JP2984289B2 - Method for producing copolyester carbonate - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a copolyestercarbonate, and more particularly, to a molded article having good hue and improved fluidity of a resin, and The present invention relates to a method for producing a copolyestercarbonate capable of efficiently obtaining a copolyestercarbonate having excellent mechanical properties and heat resistance.

Technical background of the invention and its problems Copolycarbonate can be applied to various uses because the formed product is excellent in mechanical properties such as impact resistance and heat resistance. As a method for producing such a copolyestercarbonate, for example, a method by melt polycondensation of an organic dicarboxylic acid, a diaryl carbonate, and an organic dihydroxy compound is known (see Japanese Patent Publication No. 38-29929).

However, it is not possible to obtain a copolyester carbonate having a satisfactory hue while maintaining the original sufficient mechanical properties and heat resistance by this method.
In other words, there is a problem in that when the copolyestercarbonate having the original sufficient mechanical properties and heat resistance is obtained by this method, the hue of the obtained copolyestercarbonate is deteriorated.

On the other hand, a method of directly reacting an organic dicarboxylic ester (interfacial method) is also known. However, a copolyester carbonate having good hue cannot be obtained by this method, and an aliphatic group having a short chain length cannot be obtained. There is a problem that it is difficult to obtain a contained copolymer.

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and found that aliphatic dicarboxylic acid and / or aliphatic dicarboxylic acid ester and carbonate diester and aromatic organic dihydroxy compound, or aliphatic dicarboxylic acid Melt polycondensation of an acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound in the presence of a specific catalyst provides good hue and improved fluidity. In addition, it is possible to efficiently obtain a copolyestercarbonate having excellent mechanical properties and heat resistance, and according to this method, the short chain length, which was difficult to obtain by the conventional interface method It has been found that a copolymer containing an aliphatic group of formula (1) can be easily obtained, and the present invention has been completed.

Object of the Invention The present invention is to solve the problems associated with the prior art as described above, while the hue of the molded body is good, while maintaining excellent mechanical properties and heat resistance etc. It is an object of the present invention to provide a method for producing a copolyestercarbonate having high fluidity.

SUMMARY OF THE INVENTION The first method for producing a copolyestercarbonate according to the present invention comprises the steps of: (a) adding 10 moles to 1 mole of an aromatic organic dihydroxy compound;
^-8 to 10 ^-5 moles of a catalyst comprising an alkali metal compound or an alkaline earth metal compound, or (a) 10 moles per mole of an aromatic organic dihydroxy compound.
^In the presence of a catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol, and (b) a nitrogen-containing basic compound and / or (c) boric acid or a borate ester, It is characterized in that melt polycondensation of an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a carbonic acid diester, and an aromatic organic dihydroxy group compound.

The second method for producing a copolyestercarbonate according to the present invention comprises: (a) 10 mols per 1 mol of an aromatic organic dihydroxy compound.
Catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol, or (a) 10 mol per mol of an aromatic organic dihydroxy compound.
^In the presence of a catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol and (b) a nitrogen-containing basic compound and / or (c) boric acid or a borate ester; A dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound are converted to a carbonic acid diester having 17 to 50 carbon atoms or a phenol having 10 to 40 carbon atoms. 0.05 to 15 mol% per 1 mol of the organic dihydroxy compound
It is characterized in that it is subjected to melt polycondensation in a reaction system coexisting in an amount within the range described above.

The third method for producing a copolyestercarbonate according to the present invention comprises the steps of:
Catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol, or (a) 10 mol per mol of an aromatic organic dihydroxy compound.
^In the presence of a catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol and (b) a nitrogen-containing basic compound and / or (c) boric acid or a borate ester; A dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound are converted to a diester of carbonic acid having 13 to 16 carbon atoms or a phenol having 10 to 25 carbon atoms. 0.05 to 15 mol% per 1 mol of the organic dihydroxy compound
It is characterized in that it is subjected to melt polycondensation in a reaction system coexisting in an amount within the range described above.

According to the method for producing a copolyestercarbonate according to the present invention, using a specific catalyst, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound, Because of the melt polycondensation, it is possible to produce a copolymer having a very good hue. At least the conventionally known interface method cannot produce a copolymer having an excellent hue as obtained by the production method of the present invention.

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

In the first method for producing a copolyestercarbonate 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 used in the present invention can be represented by, for example, the following formula [I].

