Salts of aryl sulfonic acids as polymerization catalysts

Abstract

This invention relates to salts of aryl sulfonic acids useful in catalyst systems in melt polymerizations. Suitable alkali metal salts of aryl sulfonic acids include alkali metal salts of p-toluenesulfonic acid. The invention further relates to polycarbonates prepared using the catalyst systems of the present invention, and articles made from these polycarbonates.

Description

FIELD OF THE INVENTION

This invention relates to salts of aryl sulfonic acids useful in catalyst systems in melt polymerizations. Suitable alkali metal salts of aryl sulfonic acids include alkali metal salts of p-toluenesulfonic acid. The invention further relates to polycarbonates prepared using the catalyst systems of the present invention, and articles made from these polycarbonates.

BACKGROUND OF THE INVENTION

Conventional industrial plants synthesize polycarbonate by mixing together an aqueous solution of dihydric compound (e.g., bisphenol-A) with an organic solvent (e.g., dichloromethane) containing a carbonyl halide (e.g., phosgene) Upon mixing the immiscible organic and aqueous phases, the dihydric compound reacts with the carbonyl halide at the phase interface. Typically, a phase transfer catalyst, such as a tertiary amine, is added to the aqueous phase to enhance this reaction. This synthesis method is commonly known as the “interfacial” synthesis method for preparing polycarbonate.

The interfacial method for making polycarbonate has several inherent disadvantages. First it is a disadvantage to operate a process which requires phosgene as a reactant due to obvious safety concerns. Second it is a disadvantage to operate a process which requires using large amounts of an organic solvent because expensive precautions must be taken to guard against any adverse environmental impact. Third, the interfacial method requires a relatively large amount of equipment and capital investment. Fourth, the polycarbonate produced by the interfacial process is prone to having inconsistent color, higher levels of particulates, and higher chlorine content, which can cause corrosion.

Some new commercial polycarbonate plants synthesize polycarbonate by a transesterification reaction whereby a diester of carbonic acid (e.g., diphenylcarbonate) is condensed with a dihydric compound (e.g., bisphenol-A). This reaction is performed without a solvent, and is driven to completion by mixing the reactants under reduced pressure and high temperature with simultaneous distillation of the phenol produced by the reaction. This synthesis technique is commonly referred to as the “melt” technique. The melt technique is superior over the interfacial technique because it does not employ phosgene, it does not require a solvent, and it uses less equipment. Moreover, the polycarbonate produced by the melt process does not contain chlorine contamination from the reactants, has lower particulate levels, and has a more consistent color. Therefore it is highly desirable to use the melt technique in a commercial manufacturing process.

In the production of polycarbonates by the melt polymerization process, alkali metal hydroxides, in particular sodium hydroxide, are used as polymerization catalysts. While alkali metal hydroxides are useful polymerization catalysts, they also effect side reactions which results in branched side reaction products. This causes changes in the melt behavior of the polycarbonate, which can lead to difficulties in processing.

It would be desirable, therefore, to develop a catalysts system which effects melt polymerization while minimizing undesirable reaction products, such as branched side reaction products.

DESCRIPTION OF THE INVENTION

The present invention addresses these concerns and provided further surprising properties.

The present invention may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein.

Before the present compositions of matter and methods are disclosed and described, it is to be understood that this invention is not limited to specific synthetic methods or to particular formulations, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

In the following specification, reference will be made to a number of terms which shall be defined to have the following meanings:

The singular forms “a”, “any” and “the” include plural referents unless the context clearly dictates otherwise.

“Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.

As used herein, the term “melt polycarbonate” refers to a polycarbonate made by the transesterification of a carbonate diester with a dihydroxy compound.

“BPA” is herein defined as bisphenol A or 2,2-bis(4-hydroxyphenyl)propane.

“Catalyst system” as used herein refers to the catalyst or catalysts that catalyze the transesterification of the dihydric phenol and the carbonic acid diester in the melt process.

The terms “diphenol” and “dihydric phenol” as used herein are synonymous.

“Catalytically effective amount” refers to the amount of the catalyst at which catalytic performance is exhibited.

In the present invention, it was unexpectedly found that a catalyst system comprising alkali metal salts of aryl sulfonic acids are effective in catalyzing melt transesterification. Typically, low levels of alkali metal hydroxides are used as melt polymerization catalysts, usually in the range of about 1.0×10 −7 to about 3.0×10 −6 moles of catalyst per mole of diphenol.

In the present invention it was found that at elevated temperatures and concentrations, alkali metal salts of aryl sulfonic acids are effective melt transesterification catalysts. It is advantageous to run the polymerizations at higher temperatures for running at faster production rates as well as to facilitate the removal of the phenol by-product.

In addition, it was found that the catalyst system of the present invention further provides low side reaction products, including “Fries” product and other branched side reaction products. The reduction of these products provides the advantage of increased ductility, and prevents the reduction of rheological properties which results when undesirable side reaction products, such as Fries product, are present. It was further unexpectedly found that for a given set of conditions the catalyst systems as described in the present invention product less Fries than alkali metal hydroxides, such as sodium hydroxide.

Specifically, the present invention provides a catalyst system for the production of polycarbonate by the melt process, wherein the polycarbonate has a low content of undesirable branched side reaction product, in particular Fries products. It is desirable to have Fries product of less than 1000 ppm, preferably less than 900 ppm, more preferably less than 500 ppm, even more preferably less than 200 ppm.

Polycarbonate produced by the melt process typically has higher Fries content than polycarbonates produced by the interfacial method. As used herein the term “Fries” or “fries” refers to a repeating unit in polycarbonate having the following formula (I):

where the X variable represents

or

Variable R c and R d each independently represent a hydrogen atom or a monovalent hydrocarbon group and may form a ring structure. Variable R c is a divalent hydrocarbon group.

It is very desirable to have a low Fries content in the polycarbonate product, as Fries products reduce the performance characteristics of the polycarbonate, such as the ductility. Higher Fries contents results in lower ductility. Preparing polycarbonate by the melt process results in the formation of Fries products.

The present invention relates to melt polymerization catalysts in a melt polymerization system in which a dihydric phenol and a diester of carbonic acid are reacted. Dihydric phenols which are useful in preparing the polycarbonate of the invention may be represented by the general formula

wherein:

R is independently selected from halogen, monovalent hydrocarbon, and monovalent hydrocarbonoxy radicals;

R 1 is independently selected from halogen, monovalent hydrocarbon, and monovalent hydrocarbonoxy radicals:

W is selected from divalent hydrocarbon radicals,

n and n 1 are independently selected from integers having a value of from 0 to 4 inclusive; and

b is either zero or one.

The monovalent hydrocarbon radicals represented by R and R 1 include the alkyl, cycloalkyl, aryl, aralkyl and alkaryl radicals. The preferred alkyl radicals are those containing from 1 to about 12 carbon atoms. The preferred cycloalkyl radicals are those containing from 4 to about 8 ring carbon atoms. The preferred aryl radicals are those containing from 6 to 12 ring carbon atoms, i.e., phenyl, naphthyl, and biphenyl. The preferred alkaryl and aralkyl radicals are those containing from 7 to about 14 carbon atoms.

The preferred halogen radicals represented by R and R 1 are chlorine and bromine.

The divalent hydrocarbon radicals represented by include the alkylene, alkylidene, cycloalkylene and cycloalkylidene radicals. The preferred alkylene radicals are those containing from 2 to about 30 carbon atoms. The preferred alkylidene radicals are those containing from 1 to about 30 carbon atoms. The preferred cycloalkylene and cycloalkylidene radicals are those containing from 6 to about 16 ring carbon atoms.

The monovalent hydrocarbonoxy radicals represented by R and R 1 may be represented by the formula—OR 2 wherein R 2 is a monovalent hydrocarbon radical of the type described hereinafore. Preferred monovalent hydrocarbonoxy radicals are the alkoxy and aryloxy radicals.

Suitable dihydric phenols include, but are not limited to, BPA; 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane; 2,2-bis(3.5-dimethyl-4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclohexane; 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane; 1,1-bis(4-hydroxyphenyl)decane; 1,1-bis(4-hydroxyphenyl)propane; 1,1-bis(4-hydroxyphenyl)cyclodecane; 1,1 -bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane; 4,4-dihydroxyphenyl ether; 4,4-thiodiphenol; 4-4-dihydroxy-3,3-dichlorodiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; 4,4-dihydroxy-2,5-dihydroxydiphenyl ether; BPI; 1,1-bis(4-hydroxyphenyl)-1-phenylethane; 1,1-bis(3-methyl-4-hydroxyphenyl)-1-phenylethane, and mixtures thereof. In one embodiment, the residues of dihydric phenol in the polycarbonate comprise 100 mol % of residues derived from BPA.

Optionally, polyfunctional compounds may be utilized. Suitable polyfunctional compounds used in the polymerization of branched polycarbonate include, but are not limited to,

1,1,1-tris(4-hydroxyphenyl)ethane,

4-[4-[1,1-bis(4-hydroxyphenyl)-ethyl]-dimethylbennzyl],

trimellitic anhydride,

trimellitic acid, or their acid chloride derivatives.

As the diester of carbonic acid, various compounds may be used, including, but not limited to diaryl carbonate compounds, dialkyl carbonate compounds and alkylaryl carbonate compounds. Suitable diesters of carbonic acid include, but are not limited to, diphenyl carbonate; bis(4-t-butylphenyl)carbonate; bis(2,4-dichlorophenyl)carbonate; bis(2,4,6-trichlorphenyl)carbonate; bis(2-cyanophenyl)carbonate; bis(o-nitrophenyl)carbonate; ditolyl carbonate; m-cresol carbonate; dinaphthyl carbonate; bis(diphenyl)carbonate; diethylcarbonate; dimethyl carbonate; dibutyl carbonate; dicyclohexyl carbonate; and mixtures thereof. Of these, diphenyl carbonate is preferred. If two or more of these compound are utilized, it is preferable that one is diphenyl carbonate.

In the process of the present invention, an endcapping agent may optionally be used. Suitable endcapping agents include monovalent aromatic hydroxy compounds, haloformate derivatives of monovalent aromatic hydroxy compounds, monovalent carboxylic acids, halide derivatives of monovalent carboxylic acids, and mixtures thereof.

Suitable endcapping agents include, but are not limited to phenol, p-tert-butylphenol; p-cumylphenol; p-cumylphenolcarbonate; undecanoic acid, lauric acid, stearic acid; phenyl chloroformate, t-butyl phenyl chloroformate, p-cumyl chloroformate, chroman chloroformate, octyl phenyl; nonyl phenyl chloroformate or a mixture thereof.

If present, the endcapping agent is preferably present in amounts of about 0.01 to about 0.20 moles, preferably about 0.02 to about 0.15 moles, even more preferably about 0.02 to about 0.10 moles per 1 mole of the dihydric phenol.

It was unexpectedly found that catalyst systems comprising alkali metal salts of aryl sulfonic acids are suitable as melt transesterification catalysts. It was further found that higher processing temperatures and higher catalyst loading concentrations were required for reactions catalyzed by salts of aryl sulfonic acids than for reactions catalyzed by alkali metal hydroxides, such as sodium hydroxide. Suitable alkali metal salts of aryl sulfonic acids include, but are not limited to, alkali metal salts of p-toluene sulfonic acids, such as sodium tosylate, lithium tosylate, potassium tosylate and cesium tosylate, preferably cesium

The alkali metal salts of aryl sulfonic acids were found to have varying levels of activity. The catalyst of the present invention may be introduced into the reaction system in a variety of forms. The catalyst may be added as a solid, for example a powder, or it may be dissolved in a solvent, for example water or alcohol. In one embodiment, the catalyst is introduced into the reaction system in the form of an aqueous solution. The salts may be prepared prior to introduction into the reaction system, or they may be formed in solution by the reaction of the appropriate acid and base.

The desired molecular weight of the product depends on the intended use. For example, for optical materials, the number average molecular weight of the product is preferably in the range of about 7,500 to about 9,000; while for sheet materials the number average molecular weight is preferably in the range of about 25,000 to about 30,000. Therefore, it may be desirable to approach more acidic pHs in the synthesis of polycarbonate materials relatively low molecular weights, for example, optical materials. Typically, as the aqueous solution becomes more acidic, the catalyst becomes more selective, however the molecular weight of the resultant product decreases The alkali metal salt of the aryl sulfonic acid is preferably used in an amount of from about 10 −6 to 10 −3 moles of catalyst per 1 mole of dihydric phenol compound, more preferably 10 −6 to 10 −5 moles of catalyst per 1 mole of dihydric phenol compounds. When the amount is less than 10 −6 there is a possibility that catalyst activity is not exhibited. When the amount is greater than 10 −3 moles per 1 mole of dihydric phenol, the properties of the final polycarbonate product may be adversely affected. The base, such as the quaternary ammonium salt/ and or phosphonium catalyst are preferably present in amounts of from 10 −2 to about 10 −6 , preferably 10 −2 to about 10 −5 moles per 1 mole of dihydric phenol compounds, in addition to the salt of the aryl sulfonic acid.

