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The polyamic acids from pyromellitic dianhydride, benzidine (B) and hydrazine (H) were prepared and characterized .by intrinsic viscosity measurements in dimethylformamide (DMF) solutions. The hydrolytic stability of these polymers was determined by keeping the DMF solution in presence of air at room temperature for 20 days. A decrease in qjnh was observed for the B-polymers and copolymers of B and H. This reduction was less in the copolymers.The thermal behaviour of polyamic acids and polyimides was studied by thermogravimetric and differential thermal analysis techniques. The copolyamic acids were found to be thermally more stable than polyamic acid from B at higher weight losses (about 50%), whereas copolyimides were found to be less stable than polyimide from 3. Thermal cyclodehydration of polyamic acids to polyimide occurred at lower temperatures in copolymers than the polymer of B. ZUSAMMENFASSUNG : Polyamidsauren wurden aus Pyromellithsauredianhydrid und Benzidin (B) sowie Hydrazin (H) dargestellt und durch Viskositatsmessungen in Dimethylformamid (DMF) charakterisiert. Die Hydrolysestabilitat wurde nach 2Otagiger Aufbewahrung der DMF-Losungen an der Luft bei Raumtemperatur ermittelt. Es ergab sich eine Viskositatsabnahme fur die B-Polymeren und die Copolymeren mit B und H. Diese Verminderung ist fur die Copolymeren geringer. Das thermische Verhalten der Polyamidsauren und Polyimide wurde mittels thermogravimetrischer und differentialthermoanalytischer Methoden untersucht. Die Copolyamidsauren wiesen eine groljere thermische Stabilitat als die Polyamidsauren aus B auf, wahrend die Copolyimide eine geringere Stabilitat als die Polyimide aus B aufwiesen. Die thermische Cyclodehydrierung der Pol yamidsauren zu den Polyimiden fand bei den Copolymeren bei geringeren Temperaturen als bei den B-Polymeren statt.Experimental DMF (Merck, Germany) was kept over P z 0 5 for 24 h and was then vacuum distilled at 1-2 torr. This DMF was kept over molecular sieves (3 A) for 24 h for further drying.Pyromellitic dianhydride (PMDA) (BDH) was sublimed under reduced pressure through silica gel at 1-10 torr and at temperatures of 220"-240°C. Before use the sublimed PMDA was vacuum dried for 24 h (m. p. 286°C).Benzidine (Hungary) was vacuum dried for 24h at 40°C prior to use (m.p. 127" to 129 "C).
The polyamic acids from pyromellitic dianhydride, benzidine (B) and hydrazine (H) were prepared and characterized .by intrinsic viscosity measurements in dimethylformamide (DMF) solutions. The hydrolytic stability of these polymers was determined by keeping the DMF solution in presence of air at room temperature for 20 days. A decrease in qjnh was observed for the B-polymers and copolymers of B and H. This reduction was less in the copolymers.The thermal behaviour of polyamic acids and polyimides was studied by thermogravimetric and differential thermal analysis techniques. The copolyamic acids were found to be thermally more stable than polyamic acid from B at higher weight losses (about 50%), whereas copolyimides were found to be less stable than polyimide from 3. Thermal cyclodehydration of polyamic acids to polyimide occurred at lower temperatures in copolymers than the polymer of B. ZUSAMMENFASSUNG : Polyamidsauren wurden aus Pyromellithsauredianhydrid und Benzidin (B) sowie Hydrazin (H) dargestellt und durch Viskositatsmessungen in Dimethylformamid (DMF) charakterisiert. Die Hydrolysestabilitat wurde nach 2Otagiger Aufbewahrung der DMF-Losungen an der Luft bei Raumtemperatur ermittelt. Es ergab sich eine Viskositatsabnahme fur die B-Polymeren und die Copolymeren mit B und H. Diese Verminderung ist fur die Copolymeren geringer. Das thermische Verhalten der Polyamidsauren und Polyimide wurde mittels thermogravimetrischer und differentialthermoanalytischer Methoden untersucht. Die Copolyamidsauren wiesen eine groljere thermische Stabilitat als die Polyamidsauren aus B auf, wahrend die Copolyimide eine geringere Stabilitat als die Polyimide aus B aufwiesen. Die thermische Cyclodehydrierung der Pol yamidsauren zu den Polyimiden fand bei den Copolymeren bei geringeren Temperaturen als bei den B-Polymeren statt.Experimental DMF (Merck, Germany) was kept over P z 0 5 for 24 h and was then vacuum distilled at 1-2 torr. This DMF was kept over molecular sieves (3 A) for 24 h for further drying.Pyromellitic dianhydride (PMDA) (BDH) was sublimed under reduced pressure through silica gel at 1-10 torr and at temperatures of 220"-240°C. Before use the sublimed PMDA was vacuum dried for 24 h (m. p. 286°C).Benzidine (Hungary) was vacuum dried for 24h at 40°C prior to use (m.p. 127" to 129 "C).
The effect of backbone flexibility on the thermal behaviour of the polyimides was investigated by synthesizing copolyimides based on pyromellitic dianhydride (PMDA) and benzidine (B), p-phenylene diamine (P), and p,p'-diamino diphenyl methane (D). Soluble polyamic acids were obtained by carrying the reaction in dimethyl formamide (DMF) at 0°C. The cyclodehydration of amic acid to polyimides was carried out by chemical means (acetic anhydride : pyridine). Several copolyimides were prepared by changing the molar ratios of diamines in initial monomer feed. These were characterized by evaluation of intrinsic viscosity of polyamic acid in DMF at 30 "C. The presence of amic acid and imide structures in the backbone was confirmed by IR spectra. Thermal behaviour of the polymers in air and nitrogen atmosphere was evaluated by dynamic thermogravimetry. The integral procedural decomposition temperature and activation energy of thermal degradation has been evaluated. ZUSAMMENFASSUNG:Es wurde der EinfluR der Kettenbeweglichkeit auf das thermische Verhalten der Polyimide untersucht. Die Copolyimide wurden aus Pyromellithdianhydrid (PMDA), Benzidin (B), p-Phenylendiamin (P) und p,p'-Diaminodiphenylmethan (D), hergestellt. Losliche Polyamidsaure wurde durch Ausfuhren der Reaktion in Dimethylformamid (DMF) bei 0 "C erhalten. Die cyclische Dehydrierung von Amidsauren zu Polyimiden wurde auf chemischem Wege ausgefuhrt (Acetanhydrid: Pyridin). Es wurden verschiedene Copolyimide durch Veranderung des Ausgangsmonomerenverhaltnisses hergestellt.Die Copolyimide wurden durch Bestimmen des Staudinger-Index der Polyamidsaure in DMF bei 30 " C charakterisiert. Die Anwesenheit von Amidsaure-und Imidstrukturen im Ruckgrat wurde durch IR-Spektren bestatigt. Mit Hilfe der dynamischen Thermogravimetrie wurde das thermische Verhalten der Polymeren in Luft und Stickstoff beurteilt; auRerdem sind die insgesamt ermittelte Zersetzungstemperatur und die Aktivierungsenergie des thermischen Abbaus gemessen worden.
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