KR100413534B1 - Method for preparing aromatic polycarbonate - Google Patents

Abstract

The present invention provides a method for producing an aromatic polycarbonate, characterized in that the carbon monoxide (CO) and the carbonylation of the aromatic diol and organic monool at the same time in the presence of an oxidizing agent. According to the present invention, since bisphenol-A and phenol can be reacted with carbon monoxide and an oxidizing agent to directly prepare a polycarbonate precursor, diphenyl carbonate and dimethyl carbonate adopted in the conventional commercial phosgene-free polycarbonate manufacturing process are separately provided. Since there is no need to manufacture, it is possible to reduce at least two or more synthetic processes, thereby economically synthesizing aromatic polycarbonates.

Description

Method for preparing aromatic polycarbonate {Method for preparing aromatic polycarbonate}

The present invention relates to a method for producing an aromatic polycarbonate, and more particularly, to a method for producing an aromatic polycarbonate by oxidative carbonylation of an aromatic diol such as bisphenol-A and an organic monool such as phenol. It is about.

Polycarbonate is a thermoplastic resin, an engineering plastic with excellent mechanical properties, heat resistance, and electrical properties. It has been manufactured through interfacial polycondensation with bisphenol-A using toxic phosgene, but it is not dangerous and environmentally unfriendly. Due to the process, the phosgene-free synthetic route of FIG. 1 has been proposed and is currently in progress for commercialization.

Referring to FIG. 1, first, dimethyl carbonate is obtained through carbonylation reaction of methanol in the presence of carbon monoxide and oxygen gas. Then, the dimethyl carbonate obtains methylphenyl carbonate through transesterification with phenol, and further proceeds its disproportionation or transesterification to synthesize diphenyl carbonate. The diphenyl carbonate thus obtained is converted into a precursor (MpC) having a monophenyl carbonate end group which is a polycarbonate precursor through a transesterification reaction with bisphenol-A.

Thereafter, a high molecular weight polycarbonate is produced through the self-condensation polymerization of the MpC. At this time, the molecular weight of the polymer polycarbonate is controlled according to the degree of removal of phenol produced as a by-product.

On the other hand, the oligomer obtained through oxidative carbonylation of bisphenol-A only represented by the following structural formula is an oligomer having a dihydroxy end group, and the compound is disclosed in US Pat. No. 4,187,242 and US Pat. No. 4,201,721.

According to US Pat. No. 4,187,242, DH (n = 1-5) was synthesized by carbonylating bisphenol-A, carbon monoxide and oxygen as reactants. US Patent No. 4,201,721 discloses the synthesis of DH (n ≦ 5) polycarbonate oligomers by carbonylation of only bisphenol-A.

However, according to the methods disclosed in the above patents, the catalytic reaction rotation was less than 100, so the catalytic activity was not very good.

On the other hand, the carbonylation reaction of bisphenol-A alone is carried out using a catalyst system comprising palladium chloride, copper acetate, cerium acetate, tetrabutylammonium bromide, hydroquinone, methylene chloride solvent and activated 3 ′ molecular sieve as a catalyst. Has been reported (Polymer, 40, pp 3237-3241, 1999 Polymer 41, pp 2289-2293, 2000). According to the contents of this paper, an oligomer of DH (n) form having an average molecular weight of about 3600 was obtained through a one-step oxidative carbonylation reaction, and an oligomer of DH (n) form having an average molecular weight of about 4000 was used as a starting material. After the two-step oxidation carbonylation reaction, a polycarbonate having a DH (n) form having a molecular weight of 33,000 was obtained.

By the way, the contents of the paper described above are bisphenol-A as a reactant, and carbonylation thereof to prepare polycarbonate oligomer of DH (n) form.

The technical problem to be achieved by the present invention is to provide a method for economically producing an aromatic polycarbonate compared to the conventional phosgene-free polycarbonate manufacturing process.

1 is a view showing a synthetic path of a polycarbonate not using a phosgene according to the prior art,

2 is a view showing a synthetic path of the polycarbonate according to an embodiment of the present invention.

In order to achieve the above technical problem, the present invention provides a method for producing an aromatic polycarbonate, characterized in that the carbon monoxide is oxidized at the same time in the presence of carbon monoxide (CO) and an oxidizing agent.