HOOC- In _{(CH 2) n -COOH [I} ] the above formula [I], 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, the carbonic acid diester and the aromatic organic dihydroxy compound in the presence of a specific catalyst.

Examples of such aliphatic dicarboxylic acids include succinic acid, glutanic acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid and dodecane diacid.

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

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

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

Examples of such aliphatic dicarboxylic acid esters include diphenyl esters, dimethyl esters and diethyl esters of the above-mentioned aliphatic dicarboxylic acids.

In the present invention, the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid ester can be used alone or in combination. As the aliphatic dicarboxylic acid ester, a diester is usually used as described above, but in the present invention, not only a diester but also a monoester can be used.

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

Specific examples of the carbonic diester used in the present invention include diphenyl carbonate, ditolyl carbonate,
Bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate can be mentioned.

Of these, diphenyl carbonate is particularly preferred.

These carbonic acid diesters may contain a dicarboxylic acid or a dicarboxylic acid ester. Such a dicarboxylic acid or dicarboxylic acid ester is not particularly limited in the number of carbon atoms, and specific examples thereof include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate.

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

In the above formula [III], X is —SO— or —SO ₂ —, wherein R ₁ and R ₂ are a hydrogen atom or a monovalent hydrocarbon group, and R ₃ is a divalent hydrocarbon group. Further, the aromatic may have a monovalent hydrocarbon group.

Specific examples of such an aromatic organic dihydroxy group compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-
(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 2,2-bis (4
Bis (hydroxyaryl) alkanes such as -hydroxy-3-bromophenyl) propane, bis such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane (Hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether and 4,4 '
Dihydroxyaryl ethers such as dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide and
Dihydroxydiaryl sulfides such as 4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulphoxide and
Dihydroxydiarylsulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, and 4,4'-dihydroxydiphenylsulfone and 4,4 '
And dihydroxydiarylsulfones such as -dihydroxy-3,3'-dimethyldiphenylsulfone.

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

In the present invention, the above-mentioned carbonic acid diester is usually used in an amount of 1.01 to 1 mol of the aromatic organic dihydroxy compound.
1.31.30 moles, preferably 1.02-1.20 moles.

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

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

In the second method for producing a copolyestercarbonate according to the present invention, in the presence of a specific catalyst, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound are melted. When producing a copolyestercarbonate by polycondensation, the reaction system has 17 carbon atoms.
To 50 carbonic acid diesters or phenols having 10 to 40 carbon atoms with respect to 1 mole of the aromatic organic dihydroxy compound.
The melt polycondensation reaction is carried out in a system present at 0.05 to 15 mol%, preferably 0.5 to 7 mol%.

Here, as the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester and the aromatic organic dihydroxy group compound, the compounds described in the description of the first method for producing a copolyester carbonate according to the present invention as described above, respectively. Can be used.

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

Of these, diphenyl carbonate is particularly preferred.

Further, these diphenyl carbonates may contain a dicarboxylic acid or a dicarboxylic acid ester. As such a dicarboxylic acid or dicarboxylic acid ester, there is no particular limitation on the number of carbon atoms, and various types can be used. Specifically, for example, terephthalic acid, isophthalic acid, diphenyl terephthalate and isophthalic acid Diphenyl acid.

In the second method for producing a copolyestercarbonate according to the present invention, the above-mentioned diphenyl carbonate is usually used in an amount of 1.01 to 1.30 mol, preferably 1.02 to 1.20 mol, per 1 mol of the aromatic organic dihydroxy compound. It is used in molar amounts.

In the second method for producing a copolyester carbonate according to the present invention, the carbonic acid diester having 17 to 50 carbon atoms or the pheninol having 10 to 40 carbon atoms is usually added to the aromatic organic dihydroxy group compound in an amount of from 0.05 to The melt polymerization is carried out in an amount of 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.

In the above formula, A is a group having 6 to 25 carbon atoms,
B is a group having 10 to 25 carbon atoms, and the sum of the carbon atoms of A and B is 49 or less.

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

on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol , On-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, o-cyclohexylphenol, m- Cyclohexylphenol, p-cyclohexylphenol, on-nonylphenol, mn-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylph Knol, m-naphthylphenol, p-naphthylphenol, 2,6-di-t-butylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-phenol Butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, Chroman derivatives, such as And other monohydric phenols.

