DE959497C - Process for the production of thermoplastics - Google Patents
Process for the production of thermoplasticsInfo
- Publication number
- DE959497C DE959497C DEF17167A DEF0017167A DE959497C DE 959497 C DE959497 C DE 959497C DE F17167 A DEF17167 A DE F17167A DE F0017167 A DEF0017167 A DE F0017167A DE 959497 C DE959497 C DE 959497C
- Authority
- DE
- Germany
- Prior art keywords
- weight
- parts
- diphenyl
- dioxy
- alkanes
- 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
Links
- 238000000034 method Methods 0.000 title claims description 7
- 229920001169 thermoplastic Polymers 0.000 title claims description 7
- 239000004416 thermosoftening plastic Substances 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 229920000515 polycarbonate Polymers 0.000 description 16
- 239000004417 polycarbonate Substances 0.000 description 16
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000004305 biphenyl Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- -1 alkyl radical Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000003868 ammonium compounds Chemical class 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QLRKASHXFNIPLZ-UHFFFAOYSA-M benzyl-dimethyl-phenylazanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[N+](C)(C)CC1=CC=CC=C1 QLRKASHXFNIPLZ-UHFFFAOYSA-M 0.000 description 2
- FDJUMMKAFUMWBI-UHFFFAOYSA-N chloro carbonochloridate Chemical class ClOC(Cl)=O FDJUMMKAFUMWBI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical compound CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- QAIGYXWRIHZZAA-UHFFFAOYSA-M 1-methylpyridin-1-ium;chloride Chemical compound [Cl-].C[N+]1=CC=CC=C1 QAIGYXWRIHZZAA-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- KFSZGBHNIHLIAA-UHFFFAOYSA-M benzyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CC1=CC=CC=C1 KFSZGBHNIHLIAA-UHFFFAOYSA-M 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- MMQWEMMTKXBCLU-UHFFFAOYSA-M cyclohexyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1CCCCC1 MMQWEMMTKXBCLU-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- OWGHQYPQNSZTFQ-UHFFFAOYSA-M triethyl(octadecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](CC)(CC)CC OWGHQYPQNSZTFQ-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C08G64/26—General preparatory processes using halocarbonates
- C08G64/28—General preparatory processes using halocarbonates and phenols
-
- 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
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)
Description
Verfahren zur Herstellung thermoplastischer Kunststoffe Es ist bekannt, thermoplastische Kunststoffe durch Umesterung von Dialkylcarbonaten mit Glykolen herzustellen. Die so erhaltenen Produkte haben auf Grund ihres niedrigen Erweichungspunktes keine technische Bedeutung erlangt.Process for the production of thermoplastics It is known thermoplastics by transesterification of dialkyl carbonates with glycols to manufacture. The products thus obtained have due to their low softening point has no technical significance.
Außerdem ist bekannt, durch Umsetzung von Bis-chlorameisensäureestern von Glykolen mit polyfunktionellen Phenolen oder durch Umsetzung von Bis-chlorameisensäureestern von polyfunktionellen Phenolen mit Glykolen Polycarbonate herzustellen. Man erhält so ölige bis harzartige Produkte, deren Verwendung als Weichmachungsmittel oder Bindemittel vorgeschlagen wurde.It is also known to react with bis-chloroformic acid esters of glycols with polyfunctional phenols or by converting bis-chloroformic acid esters to produce polycarbonates from polyfunctional phenols with glycols. You get so oily to resinous products, their use as plasticizers or Binder has been proposed.
Weiterhin wurden Polycarbonate durch Umsetzung von polyfunktionellen Phenolen, die mehrere OH-Gruppen an einem aromatischen Kern tragen, z. B. Hydrochinon und Resorcin, mit Phosgen hergestellt. Die auf diese Weise erhaltenen Polycarbonate sind jedoch in den gebräuchlichen Lösungsmitteln unlöslich und zersetzen sich bei ihren Schmelztemperaturen.Furthermore, polycarbonates were converted into polyfunctional ones Phenols that carry several OH groups on an aromatic nucleus, e.g. B. hydroquinone and resorcinol, made with phosgene. The polycarbonates obtained in this way however, they are insoluble in common solvents and decompose their melting temperatures.