The present invention provides a method for economically synthesizing polycarbonates by simultaneously carbonylating aromatic diols and organic monools in the presence of carbon monoxide and an oxidant. Examples of the aromatic diol include dihydroxy oligomers obtained by carbonylation of bisphenol-A, bisphenol-A derivatives and bisphenol-A; Dihydroxy diphenyl and isomers thereof; Dihydroxy naphthalene and isomers thereof; 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) octane, 4,4 ' -Dihydroxy-2,2,2-triphenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane , 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tertbutylphenyl) propane, isomers thereof and oxidation thereof At least one selected from the group consisting of dihydroxy compounds obtained by carbonylation is used.

The organic monool may be an unsubstituted or substituted aromatic ring hydroxy compound having 5 to 30 carbon atoms, an unsubstituted or substituted aliphatic hydroxy compound having 1 to 15 carbon atoms, an unsubstituted or substituted carbon atom having 3 to 10 carbon atoms. At least one selected from the group consisting of cycloaliphatic hydroxy compounds is used. Examples of the unsubstituted or substituted aromatic ring hydroxy compound having 6 to 30 carbon atoms include phenol; Cresol, xylenol, trimethylphenol, tetramethylphenol, ethylphenol, propylphenol, butylphenol, diethylphenol, methylethylphenol, methylpropylphenol, diethylphenol, dipropylphenol, methylbutylphenol, pentylphenol, hexyl Alkyl phenols such as phenol and cyclohexylphenol, and isomers thereof; Various alkoxyphenols such as methoxyphenol, ethoxyphenol, butoxyphenol, and isomers thereof; Various halogenated phenols such as fluorophenol, chlorophenol, bromophenyl, chloromethylphenyl and dichlorophenyl, and isomers thereof; Naphthol, substituted naphthols and isomers thereof; Heteroaromatic hydroxy compounds such as hydroxypyridine, hydroxycoumarin, hydroxyquinoline, isomers thereof; Arylalkyl alcohols such as benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol, phenyl butyl alcohol and methylbenzyl alcohol and the like, and isomers thereof.

And specific examples of the unsubstituted or substituted aliphatic hydroxy compound having 1 to 15 carbon atoms include methyl alcohol, ethyl alcohol, propyl alcohol, allyl alcohol, butyl alcohol, butenyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl Alcohols, nonyl alcohols, decyl alcohols, cyclohexylmethyl alcohols, isomers thereof. Specific examples of the unsubstituted or substituted alicyclic hydroxy compound having 3 to 10 carbon atoms include cyclopropyl alcohol, cyclobutyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, cycloheptyl alcohol, isomers thereof, and the like.

The organic monool of the present invention is more preferably at least one selected from the group consisting of phenol, cresol, xylenol, cumylphenol, methanol, ethanol, propanol, isobutanol and isomers thereof.

The content of the organic monool is preferably 0.01 to 10 moles with respect to 1 mole of the aromatic diol, and the yield of the aromatic polycarbonate is excellent when the organic monool is in the above range.

In addition, the oxidizing agent is not particularly limited, and air, oxygen gas, oxygen liquid, and the like may be used, and in particular, it is preferable to use oxygen gas. The oxidizing agent is used in a stoichiometric amount such that the aromatic diol and the organic monoalcohol can be reacted to obtain the desired aromatic carbonate.

On the other hand, carbon monoxide is used in a stoichiometric amount enough to obtain the desired aromatic carbonate by reacting the aromatic diol and organic monoalcohol. In general, carbon monoxide gas is supplied in the pressure range of about 0.01 to 20 MPa.

In the present invention, the reaction apparatus is not particularly limited, and generally, a batch liquid phase reactor is used.

In the oxidation carbonylation reaction of the present invention, the catalyst system is composed of a main catalyst and an inorganic promoter, an organic promoter to assist in the reoxidation of the main catalyst, and an appropriate base for activating aromatic diol and organomono alcohol.

