JP2996880B2 - Polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate having excellent color tone, heat resistance and water resistance.

[0002]

BACKGROUND OF THE INVENTION Polycarbonate is widely used because it has excellent mechanical properties such as impact resistance, and also has excellent heat resistance and transparency. As a method for producing such a polycarbonate, an aromatic organic dihydroxy compound such as bisphenol is directly reacted with phosgene (interfacial method), or an aromatic organic dihydroxy compound such as bisphenol and a carbonate such as diphenyl carbonate are used. A method of performing a transesterification reaction (polycondensation reaction) with a diester in a molten state is known.

When a polycarbonate is produced by a transesterification reaction between an aromatic organic dihydric compound and a carbonic acid diester, the aromatic organic dihydric compound and the carbonic acid diester are converted into a metal organic acid salt or an inorganic acid salt. Since the transesterification reaction is carried out in a molten state while heating under reduced pressure at a temperature of usually 250 to 330 ° C. using a catalyst such as an oxide, a hydroxide, a hydride or an alcoholate, it is compared with the above-mentioned interface method. Thus, polycarbonate can be produced at low cost. However, since the aromatic organic dihydroxy group compound and the carbonic acid diester are reacted in a molten state, there is a problem that the polycarbonate produced is inferior in color tone, heat resistance or water resistance.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the polycarbonate obtained by the melting method has a hydroxyl group terminal of 30 mol% or less of all the terminals of the polycarbonate. The present inventors have found that a polycarbonate having a sodium content of 1 ppm or less and a chlorine content of 20 ppm or less in a polycarbonate can provide a polycarbonate having excellent heat resistance and water resistance, and completed the present invention.

[0005]

An object of the present invention is to solve the problems associated with the prior art as described above, and to provide an excellent hue,
An object of the present invention is to provide a polycarbonate having heat resistance and water resistance.

[0006]

SUMMARY OF THE INVENTION The polycarbonate according to the present invention is a polycarbonate obtained by a melting method, wherein the hydroxyl terminal is 7 to 30 mol% of the total terminals of the polycarbonate, and the sodium content in the polycarbonate is 1 ppm or less. And a chlorine content of 20 ppm or less.

The polycarbonate according to the present invention has a sodium content of 0.5 ppm or less and a chlorine content of 10 ppm.
It is preferably less than pm. Further, the intrinsic viscosity [η] of the polycarbonate according to the present invention measured in methylene chloride at 20 ° C. is preferably 0.3 to 1.0 dl / g.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate according to the present invention will be specifically described below. The polycarbonate according to the present invention is a polycarbonate obtained by a melting method, and among all the terminals of the polycarbonate, a hydroxyl group terminal is 7 %.
３０30 mol% , the sodium content in the polycarbonate is 1 ppm or less, and the chlorine content is 20 ppm or less.

The polycarbonate according to the present invention as described above can be manufactured by selecting various conditions by a melting method. First, a method for producing a polycarbonate by such a melting method will be specifically described below.

The polycarbonate according to the present invention comprises, for example, an aromatic organic dihydroxy compound and a carbonic acid diester,
It is preferably produced by melt-polycondensation in the presence of a specific catalyst as described below in the presence of a specific molecular terminal agent.

In the first and second methods capable of producing the above-described polycarbonate, the aromatic polydihydroxy group compound and the carbonic acid diester are melt-polycondensed using a specific catalyst as described below. In the production of phenol, a phenol having 10 to 40 carbon atoms is present in the reaction system.

The aromatic organic dihydroxy compound used in the present invention is a compound represented by the following formula [I].

[0013]

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Specific examples of such an aromatic organic dihydroxy compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 2,2-bis (4-hydroxyphenyl) ethane.
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 Bis (hydroxyaryl) such as (4-hydroxy-t-butylphenyl) propane and 2,2-bis (4-hydroxy-3-bromophenyl) propane
Alkanes, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, Dihydroxyaryl ethers such as 4'-dihydroxy-3,3'-dimethylphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide 4,4'-dihydroxydiphenylsulfoxide, dihydroxydiarylsulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3, And dihydroxydiarylsulfones such as 3′-dimethyldiphenylsulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred. As the carbonic diester, specifically, diphenyl carbonate,
Ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like are used.

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.

When a dicarboxylic acid or a dicarboxylic acid ester as described above is used in combination with a carbonic acid diester,
A polyester polycarbonate is obtained, but in the present invention, the polyester polycarbonate may be produced as the polycarbonate.

In producing the polycarbonate in the present invention, the above-mentioned carbonic acid diester is used in an amount of 1.01 to 1.30 mol, preferably 1.02 to 1.20 mol per mol of the aromatic organic dihydroxy compound. Desirably, they are used in molar amounts.

In the present invention, when a polycarbonate is produced by melt polycondensation of an aromatic organic dihydroxy group compound and a carbonic acid diester as described above, the reaction system has 1 carbon atom.
0 to 40, preferably 15 to 40 phenols are present in an amount of 0.05 to 15 mol%, preferably 0.5 to 7 mol%, and more preferably 1 to 5 mol%, based on the aromatic organic dihydroxy compound. Let it.

