JP3262860B2 - Method for producing copolymerized polycarbonate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is to produce a copolymerized polycarbonate having excellent mechanical properties, heat resistance, moldability such as chemical resistance and fluidity, and also excellent hue and transparency. To a method for producing a copolymerized polycarbonate.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polycarbonate molded products have excellent mechanical properties such as impact resistance, and are also excellent in heat resistance and transparency, and are widely used as various mechanical parts, optical discs, automobile parts, and the like. It is used for

[0003] A polycarbonate having such properties is usually produced by an interfacial polymerization method in which an aromatic dihydroxy compound such as bisphenol A is directly reacted with phosgene. There is also known a method for producing a polycarbonate by melt polycondensation of a carbonic acid diester and the above-mentioned aromatic dihydroxy compound.

[0004] Conventional polycarbonates having a bisphenol A skeleton have problems that they are inferior in chemical resistance, high in melt viscosity during molding, and poor in fluidity. In general, polymers are more susceptible to moldings, such as the longer the melting time at high temperatures, the lower the transparency or hue.

[0005] For this reason, the emergence of a polycarbonate with further improved chemical resistance and fluidity during molding has been desired. In order to meet such demands, copolymer polycarbonates having a skeleton derived from hydroquinone, resorcin, and the like have been proposed. For example, JP-A-52-109591 proposes a method for producing a copolymerized polycarbonate using hydroquinone and / or an ester-forming derivative thereof as a part of the aromatic dihydroxy compound, and provides a copolymer having excellent solvent resistance. A polymerized polycarbonate has been obtained.

However, when the above-mentioned copolymerized polycarbonate is to be obtained by a general melt polycondensation method (ester exchange method) described in this publication,
During the polycondensation, hydroquinone is oxidized and tends to be colored brown or yellow, and the resulting copolymerized polycarbonate is sometimes colored.

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

For this reason, a copolymerized polycarbonate having excellent mechanical properties, heat resistance, and improved moldability such as chemical resistance and fluidity can be produced without coloring or impairing transparency at the time of production. It has been desired to develop a method for producing a copolymerized polycarbonate that can be used.

The present inventors have conducted intensive studies in view of the prior art as described above. As a result, (i) an aromatic dihydroxy compound (hydroquinones and resorcinols) represented by the general formula [I]; and (ii) When producing a copolymerized polycarbonate from other aromatic dihydroxy compounds,
(i) After purifying the aromatic dihydroxy compound represented by the general formula [I], the aromatic dihydroxy compound is supplied to a stirrer or a reactor in the substantial absence of oxygen to perform a polycondensation reaction, whereby a colorless copolymerization is performed. The inventors have found that polycarbonate can be efficiently produced, and have completed the present invention.

[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 copolymerized polycarbonate capable of producing a copolymerized polycarbonate having excellent transparency and hue.

[0011]

SUMMARY OF THE INVENTION The process for producing a copolymerized polycarbonate according to the present invention comprises the steps of (i) an aromatic dihydroxy compound represented by the following general formula [I]:

[0012]

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(In the formula [I], R represents a carbon number of 1 to 1, respectively.
0 hydrocarbon group or its halide or halogen, which may be the same or different, and n is 0
-4. (Ii) an aromatic dihydroxy compound other than (i) and (iii) an aromatic dihydroxy compound (i)
And copolymerizing a compound capable of forming a carbonic acid bond by reacting with (ii), (i) after purifying the aromatic dihydroxy compound represented by the general formula [I], in the substantial absence of oxygen. It is supplied to a stirrer or a reactor to perform a polycondensation reaction.

The method for producing such a copolycarbonate is described in (iii) aromatic dihydroxy compounds (i) and (i).
The compound capable of forming a carbonic acid bond by reacting with i) is preferably carried out by a melt polycondensation method using a carbonic acid diester, and is preferably from 1 × 10 ⁻⁸ to 1 × based on 1 mol of the aromatic dihydroxy compound in total. (A) melting in the presence of a catalyst comprising an alkali metal compound and / or an alkaline earth metal compound in an amount of 10 ^-3 mol, preferably in an amount of 1 × 10 ^{-7 to} 2.5 × 10 ^-6 mol Preferably, polycondensation is performed.

