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Synthesis, X-ray diffraction, and Fourier transform infrared spectroscopy of aliphatic-aromatic aramid oligomers are reported with the aim of shedding light on the effect of end-chain substituent on the morphology and structure of poly(para-phenylene terephthalamide) or PPTA. Three types of X-ray powder diffraction patterns were observed: one similar to that of PPTA form I, one similar to that of PPTA form II, and an additional form never reported. Some compounds, differing by their internal distribution of amide-aromatic rings, adopt two different crystal structures, whereas compounds having the same internal amide-aromatic arrangements, but differing by the nature of the end-groups, can adopt the same crystal structure. This clearly shows that both factors influence the packing adopted by the chains. Single-crystal structures of two polymorphs of a nitro-terminated model compound were resolved; both forms incorporate dimethyl formamide, and both show completely different packing. Infrared amide I and II band positions of most studied compounds match those observed for PPTA forms I or II, indicating that they exhibit planar hydrogen bonded sheets of molecules.Résumé : La synthèse et des études de diffraction des rayons X, et de spectroscopie infrarouge à transformée de Fourier ont été effectués sur des oligomères aramides, dans le but de fournir des informations sur l'effet de substituants en bout de chaîne sur la morphologie et la structure du poly(para-phénylene téréphthalamide), ou PPTA. Trois types de clichés de diffraction de poudre ont été observés: un similaire à celui de la forme I du PPTA, un similaire à celui de la forme II, et une forme additionnelle jamais rapportée auparavant. Certains composés modèles qui diffèrent de par leur distribution interne de cycles aromatiques et de groupements amides adoptent des structures cristallines différentes, alors que certains composes modèles ayant le même arrangement interne de cycles aromatiques, adoptent la même structure cristalline. Ceci démontre clairement que ces deux facteurs influencent l'arrangement moléculaire adopté par les chaînes. Les structures cristallines de monocristaux de deux polymorphes d'un composé modèle ayant un substituant nitro en bout de chaîne ont été résolues, les deux incluent des molécules de diméthylformamide, et les deux adoptent des types d'empilement moléculaire complètement différents. En spectroscopie infrarouge, les positions des bandes amide I et II de la plupart des composes étudiés correspondent à celles observées pour les formes I et II du PPTA, indiquant que ces composés possèdent probablement des feuillets de molécules assemblées par liaison hydrogène.Mots-clés : aramide, structure cristalline, poly(para-phénylène téréphtalamide).
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