Die nach den beschriebenen Verfahren hergestellten Produkte haben auf Grund ihrer Eigenschaften als Kunststoffe keine praktische Bedeutung erlangt.The products manufactured according to the processes described have has no practical significance due to their properties as plastics.
Nach der deutschen Patentanmeldung F 13040 IVb/39c erhält man technisch hochwertige thermoplastische Kunststoffe durch Überführung von Dimonooxyaryl-alkanen in Polycarbonate.According to the German patent application F 13040 IVb / 39c one obtains technically high quality thermoplastics through conversion of dimonooxyaryl alkanes in polycarbonates.
Es wurde nun gefunden, daß man in organischen Lösungsmittel lösliche, thermoplastische, bei höheren Temperaturen ohne Zersetzung schmelzende Polyesterkunststoffe mit wertvollen technischen Eigenschaften durch Überführung von Dioxyverbindungen in hochmolekulare Polycarbonate in verhältnismäßig kurzer Reaktionszeit dadurch erhalten kann, daß man Di-monooxyaryl-alkane mit Phosgen oder mit Bis-chlorkohlensäureestern von Di-monooxyaryl-alkanen in wäßrig alkalischer Lösung oder Suspension unter Zusatz geringer Mengen quaternärer Ammoniumverbindungen in Form der freien Basen oder als Salze, vorteilhaft in Gegenwart inerter organischer Lösungsmittel, umsetzt.It has now been found that soluble in organic solvents, thermoplastic, melting at higher temperatures without decomposition Polyester plastics with valuable technical properties due to the conversion of dioxy compounds in high molecular weight polycarbonates in a relatively short reaction time can be obtained by using di-monooxyaryl-alkanes with phosgene or with bis-chlorocarbonic acid esters of di-monooxyaryl-alkanes in aqueous alkaline solution or suspension with addition small amounts of quaternary ammonium compounds in the form of the free bases or as Salts, advantageously in the presence of inert organic solvents, reacted.
In den zu verwendenden Di-monooxyaryl-alkanen können beide Arylreste gleich oder verschieden sein. Ferner können die Arylreste Substituenten tragen, die bei der Umsetzung zu Polycarbonaten nicht zu reagieren vermögen, wie Halogen oder Alkylgruppen, z. B. die Methyl-, Äthyl-, Propyl-oder tert.-Butylgruppe. Der die beiden Benzolringe verbindende Alkylrest der Di-monooxyaryl-alkane kann sowohl aus einer offenen Kette als auch aus einem cycloaliphatischen Ring bestehen und gegebenenfalls durch einen Arylrest substituiert sein.Both aryl radicals can be used in the di-monooxyaryl-alkanes be the same or different. Furthermore, the aryl radicals can carry substituents, which are unable to react when converted to polycarbonates, such as halogen or alkyl groups, e.g. B. the methyl, ethyl, propyl or tert-butyl group. Of the the alkyl radical of the di-monooxyaryl-alkane connecting the two benzene rings can be both consist of an open chain as well as a cycloaliphatic ring and optionally substituted by an aryl radical.