Further, in the method for producing a copolymerized polycarbonate 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 melt-polycondensation as described above. It is more preferable to perform a decompression treatment.

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

[0017]

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

[0018]

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(In the formula [I], R represents a carbon number of 1 to 1 respectively.
0 hydrocarbon group or its halide or halogen, which may be the same or different, and n is 0
-4. (Ii) an aromatic dihydroxy compound other than (i) and (iii) an aromatic dihydroxy compound (i)
And (ii) copolymerizing a compound capable of forming a carbonic acid bond by reacting with (ii) to produce a copolymerized polycarbonate, (i) after purifying the aromatic dihydroxy compound represented by the above general formula [I] , Fed 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 general formula [I],
Specifically, resorcin, 3-methyl resorcin, 3-ethyl resorcin, 3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl resorcin, 3-phenyl resorcin,
Substituted resorcinol such as cumyl resorcin, 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 preferred. In the present invention, when producing a copolymerized polycarbonate, the above-mentioned (i) formula [I]
The aromatic dihydroxy compound represented by is used after being purified as described below. The purified (i) aromatic dihydroxy compound is used in an amount of preferably 2 to 90 mol%, more preferably 2 to 40 mol% in the aromatic dihydroxy compound.

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

Such (ii) other aromatic dihydroxy compounds are not particularly limited, and may be the following aromatic dihydroxy compounds usually used in forming polycarbonate.

[0024]

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Wherein R ¹ and R ² are a hydrogen atom or a monovalent hydrocarbon group, and R ³ is a divalent hydrocarbon group. R ⁴ and R ⁵ are a halogen or a monovalent hydrocarbon group, which may be the same or different. p and q represent an integer of 0 to 4. Examples of such aromatic dihydroxy compounds include 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, etc. Bis (hydroxyaryl) cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3 '
Dihydroxyaryl ethers such as -dimethylphenyl ether, 4,4'-dihydroxydiphenylsulfide, dihydroxydiarylsulfides such as 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide, 4,
Dihydroxydiarylsulfoxides such as 4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxy-3,3'-
And dihydroxydiarylsulfones such as dimethyldiphenylsulfone.

Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferred. Also used in the present invention (iii) aromatic dihydroxy compounds (i) and (i)
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, diethyl Examples include carbonate, dimethyl carbonate, dibutyl carbonate, diester carbonate such as dicyclohexyl carbonate, and carbonyl halide compounds such as phosgene.

Of these, diphenyl carbonate is particularly preferred. In the present invention, in producing the copolymerized polycarbonate, the diester carbonate is preferably 50 mol%, more preferably 30 mol% or less, based on 100 mol% of the diester carbonate, and more preferably 30 mol% or less. , A dicarboxylic acid halide.

Examples of such dicarboxylic acids or dicarboxylic acid esters and dicarboxylic acid halides include terephthalic acid, isophthalic acid, sebacic acid, decandioic acid, and the like.
Dodecane diacid, diphenyl sebacate, diphenyl terephthalate, diphenyl isophthalate, diphenyl decane diacid, diphenyl dodecane diacid, terephthalic chloride, isophthalic chloride, sebacic chloride, decandioic chloride, dodecane dichloride, and the like. Can be

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

In the present invention, when producing a copolymerized polycarbonate, the compound (iii) capable of forming a carbonic acid bond by reacting with the aromatic dihydroxy compound as described above is 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 the copolymerized polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound and the carbonic acid diester.

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,
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 preferred. .

When a polyfunctional compound is used, it is usually 0.03 with respect to 1 mol of the total amount of the aromatic dihydroxy compound.
It is preferably used in an amount of 0.001 to 0.02 mol, 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 compound (iii) capable of forming a carbonic acid bond with these (i) and (ii). Thus, a copolymerized polycarbonate is produced.

