JPH05170894A - Production of aromatic polycarbonate resin - Google Patents

Abstract

PURPOSE:To produce an aromatic polycarbonate resin which contains no halogen, has excellent thermal stability and is free from environmental pollution. CONSTITUTION:An aromatic polycarbonate resin is produced by reacting an aromatic polycarbonate oligomer having a chloroformate group with a monohydric phenol compound to obtain an aromatic polycarbonate oligomer having a phenyl carbonate group and transesterifying the oligomer to achieve a higher degree of polymerization, wherein an aromatic polycarbonate oligomer having a chloroformate group dissolved in a non-halogenated solvent and an aqueous solution of an alkali salt of a monohydric phenol compound, the equivalent ratio of the phenol compound to the chloroformate group being 1-10, are subjected to interfacial reaction under conditions such that the pH value of the reaction mixture is 12 or less to obtain an aromatic polycarbonate oligomer having a phenyl carbonate group which is soluble in a non-halogenated organic solvent and the oligomer is subjected to melt polymerization and/or solid phase polymerization to produce a non-halogenated aromatic polycarbonate resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aromatic polycarbonate resin, particularly a halogen-free aromatic polycarbonate resin which does not pollute the environment.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins have been widely used as engineering plastics for applications that make good use of their impact resistance, dimensional stability and transparency.

As an industrial production method, an interfacial polymerization method using phosgene is generally carried out. As the solvent, a halogen-based solvent such as methylene chloride has been preferably used because the solubility of the high molecular weight aromatic polycarbonate resin is good. However, in the process using a halogen-based solvent, it is extremely difficult to finally remove the solvent remaining in the polymer because the solvent has a high polymer affinity. Therefore, it is necessary to dry the produced aromatic polycarbonate resin at high temperature for a long time, which is a problem in the production process. Further, in a low boiling point solvent such as methylene chloride, the solvent is liable to volatilize and pollute the environment, but in order to prevent this, there is a problem that the manufacturing cost of the plant becomes high.

On the other hand, as an interfacial polymerization method for an aromatic polycarbonate resin using a non-halogen solvent, a method using a hydrocarbon solvent such as toluene or xylene has been known so far. In this case, the molecular weight of the polymer is not less than a certain level. It is known that when it becomes very large, it precipitates. Therefore, the molecular weight distribution occurs in the surface layer and inside the precipitate,
It was difficult to remove by-products such as inorganic salts taken in the precipitate. For example, Che by Schnell
mystry and Physics of Poly
According to carbonates, when an aromatic polycarbonate resin was synthesized by an interfacial method using a xylene homolog as an organic solvent, the obtained polymer was a solvent-swollen white solid, and the obtained particulate polymer was 100%. ℃
It is described that halogen could not be completely removed by alkali extraction with.

JP-A-2-11627 describes a method for producing an aromatic polycarbonate resin by interfacial polymerization using a mixed solvent of an aromatic hydrocarbon and an alkane and / or a cycloalkane as an organic layer. ..
However, in this method, a special device (described as a kneader) is used to remove inorganic salts and halogen components from the polycarbonate resin swollen in the solvent, or the generated polymer is once dissolved in methylene chloride to perform a washing step. Need of

Further, in Japanese Patent Application No. 3-195726, a partially crystalline oligomer precondensate is produced by an interfacial method using water and a non-halogen organic solvent in the first step, and melted or solid-phase polymerized in the second step. Discloses a method of obtaining a high-molecular-weight aromatic polycarbonate resin by carrying out the latter-stage condensation.
In this method, in the first step, in producing an aromatic polycarbonate oligomer from a chain stopper such as an aromatic dihydroxy compound, a monofunctional phenol compound and phosgene, by using a predetermined amount of the chain stopper,
A method of controlling the molecular weight of the oligomer is used. However, when an aromatic polycarbonate oligomer having a low molecular weight is produced by this method, it is inevitable that diphenyl carbonate will be produced as a by-product because it is necessary to use a large amount of phenol, which is a problem for industrial implementation. ..

When the amount of phenol added is small in the method of the first stage of JP-A-3-195726, the production of diphenyl carbonate can be suppressed, but the molecular weight of the obtained oligomer becomes large. Therefore, as described in Examples, it is unavoidable that precipitates are generated during the production of aromatic polycarbonate oligomers (Examples 1 and 3). Therefore, in order to remove impurities from the oligomer by washing, the shape of the precipitate should be reduced,
This method is not always a simple method because it requires some measures such as repeated washing.