As the main catalyst, a group VIII B element or a group VIII B element-containing compound is used. The group VIII element is a metal selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), osbium (Os), iridium (Ir), platinum (Pt), and the Group VIII B element As the containing compound, a metal oxide selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), osbium (Os), iridium (Ir), platinum (Pt) or a metal containing salt thereof is used. The Group VIII B element-containing salts include Group VIII B-containing acetates, nitrates, acetylacetonates, halides, sulfates, oxalates, carbonates, propionates, hydroxides, tartrates, and the like. More specific examples include palladium, rhodium, ruthenium acetate, chloride, bromide, nitrate salts and the like.

As the inorganic promoter, at least one metal selected from among cerium (Ce), copper (Cu), cobalt (Co), manganese (Mn), and lead (Pb), a metal oxide, or a metal containing salt thereof is used. Specific examples of the metal-containing salts here include cerium acetate monohydrate, cerium carbonate, cerium chloride, cerium nitrate, copper acetate, copper nitrate, copper (I) chloride, copper (II) chloride, copper carbonate, copper (I) oxide , Copper (II) oxide, cobalt acetate, cobalt acetylacetonate, cobalt carbonate, cobalt chloride, manganese acetate, manganese carbonate, manganese carbonyl compounds and the like. More specific examples are copper acetate, copper nitrate, copper (I) oxide, cerium acetate, cerium nitrate, cobalt acetate, manganese carbonate.

As the organic promoter, at least one selected from the group consisting of benzoquinone, hydroquinone, anthraquinone, naphthaquinone, quinoline and the like and derivatives thereof is used.

In addition, the base may be used as long as it is a compound capable of activating an aromatic diol and an organomono alcohol, and specific examples of such a base include alkali metal and alkaline earth metal; Quaternary ammonium compounds, quaternary phosphonium compounds or tertiary sulfonium compounds, alkali or alkaline earth metal hydroxides, salts of strong bases and weak acids, primary, secondary or secondary amines may be used and one or two of them for proper activation. Can be used over. Specific examples of such compounds include metals such as lithium, sodium, potassium, magnesium, and the like; Quaternary ammonium hydroxides; Tetraethyl phosphonium hydroxide; Sodium, potassium, lithium and potassium hydroxides, carbonates; Tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium iodide; Quaternary phosphonium; Tertiary sulfonium; Sodium acetate, sodium benzoate, sodium methylate, sodium thiosulfate, sodium hydride, sodium borohydride, potassium fluoride; Triethylamine, trimethylamine, allyldiethylamine, benzyldimethylamine, dioctylbenzylamine, dimethylphenethylamine, 1-dimethylamino-2-phenyl-propane, N, N, N ', N'-tetramethylenediamine , 2,2,6,6-tetramethylpyridine, N-methyl piperidine, pyridine, 2,2,6,6, N-pentamethylpiperidine; is used.

The content of the main catalyst is 0.00001 to 0.1 mol based on 1 mol of aromatic diol, the content of the inorganic promoter is 0.001 to 0.2 mol, the content of the organic promoter is 0.001 to 0.2 mol, The content is used from 0.001 to 2 moles.

In addition, the carbonylation reaction of this invention does not necessarily need to use a solvent. However, when using a solvent, the reaction is made more smoothly. In this case, any solvent may be used as long as it has compatibility with an aromatic diol and an organic monool, and specific examples thereof include tetrahydrofuran, methylene chloride, chlorobenzene, anisol, benzene, toluene, pentanone, and cyclohexane. Fluorobenzene, nitrobenzene, N, N-dimethylacetamide, 1-methyl-2-pyrrolidinone, normal hexane, dimethyl ether, dimethyl carbonate and the like. And the content of this solvent is used from 0.001 to 50 parts by weight based on 1 part by weight of aromatic diol.

Hereinafter, a method of manufacturing a polycarbonate according to an exemplary embodiment of the present invention will be described with reference to the accompanying drawings. In this embodiment, bisphenol-A is used as the aromatic diol, phenol is used as the organic monool, O ₂ gas is used as the oxidizing agent, palladium acetate as the main catalyst and cerium acetate as the inorganic promoter. , Benzoquinone as an organic promoter and tetrabutylammonium bromide as a base are used.

