EP0000753B1 - Process for the preparation of polycarbonates and the polycarbonates obtained - Google Patents
Process for the preparation of polycarbonates and the polycarbonates obtained Download PDFInfo
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- EP0000753B1 EP0000753B1 EP78100539A EP78100539A EP0000753B1 EP 0000753 B1 EP0000753 B1 EP 0000753B1 EP 78100539 A EP78100539 A EP 78100539A EP 78100539 A EP78100539 A EP 78100539A EP 0000753 B1 EP0000753 B1 EP 0000753B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/22—General preparatory processes using carbonyl halides
- C08G64/24—General preparatory processes using carbonyl halides and phenols
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- the present invention relates to a process for the preparation of aromatic polycarbonates according to the phase interface process from diphenols, which is characterized in that the catalysts used are N-ethylpyrrolidine, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine or N-isopropylmorpholine in amounts of 0.01 mol% to 10 mol%, based on moles of diphenols used.
- the present invention also relates to the polycarbonates obtainable according to the process, which are notable for high light transmission and low yellowing tendency even after higher temperatures.
- the color stabilization of aromatic polycarbonates has hitherto preferably been carried out by adding additives, in particular phosphites (cf. DE-AS-1 128 653, DE-AS 2 140 207 and DE-OS 2 255 639), optionally in combination with other additives, for example with oxetane compounds (DE-OS 2 510 463).
- additives in particular phosphites (cf. DE-AS-1 128 653, DE-AS 2 140 207 and DE-OS 2 255 639), optionally in combination with other additives, for example with oxetane compounds (DE-OS 2 510 463).
- the method according to the invention uses a completely different principle, in that it uses the above-mentioned catalysts as catalysts in polycarbonate production by the two-phase interfacial polycondensation process (cf. DE-PS 959 497, DE-PS 1046311 and DE-PS 2 410 716) .
- N-methylpiperazine is used only with poor success as a catalyst for the production of polycarbonates. (Compare column 1, line 69 to column 2, line 27).
- polyamines including cyclic polyamines such as N, N-diethylpiperazine, are used for the production of polycarbonates.
- cyclic polyamines such as N, N-diethylpiperazine
- N-alkyl morpholines can be used as catalysts for the production of polycarbonates.
- special N-alkylmorpholines lead to polycarbonates with improved thermal stability compared to the catalysts also mentioned in these references, such as, for example, triethylamine.
- GB-PS 1072161 (see in particular page 2, lines 28 ff) describes the preparation of polycarbonates from di- ( ⁇ -trihalogen-a-hydroxyethoxy) alkanes, it being possible, inter alia, to use N-methylmorpholine as the tertiary base.
- N-methylmorpholine is not suitable as a catalyst according to the present invention.
- from 0.01 to 10 mol% preferably from 0.05 to 5 mol% and in particular from 0.05 to 2 mol%, based on moles of diphenols used, are used on the catalysts mentioned at the outset.
- N-ethylpiperidine is particularly suitable.
- the high molecular weight polycarbonates are produced according to the invention by the phase interface process.
- Diphenols in particular dihydroxydiarylalkanes or -cycloalkanes, for which, in addition to the unsubstituted dihydroxydiarylalkanes or -cycloalkanes, those which are substituted in the o-position to the phenolic hydroxyl groups are also suitable in the aqueous-alkaline phase, and one is used for the Added suitable polycarbonate solvent.
- phosgene is introduced at a temperature between 0 and 100 ° C and a pH between 9 and 14. The polycondensation takes place after the phosgenation.
- the catalysts suitable according to the invention can be added either before introducing phosgene or after introducing phosgene before polycondensation.
- the phosgene introduction times are between 1 and 60 minutes, the post-condensation between 2 and 120 minutes.
- the organic polymer solution is separated off and washed free of electrolytes with water.
- the polycarbonate can then be removed by evaporation of the solvent or by precipitation with non-solvents, e.g. Methanol or gasoline can be isolated.
- the polycarbonates produced by the process according to the invention can also be branched in a known manner.
- Suitable diphenols are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis- (hydroxyphenyl) alkanes, such as, for example, C1-CS-alkylene- or C 2 -C 8 -alkylidene bisphenols, bis- (hydroxyphenyl) cycloalkanes, for example Cs-Cs-cycloalkylene or C 5 -C 6 -cycloalkylidene bisphenols, bis - (hydroxyphenyl) sulfides, ethers, ketones, sulfoxides or sulfones.