In the present invention, when producing a copolymerized polycarbonate, the above-mentioned (i) the aromatic dihydroxy compound represented by the general formula [I] is purified and supplied to a 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, water or toluene, ethanol,
Examples thereof include a recrystallization method using an organic solvent such as ether and methyl isobutyl ketone, and a distillation method. Among these methods, (i) the 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 distillation after recrystallization in multiple steps.

In the present invention, the high-purity (i) aromatic dihydroxy compound thus purified is supplied to a 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 substantially without coming into contact with oxygen, for example, a stirrer or a reactor may be directly connected from a still or a recrystallization apparatus by a pipe or the like. What is necessary is just to supply to a polymerization system. At this time, (i) the aromatic dihydroxy compound may be supplied to a polymerization system substantially in the absence of oxygen together with an inert gas such as nitrogen.

The (i) aromatic dihydroxy compound is very easily oxidized, and even if the (i) aromatic dihydroxy compound purified as described above is once contacted with oxygen,
When used in a polymerization system, it is difficult to obtain a copolymerized polycarbonate having excellent hue and transparency.

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

In the present invention, (i) the aromatic dihydroxy compound represented by the above formula [I], (ii) another aromatic dihydroxy compound and (iii) a carbonic acid diester are used in the presence of a catalyst. It is preferable to produce a copolymerized polycarbonate by melt polycondensation. Hereinafter, the melt polycondensation method will be described.

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, and alcoholates of alkali metals and alkaline earth metals. And the like.

More specifically, such alkali metal compounds include sodium hydroxide, potassium hydroxide,
Lithium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride , Lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium Salts, dilithium salts, phenol sodium salts, 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 carbonate. 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
And / or an alkaline earth metal compound (a)
Usually, 1 × 10
^-8~ 1 × 10 ^-3Mol, preferably 1 × 10^-7~ 1 × 10
^-FiveMol, particularly preferably 1 × 10^-7~ 2.5 × 10^-6Mo
Used in the amount of oil.

When the amount of the alkali metal compound or 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 increased. While maintaining, it is possible to add an acidic compound (described below) in an amount that does not adversely affect the properties of the obtained copolymerized polycarbonate, thereby sufficiently neutralizing or weakening the basicity of these compounds,
A copolymerized polycarbonate having excellent hue, heat resistance, water resistance, and weather resistance and excellent long-term melt stability can be obtained.

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

Examples of such a basic compound (b) include a nitrogen-containing basic compound which is easily decomposed or volatile at a high temperature, and specific examples include the following compounds.

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 an araryl group and the like, tertiary amines such as trimethylamine, triethylamine, dimethylbenzylamine and triphenylamine, R ₂ NH (where R is an alkyl group such as methyl and ethyl, and an aryl group such as phenyl and toluyl) Etc.)
In secondary amines represented, primary amines represented by RNH ₂ (wherein R is as defined above), pyridine, dimethylaminopyridine, pyridine such as 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, particularly tetraalkylammonium hydroxides for electronic use, which contain 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. B (OR) _n (OH) _{3-n In the} formula, R is alkyl such as methyl and ethyl, aryl such as phenyl and the like, 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 mentioned.

Preferred combinations used as a catalyst in the present invention include a combination consisting 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 / or
Alternatively, the alkaline earth metal compound is used in an amount as described above, and (b) the nitrogen-containing basic compound is 1 × 10 ^-6 to 1 × 10 ^-1 mol, based on 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 to be used is 1 × 10 ⁻⁶ to 1 × 1 per 1 mol of the total amount of the aromatic dihydroxy compound.
The amount of 0 to ¹ mol is preferred in that the transesterification reaction and the polymerization reaction proceed at a sufficient rate, and a copolymerized polycarbonate having excellent hue, heat resistance and water resistance can be obtained.

As described above, a catalyst obtained by combining (a) an alkali metal compound and / or an alkaline earth metal compound with (b) a nitrogen-containing basic compound is excellent in heat resistance and water resistance and has improved color tone. A high molecular weight copolymerized polycarbonate 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 comprising 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 the catalyst comprising such a combination,
(a) The alkali metal compound or alkaline earth metal compound and (b) the nitrogen-containing basic compound are preferably used in the amounts described above.