Als Beispiele für Di-monooxyaryl-alkane der gekennzeichneten Art mögen (4, 4'- Dioxy -diphenyl) - methan, 2,2 - (4, 4'- Dioxy - diphenyl -propan, I, I - (4., 4.' - Dioxy - diphenyl) - cyclohexan, I , I-(4,4 -D ioxy -3, 3'-dimethyl-diphenyl-cyclohexan, 2, 2-(2, 2'-Dioxy-4,, 4'-di-tert.-butyl-diphenyl)-propan, 3, 4-(4, 4@-Dioxy-diphenyl)-hexan und I, I-(4.4 -Dioxy-diphenyl)-i-phenyl-äthan genannt sein, ferner Methanderivate, die außer zwei Oxyarylgruppen noch einen Alkylrest mit mindestens zwei und einen zweiten Alkylrest mit einem oder mehreren Kohlenstoffatomen tragen, z. B. 2, 2-(4, q.'-Dioxy-diphenyl)-butan, 2, 2-(4, 4'-Dioxydiphenyl) - pentan, 3, 3 - (4, 4' - Dioxy - diphenyl)-pentan, 2, 2-(4, 4'-Dioxy-diphenyl) -3-methyl-butan, 2, 2-(4, 4'-D.ioxy-diphenyl)-hexan, 2, 2-(4, 4'-Dioxydiphenyl)-4-methyl-pentan, 2, 2-(4, 4'-Dioxy-diphenyl)-heptan, 4, 4-(4, 4'-Dioxy-diphenyl)-heptan und 2, 2-(4, 4 -Dioxy-diphenyl)-tridecan. Diese Verbindungen können durch Kondensation von Aldehyden bzw. Ketonen mit Phenolen in bekannter Weise leicht hergestellt werden.As examples of di-monooxyaryl-alkanes of the type indicated like (4,4'-Dioxy-diphenyl) methane, 2,2 - (4,4'-Dioxy-diphenyl-propane, I, I. - (4., 4. '- Dioxy - diphenyl) - cyclohexane, I, I- (4,4 -D ioxy -3, 3'-dimethyl-diphenyl-cyclohexane, 2, 2- (2, 2'-dioxy-4, 4'-di-tert-butyl-diphenyl) -propane, 3, 4- (4, 4 @ -dioxy-diphenyl) -hexane and I, I- (4.4 -Dioxy-diphenyl) -i-phenyl-ethane, also methane derivatives, which apart from two oxyaryl groups also have an alkyl radical with at least two and one carry second alkyl radical with one or more carbon atoms, z. B. 2, 2- (4, q .'-Dioxy-diphenyl) -butane, 2, 2- (4, 4'-dioxydiphenyl) - pentane, 3, 3 - (4, 4 '- Dioxy-diphenyl) pentane, 2, 2- (4, 4'-Dioxy-diphenyl) -3-methyl-butane, 2, 2- (4, 4'-D.ioxy-diphenyl) -hexane, 2, 2- (4, 4'-dioxydiphenyl) -4-methyl-pentane, 2, 2- (4, 4'-dioxy-diphenyl) -heptane, 4, 4- (4, 4'-dioxy-diphenyl) -heptane and 2, 2- (4, 4-dioxy-diphenyl) -tridecane. These compounds can be formed by condensation of aldehydes or ketones with phenols can be easily produced in a known manner.
Es körnen auch Mischungen verschiedener Dimonooxyaryl-alkane zur Erzielung besonderer Eigenschaften eingesetzt werden.Mixtures of different dimonooxyaryl alkanes can also be used to achieve this special properties are used.
Als erfindungsgemäß zuzusetzende quarternäre Ammoniumverbindungen seien genannt: Tetramethylammoniumhydroxyd, Triäthyloctadecylammoniumchlorid, Trimethylbenzylammoniumfluorid, Triäthylbenzylammoniumchlorid, Dimethyldodecylammoniumchlorid, Dimethylbenzylphenylammoniumchlorid, Trimethylcyclohexylammoniumbromid und N-Methylpyridiniumchlorid.As quaternary ammonium compounds to be added according to the invention may be mentioned: tetramethylammonium hydroxide, triethyloctadecylammonium chloride, trimethylbenzylammonium fluoride, Triethylbenzylammonium chloride, dimethyldodecylammonium chloride, dimethylbenzylphenylammonium chloride, Trimethylcyclohexylammonium bromide and N-methylpyridinium chloride.