- ⁇ , ⁇ '- bis - (hydroxyphenyl) - diisopropylbenzenes and the corresponding nuclear alkylated or nuclear halogenated compounds Polycarbonates based on bis (4-hydroxyphenyl) propane-2,2 (bisphenol A), bis (4-hydroxy-3,5-dichlorophenyl) propane-2,2 (tetrachlorobisphenol A), bis are preferred - (4-hydroxy-3,5-dibromophenyl) propane - 2,2 (tetrabromobisphenol A), bis - (4-hydroxy-3,5-dimethylphenyl) propane - 2,2 (tetramethylbisphenol A), bis - ( 4-hydroxy-3-methyl-phenyl) -propane-2,2, bis - (4-hydroxyphenyl) -cyclohexane-1,1 (bisphenol Z) and based on trinuclear bisphenols such as a, a '- bis - (4 - hydroxy-phenyl) - diis
- the catalyst (see examples) is added to the resulting solution and the mixture is stirred for a further 15 minutes.
- a highly viscous solution is obtained, the viscosity of which is regulated by adding methylene chloride.
- the aqueous phase is separated off.
- the organic phase is washed free of salt and alkali with water.
- Polycarbonate is isolated from the washed-out solution and dried.
- the polycarbonate has a relative viscosity of 1.30-1.31, measured in a 0.5% solution of methylene chloride at 20 ° C. This corresponds approximately to a molecular weight of 34,000.
- the polycarbonate thus obtained is extruded and granulated.
- the reaction temperature is 72 ° C; the concentration of OH ions in the aqueous reaction phase is 0.08%.
- the average residence time is 1.4 minutes.
- the emulsion flowing out of the pump-around reactor is fed with additional sodium hydroxide solution to increase the OH concentration to 0.3 to 0.35%.
- the oligocarbonate is condensed in a reaction tube as described in DE-OS 1 920 302 or US Pat. No. 3,674,740.
- the average residence time is 4 minutes; the temperature 83 ° C.
- the aqueous reaction phase contains 0.32% OH ⁇ and 0.51% C0 3 ; There is no evidence of bisphenol.
- the polycarbonate solution is washed free of electrolytes, evaporated and isolated using an evaporation extruder.
- the polycarbonate has a relative viscosity of 1.30 to 1.31, measured in a 0.5% solution of methylene chloride at 20 ° C. This corresponds approximately to a molecular weight of 34,000.
- the polycarbonates were processed into test specimens.
- the test specimens are annealed at 140 ° C in a drying cabinet.
- the light transmission was measured according to DIN 5033 and DIN 4646 using a spectrophotometer.
- the drop in light transmission at 420 nm in the course of the heat treatment is a measure of the increasing discoloration of the test specimen.
Description
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von aromatischen Polycarbonaten nach dem Phasengrenzflächenverfahren aus Diphenolen, das dadurch gekennzeichnet, ist, daß man als Katalysatoren N-Ethylpyrrolidin, N-Ethylpiperidin, N-Ethylmorpholin, N-Isopropylpiperidin oder N-Isopropylmorpholin in Mengen von 0,01 Mol-% bis 10 Mol-%, bezogen auf Mole an eingesetzten Diphenolen, verwendet.The present invention relates to a process for the preparation of aromatic polycarbonates according to the phase interface process from diphenols, which is characterized in that the catalysts used are N-ethylpyrrolidine, N-ethylpiperidine, N-ethylmorpholine, N-isopropylpiperidine or N-isopropylmorpholine in amounts of 0.01 mol% to 10 mol%, based on moles of diphenols used.
Gegenstand der vorliegenden Erfindung sind außerdem die verfahrensgemäß erhältlichen Polycarbonate, die sich durch hohe Lichttransmission und geringe Vergilbungstendenz auch nach höherer Temperaturbelastung auszeichnen.The present invention also relates to the polycarbonates obtainable according to the process, which are notable for high light transmission and low yellowing tendency even after higher temperatures.
Die Farbstabilisierung von aromatischen Polycarbonaten erfolgte bisher vorzugsweise durch den Zusatz von Additiven, insbesondere von Phosphiten (vgl. DE-AS - 1 128 653, DE-AS 2 140 207 und DE-OS 2 255 639) gegebenenfalls in Kombination mit anderen Additiven wie beispielsweise mit Oxetanverbindungen (DE-OS 2 510 463).The color stabilization of aromatic polycarbonates has hitherto preferably been carried out by adding additives, in particular phosphites (cf. DE-AS-1 128 653, DE-AS 2 140 207 and DE-OS 2 255 639), optionally in combination with other additives, for example with oxetane compounds (DE-OS 2 510 463).