Among such phenols, binuclear phenols having two or more aromatic rings are preferable, and p-cumylphenol, p-phenylphenol and the like are particularly preferable.

As the carbonic acid diester as described above, specifically,
For example, the following compounds are used.

In the formula, R ₁ is a hydrocarbon group having 3 to 36 carbon atoms.

Wherein, R ₂ represents a hydrocarbon group having 1 to 19 carbon atoms, R ₃
Represents a hydrocarbon group having 3 to 19 carbon atoms, and the sum of the carbon atoms of R ₂ and R ₃ is 37 or less. Further, R ₂ and R ₃ may be the same group or different groups.

In the formula, R ₄ is a hydrocarbon group having 1 to 30 carbon atoms,
R ₅ is a hydrocarbon group having 1 to 20 carbon atoms, and the sum of the carbon atoms of R ₄ and R ₅ is 3 or more and 36 or less. Note that R ₄ and
R ₅ may be the same or different.

In the formula, R ₆ is a hydrocarbon group having 4 to 37 carbon atoms.

In the formula, R ₇ has 1 to 30 carbon atoms, and R ₈ has 2 carbon atoms.
A 20 hydrocarbon group, the sum of the number of carbon atoms of R7 and R ₈ are
36 or less. Further, R ₇ and R ₈ may be the same or different.

As the carbonic acid diester used in the present invention as described above, more specifically, the following compounds are preferably used.

Carbobutoxy phenyl phenyl carbonate, methyl phenyl butyl phenyl carbonate, ethyl phenyl butyl phenyl carbonate, dibutyl phenyl carbonate, biphenyl phenyl carbonate, dibiphenyl carbonate, cumyl phenyl phenyl carbonate, dicumyl phenyl carbonate, naphthyl phenyl phenyl phenyl carbonate, dinaphthyl phenyl carbonate , Carbopropoxyphenyl phenyl carbonate,
Carboheptoxyphenylphenyl carbonate, carbomethoxy t-butylphenylphenyl carbonate,
Carboprotoxyphenylmethylphenylphenyl carbonate, chromanylphenyl carbonate, dichromanyl carbonate and the like.

When the amount of the carbonic acid diester is in the range of 0.05 mol% to 15 mol% with respect to 1 mol of the aromatic organic dihydroxy compound, the hydroxyl group terminal of the obtained copolyester carbonate is blocked, The hue is good, and the fluidity is improved, as well as the mechanical properties and heat resistance,
A copolyestercarbonate having sufficiently excellent water resistance is obtained, and the polycondensation reaction rate is increased.

Such a carbonic acid diester may be previously added to the reaction system in its entirety, or may be partially added to the reaction system in advance, and the remainder may be added as the reaction proceeds. Further, in some cases, the whole amount may be added to the reaction system after the polycondensation reaction between the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester, the diphenyl carbonate, and the aromatic organic dihydroxy compound partially proceeds. .

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

In the third method for producing a copolyestercarbonate according to the present invention, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound are melted in the presence of a specific catalyst. When producing a copolyestercarbonate by polycondensation, the reaction system has 13 carbon atoms.
Carbonic acid diesters of up to 16 or phenols having 10 to 25 carbon atoms are present.

As the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester and the aromatic organic dihydroxy group compound, the aliphatic dicarboxylic acid and the aliphatic dicarboxylic acid used in the first method for producing a copolyestercarbonate according to the present invention as described above, respectively. The same compounds as the aliphatic dicarboxylic acid esters and the aromatic organic dihydric compounds are used.

As the diphenyl carbonate, the same compound as the diphenyl carbonate used in the second method for producing a copolyester carbonate according to the present invention as described above is used.

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

In the third method for producing a copolyestercarbonate according to the present invention, the carbonic acid diester having 13 to 16 carbon atoms or the phenol having 10 to 25 carbon atoms is usually added to the aromatic organic dihydroxy group compound in an amount of 0.05 to 0.05. 1515 mol%, preferably 0.5-7 mol%, more preferably 1-5 mol%.

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

The amount of the carbonic acid diester or phenol is 0.05 to 1 mol of the aromatic organic dihydroxy compound.
When the molar ratio is in the range of 15 mol% to 15 mol%, the hydroxyl group terminal of the obtained copolyester carbonate is sealed, so that the hue is good, the fluidity is improved, and the mechanical properties, heat resistance, and water resistance are improved. A copolyestercarbonate having sufficiently excellent properties is obtained.

