JPH06136109A - Production of copolycarbonate - Google Patents

Abstract

PURPOSE:To obtain a copolycarbonate excellent in strengths, heat resistance, etc., by subjecting an arom. dihydroxy compd. contg. a previously purified specific compd. to polycondensation with a carbonic-ester-forming compd. in the absence of oxygen. CONSTITUTION:An arom. dihydroxy compd. of the formula (wherein R is an optionally halogenated 1-10C hydrocarbon group or halogen; n is 0-4) (e.g. resorcin) is purified e.g. by distillation. The purified dihydroxy compd. is fed into an agitator or a reactor contg. no oxygen, wherein the compd. and another arom. dihydroxy compd. [e.g. bis(4-hydroxyphenyl)methane] are subjected to polycondensation with a compd. which reacts with the above two dihydroxy compds. to form carbonic ester bonds (e.g. diphenyl carbonate), giving a copolycarbonate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is to produce a copolycarbonate which is excellent not only in mechanical properties and heat resistance but also in moldability such as chemical resistance and fluidity, and also in hue and transparency. And a method for producing a copolycarbonate capable of

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polycarbonate molded products have excellent mechanical properties such as impact resistance, heat resistance and transparency, and are widely used as various mechanical parts, optical discs, automobile parts, etc. Is used for.

Polycarbonates having such characteristics are usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene. Also known is a method for producing a polycarbonate by melt polycondensation of a carbonic acid diester and the above aromatic dihydroxy compound.

The conventional polycarbonate having a bisphenol A skeleton has a problem that it is inferior in chemical resistance, has a high melt viscosity at the time of molding, and is inferior in fluidity. Generally, a polymer tends to be affected by its molded article such that transparency or hue decreases as the melting time at a high temperature increases.

Therefore, it is desired to develop a polycarbonate having further improved chemical resistance and fluidity during molding. To meet such demands, a copolycarbonate having a skeleton derived from hydroquinone, resorcin, etc. has been proposed. For example, Japanese Unexamined Patent Publication (Kokai) No. 52-109591 proposes a method for producing a copolycarbonate using hydroquinone and / or its ester-forming derivative as a part of an aromatic dihydroxy compound, and a copolymer having excellent solvent resistance is proposed. A polymerized polycarbonate is obtained.

However, when it is attempted to obtain the above copolycarbonate by the general melt polycondensation method (ester exchange method) described in this publication,
Hydroquinone was easily oxidized during polycondensation and was colored brown or yellow, and the resulting copolymerized polycarbonate was sometimes colored.

On the other hand, when bisphenol A and hydroquinone are copolymerized by an interfacial polymerization method in which an aromatic dihydroxy compound and phosgene are directly reacted, a low molecular weight copolycarbonate is precipitated during the polymerization, resulting in a high molecular weight It is difficult to obtain polycarbonate. Moreover, in the interfacial polymerization method, since phosgene is used, the aromatic dihydroxy compound must be used as an aqueous alkaline solution in order to neutralize the generated hydrogen chloride, which easily causes the hydroquinones and resorcins to be colored. ,
It was difficult to obtain a copolycarbonate having a good hue.

Therefore, a copolycarbonate having excellent mechanical properties, heat resistance, and improved moldability such as chemical resistance and fluidity can be produced without coloring or impairing transparency during production. The advent of a method for producing a copolycarbonate capable of producing a copolycarbonate has been desired.

The present inventors have conducted extensive studies in view of the above-mentioned prior art, and as a result, (i) an aromatic dihydroxy compound (hydroquinone, resorcin) represented by the general formula [I], and (ii) In producing a copolycarbonate from an aromatic dihydroxy compound other than this,
(i) Copolymerization without coloring by purifying the aromatic dihydroxy compound represented by the general formula [I] and then supplying it to a stirrer or a reactor in the substantial absence of oxygen to carry out a polycondensation reaction. The present invention has been completed by finding that polycarbonate can be efficiently produced.

[0010]

The object of the present invention is not only excellent in mechanical properties and heat resistance, but also excellent in moldability such as chemical resistance and fluidity.
Moreover, it is an object of the present invention to provide a method for producing a copolycarbonate capable of producing a copolycarbonate having excellent transparency and hue.

[0011]

SUMMARY OF THE INVENTION A method for producing a copolycarbonate according to the present invention comprises (i) an aromatic dihydroxy compound represented by the following general formula [I]:

[0012]

[Chemical 2]

(In the formula [I], each R has 1 to 1 carbon atoms.
A hydrocarbon group of 0 or a halide thereof, or a halogen, which may be the same or different, and n is 0
Is an integer of ~ 4. ) (Ii) an aromatic dihydroxy compound other than (i), and (iii) an aromatic dihydroxy compound (i)
And (ii) upon copolymerization with a compound capable of forming a carbonic acid bond, (i) after purifying the aromatic dihydroxy compound represented by the general formula [I], in the substantial absence of oxygen. It is characterized in that it is supplied to a stirrer or a reactor to carry out a polycondensation reaction.