As the phenols having 10 to 40 carbon atoms as described above, the following compounds are used. 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 o-phenylphenol m-phenylphenol p-phenylphenol on-nonylphenol mn-nonylphenol pn-nonylphenol o-cumylphenol m-cumylphenol p-cou Millphenol o-naphthylphenol m-naphthylphenol p-naphthylphenol 2,6-di-t-butylphenol 2,5-di-t-butylphenol 2,4-di-t- Chill phenol 3,5-di -t- phenol 2,5-dicumyl phenol 3,5-dicumyl phenol

[0021]

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Monohydric phenols such as Among such phenols, binuclear phenols having two aromatic nuclei are preferable, and p-cumylphenol and p-phenylphenol are particularly preferable.

The amount of the phenols is 0.05 mol% with respect to 1 mol of the aromatic organic dihydroxy compound.
When the content is within the range of 15 to 15 mol%, the hydroxyl terminal of the obtained polycarbonate is blocked, a polycarbonate having sufficiently excellent heat resistance and water resistance is obtained, and the polycondensation reaction rate is increased.

Such phenols may be added in advance to the reaction system in their 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 aromatic organic dihydroxy compound and the carbonic acid diester partially proceeds.

Next, third and fourth production methods capable of producing the polycarbonate according to the present invention will be described. In the third and fourth methods for producing a polycarbonate according to the present invention, when an aromatic organic dihydroxy compound and diphenyl carbonate are melt-polycondensed using a specific catalyst as described below, a polycarbonate is produced. And a carbonic acid diester having 17 to 50 carbon atoms is present in the reaction system.

As the aromatic organic dihydroxy compound, the same compound as the aromatic organic dihydroxy compound used in the first production method as described above is used. As diphenyl carbonates, aromatic carbonic diesters having 13 to 16 carbon atoms are usually used. Specifically, diphenyl carbonate, triphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl Carbonate or the like is used.

Of these, diphenyl carbonate is particularly preferred. Further, these diphenyl carbonates may contain a dicarboxylic acid or a dicarboxylic acid ester. Such a dicarboxylic acid or dicarboxylic acid ester is not particularly limited in carbon number,
Specific examples include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate.

When the above-mentioned dicarboxylic acid or dicarboxylic acid ester is used in combination with diphenyl carbonate, a polyester polycarbonate is obtained. In the present invention, the polyester polycarbonate may be produced as the polycarbonate.

In the third and fourth methods for producing polycarbonate, the above-mentioned diphenyl carbonates are
1.01 to 1 mole of aromatic organic dihydroxy compound
It is desirably used in an amount of .about.1.30 mol, preferably 1.02 to 1.20 mol.

In the third and fourth methods for producing polycarbonate, the carbonic acid diester having 17 to 50 carbon atoms is added in an amount of 0.05 to 15 mol% based on the aromatic organic dihydroxy compound.
Preferably it is present in an amount of 1 to 5 mol%.

As such a carbonic acid diester having 17 to 50 carbon atoms, a compound represented by the general formula:

[0032]

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Wherein 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 numbers of A and B is 49 or less. ) Is used.
As the above-mentioned carbonic acid diester, specifically, for example, the following compounds are used.

[0034]

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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 diphenyl carbonate, biphenyl phenyl carbonate, dibiphenyl carbonate, cumyl phenyl phenyl carbonate, dicumyl phenyl carbonate, naphthyl phenyl phenyl carbonate, dinaphthyl phenyl carbonate, carbopropoxy phenyl phenyl carbonate, carboheptoxy phenyl phenyl carbonate, carbomethoxy t- Butylphenylphenyl carbonate, carboxypropylphenylmethylphenylphenyl 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 terminal of the obtained polycarbonate is blocked. Therefore, a polycarbonate sufficiently excellent in heat resistance and water resistance can be obtained, and the polycondensation reaction rate increases.

Such a diester carbonate 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 aromatic organic dihydroxy compound and the carbonic acid diester partially proceeds.

Next, fifth and sixth production methods capable of producing the polycarbonate according to the present invention will be specifically described.
In the fifth and sixth methods for producing polycarbonate, when a polycarbonate is produced by melt polycondensation of an aromatic organic dihydroxy group compound and diphenyl carbonate using a specific catalyst as described later, carbon is added to the reaction system. There are 13 to 16 carbonic acid diesters present.

As the aromatic organic dihydroxy compound, the same compound as the aromatic organic dihydroxy compound used in the above-mentioned first method for producing polycarbonate is used.

The diphenyl carbonates include:
Compounds similar to the diphenyl carbonates used in the above third and fourth polycarbonate production methods are used.

In producing the polycarbonate in the present invention, the above diphenyl carbonate is used in an amount of 1.01 to 1.0 with respect to 1 mole of the aromatic organic dihydroxy compound.
It is preferably used in an amount of 30 mol, preferably 1.02 to 1.20 mol.

