DE2055211A1 - Polyamides of 1,4-benzoquinone tetracarboxylic acids - - prepd by polycondensation with diamino cpds - Google Patents
Polyamides of 1,4-benzoquinone tetracarboxylic acids - - prepd by polycondensation with diamino cpdsInfo
- Publication number
- DE2055211A1 DE2055211A1 DE19702055211 DE2055211A DE2055211A1 DE 2055211 A1 DE2055211 A1 DE 2055211A1 DE 19702055211 DE19702055211 DE 19702055211 DE 2055211 A DE2055211 A DE 2055211A DE 2055211 A1 DE2055211 A1 DE 2055211A1
- Authority
- DE
- Germany
- Prior art keywords
- polyimides
- polycondensation
- diamino
- benzoquinone
- cpds
- 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.)
- Pending
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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
Polyimide der 1, 4-Benzochinontetracarbonsäure Polyimide, die z.B. aus Pyromellithsäuredianhydrid und aromatischen Diaminen herstellbar sind, besitzen eine sehr gute thermische Stabilität. Diese Polyimide sind unschmelzbar und in organischen Lösungsmitteln völlig unlöslich. Sie müssen daher in Form ihrer "Precursors", den Polyamidcarbonsäuren, in subtilen Verfahren verarbeitet werden; hinzu kommt, daß die Lösungen der Polyamidcarbonsäuren sehr instabil sind, da nach kurzer Zeit polymeres Material ausfällt. Dadurch werden sie unbrauchbar. Polyimides of 1,4-benzoquinone tetracarboxylic acid Polyimides, e.g. can be prepared from pyromellitic dianhydride and aromatic diamines very good thermal stability. These polyimides are infusible and organic Solvents completely insoluble. They must therefore be in the form of their "precursors", the Polyamide carboxylic acids, processed in subtle procedures; in addition, that the solutions of the polyamide carboxylic acids are very unstable since after polymer material precipitates in a short time. This makes them unusable.
Es wurde nun gefunden, daß Polyimide, die aus 1,4-Benzochinontetracarbonsäureanhydrid (BCTA) und Diaminen hergestellt werden, entweder in der Chinon-Imidform in organischen Lösungsmitteln löslich sind oder nach Reduktion zur Hydrochinon-Imidform in organischen Lösungsmitteln bzw.It has now been found that polyimides obtained from 1,4-benzoquinone tetracarboxylic acid anhydride (BCTA) and diamines are produced, either in the quinone-imide form in organic Solvents are soluble or, after reduction to the hydroquinone-imide form, in organic Solvents or
in wäßrigem Ammoniak löslich werden. Die Überführung der gelösten Hydrochinonimide in die Chinonimide erfolgt durch Oxydation mit Luftsauerstoff oder anderen Oxydationsmitteln.become soluble in aqueous ammonia. The transfer of the solved Hydroquinonimide into the quinonimide takes place by oxidation with atmospheric oxygen or other oxidizing agents.
Mit den erfindungsgemäßen Polymeren können in einfacher Weise stabile Polyimidlösungen hergestellt werden, die sich ohne Schwierigkeiten zu thermostabilen Filmen, Folien, Fasern und oberzugen verarbeiten lassen.With the polymers according to the invention, stable Polyimide solutions can be produced, which can be thermostable without difficulty Have films, foils, fibers and coverings processed.
Die Herstellung der erfindungsgemäßen Polymeren erfolgt durch Polykondensation von 1,4-Benzochinontetracarbonsäureanhydrid mit Diaminoverbindungen nach bekannten Verfahren. Als Diaminoverbindungen können Hexamethylendiamin, die Phenylendiamine, Benzidin, 4,4'-Diaminodiphenylaether, 4,4'-Diaminodiphenylmethan u.äO eingesetzt werden0 Es ist auch möglich, Diaminoverbindungen mit chinoiden Gruppen zu verwenden, z.B. die Diaminoanthrachinone0 Fu'r die Polykondensation können das BCTA und die Diaminoanthrachinone in ihrer reduzierten Form eingesetzt werden.The polymers according to the invention are produced by polycondensation of 1,4-benzoquinone tetracarboxylic anhydride with diamino compounds according to known methods Procedure. As diamino compounds, hexamethylenediamine, the phenylenediamines, Benzidine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane etc. It is also possible to use diamino compounds with quinoid groups to use, e.g. the diaminoanthraquinones0 for the polycondensation can do that BCTA and the diaminoanthraquinones are used in their reduced form.
Die Polykondensation erfolgt in Lösung oder Substanz bei Temperaturen von Raumtemperatur bis 35O0C.The polycondensation takes place in solution or substance at temperatures from room temperature to 35O0C.
Die erfindungsgemäßen Polymeren lösen sich zum Teil in organischen Lösungsmitteln. Sie sind generell in einer Dithionit-Kupe löslich; aus der Kupe können durch Reoxydation mit Luft oder anderen Oxydationsmitteln (z.B.Some of the polymers according to the invention dissolve in organic compounds Solvents. They are generally soluble in a dithionite cup; out of the cup can by reoxidation with air or other oxidizing agents (e.g.