(C) Boric acid or boric acid ester is 1 × 10 ^{-8 with} respect to 1 mol of the total amount of the aromatic dihydroxy compound.
１1 × 10 ^-1 mol, preferably 1 × 10 ^-7 to 1 × 10 ^-2
Mole, more preferably 1 × 10 ^-6 to 1 × 10 ^-4 mole.

(C) The amount of boric acid or boric acid ester used is 1 × with respect to 1 mole of the total amount of the aromatic dihydroxy compound.
The molar ratio of 10 ^-8 to 1 × 10 ^-1 is preferred because a molecular weight is less likely to be reduced after heat aging, and a copolymer 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 comprising boric acid or boric acid ester is excellent in transparency, heat resistance and water resistance and also has improved color tone, and can produce a high molecular weight copolymerized polycarbonate with high polymerization activity.

The polycondensation reaction between (i) the aromatic dihydroxy compound represented by the formula [I], (ii) another aromatic dihydroxy compound and (iii) carbonic acid diester using such a catalyst has been known. The reaction can be carried out under the same conditions as those for the polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester.

Specifically, 80 to 250 ° C., preferably 100 to 230 ° C., more preferably 120 to 190 ° C.
The aromatic dihydroxy compound is reacted with the carbonic acid diester at a temperature of 0 to 5 hours, preferably 0 to 4 hours, more preferably 0 to 3 hours under normal pressure. Next, the reaction temperature is increased while reducing the pressure of the reaction system, and the reaction between the aromatic dihydroxy compound and the carbonic acid diester is carried out. Finally, the reaction is carried out under a reduced pressure of 5 mmHg or less, preferably 1 mmHg or less.
A polycondensation reaction between the aromatic dihydroxy compound and the carbonic acid diester is performed at a temperature of about 320 ° C.

The above-mentioned polycondensation reaction may be carried out continuously or batchwise. The reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The copolymerized polycarbonate 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 copolymerized polycarbonate according to the present invention, it is preferable to add an acidic compound and, if necessary, an epoxy compound to the thus obtained reaction product, that is, the copolymerized polycarbonate.

The acidic compound used in the present invention may be a Lewis acid compound, a Bronsted 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, particularly in an aqueous solution at 25 ° C. When an acidic compound having such a pKa value is used, the alkali metal or alkaline earth metal used as a catalyst can be neutralized, and the obtained copolymerized polycarbonate can be stabilized.

Specific examples of the Lewis acid compound include boron compounds such as zinc borate and boron phosphate, and B (OC
Borate esters such as H ₃ ) ₃ , B (OEt) ₃ and B (OPh) ₃ ; aluminum compounds such as aluminum stearate and aluminum silicate; zirconium carbonate;
Alkoxide zirconium, zirconium compounds such as zirconium hydroxycarboxylate, gallium phosphide,
Gallium compounds such as gallium antimonide, germanium compounds such as germanium oxide and organogermanium, tetra and hexaorganotin, PhOSn (B
_{u) 2 OSn (Bu) 2} OPh tin compounds such as antimony oxide, antimony compounds such as alkyl antimony, bismuth oxide, bismuth compounds such as an alkyl _{bismuth, (CH 3 COO) 2 Zn} , zinc compounds such as zinc stearate, Examples thereof include titanium compounds such as alkoxytitanium and titanium oxide.

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

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, 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,
And sulfonic acid compounds such as methyl acrylate-sulfonated styrene copolymer.

Examples of the acid ester containing a sulfur atom include:
Compounds having a pKa of 3 or less in an acid residue portion, such as methyl, ethyl, butyl, octyl or phenyl ester of dimethyl sulfate, diethyl sulfate, p-toluenesulfonic acid, and phenylester and benzenesulfonic acid are used. .