In such a method for producing a polycarbonate, the carbonic acid diester having 13 to 16 carbon atoms is, in addition to the carbonic acid diester shown below, the carbonic acid diester having 13 to 16 carbon atoms.
Sixteen diphenyl carbonates 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 carbonic acid diester is present in an amount of 0.05 to 1 based on 1 mole of the aromatic organic dihydroxy compound.
When the content is within the range of 5 mol%, the hydroxyl terminal of the obtained polycarbonate is sealed, so that a polycarbonate having sufficiently excellent heat resistance and water resistance can be obtained.

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 aromatic organic dihydroxy compound and the carbonic acid diester partially proceeds.

In the method for producing a polycarbonate as described above, the total chlorine content contained in the above-mentioned starting materials is preferably 20 ppm or less, more preferably 10 ppm or less.

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. It means the amount, and can be measured by analysis such as ion chromatography.

It is preferable that the total chlorine content in the starting materials is 20 ppm or less, since a polycarbonate having a good hue can be obtained. In order to reduce the total chlorine content in the starting materials as described above to 20 ppm or less, these raw materials should have a pH of 6.0 to 9.0, preferably a pH of 7.0 to 8.0.
5 More preferably, the pH may be 7.0 to 8.0, and the temperature may be 78 to 105 ° C, preferably 80 to 100 ° C, more preferably 80 to 90 ° C for washing with warm water.

Examples of the weakly basic solution used for washing the above-mentioned carbonate diester include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium hydroxide, sodium hydrogen carbonate, and the like. Aqueous solutions such as potassium hydrogen carbonate and tetramethylammonium hydroxide are used. Among them, aqueous solutions such as sodium hydrogen carbonate, sodium carbonate, potassium hydrogen carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate are particularly preferable.

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 material is preferably not more than 1.0 ppm, more preferably not more than 0.5 ppm. When the sodium content is equal to or less than the above amount, a polycarbonate having no further coloring can be obtained.

The content of sodium ions contained in the starting material is 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 as described above to the above-mentioned value or less, a purification method such as distillation, recrystallization, and an adduct method with phenol may be employed.

In the above first, third and fifth methods for producing polycarbonate, the method for producing a polycarbonate by melt polycondensing an aromatic organic dihydroxy compound and a carbonic acid diester, In producing a polycarbonate by melt polycondensation of a dihydroxy group compound and diphenyl carbonate, a catalyst comprising (a) a nitrogen-containing basic compound and (b) an alkali metal compound or an alkaline earth metal compound is used. The (a) nitrogen-containing basic compounds include tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH),
Trimethylbenzyl ammonium hydroxide (φ-C
Ammonium hydroxides having an alkyl, aryl, araryl group or the like such as H ₂ (Me) ₃ NOH);
Tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine;
_A secondary amine represented by 2NH (wherein R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toluyl); and RNH ₂ (where R is the same as described above). Primary amines, ammonia, tetramethylammonium borohydride (Me ₄ NBH
₄ ), tetrabutylammonium borohydride (B
Basic salts such as u ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh ₄ ), and tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄ ) are used.

Of these, tetraalkylammonium hydroxides are particularly preferred. (b) As the alkali metal compound, specifically, 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, benzoate Potassium acid, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, phenol sodium salt, potassium salt, lithium salt Are used.

As the alkaline earth metal compound (b), specifically, calcium hydroxide, barium hydroxide,
Magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate , Barium stearate, magnesium stearate, strontium stearate and the like are used.

The (a) nitrogen-containing basic compound as described above is
10 ^-6 to 1 mol of the aromatic organic dihydroxy group compound
In an amount of 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol, and (b) the alkali metal compound or alkaline earth metal compound is 10 ^-8 to 10 ^-3 mol, preferably 10 ^-7 to 10 ^-4. It is particularly preferably used in a molar amount of 10 ^-7 to 10 ^-5 mol.

(A) When the amount of the nitrogen-containing basic compound is 10 ^-6 to 10 ^-1 mol per mol of the aromatic organic dihydroxy compound, the transesterification reaction and the polymerization reaction proceed at a sufficient rate. Further, a polycarbonate excellent in hue, heat resistance, water resistance and the like can be obtained, which is preferable.

(B) when the amount of the alkali metal compound or the alkaline earth metal compound is one of the aromatic organic dihydroxy compound 1
When the amount is 10 ^-8 to 10 ^-3 mol, the polymerization activity can be increased, and a polycarbonate excellent in hue, heat resistance and water resistance can be obtained.

Thus, (a) the nitrogen-containing basic compound and (b)
A catalyst comprising an alkali metal compound or an alkaline earth metal compound has a high polymerization activity and can produce a high-molecular-weight polycarbonate, and the obtained polycarbonate has excellent heat resistance and water resistance, and further has a color tone. Are improved and excellent in transparency.