Gegenüber diesen Methoden zur Farbstabilisierung von Polycarbonaten benutzt die erfindungsgemäße Methode ein völlig anderes Prinzip, indem sie als Katalysatoren bei der Polycarbonatherstellung nach dem Zweiphasengrenzflächenpolykondensationsverfahren (vgl. DE-PS 959 497 DE-PS 1046311 und DE-PS 2 410 716) die eingangs genannten verwendet.Compared to these methods for color stabilization of polycarbonates, the method according to the invention uses a completely different principle, in that it uses the above-mentioned catalysts as catalysts in polycarbonate production by the two-phase interfacial polycondensation process (cf. DE-PS 959 497, DE-PS 1046311 and DE-PS 2 410 716) .
Gemäß US-PS 3 220 975 wird N-Methylpiperazin nur mit schlechtem Erfolg als Katalysator für die Herstellung von Polycarbonaten eingesetzt. (Vergleiche Spalte 1, Zeile 69 bis Spalte 2, Zeile 27).According to US Pat. No. 3,220,975, N-methylpiperazine is used only with poor success as a catalyst for the production of polycarbonates. (Compare column 1, line 69 to column 2, line 27).
Gemäß japanischer Auslegeschrift Nr. 11447/1972 (siehe Chem. Zentralblatt Nr. 32 vom. 4.8.1965, Seite 10098, Nr. 2837) werden Polyamine, unter anderem auch cyclische Polyamine wie N,N-Diethylpiperazin für die Polycarbonatherstellung eingesetzt. Der Einsatz der erfindungsgemäßen Katalysatoren is darin weder vorbeschrieben noch nahegelegt.According to Japanese Patent Application No. 11447/1972 (see Chem. Zentralblatt No. 32 of 4.8.1965, page 10098, No. 2837), polyamines, including cyclic polyamines such as N, N-diethylpiperazine, are used for the production of polycarbonates. The use of the catalysts according to the invention is neither previously described nor suggested.
Gemäß DE-AS 21 01 700 und gemäß DE-OS 23 05 144 können N-Alkyl-morpholine als Katalysatoren für die Polycarbonatherstellung eingesetzt werden. Es war jedoch daraus nicht zu entnehmen, daß spezielle N-Alkylmorpholine gegenüber den in diesen Literaturstellen ebenfalls genannten Katalysatoren wie beispielsweise Triethylamin zu Polycarbonaten mit verbesserter thermischer Beständigkeit führen.According to DE-AS 21 01 700 and DE-OS 23 05 144, N-alkyl morpholines can be used as catalysts for the production of polycarbonates. However, it could not be inferred from this that special N-alkylmorpholines lead to polycarbonates with improved thermal stability compared to the catalysts also mentioned in these references, such as, for example, triethylamine.
GB-PS 1072161 (siehe insbesondere Seite 2, Zeilen 28 ff) beschreibt die Herstellung von Polycarbonaten aus Di-(ß-trihalogen-a-hydroxyethoxy)-alkanen, wobei unter anderem N-Methyl-morpholin als tertiäre Base verwendet werden kann. Abgesehen von dem äquimolaren Einsatz der tertiären Basen, also abgesehen von der unterschiedlichen Menge an tertiärer Base, verglichen mit der Katalysatormenge gemäß vorliegender Erfindung, hat sich gezeigt, daß N-Methylmorpholin als Katalysator gemäß vorliegender Erfindung nicht geeignet ist.GB-PS 1072161 (see in particular page 2, lines 28 ff) describes the preparation of polycarbonates from di- (β-trihalogen-a-hydroxyethoxy) alkanes, it being possible, inter alia, to use N-methylmorpholine as the tertiary base. Apart from the equimolar use of the tertiary bases, that is to say apart from the different amount of tertiary base compared to the amount of catalyst according to the present invention, it has been shown that N-methylmorpholine is not suitable as a catalyst according to the present invention.
Erfindungsgemäß werden von 0,01 bis 10 Mol-%, vorzugsweise von 0,05 bis 5 Mol-% und insbesondere von 0,05 bis 2 Mol-%, bezogen auf Mole an eingesetzten Diphenolen, an den eingangs genannten katalysatoren eingesetzt.According to the invention, from 0.01 to 10 mol%, preferably from 0.05 to 5 mol% and in particular from 0.05 to 2 mol%, based on moles of diphenols used, are used on the catalysts mentioned at the outset.
Besonders geeignet ist: N-Ethylpiperidin.N-ethylpiperidine is particularly suitable.
