EP0000753A1 - Process for the preparation of polycarbonates and the polycarbonates obtained - Google Patents

Process for the preparation of polycarbonates and the polycarbonates obtained Download PDF

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Publication number
EP0000753A1
EP0000753A1 EP7878100539A EP78100539A EP0000753A1 EP 0000753 A1 EP0000753 A1 EP 0000753A1 EP 7878100539 A EP7878100539 A EP 7878100539A EP 78100539 A EP78100539 A EP 78100539A EP 0000753 A1 EP0000753 A1 EP 0000753A1
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Prior art keywords
polycarbonates
parts
alkyl
teile
azabicyclo
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German (de)
French (fr)
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EP0000753B1 (en
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Wolfgang Dr. Alewelt
Dieter Dr. Margotte
Claus Dr. Wulff
Hugo Dr. Vernaleken
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Bayer AG
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Bayer AG
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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

Definitions

  • the present invention also relates to the polycarbonates obtainable according to the process, which are: characterized by high light transmission and low yellowing tendency even after high temperatures.
  • the color stabilization of aromatic polycarbonates has hitherto preferably been carried out by adding additives, in particular phosphites (cf. DT-AS 1 128 653 (Le 1926), DT - A S 2 140 207, (Le A 1.3 917) and DT- OS 2 255 639 (Le A 14 709)) optionally in combination with other additives such as, for example, with oxetane compounds (DT-OS 2 510 463 (Le A 16 231)).
  • additives in particular phosphites (cf. DT-AS 1 128 653 (Le 1926), DT - A S 2 140 207, (Le A 1.3 917) and DT- OS 2 255 639 (Le A 14 709)
  • additives in particular phosphites (cf. DT-AS 1 128 653 (Le 1926), DT - A S 2 140 207, (Le A 1.3 917) and DT- OS 2 255 639 (Le A 14 709)) optionally
  • the method according to the invention uses a completely different principle in that it serves as catalysts in the production of polycarbonates by the two-phase interfacial polycondensation process (cf. DT-PS 959 497 (Le 1693), DT-PS 1 O46 311 (Le 1 7 4 7) and D T-PS 2 410 716 (Le A 15 514)) cyclic aza compounds.
  • Monocyclic and bicyclic compounds are particularly suitable as cyclic aza compounds, and in this case in turn preferably those of the pyrroliain type, piperidine type and morpholine type.
  • the cyclic aza compounds preferably have between 4 and 20 C atoms, in particular between 5 and 12 C atoms.
  • cyclic aza compounds from 0.01 to 10 mol%, preferably from 0.05) to 5 mol, - and in particular from 0.05 to 2 mol%, based on the mol of diphenols used, of cyclic aza compounds are used.
  • Cyclic aza compounds in the sense of the present invention are those which contain neither a donut bond to an aza nitrogen atom nor a secondary amine group.
  • the cyclic aza compounds must also not contain any substituents which are reactive under the conditions of the phase interface process.
  • 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 addition of the cyclic aza compounds as a catalyst can both before introducing phosgene and 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 isolated by evaporation of the solvent or by precipitation with non-solvents, such as methanol or gasoline.
  • the polycarbonates produced by the process according to the invention can also be branched in a known manner.
  • Suitable diphenols are e.g. B. hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, such as C 1 -C 8 alkylene or C 2 -C 8 alkylidene bisphenols, bis- '(hydroxyphenyl) cycloalkanes such as for example C5-C6-cycloalkylene or C 5 -C 6 -cycloalkylidene bisphenols, bis (hydroxy - phenyl) sulfides, ethers, ketones, sulfoxides or sulfones.
  • B. hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl bis (hydroxyphenyl) alkanes, such as C 1 -C 8 alkylene or C 2 -C 8 alkylidene bisphenols, bis- '(hydroxyphenyl) cycloalkanes such as for example C5-
  • A ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes and the corresponding ring-alkylated or ring-halogenated compounds.
  • Polycarbonates based on bis- (4-hydroxy-phenyl) propane-2,2 (bisphenol A), bis- (4-hydroxy-3,5-dichlorophenyl) propane-2,2 (tetrachlorobisphenol A) are preferred.
  • 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 DT-OS 1 920 302 or US Pat. No. 3,674,740.
  • the average residence time is 4 minutes; the temperature 83 ° C.
  • 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.