In the second, fourth, and sixth methods for producing polycarbonate, the method for producing a polycarbonate by melt polycondensation of an aromatic organic dihydroxy compound and a carbonic acid diester, or the method of producing an aromatic organic dihydroxy compound, When producing polycarbonate by melt polycondensation of diphenyl carbonate and (a) a nitrogen-containing basic compound,
A catalyst comprising (b) an alkali metal compound or an alkaline earth metal compound and (c) boric acid or a borate ester is used.

As (a) the nitrogen-containing basic compound and (b) the alkali metal compound or the alkaline earth metal compound, the compounds described above are used. (c) As boric acid or borate ester, boric acid or a general formula B (OR) _n (OH) _3-n (where R is an alkyl such as methyl and ethyl, an aryl such as phenyl, 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. Is used.

The (a) nitrogen-containing basic compound as described above is
10 ^-6 to 1 mol of the aromatic organic dihydroxy group compound
(B) in an amount of 10 ^-1 mol, preferably 10 ^-5 to 10 ^-2 mol
The alkali metal compound or alkaline earth metal compound is
10 ^-8 to 10 ^-3 mol, preferably 10 ^-7 to 10 ^-4 mol, particularly preferably 10 ^-7 to 10 ^-5 mol, and (c)
The boric acid or borate ester is used in an amount of 10 ^-8 to 10 ^-1 mol, preferably 10 ^-7 to 10 ^-2 mol, particularly preferably 10 ^-10
It is used in an amount of ^-6 to 10 ^-4 mol.

(A) When the amount of the nitrogen-containing basic compound is 10 ^-6 to 10 ^-1 mol per 1 mol of the aromatic organic dihydroxy compound, the transesterification reaction and the polymerization reaction proceed at a sufficient rate. Further, a polycarbonate excellent in hue, heat resistance, water resistance and the like can be obtained, which is preferable.

(B) When the amount of the alkali metal compound or the alkaline earth metal compound is 10 ^-8 to 10 ^-3 mol per 1 mol of the aromatic organic dihydroxy compound, the polymerization activity can be increased. Further, a polycarbonate excellent in hue, heat resistance and water resistance can be obtained, which is preferable.

Also, (c) the amount of boric acid or borate ester is from 10 ^-8 to 1 mol per mole of the aromatic organic dihydroxy compound.
When the amount is 10 ^-1 mol, a decrease in molecular weight after thermal aging hardly occurs, and a polycarbonate excellent in hue, heat resistance and water resistance is obtained, which is preferable.

Thus, (a) the nitrogen-containing basic compound and (b)
An alkali metal compound or an alkaline earth metal compound;
(c) The catalyst comprising boric acid or borate ester has a higher polymerization activity and can produce a high-molecular-weight polycarbonate, and the obtained polycarbonate is more excellent in heat resistance and water resistance. The upper color tone is further improved and the transparency is excellent.

In the present invention, the polycondensation reaction between an aromatic organic dihydroxy compound and a carbonic acid diester or the polycondensation reaction between an aromatic organic dihydroxy compound and diphenyl carbonate is carried out in a conventionally known method for producing polycarbonate. The reaction can be carried out under the same conditions as the polycondensation reaction. Specifically, the first-stage reaction is carried out at 80 to 250 ° C, preferably 100 to 230 ° C, more preferably 120 to 1 ° C.
The reaction is carried out at a temperature of 90 ° C. for 0 to 5 hours, preferably 0 to 4 hours, more preferably 0.25 to 3 hours, at normal pressure. Then, the reaction temperature is increased while reducing the pressure of the reaction system, and the reaction is further carried out.
A polycondensation reaction between an aromatic organic dihydroxy compound and a carbonic acid diester is performed at a temperature of ° C.

The above-mentioned polycondensation reaction may be carried out continuously or batchwise. 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, the reaction system has 10 carbon atoms.
When a polycarbonate is produced by melt-polycondensing an aromatic organic dihydroxy group compound and a carbonic acid diester in the presence of phenols of from 40 to 40, the hydroxyl group terminal is 30 mol% or less, preferably 20 mol%, of all the terminals of the obtained polycarbonate.
Mol% or less, more preferably 10 to 20 mol%,
Moreover, a polycarbonate having an intrinsic viscosity [η] of 0.3 to 1.0 dl / g measured in methylene chloride at 20 ° C. is obtained. Furthermore, the polycarbonate obtained by the present invention has an excellent color tone, and also has excellent tensile strength and elongation after a boiling water test.

When a polycarbonate is produced by melt polycondensation of an aromatic organic dihydroxy compound and diphenyl carbonate in the presence of a carbonic acid diester having 17 to 50 carbon atoms in the reaction system, The hydroxyl group terminal is 30 mol% or less, preferably 20 mol% or less, more preferably 10 to 20 mol%, and the intrinsic viscosity [η] measured in methylene chloride at 20 ° C. is 0.3 to 1.0 dl / g. A polycarbonate is obtained. Further polycarbonate obtained by the present invention,
It has an excellent color tone, and also has excellent tensile strength and elongation after the boiling water test.

