DE102004030664A1 - Composition, useful to prepare e.g. molded parts (optical components, foils, photometric applications, safety disks, electrical junction boxes or lamp covers), comprises a polycarbonate and an ester of organic sulfur containing acids - Google Patents

Abstract

Composition (I) comprises a polycarbonate and an ester of organic sulfur containing acids. An independent claim is also included for molded parts, molded articles and extrudates obtained from (I).

Description

object of this invention are compositions with improved thermostability containing polycarbonate and bridged Esters of organic sulfur-containing acids and moldings and Extrudates of these modified polycarbonate compositions, the compositions also also degradation products of the bridged esters of organic sulfur-containing acids.

The production processes for polycarbonate are known from the literature and described in many applications:
For the preparation of polycarbonates by the phase interface or melt transesterification method, see "Schnell", Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964, p. 33 et seq., And Polymer Reviews, Volume 10, "Condensation Polymers by Interfacial and Solution Methods," Paul W. Morgan, Interscience Publishers, New York 1965, Ch. VIII, p. 325 and EP-A 971790.

polycarbonates need under the influence of high temperatures stabilizers against discoloration, chemical reactions of the additives and degradation reactions. Especially Polycarbonate types for optical applications can exposed to high temperature loads during further processing be that to the unwanted Formation of monomers by degradation reactions, the loss of molecular weight or to chemical reactions of additives, such as the incorporation into the polymer chain as well as the degradation of the additives that the effectiveness of additives adversely affect lead.

Stabilization against high temperatures is known with phosphorus-organic compounds such as phosphines ( US 4 092 288 B ) or phosphites ( JP 54036363 A ). Also known is the stabilization with onium salts, such as tetraalkyl phosphonium and ammonium salts, dodecyl benzene sulfonic acid and with acids or a simple acid ester of an acid containing a sulfur atom, such as n-butyl tosylate (JP 08-059975 A).

Organophosphorus Thermostabilizers are usually in orders of magnitude of several 100 ppm added to the polycarbonate. Especially with polycarbonate types for optical However, applications are aimed at, only minimal amounts of additives to use. So are supposed to be unwanted Effects of particle formation or molding problems in injection molding repressed and ensures a positive overall performance of the material become.

Out establish the economy are also very small amounts of additives desirable.

When detrimental prove in the described free acids and easily cleavable esters whose corrosive properties at high Temperatures and concentration, such as those at a technical dosage of stabilizers may occur. It is great Advantage of using stabilizers which are the materials of the apparatus do not affect particles, metallic cations and safety defects submissions. Furthermore, much of the described free acids and easily cleavable esters easily volatile. That makes an indispensable constant and clean dosage of quencher in a continuous Interference in the melt stream.

One Another disadvantage of many acid ester stabilizers is that they are big too fast Amounts of free acids to generate. A surplus of free acid For example, it catalyzes reactions of the polycarbonates with others Additives such as mold release agents or even promotes re-reactions in the case of melt polycarbonate with release phenol of diphenyl carbonate. Small amounts of excess ester-bound acid, the the free acid very slowly under thermal stress during further processing of the stabilized polycarbonate release, however, are quite desirable. she increase the thermal capacity of the polycarbonate.

It was therefore an object to find thermal stabilizers for polycarbonate, which must be used only in small amounts, non-corrosive and difficultly volatile and at the same time easily soluble and metered in inert solvents or process-specific components. Likewise, the stabilizers Never generate larger excesses of free acid in the polycarbonate to avoid degradation reactions of polycarbonate to form carbonates or to inhibit reactions with the additives. Instead, a slow generation of the free acids is desired. It is particularly desirable if the stabilizer does not completely form all possible free acid during incorporation into the polycarbonate and any subsequent steps. Thus, it can again have an effect on further processing after granulation of the polycarbonate, such as injection molding (long-term effect by successive release of the free acid in all thermal load steps).

Surprised was now found that bridged Esters of organic sulfur-containing acids the desired Balanced properties and excellent for thermal stabilization of Polycarbonates are suitable. So set these stabilizers surprisingly only slowly and in stages free the corresponding free acids. Furthermore are they so fleeting in themselves, that they are also longer Residence times hardly evaporate from the polycarbonate melt. Surprisingly show the stabilizers even at high temperatures and concentrations no corrosive behavior towards usually used metallic materials such as 1.4571 or 1. 4541 (steel key 2001, Publisher: Steel key Wegst GmbH, Th-Heuss-Strasse 36, D-71672 Marbach) and Ni-base alloys of the type C, such. B. 2.4605 or 2.4610 (steel key 2001, Publisher: Stahlschlüssel Wegst GmbH, Th-Heuss-Strasse 36, D-71672 Marbach).

This In particular, it is amazing how to stabilize Polycarbonate in general can make no predictions whether the Stabilizers the desired Properties such as low volatility, solubility in process-inherent solvents Corrosion-free and slow acid release in the right way Unite measure.

object of this invention are therefore compositions containing improved thermostability Polycarbonate and bridged Esters of organic sulfur-containing acids, as well as moldings and Extrudates of these modified polycarbonate compositions, the compositions furthermore also degradation products of these bridged Contain esters.

• a) der Formel (I)
  
  in welcher R¹ unabhängig für Wasserstoff oder für C₁-C₂₀-Alkyl, vorzugsweise für C₁-C₈-Alkyl, besonders bevorzugt für unsubstituiertes C₁-C₆-Alkyl, ganz besonders bevorzugt für C₁-C₄-Alkyl, wobei Alkyl durch Halogen substituiert sein kann, insbesondere für Wasserstoff oder Methyl steht, R² und R³ unabhängig voneinander für Wasserstoff, oder für C₁-C₆-Alkyl, C₄-C₃₀-Alkylcarboxyl, vorzugsweise C₁-C₄-Alkyl, C₆-C₂₅-Alkylcarboxyl, besonders bevorzugt für C₈-C₂₀-Alkylcarboxyl, insbesondere für Wasserstoff, C₁₇-Alkylcarboxyl oder C₁₅-Alkylcarboxyl oder für den Rest
  
  stehen, worin R¹ die oben genannte Bedeutung hat, n für eine ganze Zahl von 0 bis 8, vorzugsweise 0 bis 6, insbesondere 0, 1 oder 2 steht,
• b) der Formel (II)
  
  in welcher R¹ die oben genannte Bedeutung hat,
• c) der Formel
  
  in welcher R¹ die oben genannte Bedeutung hat und
• d) der Formel (IV)
  
  in welcher R¹ und n die oben genannte Bedeutung haben, und R⁴ für C₄-C₃₀-Alkylcarboxyl, vorzugsweise C₆-C₂₅-Alkylcarboxyl, besonders bevorzugt für C₈-C₂₀-Alkylcarboxyl, insbesondere für, C₁₇Alkylcarboxyl oder C_{1 5}-Alkylcarboxyl oder für folgenden Rest
  
  wobei R¹ die oben genannte Bedeutung hat, steht und
• e) der Formel (V), (VI), (VII), (Ib), (IVb)
  
  
  
  in welcher R¹ und n die oben genannte Bedeutung haben, und R⁵ und R⁶ unabhängig für Wasserstoff oder für C₁-C₂₀-Alkyl, vorzugsweise für C₁-C₈-Alkyl, besonders bevorzugt für C₁-C₆-Alkyl, ganz besonders bevorzugt für C₁-C₄-Alkyl, wobei Alkyl durch Halogen substituiert sein kann, insbesondere für Wasserstoff oder Methyl steht, und R¹¹ unabhängig für Wasserstoff oder Di-(C₁-C₄)-Alkylamino, vorzugsweise für Wasserstoff oder Dimethylamino steht.