In Japanese Patent Laid-Open Publication No. 1-271426, a three-step method comprising 1) production of oligocarbonate using phosgene, 2) crystallization of the obtained oligocarbonate, and 3) solid phase polycondensation of crystallized oligocarbonate A method for making a molecular weight aromatic polycarbonate resin is described. However, here, a method of using a halogen-based solvent such as methylene chloride as a solvent in the production of an oligomer is illustrated in the examples, and it is not mentioned that an aromatic polycarbonate resin containing no chlorine can be obtained.

As described above, a method for easily producing an aromatic polycarbonate resin containing no halogen component as an impurity has not been established so far.

[0010]

DISCLOSURE OF THE INVENTION The present invention solves the problems of the conventional method for producing an aromatic polycarbonate resin by the interfacial method, and simplifies the aromatic polycarbonate resin containing no halogen component. To provide a manufacturing method.

[0011]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a method for easily producing an aromatic polycarbonate resin containing no halogen compound, and as a result, have found that a low molecular weight aromatic compound soluble in a non-halogen organic solvent is used. The present invention has been accomplished by finding the conditions for producing a polycarbonate oligomer in a high yield, and solving the above problems by increasing the molecular weight of the aromatic polycarbonate oligomer obtained here by a transesterification method in a post-polymerization step, and arrived at the present invention. ..

That is, according to the present invention, a chloroformate group-containing aromatic polycarbonate oligomer is reacted with a monofunctional phenol compound to produce a phenyl carbonate group-containing aromatic polycarbonate oligomer, which is further subjected to a transesterification method. In producing an aromatic polycarbonate resin with a high degree of polymerization, a chloroformate group-containing aromatic polycarbonate oligomer dissolved in a non-halogen solvent and 1 to 10 equivalents of monofunctionality per 1 equivalent of the chloroformate group By interfacially reacting with an aqueous solution of an alkaline salt of a phenol compound under the condition that the pH of the reaction solution is 12 or less, a phenyl carbonate group-containing aromatic polycarbonate oligomer soluble in a non-halogen organic solvent is produced, and this is melt-polymerized. And / or raw materials for solid state polymerization That is a process for producing an aromatic polycarbonate resin containing no halogen.

The present invention will be described in detail below.

As the non-halogen organic solvent in the present invention, any solvent can be used as long as it dissolves the aromatic polycarbonate oligomer and has low miscibility with water. Examples of the solvent satisfying these conditions include aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, isopropylbenzene, and 1,3,5-trimethylbenzene, anisole, benzyl ethyl ether, ethyl phenyl ether, diphenyl ether, etc. And aromatic ketone solvents such as cyclohexanone, 2-hexanone, 2-heptanone, and 3-heptanone. Among these, particularly preferable organic solvents are aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene, and aromatic ether solvents such as anisole. Further, these solvents may be used as a mixed solvent of two or more kinds, or depending on the use, a halogen-based solvent may be added and used within a range not impairing the effects of the present invention.

The chloroformate group-containing aromatic polycarbonate oligomer used in the present invention is obtained by blowing phosgene into a mixture of an alkaline aqueous solution of an aromatic dihydroxy compound and an organic solvent.

As the aromatic dihydroxy compound used as a raw material, those represented by the general formula (I) are used.

[0017]

[Chemical 1]

In the formula, R ¹ and R ² each independently represent a hydrogen atom, a halogen, an alkyl group, an alkenyl group or an optionally substituted aryl group, and X is

[0019]

[Chemical 2]

(However, R ³ and R ⁴ are each independently a hydrogen atom,
Or represents an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms),

[0021]

[Chemical 3]

(Cycloalkylene group: n is an integer from 2 to 4), -O-, -CO-, -S-, -SO- and the like.

Particularly preferred are bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane and 2,2-bis ( 4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl)
Pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-
Methyl pentane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4) -Hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-
4-hydroxyphenyl) propane, 2,2-bis (4
-Hydroxyphenyl) hexafluoropropane, bis (4-hydroxyphenyl) phenylmethane, 1,1-
Bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) dibenzylmethane, 1,1-bis (4-hydroxyphenyl)
-Cyclopentane, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy Examples thereof include diphenyl sulfone and phenolphthalein.

These aromatic dihydroxy compounds may be used alone or as a mixture.