Among such acidic compounds, acidic compounds containing a sulfur atom, a phosphorus atom and the like are preferred, and acidic compounds containing a sulfur atom are particularly preferred. The acidic compound to be added to the reaction product is used in an amount capable of neutralizing or weakening the influence of the remaining alkaline compound by adding to the copolymerized polycarbonate as the reaction product. For example, based on 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, particularly preferably 0.5 to 30 mol.

Particularly when the acidic compound is a Lewis acid or a Bronsted acid having a pKa greater than 3,
0.01 to 500 mol, preferably 0.1 to 50 mol,
More preferably, it is used in an amount of 0.1 to 30 mol. When the acidic compound is an ester of a Bronsted acid or an acid containing a sulfur atom having a pKa of 3 or less, 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 comprises 1
The molecule has one or more epoxy groups. Specific examples of such an epoxy compound include epoxidized soybean oil,
Epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, t-butylphenyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-
Epoxycyclohexylcarboxylate, 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'-methylsilohexylcarboxylate, bisphenol-A diglycidyl ether, tetrabromo Bisphenol-A glycidyl ether, diglycidyl ester of phthalic acid, diglycidyl ester of hexahydrophthalic acid, 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 Carboxylate and the like.

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

These are used alone or in combination. In the present invention, such an epoxy compound is
1 to 2000 pp for the above copolymerized polycarbonate
It is preferably added in an amount of m, preferably in an amount of 10 to 1000 ppm.

In the present invention, it is preferable to subject the copolymerized polycarbonate obtained by the polycondensation reaction to the addition of an acidic compound and, if necessary, an epoxy compound, and then to perform a vacuum treatment.

In performing such a decompression treatment, the treatment apparatus is not particularly limited. For example, a reactor with a decompression device may be used, or an extruder with a decompression device may be used.

When a 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 performing the decompression treatment in the reactor as described above, the pressure is 0.05 to 750 mm.
Hg, preferably under the condition of 0.05 to 5 mmHg.

It is preferable to perform such a reduced pressure treatment 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 decompression treatment is preferably performed at a temperature of about 240 to 350 ° C.

When the depressurizing treatment is performed in the extruder, either a single-screw extruder with a vent or a twin-screw extruder may be used, and the pelletizing may be performed while the depressurizing treatment is performed by the extruder.

When the vacuum treatment is performed in the extruder,
The reduced pressure treatment is performed at a pressure of 1 to 750 mmHg, preferably 5 to 70 mmHg.
It is performed under the condition of 0 mmHg. In this way, preferably after adding an acidic compound, an epoxy compound, a phosphorus compound to the copolymerized polycarbonate which is a reaction product,
By performing the decompression treatment, it is possible to obtain a copolymerized polycarbonate in which residual monomers and oligomers are reduced.

The copolymerized polycarbonate obtained as described above comprises (i) a structural unit derived from the aromatic dihydroxy compound represented by the formula [I] and (ii) a structural unit derived from another aromatic dihydroxy compound. As a random copolymer with the structural units.

The copolymerized polycarbonate 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 (ii) the structural unit derived from another aromatic dihydroxy compound is preferably 98 to 90 mol%, more preferably 2 to 40 mol%, and preferably 98 to 98 mol%.
In an amount of 10 mol%, more preferably 98 to 60 mol%
It is contained in the amount of.

In the copolymerized polycarbonate, when the structural unit derived from the polyfunctional compound is 100 mol% based on the structural unit derived from the aromatic dihydroxy compound, the amount is preferably 3 mol% or less, more preferably 0 mol%. 0.1 to 2 mol%, more preferably 0.1 to 1 mol%.

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

The production of a copolymerized polycarbonate by the above-mentioned melt polycondensation is preferable from the viewpoint of environmental health because toxic substances such as phosgene and methylene chloride are not used.
When an aromatic dihydroxy compound containing a resorcinol or a hydroquinone represented by the above formula [I] is directly reacted with phosgene to produce a copolymerized polycarbonate, the transparency or hue of the obtained copolymerized polycarbonate decreases. May be. On the other hand, when a copolymerized polycarbonate containing a structural unit derived from the aromatic dihydroxy compound represented by the above formula [I] is produced by the above-described melt polycondensation method, excellent transparency and excellent hue are obtained. It is preferable because a copolymerized polycarbonate can be produced.