Preferred thermal stabilizers suitable according to the invention are bridged esters of organic sulfur-containing acids selected from at least one compound

• a) of the formula (I)
  
  in which R ^{1 is} independently hydrogen or C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₈ -alkyl, more preferably unsubstituted C ₁ -C ₆ -alkyl, most preferably C ₁ -C ₄ -alkyl where alkyl may be substituted by halogen, in particular hydrogen or methyl, R ² and R ^{3 are} independently hydrogen, or C ₁ -C ₆ alkyl, C ₄ -C ₃₀ alkylcarboxyl, preferably C ₁ -C ₄ Alkyl, C ₆ -C ₂₅ -alkylcarboxyl, particularly preferably C ₈ -C ₂₀ -alkylcarboxyl, in particular hydrogen, C ₁₇ -alkylcarboxyl or C ₁₅ -alkylcarboxyl or the radical
  
  in which R ^{1 has} the abovementioned meaning, n is an integer from 0 to 8, preferably 0 to 6, in particular 0, 1 or 2,
• b) of the formula (II)
  
  in which R ^{1 has} the abovementioned meaning,
• c) the formula
  
  in which R ^{1 has} the abovementioned meaning and
• d) of the formula (IV)
  
  in which R ¹ and n have the abovementioned meaning, and R ^{4 is} C ₄ -C ₃₀ -alkylcarboxyl, preferably C ₆ -C ₂₅ -alkylcarboxyl, particularly preferably C ₈ -C ₂₀ -alkylcarboxyl, especially for, C ₁₇ alkylcarboxyl or C _{1 5} alkyl carboxyl or the following radical
  
  where R ^{1 has} the abovementioned meaning, and
• e) of the formula (V), (VI), (VII), (Ib), (IVb)
  
  
  
  in which R ¹ and n have the abovementioned meaning, and R ⁵ and R ^{6 are} each independently hydrogen or C ₁ -C ₂₀ -alkyl, preferably C ₁ -C ₈ -alkyl, more preferably C ₁ -C ₆ - Alkyl, most preferably C ₁ -C ₄ alkyl, wherein alkyl may be substituted by halogen, in particular hydrogen or methyl, and R ^{11 is} independently hydrogen or di (C ₁ -C ₄ ) alkylamino, preferably Hydrogen or dimethylamino stands.

Very particular preference is given to the following subject stabilizers of the formulas (Ia) to (Ik):

The Thermostabilizers according to the invention can individually or in any mixtures or several different Mixtures of the polymer melt can be added. The thermal stabilizers according to the invention can also in mixtures with free acids, such as ortho-phosphoric acid may be added.

The Preparation of the bridged esters of the invention of organic sulfur-containing acids is carried out according to customary For example, by alcoholysis from the benzenesulfonyl chloride or toluenesulfonyl with the corresponding polyhydric alcohols (see Organikum, Wiley-VCH Verlag, 20th edition, Weinheim, p. 606/1999).

The Polycarbonate, for example, after the melt transesterification process getting produced. The production of aromatic oligo- or Polycarbonates after the melt transesterification process is known from the literature and for example in the Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964) and in DE-C 10 31 512, US-A 3,022,272, US-A 5,340,905 and US-A 5,399,659.

According to this Methods are aromatic dihydroxy compounds, with carbonic acid diesters with the aid of suitable catalysts and, if appropriate other additives in the melt transesterified.

to execution of the method, for example, a plant design, as they in WO 02/077 067, can be used.

For the preparation of polycarbonates, suitable dihydroxyaryl compounds are those of the formula (VIII) HO-Z-OH (VIII) in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members.

Examples for dihydroxyaryl compounds are: dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, Bis (hydroxyphenyl) aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, 1,1'-bis (hydroxyphenyl) -diisopropylbenzenes, and their nuclear alkylated and nuclear halogenated compounds.

These and other suitable dihydroxyaryl compounds are e.g. in U.S. Patents 2,970,131, 2,991,273, 2,999,835, 2,999 846, 3,028,365, 3,062,781, 3,148,172, 3,271,367, 3,275,601, 4,982,014, in German Patent Specifications 1 570 703, 2 063 050, 2 036 052, 2 211 956, 3 832 396, the French Patent 1,561,518, and in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pp. 28 ff., P.102ff., And in D.G. Legrand, J.T. Bendler, Handbook of Polycarbonates Science and Technology, Marcel Dekker New York 2000, pp. 72ff. ".

preferred Dihydroxyaryl compounds are, for example: resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) -methane, Bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, bis- (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, 1,1-bis (4-hydroxyphenyl) -1- (1-naphthyl) -ethane, 1,1-bis- (4-hydroxyphenyl ) -1- (2-naphthyl) ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxyphenyl) - 1-phenyl-propane, 2,2-bis (4-hydroxyphenyl) hexafluoro-propane, 2,4-bis (4-hydroxyphenyl) -2-methyl-butane, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl ) -2-methyl butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, 1,1'-bis (4-hydroxyphenyl) -3-diisopropylbenzene, 1,1'-bis (4-hydroxyphenyl) -4-diisopropylbenzene, 1,3-bis [2- (3,5-dimethyl-4-hydroxyphenyl) -2-propyl] -benzene, Bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, Bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone and 2,2 ', 3,3'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi- [1H- indene] -5,5'-diol.

Especially preferred dihydroxyaryl compounds are: resorcinol, 4,4'-dihydroxydiphenyl, Bis (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, bis (4-hydroxyphenyl) -1- (1-naphthyl) -ethane, Bis- (4-hydroxyphenyl) -1- (2-naphthyl) -ethane, 2,2-bis- (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) -3,3,5-trimethyl-cyclohexane, 1,1'-bis (4-hydroxyphenyl) -3-diisopropyl-benzene and 1,1'-bis (4-hydroxyphenyl) -4-diisopropylbenzene.

All particularly preferred are: 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane and bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

It can both a dihydroxyaryl compound to form homopolycarbonates as well as various dihydroxyaryl compounds to form Copolycarbonates are used.

Instead of The monomeric Dihydroxyarylverbindungen can also low molecular weight, predominantly OH endgruppengestoppte Oligocarbonate be used as starting compound.

The Dihydroxyaryl compounds can also with residual contents of Monohydroxyarylverbindungen, from which they were prepared or the low molecular weight oligocarbonates with residual contents of monohydroxyaryl compounds used in the preparation were eliminated from the oligomers used. The residual contents The monomer hydroxyaryl compounds can be up to 20%, preferably 10%, more preferably up to 5%, and most preferably until to 2% (see, e.g., EP-A 1 240 232).

The used Dihydroxyarylverbindungen, as well as all others of Synthesis added raw materials, chemicals and auxiliaries can with from their own synthesis, handling and storage Contaminants may be contaminated, although it is desirable and objective with preferably clean raw materials, chemicals and auxiliary materials.

wobei R, R' und R'' unabhängig voneinander gleich oder verschieden für Wasserstoff, gegebenenfalls verzweigtes C₁-C₃₄ Alkyl, C₇-C₃₄-Alkylaryl oder C₆-C₃₄-Aryl stehen, R weiterhin auch -COO-R''' bedeuten kann, wobei R''' für Wasserstoff, gegebenenfalls verzweigtes C₁-C₃₄ Alkyl, C₇-C₃₄-Alkylaryl oder C₆-C₃₄-Aryl steht.Suitable diaryl carbonates for the reaction with the dihydroxyaryl compounds are those of the formula (IX)

wherein R, R 'and R''are ₃₄ aryl independently the same or different and represent hydrogen, optionally branched C ₁ -C ₃₄ alkyl, C ₇ -C ₃₄ alkylaryl or C ₆ -C, R furthermore also -COO-R ''', where R''' is hydrogen, optionally branched C ₁ -C ₃₄ alkyl, C ₇ -C ₃₄ alkylaryl or C ₆ -C ₃₄ aryl.