Such a carbonic acid diester or phenol may be previously added to the reaction system in its entirety, or may be partially added to the reaction system in advance, and the remainder may be added as the reaction proceeds. Further, in some cases, the whole amount may be added to the reaction system after the polycondensation reaction between the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester, the diphenyl carbonate, and the aromatic organic dihydroxy compound partially proceeds. .

Further, 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 material as described above, and particularly, the chlorine content in the starting material, By setting the content to 20 ppm or less, preferably 10 ppm or less, a copolymer having particularly high transparency can be obtained.

As used herein, the term "chlorine content" refers to the content of chlorine in an acid such as hydrochloric acid or in a salt such as sodium chloride or potassium chloride, or in an organic compound such as phenylchloroformate or methylene chloride. And can be measured by analysis such as ion chromatography.

20 ppm of the total chlorine content in the starting materials as described above
In order to make the following, for example, these raw materials, pH value 6.0 ~
9.0, preferably 7.0 to 8.5, more preferably 7.0 to 8.0
And the temperature is 78-105 ° C., preferably 80-100 ° C.
C., more preferably with warm water at 80 to 90.degree.

When washing the carbonic acid diester and phenyl carbonate as described above, it is effective to use a weakly basic solution. Examples of such a weakly basic aqueous solution include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and tetramethylammonium hydroxide. A dissolved aqueous solution is used, and among them, an aqueous solution of sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate is particularly preferable.

Further, it is preferable that the carbonic acid diester and the diphenyl carbonate are washed with the above-mentioned warm water and then further distilled.

In the present invention, the total content of sodium ions contained in the above-mentioned starting materials is preferably set to 1.0 ppm or less, more preferably 0.5 ppm or less. By using the above-mentioned sodium content, it is possible to obtain a copolyestercarbonate without further coloring.

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

In order to reduce the content of sodium ions contained in the starting material to the above value or less, a purification method such as distillation, recrystallization, and an adduct method with phenol may be employed.

In the first to third methods for producing a copolyester carbonate according to the present invention, the copolyester is prepared by melt polycondensation of an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a carbonic acid diester, and an aromatic organic dihydroxy compound. In the production of a carbonate, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate and an aromatic organic dihydroxy compound are subjected to melt polycondensation in the presence of a catalyst described below to obtain a copolymer. Manufacture polyester carbonate.

That is, the catalyst used in the present invention includes (a) an alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of the aromatic organic dihydroxy compound. A catalyst comprising (a) an alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of an aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound. Catalyst, (a) 10 ^-8 to 10 ^-5 mole amount of alkali metal compound or alkaline earth metal compound per 1 mole of aromatic organic dihydroxy compound, and (c) boric acid or borate ester (A) an alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of an aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound;
(C) There is a catalyst comprising boric acid or borate ester.

Here, specific examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, 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, disodium hydrogen phosphate And dipotassium hydrogen phosphate, dilithium hydrogen phosphate, and disodium, dipotassium and ditylium salts of bisphenol A, sodium, potassium and lithium salts of phenol.

Specific examples of the alkaline earth metal compound 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) is 10 ^-8 to 10 ^-5 mol, particularly preferably 10 ^-7 to 10 mol, per 1 mol of the aromatic organic dihydroxy compound.
Used in a proportion of ^-5 mol.

The amount of the alkali metal compound or alkaline earth metal compound is based on 1 mole of the aromatic organic dihydroxy compound.
When it is 10 ^-8 to 10 ^-5 mol, the polymerization activity can be increased, and a copolyester carbonate excellent in hue, fluidity, mechanical properties, heat resistance and water resistance can be obtained.

Specific examples of the nitrogen-containing basic compound include tetramethyl ammonium hydroxide (Me ₄ NOH), tetraethyl ammonium hydroxide (Et ₄ NOH), tetrabutyl ammonium hydroxide (Bu ₄ NOH), and trimethylbenzyl ammonium hydroxide. Ammonium hydroxides having an alkyl group, an aryl group, an araryl group, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, and triphenylamine; R ₂ NH (where R is methyl, ethyl, etc.) Alkyl, phenyl,
Secondary amines represented by an aryl group such as toluyl, etc.), primary amines represented by RNH ₂ (where R is the same as described above), ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄₎ ), tetrabutylammonium borohydride (Bu ₄ NBH _4), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎
And the like.