Further, in the present invention, the copolymerized polycarbonate obtained as described above may be added to a conventional heat-resistant stabilizer, an ultraviolet absorber, a releasing agent, or the like within a range not to impair 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, mechanical properties, heat resistance, moldability such as chemical resistance and fluidity are excellent, and hue and transparency are improved. It is possible to produce an excellent copolymerized polycarbonate.

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

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

[0091]

EXAMPLES The physical property measurement and test method are shown below. [Intrinsic viscosity [IV]] It was measured in methylene chloride at 20 ° C using an Ubbelohde viscometer.

[Melt flow rate (MFR; g / 10)
Min)] in accordance with JIS K-7210, at a temperature of 300 ° C. and a load of 1.2 kg. [Yellowness (YI)] An injection molded plate having a thickness of 3 mm is 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 the X, Y, and Z values are determined as follows.
Nippon Denshoku Industries Co., Ltd. Colorand Color Difference 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 was measured using an injection molded plate for measuring hue.

[Haze] NDH- of Nippon Denshoku Industries Co., Ltd.
Using 200, the haze of the injection molded plate for hue measurement was measured.

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

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

[0097]

Example 1 0.33 mmol of bisphenol A (manufactured by Nippon GE Plastics Co., Ltd.) and 0.11 mmol of resorcinol (manufactured by Mitsui Petrochemical Industry Co., Ltd.) supplied by distillation after purification. And 0.46 mmol of diphenyl carbonate (manufactured by Any)
, And melted at 140 ° C. to maintain this level at 0.12 mmol / hr of bisphenol A and 0.04 mmol / hr of resorcinol,
While feeding diphenyl carbonate at a rate of 0.16 km / h, the mixed solution is fed to a second 50-liter stirred tank at a rate of 0.16 km / h in terms of an aromatic dihydroxy compound. The temperature of this tank type stirring tank is 18
Keep at 0 ° C.

[0098] The hourly 0.04 moles of sodium hydroxide of tetramethylammonium hydroxide as a catalyst per hour 0.00016 mol (1 × 10 ^-6 6 mol / mol - aromatic dihydroxy compound) is added, the residence time is 30 minutes Adjust the level to stir and stir.

Next, this reaction solution is fed into a 50-liter stirred tank at a third temperature of 210 ° C. and a pressure of 200 mmHg at a rate of 0.16 km / h in terms of an aromatic dihydroxy compound. The level is adjusted so that the residence time is 30 minutes, and the mixture is stirred while phenol is distilled off.

Next, the reaction solution is fed to the next 50-liter stirred tank at a fourth temperature of 240 ° C. and a pressure of 15 mmHg at a rate of 0.16 kmol / hour in terms of an aromatic dihydroxy compound. The level is adjusted so that the residence time is 30 minutes, and the mixture is stirred while phenol is distilled off.

Next, the pressure of the reaction product was increased by a gear pump, and the reaction product was fed into a centrifugal thin film evaporator in an amount of 0.16 kmol / hour in terms of an aromatic dihydroxy compound, to proceed the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. 290 ° C with a gear pump from the bottom of the evaporator,
0.1 hour in terms of aromatic dihydroxy compound in a biaxial horizontal stirring polymerization tank (L / D = 3, stirring blade rotation diameter 220 mm, internal volume 80 liters) controlled to 0.2 mmHg.
6 kilomoles (about 40 kg / hour) each, and residence time 3
Polymerization was performed at 0 minutes.

Next, in the melted state, the polymer was fed to a twin-screw extruder (L / D = 17.5, barrel temperature 280 ° C.) using a gear pump at 0.16 kmol (approx. 40 kg / hour), and kneaded continuously with 0.00032 mol / h of p-toluene butyl sulphonate (2 times the molar amount of sodium hydroxide used as a catalyst), made into a strand through a die, and cut with a cutter. To obtain pellets.

Table 1 shows the results.

[0104]

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

Table 1 shows the results.