Such Diaryl carbonates are, for example: diphenyl carbonate, methyl phenyl phenyl carbonates and di (methylphenyl) carbonates, 4-ethylphenyl phenyl carbonate, Di (4-ethylphenyl) carbonate, 4-n-propylphenyl phenyl carbonate, Di (4-n-propylphenyl) carbonate, 4-iso-propylphenyl-phenyl carbonate, di- (4-iso-propylphenyl) -carbonate, 4-n-butylphenyl phenyl carbonate, di- (4-n-butylphenyl) carbonate, 4-iso-butylphenyl phenyl carbonate, di (4-iso-butylphenyl) carbonate, 4-tert-butylphenyl phenyl carbonate, Di (4-tert-butylphenyl) carbonate, 4-n-pentylphenyl phenyl carbonate, Di (4-n-pentylphenyl) carbonate, 4-n-hexylphenyl phenyl carbonate, di (4-n-hexylphenyl) carbonate, 4-iso-octylphenyl-phenyl-carbonate, di- (4-iso-octylphenyl) -carbonate, 4-n-nonylphenyl-phenyl-carbonate, di- (4-n-nonylphenyl) -carbonate, 4-cyclohexylphenyl phenyl carbonate, di- (4-cyclohexylphenyl) carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1-methyl-1-phenylethyl) -phenyl] -carbonate, Biphenyl-4-yl-phenyl-carbonate, di- (biphenyl-4-yl) -carbonate, 4- (1-naphthyl) -phenyl-phenyl-carbonate, 4- (2-naphthyl) -phenyl-phenyl-carbonate, di- [4- (1-naphthyl) -phenyl] -carbonate, Di- [4- (2-naphthyl) phenyl] carbonate, 4-phenoxyphenyl phenyl carbonate, Di (4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di (3-pentadecylphenyl) carbonate, 4-trityl phenyl phenyl carbonate, Di (4-tritylphenyl) carbonate, methyl salicylate phenyl carbonate, di (methyl salicylate) carbonate, Ethyl salicylate phenyl carbonate, di (ethyl salicylate) carbonate, n-propyl salicylate phenyl carbonate, Di (n-propyl salicylate) carbonate, iso-propyl salicylate phenyl carbonate, Di- (iso-propyl-salicylate) -carbonate, n-butyl-salicylate-phenyl-carbonate, Di (n-butylsalicylate) carbonate, iso-butyl salicylate phenyl carbonate, Di (iso-butylsalicylate) carbonate, tert-butyl salicylate phenyl carbonate, di- (tert-butylsalicylate) carbonate, Di (phenyl salicylate) carbonate and di (benzyl salicylate) carbonate.

preferred Diaryl compounds are: diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di (4-tert-butylphenyl) carbonate, Biphenyl-4-yl-phenyl-carbonate, di (biphenyl-4-yl) -carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate and di [4- (1-methyl-1-phenylethyl) phenyl] carbonate.

Especially preferred is: diphenyl carbonate.

The Diaryl carbonates can also with residual contents of Monohydroxyarylverbindungen, from which they were produced are used. The residual contents of monohydroxyaryl compounds can up to 20%, preferably 10%, more preferably up to 5% and most preferably up to 2%.

Based the diaryl carbonates in general are added to the dihydroxyaryl compound with 1.02 to 1.30 mol, preferably with 1.04 to 1.25 mol, especially preferably from 1.06 to 1.22 mol, most preferably from 1.06 used to 1.20 moles per mole Dihydroxyarylverbindung. It can too Mixtures of the above diaryl carbonates are used.

wobei R, R' und R'' die bei Formel (IX) genannte Bedeutung haben mit der Maßgabe, dass in diesem Fall R nicht H sein kann, wohl aber R' und R'' H sein können.For controlling or changing the end groups it is additionally possible to use a monohydroxyaryl compound which was not used for the preparation of the diaryl carbonate used. It is represented by the following general formula (X):

wherein R, R 'and R "have the meaning given in formula (IX) with the proviso that in this case R can not be H, but R' and R" can be H.

Such Monohydroxyaryl compounds are, for example: 1-, 2- or 3-methylphenol, 2,4-dimethylphenol 4-ethylphenol, 4-n-propylphenol, 4-iso-propylphenol, 4-n-butylphenol, 4-iso-butylphenol, 4-tert-butylphenol, 4-n-pentylphenol, 4-n-hexylphenol, 4-iso-octylphenol, 4-n-nonylphenol, 3-pentadecylphenol, 4-cyclohexylphenol, 4- (1-methyl-1-phenylethyl) -phenol, 4-phenylphenol, 4-phenoxyphenol, 4- (1-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, Methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-butyl salicylate, tert-butyl salicylate, phenyl salicylate and benzyl salicylate.

Prefers are: 4-tert-butylphenol, 4-iso-octylphenol and 3-pentadecylphenol.

there is to choose a Monohydroxyarylverbindung whose boiling point above the the monohydroxyaryl compound used to make the Diarylcarbonates was used. The monohydroxyaryl compound can be added at any time in the course of the reaction. she is preferably added at the beginning of the reaction or else at Any point in the process. The proportion of free monohydroxyaryl compound can be 0.2 - 20 Mol%, preferably 0.4-10 Mole%, based on the dihydroxyaryl compound.

The End groups can also by concomitant use of a diaryl carbonate, its base Monohydroxyarylverbindung a higher one Boiling point has been used as the basic monohydroxyaryl compound of the mainly used Diarylcarbonates, changed become. Again, the diaryl carbonate can be used at any time Reaction course can be added. It is preferred at the beginning of the Reaction added or else at any point in the process. The proportion of the diaryl carbonate with the higher-boiling base monohydroxyaryl compound on the total Diarylcarbonatmenge used 1 to 40 mol %, preferably 1 - 20 Mole% and more preferably 1-10 mole%.

wobei R^7-10 dieselben oder verschiedene C₁-C₁₀-Alkyle, C₆-C₁₄-Aryle, C₇-C₁₅-Arylalkyle oder C₅-C₆-Cycloalkyle, bevorzugt Methyl oder C₆-C₁₄-Aryle, besonders bevorzugt Methyl oder Phenyl sein können, und X^– ein Anion wie Hydroxyd, Sulfat, Hydrogensulfat, Hydrogencarbonat, Carbonat oder ein Halogenid, bevorzugt Chlorid oder ein Alkylat bzw. Arylat der Formel -OR sein kann, wobei R ein C₆-C₁₄-Aryl, C₇-C_{1 5}-Arylalkyl oder C₅-C₆-Cycloalkyl, bevorzugt Phenyl sein kann.Catalysts used in the melt transesterification process for the preparation of polycarbonates are the basic catalysts known in the literature, such as alkali metal and alkaline earth metal hydroxides and oxides, but also ammonium or phosphonium salts, hereinafter referred to as onium salts. Preference is given in the synthesis to onium salts, particularly preferred Phosphonium salts used. Phosphonium salts in the context of the invention are those of the general formula (XI)

where R ^{7-10 are the} same or different C ₁ -C ₁₀ -alkyls, C ₆ -C ₁₄ -aryls, C ₇ -C ₁₅ -arylalkyls or C ₅ -C ₆ -cycloalkyls, preferably methyl or C ₆ -C ₁₄ -aryls , particularly preferably methyl or phenyl, and X ^{- may be} an anion such as hydroxide, sulfate, hydrogensulfate, bicarbonate, carbonate or a halide, preferably chloride or an alkylate or arylate of the formula -OR, where R is a C ₆ -C ₁₄ aryl, C ₇ -C _{1 5} -arylalkyl or C ₅ -C ₆ cycloalkyl preferably, phenyl may be.

Preferred catalysts are tetraphenylphosphonium chloride, tetraphenylphosphonium hydroxide and tetraphenylphosphonium phenolate, particularly preferred is tetraphenylphosphonium phenolate.

They are preferably used in amounts of from 10 ^-8 to 10 ^-3 mol, based on one mol of dihydroxyaryl compound, particularly preferably in amounts of from 10 ^-7 to 10 ^-4 mol.

Further Catalysts can alone or in addition to the onium salt as cocatalyst, to speed to increase the polycondensation.

To belong the alkaline salts of alkali metals and alkaline earth metals, such as hydroxides, alkoxides and aryl oxides of lithium, sodium and potassium, preferably hydroxides, alkoxides or aryloxyde of sodium. At the Most preferred are sodium hydroxide and sodium phenolate, as well also the disodium salt of 2,2-bis (4-hydroxyphenyl) propane.

The Amounts of alkaline salts of alkali metals and alkaline earth metals alone or as cocatalyst in the range of 1 to 500 ppb, preferably 5 to 300 ppb and on most preferably 5 to 200 ppb, each calculated as sodium and based on polycarbonate to be formed.

The alkaline salts of alkali metals and alkaline earth metals can already in the production of oligocarbonates, that is at the beginning the synthesis, used or even before the polycondensation be mixed to unwanted Suppress side reactions.

Further there is also the possibility supplementary Amounts of onium catalysts of the same type or another add to the polycondensation.