Die erfindungsgemäße Herstellung der hochmolekularen Polycarbonate erfolgt nach dem Phasengrenzflächenverfahren. Dazu werden Diphenole, insbesondere Dihydroxydiarylalkane bzw. -cycloalkane, wobei neben den unsubstituierten Dihydroxydiarylalkanen bzw. -cycloalkanen auch solche geeignet sind, die in o-Stellung zu den phenolischen Hydroxylgruppen substituiert sind, in wäßrig-alkalischer Phase gelöst, und es wird ein für das Polycarbonat geeignetes Lösungsmittel zugefügt. Dann wird bei einer Temperatur zwischen 0 und 100°C und einem pH-Wert zwischen 9 und 14 Phosgen eingeleitet. Nach dem Phosgenieren erfolgt die Polykondensation. Die Zugabe der erfindungsgemäß geeigneten Katalysatoren kann sowohl vor dem Phosgeneinleiten wie auch nach dem Phosgeneinleiten vor der Polykondensation erfolgen. Die Phosgeneinleitungszeiten betragen zwischen 1 und 60 Minuten, die Nachkondensation zwischen 2 und 120 Minuten. Zur Isolierung der fertigen Polycarbonate wird die organische Polymerlösung abgetrennt und mit Wasser elektrolytfrei gewaschen. Anschließend kann das Polycarbonat durch Abdampfen des Lösungsmittels oder durch Ausfällen mit Nichtlösungsmitteln, wie z.B. Methanol oder Benzin isoliert werden. Die nach dem erfindungsgemäßen Verfahren hergestellten Polycarbonate können in bekannter Weise auch verzweigt sein.The high molecular weight polycarbonates are produced according to the invention by the phase interface process. Diphenols, in particular dihydroxydiarylalkanes or -cycloalkanes, for which, in addition to the unsubstituted dihydroxydiarylalkanes or -cycloalkanes, those which are substituted in the o-position to the phenolic hydroxyl groups are also suitable in the aqueous-alkaline phase, and one is used for the Added suitable polycarbonate solvent. Then phosgene is introduced at a temperature between 0 and 100 ° C and a pH between 9 and 14. The polycondensation takes place after the phosgenation. The catalysts suitable according to the invention can be added either before introducing phosgene or after introducing phosgene before polycondensation. The phosgene introduction times are between 1 and 60 minutes, the post-condensation between 2 and 120 minutes. To isolate the finished polycarbonates, the organic polymer solution is separated off and washed free of electrolytes with water. The polycarbonate can then be removed by evaporation of the solvent or by precipitation with non-solvents, e.g. Methanol or gasoline can be isolated. The polycarbonates produced by the process according to the invention can also be branched in a known manner.
Die erfindungsgemäß erhältlichen Polycarbonate haben mittlere Molekulargewichte (Mw = Gewichtsmittel) zwischen 10.000 und 200.000, vorzugsweise zwischen 20.000 und 100.000, die aus der relativen Viskosität der Polycarbonate (gemessen in Methylenchlorid bei 25°C und einer Konzentration von 0,5 Gew.-%) ermittelt werden können.The polycarbonates obtainable according to the invention have average molecular weights (M w = weight average) between 10,000 and 200,000, preferably between 20,000 and 100,000, which are based on the relative viscosity of the polycarbonates (measured in methylene chloride at 25 ° C. and a concentration of 0.5% by weight ) can be determined.
Geeignete Diphenole sind z.B. Hydrochinon, Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(hydroxyphenyl)-alkane, wie beispielsweise C1-CS-Alkylen- bzw. C2―C8-Alkylidenbisphenole, Bis-(hydroxyphenyl)-cycloalkane wie beispielsweise Cs-Cs-Cycloalkylen- bzw. C5―C6-Cycloalkyliden - bisphenole, Bis - (hydroxyphenyl) - sulfide, -ether, -ketone, -sulfoxide oder -sulfone. Ferner α,α' - Bis - (hydroxyphenyl) - diisopropylbenzole sowie die entsprechenden kernalkylierten bzw. kernhalogenierten Verbindungen. Bevorzugt sind Polycarbonate auf Basis Bis - (4 - hydroxyphenyl) - propan - 2,2 (Bisphenol A), Bis - (4-hydroxy - 3,5 - dichlor - phenyl) - propan - 2,2 (Tetrachlorbisphenol A), Bis - (4 - hydroxy - 3,5-dibromophenyl) - propan - 2,2 (Tetrabrombisphenol A), Bis - (4 - hydroxy - 3,5 - dimethylphenyl) - propan - 2,2 (Tetramethylbisphenol A), Bis - (4 - hydroxy - 3 - methyl - phenyl) - propan-2,2, Bis - (4 - hydroxyphenyl) - cyclohexan - 1,1 (Bisphenol Z) sowie auf Basis von Dreikernbisphenolen wie a,a' - Bis - (4 - hydroxy - phenyl)-p - diisopropylbenzol.Suitable diphenols are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis- (hydroxyphenyl) alkanes, such