Of these, tetraalkylammonium hydroxides are particularly preferred.

The nitrogen-containing basic compound as described above is used in a proportion of 10 ^-6 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 ^-6 to 10 ^-1 mol per 1 mol of the aromatic organic dihydroxy group compound, the transesterification reaction and the polymerization reaction proceed at a sufficient rate, and the hue,
A copolyester carbonate having excellent fluidity, mechanical properties, heat resistance and water resistance can be obtained.

(C) As boric acid or boric acid ester, boric acid or a compound of the formula B (OR) _n (OH) _3-n (where R is an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, etc.) And n is 1, 2 or 3).

Specific examples of such borate esters include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate and trinaphthyl borate. it can.

Boric acid or boric acid esters described above, with respect to 1 mole of the aromatic organic dihydroxy compound, usually 10 ^-8 to 10 ^-1 mol, preferably 10 ^-7 to 10 ^-2 mol, particularly preferably 10 ^{- 6} to
Used in 10 ^-4 molar amounts.

When the amount of boric acid or boric acid ester is 10 ^-8 to 10 ^-1 mol per 1 mol of the aromatic organic dihydroxy compound, a decrease in molecular weight after heat aging hardly occurs, and further, hue, fluidity, A copolyester carbonate having excellent heat resistance and water resistance can be obtained.

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

The catalyst comprising the above (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, and The resulting copolyestercarbonate has excellent fluidity, mechanical properties, heat resistance and water resistance, and further improved hue.

Further, (a) an alkali metal compound or an alkaline earth metal compound, (b) a nitrogen-containing basic compound,
(C) a catalyst comprising boric acid or a borate ester,
It has a higher polymerization activity and can produce a high molecular weight copolyestercarbonate.Moreover, the obtained copolyestercarbonate has further excellent fluidity, mechanical properties, heat resistance and water resistance, and furthermore has a hue. Further improvements have been made.

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

Specifically, the first-stage reaction is performed at a temperature of 80 to 250 ° C, preferably 100 to 230 ° C, more preferably 120 to 190 ° C, for 0 to 5 hours, preferably 0 to 4 hours, and more preferably. Is carried out at normal pressure for 0.25 to 3 hours. Then, the reaction temperature is increased while reducing the pressure of the reaction system, and the reaction is further performed. Finally, the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester and the carbonate diester are heated at a temperature of 240 to 320 ° C. under a reduced pressure of 1 mmHg or less. Or a polycondensation reaction with an aromatic organic dihydroxy compound or an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester with a diphenyl carbonate and an aromatic organic dihydroxy compound.

The polycondensation reaction as described above may be performed in a continuous manner or in a batch manner. The reaction apparatus used for performing the above polycondensation reaction may be a tank type, a tube type, or a column type.

As described above, when an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a carbonic acid diester, and an aromatic organic dihydroxy compound are melt-polycondensed to produce a copolyester carbonate, the obtained copolyester carbonate is Of all the terminals, the hydroxyl terminal is usually 30
% Or less, preferably 20% or less, more preferably 10 to 20%.
%, And the intrinsic viscosity [η] measured in methylene chloride at 20 ° C. is usually in the range of 0.3 to 1.0 dl / g.

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

Further, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate and an aromatic organic compound are added to the reaction system in the presence of a carbonic acid diester having 17 to 50 carbon atoms or a phenol having 10 to 40 carbon atoms. When a copolyestercarbonate is produced by melt polycondensation with a dihydroxy group compound, the hydroxyl group ends are usually 30% or less, preferably 20% or less, more preferably 10 to 20%, of all the terminals of the usually obtained copolyestercarbonate. In addition, a copolyester carbonate having an intrinsic viscosity [η] measured in methylene chloride at 20 ° C. of usually 0.3 to 1.0 dl / g is obtained. Further, the copolyester carbonate obtained by the present invention has good hue and improved fluidity.

Also, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate and an aromatic dicarboxylic acid are used in the reaction system in the presence of a carbonic acid diester having 13 to 16 carbon atoms or a phenol having 10 to 25 carbon atoms. When a copolyestercarbonate is produced by melt polycondensation with an organic dihydroxy group compound, the hydroxyl group end is usually 30% or less, preferably 20% or less, more preferably 10 to 20%, of all the terminals of the usually obtained copolyestercarbonate. Further, a copolyester carbonate having an intrinsic viscosity [η] measured in methylene chloride at 20 ° C. of usually 0.3 to 1.0 dl / g is obtained. Further, the copolyester carbonate obtained by the present invention has good hue and improved fluidity.