The Addition of the catalysts takes place in solution in order to dosing harmful excess concentrations to avoid. The solvents are systemic and procedural inherent Compounds such as dihydroxyaryl compounds, diaryl carbonates or monohydroxyaryl compounds. Particular preference is given to monohydroxyaryl compounds, because the expert is familiar is that the dihydroxyaryl and diaryl carbonates already slightly elevated Temperatures, especially under the influence of the catalyst, easily change and decompose. These include polycarbonate grades. At the technically significant transesterification process for the production of polycarbonate is the preferred compound phenol. Phenol is also suitable for this reason already mandatory, because the catalyst preferably used Tetraphenylphosphoniumphenolat is isolated in the production as a mixed crystal with phenol.

beschrieben, wobei
R, R' und R'' und Z die bei Formel (IX) bzw. (VIII) genannte Bedeutung haben,
n ist eine wiederholende Struktureinheit und ist durch das Molekulargewicht des Polycarbonats charakterisiert.The thermoplastic polycarbonates are represented by the formula

described, wherein
R, R 'and R "and Z have the meaning given for formula (IX) or (VIII),
n is a repeating structural unit and is characterized by the molecular weight of the polycarbonate.

kann in Formel (XII) als ganze Gruppe auch H und auf beiden Seiten verschieden sein.The rest

in formula (XII) as an entire group, H and on both sides may be different.

The obtained average weight molecular weights of the polycarbonates are generally 15,000 to 40,000, preferably 17,000 to 36,000, more preferably 17,000 to 34,000, wherein the weight average molecular weight over the relative viscosity after Mark-Houwing correlation (J.M.G. Cowie, Chemistry and Physics synthetic polymers, Vieweg textbook, Braunschweig / Wiesbaden, 1997, page 235).

The Polycarbonates have an extremely low Content of cations and anions of less than 60 ppb each, preferably <40 ppb, and more preferably <20 ppb (calculated as Na cation), where as cations are those of alkali metal and alkaline earth metals present, for example, as an impurity from the raw materials used and the phosphonium and ammonium salts can come. Other ions such as Fe, Ni, Cr, Zn, Sn, Mo, Al ions and their Homologues can be contained in the raw materials or by erosion or corrosion come from the materials of the plant used. The content of this In total, ions are less than 2 ppm, preferably less than 1 ppm and more preferably less than 0.5 ppm.

When Anions are those of inorganic acids and of organic acids in equivalent amounts (eg, chloride, sulfate, carbonate, phosphate, phosphite, oxalate, et al).

The aim So are the smallest amounts, only by using purest Raw materials can be achieved. Such pure raw materials are e.g. only after cleaning procedures like Recrystallize, distill, wash down, and the like. Ä. Available.

The Polycarbonates can be specifically branched. Suitable branching agents are those for polycarbonate production known compounds having three or more functional groups, preferably those having three or more hydroxyl groups.

Some the useful compounds having three or more phenolic hydroxyl groups are, for example: phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-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 and tetra (4-hydroxyphenyl) -methane.

Some the other trifunctional compounds are: 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

preferred Branches are: 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri- (4-hydroxyphenyl) -ethane.

The Branches are generally added in amounts of from 0.02 to 3.6 moles %, based on the Dihydroxyarylverbindung used.

The Process for the preparation of polycarbonate by the transesterification process can be designed discontinuously or continuously. After the dihydroxyaryl compounds and diaryl carbonates, if necessary with further compounds, present as a melt is in the presence suitable catalysts started the reaction. The turnover or the molecular weight becomes at increasing temperatures and falling pressures in suitable apparatus and devices by discharging the the cleaving monohydroxyaryl compound increases until the desired final state is reached. By choice of the ratio Dihydroxyaryl compound to diaryl carbonate, by choosing the procedure or plant for the production of polycarbonate given loss rate of the diaryl carbonate the vapors and optionally added compounds, such as a higher boiling Monohydroxyaryl compound, the end groups are in kind and concentration embossed.

Regarding the Way in which facility and by what method the process is running there is no limitation and restriction.

Further There is no specific limitation and limitation on the temperatures, the Prints and catalysts used to the melt transesterification reaction between the dihydroxyaryl compound and the diaryl carbonate, optionally also to perform other added reactants. Any condition is possible as long as the chosen ones Temperatures, pressures and catalysts under a melt transesterification rapid removal of the cleaved Monohydroxyarylverbindung enable.

The Temperatures above the whole process is generally between 180 and 330 ° C, the prints between 15 bar, absolute and 0.01 mbar, absolute.

Most of time a continuous procedure is chosen because that is beneficial to product quality.

Preferably, the continuous process for producing polycarbonates is characterized characterized in that one or more dihydroxyaryl compounds with the diaryl carbonate, optionally also other added reactants using catalysts, after a precondensation without separating the Monohydroxyarylverbindung formed in then then subsequent Reaktioes evaporator stages at gradually increasing temperatures and gradually falling pressure the Molecular weight is built up to the desired level.

The for the individual reaction-evaporator stages suitable devices, Apparatus and reactors are according to the process heat exchangers, Expansion apparatus, separators, columns, evaporators, stirred tanks and Reactors or other commercially available Apparatus which the necessary Dwell time at selected Provide temperatures and printing. The selected devices must the necessary heat input enable and be engineered to be the ever-growing one melt viscosities satisfy.

All Devices are over Pumps, piping and valves connected. The pipelines between all facilities should of course be as short as possible and the bends the lines as low as possible be kept to unnecessary extended To avoid residence times. Here are the outer, that is technical General conditions and concerns for Assemblies of chemical plants.

to execution the method according to a preferred continuous procedure can they Reactants either melted together or the solid dihydroxyaryl compound in the diaryl carbonate melt or the solid diaryl carbonate in the melt of the dihydroxyaryl compound solved or both raw materials are considered melt, preferably directly from the manufacturing, merged. The residence times of the separate melting of the raw materials, in particular those of the melt of the dihydroxyaryl compound become as short as possible set. The melt mixture, however, because of the comparison to the individual raw materials lowered melting point of the raw material mixture stay longer at correspondingly lower temperatures without sacrificing quality.

After that the catalyst is added, preferably dissolved in phenol, and the melt heated to the reaction temperature. This is at the beginning of the technical significant process for the production of polycarbonate from 2,2-bis (4-hydroxyphenyl) propane and diphenyl carbonate 180 to 220 ° C, preferably 190 to 210 ° C, most preferably 190 ° C. At residence times of 15 to 90 minutes, preferably 30 to 60 minutes, is the reaction equilibrium adjusted without the formed Hydroxyarylverbindung is removed. The reaction can be carried out at atmospheric pressure, but for technical reasons also with overpressure be driven. The preferred pressure in technical systems is 2 to 15 bar absolute.

The Melt mixture is placed in a first vacuum chamber whose pressure is on 100 to 400 mbar, preferably set to 150 to 300 mbar is relaxed and immediately afterwards in a suitable device heated to the inlet temperature again at the same pressure. at the relaxation process, the resulting hydroxyaryl compound evaporated with remaining monomers. After a stay from 5 to 30 min in a sump template if necessary with pumping at the same Pressure and same temperature, the reaction mixture in a second vacuum chamber whose pressure is 50 to 200 mbar, preferably 80 to 150 mbar, relaxed and immediately thereafter in a suitable device at the same pressure to a temperature of 190 to 250 ° C, preferably 210 to 240 ° C, especially preferably 210 to 230 ° C, heated. Again, the resulting hydroxyaryl compound is still with evaporated existing monomers. After a residence time of 5 to 30 min in a sump template, if necessary with pumped circulation, at the same pressure and the same temperature, the reaction mixture is in a third Vacuum chamber whose pressure 30 to 150 mbar, preferably 50 to 120 mbar, relaxed and immediately afterwards in a suitable device at same pressure to a temperature of 220 to 280 ° C, preferably 240 to 270 ° C, more preferably 240 to 260 ° C, heated. Again, the resulting hydroxyaryl compound is still with evaporated existing monomers. After a residence time of 5 to 20 min in a sump template if necessary with pumping at the same pressure and the same temperature, the reaction mixture in another Vacuum chamber whose pressure at 5 to 100 mbar, preferably 15 to 100 mbar, more preferably 20 to 80 mbar, relaxed and immediately thereafter in a suitable device at the same pressure to a temperature from 250 to 300 ° C, preferably 260 to 290 ° C, more preferably 260 to 280 ° C, heated. Again, the resulting hydroxyaryl compound is still with evaporated existing monomers.

The number of these stages, here exemplarily 4, can vary between 2 and 6. The temperatures and pressures are to be adjusted accordingly when changing the step to obtain comparable results. The achieved in these stages rel. Viscosity of the oligomeric carbonate is between 1.04 and 1.20, preferably between 1.05 and 1.15, more preferably between 1.06 and 1.10.

The thus produced oligocarbonate is after a residence time of 5 to 20 min in a sump template if necessary with pumping at the same pressure and the same temperature as in the last flash / evaporator stage promoted in a disk or basket reactor and at 250 to 310 ° C, preferably 250 to 290 ° C, more preferably 250 to 280 ° C, at pressures of 1 to 15 mbar, preferably 2 to 10 mbar, at residence times from 30 to 90 minutes, preferably 30 to 60 minutes, further condensed. The product reaches a rel. Viscosity of 1.12 to 1.28, preferred 1.13 to 1.26, more preferably 1.13 to 1.24.

The leaving this reactor melt is in another disk or basket reactor to the desired final viscosity or brought the final molecular weight. The temperatures are 270 to 330 ° C, preferably 280 to 320 ° C, particularly preferably 280 to 310 ° C, the pressure 0.01 to 3 mbar, preferably 0.2 to 2 mbar, at residence times from 60 to 180 minutes, preferably 75 to 150 minutes. The rel. Viscosities are on the for the intended application necessary Level and are 1.18 to 1.40, preferably 1.18 to 1.36, more preferably 1.18 to 1.34.

The Function of the two basket reactors can also be done in a basket reactor be summarized.

The vapors from all process stages are directly derived, collected and worked up. This workup is usually carried out by distillation, for high purities of the recovered To reach substances. This can, for example, according to German Patent Application No. 10 100 404. A recovery and isolation the cleaved Monohydroxyarylverbindung in its purest form from economic and ecological Of course. The monohydroxyaryl compound can be used directly to prepare a dihydroxyaryl compound or a diaryl carbonate.

The disk or basket reactors are characterized by the fact that they provide a very large, constantly renewing surface on a vacuum at high residence times. The disk or basket reactors are geometrically formed according to the melt viscosities of the products. Suitable examples are reactors, as in the DE 44 47 422 C2 and EP A 1 253 163, or two-shaft reactors, as described in WO A 99/28 370.

The Oligocarbonates, also very low molecular weight, and the finished polycarbonates are usually using gear pumps, screws different Type or displacement pumps promoted special design.

Especially suitable materials for the manufacture of apparatus, reactors, pipelines, Pumps and fittings are stainless steel types Cr Ni (Mo) 18/10 such as B. 1.4571 or 1. 4541 (Stahlschlüssel 2001, Publisher: Stahlschlüssel Wegst GmbH, Th-Heuss-Strasse 36, D-71672 Marbach) and Ni-base alloys of the type C, such. B. 2.4605 or 2.4610 (steel key 2001, Publisher: Stahlschlüssel Wegst GmbH, Th-Heuss-Strasse 36, D-71672 Marbach). The stainless steels are up to process temperatures from about 290 ° C and the Ni-base alloys at process temperatures above about 290 ° C used.

• • Schnell, „Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, S. 33-70;
• • D.C. Prevorsek, B.T. Debona und Y. Kesten, Corporate Research Center, Allied Chemical Corporation, Morristown, New Jersey 07960: „Synthesis of Poly(ester Carbonate) Copolymers" in Journal of Polymer Science, Polymer Chemistry Edition, Vol. 18,(1980)"; S. 75-90,
• • D. Freitag, U. Grigo, P.R. Müller, N. Nouvertne', BAYER AG, „Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 1 1, Second Edition, 1988, S. 651-692 und schließlich
• • Dres. U. Grigo, K. Kircher und P. R- Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag München, Wien 1992, S. 118-145,

sowie z.B. in EP-A 0 517 044 und vielen anderen Patentanmeldungen.However, the polycarbonate can also be prepared, for example, by the interfacial process. This process for polycarbonate synthesis has been widely described in the literature, including, inter alia

• • 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. 1980) "; Pp. 75-90,
• • Friday, U. Grigo, PR Müller, N. Nouvertne ', BAYER AG, "Polycarbonates" in Encyclopaedia of Polymer Science and Engineering, Vol. 11, Second Edition, 1988, pp. 651-692, and finally
• Dres. U. Grigo, K. Kircher and P. R- Müller "Polycarbonates" in Becker / Braun, Plastics Handbook, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna 1992, p 118-145,

and for example in EP-A 0 517 044 and many other patent applications.

According to this process, the phosgenation of a disodium salt of a bisphenol (or a mixture of different bisphenols) initially introduced in aqueous alkaline solution (or suspension) is carried out in the presence of an inert organic solvent or solvent mixture containing a second Pha It trains. The resulting, mainly present in the organic phase, oligocarbonates are condensed with the aid of suitable catalysts to high molecular weight, dissolved in the organic phase, polycarbonates. The organic phase is finally separated and the polycarbonate isolated from it by various work-up steps.

In This process is an aqueous Phase of NaOH, one or more bisphenols and water used, the concentration of these aqueous solution in terms of the sum of the bisphenols, not as sodium salt but as free Calculated bisphenol, between 1 and 30 wt .-%, preferably between 3 and 25% by weight, more preferably between 3 and 8% by weight for polycarbonates with a Mw> 45000 and 12 to 22 wt .-% for Polycarbonates having a Mw <45000, can vary. It may be necessary at higher concentrations be the solutions to temper. The solution The sodium hydroxide used in the bisphenols may be solid or aqueous sodium hydroxide be used. The concentration of the sodium hydroxide solution depends after the target concentration of the desired bisphenolate, lies but usually between 5 and 25 wt .-%, preferably 5 and 10 wt .-%, or else is chosen more concentrated and then with Diluted with water. In the method with subsequent dilution are sodium hydroxide solutions with concentrations between 15 and 75 wt .-%, preferably 25 and 55 wt .-%, optionally tempered, used. Of the Alkali content per mole of bisphenol is very much the structure of the bisphenol dependent, but usually moves between 0.25 moles of alkali / mole of bisphenol and 5.00 moles of alkali / mole of bisphenol, preferably 1.5-2.5 moles Alkali / mol bisphenol and in the case that bisphenol A as sole Bisphenol is used, 1.85 - 2.15 mol of alkali. If more than one bisphenol is used, these can solved together become. However, it may be advantageous to separate the bisphenols to dissolve in an optimal alkaline phase and the solutions separated to dose or combined to feed the reaction. Farther it may be advantageous that the bisphenols or not in caustic soda but in with additional Alkali-equipped, diluted bisphenolate to solve. The dissolution processes can of solid bisphenol, usually in flakes or prills or even from melted bisphenol go out. The sodium hydroxide used or the caustic soda can by the amalgam process or the so-called Membrane process have been produced. Both procedures will be used for a long time and are familiar to the expert. Prefers caustic soda from the membrane process is used.

The so prepared aqueous Phase is combined with an organic phase consisting of solvents for polycarbonate, the opposite are inert to the reactants and form a second phase, phosgenated.

The optionally applied dosage of bisphenol after or during the Phosgene induction can be carried out as long as phosgene or its immediate derivatives, the chloroformate in the reaction solution available.

The Synthesis of polycarbonates from bisphenols and phosgene in alkaline Milieu is an exothermic reaction and is in a temperature range from -5 ° C up to 100 ° C, preferably 15 ° C up to 80 ° C, most preferably 25-65 ° C carried out, depending on the solvent or solvent mixture if necessary under overpressure has to be worked.

For the production the invention to be used Polycarbonates suitable diphenols are, for example, hydroquinone, Resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxy-phenyl) -cycloalkanes, Bis (hydroxyphenyl) sulphides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, Bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, (α, α'-bis (hydroxyphenyl) diisopropylbenzenes diisopropylbenzenes, and their alkylated, nuclear-alkylated and ring-halogenated Links.

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, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -m / p diisopropylbenzene, 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, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -m / p-diisopropylbenzene and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Especially preferred diphenols are 4,4'-dihydroxydiphenyl, 1,1-bis (4-hydroxyphenyl) phenyl ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

These and other suitable diphenols are described, for example, in US Pat. Nos. 2,999,835, 3,148,172, 2,991,273, 3,271 367, 4,982,014 and 2,999,846, in German Offenlegungsschriften 1,570,703, 2,063,050, 2,036,052, 2,211,956 and 3,832,396, French Patent 1,561,518, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pp. 28ff; p.102ff., and in "DG Legrand, JT Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, pp. 72ff." described.

in the In the case of homopolycarbonates, only one diphenol is used, in the In the case of copolycarbonates, several diphenols are used, where Of course the bisphenols used, as well as all other added to the synthesis Chemicals and auxiliaries with those from their own synthesis, Handling and storage contaminated contaminants could be, although it is desirable is, as possible to work on clean raw materials.