When a polycarbonate is produced by melt polycondensation of an aromatic organic dihydroxy compound with diphenyl carbonate in the presence of a carbonic acid diester having 13 to 16 carbon atoms in the reaction system, The hydroxyl group terminal is 30 mol% or less, preferably 20 mol% or less, more preferably 10 to 20 mol%, and the intrinsic viscosity [η] measured in methylene chloride at 20 ° C. is 0.3 to 1.0 dl / g. A polycarbonate is obtained. Further polycarbonate obtained by the present invention,
It has an excellent color tone, and also has excellent tensile strength and elongation after the boiling water test.

The polycarbonate according to the present invention is a polycarbonate produced by the above-mentioned melting method. As described above, the hydroxyl group terminal accounts for 7 to 30 mol% of all the polycarbonate terminals. The sodium content is 1 ppm or less and the chlorine content is 20 ppm or less.

A polycarbonate having a hydroxyl group terminal within the above range among all polycarbonate terminals is particularly excellent in color tone, heat resistance and water resistance. The polycarbonate according to the present invention has a sodium content of 1.0 ppm or less, preferably 0.5 ppm or less, and a chlorine content of 20 ppm or less, preferably 10 ppm or less.

[0073] Polycarbonate according to the present invention is hydroxyl-terminated of its total end is 7 to 30 mol%, preferably 7-25 mol%, particularly preferably 10 to 20 mol%. As described above, the sodium content is 1.0 ppm or less, preferably 0.5 ppm or less, and the chlorine content is 2 ppm or less.
Polycarbonate having 0 ppm or less, preferably 10 ppm or less, has a hydroxyl group terminal of 7 to 30 mol%, preferably 7 to 25 mol%, more preferably 10 to 2 mol% of all terminals.
Even if it is 0 mol%, it has excellent heat resistance and water resistance, and has little coloring.

This means that, even when the polycarbonate has a hydroxyl terminal which is an active site, when the sodium content or the chlorine content is small, the hydroxyl terminal is less likely to react, and therefore the polycarbonate is less likely to be colored. Means that. Moreover, among all the terminals of the polycarbonate, the polycarbonate having a hydroxyl group terminal in the above-mentioned range contains an appropriate amount of the hydroxyl terminal, and thus has an active site when producing a polymer alloy or the like.

The polycarbonate according to the present invention has an initial hue, water resistance and water resistance when the total content of alkali metals other than sodium, such as lithium, potassium and cesium, and alkaline earth metals such as beryllium, magnesium and calcium is also 1 ppm. It is preferable because it has excellent heat resistance.

Further, the polycarbonate according to the present invention comprises:
The intrinsic viscosity [η] measured in methylene chloride at 20 ° C. is preferably 0.3 to 1.0 dl / g.

[0077]

Industrial Applicability The polycarbonate according to the present invention is a polycarbonate obtained by a melting method, wherein a hydroxyl group terminal is capped at a specific amount among all terminals of the polycarbonate, and a sodium content and a chlorine content are not more than a specific amount. Color, heat resistance and water resistance (hydrolysis resistance)
Is excellent.

Further, the polycarbonate according to the present invention comprises:
It has excellent color tone and also excellent tensile strength after boiling water test.

[0079]

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

In the following examples, the physical properties of the polycarbonate were measured as follows. Intrinsic viscosity [η] (IV): Measured in methylene chloride at 20 ° C. using an Ubbelohde viscometer.

Hue (b value): La of a 2 mm thick pressed sheet
b value is Nippon Denshoku Industries Co., Ltd.
It was measured by transmission method using eter ND-1001 DP, and the b value was used as a measure of yellowness.

Thermal aging test (1): A pellet dried at 120 ° C. and 400 mmHg for 12 hours was placed in a Teflon Petri dish (40 mm).
4.5) weighed into a 250 ° C gear oven (GHPS-21)
2 1 during Tabai Manufacturing Co., air replacement rate 71.6 times / hour)
After holding for 6 hours, it was gradually cooled to room temperature. This sample is 2mm
The press sheet is made thick and the hue (b
Values) and IV were measured.

Heat aging test (2): Heat aging test for 1000 hours in a 140 ° C. gear oven (GHPS-212 Tabai Seisakusho, air exchange rate 71.6 times / hour) using a 3 mm-thick press sheet. Was performed. The hue of this sample was measured and the yellowness (YI) was calculated.

[0084]

(Equation 1)

Water resistance test (1): A dumbbell having a width of 5 mm and a length of 5 cm was punched out of a pressed sheet having a thickness of 0.5 mm, immersed in boiling water, taken out after 1 day, 3 days, and 7 days. Within 1 hour after removal, the distance between the chucks is 30 mm, the pulling speed is 50 mm / min, and the measuring range is 50 using Instron 1132.
A tensile test was performed in kg to measure the elongation (%).

Water resistance test (2): A press sheet having a thickness of 3 mm was immersed in water in an autoclave, and dried at 125 ° C. in an oven.
Hold for days. Nippon Denshoku Industries Co., Ltd.
Haze was measured with NDH-200.