Der Zusatz dieser quarternären Ammoniumverbindungen beschleunigt die Kondensationsreaktion, so daß man hochmolekulare Produkte in der Regel schon innerhalb etwa 1/2 bis 2 Stunden erhalten kann. Falls man in Gegenwart vor, inerten orgaschen Lösungsmitteln, die mit Wasser nur wenig oder gar nicht mischbar sind, arbeitet, wird durch die Ammoniumverbindungen im allgemeinen auch die Gefahr des Gelierens der in den Lösungsmitteln gelösten Polycarbonate vermindert. Um diese Wirkungen herbeizuführen, genügen im allgemeinen Mengen von etwa o,o5 bis etwa 5 Gewichtsprozent der Ammoniumverbindungen, bezogen auf die eingesetzte Menge der Di-monooxyaryl-alkane. Die Ammoniumverbindungen kann man vor oder während der Umsetzung den Gemischen zusetzen.The addition of these quaternary ammonium compounds accelerates the Condensation reaction, so that high molecular weight products are usually already within can get about 1/2 to 2 hours. If you are in the presence, inert orgaschen Solvents that are only slightly or not at all miscible with water works, the ammonium compounds generally also reduce the risk of gelling of the polycarbonates dissolved in the solvents is reduced. To these effects To bring about, amounts of about 0.05 to about 5 percent by weight are generally sufficient the ammonium compounds, based on the amount of di-monooxyaryl-alkanes used. The ammonium compounds can be added to the mixtures before or during the reaction.
Arbeitet man ohne Zusatz von organischen Lösungsmitteln, so fallen die Polycarbonate während ihrer Bildung aus der wäßrigen Lösung in Form von Pulvern aus. Im allgemeinen ist es jedoch vorteilhaft, organische Lösungsmittel, in denen sich die entstehenden Polycarbonate lösen, dem Reaktionsgemisch zuzusetzen. Hierfür eignen sich z. B. Kohlenwasserstoffe, wie Benzol, Toluol und Xylol, sowie chlorierte Kohlenwasserstoffe, wie Methylenchlorid und Chloroform.If one works without the addition of organic solvents, then fall the polycarbonates during their formation from the aqueous solution in the form of powders the end. In general, however, it is advantageous to use organic solvents in which the polycarbonates formed dissolve, to be added to the reaction mixture. Therefor are suitable e.g. B. hydrocarbons such as benzene, toluene and xylene, as well as chlorinated ones Hydrocarbons such as methylene chloride and chloroform.
Im allgemeinen ist es weiterhin vorteilhaft, eine geringe Menge eines Reduktionsmittels, wie Natriumdithionit oder freies Phenol, zuzusetzen.In general, it is also advantageous to use a small amount of one Adding reducing agents such as sodium dithionite or free phenol.
Die erfindungsgemäß hergestellten Polycarbonate sind thermoplastische, elastische Kunststoffe, deren Erweichungspunkt bzw. Schmelzpunkt und deren physikalische Eigenschaften stark von der Art des verwendeten Di-monooxyaryl-alkans abhängen. Sie sind in einer Reihe organischer Lösungsmittel, wie Methylenchlorid, Chloroform, Pyridin, einige auch in aromatischen Kohlenwasserstoffeen, wie Benzol, Toluol und o-, m- und p-Xylol, sowie in Estern, wie Äthyl- oder Butylacetat, und Ketonen, wie Aceton, löslich und können aus Lösungen zu verformten Körpern, wie Filmen und Fasern, verarbeitet werden. Sie sind ohne Zersetzung schmelzbar und können deshalb durch Pressen, Spritzen, Flammspritzen zu wertvollen Formkörpern oder Überzügen verarbeitet werden.The polycarbonates produced according to the invention are thermoplastic, elastic plastics, their softening point or melting point and their physical Properties strongly depend on the type of di-monooxyaryl alkane used. They are in a number of organic solvents, such as methylene chloride, chloroform, Pyridine, some also in aromatic hydrocarbons, such as benzene, and toluene o-, m- and p-xylene, and in esters, such as ethyl or butyl acetate, and ketones, such as Acetone, soluble and can be transformed from solutions into deformed bodies, such as films and fibers, are processed. They can be melted without decomposition and can therefore pass through Pressing, spraying, flame spraying processed into valuable molded bodies or coatings will.