The organic phase may consist of one or mixtures of several solvents consist. Suitable solvents are chlorinated hydrocarbons (aliphatic and / or aromatic), preferably dichloromethane, trichlorethylene, 1,1,1-trichloroethane, 1,1,2-trichloroethane and chlorobenzene and mixtures thereof. It can also be aromatic Hydrocarbons such as benzene, toluene, m / p / o-xylene or aromatic Ether such as anisole alone, in admixture or in addition or in admixture with chlorinated hydrocarbons are used. Another embodiment The synthesis uses solvents which polycarbonate does not solve but only simmer. It can therefore also precipitant for polycarbonate in combination with solvents be used. Where then as a solvent in the aqueous Phase soluble solvent such as tetrahydrofuran, 1,3 / 1,4-dioxane or 1,3-dioxolane can be when the solvent partner forms the second organic phase.

The both phases which form the reaction mixture are mixed to to accelerate the reaction. This is done by adding energy via shear, i.e. Pumps or stirrers or by static mixer or by generating turbulent flow means Nozzles and / or Dazzle. Combinations of these measures are also applied, often repeated in temporal or apparative sequence. When Become a stirrer preferably anchor, propeller, MIG stirrer, etc. used as they e.g. in the Ullmann, "Encyclopedia of Industrial Chemistry ", 5th edition, Vol B2, p 251 ff. Are described. As pumps are Centrifugal pumps, often multi-stage, with 2 to 9 stages preferred are used. As nozzles and / or diaphragms are pinhole or in their place tapered pieces of pipe or also Venturi or Lefos nozzles used.

Of the Entry of the phosgene can be gaseous or liquid or solved in solvent respectively. The excess used to phosgene, based on the sum of the bisphenols used between 3 and 100 mol%, preferably between 5 and 50 mol%. Where about unique or repeated addition of caustic soda or equivalent Post-dosing of bisphenolate solution the pH of the aqueous Phase during and after the phosgene dosage in the alkaline range, preferred between 8.5 and 12 while it is being added to the catalyst should be at 10 to 14. The temperature during the phosgenation is 25 to 85 ° C, preferred 35 to 65 ° C, depending on the solvent used also under overpressure can be worked.

The Phosgene dosage can be directly into the described mixture of organic and aqueous Phase or in whole or in part, before the mixture the phases, in one of the two phases, which subsequently with the corresponding other phase is mixed. Furthermore, that can All or part of phosgene in a recycled partial stream of the synthesis mixture be dosed from both phases, this partial stream preferably is returned before the catalyst addition. In another embodiment the described aqueous Phase mixed with the phosgene-containing organic phase and subsequently after a residence time of 1 second to 5 minutes, preferably 3 seconds to 2 minutes the above mentioned recirculated partial flow added or the two phases, the aqueous phase described with the phosgene-containing organic phase are directly in the above mentioned recirculated partial flow mixed. In all these embodiments the pH ranges described above must be taken into account and if necessary by single or multiple replenishment of caustic soda or to comply with the appropriate post-dosing of bisphenolate solution. Likewise must the temperature range optionally by cooling or dilution of Reaction mixture can be maintained.

The execution The polycarbonate synthesis can be continuous or batchwise happen. The reaction can therefore in stirred tanks, tubular reactors, Umpumpreaktoren or stirred tank cascades or combinations thereof, wherein by using the already mentioned Ensuring mixing organs is that aqueous and organic phase as possible only then segregate when the synthesis mixture has reacted, i.e. no saponifiable chlorine of phosgene or chloroformates contains more.

The monofunctional chain terminators needed to control molecular weight, such as phenol or alkylphenols, in particular phenol, p-tert-butylphenol, iso-octylphenol, cumylphenol, their chloroformates or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are either with fed to the bisphenolate or the bisphenolates of the reaction or but added at any point in the synthesis, as long as in the reaction mixture still phosgene or Chlorkohlensäureendgruppen are present, or in the case of acid chlorides and chloroformate as a chain terminator, as long as enough phenolic end groups of the forming polymer are available. Preferably, however, the chain terminator (s) are after the Added phosgenation in one place or at a time, though no phosgene is present, but the catalyst is not dosed yet was, or they are in front of the catalyst, with the catalyst dosed together or in parallel.

In In the same way, any possible branching or Adding branching mixtures to the synthesis, but usually before the Chain terminators. Usually trisphenols, quarterphenols or acid chlorides of tri- or tetracarboxylic acids are used, or mixtures of polyphenols or acid chlorides.

For example, some of the useful compounds having three or more than three phenolic hydroxyl 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.

Some the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.

preferred Branches are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tris- (4-hydroxyphenyl) -ethane.

The in phase interface synthesis used catalysts are tert. Amines, in particular triethylamine, Tributylamine, trioctylamine, N-ethylpiperidine, N-methylpiperidine, N-i / n-propylpiperidine; quaternary ammonium salts such as tetrabutylammonium / tributylbenzylammonium / tetraethylammonium hydroxide / chloride / bromide / hydrogensulfate tetrafluoroborate; and the phosphonium compounds corresponding to the ammonium compounds. Ammonium and phosphonium compounds also become common in this context referred to as onium compounds.

These Compounds are typical phase interface catalysts in the literature described, commercially available and familiar to those skilled in the art. The catalysts can individually, in a mixture or else next to and after the synthesis are added, if appropriate, also before the phosgenation, preferably however, are dosages after phosgene entry, unless it becomes an onium compound or mixtures of onium compounds used as catalysts, then an addition is made before the phosgene dosage prefers.

The Dosing of the catalyst or catalysts may be in bulk, in an inert solvent, preferably that of polycarbonate synthesis, or as an aqueous solution, im Trap of tert. Amines then as their ammonium salts with acids, preferably Mineral acids, especially hydrochloric acid, respectively. When using several catalysts or the dosage of subsets of the total catalyst amount may of course also different Dosage made in different places or at different times become.

The Total amount of catalysts used is between 0.001 to 10 mol% based on moles of bisphenols, preferably 0.01 to 8 mol%, particularly preferably 0.05 to 5 mol%.

After entry of the phosgene, it may be advantageous to mix the organic phase and the aqueous phase for a certain time, before any branching agent, if this is not together with the Bisphenolate is metered, chain terminator and catalyst are added. Such a stirring time may be advantageous after each dosage. These stirring times, insofar as they are inserted, are between 10 seconds and 60 minutes, preferably between 30 seconds and 40 minutes, particularly preferably between 1 and 15 minutes.

The reacted, at most still traces, preferably <2 ppm, of chlorocarbonic acid esters containing at least two-phase reaction mixture is allowed for phase separation. The aqueous alkaline phase is possibly whole or in part as watery Phase back directed into the Polycarbonatsynthese or wastewater treatment supplied where solvent and catalyst components be separated and recycled. 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 particular one pH, e.g. by sodium hydroxide, the salt separated, which z. B. the Chloralkali electrolysis supplied can be while the watery Phase is optionally returned to the synthesis.

The organic, the polymer-containing phase must now from all contaminants be cleaned alkaline, ionic or catalytic type. It contains also after one or more settling operations, possibly supported by runs by settling kettle, stirred tank, Coalescers or separators or combinations of these measures - where optionally water in each or some separation steps, if appropriate dosed using active or passive mixing devices can - still Proportions of aqueous alkaline phase in fine droplets and the catalyst, usually a tert. Amine.

To This coarse separation of the alkaline, aqueous phase is the organic Phase one or more times with diluted acids, Mineral, carbon hydroxycarboxylic and / or sulfonic acids washed. Preferred are aqueous mineral acids especially hydrochloric acid, Phosphorous acid and phosphoric acid or mixtures of these acids. The concentration of these acids should be in the range of 0.001 to 50% by weight, preferably 0.01 to 5% by weight. lie.

Farther The organic phase is treated with deionized or distilled water repeatedly washed. The separation of, optionally with parts the aqueous Phase dispersed, organic phase after the individual washing steps happens by means of settling boiler, stirred tank, coalescer or separators or combinations of these measures, wherein the wash water optionally between the washing steps using can be added to active or passive mixing organs.

Between These washing steps or after washing may optionally acids, preferably solved in the solvent which of the polymer solution is to be admitted. Hydrogen chloride gas is preferred here and phosphoric acid or phosphorous acid used, which may also be used as mixtures can.