Press sheet preparation conditions: 120 ° C., 400
The pellets dried at 12 mmHg for 12 hours were preheated at 280 ° C. for 10 minutes, pressed at 280 ° C. for 5 minutes at 100 kg / cm ³ , and cold pressed at room temperature for 5 minutes.

Terminal group structure: 0.4 g of a sample was dissolved in 3 ml of chloroform, and the terminal OH group and structure were measured at 40 ° C. using ¹³ C-NMR (GX-270, manufactured by JEOL Ltd.). . The terminal OH group concentration was calculated as a ratio (%) to the total terminal group concentration.

Terminal OH group concentration: 0.25 g of a sample was taken as 1
It was dissolved in 0 ml of methylene chloride, and the absorbance of OH groups at around 3580 cm ^-1 was measured using FT-IR (FT-IR4300, manufactured by Shimadzu Corporation) to calculate the terminal OH group concentration.

Sodium content in the polymer: 20 g of the polymer was incinerated, and an atomic absorption spectrometer (Hitachi, Ltd .: Hitachi, Ltd.)
180-80) to the limit of 0.05 ppm.

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

[0092]

Example 1 In a 500 ml glass reactor, diphenyl carbonate (diphenyl carbonate manufactured by Any Co., Ltd. was washed twice with hot water of 80 ° C. and pH 7 and distilled at a yield of 90%;
Content 0.05ppm or less, Cl content 15.0ppm) 141.24g
(0.660 mol) and bisphenol A (manufactured by Nippon GE Plastics; Na content 0.10 ppm, Cl content 0.8 ppm) 13
6.8 g (0.600 mol)

[0093]

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(0.03 mol; 5 mol% / bisphenol A) and 3.0 mg of an aqueous solution of 3% boric acid H ₃ BO ₃ (H ₃ BO)
₃ 0.025 × 10 ^-4 mol / bisphenol A1 mol) and N ₂
The mixture was placed under an atmosphere, heated at 180 ° C., and stirred with a Ni stirring bar for 30 minutes. Subsequently, 91.2 mg (Me ₄ NOH 2.5 × 10 ⁻⁴ mol / bisphenol A 1 mol) of a 15% aqueous solution of tetramethylammonium hydroxide Me ₄ NOH (manufactured by Toyo Gosei Co., Ltd.) and 0.1% sodium hydroxide NaOH were used.
12.0 mg (NaOH 0.005 × 10 ⁻⁴ mol / bisphenol A1 mol) was added, and the mixture was further stirred at 180 ° C. under a N ₂ atmosphere for 30 minutes to carry out a transesterification reaction.

Thereafter, the temperature was raised to 210 ° C. and gradually increased to 200 ° C.
The pressure was reduced to mmHg, and the temperature was further increased to 240 ° C for 1 hour.
20 mm at 0 mmHg, gradually reduce the pressure to 150 mmHg for 20 minutes,
After further reducing the pressure to 100 mmHg for 20 minutes and reducing the pressure to 15 mmHg for 0.5 hours, the temperature was raised to 270 ° C., and finally the pressure was reduced to 0.5 mmHg for a reaction for 2.0 hours.

As described above, IV 0.50 d
1 / g of polycarbonate was obtained. The terminal OH group concentration of this polycarbonate was 14%. Table 1 shows the results
Shown in

[0097]

Example 2 136.1 diphenyl carbonate (used in Example 1) in a 500 ml glass reactor
g (0.636 mol), 136.8 g (0.600 mol) of bisphenol A (used in Example 1), and p-cumylphenylphenyl carbonate

[0098]

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9.960 g (0.03 mol; 5 mol% / bisphenol A) and 3.0 mg of a 3% aqueous solution of H ₃ BO ₃ boric acid (H
₃ BO ₃ 0.025 × 10 ^-4 mol / bisphenol A 1 mol) under N ₂ atmosphere, heat at 180 ° C., and
i The mixture was stirred with a stirring rod. Next, 91.2 mg (Me ₄ NOH 2.5 × 10 ⁻⁴ mol / bisphenol A 1 mol) of a 15% aqueous solution of tetramethylammonium hydroxide Me ₄ NOH (manufactured by Toyo Gosei Co., Ltd.) and sodium hydroxide NaOH
12.0 mg of a 0.1% aqueous solution (NaOH 0.005 × 10 ⁻⁴ mol / bisphenol A 1 mol) was added, and the mixture was further added at 180 ° C. and N _2.
The mixture was stirred for 30 minutes in an atmosphere to perform a transesterification reaction.

Thereafter, the temperature was raised to 210 ° C. and gradually increased to 200 ° C.
The pressure was reduced to mmHg, and the temperature was further increased to 240 ° C for 1 hour.
20 mm at 0 mmHg, gradually reduce the pressure to 150 mmHg for 20 minutes,
After further reducing the pressure to 100 mmHg for 20 minutes and reducing the pressure to 15 mmHg for 0.5 hours, the temperature was raised to 270 ° C., and finally the pressure was reduced to 0.5 mmHg for a reaction for 2.0 hours.