The method for producing such a copolycarbonate comprises (iii) the aromatic dihydroxy compounds (i) and (i)
As the compound capable of reacting with i) to form a carbonic acid bond, it is preferably carried out by a melt polycondensation method using a carbonic acid diester, and 1 × 10 ⁻⁸ to 1 × with respect to 1 mol of the total amount of the aromatic dihydroxy compound. Melt in the presence of a catalyst containing (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of 10 ⁻³ mol, preferably 1 × 10 ^{−7 to} 2.5 × 10 ⁻⁶ mol. It is preferable to carry out polycondensation.

Further, in the method for producing a copolycarbonate according to the present invention, it is preferable to add an acidic compound and, if necessary, an epoxy compound to the reaction product obtained by the melt polycondensation as described above. It is more preferable to apply a reduced pressure treatment.

Further, (i) the aromatic dihydroxy compound represented by the general formula [I] is preferably resorcin or hydroquinone. These are purified by a recrystallization method and / or a distillation method.

[0017]

DETAILED DESCRIPTION OF THE INVENTION The method for producing the copolycarbonate according to the present invention will be specifically described. In the method for producing a copolycarbonate according to the present invention, (i) an aromatic dihydroxy compound represented by the following general formula [I],

[0018]

[Chemical 3]

(In the formula [I], each R has 1 to 1 carbon atoms.
A hydrocarbon group of 0 or a halide thereof, or a halogen, which may be the same or different, and n is 0
Is an integer of ~ 4. ) (Ii) an aromatic dihydroxy compound other than (i), and (iii) an aromatic dihydroxy compound (i)
And (ii) reacting with a compound capable of forming a carbonic acid bond to produce a copolycarbonate, (i) after purifying the aromatic dihydroxy compound represented by the general formula [I]. , To a stirrer or reactor in the substantial absence of oxygen.

First, these compounds (i) used in the present invention
, (Ii) and (iii) will be described. As the aromatic dihydroxy compound represented by the above general formula [I],
Specifically, resorcin, 3-methylresorcin, 3-ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-
Substituted resorcins such as cumylresorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin, catechol, hydroquinone, 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone , 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,
Substituted hydroquinones such as 6-tetra-t-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone can be mentioned.

Of these, resorcin and hydroquinone are particularly preferable. In the present invention, in producing a copolycarbonate, the above formula (i) [I]
The aromatic dihydroxy compound represented by is purified and used as described below. The purified (i) aromatic dihydroxy compound is used in the aromatic dihydroxy compound in an amount of preferably 2 to 90 mol%, more preferably 2 to 40 mol%.

(Ii) The aromatic dihydroxy compound other than the above (i) is 100 mol% of the aromatic dihydroxy compound.
Is used, the amount is preferably 98 to 10 mol%, more preferably 98 to 60 mol%.

The other aromatic dihydroxy compound (ii) is not particularly limited and may be the following aromatic dihydroxy compound which is usually used in forming a polycarbonate.

[0024]

[Chemical 4]

Wherein R ¹ and R ² are hydrogen atoms or monovalent hydrocarbon groups, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are halogen or a monovalent hydrocarbon group, and these may be the same or different. p and q represent the integer of 0-4. ) Such aromatic dihydroxy compounds include, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 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, 2,2
-Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3-bromophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
-Dihydroxy aryl ethers such as dimethyl phenyl ether, 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide and other dihydroxydiaryl sulfoxides, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-
Examples thereof include dihydroxydiaryl sulfones such as dimethyldiphenyl sulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferable. Also used in the present invention (iii) aromatic dihydroxy compounds (i) and (i
Specific examples of the compound that reacts with i) to introduce a carbonic acid bond include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, and diethyl. Carbonate, dimethyl carbonate, dibutyl carbonate, carbonic acid diester such as dicyclohexyl carbonate, and carbonyl halide compounds such as phosgene.

Of these, diphenyl carbonate is particularly preferable. In the present invention, when producing a copolycarbonate, the above-mentioned carbonic acid diester is preferably 50 mol%, more preferably 30 mol% or less, when the carbonic acid diester is 100 mol%. , A dicarboxylic acid halide may be contained.

Examples of such dicarboxylic acid or dicarboxylic acid ester and dicarboxylic acid halide include terephthalic acid, isophthalic acid, sebacic acid, decanedioic acid,
Dodecanedioic acid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decanedioate, diphenyl dodecanedioate, terephthalic acid chloride, isophthalic acid chloride, sebacic acid chloride, decanedioic acid chloride, dodecanedioic acid chloride, etc. To be

When the polycarboxylic acid diester containing such a dicarboxylic acid or dicarboxylic acid ester and the aromatic dihydroxy compound are polycondensed, a polyester polycarbonate is obtained.