When the aromatic polycarbonate oligomer containing a chloroformate group is produced, the molecular weight of the oligomer and the ratio of the hydroxyl group to the chloroformate group in the oligomer can be arbitrarily adjusted by controlling the reaction conditions. ..

The molecular weight of the aromatic polycarbonate oligomer containing a chloroformate group is 5,000 in terms of number average molecular weight.
Those having a number average molecular weight of 3,000 or less are preferably used, and those having a number average molecular weight of 3,000 or less are preferably used. If the molecular weight of the chloroformate group-containing aromatic polycarbonate oligomer is too large, the solubility in an organic solvent becomes extremely poor, which is not preferable. The number average molecular weight used here is obtained from the terminal group based on the definition given in the examples.

The proportion of chloroformate groups in all the terminal groups of the chloroformate-containing aromatic polycarbonate oligomer must be at least 50% or more, preferably 55 mol% or more. When the proportion of the chloroformate group is 50 mol% or less, the molecular weight does not increase even if the phenyl carbonate group-containing aromatic polycarbonate oligomer produced from the obtained chloroformate group-containing aromatic polycarbonate oligomer is melt-polymerized as a raw material.

Next, in the present invention, an aromatic polycarbonate oligomer having a chloroformate end group is reacted with an excess amount of a monofunctional phenol compound to produce an aromatic polycarbonate oligomer having a phenyl carbonate end group.

Examples of monofunctional phenol compounds used for such purposes include those represented by the general formula (II)

[0030]

[Chemical 4]

(In the formula, R, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and 6 carbon atoms
To 30 optionally substituted aryl groups, m
Is 1 to 4) and the like. Specific examples include cresol, methoxyphenol, tert-
Butylphenol, aminophenol, hexylphenol, octylphenol, cumylphenol, phenylphenol, xylenol and the like can be mentioned.

In producing the phenyl carbonate end group-containing aromatic polycarbonate oligomer, the chloroformate group-containing aromatic polycarbonate oligomer dissolved in an organic solvent and an aqueous alkaline salt solution of a monofunctional phenol compound are mixed and reacted.

At this time, a salt of a phenol compound (phenolate) which reacts with the chloroformate group in the oligomer.
Is 1 to 10 mol, preferably 1.05 to 3 mol, per mol of the chloroformate group. 1 mol of phenolate to 1 mol of chloroformate group in oligomer
If it is less than the molar amount, there is a problem that the reaction is not completed and unreacted chloroformate groups remain, or the molecular weight of the oligomer increases during the reaction with the phenolate. If the phenolate exceeds 10 moles, it is industrially disadvantageous because the number of washing steps for removing the residual phenol compound from the organic solvent increases.

Further, in the reaction of the phenol compound with the chloroformate group-containing aromatic polycarbonate oligomer, the phenol compound which is not an alkali salt is 0 to 10 moles, preferably 0 to 1 mole of the chloroformate group. It is also possible for 3 mol to be present.

In the reaction of the chloroformate group-containing aromatic polycarbonate oligomer and the phenol compound, the pH of the aqueous layer in the reaction mixture is preferably 10-12. When the pH is lower than 10, the reaction proceeds slowly because the amount of phenolate in the aqueous layer is small. On the other hand, when the pH of the aqueous layer exceeds 12, the molecular weight of the oligomer tends to increase during the reaction, which is unsuitable for producing an oligomer soluble in a non-halogen organic solvent.

In the reaction of a chloroformate group-containing aromatic polycarbonate oligomer with a phenol compound,
The emulsion may be of W / O type or O / W type, but the volume ratio of the water layer and the oil layer is 0.1: 1.0 to 2.0 :.
A range of 1.0 is preferred. Volume ratio of water layer and oil layer is 0.1
In the following cases, it becomes difficult to charge the alkali salt of the phenol compound in excess with respect to the chloroformate group in the oligomer. Further, when the volume ratio of the water layer and the oil layer is 2 or more, the amount of the chloroformate group-containing aromatic polycarbonate oligomer charged per batch becomes small, resulting in poor productivity.

In carrying out the reaction of the chloroformate group-containing aromatic polycarbonate oligomer with the phenolate, the reaction may be carried out without a catalyst, but if necessary, a known catalyst used in a usual interfacial method may be used. It can also be added. Specifically as such a catalyst,
Tertiary amines such as triethylamine and tripropylamine, and quaternary salts of amines such as benzyltributylammonium chloride are used.