as, for example, C1-CS-alkylene- or C 2 -C 8 -alkylidene bisphenols, bis- (hydroxyphenyl) cycloalkanes, for example Cs-Cs-cycloalkylene or C 5 -C 6 -cycloalkylidene bisphenols, bis - (hydroxyphenyl) sulfides, ethers, ketones, sulfoxides or sulfones. Furthermore, α, α '- bis - (hydroxyphenyl) - diisopropylbenzenes and the corresponding nuclear alkylated or nuclear halogenated compounds. Polycarbonates based on bis (4-hydroxyphenyl) propane-2,2 (bisphenol A), bis (4-hydroxy-3,5-dichlorophenyl) propane-2,2 (tetrachlorobisphenol A), bis are preferred - (4-hydroxy-3,5-dibromophenyl) propane - 2,2 (tetrabromobisphenol A), bis - (4-hydroxy-3,5-dimethylphenyl) propane - 2,2 (tetramethylbisphenol A), bis - ( 4-hydroxy-3-methyl-phenyl) -propane-2,2, bis - (4-hydroxyphenyl) -cyclohexane-1,1 (bisphenol Z) and based on trinuclear bisphenols such as a, a '- bis - (4 - hydroxy-phenyl) -p-diisopropylbenzene.
Weitere für die Herstellung von Polycarbonaten geeignete Diphenole sind in den US-Patenten 3 028 265, 2 999 835, 3 148 172,3271 386, 2 991 273,3271 367, 3280078, 3014891, 2 999 846 sowie den deutschen Offenlegungsschriften 2 063 050, 2 063 052, 2211 957 und 2211 956 beschrieben.Further diphenols suitable for the production of polycarbonates are described in US Pat. Nos. 3,028,265, 2,999,835, 3,148,172,3271,386, 2,991,273,3271,367, 32,80078, 3014,891, 2,999,846 and German Offenlegungsschriften 2,063,050 , 2 063 052, 2211 957 and 2211 956.
Die in den folgenden Beispielen verwendeten Ausgangsmaterialien werden wie folgt charakterisiert (Teile = Gew. Teile):The starting materials used in the following examples are characterized as follows (parts = parts by weight):
456 Teile 2,2-Bis-(4-hydroxyphenyl)-propan und 9,5 Teile p.-tert.-Butylphenol werden in 1,5 I Wasser suspendiert. In einem 3-Halskolben ausgestattet mit Rührer und Gaseinleitungsrohr, wird der Sauerstoff aus der Reaktionsmischung entfernt, indem unter Rühren 15 Min. lang Stickstoff durch die Reaktionsmischung geleitet wird. Dann werden 355 Teile 45%ige Natronlauge und 1000 Teile Methylenchlorid zugegeben. Die Mischung wird auf 25°C abgekühlt. Unter Aufrechterhaltung dieser Temperatur durch Kühlen werden 237 Teile Phosgen während einer Zeitdauer von 60 Min. zugegeben. Eine zusätzliche Menge von je 75 Teilen einer 45%igen Natronlauge wird nach 15 und 30 Min. zugegeben, nachdem die Phosgenaufnahme begonnen hat, Zu der entstandenen Lösung wird der, Katalysator (siehe Beispiele) zugegeben und die Mischung weitere 15 Min. gerührt. Eine hochviskose Lösung wird erhalten, deren Viskosität durch Zugabe von Methylenchlorid reguliert wird. Die wäßrige Phase wird abgetrennt. Die organische Phase wird mit Wasser salz- und alkalifrei gewashcen. Polycarbonat wird aus der ausgewaschenen Lösung isoliert und getrocknet. Das Polycarbonat hat eine relative Viskosität von 1,30-1,31, gemessen in einer 0,5%igen Lösung von Methylenchlorid bei 20°C. Das entspricht ungefähr einem Molekulargewicht von 34.000. Das so gewonnene Polycarbonat wird extrudiert und granuliert.456 parts of 2,2-bis (4-hydroxyphenyl) propane and 9.5 parts of p.-tert-butylphenol are suspended in 1.5 l of water. In a 3-neck flask equipped with a stirrer and gas inlet tube, the oxygen is removed from the reaction mixture by passing nitrogen through the reaction mixture with stirring for 15 minutes. Then 355 parts of 45% sodium hydroxide solution and 1000 parts of methylene chloride are added. The mixture is cooled to 25 ° C. While maintaining this temperature by cooling, 237 parts of phosgene are added over a period of 60 minutes. An additional amount of 75 parts of a 45% sodium hydroxide solution is added after 15 and 30 minutes after the phosgene has started. The catalyst (see examples) is added to the resulting solution and the mixture is stirred for a further 15 minutes. A highly viscous solution is obtained, the viscosity of which is regulated by adding methylene chloride. The aqueous phase is separated off. The organic phase is washed free of salt and alkali with water. Polycarbonate is isolated from the washed-out solution and dried. The polycarbonate has a relative viscosity of 1.30-1.31, measured in a 0.5% solution of methylene chloride at 20 ° C. This corresponds approximately to a molecular weight of 34,000. The polycarbonate thus obtained is extruded and granulated.