Überraschenderweise erhält man nach dem vorliegenden Verfahren, besonders bei Verwendung von 4, 4'-Di-monooxyaryl-alkanen, wie 4, 4'-Dioxydiphenyl-methan und 2, 2-(4, q.'-Dioxy-diphenyl)-propan oder I, I-(4, 4'-Dioxy-diphenyl)-cyclohexan, kristallisierbare, lineare Polycarbonate, aus denen Filme und Fasern aus der Schmelze oder aus der Lösung hergestellt werden können, die durch Verstrecken orientierbar sind. Durch den Streckvorgang wird die Festigkeit dieser Produkte wesentlich erhöht, während die Dehnung herabgesetzt wird.Surprisingly, according to the present process, particularly when using 4,4'-di-monooxyaryl-alkanes, such as 4,4'-dioxydiphenyl-methane and 2, 2- (4, q .'-dioxy-diphenyl) -propane or I, I- (4, 4'-dioxy-diphenyl) -cyclohexane, crystallizable, linear polycarbonates that make films and fibers from the melt or can be produced from the solution, which can be oriented by stretching are. The stretching process significantly increases the strength of these products, while the elongation is decreased.
Die erfindungsgemäß hergestellten Polycarbonate können auch in Verbindung mit Weichmachern, wie Trikresylphosphat, oder Füllstoffen, wie Asbest und Glasfasern, verarbeitet werden.The polycarbonates produced according to the invention can also be used in conjunction with plasticizers such as tricresyl phosphate or fillers such as asbestos and glass fibers, are processed.
Beispiel I In ein Gemisch aus 137,5 Gewichtsteilen 2, 2-(4, 4'-Dioxy-diphenyl)-propan, 70o Gewichtsteilen Wasser, 33o Gewichtsteilen Methylenchlorid, 68,5 Gewichtsteilen Natriumhydroxyd leitet man unter Rühren bei 251 in 120 Minuten 71,5 Gewichtsteile Phosgen. Dann gibt man 3 Gewichtsteile Triäthylbenzylammoniumchlorid hinzu. 3o bis 40 Minuten nach Zugabe läuft die zunächst in Form von feinen Tröpfchen in der alkalisch wäBrigen Lösung verteilte organische Lösung zu einem zähen 'feig zusammen, der nach Aufarbeitung ein hochmolekulares Polycarbonat ergibt.Example I Into a mixture of 137.5 parts by weight of 2, 2- (4, 4'-dioxy-diphenyl) propane, 70o by weight of water, 33o parts by weight methylene chloride 68.5 parts by weight of sodium hydroxide is passed under stirring at 251 in 120 minutes 71 , 5 parts by weight of phosgene. Then 3 parts by weight of triethylbenzylammonium chloride are added. 30 to 40 minutes after the addition, the organic solution, initially distributed in the form of fine droplets in the alkaline aqueous solution, converges to form a viscous fig which, after working up, results in a high molecular weight polycarbonate.
Beispiel 2 In ein Gemisch aus 137,5 Gewichtsteilen 2, 2- (4, 4'-Dioxy-diphenyl) -propan, 7oo Teilen Wasser, ioo Gewichtsteilen Methylenchlorid, 68,5 Gewichtsteilen Natriumhydroxyd und 4 Gewichtsteilen Dimethylphenylbenzylammoniumchlorid leitet man in 2 Stunden unter Rühren bei 25° 7i,5 Gewichtsteile Phosgen ein. Man rührt noch i Stunde bei 25°. Das körnige Reaktionsprodukt ergibt nach Waschen und Trocknen ein hochmolekulares, technisch brauchbares Polycarbonat.Example 2 In a mixture of 137.5 parts by weight of 2, 2- (4, 4'-dioxy-diphenyl) propane, 700 parts of water, 100 parts by weight of methylene chloride, 68.5 parts by weight Sodium hydroxide and 4 parts by weight of dimethylphenylbenzylammonium chloride conducts one in 2 hours with stirring at 25 ° 7i, 5 parts by weight of phosgene. One stirs another hour at 25 °. The granular reaction product results after washing and drying a high molecular weight, technically useful polycarbonate.
