DE102008008841A1 - Preparing (co)polycarbonate or diaryl carbonate, useful in e.g. sunglasses, comprises converting di-, mono-phenol and phosgene to chloroformic acid aryl ester, oligo- or diaryl-carbonate, and reacting the product under alkaline solution - Google Patents

Abstract

Continuously preparing polycarbonate or copolycarbonate and/or diaryl carbonate comprises (a) continuously producing a mixture of an organic phase containing a solvent suitable for the polycarbonate and/or diaryl carbonate, and aqueous phase containing a solvent suitable for diphenol, monophenol, water and alkaline solution; (b) converting the diphenol, monophenol and phosgene to oligocarbonate and/or chloroformic acid aryl ester and/or diaryl carbonate; and (c) reacting an oligocarbonate, chloroformic acid aryl ester and/or diaryl carbonate under the addition of alkaline solution. Continuous preparation of polycarbonate or copolycarbonate and/or diaryl carbonate after the interfacial phase process of at least a diphenol and/or monophenol, phosgene and at least a catalyst optionally in the presence of at least a chain breaker and/or brancher, comprises (a) continuously producing a mixture of an organic and aqueous phase, where the organic phase contains at least a solvent suitable for the polycarbonate and/or diaryl carbonate and the phosgene and the aqueous phase contains the diphenol, monophenol, water and alkaline solution; (b) converting the diphenol, monophenol and phosgene to oligocarbonate and/or chloroformic acid aryl ester and/or diaryl carbonate; and (c) subsequently reacting an oligocarbonate, chloroformic acid aryl ester and/or diaryl carbonate in at least a reactor under the addition of further alkaline solution, optionally chain breaker and optionally at least a further catalyst, where: the steps (a) and (b) takes place in one or more pump(s), which have at least an inlet for the organic and aqueous phase and optionally further inlet for catalyst, chain breaker, brancher and/or alkali solution, respectively, and at least an outlet for the oligocarbon containing and/or chloroformic acid aryl ester-diaryl carbonate mixture; and the pump has thermostatic temperature and operates in stator-rotor principle.

Description

object The present invention is a method for continuous Preparation of Polycarbonates by the Phase Interface Method in which both the mixture of organic and aqueous Phase as well as the upstream oligomerization step in a special pump.

The polycarbonate preparation according to the interfacial process is already known from Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, pp. 33-70 ; DC Prevorsek, BT Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, NJ 07960: "Synthesis of Poly (ester Carbonate) Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 18, (1980 ) "; Pp. 75-90 . D. Freitag, U. Grigo, PR Muller, N. Nouvertne ', BAYER AG, "Polycarbonates" in Encyclopaedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pp. 651-692 and finally from Dres. U. Grigo, K. Kircher and P. R-Müller "Polycarbonates" in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, p. 118-145 been described.

Furthermore, also in EP-A 0 517 044 or EP-A 520 272 the interfacial process for the production of polycarbonate is described.

to Production of Polycarbonate by the Phase Interface Process the phosgenation takes place in aqueous-alkaline Solution or suspension submitted disodium salt of a Bisphenols or a mixture of different bisphenols in the presence an inert organic solvent or solvent mixture, which in addition to the aqueous a second organic phase formed. The resulting, mainly in the organic Phase present, oligocarbonates are using suitable catalysts to high molecular weight dissolved in the organic phase, Polycarbonates condensed, the molecular weight by suitable chain terminators (monofunctional phenols) controlled can be. The organic phase is finally separated and the polycarbonate by various work-up steps isolated.

The The polycarbonate synthesis can be carried out continuously or discontinuously. The reaction can therefore be found in Stirred tanks, tubular reactors, pumped-circulation reactors or stirred tank cascades or combinations thereof, wherein by using the already to ensure that mixing is aqueous and organic phase only then segregate when the synthesis mixture has reacted, d. H. no saponifiable Chlorine of phosgene or chloroformates more contains.

The first step for the construction of the oligocarbonates is carried out according to the prior art, for example in a pumped circulation reactor; see, for. B. EP 1 249 463 A1 . US 2004/0158026 A1 . US 6,613,868 B2 , In Umpumpreaktor done here the mixing of the introduced phosgene with also introduced disodium salt of a bisphenol (or a mixture of different bisphenols) and the first Oligomerisierungsschritte. Resulting Chloroformiatgruppen react with existing phenolate end groups to growing oligomers containing different end groups (phenolate or chloroformate or from both mixed species). A certain amount of added bisphenol is still unreacted in the mixture. Although the Umpumpreaktor to the effect that dosing or concentration fluctuations can not undamped penetrate to the final product, but rather by backmixing at set Umpumpverhältnis to inflow or outflow of the reaction mixture, an equilibration of fluctuations is achieved. However, a significant disadvantage is that relatively large molecular weight distributions arise for large-scale advantageous parameter settings. Another disadvantage is the fact that Umpumpreaktoren represent relatively bulky assemblies.

It There was therefore a need for a continuous interfacial process for the production of polycarbonate, with which the loading of the from this process resulting wastewater with diphenol on can be reduced. Further desirable would be besides, that in such a process polycarbonates with narrow molecular weight distribution would be obtained without that z. B. Unbalanced concentration fluctuations until Can penetrate end product (no plug-flow behavior).

Surprisingly, it has been found that a significant reduction of the diphenol load of the wastewater can be achieved if, in the phase boundary process for the production of polycarbonates, both the mixture of the organic and aqueous phase and the upstream oligomerization step take place in a special pump. Advantageously, even in this process, concentration fluctuations do not pass unattenuated to the final product, so that the process according to the invention has the advantages of the known method according to the prior art, but eliminates its disadvantages. An increased diphenol load of the wastewater requires, as a countermeasure, an increase in the addition of phosgene and sodium hydroxide in order to complete the conversion of the diphenol. Due to the significantly reduced diphenol load of the wastewater according to the method according to the invention therefore, in addition, such an increase of the phosgene and sodium hydroxide additive can be avoided. This is advantageous, inter alia, from an economic point of view.

• (a) kontinuierlich eine Mischung der organischen und wässrigen Phase erzeugt wird, wobei die organische Phase wenigstens ein für das Polycarbonat geeignetes Lösungsmittel und ganz oder teilweise das Phosgen enthält und die wässrige Phase das oder die Diphenol(e), Wasser und Alkalilauge enthält,
• (b) eine Umsetzung des oder der Diphenol(e) und Phosgen zu Oligocarbonaten erfolgt,
• (c) die Oligocarbonate anschließend in wenigstens einem Reaktor unter Zugabe von weiterer Alkalilauge, gegebenenfalls Kettenabbrecher(n) und gegebenenfalls wenigstens eines weiteren Katalysators aufkondensiert werden,

dadurch gekennzeichnet, dass die kontinuierliche Mischung der organischen und wässrigen Phase unter (a) und die Umsetzung zu Oligocarbonaten unter (b) in einer oder mehreren Pumpe(n) erfolgen, die

• – nach dem Stator-Rotor-Prinzip arbeitet (arbeiten)
• – thermostatisierbar ist (sind) und
• – wenigstens jeweils einen Zugang für die organische und die wässrige Phase und gegebenenfalls weitere Zugänge für Kettenabbrecher, Verzweiger und/oder zusätzlich Alkalilauge sowie wenigstens einen Ausgang für die oligocarbonathaltige Mischung aufweist (aufweisen).