In the present invention, when producing a copolycarbonate, the compound (iii) capable of reacting with the aromatic dihydroxy compound to form a carbonic acid bond is (a) based on 1 mol of the total amount of the aromatic dihydroxy compound. 1.0-
It is desirable to use it in an amount of 1.30 mol, preferably 1.01 to 1.20 mol.

In the present invention, when producing a copolycarbonate, a polyfunctional compound having three or more functional groups in one molecule may be used together with the aromatic dihydroxy compound and the carbonic acid diester as described above.

As such a polyfunctional compound, a compound having a phenolic hydroxyl group or a carboxyl group is preferable, and a compound having three phenolic hydroxyl groups is particularly preferably used. Specifically, for example, 1,1,1-
Tris (4-hydroxyphenyl) ethane, 2,2 ', 2 "-Tris (4-hydroxyphenyl) diisopropylbenzene, α
-Methyl-α, α ', α'-tris (4-hydroxyphenyl) -1,
4-diethylbenzene, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) ) -Heptane-2,1,3,5-tri (4-hydroxyphenyl)
Benzene, 2,2-bis- [4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,
Examples include 3,5-benzenetricarboxylic acid and pyromellitic acid.

Of these, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are preferable. .

When a polyfunctional compound is used, it is usually 0.03 per 1 mol of the total amount of the aromatic dihydroxy compound.
It is used in an amount of not more than 0.001 mol, preferably 0.001 to 0.02 mol, and more preferably 0.001 to 0.01 mol.

In the present invention, the aromatic dihydroxy compounds (i) and (ii) supplied as described above are copolymerized with the compounds (iii) capable of forming a carbonic acid bond with these (i) and (ii). Then, a copolycarbonate is produced.

In the present invention, when producing a copolycarbonate, the above-mentioned (i) aromatic dihydroxy compound represented by the general formula [I] is purified and supplied to the polymerization system. The purification method is not particularly limited as long as it is a general method for purifying an aromatic dihydroxy compound. For example, as a purification method, water or toluene, ethanol,
A recrystallization method or a distillation method using an organic solvent such as ether or methyl isobutyl ketone can be used. Among these methods, the (i) aromatic dihydroxy compound may be appropriately purified by a purification method suitable for each compound. Specifically, hydroquinones can be usually purified by repeating recrystallization with methyl isobutyl ketone or water in multiple steps, and resorcin can be purified by recrystallization in multiple steps and then distilled.

In the present invention, the highly purified (i) aromatic dihydroxy compound thus purified is supplied to the polymerization system.
Further, in the present invention, the purified (i) aromatic dihydroxy compound is supplied to a polymerization system such as a stirrer or a reactor in a substantial absence, that is, without contact with oxygen.

(I) In order to supply the aromatic dihydroxy compound to the polymerization system without substantially contacting with oxygen, for example, a distiller or a recrystallizer may be directly connected to a stirrer or a reactor by piping. It may be supplied to the polymerization system. At this time, the (i) aromatic dihydroxy compound may be supplied together with an inert gas such as nitrogen to the polymerization system in the substantial absence of oxygen.

It should be noted that (i) the aromatic dihydroxy compound is very easily oxidized, and even the (i) aromatic dihydroxy compound purified as described above, once contacted with oxygen,
When used in a polymerization system, it is difficult to obtain a copolycarbonate excellent in hue and transparency.

In the present invention, the aromatic dihydroxy compounds (i) and (ii) and the compound (iii) capable of reacting with these (i) and (ii) to form a carbonic acid bond are substantially oxygen-immiscible. Copolymerize (polycondensate) in the presence. At this time, an interfacial method or a solution method using a carbonyl halide such as phosgene as a compound (iii) capable of forming a carbonic acid bond, or a melt polycondensation method using a carbonic acid diester as a compound (iii) capable of forming a carbonic acid bond, a solid method. A phase polymerization method or the like can be adopted, and the polycondensation method is not particularly limited.

In the present invention, among these, (i) an aromatic dihydroxy compound represented by the above formula [I], (ii) another aromatic dihydroxy compound and (iii) a carbonic acid diester in the presence of a catalyst. It is preferable to produce a copolycarbonate by melt polycondensation. The melt polycondensation method will be described below.

As the catalyst, (a) an alkali metal compound and / or an alkaline earth metal compound is used. Specific examples of the alkali metal compound and the alkaline earth metal compound (a) include organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of alkali metals and alkaline earth metals. And the like are preferable.

More specifically, such alkali metal compounds 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 phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium Salts, dilithium salts, sodium salts of phenol, potassium salts, lithium salts and the like are used.

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 and carbonic acid. Calcium, 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.

These compounds may be used alone or in combination.
Can be used. Such alkali metal compounds
And / or the alkaline earth metal compound (a) is an aromatic diamine.
Usually 1 × 10 with respect to 1 mol of the total amount of the hydroxy compound.
^-8~ 1 x 10 ^-3Mol, preferably 1 × 10^-7~ 1 x 10
^-FiveMol, particularly preferably 1 × 10^-7~ 2.5 × 10^-6Mo
Used in the amount of le.