Beispiel 3 In ein Gemisch aus 68,8 Gewichtsteilen 2, 2- (4, 4'-Dioxy-diphenyl) -propan, 81 Gewichtsteilen 4, 4'-Dioxy-diphenyl-i, i-cyclohexan, 70o Teilen Wasser, 33o Gewichtsteilen Methylenchlorid, 68,5 Gewichtsteilen Natriumhydroxyd leitet man bei 25° unter Rühren in i2o Minuten 71,5 Gewichtsteile Phosgen ein. Man gibt 3 g Triäthylbenzylammoniumchlorid hinzu. Nach 30 Minuten läuft die organische Schicht zu einem hochviskosen Teig zusammen, der nach Aufarbeitung ein hochmolekulares Polycarbonat von brauchbaren Eigenschaften ergibt. Beispiel 4 In ein Gemisch aus iio,i Gewichtsteilen 2, 2-(4, 4'-Dioxy-diphenyl)-propan, ^4,i Gewichtsteilen 4, 4'-Dioxy-diphenyl-methan, 6oo Teilen Wasser, 6oo Gewichtsteilen Methylenchlorid, 68,5 Gewichtsteilen Natriumhydroxyd und o,i Gewichtsteilen Natriumdithionit leitet man unter Rühren bei 25° in 2 Stunden 71,5 Gewichtsteile Phosgen ein. Man gibt 3 Gewichtsteile Triäthylbenzylammoniumchlorid hinzu. Nach istündigem weiterem Rühren wird die organische Lösung hochviskos und ergibt nach Aufarbeitung ein hochmolekulares Polycarbonat.Example 3 In a mixture of 68.8 parts by weight of 2,2- (4,4'-dioxy-diphenyl) -propane, 81 parts by weight of 4,4'-dioxydiphenyl-i, i-cyclohexane, 70o parts of water, 33o parts by weight Methylene chloride, 68.5 parts by weight of sodium hydroxide, 71.5 parts by weight of phosgene are passed in at 25 ° with stirring in the course of 12 minutes. 3 g of triethylbenzylammonium chloride are added. After 30 minutes, the organic layer converges to form a highly viscous dough which, after working up, gives a high molecular weight polycarbonate with useful properties. Example 4 In a mixture of iio, i parts by weight of 2, 2- (4, 4'-dioxy-diphenyl) -propane, ^ 4, i parts by weight of 4,4'-dioxy-diphenyl-methane, 600 parts of water, 600 parts by weight of methylene chloride 68.5 parts by weight of sodium hydroxide and 0.1 parts by weight of sodium dithionite are passed in 71.5 parts by weight of phosgene with stirring at 25 ° in 2 hours. 3 parts by weight of triethylbenzylammonium chloride are added. After stirring for another hour, the organic solution becomes highly viscous and, after working up, gives a high molecular weight polycarbonate.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF17167A DE959497C (en) | 1955-03-27 | 1955-03-27 | Process for the production of thermoplastics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF17167A DE959497C (en) | 1955-03-27 | 1955-03-27 | Process for the production of thermoplastics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE959497C true DE959497C (en) | 1957-03-07 |
Family
ID=7088491
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF17167A Expired DE959497C (en) | 1955-03-27 | 1955-03-27 | Process for the production of thermoplastics |
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| Country | Link |
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| DE (1) | DE959497C (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1301110B (en) * | 1957-11-13 | 1958-04-25 | Gevaert Photo Prod Nv | Process for the production of high polymer linear polyesters |
| DE1149533B (en) * | 1957-04-02 | 1963-05-30 | Gevaert Photo Prod Nv | Process for the production of high polymer linear aromatic polyesters |