The present invention therefore provides a process for the continuous preparation of polycarbonates or copolycarbonates by the interfacial process of at least one diphenol, phosgene and at least one catalyst optionally in the presence of at least one chain terminator and / or branching agent, characterized in that

• (a) continuously producing a mixture of the organic and aqueous phases, the organic phase containing at least one solvent suitable for the polycarbonate and wholly or partially containing the phosgene and the aqueous phase containing the diphenol (s), water and alkali metal hydroxide,
• (b) reacting the diphenol (s) and phosgene to give oligocarbonates,
• (c) the oligocarbonates are subsequently condensed in at least one reactor with addition of further alkali metal hydroxide solution, optionally chain terminator (s) and optionally at least one further catalyst,

characterized in that the continuous mixing of the organic and aqueous phases under (a) and the conversion to oligocarbonates under (b) take place in one or more pump (s) which

• - works (works) according to the stator-rotor principle
• - Is thermostatable (are) and
• - Has at least one access for the organic and the aqueous phase and optionally further accesses for chain terminators, branching and / or additionally alkali metal hydroxide and at least one outlet for the oligocarbonathaltige mixture (have).

The Pump (s) used in the invention are preferred built according to the single or multi-chamber principle.

The organic phase may be the required phosgene before mixing already completely or partially contained with the aqueous phase. The organic phase preferably contains before the mixture already all the phosgene required including the one used Excess phosgene.

Of the Entry of the phosgene into the organic phase can be gaseous or liquid. The excess used to phosgene, based on the sum of the diphenols used preferably between 3 and 100 mol%, more preferably between 5 and 50 mol%.

Of the pH of the aqueous phase should be above or below single or multiple replenishment of caustic during and after the phosgene dosage in the alkaline range preferably between 8.5 and 12 are kept while it is after the catalyst addition should be at 10 to 14.

The Phosgene dosage takes place before mixing with the aqueous Phase completely or partially directly into the organic phase. any Partial quantities of phosgene can also be added before mixing with the aqueous phase in the aqueous phase or after mixing with the aqueous phase in the resulting Emulsion be metered. Furthermore, the phosgene can be whole or partially in a recirculated partial flow of Synthesis mixture of both phases are dosed, this Partial stream preferably recirculated before the catalyst addition becomes. Particularly preferred is the complete phosgene dosage before mixing with the aqueous phase directly into the organic phase. In all these embodiments are observe the pH ranges described above and, if necessary by single or multiple replenishment of caustic soda or appropriate dosage of diphenol (at) solution to comply. Likewise, the temperature range may need cooling or dilution.

The Synthesis of polycarbonates from dihydroxydiarylalkanes and phosgene in an alkaline environment is an exothermic reaction and is in one Temperature range from -5 ° C to 100 ° C, preferably 15 ° C to 80 ° C, most preferably 25 to 65 ° C performed.

Therefore it is necessary that the invention for the mixture and the preceding oligomerization step used (s) Pump (s) to a temperature of -5 ° C to 100 ° C, preferably from 15 ° C to 80 ° C, more preferably from 25 ° C to 65 ° C is thermostatable (are).

ever according to solvent or solvent mixture be operated under normal pressure or under pressure. The pump (s) used according to the invention can for system pressures up to 350 bar and 450 ° C be interpreted. They are thus for use in one wide process window suitable.

At the Phase interface method is preferably in pressure ranges from 1 to 50 bar, more preferably in ranges from 1 to 10 worked bar.

The organic phase may be one or mixtures of several solvents contain. Suitable solvents are aromatic and / or aliphatic chlorinated hydrocarbons, preferably dichloromethane, trichlorethylene, 1,1,1-trichloroethane, 1,1,2-trichloroethane and chlorobenzene and their Mixtures. However, they can also be aromatic hydrocarbons such as benzene, toluene, m- / p- / o-xylene or aromatic ethers such as anisole alone, in admixture or in addition or in admixture with chlorinated hydrocarbons are used are preferred Dichloromethane and chlorobenzene and mixtures thereof. Another embodiment the synthesis uses solvents which polycarbonate do not solve but only swell. It can therefore also Non-solvent for polycarbonate in combination be used with solvents. Then as a solvent also in the aqueous phase soluble solvents such as tetrahydrofuran, 1,3- or 1,4-dioxane or 1,3-dioxolane can be when the solvent partner the forms second organic phase.

Suitable diphenols are those of the general formula HO-Z-OH wherein Z is a divalent organic radical of 6 to 30 carbon atoms containing one or more aromatic groups. Examples of such compounds which can be used in the process according to the invention are dihydroxydiarylalkanes such as hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl ) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, α, α'-bis (hydroxyphenyl) diisopropylbenzenes, bis (hydroxyphenyl) phthalimidines and their alkylated , nuclear alkylated and nuclear halogenated compounds.

preferred Diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A (BPA)), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, Bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, Bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-Bis- [2- (3,5-dimethyl-4-hydroxyphenyl) -2-propyl] -benzene, 1,1-bis (4-hydroxyphenyl) -cyclohexane, 2-hydrocarbyl-3,3- Phthalimidines bis (4-hydroxyaryl), 3,3-bis (4-hydroxyaryl) -1-aryl-1H-indol-2-one, 2,2-bis (4-hydroxyaryl) -1-aryl-1H-indol-2-one and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).

Especially preferred diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis (4-hydroxyphenyl) -phenylethane, 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A (BPA)), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis- (4-hydroxyphenyl ) cyclohexane, 2-Hydrocarbyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 3,3-bis (4-hydroxyphenyl) -1-phenyl-1H-indol-2-one, 2,2-bis (4-hydroxyphenyl) -1-phenyl-1H-indol-2-one, 3,3-bis (4-hydroxyphenyl) -1-methyl-1H-indol-2-one, 2,2-bis (4-hydroxyphenyl) -1-methyl-1H-indol-2-one, 3,3-bis (4-hydroxyphenyl) -N-methyl-phthalimidine, 3,3-bis (4-hydroxyphenyl) -N-phenyl-phthalimidine and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Bisphenol TMC).

These and other suitable diphenols are z. Tie US-A 2,999,835 . US-A 3,148,172 US-A 2,991,273 . US-A 3,271,367 . US-A 4,982,014 and US-A 2,999,846 in the German Offenlegungsschriften DE-A 1 570 703 . DE-A 2 063 050 . DE-A 2 036 052 . DE-A 2 211 956 and DE-A 3 832 396 , the French patent FR-A 1 561 518 , in the monograph of H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, p28ff; Pp. 102ff and from DG Legrand, JT Bendler, Handbook of Polycarbonates Science and Technology, Marcel Dekker New York 2000, p. 72ff. described.

In the case of the preparation of homopolycarbonates according to the invention, only one diphenol is used, in the case of the inventive preparation of copolycarbonates several diphenols are used, of course, the diphenols used, as well as all other chemicals added to the synthesis and auxiliaries with those from their own synthesis, handling and Storage contaminants may be contaminated, although it is desirable to use as clean as possible raw materials work.

Under In the context of the invention, alkali metal hydroxide is preferably sodium hydroxide solution, potassium hydroxide solution or mixtures of these, particularly preferably sodium hydroxide to understand.

The aqueous phase in the process according to the invention contains alkali metal hydroxide, one or more diphenols and water, the concentration of this aqueous solution being calculated as the sum of the diphenols, not as sodium salt but as free diphenol, preferably between 1 and 30% by weight, more preferably between 3 and 25 wt .-%, based on the total weight of the aqueous solution may vary. Most preferably, the concentration of this aqueous solution with respect to the sum of the diphenols between 3 and 8 wt .-% for polycarbonates having an M _W of greater than 45000 gmol ^-1 and between 12 to 22 wt .-% for polycarbonates with an M _W vary from 45000 or smaller. It may be necessary at higher concentrations to temper the solutions. The alkali hydroxide used to dissolve the diphenols, e.g. For example, sodium or potassium hydroxide, solid or can be used as the corresponding aqueous alkali. The concentration of the alkali metal hydroxide depends on the target concentration of the desired diphenol solution, but is usually between 5 and 25 wt .-%, preferably 5 and 10 wt .-% based on 100% alkali hydroxide, or is more concentrated and then selected Diluted with water. In the method with subsequent dilution alkali solutions are used with concentrations between 15 and 75 wt .-%, preferably 25 and 55 wt .-%, optionally tempered. The alkali content per mole of diphenol depends on the structure of the diphenol, but generally ranges from 0.25 moles of alkali / mole of diphenol to 5.00 moles of alkali / mole of diphenol, preferably from 1.5 to 2.5 moles of alkali / mol diphenol, and in the most preferred case bisphenol A is used as the sole diphenol, from 1.85 to 2.15 moles of alkali. If more than one diphenol is used, they can be dissolved together. Since the solubility of diphenols very much depends on the amount of alkali used, it may be advantageous to have instead of a solution with two diphenols better two solutions each with a dissolved in a suitable alkali metal diphenol, which are then metered separately so that the correct Mixing ratio arises. Furthermore, it may be advantageous not to dissolve the diphenol (s) in alkali solution but in dilute diphenol solution equipped with additional alkali. The dissolution processes can be based on solid diphenol, usually in flakes or prills or molten diphenol. In the case of sodium hydroxide or sodium hydroxide solution, the alkali hydroxide or alkali lye used can be prepared, for example, by the amalgam process or the so-called membrane process. Both methods have been used for a long time and are familiar to the person skilled in the art. In the case of caustic soda, preference is given to using those prepared by the membrane process.

In such an aqueous solution and / or the aqueous Phase are the diphenol (s) in whole or in part in the form the corresponding alkali metal salts or dialkali salts.

in the inventive methods are for the mixture of the organic and aqueous phase and the upstream oligomerization step one or more pump (s) used. Several pumps can be used in industrial applications Scale used for capacity reasons become. In the case of using several pumps, these can both parallel and in series. Preferred would be a parallel connection of several pumps. The pump takes over in the process according to the invention the function of a mixing unit for mixing the organic and aqueous phase to Production of a corresponding emulsion, the function of the reaction space for the construction of oligocarbonates and the function of continuous delivery of the reaction mixture.

The According to the invention used according to pumps the stator-rotor principle. This will be in the mixture of the two In particular, energy travels through shear in the reaction mixture entered. As a result, the resulting emulsion has sufficient large phase interface, allowing for optimal Oligomerization can take place at this phase interface.

In the case of the pumps used in accordance with the invention, the pump housing preferably constitutes the stator, and one or more rotors are located in the interior of the pump. In the case of multiple rotors, these are preferably applied to the same rotor axis. The pumps used according to the invention are preferably centrifugal pumps. In preferred embodiments, these are centrifugal pumps whose impeller (rotor) has a peripheral design (peripheral wheel pump). In further preferred embodiments, these are centrifugal pumps whose impeller (rotor) has a radial design (radial wheel pump). Particularly preferred according to the invention are pumps which operate on the principle of Peripheralradpumpe. Such centrifugal pumps and their mode of operation are known to the person skilled in the art (cf. DE 42 20 239 A1 ) and commercially available. The principle of such a pump used in the invention is exemplary and schematic in 1 shown. There are both embodiments with single or Mehrfachspalttöpfen such. B. double-gap pots, suitable.

1 : Schematic representation of the principle of a Peripheralradpumpe with rotating inner device

In the 1 used abbreviations stand for

1

Phosgene / solvent influx

2

influx aqueous / alkaline sodium bisphenolate solution

3

Caustic soda influx (NaOH-influx)

4

Abgeführtes reaction

R

rotating interior device

S

shovel on the rotating inn device

K

circulation channel

RZ

Reaction inlet side (Suction side)

RA

Reaction discharge side (Face)

P

static Housing of Peripheralradpumpe with rotating inner device

In the 1 Peripheralradpumpe shown has a static housing P, a rotating inner device R with blades S (here designed as a paddle wheel) and a resulting resulting in the housing channel K from the suction to the pressure side down. The peripheral pump can create relatively high pressures for a flow pump at low flow rates and small size. During conveyance, the transported reaction mixture between the blades S releases its energy to the reaction mixture conveyed in the circulation channel. The increase in pressure takes place by exchange of pulses, in that the fluid flowing at greater speed in the blades of the impeller delivers the energy to the fluid rotating at a lower speed in the circulation channel.

The Pumps used in the invention are thermostatable, d. H. have an inlet and outlet for a Thermostatisierflüssigkeit on. Flow space for this Thermostatisierflüssigkeit and reaction space for the reaction mixture are so separated from each other, that no mass transfer but a heat exchange can be done.

The pumps used according to the invention have at least one access for the organic and the aqueous phase as well as at least one exit for the oligocarbonate-containing reaction mixture as feed to the reaction space (cf. 1 ). In preferred embodiments, further accesses to chain terminators, branching agents, additional caustic and / or diphenol (at) solution are preferred. The catalyst is preferably added at a later time to a downstream residence reactor. A schematic exemplary structure for such a reaction according to the invention is shown in FIG 2 shown.

The representation in 2 is to be regarded as merely exemplary in terms of the number of downstream residence reactors. It can also be followed by more or less than two residence reactors.

2 : Schematic structure for the production of polycarbonate according to the interfacial process using a Peripheralradpumpe

In the 2 used abbreviations stand for

1

Phosgene / solvent influx

2

influx aqueous / alkaline sodium bisphenolate solution

3

First caustic soda inflow (NaOH inflow 1 )

4

Abgeführtes reaction

5

Second sodium hydroxide feed (NaOH feed 2 )

6

chain terminators

7

catalyst

pp

Peripheralradpumpe

ST

static mixer

VR1

residence reactor 1

VR2

residence reactor 2 (optional)

WT

heat exchangers

DEH

Booster pump

TG

separation vessel

W

subsequent Laundry

In a further embodiment of the method according to the invention, the pump used according to the invention may also be followed by a circulating pump instead of an immersion reactor. This embodiment variant of the method according to the invention would have the advantage that existing systems could be used by connecting a pump used in accordance with the invention without requiring extensive modifications to the systems. A schematic exemplary structure for such a reaction according to the invention is shown in FIG 2a shown. The representation in 2a is to be regarded as merely exemplary in terms of the number of downstream residence reactors. It can also be followed by more or less than two residence reactors.

In a variant of the method with the invention used Pump downstream Umpumpreaktor the starting materials, such as The diphenolate solution or the first caustic soda feed, either completely added to the pump or optionally proportionately supplied only to the downstream Umpumpreaktor become.

2a : Schematic structure for the production of polycarbonate according to the interfacial process using a Peripheralradpumpe with downstream Umpumpreaktor

In the 2a in addition to the in 2 used abbreviations stand for

2 '

optional Influx of a portion of aqueous / alkaline sodium bisphenolate solution

3 '

optional feed of a portion of the first caustic soda feed (NaOH feed 1' )

EC

degassing vessel

UR

circulating reactor

AT

discharge pump

P

pump to maintain the circulation

The Residence time of the reaction mixture in the invention used Pump is preferably 20 seconds to 10 minutes, especially preferably 30 seconds to 5 minutes and most preferably 30 seconds to 3 minutes.

to Control of the molecular weight may optionally be the addition of one or more monofunctional chain terminators, such as phenol or alkylphenols, in particular phenol, p-tert-butylphenol, iso-octylphenol, Cumylphenol, their chloroformate or acid chlorides of monocarboxylic acids or mixtures of these chain terminators to be required. Such chain terminators are optionally either fed with the dihydroxydiarylalkane (s) of the reaction or added at any point in the synthesis, as long as phosgene or Chlorkohlensäureendgruppen in the reaction mixture are present or in the case of acid chlorides and chloroformate as chain terminators as long as enough phenolic end groups of the forming polymer are available. Preferably the chain terminator (s) after phosgenation on a Added or added at a time, at or to which no phosgene more is present, but the catalyst has not yet been added, d. H. they can be in front of the catalyst, with the catalyst be dosed together or in parallel.

In the same way may optionally one or more Branching or branching mixtures are added to the synthesis. Usually however, such branching agents are placed in front of the chain terminator (s) added. For example, as branching trisphenols, quarter phenols, Acid chlorides of tri- or tetracarboxylic acids or mixtures of polyphenols or acid chlorides used.

Examples of branching compounds having three or more than three phenolic hydros xyl groups are phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis (4 , 4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, tetra (4-hydroxyphenyl) -methane.

Examples for other trifunctional compounds suitable as branching agents are 2,4-dihydroxybenzoic acid, trimesic acid, Cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

Especially preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) ethane.

When Catalysts for the invention Processes are preferably tertiary amines, such as. Triethylamine, tributylamine, trioctylamine, N-ethylpiperidine, N-methylpiperidine or N-i / n-propylpiperidine, quaternary ammonium salts as z. B. tetrabutylammonium, tributylbenzylammonium, tetraethylammonium hydroxide, chloride, bromide, hydrogen sulfate or tetrafluoroborate and the foregoing said ammonium compounds corresponding phosphonium compounds. These compounds are typical phase interface catalysts described in the literature, commercially available and the person skilled in the art. The catalysts can individually, in admixture or else next to and in succession to the invention Be added, optionally also before the phosgenation, however, dosages after phosgene entry are preferred unless it becomes an onium compound - d. H. Ammonium- or phosphonium compound - or mixtures of onium compounds used as catalysts. In the case of such onium salt catalysis it is preferable to add before the phosgene dosage. The dosage the catalyst or catalysts can be used in bulk, in one inert solvent, preferably the or one of these the organic phase in the polycarbonate synthesis, or as take place aqueous solution. In case of use of tertiary amines as a catalyst, for example their dosage in aqueous solution as their Ammonium salts with acids, preferably mineral acids, hydrochloric acid in particular. When using several Catalysts or the metering of subsets of the total catalyst amount can of course also different dosage ways made in different places or at different times become. The total amount of catalysts used is between 0.001 to 10 mol%, preferably 0.01 to 8 mol%, particularly preferably 0.05 to 5 mol% based on moles diphenols used.

worin
u für 0 oder eine ganze Zahl von 1 bis 20, bevorzugt für 0 oder eine ganze Zahl von 1 bis 12, besonders bevorzugt für 0 oder eine ganze Zahl von 1 bis 8 steht,
y für eine ganze Zahl von 1 bis 20, bevorzugt von 1 bis 12, besonders bevorzugt von 1 bis 8, und
z für 0 oder eine ganze Zahl von 1 bis 20, bevorzugt für 0 oder eine ganze Zahl von 1 bis 12, besonders bevorzugt für 0 oder eine ganze Zahl von 1 bis 8 steht.Oligocarbonates are in the context of the invention preferably those of the general formulas (I), (II) and / or (III),

wherein
u is 0 or an integer from 1 to 20, preferably 0 or an integer from 1 to 12, particularly preferably 0 or an integer from 1 to 8,
y is an integer from 1 to 20, preferably from 1 to 12, particularly preferably from 1 to 8, and
z is 0 or an integer from 1 to 20, preferably 0 or an integer from 1 to 12, more preferably 0 or an integer from 1 to 8.

Such oligomers preferably have an average molecular weight M _w of up to 5000 g / mol, preferably up to 3500 g / mol, very particularly preferably up to 2000 g / mol.

The average molecular weight agents given herein are weight average (M _w ) determined by gel permeation chromatography (GPC) using polycarbonate as the standard. The detection of eluate signals, for example, by using the refractive index or by UV absorption in the range of z. B. 254 nm.

From the pump or pumps, the oligocarbonate-containing reaction mixture is condensed in at least one reactor with addition of further alkali metal hydroxide, optionally chain terminator (s) and optionally at least one further catalyst to give polycarbonates. In preferred embodiments, the condensation takes place in a cascade of a plurality of reactors connected in series. Suitable reactors for the condensation come any reactor designs, such as. B. stirred tank, tubular reactors, Umpumpreaktoren, their cascades or combinations thereof in question (see. 2 or 5 ).

to Processing of the reacted, at most still traces, preferably contains less than 2 ppm of chlorocarbonic acid esters, At least two-phase reaction mixture is allowed to settle for phase separation. The aqueous alkaline phase is optionally completely or partially back to the polycarbonate synthesis as aqueous Phase passed or fed to the wastewater treatment, where solvent and catalyst components separated and optionally recycled to the polycarbonate synthesis become. In another variant of the workup is after separation the organic impurities, in particular of solvents and polymer residues, and optionally after adjustment of a certain pH, z. B. by sodium hydroxide, the salt separated, which z. B. the chloralkali electrolysis are supplied may, while the aqueous phase optionally again the polycarbonate synthesis is supplied.

The organic, the polycarbonate-containing phase can subsequently to remove contaminants alkaline, ionic or catalytic Be sorted in various ways known to those skilled in the art.

The organic phase usually also includes one or several settling operations, possibly supported through passages through settling kettle, stirred tank, Coalescers or separators or combinations of these measures - where optionally water in each or a few separation steps below Circumstances using active or passive mixing devices can be added - still shares the aqueous alkaline phase in fine droplets as well as the one or the other Catalyst (s). After this coarse separation of the alkaline, aqueous phase, the organic phase can be one or more times with dilute acids, mineral, carbon hydroxycarbon and / or sulfonic acids are washed. Preferred are aqueous mineral acids, in particular hydrochloric acid, Phosphoric acid, phosphoric acid or mixtures of these Acids. The concentration of these acids should be preferably in the range 0.001 to 50 wt .-%, preferably 0.01 to 5 wt .-% are. Furthermore, the organic phase with desalted or distilled water repeatedly. The separation which, optionally dispersed with parts of the aqueous phase, organic phase after each wash is done by means of Settling vessel, stirred tank, coalescer or separators or Combinations of these measures, with the washing water between the washing steps optionally using active or can be added to passive mixing devices. Between these washes or even after washing, acids, preferably dissolved in the solvent which the Polymer solution is based, are added. Prefers Here are hydrogen chloride gas, phosphoric acid or phosphorous Acid, which may also be used as mixtures can be used. The purified polycarbonate solution thus obtained should preferably not more than 5% by weight after the last separation process, preferably less than 1% by weight, most preferably less as 0.5 wt .-% water.

The Isolation of the polycarbonate from the solution can be achieved by Evaporation of the solvent by means of temperature, vacuum or a heated towing gas. Other isolation methods are, for example, crystallization and precipitation.