The molecular weight of the obtained aromatic polycarbonate oligomer containing a phenylcarbourate group can be adjusted by selecting appropriate reaction conditions. In order to make it soluble in a non-halogen solvent, a phenolate is used. It is necessary to suppress the increase in molecular weight during the reaction. The term "soluble state" as used herein means that when a phenyl carbonate group-containing polycarbonate oligomer obtained by using, for example, Kiriyama funnel filter paper No. 5C (capture particle size of 1 micron or more) is filtered, solid matter is present on the filter paper. It refers to things that do not remain.

The solubility of the phenyl carbonate group-containing aromatic polycarbonate oligomer varies greatly depending on the type of solvent, temperature, average molecular weight of the oligomer, and molecular weight distribution. When the reaction is carried out at 25 ° C. using a non-halogen organic solvent, the number average degree of polymerization of the phenyl carbonate group-containing aromatic polycarbonate oligomer is 3,000.
It is necessary to be 2,000 or less, preferably 2,000 or less, more preferably 1,000 or less. Here, the number average molecular weight of the oligomer is calculated from the amount of end groups by the formula shown in the examples.

The molecular weight distribution of the oligomer molecular weight is
When measured by C, the upper limit on the high molecular weight side is 10,000.
It is necessary that the molecular weight is below, and more preferably the molecular weight is below 5,000. When the oligomer having a molecular weight of 10,000 or more is contained, the solubility in an organic solvent is extremely low, so that even if the number average molecular weight satisfies the above conditions, only the high molecular weight component will be precipitated. It is unsuitable as the organic solvent-soluble aromatic polycarbonate oligomer of the invention. Here, the molecular weight of GPC is converted with a polystyrene standard.

Next, a second-stage polymerization reaction is carried out by the melting method using the obtained phenyl carbonate-terminated aromatic polycarbonate oligomer as a raw material.

At this time, it is desirable that the low-molecular-weight phenyl carbonate group-containing polycarbonate oligomer produced by the interfacial method is taken out from the solvent and used for further increasing the molecular weight by melt polymerization.

As one of the methods for extracting the oligomer, there is a method for precipitating the polycarbonate oligomer with a poor solvent. As the poor solvent, hexane, heptane, aliphatic hydrocarbons such as petroleum ether and methanol,
Alcohols such as ethanol and ethers such as diethyl ether and dipropyl ether are used.

Another method for extracting the oligomer is as follows:
A method of distilling off the solvent can also be used. To distill off the solvent, heating or reduced pressure is used according to a known method, and if necessary, heating and reduced pressure may be used together. Further, by concentrating at a high temperature, a highly concentrated phenyl carbonate group-containing aromatic polycarbonate oligomer solution can be obtained in a uniform state. For example, it is possible to continuously obtain a melt of the phenyl carbonate group-containing oligomer by continuously concentrating the solvent while gradually distilling the solvent in the extruder.

When the second-stage polymerization reaction by the melting method is performed using the obtained phenyl carbonate group-containing aromatic polycarbonate oligomer as a raw material, in addition to the phenyl carbonate terminal oligomer, the aromatic dihydroxy compound represented by the formula (I) is used. A compound may be added. At this time,
The amount of all phenyl carbonate groups is 1 to 2 equivalents, preferably 1. 2 equivalents, relative to 1 equivalent of all hydroxyl groups (the sum of hydroxyl groups in the phenyl carbonate group-containing polycarbonate oligomer and the hydroxyl groups in the added aromatic dihydroxy compound).
It is used in the range of 05 to 1.5 equivalents.

When the equivalent of all phenyl carbonate groups is less than 1 equivalent to 1 equivalent of all hydroxyl groups, a high molecular weight aromatic polycarbonate resin cannot be obtained by melt polymerization. On the other hand, if the equivalent of all phenyl carbonate groups exceeds 2 equivalents relative to 1 equivalent of all hydroxyl groups, the melting rate becomes slow, which is not preferable.

In the process for producing an aromatic polycarbonate resin of the present invention, a branched polycarbonate is prepared by adding a trifunctional or higher polyfunctional compound such as phloroglucin or 1,1,1-tris (4-hydroxyphenyl) -ethane. It is also possible to

It is also possible to add a terephthalic acid or a dicarboxylic acid such as isophthalic acid to obtain an aromatic polyester polycarbonate resin.