The ratio of the base cocatalyst, if present, to the alkali metal salt of the aryl sulfonic acid by moles is preferably in the range of from about 1.0 to about 10,000, more preferably from about 10 to about 1000, even more preferably from about 25 to about 500.

The reaction conditions of the melt polymerization are important. It was unexpectedly found that the alkali metal salts of the aryl sulfonic acids are inactive at temperatures below about 300° C. Further, it was found that longer reaction times were necessary. The pressure may be at atmospheric, or at an added pressure of from atmospheric to about 15 torr in the initial stages of the reaction, and at a reduced pressure at later stages, for example in the range of about 0.2 to about 15 torr. The reaction time is generally about 0.1 hours to about 10 hours.

The melt polymerization may be accomplished in one or more stages. In one embodiment, the process is conducted as a two stage process. The first stage is conducted at a temperature of 270° C. or lower, preferably 80 to 250° C., more preferably 100 to 230° C. The duration of the first stage is preferably 0 to 5 hours, even more preferably 0 to 3 hours at a pressure form atmospheric pressure to 100 torr, with a nitrogen atmosphere preferred.

In the second stage, the alkali metal salt of the aryl sulfonic acid is introduced into the product from the first stage and further polycondensation is conducted. The alkali metal salt of the aryl sulfonic acid may be added in its entire amount in the second stage, or it may be added in batches in the second and subsequent stages so that the total amount is within the aforementioned ranges. The sulfonate salts are significantly less active than the corresponding alkali metal hydroxides; by significant it is meant is greater than five times less active with Na salt. However the use of high temperature to remove phenol while not making Fries product is an advantage. Additionally, the use of the Cs salt offers good reaction rates and lower Fries as compared to NaOH.

It is preferable in the second and subsequent stages of the polycondensation step for the reaction temperature to be raised while the reaction system is reduced in pressure compared to the first stage, thus bringing about a reaction between the bisphenol and the carbonic acid diester, and for the bisphenol and the carbonic acid diester finally to be subjected to a polycondensation reaction at above about 280°, preferably above about 300° C., more preferably at from about 310° to about 330° C., even more preferably around about 310° C., under reduced pressure of 5 mm Hg or less, and preferably 1 mm Hg or less. In the present invention, it was found that the reaction time was increased, as compared to alkali metal hydroxide catalysts, such as sodium hydroxide. Suitable reaction times for the second stage are from 20 minutes to 2 hours.

If the melt polymerization is conducted in more than one stage, it is preferable to add the base, if desired, such as TMAH in an earlier stage than the salt of the aryl sulfonic acid. In particular, it is preferable to add the base to the reactor before the temperature reaches 220° C., preferably before it reaches 200° C.

Additives may also be added to the polycarbonate product as long as they do not adversely affect the properties of the product. These additives include a wide range of substances that are conventionally added to the polycarbonates for a variety of purposes. Specific examples include heat stabilizers, epoxy compounds, ultraviolet absorbers, mold release agents, colorants, antistatic agents, slipping agents, anti-blocking agents, lubricants, antifogging agents, natural oils, synthetic oils, waxes, organic fillers, flame retardants, inorganic fillers and any other commonly known class of additives.

The reaction can be conducted as a batch or a continuous process. Any desired apparatus can be used for the reaction. The material and the structure of the reactor used in the present invention is not particularly limited as long as the reactor has an ordinary capability of stirring. It is preferable that the reactor is capable of stirring in high viscosity conditions as the viscosity of the reaction system is increased in later stages of the reaction.

EXAMPLES

The following examples are set forth to provide those of ordinary skill in the are with a complete description of how the compositions of matter and methods claimed herein are made and evaluated, and are not intended to limit the scope of what the inventors regard as their invention. Efforts have been made to insure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are by weight, temperature is in ° C.