In einem Umpumpreaktor mit 4,25 I Reaktionsvolumen, wie in DE-AS 2410716 beschrieben, werden folgende Lösungen eingepumpt:
Die Reaktionstemperatur beträgt 72°C; die Konzentration der OH-Ionen in der wäßrigen Reaktionsphase 0,08%. Die mittlere Verweilzeit beträgt 1,4 Min.The reaction temperature is 72 ° C; the concentration of OH ions in the aqueous reaction phase is 0.08%. The average residence time is 1.4 minutes.
Der aus dem Umpumpreaktor abfließenden Emulsion wird zur Erhöhung der OH-Konzentration auf 0,3 bis 0,35% weitere Natronlauge zugeführt. Die Aufkondensation des Oligocarbonats wird in einem Reaktionsrohr, wie es in DE-OS 1 920 302 bzw. US-PS 3 674 740 beschrieben, durchgeführt. Die mittlere Verweilzeit beträgt 4 Min.; die Temperatur 83°C.The emulsion flowing out of the pump-around reactor is fed with additional sodium hydroxide solution to increase the OH concentration to 0.3 to 0.35%. The oligocarbonate is condensed in a reaction tube as described in DE-OS 1 920 302 or US Pat. No. 3,674,740. The average residence time is 4 minutes; the temperature 83 ° C.
Die wäßrige Reaktionsphase enthält 0,32% OH― und 0,51 % C03; Bisphenol ist nicht nachzuweisen.The aqueous reaction phase contains 0.32% OH― and 0.51% C0 3 ; There is no evidence of bisphenol.
Die Polycarbonatlösung, deren Feststoffgehalt 15,1% beträgt, wird elektrolytfrei gewaschen, eingedampft und über einen Ausdampfextruder isoliert. Das Polycarbonat hat eine relative Viskosität von 1,30 bis 1,31, gemessen in einer 0,5%igen Lösung von Methylenchlorid bei 20°C. Das entspricht ungefähr einem Molekulargewicht von 34.000.The polycarbonate solution, the solids content of which is 15.1%, is washed free of electrolytes, evaporated and isolated using an evaporation extruder. The polycarbonate has a relative viscosity of 1.30 to 1.31, measured in a 0.5% solution of methylene chloride at 20 ° C. This corresponds approximately to a molecular weight of 34,000.
Folgende Katalysatoren werden zur Herstellung von Polycarbonat eingesetzt:
- Beispiel 1 (Vergleichsversuch): 1,6 Teile Triethylamin, Verfahren 1.
- Beispiel 2 (Vergleichsversuch): 0,575 Teile Triethylamin, Verfahren 2.
- Beispiel 3: 1,8 teile N-Ethylpiperidin, Verfahren 1.
- Beispiel 4: 0,31 Teile N-Isopropylpiperidin, Verfahren 2.
- Beispiel 5: 1,8 Teile N-Ethylmorpholin, Verfahren 1.
- Beispiel 6: 1,0 Teile N-Ethylpyrolidin, Verfahren 1.
- Beispiel 7: 0,46 Teile N-Isopropylmorpholin, Verfahren 2.
- Beispiel 8 (Vergleichsversuch): Ein Polycarbonat aus 95 Mol % Bisphenol A und 5 Mol % tetrabrombisphenol A, hergestellt nach dem Verfahren 1 mit 1,5 Teilen Triethylamin mit einer rel. Viskosität von 1,32.
- Beispiel 9: Polycarbonat aus Beispiel 8, hergestellt nach dem Verfahren 1, mit 0,6 Teilen N-Ethylpiperidin.
- Example 1 (comparative test): 1.6 parts of triethylamine, method 1.
- Example 2 (comparative test): 0.575 parts of triethylamine, method 2.
- Example 3: 1.8 parts N-ethylpiperidine, Method 1.
