Étude de l'état solide des copolymères du chlorure de vinylidène avec le chlorure de vinyle, l'acrylonitrile et le méthacrylate de méthyle, 1. Structure des copolymères, modélisation mathématique en relation avec la structure chimique des chaînes

Abstract

AbstractThe properties of a random copolymer are not only determined by composition, but also by the repartition of the monomeric units along the chain. In order to explain the properties of such a copolymer it is necessary to know the sequence distribution or microstructure, each sequence by itself showing structural characteristics: length, relative position, etc. It is thus necessary to conduct a precise synthesis process, and to know the kinetic parameters of the polymerization reaction. Knowledge of the kinetic invariants and monomer feed composition gives access to the theoretical sequence distribution. By different physicochemical methods (NMR, IR and UV spectroscopy), the results obtained by calculation are confirmed. Specifically the effect of microstructure and composition on the properties of some vinylidene chloride (VDC) copolymers with acrylonitrile (AN), vinyl chloride (VC) and methyl methacrylate (MMA) is studied. VDC leads to a very cristalline polymer, whereas PVC generally shows very poor cristallinity, and PAN shows particular structural characteristics. VDC copolymers can easily crystallize when they are rich in VDC. Generally the polymers are semi‐crystalline with an amorphous phase. A theoretical model accounting for the lamellar structure and crystallinity of VDC copolymers is described. It utilizes the microstructural data, obtained by a kinetic study and some simple hypotheses, among them the possibility for molecules to slide along each other. This sliding brings together the material which is crystallizable in determined areas. It is thus possible to explain the presence of crystallinity peaks, or at least of paracrystallinity, up to a relatively high amount of comonomer MMA, AN and especially VC in the diffractograms of VDC copolymers with MMA, AN and VC. The paracrystalline domains are defined as areas which can present some degree of order at great distance, with a relatively high amount of comonomer defects.