When the amount of the alkali metal compound or the alkaline earth metal compound (a) used is 1 × 10 ^-8 to 1 × 10 ^-3 mol per 1 mol of the total amount of the aromatic dihydroxy compound, the polymerization activity is high. An acidic compound (which will be described later) can be added in an amount that does not adversely affect the properties of the obtained copolycarbonate while being maintained, and the basicity of these compounds can be sufficiently neutralized or weakened,
It is possible to obtain a copolycarbonate having excellent hue, heat resistance, water resistance, and weather resistance, and excellent melt stability for a long time.

In the present invention, as a catalyst, together with (a) an alkali metal compound and / or an alkaline earth metal compound as described above, (b) a basic compound and / or
(c) A boric acid compound can be used.

Examples of the basic compound (b) include nitrogen-containing basic compounds which are easily decomposable or volatile at high temperature, and specifically, the following compounds can be mentioned.

Tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), trimethylbenzylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH ) Such as alkyl, aryl,
Ammonium hydroxides having araryl groups, etc., tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, R ₂ NH (wherein R is an alkyl group such as methyl or ethyl, an aryl group such as phenyl or toluyl). Etc.)
Secondary amines represented by RNH ₂ (wherein R is the same as above), pyridines such as pyridine, dimethylaminopyridine, pyrrolidinopyridine, 2-methylimidazole, 2-phenyl Imidazoles such as imidazole, or ammonia, tetramethylammonium borohydride (Me ₄ NBH ₄ ), tetrabutylammonium borohydride (Bu ₄ NBH ₄ ), tetrabutylammonium tetraphenylborate (Bu ₄ N
BPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh ₄₎ basic salts, such as.

Of these, tetraalkylammonium hydroxides, especially electronic tetraalkylammonium hydroxides containing few metal impurities, are preferably used.

Examples of the boric acid compound (c) include boric acid and boric acid esters represented by the following general formula. In the formula B (OR) _n (OH) _3-n , R is alkyl such as methyl or ethyl, aryl such as phenyl, and n is 1, 2 or 3.

Specific examples of the borate ester include trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Is mentioned.

The preferred combination used as a catalyst in the present invention is a combination of (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound.

At this time, (a) an alkali metal compound and /
Alternatively, the alkaline earth metal compound is used in the amount as described above, and (b) the nitrogen-containing basic compound is 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol, relative to 1 mol of the total amount of the aromatic dihydroxy compound, It is preferably used in an amount of 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol. (b) The amount of the nitrogen-containing basic compound used is 1 × 10 ⁻⁶ to 1 × 1 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferable that the content is 0 ^-1 mol because the transesterification reaction and the polymerization reaction proceed at a sufficient rate and a copolycarbonate excellent in hue, heat resistance and water resistance can be obtained.

Thus, the catalyst obtained by combining (a) an alkali metal compound and / or an alkaline earth metal compound and (b) a nitrogen-containing basic compound is excellent in heat resistance and water resistance and has improved color tone. A high-molecular weight copolycarbonate having excellent transparency can be produced with high polymerization activity.

Further, in the present invention, a catalyst comprising a combination of (a) an alkali metal compound and / or an alkaline earth metal compound and (c) boric acid or a borate ester, and (a) an alkali metal compound and / or Alternatively, a catalyst composed of a combination of an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a borate ester is preferably used.

In a catalyst composed of such a combination,
The alkali metal compound or alkaline earth metal compound (a) and the nitrogen-containing basic compound (b) are preferably used in the amounts described above.

(C) Boric acid or boric acid ester is used in an amount of 1 × 10 ^-8 per 1 mol of the total amount of aromatic dihydroxy compound.
~ 1 x 10 ^-1 mol, preferably 1 x 10 ^-7 to 1 x 10 ^-2
It is used in an amount of 1 mol, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol.

(C) The amount of boric acid or boric acid ester used is 1 × with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferable that it is 10 ⁻⁸ to 1 × 10 ⁻¹ mol because the molecular weight does not easily decrease after heat aging, and a copolymerized polycarbonate excellent in hue, heat resistance and water resistance can be obtained.

In particular, (a) an alkali metal compound or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c)
The catalyst composed of boric acid or boric acid ester is excellent in transparency, heat resistance and water resistance and has an improved color tone, and can produce a high molecular weight copolycarbonate with high polymerization activity.

The polycondensation reaction of (i) an aromatic dihydroxy compound represented by the formula [I], (ii) another aromatic dihydroxy compound and (iii) a carbonic acid diester using such a catalyst is conventionally known. The polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester can be performed under the same conditions.

Specifically, it is 80 to 250 ° C, preferably 100 to 230 ° C, more preferably 120 to 190 ° C.
At the temperature of 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours, under normal pressure, the aromatic dihydroxy compound and the carbonic acid diester are reacted. Then, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally, under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.
A polycondensation reaction of an aromatic dihydroxy compound and a carbonic acid diester is carried out at a temperature of 320 ° C.