- Example 4: 0.31 part of N-isopropylpiperidine, Method 2.
- Example 5: 1.8 parts of N-ethylmorpholine, method 1.
- Example 6: 1.0 part N-ethyl pyrolidine, method 1.
- Example 7: 0.46 parts of N-isopropylmorpholine, method 2.
- Example 8 (comparative experiment): A polycarbonate composed of 95 mol% bisphenol A and 5 mol% tetrabromobisphenol A, produced by process 1 with 1.5 parts triethylamine with a rel. Viscosity of 1.32.
- Example 9: Polycarbonate from Example 8, produced by process 1, with 0.6 part of N-ethylpiperidine.
Die Polycarbonate wurden zu Prüfkörpern verarbeitet. Die Prüfkörper werden bei 140°C im Trockenschrank getempert. Mit Hilfe eines Spektralphotometers wurde die Lichttransmission nach DIN 5033 und DIN 4646 gemessen. Der Abfall der Lichttransmission bei 420 nm im Verlauf der Wärmebehandlung ist ein Maß für die zunehmende Verfärbung des Prüfkörpers.The polycarbonates were processed into test specimens. The test specimens are annealed at 140 ° C in a drying cabinet. The light transmission was measured according to DIN 5033 and DIN 4646 using a spectrophotometer. The drop in light transmission at 420 nm in the course of the heat treatment is a measure of the increasing discoloration of the test specimen.
Lichttransmission der Polycarbonatprüfstäbe bei 420 nm und einer Schichdicke von 4 mm nach Temperung bei 140°C.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772735775 DE2735775A1 (en) | 1977-08-09 | 1977-08-09 | PROCESS FOR THE PRODUCTION OF POLYCARBONATE |
| DE2735775 | 1977-08-09 |
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| Publication Number | Publication Date |
|---|---|
| EP0000753A1 EP0000753A1 (en) | 1979-02-21 |
| EP0000753B1 true EP0000753B1 (en) | 1980-12-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100539A Expired EP0000753B1 (en) | 1977-08-09 | 1978-07-28 | Process for the preparation of polycarbonates and the polycarbonates obtained |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4346210A (en) |
| EP (1) | EP0000753B1 (en) |
| JP (1) | JPS6053049B2 (en) |
| BR (1) | BR7805075A (en) |
| DE (2) | DE2735775A1 (en) |
| IT (1) | IT1106867B (en) |
| SU (1) | SU1020006A3 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4233345A1 (en) * | 1992-10-05 | 1994-04-07 | Bayer Ag | Process for the preparation of polycarbonates and polyestercarbonates |
| DE19728805A1 (en) * | 1997-07-05 | 1999-01-07 | Bayer Ag | Process for the production of polycarbonate |
| DE19744693A1 (en) * | 1997-10-10 | 1999-04-15 | Bayer Ag | Production of thermoplastic copolycarbonates useful for moldings resistant to chemicals |
| US5973103A (en) * | 1998-10-22 | 1999-10-26 | General Electric Company | Continuous interfacial method for preparing aromatic polycarbonates |
Family Cites Families (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3014891A (en) | 1961-12-26 | Resinous compositions | ||
| DE1007996B (en) | 1955-03-26 | 1957-05-09 | Bayer Ag | Process for the production of thermoplastics |
| DE959497C (en) | 1955-03-27 | 1957-03-07 | Bayer Ag | Process for the production of thermoplastics |
| US3275601A (en) * | 1956-01-04 | 1966-09-27 | Bayer Ag | Manufacture of polycarbonates using tertiary amines, quaternary amines and salts thereof as catalysts |
| DE1046311B (en) | 1956-04-06 | 1958-12-11 | Bayer Ag | Process for the production of polycarbonates |
| US2991273A (en) | 1956-07-07 | 1961-07-04 | Bayer Ag | Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates |
| US3148172A (en) | 1956-07-19 | 1964-09-08 | Gen Electric | Polycarbonates of dihydroxyaryl ethers |
| US2999846A (en) | 1956-11-30 | 1961-09-12 | Schnell Hermann | High molecular weight thermoplastic aromatic sulfoxy polycarbonates |