Referring to FIG. 2, a solvent and a carbonylation catalyst are added to bisphenol-A and phenol, and carbonylation is simultaneously performed under carbon monoxide and oxygen gas atmosphere to obtain a precursor (MpC) having a monophenyl carbonate terminal. Wherein n is 1 to 10 and the weight average molecular weight of this MpC is in the range of 350 to 3000.

In the oxidative carbonylation reaction, removal of water generated as a reaction by-product using a dehydrating agent may increase the yield of MpC. In this case, an activated 3 ′ or 4 ′ molecular sieve is used as the dehydrating agent.

It is preferable that the temperature of the said oxidation carbonylation reaction is 50-200 degreeC. If the reaction temperature is less than 50 ℃, there is a problem that the activation of the reactants is very low, if it exceeds 200 ℃ there is a problem that the absorption of carbon monoxide and oxygen in the solvent and adsorption to the catalyst is very low and by-products increase.

The content of the phenol is 0.01 to 10 moles based on 1 mole of bisphenol-A, oxygen gas is supplied in a pressure range of about 0.001 to 5 MPa, carbon monoxide gas is supplied in a pressure range of about 0.01 to 20 MPa do.

Tetrahydrofuran, methylene chloride, chlorobenzene, anisol, cyclohexane and the like are used as the solvent, and the content thereof is used in an amount of 0.001 to 50 parts by weight based on 1 part by weight of bisphenol-A.

Thereafter, the polycarbonate having a high molecular weight can be obtained by self-condensation of the MpC obtained according to the above process while distilling phenol off. At this time, the self-condensation polymerization is carried out by continuously removing phenol at a temperature of 200 to 350 ° C. and a vacuum of 400 to 0.01 Torr under a catalyst of a general ester exchange reaction.

In the above-mentioned carbonylation reaction, palladium acetate, cerium acetate, benzoquinone is used as the catalyst system, tetrabutylammonium bromide as the base and tetrahydrofuran as the solvent are used.

The reaction product prepared by the preparation method of the present invention confirms its structure and quantification through qualitative and quantitative analysis using reverse phase liquid chromatography, gas chromatography and mass spectrometry.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited only to the following examples.

<Example 1>

100㎖ addition of bisphenol -A with phenol 30mmol 30mmol in a high pressure reactor (Parr) and, where the _{(CH 3 C0 2) 2 Pd} 0.06mmol, (CH 3 C0 2) 2 Ce · H 2 0 0.3mmol, [CH 3 (CH ₂ ) ₃ )] ₄ NBr 1.5 mmol, benzoquinone 1.5 mmol and tetrahydrofuran 30 ml were added, and then oxygen gas was purged into the reactor. 5 MPa of carbon monoxide gas and 0.5 MPa of oxygen gas were continuously fed into the reactor, and the reaction mixture was stirred. The temperature of the reaction mixture was then raised to 100 ° C. using an electric furnace and allowed to react at this temperature for 4 hours.

Upon completion of the reaction, the reactor was cooled with ice water to give a reaction product. At this time, the reaction product was analyzed by reverse phase liquid chromatography and gas chromatography.

Reverse phase liquid chromatography analysis showed the main products of MpC (n = 1) 3.0mmol, MpC (n = 2) 0.2mmol, DH (n = 1) 3.65mmol, DH (n = 2) 0.3mmol, and MpC and DH with n of 3 to 5 were observed to decrease with increasing n. The conversion rate of bisphenol-A was about 45%, bisphenol-A per mole of palladium was 226 or more, and the side reactions showed mass selectivity of 13% relative to the total product.

As a result of gas chromatography analysis, the conversion rate of phenol was 15%, and the rotational speed of catalysis of phenol per mol of palladium was 75. 0.3 mmol of diphenyl carbonate was formed and present in the reactor.

Synthesis of DH (n) by the carbonylation of bisphenol-A from Example 1 and the synthesis of MpC polycarbonate precursor in the same reactor through the co-oxidation carbonylation reaction of bisphenol-A and phenol in one reactor I could see that.

<Example 2>

The carbonylation reaction was carried out in the same manner as in Example 1, except that 4 g of the 3 ′ molecular sieve activated by dehydration at 400 ° C. was added during the reaction of bisphenol-A with phenol.