Wasserstoffsuperoxyd) Filme, Folien, Fasern und Uberzüge hergestellt werden. Es ist auch möglich, die chinoiden Polymeren zunächst zur Hydrochinonform zu reduzieren, dann die isolierte llydrochinonform in Ammoniak oder einer anderen leicht flüchtigen Base zu lösen und anschließend zu reoxydieren. Nach diesem Verfahren werden völlig salzfreie Produkte erhalten. Es ist weiterhin möglich, anstelle der Ilydrochinonform mit freien Hydroxygruppen die entsprechenden Schwefel säureester (analog den Küpenfarbstoffestern) zu verarbeiten.Hydrogen peroxide) films, foils, fibers and coatings will. It is also possible to first convert the quinoid polymers into the hydroquinone form to reduce, then the isolated form of llydroquinone in ammonia or another to dissolve volatile base and then reoxidize. According to this procedure completely salt-free products are obtained. It is still possible to replace the Ilydroquinone form with free hydroxyl groups the corresponding sulfuric acid ester (analogous to the vat dye esters) to be processed.
Die erfindungsgemäßen Polymeren besitzen eine ausgezeichnete thermische Stabilität. Sie sind beständig gegen den Angriff chemischer Reagentien sowie gegen Strahlung. Wegen ihrer intensiven Eigenfarbe sind sie ohne den Zusatz weiterer Farbstoffe als farbige Fasern, Folien und Lacke verwendbar.The polymers of the invention have excellent thermal properties Stability. They are resistant to attack by chemical reagents as well as against Radiation. Because of their intense color, they do not require the addition of other colorants can be used as colored fibers, foils and lacquers.
Das folgende Beispiel dient der näheren Erläuterung der Erfindung: 24,8 g 1,4-Benzochinontetracarbonsäureanhydrid und 20,2 g 1,4-Diaminodiphenylaether wurden in 250 ml Dimethylacetamid 5 h bei 50 0C unter Rührern im Stickstoffstrom polykondensiert. Die viskose Lösung wurde anschließend auf 200°C erhitzt, wobei das Polybenzochinonimid ausfiel; es wurde abgesaugt, gründlich mit Aceton gewaschen und im Vakuumtrockenschrank bei 1100C getrocknet.The following example serves to explain the invention in more detail: 24.8 g 1,4-benzoquinone tetracarboxylic acid anhydride and 20.2 g 1,4-diaminodiphenyl ether were in 250 ml of dimethylacetamide for 5 h at 50 ° C. with stirring in a stream of nitrogen polycondensed. The viscous solution was then heated to 200 ° C., with the polybenzoquinonimide precipitated; it was filtered off with suction, washed thoroughly with acetone and dried in a vacuum drying cabinet at 1100C.
Die Ausbeute betrug 93, die reduzierte Viskosität 0,8 dl/g (gemessen an einer 0,596igen Lösung in konzentrierter Schwefelsäure bei 300C). Bei der thermogravimetrischen Analyse (Aufheizrate 50C pro Minute) war das Produkt bis 4800C völlig thermostabil, danach erfolgte ein langsamer Abbau.The yield was 93, the reduced viscosity 0.8 dl / g (measured on a 0.596 solution in concentrated sulfuric acid at 300C). With the thermogravimetric Analysis (heating rate 50C per minute) the product was completely thermostable up to 4800C, thereafter a slow degradation took place.
Zur Verarbeitung wurde das Polybenzochinonimid mit einer Natrium Dithionit-Küpe zum Polybenzohydrochinonimid reduzielt dieses anschließend mit verdünnter Schwefelsäure ausgefällt und durch Absaugen isoliert, Zur Herstellung von Filmen, Fasern, Folien und Überzügen wurde eine ammoniakalische Lösung des Polybenzohydrochinonimids an der Luft reoxydiert.The polybenzoquinonimide was processed with a sodium dithionite vat This is then reduced to polybenzohydroquinonimide with dilute sulfuric acid precipitated and isolated by suction, for the production of films, fibers, foils and coatings was an ammoniacal solution of the polybenzohydroquinonimide on the air reoxidizes.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19702055211 DE2055211A1 (en) | 1970-11-10 | 1970-11-10 | Polyamides of 1,4-benzoquinone tetracarboxylic acids - - prepd by polycondensation with diamino cpds |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19702055211 DE2055211A1 (en) | 1970-11-10 | 1970-11-10 | Polyamides of 1,4-benzoquinone tetracarboxylic acids - - prepd by polycondensation with diamino cpds |
Publications (1)
Publication Number | Publication Date |
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DE2055211A1 true DE2055211A1 (en) | 1972-05-25 |
Family
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Family Applications (1)
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DE19702055211 Pending DE2055211A1 (en) | 1970-11-10 | 1970-11-10 | Polyamides of 1,4-benzoquinone tetracarboxylic acids - - prepd by polycondensation with diamino cpds |
Country Status (1)
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DE (1) | DE2055211A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11081255B2 (en) | 2016-01-07 | 2021-08-03 | Coroplast Fritz Müller Gmbh & Co. Kg | High-temperature and flame-resistant colored adhesive tape, use of a substrate for its manufacture, and cable harness including such an adhesive tape |
-
1970
- 1970-11-10 DE DE19702055211 patent/DE2055211A1/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11081255B2 (en) | 2016-01-07 | 2021-08-03 | Coroplast Fritz Müller Gmbh & Co. Kg | High-temperature and flame-resistant colored adhesive tape, use of a substrate for its manufacture, and cable harness including such an adhesive tape |
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