Is the concentration of the polycarbonate solution and possibly also the isolation of the polycarbo Nats by distilling off the solvent, optionally by overheating and relaxation, it is called a "flash process." Such a method is known in the art and, for example, in "Thermal Separation Methods", VCH Verlagsanstalt 1988, p. 114 described. If, instead, a heated carrier gas is sprayed together with the solution to be evaporated, this is referred to as "spray evaporation / spray drying", which is described by way of example in US Pat Vauck, "Basic Operations of Chemical Process Engineering", Deutscher Verlag für Grundstoffindustrie 2000, 11th edition, p. 690 is described. All of these methods are described in the patent literature and textbooks and are familiar to those skilled in the art.

at the removal of the solvent by temperature (distilling off) or the technically more effective flash method one highly concentrated polycarbonate melts. In the flash process Polymer solutions are repeated under slight overpressure heated to temperatures above the boiling point under atmospheric pressure and these, with respect to normal pressure, overheated Solutions then in a vessel with lower pressure, z. B. normal pressure, relaxed. It can be done by Advantage, the concentration levels, or in other words the temperature levels of overheating do not become too high but rather a two- to four-step procedure choose.

From the high-concentration polycarbonate melts thus obtained, the residues of the solvent can be either directly from the melt with Ausdampfextrudern (see, eg. BE-A 866 991 . EP-A 0 411 510 . US Pat. No. 4,980,105 . DE-A 33 32 065 ), Thin-film evaporators (cf. EP-A 0 267 025 ), Falling film evaporators, strand evaporators or by friction compacting (cf. EP-A 0 460 450 ), optionally also with the addition of an entrainer, such as nitrogen or carbon dioxide, or by using a vacuum (cf. EP-A 0 039 96 . EP-A 0 256 003 . US Pat. No. 4,423,207 ), alternatively also by subsequent crystallization (cf. DE-A 34 29 960 ) and / or heating out the residues of the solvent in the solid phase (cf. US-A 3,986,269 . DE-A 20 53 876 ). These methods and the devices required for this purpose are described in the literature and familiar to the expert.

Polycarbonate granules can - if possible - through direct spinning of the melt and subsequent granulation or by using ejection extruders from those in the air or being spun under liquid, usually water, to be obtained. If extruders are used, the polycarbonate melt can be used before the extruder, if necessary using static mixers or by side extruder in this extruder, add additives.

alternative For example, the polycarbonate solution may be spray-evaporated be subjected. Upon spraying, the polycarbonate solution becomes optionally after heating either in a vessel with Evaporate underpressure or with a nozzle a heated carrier gas, e.g. As nitrogen, argon or Steam atomized in a vessel at atmospheric pressure. In both cases you get in dependence from the concentration of polymer solution powder (diluted) or flakes (concentrated) of the polymer from which, if appropriate also the last residues of the solvent as above removed Need to become. Subsequently, by means of a Compounding extruders and subsequent spinning granules to be obtained. Again, additives, as described above, in the periphery or in the extruder itself. often It may be necessary before extrusion due to the low Bulk density of the powder and flakes a compaction step to go through for the polymer powder.

alternative may be from the washed and optionally still concentrated Polycarbonate solution by adding a non-solvent For polycarbonate, the polymer largely precipitated become. The non-solvents act as precipitant. It is advantageous here, first a small amount of the non-solvent and, if necessary, waiting times between additions of the batches of non-solvent. It can also be advantageous to use different non-solvent. Use as precipitant find here z. B. aliphatic or cycloaliphatic hydrocarbons, in particular heptane, i-octane or cyclohexane, alcohols such. As methanol, ethanol or i-propanol, ketones, such as. As acetone, or mixtures of these. In the precipitation is usually the polymer solution slowly added to the precipitant. The thus obtained Polycarbonates are described as in the spray evaporation processed into granules and optionally additiviert.

To Other processes include precipitation and crystallization products or amorphous solidified products in fine-grained form by passing over vaporizing one or more non-solvents for Polycarbonate, with simultaneous heating below the glass transition temperature crystallized and further to higher molecular weights condensed. If necessary, these are oligomers with different end groups (phenolic and chain terminator ends) This is called solid phase condensation.

Of the Addition of additives serves to extend the useful life or improving the color stability (stabilizers), the simplification of processing (eg demoulding agents, flow aids, Antistatics) or the adaptation of the polymer properties to certain Loads (impact modifiers, such as rubbers, flame retardants, Colorant, glass fibers).

These Additives can be used individually or in any mixtures, together or in several different mixtures of the polymer melt be added. This can be done directly in the isolation of the polymer or but after melting of granules in a so-called compounding step respectively. In this case, the additives or their Mixtures as a solid, preferably as a powder, or as a melt be added to the polymer melt. Another type of dosage is the use of masterbatches or mixtures of masterbatches the additives or additive mixtures.

Suitable additives are described, for example, in " Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 ", in the " Plastics Additives Handbook, Hans Zweifel, Hanser, Munich 2001 ".

Suitable antioxidants or thermal stabilizers are, for example:
Alkylated monophenols, alkylthiomethylphenols, hydroquinones and alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, O-, N- and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, acylaminophenols, esters of β- (3,5-di-tert-butyl) butyl-4-hydroxyphenyl) propionic acid, esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, esters of β- (3,5-dicyclohexyl-4-hydroxyphenyl) propionic acid, esters of 3, 5-di-tert-butyl-4-hydroxyphenylacetic acid, amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, suitable thiosynergists, secondary antioxidants, phosphites, phosphonites, phosphonates and phosphanes, benzofuranones or indolinones ,

preferred Antioxidants or thermal stabilizers are organic phosphites, Phosphonates and phosphanes, mostly those where the organic Residues wholly or partly of optionally substituted aromatic Remains exist.

When Complexing agent for heavy metals and for neutralization of alkali traces are, for example, o- or m-phosphoric acids, fully or partially esterified phosphates or phosphites suitable.

When Light stabilizers (UV absorbers) are, for example, 2- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, esters of substituted and unsubstituted Benzoic acids, acrylates, hindered amines, oxamides, 2- (2-hydroxyphenyl) -1,3,5-triazines or substituted benzotriazoles suitable, particularly preferred are substituted benzotriazoles.

polypropylene glycols alone or in combination with z. As sulfones or sulfonamides as stabilizers can fight against the injury be used by gamma rays.

These and other stabilizers may be used alone or in combinations be used and added to the polymer in the forms mentioned become.

Furthermore can processing aids such as mold release agents, such as derivatives of long-chain fatty acids added become. Preferably z. Pentaerythritol tetrastearate and glycerol monostearate. They are used alone or in admixture preferably in an amount of 0.02 to 1 wt .-%, based on the composition of the composition used. Suitable flame retardant additives are phosphate esters, i. H. triphenyl Resorcinol diphosphoric acid esters, bromine-containing compounds, such as brominated phosphoric acid esters, brominated oligocarbonates and polycarbonates, and preferably salts of fluorinated organic Sulfonic acids. Suitable tougheners are butadiene rubber with grafted styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubbers with grafted maleic anhydride, ethyl and butyl acrylate rubbers with grafted methyl methacrylate or styrene-acrylonitrile, interpenetrating Siloxane and acrylate networks with grafted methyl methacrylate or styrene-acrylonitrile.

Of Further, colorants such as organic dyes or Pigments and inorganic pigments, IR absorbers, individually, in a mixture or in combination with stabilizers, glass fibers, glass (hollow) balls or inorganic fillers.