Upon completion of the reaction, the reactor was cooled with ice water to give a reaction product. At this time, the reaction product was analyzed by reverse phase liquid chromatography and gas chromatography.

Reversed-phase liquid chromatography analysis showed that the conversion of bisphenol-A was increased to about 65%, the number of bisphenol-A catalysts per mole of palladium was above 325, and the side reactions were reduced to 7% mass selectivity relative to the total product. In addition, the mass selectivity of DH (n) was reduced by more than 13% compared with the other case (Example 1) by using 3Å molecular sieve, and thus the composition of MpC (n = 1) and MpC (n = 2). Increased.

As a result of gas chromatography analysis, the conversion of phenol increased to about 25% and the number of rotations of catalysis of phenol per mole of palladium was 130.

It can be seen from Example 2 that the conversion of each reactant and the selectivity to MpC can be increased by removing the byproduct water in the synthesis of the polycarbonate precursor MpC by the co-oxidation carbonylation of bisphenol-A and phenol. there was.

Comparative Example 1

100㎖ addition of bisphenol -A 30mmol in a high pressure reactor (Parr), and here, _{(CH 3 C0 2) 2 Pd} 0.06mmol, (CH 3 C0 2) 2 Ce · H 2 0 0.3mmol, [CH 3 (CH 2 ₃ )] ₄ NBr 1.5 mmol, benzoquinone 1.5 mmol and 30 ml tetrahydrofuran were added, and then oxygen gas was purged into the reactor. 5 MPa of carbon monoxide gas and 0.5 MPa of oxygen gas were continuously fed into the reactor, and the reaction mixture was stirred. The temperature of the reaction mixture was then raised to 100 ° C. using an electric furnace and allowed to react for 4 hours at ionicity.

After the reaction was completed, the reactor was cooled with ice water to obtain a reaction product. At this time, the reaction product was analyzed by reverse phase liquid chromatography.

Reversed phase liquid chromatography analysis showed that DH (n = 1) 4.55 mmol, DH (n = 2) 0.5 mmol, and DH (n = 3) and DH (n = 4) in small amounts, DH (n = 5) A small amount was observed. The conversion rate of bisphenol-A was about 42%, and the bisphenol-A rotation rate per mole of palladium was 210. No polycarbonate precursor and diphenylcarbonate in MpC form were produced.

It can be seen from Comparative Example 1 that DH (n) is produced by carbonylation of bisphenol-A. Therefore, it was confirmed that MpC (n) is produced only under reaction conditions in which bisphenol-A and phenol are present at the same time.

Comparative Example 2

Adding a phenol to 30mmol 100㎖ high pressure reactor (Parr), and here, _{(CH 3 C0 2) 2 Pd} 0.06mmol, (CH 3 C0 2) 2 Ce · H 2 0 0.3mmol, [CH 3 (CH 2) 3 )] ₄ NBr 1.5 mmol, benzoquinone 1.5 mmol and tetrahydrofuran 30 ml were added, and then oxygen gas was purged into the reactor. 5 MPa of carbon monoxide gas and 0.5 MPa of oxygen gas were continuously fed into the reactor, and the reaction mixture was stirred. The temperature of the reaction mixture was then raised to 100 ° C. using an electric furnace and allowed to react for 4 hours at ionicity.

After the reaction was completed, the reactor was cooled with ice water to obtain a reaction product. At this time, the reaction product was analyzed by reverse phase liquid chromatography and gas chromatography.

Reversed phase liquid chromatography analysis showed no polycarbonate oligomer DH (n) or polycarbonate precursor MpC.

Gas chromatographic analysis showed that the conversion of phenol was about 8%, the catalytic reaction speed of phenol per mole of palladium was 40 and 0.85 mmol of diphenyl carbonate was produced.

It can be seen from Comparative Example 2 that diphenyl carbonate is produced by carbonylation of phenol. Therefore, it was confirmed that MpC (n) is produced only under reaction conditions in which bisphenol-A and phenol are present at the same time.