Effect of the Invention In the first method for producing a copolyestercarbonate according to the present invention, an aliphatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a carbonic acid diester and an aromatic organic dihydroxy compound are melted using a specific catalyst. Polycondensation produces polycarbonate, so copolyester carbonates with good hue, improved fluidity, and excellent mechanical properties, heat resistance, and water resistance (hydrolysis resistance) can get.

Further, in the second method for producing a copolyestercarbonate according to the present invention, the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester, the diphenyl carbonate, and the aromatic organic dihydroxy compound are formed using a specific catalyst. Melt polycondensation and the presence of a specific amount of carbonic acid diester with 17 to 50 carbon atoms in the reaction system provide good hue, improved fluidity, and excellent mechanical properties Thus, a copolyestercarbonate having heat resistance and water resistance (hydrolysis resistance) can be obtained.

Further, in the third method for producing a copolyester carbonate according to the present invention, the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester, the diphenyl carbonate, and the aromatic organic dihydroxy compound are melted using a specific catalyst. Since the polycondensation and the specific amount of carbonic acid diester having 13 to 16 carbon atoms are present in the reaction system, the hue is good, and the fluidity is improved, and excellent mechanical properties, A copolyester carbonate having heat resistance and water resistance (hydrolysis resistance) is obtained.

Moreover, according to the first to third methods for producing a copolyester carbonate according to the present invention, a copolymer containing an aliphatic group having a short chain length, which has been difficult to obtain by a conventional interface method, can be easily obtained. be able to.

The present invention will be described with reference to examples, but the present invention is not limited to these examples.

Examples The physical properties of the polycarbonate obtained in the following examples were measured as described below.

Resin composition: 0.4 g of a sample was dissolved in 3 ml of chloroform, and the terminal structure and ratio were measured at 40 ° C. using ¹³ C-NMR (GX-270, manufactured by JEOL Ltd.).

Intrinsic viscosity [η]: Measured in methylene chloride (0.5 g / dl) at 20 ° C. using an Ubbelohde viscometer.

Hue (YI): Nippon Denshoku Industries Co., Ltd. Color and Color Defference Meter
It was measured by a transmission method using ND-1001 DP, and the yellowness (YI) was calculated.

Melt index (MI): Measured at 300 ° C and 1.2 kg weight according to the method specified in JIS K7210 (g / 10
Minutes).

Press sheet preparation conditions: 120 ° C, 400 mm Hg, pellets dried for 12 hours, preheated at 280 ° C for 10 minutes, then 100k for 5 minutes at 280 ° C
g / cm ² and cold pressing at room temperature for 5 minutes.

A polymer having a sodium content of 20 in the polymer was ashed and measured to a limit value of 0.05 ppm by atomic absorption (Hitachi 180-80, manufactured by Hitachi, Ltd.).

Chlorine content in polymer: 50 mg of polymer was gasified by the Schoriger method to form an aqueous solution, and ion chromatography (manufactured by Dionex: Ion Chromatograph 2000)
Using i), measurement was performed up to the limit value of 0.05 ppm.

Water resistance test: The press sheet was evaluated by observing changes in appearance after immersing the press sheet in hot water of 80 ° C. for 24 hours.

Example 1 In a 100-ml glass reactor, diphenyl dodecanoate (a product of dodecanedioic acid and diphenyl carbonate synthesized by a melting reaction (230 ° C.) using lithium hydroxide as a catalyst) was recrystallized and purified. 4.6 g (0.02 mol) of 0.05 ppm or less, chlorine content of 0.1 ppm or less) and diphenyl carbonate (Bayer's diphenyl carbonate
It was washed twice with warm water at 0 ° C. and pH 7.0, and purified by distillation at a yield of 90%. Na content 0.05ppm or less, chlorine content 0.05ppm or less)
43.7 g (0.204 mol), 45.6 g (0.200 mol) of bisphenol A (Na content: 0.05 ppm or less, chlorine content: 1.0 ppm, manufactured by Nippon GE Plastics Co., Ltd.) and boric acid H ₃ BO ₃ (Wako Reagent Co., Ltd.) 0.031 mg (0.025 × 10 ⁻⁴ mol / bisphenol A 1 mol) was added under N ₂ atmosphere, heated at 180 ° C., and stirred with a Ni stirring bar for 30 minutes.

Then, tetramethylammonium hydroxide
Me ₄ NOH 15% aqueous solution (Toyo Gosei Co., Ltd.) 30.3 mg (2.5 × 1
0 ^-4 mol / bisphenol A 1 mol) and sodium hydroxide N
aOH (special grade manufactured by Wako Reagent Co., Ltd.) 0.008 mg (0.01 × 10 ^-4 mol /
Bisphenol A 1 mol) and added further 180 ° C., N ₂
The mixture was stirred for 30 minutes under an atmosphere to perform a transesterification reaction.

After that, the temperature was raised to 210 ° C, gradually reduced to 200 mm Hg, and further increased to 240 ° C for 1 hour, then reduced to 200 mm Hg for 20 minutes, gradually reduced to 150 mm Hg for 20 minutes, and further reduced to 100 mm Hg.
After reacting for 0.5 hour by reducing the pressure to 15 mm Hg for 20 minutes, 270
C., and finally reduced to 0.5 mm Hg, and reacted for 2.0 hours.

As described above, [η] 0.54, YI 1.90, MI
16 copolyestercarbonates were obtained.

 Table 1 shows the results.

Example 2 In a 100 ml glass reactor, dodecane diacid (a special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. was recrystallized and purified. Na content)
0.5g or less, chlorine content 0.1ppm or less) 4.6g (0.02mol)
And diphenyl carbonate (Bayer diphenyl carbonate was washed twice with warm water at 80 ° C. and pH 7.0, and the yield was
Distilled at 90%. Na content: 0.05 ppm or less, chlorine content: 0.05p
pm or less) 52.2 g (0.244 mol), 45.6 g (0.200 mol) of bisphenol A (Na content 0.05 ppm or less, chlorine content 1.0 ppm, manufactured by Nippon GE Plastics Co., Ltd.), and boric acid H ₃ B
O ₃ (special grade, manufactured by Wako Reagent Co., Ltd.) 0.031 mg (0.025 × 10 ^-4 mol /
1 mol of bisphenol A was heated to 180 ° C. under an N ₂ atmosphere and stirred with a Ni stirring bar for 30 minutes.

Then, tetramethylammonium hydroxide
Me ₄ NOH 15% aqueous solution (Toyo Gosei Co., Ltd.) 30.3 mg (2.5 × 1
0 ^-4 mol / bisphenol A 1 mol) and sodium hydroxide N
aOH (special grade, manufactured by Wako Reagent Co., Ltd.) 0.08 mg (0.1 × 10 ⁻⁴ mol / bisphenol A 1 mol) was added, and the mixture was stirred at 250 ° C. under an N ₂ atmosphere for 2 hours to remove the ester while removing CO _2. The reaction was carried out.

Thereafter, the temperature was lowered to 210 ° C, gradually reduced to 200 mm Hg, further increased to 240 ° C for 1 hour, further reduced to 200 mm Hg for 20 minutes, gradually reduced to 150 mm Hg for 20 minutes, and further reduced to 100 mm Hg.
After reacting for 0.5 hour by reducing the pressure to 15 mm Hg for 20 minutes, 270
C., and finally reduced to 0.5 mm Hg, and reacted for 2.0 hours.

As described above, [η] 0.53, YI 2.20, MI
16 copolyestercarbonates were obtained.

 Table 1 shows the results.

Example 3 A copolyester carbonate was obtained in the same manner as in Example 1, except that 11.9 g (0.04 mol) of diphenyl adipate was used in place of diphenyl dodecane diacid.

 Table 1 shows the results.

Example 4 A copolyester carbonate was obtained in the same manner as in Example 1, except that 6.8 g (0.02 mol) of diphenyl azelate was used in place of diphenyl dodecane diacid.

 Table 1 shows the results.

Example 5 Example 2 was repeated, except that 5.8 g (0.04 mol) of adipic acid (manufactured by Wako Pure Chemical Industries, Ltd., a special grade of reagent was used and recrystallized) was used in place of dodecanedioic acid. A copolyester carbonate was obtained in the same manner as described above.

 Table 1 shows the results.