The polycondensation reaction as described above may be carried out continuously or batchwise. Further, the reaction apparatus used for carrying out the above reaction may be a tank type, a tube type or a column type.

The copolycarbonate thus obtained usually has an intrinsic viscosity [η] of 0.2 to 1.2 dl.
/ G, preferably 0.3 to 1.0 dl / g. In the method for producing a copolycarbonate according to the present invention, it is preferable to add an acidic compound and, if necessary, an epoxy compound to the reaction product thus obtained, that is, the copolycarbonate.

The acidic compound used in the present invention may be a Lewis acid compound or a Bronsted acid compound as long as it can neutralize an alkaline compound such as an alkali metal compound or an alkaline earth metal compound used as a catalyst. It may be a strong acid ester containing a sulfur atom.

The Bronsted acid compound used in the present invention has a pKa of 5 or less, preferably 3 or less, especially in an aqueous solution at 25 ° C. By using an acidic compound having a pKa of such a value, the alkali metal or alkaline earth metal used as a catalyst can be neutralized, and the resulting copolycarbonate can be stabilized.

Specific examples of the Lewis acid compound include boron compounds such as zinc borate and boron phosphate, and B (OC
H ₃ ) ₃ , B (OEt) ₃ , B (OPh) ₃ and other borate esters, aluminum stearate, aluminum silicate and other aluminum compounds, zirconium carbonate,
Zirconium compounds such as zirconium alkoxide and zirconium hydroxycarboxylate, gallium phosphide,
Gallium compounds such as gallium antimonide, germanium oxides, germanium compounds such as organic germanium, tetra and hexaorgano tin, PhOSn (B
u) ₂ OSn (Bu) ₂ OPh and other tin compounds, antimony oxide and antimony compounds such as alkyl antimony, bismuth oxide and bismuth compounds such as alkyl bismuth, (CH ₃ COO) ₂ Zn, zinc compounds such as zinc stearate, Examples thereof include titanium compounds such as alkoxy titanium and titanium oxide.

In the above formula, Ph represents a phenyl group, Et represents an ethyl group, and Bu represents a butyl group.

Specific examples of the Bronsted acid compound include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, boric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, sulfurous acid and adipic acid. , Azelaic acid, dodecanoic acid, L-ascorbic acid, aspartic acid, benzoic acid, formic acid, acetic acid,
Citric acid, glutamic acid, salicylic acid, nicotinic acid, fumaric acid, maleic acid, oxalic acid, benzenesulfinic acid, toluenesulfinic acid and benzenesulfonic acid,
p-toluenesulfonic acid, trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene,
Examples thereof include compounds of sulfonic acids such as methyl acrylate-sulfonated styrene copolymer.

As the ester of an acid containing a sulfur atom,
Dimethylsulfate, diethylsulfate, p-toluene sulfonic acid methyl, ethyl, butyl, octyl or phenyl ester, benzene sulfonic acid methyl, ethyl, butyl, octyl, etc. are used. .

Among such acidic compounds, an acidic compound containing a sulfur atom, a phosphorus atom and the like is preferable, and an acidic compound containing a sulfur atom is particularly preferable. The acidic compound added to the reaction product is used in an amount capable of neutralizing or weakening the influence of the remaining alkaline compound by adding it to the copolymerization polycarbonate which is the reaction product. For example, with respect to 1 mol of the alkali metal compound and / or the alkaline earth metal compound remaining in the copolymerized polycarbonate which is a reaction product,
It is used in an amount of 0.01 to 500 mol, preferably 0.1 to 100 mol, more preferably 0.1 to 50 mol, and particularly preferably 0.5 to 30 mol.

Particularly when the acidic compound is a Lewis acid or a Bronsted acid having a pKa of greater than 3,
0.01-500 mol, preferably 0.1-50 mol,
It is more preferably used in an amount of 0.1 to 30 mol, and when the acidic compound is a Bronsted acid having a pKa of 3 or less or an ester of an acid containing a sulfur atom, 0.01 to 500 mol, preferably Is used in an amount of 0.1 to 15 mol, more preferably 0.1 to 7 mol.