Polycarbonate melts produced by isolation of the polymer or by compounding can be spun through a die head in strand form, filled with gas, e.g. As air or nitrogen, or one Coolant, usually water, cooled and the solidified strands in commercial granulators with cutting the z. B. are on a rotating roll, in air, under inert gas such as nitrogen or argon or under water granulated. Depending on the apparatus design, columnar granules with a round or elliptical cross section and a rough or smooth surface are formed. The cut edges may be smooth or have a glassy break with broken cut edges or left-over residues at the cut edges. Desirable is a uniformly shaped as possible granules with as few remaining supernatants at the cutting edges. Furthermore, the dust content in the granules is to be kept as low as possible, preferably below 100 mg / kg of granules. The diameter of the granules should be between 0.5 mm and 10 mm, preferably 1 to 8 mm, particularly preferably 3 to 6 mm. While the length of the granules should be between 1 to 10 mm, preferably between 2 to 8 mm and the weight between 10 and 50 mg preferably between 15 and 30 mg. Preferably, a granulate whose ratio of diameter, with an elliptical cross section of the average diameter, to the length 0.8 to 1.2, more preferably one with the ratio of about 1. These parameters are subject to size distributions, preferred are very narrow distributions, ie as uniformly sized granules.

Cooling, Spinning, granulation and subsequent transport or conveying the granulate with gas or liquid, and subsequent storage, optionally after one Mixing or homogenization process, should be designed so that possible, despite the possibly existing static Charges no impurities on the polymer, strand or Granule surface are applied, such as Dust, abrasion from the machines, aerosol-like lubricants and others Liquids and salts from possibly used Water baths or cooling.

The produced by the process according to the invention Polymers are also the subject of the present application.

The produced by the process according to the invention Polymers have a narrow molecular weight distribution, preferably even narrower than those of the prior art with the interfacial process produced. Preferably, those according to the invention Process produced polymers a nonuniformity U of 1.1 to 1.6 (depending on the viscosity of the polycarbonates produced).

The Polycarbonates prepared according to the invention are suitable For example, for the production of extrudates and moldings, especially those for use in the transparent area, all especially in the field of optical applications such. B. plates, web plates, Glazings, diffusers, lamp covers or optical data storage, such as Audio CD, CD-R (W), DVD, DVD-R (W), Minidiscs in their various only readable or rewritable if necessary also repeatedly writable embodiments.

• 1. Sicherheitsscheiben, die bekanntlich in vielen Bereichen von Gebäuden, Fahrzeugen und Flugzeugen erforderlich sind, sowie als Schilde von Helmen.
• 2. Folien
• 3. Blaskörper (s. a. US-A 2 964 794 ), beispielsweise 1 bis 5 Gallon Wasserflaschen.
• 4. Lichtdurchlässige Platten, wie Massivplatten oder insbesondere Hohlkammerplatten, beispielsweise zum Abdecken von Gebäuden wie Bahnhöfen, Gewächshäusern und Beleuchtungsanlagen.
• 5. Optische Datenspeicher, wie Audio CD's, CD-R(W)'s, DCD's, DVD-R(W)'s, Minidiscs und den Folgeentwicklungen
• 6. Ampelgehäuse oder Verkehrsschilder
• 7. Schaumstoffe mit offener oder geschlossener gegebenenfalls bedruckbarer Oberfläche
• 8. Fäden und Drähte (s. a. DE-A 11 37 167 )
• 9. Lichttechnische Anwendungen, gegebenenfalls unter Verwendung von Glasfasern für Anwendungen im transluzenten Bereich
• 10. Transluzente Einstellungen mit einem Gehalt an Bariumsulfat und oder Titandioxid und oder Zirkoniumoxid bzw. organischen polymeren Acrylatkautschuken ( EP-A 0 634 445 , EP-A 0 269 324 ) zur Herstellung von lichtdurchlässigen und lichtstreuenden Formteilen.
• 11. Präzisionsspritzgussteile, wie Halterungen, z. B. Linsenhalterungen; hier werden gegebenenfalls Polycarbonate mit Glasfasern und einem gegebenenfalls zusätzlichen Gehalt von 1–10 Gew.-% Molybdändisulfid (bez. auf die gesamte Formmasse) verwendet.
• 12. optische Geräteteile, insbesondere Linsen für Foto- und Filmkameras ( DE-A 27 01 173 ).
• 13. Lichtübertragungsträger, insbesondere Lichtleiterkabel ( EP-A 0 089 801 ) und Beleuchtungsleisten
• 14. Elektroisolierstoffe für elektrische Leiter und für Steckergehäuse und Steckverbinder sowie Kondensatoren.
• 15. Mobiltelefongehäuse.
• 16. Network interface devices
• 17. Trägermaterialien für organische Fotoleiter
• 18. Leuchten, Scheinwerferlampen, Streulichtscheiben oder innere Linsen.
• 19. Medizinische Anwendungen wie Oxygenatoren, Dialysatoren.
• 20. Lebensmittelanwendungen, wie Flaschen, Geschirr und Schokoladenformen.
• 21. Anwendungen im Automobilbereich, wie Verglasungen oder in Form von Elends mit ABS als Stoßfänger.
• 22. Sportartikel wie Slalomstangen, Skischuhschnallen.
• 23. Haushaltsartikel, wie Küchenspülen, Waschbecken, Briefkästen
• 24. Gehäuse, wie Elektroverteilerkästen
• 25. Gehäuse für elektrische Geräte wie Zahnbürsten, Föne, Kaffeemaschinen, Werkzeugmaschinen, wie Bohr-, Fräs-, Hobelmaschinen und Sägen
• 26. Waschmaschinen-Bullaugen
• 27. Schutzbrillen, Sonnenbrillen, Korrekturbrillen bzw. deren Linsen.
• 28. Lampenabdeckungen
• 29. Verpackungsfolien
• 30. Chip-Boxen, Chipträger, Boxen für Si-Wafer
• 31. Sonstige Anwendungen wie Stallmasttüren oder Tierkäfige.

Further applications are, for example, but without limiting the subject matter of the present invention:

• 1. Safety discs, which are known to be required in many areas of buildings, vehicles and aircraft, as well as shields of helmets.
• 2. Slides
• 3. Blow body (sa US-A 2,964,794 ), for example 1 to 5 gallons of water bottles.
• 4. Translucent panels, such as solid sheets or in particular hollow panels, for example, for covering buildings such as stations, greenhouses and lighting systems.
• 5. Optical data storage, such as Audio CD's, CD-R (W) 's, DCD's, DVD-R (W)' s, Mini Discs and subsequent developments
• 6. traffic light housing or traffic signs
• 7. Foams with open or closed optionally printable surface
• 8. Threads and wires (sa DE-A 11 37 167 )
• 9. Lighting applications, optionally using glass fibers for translucent applications
• 10. Translucent settings containing barium sulfate and or titanium dioxide and or zirconium oxide or organic polymeric acrylate rubbers ( EP-A 0 634 445 . EP-A 0 269 324 ) for the production of translucent and light-scattering moldings.
• 11. Precision injection molded parts, such as holders, e.g. B. lens mounts; Optionally polycarbonates with glass fibers and an optionally additional content of 1-10% by weight of molybdenum disulphide (based on the entire molding composition) are used here.
• 12. optical device parts, in particular lenses for photo and film cameras ( DE-A 27 01 173 ).
• 13. light transmission carrier, in particular optical fiber cable ( EP-A 0 089 801 ) and lighting strips
• 14. Electrical insulating materials for electrical conductors and for connector housings and connectors as well as capacitors.
• 15. Cellphone case.
• 16. Network interface devices
• 17. Support materials for organic photoconductors
• 18. Lights, Headlamps, Scatterers or Inner Lenses.
• 19. Medical applications such as oxygenators, dialyzers.
• 20. Food applications, such as bottles, dishes and chocolate molds.
• 21. Applications in the automotive sector, such as glazing or in the form of misery with ABS as a bumper.
• 22. Sporting goods like slalom poles, ski boot buckles.
• 23. Household items, such as kitchen sinks, sinks, mailboxes
• 24. Housing, such as electrical distribution boxes
• 25. Housing for electrical appliances such as toothbrushes, hair driers, coffee machines, machine tools, such as drilling, milling, planing machines and saws
• 26. Washing machine portholes
• 27. Goggles, sunglasses, corrective glasses or their lenses.
• 28. Lamp covers
• 29. Packaging films
• 30. Chip boxes, chip carriers, boxes for Si wafers
• 31. Other applications such as stable or animal cages.