Comparative Example 1 In Example 2, the amount of sodium hydroxide used was reduced to 0.00.
8 mg (from 0.1 × 10 ^-4 mol / bisphenol A 1 mol to 2.0 mg
(2.5 × 10 ⁻⁴ mol / bisphenol A 1 mol), except that copolyester carbonate was obtained in the same manner as in Example 2.

 Table 1 shows the results.

Comparative Example 2 Hue (YI) and melt index of a homopolycarbonate ([η] 0.54, manufactured by GE Plastics Corporation) were determined.

 Table 1 shows the results.

Continuation of the front page (56) References JP-A-60-186529 (JP, A) JP-A-2-124934 (JP, A) JP-A-3-203928 (JP, A) JP-A-2-169625 (JP) , A) JP-B-47-14743 (JP, B1) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 63/00-63/91

Claims (9)

(57) [Claims] 1. A catalyst comprising (a) an alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of an aromatic organic dihydroxy compound, or (a) an aromatic compound 10 moles per mole of the organic dihydroxy group compound
^In the presence of a catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol, and (b) a nitrogen-containing basic compound and / or (c) boric acid or a borate ester, A process for producing a copolyestercarbonate, comprising melt-polycondensing an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a carbonic acid diester, and an aromatic organic dihydroxy group compound. 2. An alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mole per 1 mole of an aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound. Or (a) 10 moles per mole of an aromatic organic dihydroxy compound.
^A catalyst comprising any one of ^-8 to 10 ^-5 moles of an alkali metal compound or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a borate ester. 2. The method for producing a copolyester carbonate according to claim 1. 3. The copolyester according to claim 1, wherein the use ratio of the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester to the aromatic organic dihydroxy compound is 1 to 50 mol%. Method for producing carbonate. 4. A catalyst comprising (a) an alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mol per 1 mol of an aromatic organic dihydroxy compound, or (a) an aromatic compound. 10 moles per mole of the organic dihydroxy group compound
^In the presence of a catalyst comprising an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol, and (b) a nitrogen-containing basic compound and / or (c) boric acid or a borate ester, An aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound into a carbonic diester having 17 to 50 carbon atoms or a carbon diester having 10 to 10 carbon atoms.
40 to 40 phenols are the aromatic organic dihydroxy compound 1
A process for producing a copolyestercarbonate, comprising melt-polycondensing in a reaction system coexisting in an amount within a range of 0.05 to 15 mol% based on mol. 5. An alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mol per mol of (a) an aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound. Or (a) 10 moles per mole of an aromatic organic dihydroxy compound.
^-8 to 10 ^-5 moles of an alkali metal compound or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c)
The method for producing a copolyestercarbonate according to claim 4, wherein one of a catalyst comprising boric acid and a borate ester is used. 6. The copolyester according to claim 4, wherein the use ratio of the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester to the aromatic organic dihydroxy compound is 1 to 50 mol%. Method for producing carbonate. 7. A catalyst comprising (a) an alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mole per mole of an aromatic organic dihydroxy compound, or (a) an aromatic compound. 10 moles per mole of the organic dihydroxy group compound
^In the presence of a catalyst consisting of an alkali metal compound or an alkaline earth metal compound in an amount of from ^-8 to 10 ^-5 mol and (b) a nitrogen-containing basic compound and / or (c) boric acid or borate ester, An aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid ester, a diphenyl carbonate, and an aromatic organic dihydroxy compound into a carbonic diester having 13 to 16 carbon atoms or a carbonic diester having 10 to 16 carbon atoms.
To 25 phenols are the aromatic organic dihydroxy compound 1
A process for producing a copolyestercarbonate, comprising melt-polycondensing in a reaction system coexisting in an amount within a range of 0.05 to 15 mol% based on mol. 8. An alkali metal compound or an alkaline earth metal compound in an amount of 10 ^-8 to 10 ^-5 mole per 1 mole of an aromatic organic dihydroxy compound, and (b) a nitrogen-containing basic compound. Or (a) 10 moles per mole of an aromatic organic dihydroxy compound.
^-8 to 10 ^-5 moles of an alkali metal compound or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c)
The method for producing a copolyestercarbonate according to claim 7, wherein one of a catalyst comprising boric acid and a borate ester is used. 9. The copolyester according to claim 7, wherein the ratio of the aliphatic dicarboxylic acid and / or the aliphatic dicarboxylic acid ester to the aromatic organic dihydroxy compound is 1 to 50 mol%. Method for producing carbonate.