[0106]

Examples 3 and 4 In Example 1, hydroquinone (manufactured by Mitsui Petrochemical Industry Co., Ltd.) and bisphenol A, which were supplied directly after recrystallization instead of resorcinol, were used in the amounts shown in Table 1. Pellets were obtained in the same manner as in Example 1 except for the presence of the pellets.

Table 1 shows the results.

[0108]

Comparative Examples 1 to 4 Pellets were obtained in the same manner as in Example 1 except that purification was not performed and resorcin or hydroquinone was used in the form shown in Table 1 in the form of a commercial product. .

Table 1 shows the results.

[0110]

Comparative Example 5 Example 1 was repeated except that resorcinol, which had been distilled and purified and then taken out of the system and stored in a plastic bag for one week, was used in the amount shown in Table 1 without purification. Pellets were obtained in the same manner.

The results are shown in Table 1.

[0112]

Comparative Example 6 Example 1 was repeated except that hydroquinone, which was recrystallized and purified and then taken out of the system and stored in a plastic bag for one week, was used in the amount shown in Table 1 without purification. A pellet was obtained in the same manner as described above.

Table 1 shows the results.

[0114]

[Table 1]

[0115]

[Table 2]

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takashi Nagai 1-2-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Japan GE Plastics Co., Ltd. (56) References JP-A-52-144095 (JP) JP-A-4-175368 (JP, A) JP-A-63-10623 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 64/00-64/42

Claims (13)

(57) [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 a halogen, and may be the same or different, and n is an integer of 0 to 4.) (Ii) a copolymerized polycarbonate obtained by copolymerizing (ii) an aromatic dihydroxy compound other than the above (i) and (iii) a compound capable of forming a carbonic acid bond by reacting with the aromatic dihydroxy compounds (i) and (ii). (I) purifying the aromatic dihydroxy compound represented by the above general formula [I] and then supplying it to a stirrer or a reactor in the substantial absence of oxygen to cause a polycondensation reaction. A method for producing a copolymerized polycarbonate. 2. Copolymerization of (i) an aromatic dihydroxy compound represented by the above general formula [I], (ii) an aromatic dihydroxy compound other than the above (i), and (iii) a diester carbonate. In producing the polymerized polycarbonate, (i) after purifying the aromatic dihydroxy compound represented by the above general formula [I], supplying the aromatic dihydroxy compound to a stirrer or a reactor in the substantial absence of oxygen, in the presence of a catalyst; And subjecting the mixture to melt polycondensation. 3. The process for producing a copolymerized polycarbonate 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 method according to claim 3, wherein an acidic compound and, if necessary, an epoxy compound are added to the reaction product obtained by melt polycondensation, and then the reaction product is subjected to a reduced pressure treatment. A method for producing a copolymerized polycarbonate. 5. The method for producing a copolymerized polycarbonate 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, (b) a nitrogen-containing basic compound and / or (c) boric acid or a borate ester. A method for producing the copolymerized polycarbonate according to any one of claims 2 to 4. 7. Use of (a) an alkali metal compound and / or an alkaline earth metal compound in an amount of 1 × 10 ^-8 to 1 × 10 ^-3 mol per 1 mol of the total amount of the aromatic dihydroxy compound. The method for producing a copolymerized polycarbonate according to claim 5 or 6, wherein (A) An alkali metal compound and / or an alkaline earth metal compound is used 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 copolymerized polycarbonate according to claim 5, wherein the polycarbonate 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 the aromatic dihydroxy compound is 100 mol%. The method for producing a copolymerized polycarbonate according to claim 1 or 2, wherein: 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 the aromatic dihydroxy compound is 100 mol%. The method for producing a copolymerized polycarbonate according to claim 1 or 2, wherein: 12. The process for producing a copolymerized polycarbonate according to claim 1, wherein (i) the aromatic dihydroxy compound represented by the general formula [I] is resorcin. 13. The method for producing a copolymerized polycarbonate according to claim 1, wherein (i) the aromatic dihydroxy compound represented by the general formula [I] is hydroquinone.