Molecular weights are reported as number average (M n ) and were determined by GPC analysis of polycarbonate prepared by melt polymerization. Standards of polystyrene were used to construct a universal calibration against which polycarbonate could be measured using the Mark-Houwink equation. The temperature of the columns was 25° C. and the mobile phase was chloroform.

Fries content was measured by the KOH methanolysis of resin and is reported as parts per million (ppm). The content of Fries for each of the melt polycarbonates listed in Table 1 was determined as follows. First, 0.50 grams of polycarbonate was dissolved in 4.0 ml of THF (containing p-terphenyl as internal standard). Next, 3.0 ml of 18% KOH in methanol was added to this solution. The resulting mixture was stirred for two hours at this temperature. Next, 1.0 ml of acetic acid was added, and the mixture was stirred for 5 minutes. Potassium acetate was allowed to crystallize over 1 hour. The solid was filtered off and the resulting filtrate was analyzed by liquid chromatograph using p-terphenyl as the internal standard.

TABLE 1
EXAMPLE	pTSA (mole/mole NaOH)	Mn
1	2.5 × 10 −4 moles TMAH	1500
2	0	8029
3	0.20	5183
4	0.40	3271
5	0.60	2371
6	1.00	2330

TABLE 2
			Final
		Final Stage	Stage
		Temperature,	Time,		Fries
Example	Catalyst	° C.	minutes	Mn	(ppm)
Controls with
NaOH
1	1.0 * 10 −6	280	30	5478	154
2	1.0 * 10 −6	295	30	6256	187
3	1.0 * 10 −6	310	30	8597	471
4	5.0 * 10 −6	310	30	9100	2700
5	TMAH	310	30	1500	62
	Only
Runs using
NaOTs as a
catalyst
6	5.0 * 10 −6	280	60	1400	70
7	5.0 * 10 −6	295	60	1877	210
8	5.0 * 10 −6	310	15	1911	170
9	5.0 * 10 −6	310	30	5938	240
10	5.0 * 10 −6	310	60	9094	341
11	1.0 * 10 −6	310	15	1492	165
12	1.0 * 10 −6	310	30	2226	216
13	1.0 * 10 −6	310	60	4558	359
14	1.0 * 10 −6	325	60	9981	600
15	5.0 * 10 −6	325	15	4434	186
16	5.0 * 10 −6	325	60	13911	898
Runs using
Cesium Tosylate
as a catalyst
17	5.0 * 10 −6	310	30	7904	120

Table 1 illustrates the addition of p-toluene sulfonic acid (p-TSA) to melt polymerizations for the neutralization of sodium hydroxide; the quenching of active sodium with p-TSA. As the addition of p-TSA effectively neutralizes the sodium hydroxide during polymerization, it might be assumed that the sodium tosylate remaining from the acid-base reaction must also be inactive. It was unexpectedly found, however, in the present invention that at elevated temperatures and higher concentrations sodium tosylate can become an effective melt polymerization catalyst. In Table 1, the polymerizations were conducted under the following conditions: 1.0*10 −6 moles NaOH and 2.5*10 −4 moles TMAH/mole BPA were added to the polymerization, the final stage of the polymerization was 310° C. for 30 minutes.

Table 2, polymerizations were conducted according to the invention. Sodium and cesium tosylate were utilized as melt transesterification catalysts. As shown in the data set forth in Table 2, it is clear that at low concentrations and temperatures below about 300° C., sodium tosylate is inactive. However, temperatures at about 310° C., sodium tosylate becomes a useful catalyst. As shown in the Table, in Example 4, NaOH is used as a catalyst which provided an Mn of 9100 (1.0*10 −6 moles catalyst/mole BPA, and a 310° C. final polymerization stage for 30 minutes). The same Mn (example 10) can be achieved with sodium tosylate as a catalyst; however hi-her concentrations are needed, and the polymerization was conducted for 60 minutes at the final stage. As shown in Table 2, the cesium salt of pTSA was more active that the corresponding sodium salt.

The following conditions were utilized in the polymerizations according to the present invention:

The reactions were carried out in a 1 liter glass batch reactor equipped with a solid nickel helical agitator. The glass reactor surface was passivated by acid washing, rinsing, and subsequently drying overnight at 70° C. and stored covered until use.