Surprised could also with the inventive method the diphenol load of the waste water can be reduced.

• – nach dem Stator-Rotor-Prinzip arbeitet (arbeiten)
• – thermostatisierbar ist (sind) und
• – wenigstens jeweils einen Zugang für eine organische und eine wässrige Phase und gegebenenfalls weitere Zugänge für Kettenabbrecher, Verzweiger und/oder zusätzlich Alkalilauge sowie wenigstens einen Ausgang für die oligocarbonathaltige Mischung aufweist (aufweisen),

dadurch gekennzeichnet, dass in dieser/diesen Pumpen sowohl die kontinuierliche Mischung der organischen und wässrigen Phase, wobei die organische Phase wenigstens ein für das Polycarbonat geeignetes Lösungsmittel und ganz oder teilweise das Phosgen enthält und die wässrige Phase das oder die Diphenol(e), Wasser und Alkalilauge enthält, als auch die Umsetzung des oder der Diphenol(e) und Phosgen zu Oligocarbonaten erfolgt.The use of triple-function pumps as a mixing unit, reaction space for the oligomerization step and delivery unit is not described in the literature for the interfacial process for producing polycarbonates. The present invention therefore furthermore relates to the use of one or more pumps for the continuous production of polycarbonate by the interfacial process, wherein the pump (s)

• - works (works) according to the stator-rotor principle
• - Is thermostatable (are) and
• At least one access for an organic phase and one aqueous phase and optionally further accesses for chain terminators, branching agents and / or additionally alkali lye and at least one outlet for the mixture containing oligocarbonate (have)

characterized in that in this / these pumps both the continuous mixture of the organic and aqueous phase, wherein the organic phase contains at least one suitable for the polycarbonate solvent and wholly or partially the phosgene and the aqueous phase or the diphenol (s), water and alkali metal hydroxide, as well as the reaction of the diphenol (s) and phosgene to oligocarbonates takes place.

For this use is the preceding for the invention Method already described pumps. In particular, are suitable for this centrifugal pumps, particularly preferably Peripheralradpumpen.

The The following examples are given by way of example of the invention and are not to be considered as limiting.

Examples

In a continuous interfacial process Polycarbonates by means of different reactor concepts produced. In the experiments, the influence of the invention Use of the special pump over known reactors as Umpumprekatoren or nozzles with otherwise the same reaction settings examined.

The reaction was carried out continuously in all examples in an emulsion of water and a mixed solvent of 50% by weight of methylene chloride and 50% by weight of chlorobenzene. The chain terminator used was p-tert-butylphenol (BUP). The catalyst used was n-ethylpiperidine (EPP). After separating the aqueous phase after passing through the residence cascade from the four post-reactors NR1 to NR4 in 3 and 5 The polycarbonate solution obtained was acid washed with hydrochloric acid, and then washed neutral with dishwater with demineralized water. The thus washed polycarbonate solutions were concentrated after drying by evaporation of the solvent. A complete removal of the residual solvent in a vacuum oven at 100 ° C led to the polycarbonate.

• • Na-Bisphenolat-Lösung: Durchsatz 910,3 g/h (0,598 mol Bisphenol A/h), Na-Bisphenolat-Gehalt: 15,0 Gew.-% Na-Bisphenolat bezogen auf das Gesamtgewicht der Lösung
• • Phosgen: 72,18 g/h (0,73 mol/h)
• • Lösungsmittel: 737,7 g/h (Lösungsmittelgemisch aus 50 Gew.-% Methylenchlorid und 50 Gew.-% Chlorbenzol)
• • Natronlauge: 113,9 g/h; NaOH-Gehalt: 44 Gew.-% NaOH, bezogen auf das Gesamtgewicht der Natronlauge, zum Lösen von 136,5 g Bisphenol A
• • Natronlauge nach erstem Reaktor: 49,5 g/h; NaOH-Gehalt: 44 Gew.-% NaOH bezogen auf das Gesamtgewicht der Natronlauge
• • Kettenabbrecher BUP: 3,594 g/h (in 140,2 g/h Lösungsmittelgemisch 50:50)
• • Katalysator EPP: 0,677 g/h; (in 6,2 g/h Lösungsmittel 50:50)
• • Phosgen/Bisphenol A: 122 mol-% Phosgen bezogen auf die Stoffmenge Bisphenol A
• • EPP/Bisphenol A: 1,0 mol-% EPP bezogen auf die Stoffmenge Bisphenol A
• • BUP/Bisphenol A: 4,0 mol-% BUP bezogen auf die Stoffmenge Bisphenol A
• • Reaktionstemperatur: 34°C
• • Polycarbonatgehalt: 15,0 Gew.-% Polycarbonat, bezogen auf das Gesamtgewicht der Lösung, gelöst in vorangehend genanntem Lösungsmittel
• • Zugabe des Kettenabbrechers nach dem ersten Reaktor

The procedure was carried out in all examples with the following reaction settings:

• • Na bisphenolate solution: throughput 910.3 g / h (0.598 mol bisphenol A / h), Na bisphenolate content: 15.0% by weight Na bisphenolate based on the total weight of the solution
• Phosgene: 72.18 g / h (0.73 mol / h)
• Solvent: 737.7 g / h (solvent mixture of 50% by weight of methylene chloride and 50% by weight of chlorobenzene)
• Sodium hydroxide: 113.9 g / h; NaOH content: 44% by weight of NaOH, based on the total weight of the sodium hydroxide solution, for dissolving 136.5 g of bisphenol A
• Sodium hydroxide solution after the first reactor: 49.5 g / h; NaOH content: 44% by weight of NaOH, based on the total weight of the sodium hydroxide solution
• • Chain terminator BUP: 3.594 g / h (in 140.2 g / h solvent mixture 50:50)
• • Catalyst EPP: 0.677 g / h; (in 6.2 g / h of solvent 50:50)
• • phosgene / bisphenol A: 122 mol% phosgene based on the amount of bisphenol A
• EPP / bisphenol A: 1.0 mol% EPP based on the amount of bisphenol A
• • BUP / bisphenol A: 4.0 mol% BUP based on the amount of bisphenol A
• • Reaction temperature: 34 ° C
• Polycarbonate content: 15.0% by weight of polycarbonate, based on the total weight of the solution, dissolved in the aforesaid solvent
• • Add the chain terminator after the first reactor

The addition of the chain terminator was carried out in all examples in such a way that a comparable relative viscosity (η _rel ) was achieved for the end products.