The epoxy compound used in the present invention is 1
It has one or more epoxy groups in the molecule. Specifically as such an epoxy compound, epoxidized soybean oil,
Epoxidized linseed oil, phenyl glycidyl ether, allyl glycidyl ether, t-butyl phenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-
Epoxy cyclohexyl carboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-3 ', 4'-epoxy-6'-
Methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate, 4- (3,4-epoxy-5-methylcyclohexyl) butyl-3', 4'-epoxycyclohexylcarboxylate , 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6'-methylsiloxyhexylcarboxylate, bisphenol-A diglycidyl ether, tetrabromo Bisphenol-A glycidyl ether, phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, bis-epoxydicyclopentadienyl ether, bis-epoxyethylene glycol, bis-epoxycyclohexyl adipate Butadiene diepoxide, tetraphenyl ethylene epoxide, octyl epoxy tallate, epoxidized polybutadiene, 3,4-dimethyl-1,2-epoxycyclohexane, 3,5
-Dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t
-Butyl-1,2-epoxycyclohexane, octadecyl-
2,2-Dimethyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,
4-epoxycyclohexylcarboxylate, N-butyl
-2-Isopropyl-3,4-epoxy-5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3 ', 4'
-Epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxycyclohexyl-3 ', 4'-epoxycyclohexylcarboxylate, 4,5-epoxytetrahydrophthalic anhydride, 3-t-butyl-4,5- Epoxy tetrahydrophthalic anhydride, diethyl 4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4,5-epoxy-cis-1,2-cyclohexyldi Examples thereof include carboxylate.

Of these, alicyclic epoxy compounds are preferably used, and 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexylcarboxylate is particularly preferably used.

These may be used alone or in combination. In the present invention, such an epoxy compound,
1 to 2000 pp with respect to the above copolymerized polycarbonate
It is preferred to add in an amount of m, preferably in an amount of 10 to 1000 ppm.

Further, in the present invention, it is preferable that the copolymerized polycarbonate obtained by the polycondensation reaction is subjected to a reduced pressure treatment after adding an acidic compound and, if necessary, an epoxy compound.

In carrying out such a depressurization treatment, the treating device is not particularly limited, but for example, a reactor with a depressurizing device or an extruder with a depressurizing device may be used.

When the reactor is used, either a vertical tank reactor or a horizontal tank reactor may be used, and a horizontal tank reactor is preferably used. When the pressure reduction treatment is carried out in the reactor as described above, the pressure is 0.05 to 750 mm.
Hg is preferably carried out under the condition of 0.05 to 5 mmHg.

Such pressure reduction treatment is preferably carried out for about 10 seconds to 15 minutes when using an extruder, and for about 5 minutes to 3 hours when using a reactor. Further, the depressurization treatment is preferably performed at a temperature of about 240 to 350 ° C.

When the pressure reducing treatment is carried out in the extruder, either a single screw extruder with a vent or a twin screw extruder may be used, and the pelletizing can be performed while the pressure reducing treatment is carried out by the extruder.

When the reduced pressure treatment is carried out in the extruder,
The depressurization treatment is performed under a pressure of 1 to 750 mmHg, preferably 5 to 70.
It is carried out under the condition of 0 mmHg. Thus, to the copolymerized polycarbonate which is a reaction product, preferably after adding an acidic compound, an epoxy compound, a phosphorus compound,
The reduced pressure treatment makes it possible to obtain a copolycarbonate having reduced residual monomers and oligomers.

The copolycarbonate obtained as described above has a constitutional unit derived from (i) an aromatic dihydroxy compound represented by the formula [I] and (ii) another aromatic dihydroxy compound. It is obtained as a random copolymer with the structural unit.

Such a copolycarbonate obtained in the present invention comprises (i) a structural unit derived from an aromatic dihydroxy compound represented by the formula [I] and a structural unit derived from an aromatic dihydroxy compound. When it is 100 mol%, the amount of the structural unit derived from (ii) another aromatic dihydroxy compound is preferably 98 to 90 mol%, more preferably 2 to 40 mol%.
10 mol%, more preferably 98-60 mol%
It is contained in the amount of.

This copolymerized polycarbonate has an amount of 3 mol% or less, preferably 0, when the constitutional unit derived from the polyfunctional compound is 100 mol% of the constitutional unit derived from the aromatic dihydroxy compound. It may be contained in an amount of 0.1 to 2 mol%, more preferably 0.1 to 1 mol%.

Further, in the copolymerized polycarbonate obtained in the present invention, the above-mentioned polyester polycarbonate constituent unit may be present in an amount of 50 mol% or less, preferably 30 mol% or less.

When the copolycarbonate is produced by melt polycondensation as described above, toxic substances such as phosgene and methylene chloride are not used, which is preferable from the viewpoint of environmental hygiene.
Further, when a copolycarbonate is produced by directly reacting phosgene with an aromatic dihydroxy compound containing the resorcins or hydroquinones represented by the above formula [I], the transparency or hue of the resulting copolycarbonate decreases. I have something to do. On the other hand, when a copolymerized polycarbonate containing a constitutional unit derived from the aromatic dihydroxy compound represented by the above formula [I] is produced by the melt polycondensation method as described above, it is excellent in transparency and hue. It is preferable since a copolymerized polycarbonate can be produced.

In the present invention, the copolycarbonate obtained as described above is added to the usual heat stabilizer, ultraviolet absorber, mold release agent, within the range not impairing the object of the present invention.
Colorants, antistatic agents, slip agents, antiblocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, fillers, reinforcing materials and the like may be added. These are specifically described in Japanese Patent Application No. 3-159145.