| US3028265A (en) | 1957-05-06 | 1962-04-03 | Gen Electric | Reinforced synthetic enamel coating for electrical conductor |
| US2999835A (en) | 1959-01-02 | 1961-09-12 | Gen Electric | Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same |
| US3220975A (en) * | 1959-03-19 | 1965-11-30 | Eastman Kodak Co | Tri-isoamylamine catalyst in a process for preparing a polycarbonate |
| NL253031A (en) | 1959-06-27 | |||
| US3271368A (en) | 1963-05-02 | 1966-09-06 | Borg Warner | Sulfonate-thiocarbonate copolymers |
| DE1300274B (en) | 1963-05-22 | 1969-07-31 | Hoechst Ag | Process for the production of high molecular weight polymers on the basis of di- [beta-trihalogen-alpha-hydroxyaethoxy] alkanes |
| US3280078A (en) | 1963-09-26 | 1966-10-18 | Union Carbide Corp | Polyethylenically unsaturated polycarbonate polymers |
| US3527734A (en) | 1965-06-07 | 1970-09-08 | Union Carbide Corp | Preparation of cylobutanediol polycarbonates by direct phosgenation |
| US3428600A (en) * | 1965-06-18 | 1969-02-18 | Union Carbide Corp | Carbonate polymer synthesis |
| US3674740A (en) | 1969-04-22 | 1972-07-04 | Bayer Ag | Process of producing polycarbonate |
| DE2063050C3 (en) | 1970-12-22 | 1983-12-15 | Bayer Ag, 5090 Leverkusen | Saponification-resistant polycarbonates, processes for their production and their use |
| DE2063052A1 (en) | 1970-12-22 | 1972-07-13 | Bayer | Saponification-resistant polycarbonates |
| CH554908A (en) * | 1971-01-15 | 1974-10-15 | Basf Ag | PROCESS FOR THE CONTINUOUS MANUFACTURING OF HIGH MOLECULAR, LINEAR POLYCARBONATES. |
| US4073769A (en) * | 1971-08-11 | 1978-02-14 | Bayer Aktiengesellschaft | Esters of phosphorous acid |
| DE2140207C3 (en) * | 1971-08-11 | 1975-11-27 | Farbenfabriken Bayer Ag, 5090 Leverkusen | Stabilized aromatic polycarbonate |
| DE2211956A1 (en) | 1972-03-11 | 1973-10-25 | Bayer Ag | PROCESS FOR THE PREPARATION OF SEAP-STABLE BLOCK COPOLYCARBONATES |
| DE2211957C2 (en) | 1972-03-11 | 1982-07-01 | Bayer Ag, 5090 Leverkusen | High molecular weight random copolycarbonates |
| DE2305144C2 (en) * | 1973-02-02 | 1982-05-06 | Basf Ag, 6700 Ludwigshafen | Process for the continuous production of polycarbonates |
| DE2410716B2 (en) * | 1974-03-06 | 1977-02-10 | Bayer Ag, 5090 Leverkusen | PROCESS FOR THE PRODUCTION OF AROMATIC POLYCARBONATE USING THE METHOD OF PHASE INTERFACE CONDENSATION |
| DE2447349A1 (en) | 1974-10-04 | 1976-04-15 | Bayer Ag | PROCESS FOR THE PRODUCTION OF ALIPHATIC POLYCARBONATES AND ALIPHATICAROMATIC COPOLYCARBONATES |
| US4025489A (en) * | 1975-01-27 | 1977-05-24 | Mobay Chemical Corporation | Utilization of bisphenol-A from the alkaline phase generated in the production of polycarbonates |
| DE2510463C2 (en) | 1975-03-11 | 1986-04-03 | Bayer Ag, 5090 Leverkusen | Stabilizer mixtures and use of stabilizer mixtures to stabilize polycarbonates |
-
1977
- 1977-08-09 DE DE19772735775 patent/DE2735775A1/en not_active Withdrawn
-
1978
- 1978-07-28 DE DE7878100539T patent/DE2860295D1/en not_active Expired
- 1978-07-28 EP EP78100539A patent/EP0000753B1/en not_active Expired
- 1978-08-07 IT IT50631/78A patent/IT1106867B/en active
- 1978-08-08 SU SU782645703A patent/SU1020006A3/en active
- 1978-08-08 JP JP53095894A patent/JPS6053049B2/en not_active Expired
- 1978-08-08 BR BR7805075A patent/BR7805075A/en unknown
-
1979
- 1979-10-26 US US06/088,694 patent/US4346210A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| BR7805075A (en) | 1979-04-10 |
| SU1020006A3 (en) | 1983-05-23 |
| DE2735775A1 (en) | 1979-02-22 |
| US4346210A (en) | 1982-08-24 |
| DE2860295D1 (en) | 1981-02-19 |
| JPS5430293A (en) | 1979-03-06 |
| IT7850631A0 (en) | 1978-08-07 |
| JPS6053049B2 (en) | 1985-11-22 |
| IT1106867B (en) | 1985-11-18 |
| EP0000753A1 (en) | 1979-02-21 |
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