67 2.5.3 DSC SSA: Successive Self-nucleation and Annealing ,
,
,
,
,
,
,
3.3.3 Comparaison des résultats avec la méthode rhéologique de référence ,
3.4.3 Détermination de la distribution de la taille des cristallites : une base physique pour la méthode MF ,
, cinétique ) QOE , où Ú indique la nature du radical propageant et P représente la nature du monomère ajouté à la
, Lorsque v Q > 1, cela signifie que l'unité monomère @ Q s'ajoutera préférentiellement à R Q ? . Inversement, avec Ú et P égal à 1 ou 2 dans le cas de la copolymérisation binaire
Enfin avec v Q = 0, @ Q ne peut s'homopolymériser, et lorsque les deux rapports de réactivité sont nuls, la tendance sera à l'obtention d ,
, Il est possible de calculer les cinétiques de consommation des monomères, égales à leur vitesse d'incorporation dans le monomère comme suit, vol.17
, On suppose qu'un régime stationnaire s'établit ce qui se traduit par une concentration constante des radicaux libres et donc par leur vitesse d'inter-conversion étant la même : )
en introduisant les rapports de réactivité à l'équation (A-9), on obtient l'équation de copolymérisation donnant accès à la composition instantanée du copolymère en formation, vol.17 ,
, A.2 Détermination de la distribution des séquences
, Une approche probabiliste permet de déterminer la distribution des séquences ï,?SNèöÑ (ï) et
,
, Le modèle suivant prend l'hypothèse que la réaction se fait dans un réacteur idéalement mélangé, c'est-à-dire que l'existence d'une séquence ne dépend pas de son environnement immédiat. Ainsi, pour chaque diade formée, on applique le théorème des probabilités composées comme suit : Annexe C : Spectres RMN de l'EVA Les spectres RMN liquide obtenus nous ont permis de mettre en évidence la présence des espèces suivantes : Le spectre
, Le spectre RMN 13 C obtenu est présenté ci-dessous avec l'interprétation des signaux majeurs. A noter que le monomère acétate de vinyle est en trop faible teneur pour être détecté en RMN 13 C
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