[0088]

According to the method for producing a copolycarbonate according to the present invention as described above, the mechanical properties and heat resistance are excellent, and the moldability such as chemical resistance and fluidity is excellent, and the hue and transparency are excellent. It is also possible to produce an excellent copolycarbonate.

The copolymerized polycarbonate obtained in the present invention can be used in a wide range of applications such as food use, medical use, automobile use, electric parts, communication equipment parts, precision equipment and optical uses.

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

[0091]

[Examples] Physical property measurements and test methods are shown below. [Intrinsic Viscosity [IV]] Measured in methylene chloride at 20 ° C. using an Ubbelohde viscometer.

[Melt flow rate (MFR; g / 10
Min)] According to JISK-7210, the temperature was 300 ° C. and the load was 1.2 kg. [Yellowness (YI)] A 3 mm thick injection molded plate was molded at a cylinder temperature of 290 ° C., an injection pressure of 1000 kg / cm ² , a cycle of 45 seconds, and a mold temperature of 100 ° C., and X, Y and Z values were
Nippon Denshoku Industries Co., Ltd. Color and Color Defference Meter
Yellowness (YI) measured by transmission method using ND-1001 DP
Was measured.

YI = 100 (1.277 X-1.060Z) / Y [Light transmittance] According to the method of ASTM D 1003,
It measured using the injection molding board for hue measurement.

[Haze] NDH- from Nippon Denshoku Industries Co., Ltd.
200 was used to measure the haze of the injection-molded plate for hue measurement.

[Stability] The resin was retained in the cylinder of the injection molding machine at a temperature of 320 ° C. for 15 minutes, and injection molding was performed at that temperature. The YI and MFR of this molded plate were measured.

[Water resistance] An injection-molded plate for hue measurement was immersed in water in an autoclave and placed in an oven at 125 ° C for 5 hours.
Hold for days. Haze was measured using this test piece.

[0097]

Example 1 0.33 kmole of bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) and 0.11 kmole of resorcin (manufactured by Mitsui Petrochemical Industry Co., Ltd.) supplied by direct piping after distillation and purification. And diphenyl carbonate (Any Co.) 0.46 kmole
It was charged into a 250 liter tank-type stirring tank of No. 2, dissolved at 140 ° C., and bisphenol A was maintained at 0.12 kmol / hour and resorcin was at 0.04 kmol / hour so as to maintain this level.
While feeding 0.16 kilomoles of diphenyl carbonate per hour, 0.16 kilomoles per hour of this aromatic dihydroxy compound is fed to this second 50-liter tank-type stirring tank. The temperature of this tank type stirring tank is 18
Keep at 0 ° C.

Tetramethylammonium hydroxide was added as a catalyst in an amount of 0.04 mol / hr and sodium hydroxide was added in an amount of 0.00016 mol / hr (1 × 10 ⁻⁶ 6 mol / mol-aromatic dihydroxy compound), and the residence time was 30 minutes. Adjust the level so that

Next, the reaction solution is fed into the 50-liter tank-type stirring tank at the third temperature of 210 ° C. and the pressure of 200 mmHg at the rate of 0.16 kmole per hour in terms of the aromatic dihydroxy compound. The level is adjusted so that the residence time is 30 minutes, and stirring is performed while distilling and removing phenol.

Next, 0.16 kilomoles of this reaction solution per hour in terms of an aromatic dihydroxy compound are sent to the following 50-liter tank-type stirring tank having a fourth temperature of 240 ° C. and a pressure of 15 mmHg. The level is adjusted so that the residence time is 30 minutes, and stirring is performed while distilling and removing phenol.

Next, the pressure of this reaction product was increased by a gear pump, and 0.16 kilomoles per hour of the aromatic dihydroxy compound was fed into the centrifugal thin-film evaporator to advance the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. 290 ° C from the bottom of the evaporator with a gear pump,
In a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotating diameter 220 mm, internal volume 80 liters) controlled at 0.2 mmHg, an hourly amount of 0.1 was calculated as an aromatic dihydroxy compound.
6 kmoles (approx. 40 kg / hour) fed in, residence time 3
It was polymerized at 0 minutes.

Next, in a molten state, this polymer was mixed with a gear pump in a twin-screw extruder (L / D = 17.5, barrel temperature 280 ° C.) to obtain 0.16 kmole (about 40 kg / hour), 0.0322 mol of butyl p-toluenesulfonate per hour (2 times the molar amount of sodium hydroxide used as a catalyst) is continuously kneaded, formed into a strand through a die, and cut with a cutter. And made into pellets.

The results are shown in Table 1.

[0104]

[Example 2] In Example 1, 0.22 kmole of bisphenol A (manufactured by Japan GE Plastics Co., Ltd.) and resorcinol (manufactured by Mitsui Petrochemical Industry Co., Ltd.) supplied by direct piping after being purified by distillation. ) Pellets were obtained in the same manner as in Example 1 except that 0.22 kmole was used.