| DE1156982B (en) * | 1960-10-10 | 1963-11-07 | Dr Eugen U Dumont | Process for the production of polycondensates with carbonic acid ester and thiourea groups in the polymer unit |
| US3207777A (en) * | 1961-11-02 | 1965-09-21 | Electro Chimie Metal | Polycarbonates of polyhydroxy-perchlorobiphenyls |
| DE1210853B (en) * | 1961-05-25 | 1966-02-17 | Bayer Ag | Process for the production of carbonic acid esters or carboxylic acid esters or their anhydrides |
| DE1212983B (en) * | 1958-12-23 | 1966-03-24 | Pittsburgh Plate Glass Co | Process for the preparation of alpha, omega-bischloroformates of alkylidene diphenol carbonic acid esters |
| US3255230A (en) * | 1962-07-03 | 1966-06-07 | Union Carbide Corp | Catalytic synthesis of aryl chloroformates |
| US3326958A (en) * | 1961-05-25 | 1967-06-20 | Bayer Ag | Process for the preparation of carbonic and carboxylic acid derivatives |
| DE1248298B (en) * | 1960-05-31 | 1967-08-24 | Dow Chemical Co | Process for the production of polycarbonates |
| DE1260787B (en) * | 1960-05-31 | 1968-02-08 | Dow Chemical Co | Process for the production of polycarbonates |
| DE1271988B (en) * | 1957-04-26 | 1968-07-04 | Gevaert Photo Prod Nv | Process for the production of high polymer linear polyesters |
| EP0000753A1 (en) * | 1977-08-09 | 1979-02-21 | Bayer Ag | Process for the preparation of polycarbonates and the polycarbonates obtained |
-
1955
- 1955-03-27 DE DEF17167A patent/DE959497C/en not_active Expired
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1149533B (en) * | 1957-04-02 | 1963-05-30 | Gevaert Photo Prod Nv | Process for the production of high polymer linear aromatic polyesters |
| DE1271988B (en) * | 1957-04-26 | 1968-07-04 | Gevaert Photo Prod Nv | Process for the production of high polymer linear polyesters |
| DE1301110B (en) * | 1957-11-13 | 1958-04-25 | Gevaert Photo Prod Nv | Process for the production of high polymer linear polyesters |
| DE1212983B (en) * | 1958-12-23 | 1966-03-24 | Pittsburgh Plate Glass Co | Process for the preparation of alpha, omega-bischloroformates of alkylidene diphenol carbonic acid esters |
| DE1260787B (en) * | 1960-05-31 | 1968-02-08 | Dow Chemical Co | Process for the production of polycarbonates |
| DE1248298B (en) * | 1960-05-31 | 1967-08-24 | Dow Chemical Co | Process for the production of polycarbonates |
| DE1156982B (en) * | 1960-10-10 | 1963-11-07 | Dr Eugen U Dumont | Process for the production of polycondensates with carbonic acid ester and thiourea groups in the polymer unit |
| DE1210853B (en) * | 1961-05-25 | 1966-02-17 | Bayer Ag | Process for the production of carbonic acid esters or carboxylic acid esters or their anhydrides |
| US3326958A (en) * | 1961-05-25 | 1967-06-20 | Bayer Ag | Process for the preparation of carbonic and carboxylic acid derivatives |
| US3207777A (en) * | 1961-11-02 | 1965-09-21 | Electro Chimie Metal | Polycarbonates of polyhydroxy-perchlorobiphenyls |
| US3255230A (en) * | 1962-07-03 | 1966-06-07 | Union Carbide Corp | Catalytic synthesis of aryl chloroformates |
| EP0000753A1 (en) * | 1977-08-09 | 1979-02-21 | Bayer Ag | Process for the preparation of polycarbonates and the polycarbonates obtained |
| US4346210A (en) | 1977-08-09 | 1982-08-24 | Bayer Aktiengesellschaft | Process for the preparation of polycarbonates catalyzed by cyclic aza compounds |
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