Abstract

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 cyclische, vorzugsweise monocyclische oder bicyclische Azaverbindungen verwendet.The present invention relates to a process for the preparation of aromatic polycarbonates by the phase interface process from diphenols, which is characterized in that cyclic, preferably monocyclic or bicyclic aza compounds are used as catalysts.

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 cyclische, vorzugsweise monocyclische oder bicyclische Azaverbindungen verwendet.The present invention relates to a process for the preparation of aromatic polycarbonates by the phase interface process from diphenols, which is characterized in that cyclic, preferably monocyclic or bicyclic aza compounds are used as catalysts.

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: characterized by high light transmission and low yellowing tendency even after high temperatures.

Die Farbstabilisierung von aromatischen Polycarbonaten erfolgte bisher vorzugsweise durch den Zusatz von Additiven, insbesondere von Phosphiten (vgl. DT-AS 1 128 653 (Le 1926), DT-AS 2 140 207, (Le A 1,3 917) und DT-OS 2 255 639 (Le A 14 709)) gegebenenfalls in Kombination mit anderen Additiven wie beispielsweise mit Oxetanverbindungen (DT-OS 2 510 463 (Le A 16 231)).The color stabilization of aromatic polycarbonates has hitherto preferably been carried out by adding additives, in particular phosphites (cf. DT-AS 1 128 653 (Le 1926), DT - A S 2 140 207, (Le A 1.3 917) and DT- OS 2 255 639 (Le A 14 709)) optionally in combination with other additives such as, for example, with oxetane compounds (DT-OS 2 510 463 (Le A 16 231)).

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. DT-PS 959 497 (Le 1693), DT-PS 1 O46 311 (Le 1747) und DT-PS 2 410 716 (Le A 15 514)) cyclische Azaverbindungen verwendet.Compared to these methods for color stabilization of polycarbonates, the method according to the invention uses a completely different principle in that it serves as catalysts in the production of polycarbonates by the two-phase interfacial polycondensation process (cf. DT-PS 959 497 (Le 1693), DT-PS 1 O46 311 (Le 1 7 4 7) and D T-PS 2 410 716 (Le A 15 514)) cyclic aza compounds.

Als cyclische Azaverbindungen sind insbesondere monocyclische und bicyclische geeignet und hierbei wiederum vorzugsweise solche vom Pyrroliain-Typ, Piperidin-Typ und Morpholin-Typ. Die cyclischen Azaverbindungen haben vorzugsweise zwischen 4 und 20 C-Atome, insbesondere zwischen 5 und 12 C-Atome.Monocyclic and bicyclic compounds are particularly suitable as cyclic aza compounds, and in this case in turn preferably those of the pyrroliain type, piperidine type and morpholine type. The cyclic aza compounds preferably have between 4 and 20 C atoms, in particular between 5 and 12 C atoms.

Erfindunqsgemäß werden von 0,01 bis 10 Mol.-%, vorzugsweise von 0,05) bis 5 Mol,-% und insbesondere von 0.05 bis 2 Mol %, bezogen aut Mole n eingesetzten Diphenolen, an ccyclischen Azaverbindungen 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 the mol of diphenols used, of cyclic aza compounds are used.