In the melt polymerization, the polymerization can be carried out without a catalyst, but a known melt polymerization catalyst may be added if necessary.

As the polymerization catalyst, a known transesterification catalyst or the like is used. Specifically, in addition to alkali metal or alkaline earth metal phenolates, carbonates, acetates, hydroxides, hydrides, phosphorus compounds such as phenylphosphoric acid, phenylphosphorous acid and metal salts thereof, and quinoline-5- Sulfonic acid, stearic acid monophenyl phosphate, 2
Organic acid catalysts such as -N-phenylaminobenzoic acid, ammonium such as tetramethylammonium-tetraphenylboranate, tetraphenylphosphonium-tetraphenylboranate, phosphonium borane salt catalysts, tetrabutylammonium hydroxide, trimethylbenzylammonium hydro Ammonium hydroxides such as oxides, quaternary ammonium salts such as dimethylphenylbenzylammonium chloride and benzyltributylammonium chloride, iminodiacetic acids such as iminodiacetic acid and ethylenediaminetetraacetate, 2-methylimidazole, dimethyl-4-aminopyridine, etc. Examples include amines and salts thereof.

The polymer obtained by melt polymerization can be used as a product as it is, but when an aromatic polycarbonate resin having a higher degree of polymerization is required,
It is also possible to increase the degree of polymerization by using a conventionally known reaction in an extruder or a reaction in a solid state. When performing solid phase polymerization, it is necessary to crystallize the prepolymer obtained by melt polymerization. For this purpose, crystallization with a known solvent or crystallization by heating (see the above-mentioned book by Schnell) is required. Can be used. Particularly, crystallization with a solvent is rapid and is preferably used.

The aromatic polycarbonate resin obtained in the present invention may be added with a known heat stabilizer before use to improve its heat stability. As such a heat stabilizer, a phosphorus compound such as a phosphoric acid ester or a phosphorous acid ester, or a phenol-based antioxidant such as a hindered phenol is used.

The aromatic polycarbonate resin obtained in the present invention may be modified with other resins, if necessary, or may be a filler such as glass fiber or carbon fiber, a flame retardant, a UV absorber, and a mold release agent. Agents and colorants may be added.

[0054]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

In the following examples, unless otherwise specified,
Parts means parts by weight and% means% by weight.Polycarbonate means an aromatic polycarbonate resin, chloroformate group-containing oligomer means an aromatic polycarbonate oligomer having a chloroformate group at the end,
The phenyl carbonate group-containing oligomer means an aromatic polycarbonate oligomer having a phenyl carbonate group at the end.

The measurement items in the examples were determined according to the following methods.

1. Terminal group quantification a) Chloroformate group in oligomer The chloroformate group is decomposed with an excess amount of aniline, and the produced aniline hydrochloride is quantified with alcoholic potassium hydroxide.

B) Terminal hydroxyl group in the oligomer After dissolving the oligomer in methylene chloride acidified with acetic acid, color is developed with titanium tetrachloride and quantified with a colorimeter at a wavelength of 546 nm. {Macromol. Chem. , 88, 215
(1965)} c) Terminal phenyl carbonate group in the oligomer After the oligomer was hydrolyzed with alkali, the released phenol was quantified by liquid chromatography.

2. Measurement of molecular weight i) Number average molecular weight of oligomer The number average molecular weight was calculated from the analytical value obtained by quantifying the terminal group of

Number Average Molecular Weight Mn = 2 × 10 ⁶ / (a + b + c) a: Amount of chloroformate group in the oligomer (μeq /
g) b: Amount of terminal hydroxyl groups in the oligomer (μeq / g) c: Amount of terminal phenyl carbonate groups in the oligomer (μ
eq / g) ii) Weight average molecular weight Gel permeation chromatography (GP
The value of the weight average molecular weight measured in C) was used. (Using a calibration curve based on polystyrene standards) iii) Viscosity average molecular weight Intrinsic viscosity of a methylene chloride solution at 20 ° C. {η} (d
1 / g) was measured using an Ubbelohde viscosity tube, and the viscosity average molecular weight was calculated using the following formula.