Comparative Example 3

100㎖ addition of bisphenol -A and 30mmol of diphenyl carbonate 4.5mmol a high pressure reactor (Parr) and herein _{(CH 3 C0 2) 2 Pd} 0.06mmol, (CH 3 C0 2) 2 Ce · H 2 0 0.3mmol, [CH ₃ (CH ₂ ) ₃ )] ₄ NBr 1.5 mmol, benzoquinone 1.5 mmol and tetrahydrofuran 30 ml were added, and then oxygen gas was purged into the reactor. 5 MPa of carbon monoxide gas and 0.5 MPa of oxygen gas were continuously fed into the reactor, and the reaction mixture was stirred. The temperature of the reaction mixture was then raised to 100 ° C. using an electric furnace and allowed to react for 4 hours at ionicity.

Upon completion of the reaction, the reactor was cooled with ice water to give a reaction product. At this time, the reaction product was analyzed by reverse phase liquid chromatography and gas chromatography.

Reversed phase liquid chromatography analysis showed MpC (n = 1) 2.4 mmol, MpC (n = 2) 0.35 mmol, DH (n = 1) 4.50 mmol, DH (n = 2) 0.83 mmol, and MpC (n = 3) , MpC (n = 4), DH (n = 3), DH (n = 4), etc. were generated in small amounts, and only a small amount of MpC (n = 5) and DH (n = 5) having n of 5 were observed. The conversion rate of bisphenol-A was about 58%, and the rotation rate of the catalytic reaction of bisphenol-A per mol of palladium was 288. The conversion of diphenyl carbonate was 70% and 1.4 mmol of unreacted diphenyl carbonate was present.

The polycarbonate precursor of MpC type can be obtained through the transesterification reaction of bisphenol-A with diphenyl carbonate in addition to the reaction in which the polycarbonate oligomer of DH form is produced by oxidative carbonylation of bisphenol-A itself from Comparative Example 3 I could confirm that there is.

However, although the content of the diphenyl carbonate used in Comparative Example 3 is 22% more than the number of moles of the molecules having the total phenyl carbonate groups generated from Example 1, the content of MpC obtained according to Comparative Example 3 is Example 1 Was smaller than the case. From these results, in simultaneous carbonylation of bisphenol-A and phenol, the formation and desorption of MpC by adsorption of bisphenol-A and carbon monoxide and adsorption of phenol in the palladium catalyst occurs through one catalyst rotation. MpC was also included. Here the adsorption of bisphenol-A and phenol occurs in any order.

With this catalytic reaction system, at least four catalytic reactions occur simultaneously.

2 (bisphenol-A) + CO + 1/2 O ₂ → DH (n) + H ₂ O

2phenol + CO + 1/2 O ₂ → diphenyl carbonate + H ₂ O

Bisphenol-A / DH + diphenylcarbonate → MpC (n) + phenol

Bisphenol-A / DH + phenol + CO + 1/2 O ₂ → MpC (n) + H ₂ O

The phenol produced in the transesterification reaction of Scheme 3 is again used as reactants of Schemes 2 and 4, and as the molecular weight of the resulting polycarbonate precursor (MpC) increases, the theoretically necessary content of phenol is inversely proportional as follows.

Moles of phenol required = 1 / n

In the formula, n represents the number of monomers of the polycarbonate precursor MpC.

As described above, according to the present invention, when bisphenol reacts with phenol, carbon monoxide and oxygen gas, water is produced as a by-product. The water thus produced is removed using a dehydrating agent such as a molecular sieve to enable complete conversion of bisphenol-A and high-selective synthesis of MpC, a polycarbonate precursor.

When the polycarbonate precursor is synthesized through carbonylation according to the present invention, the transesterification of diphenyl carbonate produced from phenol with an aromatic diol such as bisphenol-A is carried out with the carbonylation reactions of bisphenol-A with phenol. Simultaneously in the reactor, the simultaneous carbonylation reaction of bisphenol-A and phenol is higher than the carbonylation reaction of bisphenol-A or oxidative carbonylation of phenol itself and the side reactions A synergistic effect of suppressing the formation of can be obtained. In particular, according to the present invention, since bisphenol-A and phenol can be reacted in the presence of carbon monoxide and an oxidizing agent to directly prepare a polycarbonate precursor, diphenyl carbonate and dimethyl carbonate adopted in the conventional phosgene-free polycarbonate manufacturing process are used. No separate manufacturing process is necessary. Therefore, at least two or more synthetic processes can be reduced compared to the polycarbonate manufacturing method according to the conventional phosgene-free technology, thereby economically synthesizing the aromatic polycarbonate.