Cyclische Azaverbindungen im Sinne vorliegender Erfindung sind solche, die weder eine Donpelbindung an Aza-Stickstoffatom, noch eine sekundäre Amin-Gruppierung enthalten. Auch dürfen die cyclischen Azaverbindungen keine unter den Bedingungen des Phasengrenzflächenverfahrens reaktive Substituenten enthalten.Cyclic aza compounds in the sense of the present invention are those which contain neither a donut bond to an aza nitrogen atom nor a secondary amine group. The cyclic aza compounds must also not contain any substituents which are reactive under the conditions of the phase interface process.

folgende Einzelverbindunqen sind beispielsweise geeignet:

  • N-C1-C6-Alkyl-pyrrolidine, N-C1-C6-Alkyl-piperidine, N-C1-C6-Alkyl-morpholine, N-C1-c6-Alkyl-dihydroindole, N-C1-C6-Alkyl-dihydroisoindole, N-C1-C6-Alkyl-tetra- hydroisochinoline, N-C1-C6-Alkyl-benzomorpholine, 1-Azabicyclo-/3.3.0/-octan, 1-Azabicyclo-/2.2.2./-octan, N-C1-C6-Alkyl-2-azabicyclo-[2.2.1]-octan, N-C1-C6-Alkyl-2-azabicyclo-/3.3.1/-nonan, N-C1-C6-Alkyl-3-azabicyclo[3.3.1]-nonan.
The following individual connections are suitable, for example:
  • NC 1 -C 6 -alkyl-pyrrolidines, NC 1 -C piperidine-6 alkyl, NC 1 -C 6 alkyl-morpholine, NC 1 -C 6 -alkyl-dihydroindoles, NC 1 -C 6 -alkyl dihydroisoindole, NC 1 -C 6 alkyl tetra hydroisoquinolines, NC 1 -C 6 alkyl benzomorpholines, 1-azabicyclo- / 3.3.0 / -octane, 1-azabicyclo- / 2.2.2 ./- octane, NC 1 - C 6 -alkyl-2-azabicyclo- [2.2.1] octane, NC 1 -C 6 -alkyl-2-azabicyclo- / 3.3.1 / -nonane, NC 1 -C 6 -alkyl-3-azabicyclo [3.3 .1] -nonan.

Besonders geeignet sind:

  • N-Äthylpyrrolidin, N-Äthylpiperidin, N-Äthylmorpholin, N-Isopropylpiperidin, N-Isopropylmorpholin.
The following are particularly suitable:
  • N-ethyl pyrrolidine, N-ethyl piperidine, N-ethyl morpholine, N-isopropyl piperidine, N-isopropyl morpholine.

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 cyclischen Azaverbindungen als Katalysator 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 addition of the cyclic aza compounds as a catalyst can both before introducing phosgene and 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 isolated by evaporation of the solvent or by precipitation with non-solvents, such as methanol or gasoline. The polycarbonates produced by the process according to the invention can also be branched in a known manner.

Die erfindungsgemäß erhältlichen Polycarbonate haben mitt- lere 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 wt .-%) can be determined.

