EP0000753B1 - Procédé de préparation de polycarbonates et polycarbonates obtenus - Google Patents

Procédé de préparation de polycarbonates et polycarbonates obtenus Download PDF

Info

Publication number
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
Authority
EP
European Patent Office
Prior art keywords
polycarbonates
polycarbonate
parts
mol
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100539A
Other languages
German (de)
English (en)
Other versions
EP0000753A1 (fr
Inventor
Wolfgang Dr. Alewelt
Dieter Dr. Margotte
Claus Dr. Wulff
Hugo Dr. Vernaleken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000753A1 publication Critical patent/EP0000753A1/fr
Application granted granted Critical
Publication of EP0000753B1 publication Critical patent/EP0000753B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (2)

1. Procédé de production de polycarbonates aromatiques par la technique à l'interface entre phases à partir de diphénols, caractérisé en ce qu'on utilise comme catalyseurs la N-éthyl- pyrrolidine, la N-éthylpipéridine, la N-éthyl- morpholine, la N-isopropylpipéridine ou la N-isopropylmorpholine en quantités de 0,01 à 10 moles % par rapport aux moles de diphénols utilisés.
2. Procédé suivant la revendication 1, caractérisé en ce qu'on utilise la N-éthylpipéridine.
EP78100539A 1977-08-09 1978-07-28 Procédé de préparation de polycarbonates et polycarbonates obtenus Expired EP0000753B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2735775 1977-08-09
DE19772735775 DE2735775A1 (de) 1977-08-09 1977-08-09 Verfahren zur herstellung von polycarbonaten

Publications (2)

Publication Number Publication Date
EP0000753A1 EP0000753A1 (fr) 1979-02-21
EP0000753B1 true EP0000753B1 (fr) 1980-12-10

Family

ID=6015937

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100539A Expired EP0000753B1 (fr) 1977-08-09 1978-07-28 Procédé de préparation de polycarbonates et polycarbonates obtenus

Country Status (7)

Country Link
US (1) US4346210A (fr)
EP (1) EP0000753B1 (fr)
JP (1) JPS6053049B2 (fr)
BR (1) BR7805075A (fr)
DE (2) DE2735775A1 (fr)
IT (1) IT1106867B (fr)
SU (1) SU1020006A3 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4233345A1 (de) * 1992-10-05 1994-04-07 Bayer Ag Verfahren zur Herstellung von Polycarbonaten und von Polyestercarbonaten
DE19728805A1 (de) * 1997-07-05 1999-01-07 Bayer Ag Verfahren zur Herstellung von Polycarbonat
DE19744693A1 (de) * 1997-10-10 1999-04-15 Bayer Ag Verfahren zur Herstellung von speziellen Copolycarbonaten durch Schmelzumesterung
US5973103A (en) * 1998-10-22 1999-10-26 General Electric Company Continuous interfacial method for preparing aromatic polycarbonates

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3014891A (en) 1961-12-26 Resinous compositions
DE1007996B (de) 1955-03-26 1957-05-09 Bayer Ag Verfahren zur Herstellung thermoplastischer Kunststoffe
DE959497C (de) 1955-03-27 1957-03-07 Bayer Ag Verfahren zur Herstellung thermoplastischer Kunststoffe
US3275601A (en) * 1956-01-04 1966-09-27 Bayer Ag Manufacture of polycarbonates using tertiary amines, quaternary amines and salts thereof as catalysts
DE1046311B (de) 1956-04-06 1958-12-11 Bayer Ag Verfahren zur Herstellung von Polycarbonaten
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
NL126830C (fr) 1959-06-27
US3271368A (en) 1963-05-02 1966-09-06 Borg Warner Sulfonate-thiocarbonate copolymers
DE1300274B (de) 1963-05-22 1969-07-31 Hoechst Ag Verfahren zur Herstellung hochmolekularer Polymerisate auf der Basis von Di-[beta-trihalogen-alpha-hydroxyaethoxy]-alkanen
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
DE2063052A1 (de) 1970-12-22 1972-07-13 Bayer Verseifungsbeständige Polycarbonate
DE2063050C3 (de) 1970-12-22 1983-12-15 Bayer Ag, 5090 Leverkusen Verseifungsbeständige Polycarbonate, Verfahren zu deren Herstellung und deren Verwendung
CH554908A (de) * 1971-01-15 1974-10-15 Basf Ag Verfahren zur kontinuierlichen herstellung hochmolekularer, linearer polycarbonate.
DE2140207C3 (de) * 1971-08-11 1975-11-27 Farbenfabriken Bayer Ag, 5090 Leverkusen Stabilisiertes aromatisches PoIycarbonat
US4073769A (en) * 1971-08-11 1978-02-14 Bayer Aktiengesellschaft Esters of phosphorous acid
DE2211956A1 (de) 1972-03-11 1973-10-25 Bayer Ag Verfahren zur herstellung verseifungsstabiler blockcopolycarbonate
DE2211957C2 (de) 1972-03-11 1982-07-01 Bayer Ag, 5090 Leverkusen Hochmolekulare statistische Copolycarbonate
DE2305144C2 (de) * 1973-02-02 1982-05-06 Basf Ag, 6700 Ludwigshafen Verfahren zur kontinuierlichen Herstellung von Polycarbonaten
DE2410716B2 (de) * 1974-03-06 1977-02-10 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung aromatischer polycarbonate nach der methode der phasengrenzflaechenkondensation
DE2447349A1 (de) 1974-10-04 1976-04-15 Bayer Ag Verfahren zur herstellung von aliphatischen polycarbonaten und aliphatischaromatischen copolycarbonaten
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 (de) 1975-03-11 1986-04-03 Bayer Ag, 5090 Leverkusen Stabilisatormischungen und Verwendung von Stabilisatormischungen zur Stabilisierung von Polycarbonaten