As described above, IV 0.50 d
1 / g of polycarbonate was obtained. The terminal OH group concentration of this polycarbonate was 14%. Table 1 shows the results
Shown in

[0102]

Example 3 A polycarbonate was obtained in the same manner as in Example 2, except that diphenyl carbonate was further used in the amount shown in Table 1 in place of using p-cumylphenylphenyl carbonate. The IV of the obtained polycarbonate was 0.52 dl / g, and the terminal OH group concentration was 14%. Table 1 shows the results.

[0103]

Example 4 In Example 1, 270 ° C., 0.5 mmHg
Polycarbonate was obtained in the same manner as in Example 1 except that the reaction was carried out under reduced pressure for 2.2 hours. The IV of the obtained polycarbonate was 0.52 dl / g, and the terminal OH group concentration was 7%. Table 1 shows the results.

[0104]

Example 5 In Example 3, 270 ° C., 0.5 mmHg
Polycarbonate was obtained in the same manner as in Example 3, except that the reaction was carried out for 2.2 hours under reduced pressure. The IV of the obtained polycarbonate was 0.52 dl / g, and the terminal OH group concentration was 7%. Table 1 shows the results.

[0105]

[Reference Example A] In Example 1, 270 ° C, 0.5 mmHg
Polycarbonate was obtained in the same manner as in Example 1 except that the reaction was performed under reduced pressure for 2.5 hours. The IV of the obtained polycarbonate was 0.53 dl / g, and the terminal OH group concentration was 2%. Table 1 shows the results.

[0106]

Reference Example B In Example 3, 270 ° C., 0.5 mmHg
Polycarbonate was obtained in the same manner as in Example 3 except that the reaction was carried out under reduced pressure for 2.5 hours. The IV of the obtained polycarbonate was 0.56 dl / g, and the terminal OH group concentration was 2%. Table 1 shows the results.

[0107]

Example 6 The procedure of Example 3 was repeated, except that the amount of NaOH to be added was changed to the amount shown in Table 1 and the reaction was carried out at 270 ° C. under a reduced pressure of 0.5 mmHg for 2.2 hours. Thus, polycarbonate was obtained. Table 1 shows the results.

[0108]

Example 7 The procedure of Example 3 was repeated except that the amount of NaOH to be added was changed to the amount shown in Table 1 and the reaction was carried out at 270 ° C. and a reduced pressure of 0.5 mmHg for 1.8 hours. Thus, polycarbonate was obtained. Table 1 shows the results.

[0109]

Examples 8 to 11 Polycarbonates were obtained in the same manner as in Example 3, except that the catalysts shown in Table 1 were used instead of NaOH in the amounts shown in Table 1. Table 1 shows the results.

[0110]

Comparative Example 1 A polycarbonate was obtained in the same manner as in Example 3 except that the catalyst used was changed as shown in Table 1 and the reaction was carried out at 270 ° C. and a reduced pressure of 0.5 mmHg for 1 hour. Was. Table 1 shows the results.

[0111]

Comparative Examples 2 to 3 A polycarbonate was obtained in the same manner as in Example 3 except that the amount of diphenyl carbonate used was changed as shown in Table 1. Table 1 shows the results.

[0112]

Comparative Example 4 Polycarbonate (IV 0.50 dl / g, terminal OH concentration 0%, Na
Table 1 shows the physical properties of the composition (content <0.05 ppm, Cl content 30 ppm).

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

[Table 3]

[0116]

[Table 4]

[0117]

[Table 5]

[0118]

[Table 6]

[0119]

Examples 12 to 14 Polycarbonates were obtained in the same manner as in Example 3, except that the catalysts shown in Table 2 were used instead of NaOH in the amounts shown in Table 2.

Table 2 shows the results.

[0121]

[Table 7]

[0122]

[Reference Example 1] Dipheni in a 100 ml glass reactor
Leucarbonate (diphenyl carbonate manufactured by Bayer)
Was washed twice with hot water at 80 ° C. and pH 7.0 and distilled at a yield of 90%;
Na content 0.05 ppm or less, Cl content 240 ppm) 47.08 g (0.2
20mol) and bisphenol A (Nippon GE Plastics)
Na content 0.05 ppm or less, Cl content 16.4 ppm) 4
5.600 g (0.200 mol) and p-cumylphenol 2.1
2 g (0.01 mol; 5 mol% / bisphenol A)
Acid H_ThreeBO_Three(Wako reagent special grade) 3.72 mg (3 × 10 ^-Four mol
/ Bisphenol A) and N_TwoPut in the atmosphere,
The mixture was heated at 180 ° C. and stirred with a Ni stirring bar for 30 minutes. Next
Ide, tetramethylammonium hydroxide M
e_FourNOH 15% aqueous solution (Toyo Gosei Co., Ltd.) 36.48 mg
(Me_FourNOH 3 × 10^-Fourmol / bisphenol A 1mol)
And sodium bicarbonate NaHCO_Three(Wako reagent special grade)
0.50 mg (0.3 x 10^-Four mol / bisphenol A 1mol
 ) At 180 ° C. and N_Two30 minutes under atmosphere
The mixture was stirred to perform a transesterification reaction.