Geeignete Diphenole sind z. B. Hydrochinon, Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(hydroxyphenyl)-alkane, wie beispielsweise C1-C8-Alkylen- bzw. C2-C8-Alkylidenbisphenole, Bis- '(hydroxyphenyl)-cycloalkane wie beispielsweise C5-C6-Cycloalkylen- bzw. C5-C6-Cycloalkyliden-bisphenole, Bis-(hydroxy- phenyl)-sulfide, -äther, -ketone, -sulfoxide oder -sulfone. Ferner A, α'-Bis-(hydroxyphenyl)-diisopropylbenzole sowie die entsprechenden kernalkylierten bzw. kernhalogenierten Verbindungen. Bevorzugt sind Polycarbonate auf Basis Bis-(4-hydroxy-phenyl)-propan-2,2 (Bisphenol A), Bis-(4-hydroxy-3,5-dichlor-phenyl)-propan-2,2 (Tetrachlorbisphenol A), Bis-(4-hydroxy-3,5-dibromphenyl)-propan-2,2 (Tetrabrombisphenol A), Bis-(4-hydroxy-3,5-dimethyl-phenyl)-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 α,α '-Bis-(4-hydroxy-phenyl)-p-diisopropylbenzol.Suitable diphenols are e.g. B. hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, such as C 1 -C 8 alkylene or C 2 -C 8 alkylidene bisphenols, bis- '(hydroxyphenyl) cycloalkanes such as for example C5-C6-cycloalkylene or C 5 -C 6 -cycloalkylidene bisphenols, bis (hydroxy - phenyl) sulfides, ethers, ketones, sulfoxides or sulfones. Furthermore, A, α'-bis (hydroxyphenyl) diisopropylbenzenes and the corresponding ring-alkylated or ring-halogenated compounds. Polycarbonates based on bis- (4-hydroxy-phenyl) propane-2,2 (bisphenol A), bis- (4-hydroxy-3,5-dichlorophenyl) propane-2,2 (tetrachlorobisphenol A) are preferred. , Bis (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-methylphenyl) propane-2,2, bis- (4th -hydroxyphenyl) -cyclohexane-1,1 (bisphenol Z) and based on trinuclear bisphenols such as α, α '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, 3 271 368, 2 991 273, 3 271 367, 3 280 078, 3 014 891, 2 999 846 sowie den deutschen Offenlegungsschriften 2 Oc3 050 (Le A 13 359), 2 063 052 (Le A 13 425), 2 211 957 (Le A 14 240) und 2 211 956 (Le A 14 249) beschrieben.Further diphenols suitable for the production of polycarbonates are described in US Pat. Nos. 3,028,265, 2,999,835, 3,148,172, 3,271,368, 2,991,273, 3,271,367, 3,280,078, 3,014,891, 2,999,846 and German Offenlegungsschriften 2 Oc3 050 (Le A 13 359), 2 063 052 (Le A 13 425), 2 211 957 (Le A 14 240) and 2 211 956 (Le A 14 249).

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):

1. Verfahren 1: (Phosgenierung in Methylenchlorid) Diskontinuierliche Herstellung eines Polycarbonats1. Method 1: (Phosgenation in methylene chloride) batch production of a polycarbonate

45c Teile 2,2-Bis-(4-hydroxyphenyl)-propan und 9,5 Teile p.-tert.-Butylphenol werden in 1,5 1 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 gewaschen. 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.45c 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 uptake 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 obtained in this way is extruded and granulated.

2. Verfahren 2 : (Phosgenierung in Chlorbenzol) Kontinuierliche Herstellung eines Polycarbonats2. Method 2: (Phosgenation in chlorobenzene) Continuous production of a polycarbonate

In einem Umpumpreaktor mit 4,25 1 Reaktionsvolumen, wie in DT-AS 2 410 716 beschrieben, werden folgende Lösungen eingepumpt:

  • 1. 91,2 Teile/Stunde einer Alkalisalzlösung von Bisphenol A folgender Zusammensetzung:
    • 130 Teile Bisphenol A
    • 631 Teile Wasser
    • 103,2 Teile 45 %ige Natronlauge
    • 0,05 Teile Natriumborhydrid
    • 2,3 Teile p.-tert.-Butylphenol Katalysator (siehe Beispiele)
  • 2. 6.7 Teile/Stunde Phosgen mit
    • 88 Teilen/Stunde Chlorbenzol und
  • 3. 0,5 Teile/Stunde 45 %ige Natronlauge.
The following solutions are pumped into a pump-around reactor with a reaction volume of 4.25 l, as described in DT-AS 2 410 716:
  • 1. 91.2 parts / hour of an alkali salt solution of bisphenol A of the following composition:
    • 130 parts of bisphenol A
    • 631 parts of water
    • 103.2 parts of 45% sodium hydroxide solution
    • 0.05 part sodium borohydride
    • 2.3 parts of p.-tert.-butylphenol catalyst (see examples)
  • 2. 6.7 parts / hour with phosgene
    • 88 parts / hour chlorobenzene and
  • 3. 0.5 parts / hour 45% sodium hydroxide solution.