Claims (11)

A method for producing an aromatic polycarbonate, wherein the carbon monoxide is oxidized at the same time in the presence of carbon monoxide (CO) and an oxidizing agent. The method of claim 1, wherein the aromatic diol, Dihydroxy oligomers obtained by carbonylation of bisphenol-A, bisphenol-A derivatives and bisphenol-A; Dihydroxy diphenyl and isomers thereof; Dihydroxy naphthalene and isomers thereof; 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 2,2-bis (4-hydroxyphenyl) octane, 4,4 ' -Dihydroxy-2,2,2-triphenylethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane , 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tertbutylphenyl) propane, isomers thereof and oxidation thereof Dihydroxy compound obtained by carbonylation; Method for producing an aromatic polycarbonate, characterized in that at least one selected from the group consisting of. The method according to claim 1, wherein the organic monool, Unsubstituted or substituted aromatic ring hydroxy compound having 5 to 30 carbon atoms, Unsubstituted or substituted aliphatic hydroxy compound having 1 to 15 carbon atoms, and Unsubstituted or substituted C3-C10 alicyclic hydroxy compound Method for producing an aromatic polycarbonate, characterized in that at least one selected from the group consisting of. The method of claim 1, wherein the organic monool is at least one selected from the group consisting of phenol, cresol, xylenol, cumylphenol, methanol, ethanol, propanol, isobutanol and isomers thereof. . The method for producing an aromatic polycarbonate according to claim 1, wherein the oxidant is oxygen gas. The method of claim 1, wherein in the oxidation carbonylation reaction, A method for producing an aromatic polycarbonate, wherein a group VIII B element or a group VIII B element-containing compound is used as the main catalyst. The method of claim 6, wherein the Group VIII B element, Metal selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), osbium (Os), iridium (Ir), platinum (Pt), The VIII group B element-containing compound, A method of producing an aromatic polycarbonate, characterized in that the metal oxide selected from ruthenium (Ru), rhodium (Rh), palladium (Pd), osbium (Os), iridium (Ir), platinum (Pt) or the metal-containing salt. The method of claim 6, wherein an inorganic promoter is further used to assist in the reoxidation of the main catalyst, The inorganic promoter is at least one metal selected from the group consisting of cerium (Ce), copper (Cu), cobalt (Co), manganese (Mn), lead (Pb), metal oxides thereof, or metal containing salts thereof. Method for producing an aromatic polycarbonate, characterized in that. The method of claim 6, wherein an organic promoter is further used to assist in the reoxidation of the main catalyst, The organic promoter is a method for producing an aromatic polycarbonate, characterized in that using at least one selected from the group consisting of benzoquinone, hydroquinone, anthraquinone, naphthaquinone, quinoline. The method for producing an aromatic polycarbonate according to claim 6, wherein a base for activating aromatic diol and organomono alcohol is further used for the main catalyst. The method according to claim 10, wherein the base, Lithium, sodium, potassium, magnesium; Quaternary ammonium hydroxides; Tetraethyl phosphonium hydroxide; Sodium, potassium, lithium and potassium hydroxides, carbonates thereof; Tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium iodide; Quaternary phosphonium; Tertiary sulfonium; Sodium acetate, sodium benzoate, sodium methylate, sodium thiosulfate, sodium hydride, sodium borohydride, potassium fluoride; Triethylamine, trimethylamine, allyldiethylamine, benzyldimethylamine, dioctylbenzylamine, dimethylphenethylamine, 1-dimethylamino-2-phenyl-propane, N, N, N ', N'-tetramethylenediamine Aromatic, characterized in that at least one selected from the group consisting of, 2,2,6,6-tetramethylpyridine, N-methyl piperidine, pyridine, 2,2,6,6, N-pentamethylpiperidine Method for producing polycarbonate.