{Η} = 1.23 × 10 ⁻⁴ (Mv) ^0.83 Example 1 (Production of phenyl carbonate group-containing oligomer) Toluene solution of chloroformate group-containing oligomer (Note 1) 200 parts Note 1: Bisphenol A Toluene solution of oligomer containing chloroformate group synthesized from and phosgene Oligomer concentration 16.4 (wt%) Chloroformate group concentration 0.60 (N) Hydroxyl concentration 0.13 (N) Toluene 128 parts baffle plate, stirring After mixing and stirring in a glass reactor equipped with an apparatus and a thermometer, a mixed solution of distilled water 113 parts sodium hydroxide 6.6 parts phenol 15.6 parts hydrosulfite 0.4 parts was added. An emulsion was formed, 0.03 parts of triethylamine was added thereto, and the mixture was reacted for 90 minutes at an internal temperature of 25 to 35 ° C. No solid precipitation was observed during this interfacial reaction. After completion of the reaction, stop the stirring and add 2
The layers were separated, and the organic layer was collected and washed with a 0.2N alkaline aqueous solution, a 0.1N hydrochloric acid aqueous solution, and distilled water in this order.

A toluene solution of this oligomer was added to 165
Toluene was distilled off by heating on an oil bath at 175 ° C., and a colorless and transparent phenyl carbonate group-containing oligomer having high viscosity was recovered. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 2,100.

(Production of High-Molecular Weight Polycarbonate) 5.0 parts of phenyl carbonate group-containing oligomer 5.0 parts of bisphenol A was placed in a branched test tube with nitrogen substitution together with zeolite, and allowed to react in an oil bath at 220 ° C. and 100 mmHg for 2 hours. After that, the temperature is gradually reduced while raising the temperature, and finally 290 ° C., 0.0
A colorless and transparent polycarbonate having a viscosity average molecular weight of 22,500 was obtained by polycondensation reaction at 5 mmHg for 1 hour. No chlorine component was detected in the obtained polycarbonate.

Example 2 (Production of Phenyl Carbonate Group-Containing Oligomer) The amount of sodium hydroxide was 13.3 parts, and the amount of phenol was 3 parts.
The interface reaction between the chloroformate group-containing oligomer and the phenolate was performed in the same manner as in Example 1 except that the amount was 1.2 parts. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 1,020.

(Production of High Molecular Weight Polycarbonate) A polycarbonate having a viscosity average molecular weight of 23,200 was obtained in the same manner as in Example 1 except that 5 parts of phenyl carbonate group-containing oligomer and 0.45 part of bisphenol A were used. No chlorine component was detected in the obtained polycarbonate. Example 3 (Production of phenyl carbonate group-containing oligomer) The amount of sodium hydroxide was 6.6 parts, and the amount of phenol was 23.
The interface reaction between the chloroformate group-containing oligomer and the phenolate was carried out in the same manner as in Example 1 except that 4 parts were used. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 860.

(Production of High-Molecular Weight Polycarbonate) Phenylcarbonate group-containing oligomer 5.0 parts Bisphenol A 0.24 part was added with a nitrogen-substituted branch-containing test tube and zeolite, and the mixture was reacted in an oil bath at 220 ° C. and 100 mmHg for 2 hours. After that, the temperature is gradually reduced while raising the temperature, and finally 270 ° C., 0.0
A colorless transparent polycarbonate having a viscosity average molecular weight of 12,800 was obtained by polycondensation reaction at 5 mmHg for 1 hour.

The low-molecular-weight polycarbonate thus obtained was crystallized in acetone vapor, then heated in an inert oven under a nitrogen stream at 180 ° C. for 2 hours, and then heated to 230 ° C. The reaction was continued for 15 hours. The viscosity average molecular weight of the obtained polycarbonate is 2
It was 7,800, and no chlorine component was detected.

Example 4 (Production of phenyl carbonate group-containing oligomer) Distilled water 264 parts Sodium hydroxide 5.6 parts Phenol 13.1 parts Hydrosulfite 0.8 parts A baffle plate, a stirrer and a thermometer were attached. After charging in a glass reactor and mixing with stirring, a mixed solution of 140 parts of toluene solution of the chloroformate group-containing oligomer used in Example 1 and 90 parts of toluene was added, and the reaction was carried out in the same manner as in Example 1. The obtained oligomer was recovered. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 1,200.

(Production of High Molecular Weight Polycarbonate) Phenylcarbonate group-containing oligomer 5.0 parts Bisphenol A 0.30 part Phenylphosphoric acid disodium salt 1 × 10 ⁻⁴ parts ^{Into a} nitrogen-substituted branch-containing test tube together with a boiling stone, oil After reacting in a bath at 220 ° C. and 100 mmHg for 2 hours, the temperature is gradually reduced while raising the temperature, and finally 280 ° C. and 0.0
By performing a polycondensation reaction at 5 mmHg for 1 hour, a colorless transparent polycarbonate having a viscosity average molecular weight of 22,700 was obtained. No chlorine component was detected in the obtained polycarbonate.

Example 5 (Production of Phenylcarbonate Group-Containing Oligomer) An interfacial reaction was carried out in the same manner as in Example 1 except that the catalyst triethylamine was not added to obtain an oligomer. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 960.

(Production of High Molecular Weight Polycarbonate) Phenylcarbonate group-containing oligomer 5.0 parts Bisphenol A 0.65 part Phenylphosphoric acid disodium salt 1 × 10 ⁻⁴ parts A nitrogen-substituted branch test tube and a boiling stone were added and oil was added. After reacting in a bath at 220 ° C. and 100 mmHg for 2 hours, the temperature was gradually reduced while raising the temperature, and finally 270 ° C. and 0.0
By performing a polycondensation reaction at 5 mmHg for 1 hour, a colorless transparent polycarbonate having a viscosity average molecular weight of 13,800 was obtained.

The prepolymer thus obtained was crystallized in acetone vapor and then heated in an inert oven under a nitrogen stream at 180 ° C. for 2 hours, after which 23
The temperature was raised to 0 ° C. and the reaction was continued for 15 hours. The viscosity average molecular weight of the obtained polycarbonate is 29,300,
No chlorine component was detected.

Comparative Example 1 (Production of Oligomer Containing Phenyl Carbonate Group) Except that the amount of sodium hydroxide was 4.3 parts and the amount of phenol was 10 parts (0.8 equivalent to 1 equivalent of chloroformate group). In the same manner as in Example 1, the interfacial reaction between the chloroformate group-containing oligomer and the phenolate was performed. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 1,250.

(Production of High Molecular Weight Polycarbonate) Polymerization was carried out in the same manner as in Example 1 except that 5 parts of the phenyl carbonate group-containing oligomer and 0.13 part of bisphenol A were used, but a high molecular weight polycarbonate was not obtained. ..

Comparative Example 2 (Production of phenylcarbonate group-containing oligomer) The amount of sodium hydroxide was 9.0 parts, and the amount of phenol was 15.
The interface reaction between the chloroformate group-containing oligomer and the phenolate was carried out in the same manner as in Example 1 except that the amount was changed to 6 parts. The pH at this time was 13.8. After the completion of the reaction, some oligomers were precipitated. The number average molecular weight of the obtained phenyl carbonate group-containing oligomer was 3,300.

(Production of High-Molecular Weight Polycarbonate) In the same manner as in Example 1 except that 5 parts of phenyl carbonate group-containing oligomer and 0.65 part of bisphenol A were used.
A polycarbonate having a viscosity average molecular weight of 22,700 was obtained. The resulting polycarbonate contains 10 chlorine components.
ppm was detected.

[0077]

The aromatic polycarbonate resin produced by the method of the present invention does not contain halogen at all, and therefore has excellent thermal stability and does not cause problems such as corrosion of the mold during molding. Therefore, it can be suitably used for applications where an aromatic polycarbonate resin has been conventionally used such as injection molding, extrusion molding and blow molding.

Further, in the method for producing an aromatic polycarbonate resin of the present invention, since a halogen-based solvent such as methylene chloride is not used, there is no fear of polluting the environment.

Claims (1)

[Claims] 1. A chlorocarbonate group-containing aromatic polycarbonate oligomer is reacted with a monofunctional phenol compound to produce a phenyl carbonate group-containing aromatic polycarbonate oligomer, which is further subjected to a high degree of polymerization using a transesterification method. To produce an aromatic polycarbonate resin, a chloroformate group-containing aromatic polycarbonate oligomer dissolved in a non-halogen solvent, and 1 to 10 per 1 equivalent of the chloroformate group
A phenyl carbonate group-containing aromatic polycarbonate oligomer soluble in a non-halogen organic solvent is produced by interfacial reaction with an equivalent amount of an aqueous solution of an alkali salt of a monofunctional phenolic compound under the condition that the pH of the reaction solution is 12 or less. A method for producing a halogen-free aromatic polycarbonate resin, which comprises using this as a raw material for melt polymerization and / or solid phase polymerization.