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 DT-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 DT-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 % CO3; Bisphenol ist nicht nachzuweisen.The aqueous reaction phase contains 0.32% OH and 0.51% CO 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 (Vergleichsbeispiel):
    • 1,6 Teile Triäthylamin, Verfahren 1
  • Beispiel 2 (Vergleichsbeispiel):
    • 0,575 Teile Triäthylamin, Verfahren 2
  • Beispiel 3:
    • 1,8 Teile N-Äthylpiperidin, Verfahren 1
  • Beispiel 4:
    • 0,31 Teile N-Isopropylpiperidin, Verfahren 2
  • Beispiel 5:
    • 1,8 Teile N-Äthylmorpholin, Verfahren 1
  • Beispiel 6:
    • 1,0 Teile N-Äthylpyrolidin, Verfahren 1
  • Beispiel 7:
    • 0,8 Teile 1-Azabicyclo-/2.2.2/-octan, Verfahren 1
  • Beispiel 8:
    • 0,46 Teile N-Isopropylmorpholin, Verfahren 2
  • Beispiel 9:
    • Ein Polycarbonat aus 95 Mol % Bisphenol A und 5 Mol % Tetrabrombisphenol A, hergestellt nach dem Verfahren 1 mit 1,5 Teilen Triäthylamin mit einer rel. Viskosität von 1,32.
  • Beispiel 10:
    • Polycarbonat aus Beispiel 9, hergestellt nach dem Verfahren 1, mit 0,6 Teilen N-Äthylpiperidin.
The following catalysts are used to manufacture polycarbonate:
  • Example 1 (comparative example):
    • 1.6 parts of triethylamine, method 1
  • Example 2 (comparative example):
    • 0.575 parts of triethylamine, Method 2
  • Example 3:
    • 1.8 parts N-ethyl piperidine, method 1
  • Example 4:
    • 0.31 part 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:
    • 0.8 parts 1-azabicyclo / 2.2.2 / octane, method 1
  • Example 8:
    • 0.46 parts N-isopropylmorpholine, method 2
  • Example 9:
    • A polycarbonate of 95 mol% bisphenol A and 5 mol% tetrabromobisphenol A, prepared by method 1 with 1.5 parts of triethylamine with a rel. Viscosity of 1.32.
  • Example 10:
    • Polycarbonate from Example 9, 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.

Figure imgb0001
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.
Figure imgb0001

Claims (4)

1. Verfahren zur Herstellung von aromatischen Polycarbonaten nach dem Phasengrenzflächenverfahren aus Diphenolen, dadurch gekennzeichnet, daß man als Katalysatoren cyclische Azaverbindungen verwendet.1. A process for the preparation of aromatic polycarbonates by the phase interface process from diphenols, characterized in that cyclic aza compounds are used as catalysts. 2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man monocyclische oder bicyclische Azaverbindungen verwendet.2. The method according to claim 1, characterized in that one uses monocyclic or bicyclic aza compounds. 3. Verfahren gemäß Anspruch 1 und 2, dadurch gekennzeichnet, daß man die Azaverbindungen in Mengen von 0,01 Mol-% bis 10 Mol-%, bezogen auf Mole an eingesetzten Diphenolent, verwendet.3. The method according to claim 1 and 2, characterized in that the aza compounds in amounts of 0.01 mol% to 10 mol%, based on moles of diphenols t used. 4. Aromatische Polycarbonate erhältlich gemäß Verfahren der Ansprüche 1 bis 3.4. Aromatic polycarbonates obtainable according to the process of claims 1 to 3.
EP78100539A 1977-08-09 1978-07-28 Process for the preparation of polycarbonates and the polycarbonates obtained Expired EP0000753B1 (en)

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WO2000023499A1 (en) * 1998-10-22 2000-04-27 General Electric Company Continuous interfacial method for preparing aromatic polycarbonates

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JPS5430293A (en) 1979-03-06
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IT1106867B (en) 1985-11-18
SU1020006A3 (en) 1983-05-23
EP0000753B1 (en) 1980-12-10
IT7850631A0 (en) 1978-08-07
US4346210A (en) 1982-08-24
DE2735775A1 (en) 1979-02-22
DE2860295D1 (en) 1981-02-19

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