Also Published As

Publication number Publication date
DE2860295D1 (en) 1981-02-19
JPS6053049B2 (ja) 1985-11-22
DE2735775A1 (de) 1979-02-22
BR7805075A (pt) 1979-04-10
IT1106867B (it) 1985-11-18
IT7850631A0 (it) 1978-08-07
US4346210A (en) 1982-08-24
JPS5430293A (en) 1979-03-06
EP0000753A1 (fr) 1979-02-21
SU1020006A3 (ru) 1983-05-23

Similar Documents

Publication Publication Date Title
DE2500092C3 (de) Verzweigte, hochmolekulare, thermoplastische und lösliche Polycarbonate
EP0006579B1 (fr) Polycarbonates à double-liaisons réticulables par des rayons UV, procédé pour leur préparation, procédé pour leur modification et les produits ainsi obtenus
EP0000732B1 (fr) Mélanges de polyarylsulfones réticulées avec des polycarbonates et leur utilisation dans la préparation de feuilles extrudées
EP0013904B1 (fr) Procédé de préparation de polycarbonates
EP0000396B1 (fr) Procédé de préparation de polycarbonates ignifugés
EP0143906A1 (fr) Procédé pour préparer des articles moulés en polycarbonate stabilisé par moulage par injection avec dégazage ou extrusion avec dégazage
DE3002762A1 (de) Verfahren zur herstellung von heterocyclisch-aromatischen oligocarbonaten mit diphenolcarbonat-endgruppen und ihre verwendung zur herstellung von thermoplastischen, hochmolekularen heterocyclisch-aromatischen copolycarbonaten
EP0001577A1 (fr) Polycarbonates thermoplastiques contenant des groupes cétone aromatiques, leur procédé de fabrication et leur utilisation pour la préparation de polycarbonates modifiés
EP0082383A1 (fr) Procédé de préparation de polycarbonates renfermant des groupements terminaux sulfonanilide
EP0078943A1 (fr) Procédé pour la fabrication de polycarbonates avec un processus de vieillissement
DE2246106C2 (de) s-Triazinringe enthaltende hochmolekulare Polycarbonate
DE2254918A1 (de) Verzweigte aromatische polycarbonate
EP0000753B1 (fr) Procédé de préparation de polycarbonates et polycarbonates obtenus
EP0414083B1 (fr) Polycarbonates stabilisés
EP0023571A1 (fr) Procédé de préparation de polycarbonates, les polycarbonates ainsi obtenus ainsi que leur utilisation
EP0075772B1 (fr) Procédé pour l'isolation de polycarbonates basés sur 4,4'-dihydroxidiphénylsulfones
EP0001823A2 (fr) Utilisation d'esters de l'acide borique pour stabiliser des polycarbonates exempts de phosphites et les masses à mouler stabilisées à base de ces polycarbonates
DE4239131C2 (de) Verfahren zur Herstellung von Polycarbonaten
EP0099990B1 (fr) Procédé de préparation de polycarbonates renfermant des groupements terminaux N-alkylperfluoro alkylsulfonamides
DE3120594A1 (de) Neue copolyestercarbonate und deren abmischung mit bekannten polycarbonaten zu thermoplastischen formmassen
EP0432580B1 (fr) Procédé en deux étapes pour la préparation de polycarbonates à partir de dihydroxydiphényl alcanes particuliers
EP0025928B1 (fr) Procédé de préparation de polycarbonates aromatiques selon le procédé à l'interface
EP0029111B1 (fr) Copolycarbonates aromatiques thermoplastiques, procédé pour leur préparation à partir de 2,2-bis(4-hydroxyphényl)-1,1,1,3,3,3-hexafluorpropane et leur utilisation
DE4241619C2 (de) Verfahren zur Herstellung von Polycarbonaten
DE2711184A1 (de) Verfahren zur herstellung farbheller polycarbonate

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): DE FR GB NL

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): DE FR GB NL

REF Corresponds to:

Ref document number: 2860295

Country of ref document: DE

Date of ref document: 19810219

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960618

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19960627

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19960719

Year of fee payment: 19

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960731

Year of fee payment: 19

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19970728

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980331

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19980201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980401

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT