STJMMARY:High molecular weight polyamides were prepared from fumaric acid dichloride and unsubstituted aliphatic diamines, by the interfacial polycondensation method.The influence exerted by the molar ratio of the reagents, by their concentration, by the acceptor of the acid and by the nature of the organic solvent on both yield and inherent viscosity of the polyfumaramide obtained from trimethylenediamine was studied.The polymers obtained are partially crystalline and infusible; on heating under vacuum they degrade a t about 290 "C. They are soluble exclusively in strong acids, such as sulphuric and trifluoroacetic acids. ZUSAMMENFASSUNG:Hochmolekulare Polyamide wurden durch Grenzflachen-Polykondensation aus Fumarsauredichlorid und unsubstituierten aliphatischen Diaminen hergestellt.Der EintluD des Molverhiltnisses der Reaktionspartner, ihrer Konzentration, des Saure-Akzeptors und der Natur des organischen Losungsmittels auf die Ausbeute und die Viskositat der aus Trimethylendiamin erhaltenen Polyfumaramide w r d e untersucht.Die erhaltenen Polymeren sind teilweise kristallin und unschmelzbar. Durch Erhitzen im Vakuum werden sie bei etwa 29OoC abgebaut. Sie sind nur in starken Sauren wie Schwefelsaure oder Trifluoressigsaure loslich.
High molecular weight unsaturated polyamides were obtained from fumaric acid dichloride and several piperazines both by interfacial and solution polycondensation. All polymers are partially crystalline and are infusible ; on heating under vacuum their degradation temperatures are ranged within 350-370°C, while in air they degrade a t rather lower temperatures (265-275°C). The polypiperazinefumaramides are soluble in strong acids and also in organic solvents such as formic acid, CHC13/CH30H and CHzClz/CH30H mixtures: from these solutions tough and transparent films can be easily cast. ZUSAMMENFASSUNG:Mittels Grenzphasen-und Losungspolykondensation wurden hochmolekulare ungesattigte Polyamide aus Fumarsaure und verschiedenen Piperazinen erhalten. Alle Polymeren sind teilweise kristallin und uuschmelzbar. Beim Erhitzen im Vakuum beobachtet man Zersetzungstemperaturen zwischen 350-370°C, wahrend in Luft wesentlich niedrigere Temperaturen (265-275 "C) festgestellt werden. Die Polymeren losen sich in starken Sauren und auch in organischen Losungsmitteln, wie Ameisensaure und CHCl3/CH30H-oder CHzClz/CH3OH-Mischungen. Aus diesen Losungen kann man leicht zahe und transparente Filme erhalten.
S UMlM A R Y :Unsaturated polyamides from methyl-fumaric (2-methyl-fumaric and 2.3-dimethylfumaric) acid dichlorides and diamines, i.e. 1.6-hexamethylenediamine, 1.10-decamethylenediamine, rn-xylylenediamine, piperazine and trans-2.5-dimethylpiperazine were synthesized by low-temperature polycondensation.The polymer structures and properties were investigated by IR, X-ray, NMR, DSC, and TGA analyses.All polyamides were found t o be soluble in several volatile organic solvents : furthermore unlike polyamides derived from unsubstituted fumaric acidpolyamides from substituted fumaric acid derived from primary diamines showed melting or softening points. ZUSAMMENFASSUNG: Ungesattigte Polyamide aus 2-Methyl-und 2.3-Dimethylfumarsaure-dichloriden und Diaminen, z.B. Hexamethylendiamin, 1 .LO-Decamethylendiamin, rn-Xylylendiamin, Piperazin nnd truns-2.5-Dimethylpiperazin, wurden durch Tieftemperatur-Polykondensation synthetisiert. Die Struktur und die Eigenschaften der Polymeren wurden mittels IR-, Kontgenstrahlen, NMR-, DSC-und TGA-Analyse untersucht.Alle Polyamide sind in verschiedenen fliichtigen Losungsmitteln Ioslich. AuBerdem zeigen alle Polyamide aus substituierten Fumarsluren und prirnaren Diaminen, im Gegensatz zu denen a m unsubstituierter Fumarsaure, Schmelz-nnd Erweichungspunkte.
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