Example 1 (comparative example)

According to experimental setup in 3 Polycarbonate was produced. In this case, such a circulating pump UR 2 was the first reactor according to 4 made of glass, to which a residence cascade of four stirred tanks (after-reactors NR1 to NR4) followed for after-reaction. In the individual reactors, the stirring elements were driven by motors M. Before and after the last after-reactor NR4 were also two gear pumps with motor M. Na bisphenolate solution, phosgene in the above solvent and sodium hydroxide were continuously supplied to the Umpumpreaktor in the above amount and backmixed by pumping with valve V7.3 open. The stirrer used was operated in the circulating pump at 1000 revolutions / min. At the outlet of the pumped circulation reactor, the reaction mixture was continuously led out of the pumped circulation reactor, added with chain terminators and into the in 3 shown dwelling cascade of four stirred tanks led to post-reaction. The catalyst was fed to the third postreactor NR3.

Example 2 (Comparative Example)

It the same experimental setup was used as in Example 1, however was closed in Umpumpreaktor UR 2, the valve V7.3, so that a backmixing was excluded. This worked the Umpumpreaktor UR 2 as a normal nozzle.

Example 3 (according to the invention):

Instead of Umpumpreaktors UR 2 in Example 1 was a Peripheralradpumpe RM according to 1 used. Otherwise, the same experimental setup was used as in Example 1 (cf. 5 ). Na bisphenolate solution, phosgene in the above-mentioned solvent and sodium hydroxide solution were continuously supplied to the pump RM in the above-mentioned amount and mixed by the blade-provided rotating peripheral gear. At the outlet of the pump RM, the reaction mixture was continuously led out of the interior of the pump, added with chain terminator and into the in 5 shown dwelling cascade of four stirred tanks led to post-reaction. The catalyst was fed to the third postreactor NR3.

Tab. 1 shows the results with regard to the polycarbonate obtained and the loading of the resulting waste water with bisphenol A (BPA). Tab. 1: example BPA content in wastewater [ppm by weight] M _w [g / mol] U η _rel 1 238 19182 1.54 1,215 2 675 19111 1.69 1,214 3 48 19353 1.51 1,218

The relative solution viscosity η _rel was determined in dichloromethane as solvent at a concentration of 5 g / l and at a temperature of 25 ° C using an Ubbelohde viscometer.

Of the BPA content in wastewater was determined by HPLC and UV detection (245 nm) after calibration with BPA.

The Results show a significant reduction of wastewater pollution with BPA according to the invention using the special Pump compared to conventional production by pumping reactor or single nozzle. In case of Inventive implementation of the interfacial process is therefore an increase in phosgene and caustic soda to complete the implementation of the diphenol not required. Therefore, this is carried out according to the invention Method also more economical than the known methods. Also, the inconsistency U, which is a measure of the width of the molecular weight distribution of the resulting polycarbonate is, could be easily obtained over the products be reduced by known methods.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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• EP 0269324A [0081]
• - DE 2701173 A [0081]
• EP 0089801A [0081]

Cited non-patent literature

• Quick, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, pp. 33-70 [0002]
• - DC Prevorsek, BT Debona and Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, NJ 07960: "Synthesis of Poly (ester Carbonate) Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 1980) "; Pp. 75-90 [0002]
• - Friday, U. Grigo, PR Müller, N. Nouvertne ', BAYER AG, "Polycarbonates" in Encyclopaedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pp. 651-692 [0002]
• Dres. U. Grigo, K. Kircher and P. R-Muller "Polycarbonates" in Becker / Braun, Kunststoff-Handbuch, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, p 118-145 [0002]
• H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, p. 28ff; Pp. 102ff [0023]
• - DG Legrand, JT Bendler, Handbook of Polycarbonates Science and Technology, Marcel Dekker New York 2000, p. 72ff. [0023]
• - "Thermal Separation Process", VCH Verlagsanstalt 1988, p. 114 [0058]
• - Vauck, "Basic Operations of Chemical Process Engineering", Deutscher Verlag für Grundstoffindustrie 2000, 11.Auflage, p. 690 [0058]
• - Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 [0067]
• - Plastics Additives Handbook, Hans Zweifel, Hanser, Munich 2001 [0067]

Claims (10)

A process for the continuous production of polycarbonates by the interfacial process from at least one diphenol, phosgene and at least one catalyst optionally in the presence of at least one chain terminator and / or branching agent, characterized in that (a) a mixture of the organic and aqueous phase is continuously produced, wherein the organic phase contains at least one solvent suitable for the polycarbonate and wholly or partly contains the phosgene and the aqueous phase contains the diphenol or (e), water and alkali lye, (b) a reaction of the diphenol (s) and phosgene to oligocarbonates , (c) the oligocarbonates are then condensed in at least one reactor with addition of further alkali metal hydroxide, optionally chain terminator (s) and optionally at least one further catalyst, characterized in that the continuous mixture of the organic and aqueous phases under (a) and the conversion into oligocarbonates under (b) takes place in one or more pump (s) which - works (works) according to the stator-rotor principle - is (are) thermostatable and - at least one access each for the organic and the aqueous phase and if appropriate further accesses for chain terminators, branching agents and / or additionally alkali metal hydroxide solution and at least one outlet for the mixture containing oligocarbonate (have). Process according to claim 1, characterized characterized in that the pump (s) has one or more rotors (exhibit). A method according to claim 1 or 2, characterized in that the pump (s) to a temperature of -5 ° C. to 100 ° C, preferably from 15 ° C to 80 ° C, particularly preferably from 25 ° C to 65 ° C is thermostatable. Method according to at least one of claims 1 to 3, characterized in that as Diphenol (e) hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, Bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, α, α'-bis (hydroxyphenyl) diisopropylbenzenes, Bis (hydroxyphenyl) phthalimidines or their alkylated, nuclear alkylated and nucleated compounds are used. Method according to at least one of claims 1 to 4, characterized in that as Diphenol (s) 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, 1,1-bis- (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis (4-hydroxyphenyl) propane (Bisphenol A, BPA), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (Bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (3,5-dimethyl-4-hydroxyphenyl) -2-propyl] benzene, 2-Hydrocarbyl-3,3-bis (4-hydroxyphenyl) phthalimidine, 3,3-bis (4-hydroxyphenyl) -1-phenyl-1H-indol-2-one, 2,2-bis (4-hydroxyphenyl) -1-phenyl-1H-indol-2-one, 3,3-bis (4-hydroxyphenyl) -1-methyl-1H-indol-2-one, 2,2-bis (4-hydroxyphenyl) -1-methyl-1H-indol-2-one, 3,3-bis (4-hydroxyphenyl) -N-methyl-phthalimidine, 3,3-bis (4-hydroxyphenyl) -N-phenyl-phthalimidine and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Bisphenol TMC) can be used. Method according to at least one of claims 1 to 5, characterized in that it at the pump or pumps to centrifugal pumps, preferably Peripheralradpumpen is. Method according to at least one of claims 1 to 6, characterized in that the the pump (s) is constructed according to the single or multi-chamber principle (are). Polycarbonate available by the method according to at least one of the claims 1 to 7. Use of one or more pumps for the continuous production of polycarbonate according to the interfacial process, wherein the pump (s) - works on the stator-rotor principle (work) - is (are) thermostatable and - at least one access for each organic and an aqueous phase and, if appropriate, further accesses for chain terminators, branching agents and / or additionally alkali lye and at least one outlet for the oligocarbonate-containing mixture, characterized in that in this / these pumps both the continuous mixture of the organic and aqueous phase, wherein the organic phase contains at least one suitable for the polycarbonate solvent and wholly or partially the phosgene and the aqueous phase or the diphenol (s), water and alkali metal hydroxide, as well as the reaction of the diphenol (s) and phosgene to oligocarbonates takes place. Use of one or more centrifugal pumps, preferred Peripheral wheel pumps according to claim 9.