen-containing basic compound and/or (c) boric acid or a boric acid ester, an aliphatic A dicarboxylic acid and/or aliphatic dicarboxylic acid ester, diphenyl carbonates, and an aromatic organic dihydroxy group compound are combined into a carbonic acid diester having 13 to 16 carbon atoms or a phenol having 10 to 25 carbon atoms. 0.05 per mole of organic dihydroxy compound
A method for producing a copolyester carbonate, which comprises carrying out melt polycondensation in a reaction system coexisting in an amount within the range of 15 mol %. (10) Claim 9, wherein the proportion of the alkali metal compound or alkaline earth metal compound is 10^-^8 to 10^-^5 mole per mole of the aromatic organic dihydroxy compound.
A method for producing the copolyester carbonate described in Section 1. (11) Consisting of (a) an alkali metal compound or alkaline earth metal compound in an amount of 10^-^4 moles or less per 1 mole of the aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound. 1 per mole of catalyst or (a) aromatic organic dihydroxy compound
Claims using either a catalyst consisting of an alkali metal compound or alkaline earth metal compound in an amount of 0^-^4 mol or less, (b) a nitrogen-containing basic compound, and (c) boric acid or a boric acid ester. A method for producing a copolyester carbonate according to item 9. (12) The method according to any one of claims 9 to 11, wherein the ratio of the aliphatic dicarboxylic acid and/or aliphatic dicarboxylic acid ester to the aromatic organic dihydroxy compound is 1 to 50 mol%. Method for producing copolyester carbonate.