The so obtained, purified polymer solution should after the last Separation process not more than 5% by weight, preferably less than 1% by weight, most preferably less than 0.5 wt .-% water.

The Isolation of the polymer from the solution can be achieved by evaporation of the solvent carried out by means of temperature, vacuum or a heated towing gas. Other isolation methods are crystallization and precipitation.

happens the concentration of the polymer solution and possibly also the isolation of the polymer by distillation the solvent, possibly by overheating and relaxation, this is called a 'flash process', see also "Thermal Separation Process", VCH Verlagsanstalt 1988, p. 114; Instead, a heated carrier gas together with the einzudampfenden solution sprayed this is referred to as "spray evaporation / spray drying" by way of example in Vauck, "Basic Operations chemical engineering ", German publisher for Basic Industry 2000, 11th ed., P. 690. All of these processes are described in the patent literature and in textbooks and those skilled in the art common.

The removal of the solvent by temperature (distilling off) or the technically more effective flash process gives highly concentrated polymer melts. In the known flash method polymer solutions are repeatedly heated under slight pressure to temperatures above the boiling point under atmospheric pressure and then, with respect to the normal pressure, overheated solutions then in a Vessel at lower pressure, eg normal pressure, relaxed. It may be advantageous to not let the Aufkonzentrationsstufen, or in other words the temperature levels of overheating to be too large but rather to choose a two- to four-step process.

Out The highly concentrated polymer melts thus obtained can be Residues of the solvent either directly from the melt with Ausdampfextrudern (BE-A 866 991, EP-A 0 411 510, US Pat. No. 4,980,105, DE-A 33 32 065), thin-film evaporators (EP-A 0 267 025), falling-film evaporators, extrudates or by friction compacting (EP-A 0 460 450), if appropriate also with the addition of an entraining agent, such as nitrogen or carbon dioxide or using vacuum (EP-A 003 996, EP-A 0 256 003, US-A 4 423 207), alternatively also by subsequent Crystallization (DE-A 3 429 960) and heating of the residues of the solvent in the solid phase (US Pat. No. 3,986,269, DE-A 2 053 876).

granules receives it is preferred by direct spinning of the melt and subsequent granulation or by using ejection extruders from those in the air or under liquid, usually water, is spun off. If extruders are used, then if necessary, the melt, before this extruder, if necessary from static mixers or through side extruders in the extruder, additives enforce.

at a spray becomes the polymer solution optionally after heating either in a vessel with negative pressure atomized or by means of a nozzle with a heated carrier gas, e.g. Nitrogen, argon or water vapor in a vessel with normal pressure atomized. In both cases receives one in dependence from the concentration of the polymer solution powder (diluted) or Flakes (concentrated) of the polymer, from which, if necessary, also the last residues of the solvent as above must be removed. Subsequently can by means of a compounding extruder and subsequent spinning Granules are obtained. Again, additives, as described above, in the periphery or in the extruder itself. often must be before extrusion due to the low bulk density of the powder and flakes a compaction step for the polymer powder can be used.

Out the washed and optionally still concentrated solution of Polycarbonate can be made by adding a precipitant for polycarbonate the polymer be precipitated largely crystalline. Here it is advantageous to first add a small amount of the precipitating agent and optionally also waiting times between the additions of the batches to precipitant appeal. It can also be beneficial, different precipitants use. Use as precipitant find here e.g. Hydrocarbons, especially heptane, i-octane, cyclohexane and alcohols such as methanol, ethanol, i-propanol.

at the precipitation usually becomes the polymer solution slowly a precipitant added here are usually alcohols such as methanol, ethanol, i-propanol., but also cyclohexane or ketones such as acetone as precipitant used.

The thus obtained materials are as described in the spray evaporation Processed granules and optionally additiviert.

To other methods are used for precipitation and crystallization products or amorphous solidified products in fine-grained Shape by passing over of fumes one or more precipitants for polycarbonate, under simultaneous heating crystallized below the glass transition temperature and on to higher ones Molecular weights condensed. Are these oligomers, optionally with different end groups (phenolic and Chain terminator ends), it is called Festphasenaufkondensation.

ThermoStab Lisa gates:

Prefers become the theme stabilizers of the invention according to the formulas (I) to (VII) after reaching the desired molecular weight of Polycarbonate added. For effective mixing of the heat stabilizer are static mixers or others to a homogeneous interference leading mixers, such as extruder, suitable. In the latter case, the Thermostabilizer over a side extruder of the polymer melt, possibly together with others Fabrics, e.g. Release agent added to the main polymer stream.

The Thermostabilizers according to the invention can individually or in any mixtures with one another or more various mixtures of the polymer melt can be added. Moreover can also mixtures of the inventive thermostabilizers with free sulfonic acid derivatives, such as. Benzene or toluene sulfonic acid are added.

The Thermosatbilisatoren preferred melting points greater than 30 ° C, preferred greater than 40 ° C and especially preferably greater than 50 ° C and boiling points at 1 mbar greater than 150 ° C, preferably greater than 200 ° C and especially preferably greater than 230 ° C.

The Bridged esters according to the invention of organic sulfur-containing acids can be present in quantities of less 100 ppm based on the polycarbonate are used, preferably smaller 50 ppm based on the polycarbonate, more preferably smaller 30 ppm and most preferably less than 15 ppm.

Prefers be at least 0.5 ppm, more preferably 1 ppm, especially preferably used 1.5 ppm thermal stabilizer or mixtures thereof. In particular, the heat stabilizers are based on the polycarbonate used in amounts of 2 to 10 ppm.

Optional can they also in mixtures with free acids, such as ortho-phosphoric acid or other additives suitable as stabilizers, e.g. Benzene- or toluene-sulfonic acids are added. The amount of free acids or other stabilizers (based on polycarbonate) up to 20 ppm, preferably up to 10 ppm, especially 0 to 5 ppm.

Regarding the Form of addition of the bridged esters of the invention Of organic sulfur-containing acids, there is no limitation. The bridged esters of the invention of organic sulfur-containing acids or their Mixtures can as a solid, ie as a powder, in solution or as a melt of Polymer melt are added. Another type of dosage is the use of a masterbatch (preferably with polycarbonate), this also includes other additives, such as other stabilizers or may contain mold release agents.

Prefers become the bridged esters of the invention of organic sulfur-containing acids in liquid form. Because the To be metered amounts are very low, are preferably solutions of Bridged esters according to the invention used.

suitable solvent are those that do not interfere with the process, are chemically inert and evaporate quickly.

When solvent come all organic solvents with a boiling point at atmospheric pressure of 30 to 300 ° C, preferably from 30 to 250 ° C and more preferably from 30 to 200 ° C as well as water - including one Crystal water - in Question. Preferably, those compounds are selected which occur in the respective processes. Any remaining remains depending on the requirement profile of the product to be manufactured, not the quality.

solvent In addition to water are alkanes, cycloalkanes and aromatics, which are also substituted could be. The Substituents can aliphatic, cycloaliphatic or aromatic radicals in different Combination and halogens or a hydroxyl group. Heteroatoms such as oxygen, can also between aliphatic, cycloaliphatic or aromatic radicals bridge members be, where the radicals may be the same or different. Further solvent can also ketones and esters of organic acids and cyclic carbonates be. Furthermore, the thermal stabilizer can also be dissolved in glycerol monostearate and added become.

Examples besides water are n-pentane, n-hexane, n-heptane and their isomers, Chlorobenzene, methanol, ethanol, propanol, butanol and their isomers, Phenol, o-, m- and p-cresol, acetone, diethyl ether, dimethyl ketone, Polyethylene glycols, polypropylene glycols, ethyl acetate, ethylene carbonate and propylene carbonate.

Prefers are suitable for the polycarbonate process water, phenol, propylene carbonate, ethylene carbonate and toluene.

Especially preferably suitable are water, phenol and propylene carbonate.

When Degradation products of the thermal stabilizers according to the invention of formulas (I) to (VII) arise free sulfonic acids as well partially esterified sulfonic acids and alcohols.

Furthermore, the polycarbonate obtained can be used to modify properties with further customary ones Additives and additives (eg auxiliaries and reinforcing agents) are provided after addition of the inhibitors of the invention. The addition of additives and additives serves the extension of the useful life (eg hydrolysis or degradation stabilizers), the improvement of color stability (eg thermal and UV stabilizers), the simplification of processing (eg demulsifier, flow aids), the improvement of performance characteristics (eg Antistatic agents), improving the flame retardant, influencing the visual impression (eg organic colorants, pigments) or the adaptation of the polymer properties to certain loads (impact modifiers, finely divided minerals, fiber, quartz, glass and carbon fibers). Everything can be combined as desired to set and achieve the desired properties. Such additives and additives are described, for example, in "Plastics Additives", R. Gächter and H. Müller, Hanser Publishers 1983.