Thereafter, the temperature was raised to 210 ° C. and gradually increased to 200 ° C.
The pressure was reduced to mmHg, and the temperature was further increased to 240 ° C for 1 hour.
20 mm at 0 mmHg, gradually reduce the pressure to 150 mmHg for 20 minutes,
After further reducing the pressure to 100 mmHg for 20 minutes and reducing the pressure to 15 mmHg for 0.5 hours, the temperature was raised to 270 ° C., and finally the pressure was reduced to 0.5 mmHg for a reaction for 2.0 hours.

As described above, IV 0.50 d
1 / g of polycarbonate was obtained. The terminal OH group concentration of this polycarbonate was 0%. Table 3 shows the results.

[0125]

Comparative Example 5 In Reference Example 1, Table 1 was used as a terminal blocking agent.
Polycarbonate was obtained in the same manner as in Reference Example 1, except that the phenols described in Table 1 were used in the amounts shown in Table 1.
Table 3 shows the results.

[0126]

Reference Examples 2 to 4 Polycarbonates were obtained in the same manner as in Reference Example 1, except that the phenols described in Table 3 were used in the amounts shown in Table 3 as terminal blocking agents. Table 3 shows the results.

[0127]

[Table 8]

[0128]

[Table 9]

[0129]

Reference Example 5 In a 100 ml glass reactor, diphenyl carbonate (used in Reference Example 1) 45.3 was used.
68 g (0.212 mol), 45.600 g (0.200 mol) of bisphenol A (used in Reference Example 1), and 2-carbomethoxy-5-t-butyl-phenylphenyl carbonate

[0130]

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3.280 g (0.01 mol; 5 mol% / bisphenol A) and boric acid H ₃ BO ₃ (special grade of Wako reagent)
72 mg (3 × 10 ⁻⁴ mol / bisphenol A 1 mol) were added under N ₂ atmosphere, heated at 180 ° C., and N
i The mixture was stirred with a stirring rod. Then, 36.48 mg (Me ₄ NOH 3 × 10 ^-4 mol / bisphenol A 1 mol) of a 15% aqueous solution of tetramethylammonium hydroxide Me ₄ NOH (manufactured by Toyo Gosei Co., Ltd.) and sodium hydrogen carbonate NaH
0.50 mg of CO ₃ (special grade of Wako reagent) (0.3 × 10 ^-4 mol /
1 mol of bisphenol A) and add another 180
The mixture was stirred at 30 ° C. for 30 minutes in a N ₂ atmosphere to carry out a transesterification reaction.

Thereafter, the temperature was raised to 210 ° C. and gradually increased to 200 ° C.
The pressure was reduced to mmHg, and the temperature was further increased to 240 ° C for 1 hour.
20 mm at 0 mmHg, gradually reduce the pressure to 150 mmHg for 20 minutes,
After further reducing the pressure to 100 mmHg for 20 minutes and reducing the pressure to 15 mmHg for 0.5 hours, the temperature was raised to 270 ° C., and finally the pressure was reduced to 0.5 mmHg for a reaction for 2.0 hours.

As described above, IV 0.51d
1 / g of polycarbonate was obtained. The terminal OH group concentration of this polycarbonate was 1%. Table 4 shows the results.

[0134]

Reference Examples 6 to 8 Polycarbonates were obtained in the same manner as in Reference Example 5, except that the diester carbonate shown in Table 4 was used in the amount shown in Table 4 as a terminal blocking agent. Table 4 shows the results.

[0135]

Comparative Example 6 In Reference Example 5, Table 4 was used as a terminal blocking agent.
Polycarbonate was obtained in the same manner as in Reference Example 5, except that the carbonate diester described in Table 4 was used in the amount shown in Table 4. Table 4 shows the results.

[0136]

Reference Example 9 In Reference Example 5, 2-carbomethoxy-5-
A polycarbonate was obtained in the same manner as in Reference Example 5, except that diphenyl carbonate was further used in an amount of 0.01 mol (5 mol% / bisphenol A) instead of using butylphenyl carbonate. Table 4 shows the results.

[0137]

[Table 10]

[0138]

[Table 11]

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-63-205318 (JP, A) JP-A-63-15842 (JP, A) JP-A-64-38433 (JP, A) JP-A-1- 158033 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (3)

(57) [Claims] 1. A polycarbonate obtained by a melting method, wherein a hydroxyl group terminal is 7 % of all polycarbonate terminals.
A polycarbonate having a sodium content of 1 ppm or less and a chlorine content of 20 ppm or less in the polycarbonate. 2. The polycarbonate according to claim 1, wherein the polycarbonate has a sodium content of 0.5 ppm or less and a chlorine content of 10 ppm or less. 3. The polycarbonate according to claim 1, wherein the intrinsic viscosity [η] of the polycarbonate measured in methylene chloride at 20 ° C. is 0.3 to 1.0 dl / g.