The temperature of the reactor was maintained using a fluidized sand bath with a PID controller and measured near the reactor and sand bath interface. The pressure of the reactor was controlled by a nitrogen bleed into the vacuum pump downstream of the distillate collection flasks and measured at higher pressures (760 mm Hg to 40 mm Hg) with a mercury barometer, and at lower pressures (40 mm Hg to 1 mm Hg) with an Edward pirani gauge.

The reactor was charged with 0.6570 mol BPA and 0.7096 mol diphenyl carbonate prior to assembly. The reactor was then assembled, scaled and the atmosphere was exchanged with nitrogen three times. With the final nitrogen exchange, the reactor was brought to about atmospheric pressure and submerged into the fluidized bath which was at 180° C. After five minutes, agitation was begun at 250 rpm. After an additional ten minutes, the reactants were fully melted and a homogeneous mixture was assumed. Tetramethyl ammonium hydroxide (TMAH, 1.32×10 −4 mol) and sodium hydroxide (NaOH, 5.00×10 −7 mol) were added sequentially after being diluted to the proper concentrations (0.220 M TMAH and 5.00×10 −3 M NaOH) with 18 Mohm water, in the examples in which NaOH was used as a catalyst. Sodium tosylate was used as received from ALDRICH chemical company, and was added as an aqueous solution. After the final catalyst was added, timing began, and the temperature was ramped to 210° C. in five minutes. Once at temperature, the pressure was reduced to 180 mm Hg and phenol distillate was immediately formed. After 25 minutes, the pressure was again reduced to 100 mm Hg and maintained for 45 minutes.

The temperature was then ramped to 240° C. in five minutes and the pressure was lowered to 15 mm Hg. These conditions were maintained for 45 minutes. The temperature was then ramped to 270° C. in five minutes and the pressure was lowered to 2 mm Hg. These conditions were maintained for 10 minutes. The temperature was then ramped to the final finishing temperature in five minutes and the pressure was reduced to 1.1 mm Hg. The finishing temperature was 280 to 325° C., depending on the experiment, except as noted otherwise. After the final stage, the reactor was removed from the sand bath and the melt was extruded into liquid nitrogen to quench the reaction.

This invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims

1. A method for the preparation of polycarbonate by the melt process comprisinga) heating, in one or more stages, a mixture comprising a diphenol and a diarylcarbonate; and b) introducing into the mixture of a), in the same stage or different stages 1) a catalytically effective amount of an alkali and/or alkali earth metal salt of an aryl sulfonic acid.

2. The method of claim 1, wherein the alkali and/or alkali earth metal salt of the aryl sulfonic acid is p-toluenesulfonic acid.

3. The method of claim 1, wherein the alkali and/or alkali earth metal salt of the aryl sulfonic acid is selected from the group consisting of sodium tosylate, lithium tosylate, potassium tosylate, cesium tosylate and a mixture thereof.

4. The method of claim 1, wherein the nonvolatile acid salt is cesium tosylate.

5. The method of claim 1, wherein the catalyst system further comprises a base.

6. The method of claim 5, wherein the base is a quaternary ammonium compound; a quaternary phosphonium compound; or a mixture thereof.

7. The method of claim 1, wherein the diphenol is bisphenol A.

8. A method of reducing the Fries content of a polycarbonate comprising preparing a polycarbonate by a melt process, the method comprising:a) heating, in one or more stages, a mixture comprising a diphenol and a diarylcarbonate; and b) introducing into the mixture of a), in the same stage or different stages 1) a catalytically effective amount of an alkali and/or alkali earth metal salt of an aryl sulfonic acid.

9. A polycarbonate prepared by the method of claim 1.

10. The method of claim 1, wherein the Fries content of the polycarbonate is less than 1000 ppm.

11. The method of claim 1, wherein the Fries content of the polycarbonate is less than 500 ppm.

12. A method of reducing the branched side products of polycarbonate comprisinga) heating, in one or more stages, a mixture comprising a diphenol and a diarylcarbonate; and b) introducing into the mixture of a), in the same stage or different stages 1) a catalytically effective amount of an alkali and/or alkali earth metal salt of an aryl sulfonic acid.