These Additives and additives can individually or in any mixtures or several different Mixtures of the polymer melt are added directly in the isolation of the polymer or after melting of Granules in a so-called compounding step.

there can the additives and additives or their mixtures as a solid, ie as a powder, or as a melt of the polymer melt be added. Another type of dosage is the use of masterbatches or mixtures of masterbatches of the additives or additive mixtures.

Of the Addition of these substances is preferably carried out on conventional Aggregates to the finished polycarbonate, but may, depending on the requirements, also at a different stage in the production process of the polycarbonate respectively.

suitable Additives are described for example in Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999 or Plastics Additives Handbook Hans Zweifel, Hanser, Munich 2,001th

• 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, Minidises 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 Blends 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. Blowing body (see 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, Minidises, 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 with a content of 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 light-transmitting and light-scattering moldings.
• 11. Precision injection molded parts, such as holders, eg lens holders; 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 equipment 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 blends 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.

The The following examples are intended to illustrate the present invention, but without restricting it to want:

The relative solution viscosity is in Dichloromethane at a concentration of 5 g / l at 25 ° C determined.

The content of phenolic OH is obtained by IR measurement. For this purpose, a difference measurement of a solution of 2 g of polymer in 50 ml of dichloromethane over pure dichloromethane is measured and the difference in extinction at 3582 cm ^-1 determined.

to Determination of residual monomers, the sample is dissolved in dichloromethane and then precipitated with acetone / methanol. After separating the precipitated Polymers, the filtrate is concentrated. The quantification of the residual monomers carried out by reverse phase chromatography in the flow agent gradient 0.04% phosphoric acid - acetonitrile. The detection takes place via UV.

Under GMS becomes a mixture of glycerol monopalmitate and glycerol monostearate Understood.

The total GMS content is composed of the free GMS (GMS _free ), the GMS carbonate (GMS-CO ₃ ) and the built-in GMS. The latter is calculated by subtraction.

One Part of the sample is at about 80 ° C hydrolyzed alkaline and then with hydrochloric acid adjusted to about pH 1. This solution is extracted with tert-butyl methyl ether and the extract dried. After derivatization, the gas chromatographic analysis is performed a capillary column in conjunction with a flame ionization detector. The quantitative Evaluation is via an internal standard and gives the total content of GMS.

One other part of the sample is dissolved in dichloromethane and derivatized. To Gas chromatographic separation on a capillary column and Detection by means of flame ionization detector (FID), the quantification takes place via a internal standard. It will be the levels of free GMS and GMS carbonate receive.

Quantification of glycerol monostearate (GMS) and glycerol monostearate carbonate (GMS carbonate) in polycarbonate by GC-FID:
Approximately 0.5 g sample are dissolved in 5 ml CH 2 Cl 2 and mixed with an internal standard (eg n-alkane). About 5 ml of tert-butyl methyl ether (MTBE) are added to this solution to precipitate the polymer. The suspension is then shaken and then centrifuged. A defined amount (3 ml) of the supernatant solution is pipetted off and concentrated to dryness under a nitrogen atmosphere. The residue is silylated with MSTFA solution (N-methyl-N- (trimethylsilyl) trifluoroacetamide). The filtered solution is chromatographed by gas chromatography (GC) (eg HP 6890). Detection is by flame ionization detector (FID).

Analytical specification for Determination of residual monomers:

The Sample is dissolved in dichloromethane and reprecipitated in acetone / methanol. The precipitated Polymer is separated off and the filtrate is concentrated. The quantification the residual monomer is by reverse phase. Chromatography in Fließmittelgradienten 0.04% phosphoric acid-acetonitrile. Detection is via UV.

In this way, the bisphenol (BPA), phenol, tert. Butylphenol (BUP), diphenyl carbonate (DPC) and di-BUP-carbonate determined. Feedstock: Polycarbonate B: relative viscosity 1,201 phenolic OH value 240 ppm DPC 80 ppm BPA 10 ppm phenol 65 ppm GMS _free 288 ppm GMS-CO ₃ <10 ppm

Thermostabilizer A:

Thermostabilizer B:

Thermosatbilizer C:

Of the Influence of the heat stabilizers according to the invention on improving the thermal stability of a polycarbonate based on the long-term thermal capacity of the polycarbonate examined.

Example A Synthesis of Thermostabilizer A:

552.6 g (6.0 mol) of glycerol from KMF and 4746 g (60 mol) of pyridine Company Aldrich be submitted under nitrogen and dissolved homogeneously. 3,196.8 g (18.1 mol) benzenesulfonyl chloride are added dropwise very slowly, with a temperature of 30-35 ° C not exceeded should be. Subsequently is 1 hour at 40 ° C touched.

Work-up:

Of the Batch is very slowly distilled into a mixture of 3 liters Water, about 4kg of ice and 3 liters of dichloromethane drained with vigorous stirring. In this case, a temperature of 35 ° C should not be exceeded.

The organic phase is subsequently precipitated in about 10 liters of methanol, filtered off with suction and washed with methanol until proof in thin-layer chromatography indicates a clean product.

The mixture is then dried to constant mass in a vacuum oven at 60 ° C.
Yield: 970 g (31.54% of theory) of white powder

analytics:

• • melting point Mp 81-83 ° C
• ¹ H-NMR (400 MHz, TMS, CDCl ₃ ) δ = 7.8 ppm (m, 6H), 7.7 (m, 3H), 7.55 (m, 6H), 4.75 (m, 1H), 4,1 (d, 4H).

example 1

2.5 kg of polycarbonate B are treated with 4 ppm of thermal stabilizer A (as powder), based on the polycarbonate homogeneously mixed on an extruder (Starting material). This mixture is in each case for 10 min. at 340 ° C and at 360 ° thermal loaded and then chemically analyzed (Table 1).

Comparative Example 1

As in Example 1, but instead of 4 ppm thermal stabilizer A 3rd ppm ortho-phosphoric acid mixed.

Table 1

The examples impressively demonstrate the improved stability of the polycarbonate under thermal stress compared to Comparative Example 1 with phosphoric acid as a stabilizer, which manifests itself in the higher proportion of free GMS, in a lower proportion of GMS-CO ₃ and in a much lower recovery rate to diphenyl carbonate DPC , The content of residual monomers (DPC) can thus be kept at a relatively low level. This is particularly important for use in optical data storage, since when spilling the polycarbonate, the evaporated monomer content can accumulate on the injection mold (stamper) (blade out), which is undesirable.

Claims (6)

Composition containing polycarbonate and bridged esters of organic sulfur-containing acids. Composition according to Claim 1, in which bridged esters of organic sulfur-containing acids are selected from at least one compound a) of the formula (I)

in which R ¹ independently represents hydrogen or unsubstituted or halogen-substituted C ₁ -C ₂₀ -alkyl, R ² and R ³ independently of one another represent hydrogen, C ₁ -C ₆ -alkyl or C ₄ -C ₃₀ -alkylcarboxyl or for Rest stands

wherein R ^{1 has} the abovementioned meaning, n is an integer from 0 to 8, preferably 0 to 6, in particular 0, 1 or 2, b) of the formula (II)

in which R ^{1 has} the abovementioned meaning, c) the formula

in which R ^{1 has} the abovementioned meaning, d) the formula (IV)

in which R ¹ and n have the abovementioned meaning, and R ^{4 is} C ₄ -C ₃₀ -alkylcarboxyl or the radical

in which R ^{1 has} the abovementioned meaning, e) of the formula (V), (VI), (VII)

in which R ¹ and n have the abovementioned meaning, and R ⁵ and R ^{6 are} independently hydrogen or unsubstituted or substituted by halogen C ₁ -C ₂₀ alkyl. A composition according to claim 1 containing bis bridged to 100 ppm Esters of organic sulfur-containing acids. Composition according to claim 1, containing degradation products the bridged Ester. Process for the preparation of compositions according to claim 1, wherein polycarbonate with the bridged esters of organic Sulfur-containing acids mixed and compounded. Molded parts, shaped bodies and extrudates available from composition according to claim 1.