The results are shown in Table 1.

[0106]

[Examples 3 to 4] In Example 1, hydroquinone (manufactured by Mitsui Petrochemical Industry Co., Ltd.) and bisphenol A, which were supplied by direct piping after recrystallization in place of resorcin, were used in the amounts shown in Table 1. Pellets were obtained in the same manner as in Example 1 except that the above was used.

The results are shown in Table 1.

[0108]

Comparative Examples 1 to 4 Pellets were obtained in the same manner as in Example 1 except that the amount of resorcinol or hydroquinone shown in Table 1 was used as it was in the commercially available form without purification. .

The results are shown in Table 1.

[0110]

Comparative Example 5 As in Example 1, except that resorcinol, which had been purified by distillation and then taken out of the system and stored in a plastic bag for 1 week, was used in the amount shown in Table 1 without being purified as it was. Pellets were obtained in the same manner.

The results are shown in Table 1.

[0112]

Comparative Example 6 Example 1 was repeated except that after recrystallizing and purifying, hydroquinone which had been taken out of the system and stored in a plastic bag for 1 week was used in the amount shown in Table 1 without being purified. Pellets were obtained in the same manner as in.

The results are shown in Table 1.

[0114]

[Table 1]

[0115]

[Table 2]

Claims (13)

[Claims] 1. An aromatic dihydroxy compound represented by the following general formula [I]: (In the formula [I], R is a hydrocarbon group having 1 to 10 carbon atoms or a halide thereof, or halogen, which may be the same or different, and n is an integer of 0 to 4. ) (Ii) A copolycarbonate obtained by copolymerizing an aromatic dihydroxy compound other than (i) above with (iii) a compound capable of reacting with aromatic dihydroxy compounds (i) and (ii) to form a carbonic acid bond. In the production of (i), after purifying the aromatic dihydroxy compound represented by the general formula [I], it is supplied to a stirrer or a reactor in the substantial absence of oxygen for polycondensation reaction. A method for producing a copolycarbonate characterized by the above. 2. A copolymer obtained by copolymerizing (i) an aromatic dihydroxy compound represented by the above general formula [I], (ii) an aromatic dihydroxy compound other than (i) above, and (iii) a carbonic acid diester. In producing a polymerized polycarbonate, (i) after purifying the aromatic dihydroxy compound represented by the general formula [I], it is supplied to a stirrer or a reactor in the substantial absence of oxygen, and in the presence of a catalyst. 1. A method for producing a copolycarbonate, which comprises melt-polycondensing. 3. The method for producing a copolycarbonate according to claim 2, wherein an acidic compound and, if necessary, an epoxy compound are added to the reaction product obtained by melt polycondensation. 4. The reaction product obtained by melt polycondensation, after adding an acidic compound and, if necessary, an epoxy compound, and then subjecting the reaction product to a reduced pressure treatment. A method for producing a copolycarbonate according to claim 1. 5. The method for producing a copolycarbonate according to claim 2, wherein the catalyst is (a) an alkali metal compound and / or an alkaline earth metal compound. 6. A catalyst comprising (a) an alkali metal compound and / or an alkaline earth metal compound, and (b) a nitrogen-containing basic compound and / or (c) boric acid or a boric acid ester. The method for producing the copolycarbonate according to any one of claims 2 to 4. 7. (a) Use of an alkali metal compound and / or an alkaline earth metal compound in an amount of 1 × 10 ⁻⁸ to 1 × 10 ⁻³ mol based on 1 mol of the total amount of the aromatic dihydroxy compound. 7. The method for producing a copolycarbonate according to claim 5 or 6. 8. (a) An alkali metal compound and / or an alkaline earth metal compound in an amount of 1 × 10 ^{−7 to} 2.5 × 10 ⁻⁶ mol per 1 mol of the total amount of the aromatic dihydroxy compound. The method for producing a copolycarbonate according to claim 5 or 6, which is used. 9. The copolymerized polycarbonate according to claim 1, wherein (i) the aromatic dihydroxy compound represented by the general formula [I] is purified by a recrystallization method and / or a distillation method. Production method. 10. The purified (i) aromatic dihydroxy compound represented by the general formula [I] is used in an amount of 2 to 90 mol% when the total amount of aromatic dihydroxy compounds is 100 mol%. The method for producing a copolycarbonate according to claim 1 or 2, characterized in that. 11. The purified (i) aromatic dihydroxy compound represented by the general formula [I] is used in an amount of 2 to 40 mol% when the total amount of aromatic dihydroxy compounds is 100 mol%. The method for producing a copolycarbonate according to claim 1 or 2, characterized in that. 12. The method for producing a copolycarbonate according to claim 1, wherein (i) the aromatic dihydroxy compound represented by the general formula [I] is resorcin. 13. The method for producing a copolycarbonate according to claim 1, wherein (i) the aromatic dihydroxy compound represented by the general formula [I] is hydroquinone.