CRYSTALLIZATION KINETICS FOR SEMICRYSTALLINE RANDOM COPOLYMERS OF VINYLIDENE-CHLORIDE (VDC) WITH METHYL ACRYLATE (MA), AND THE EFFECTS ON THE INTERNAL MORPHOLOGY OF THE RESIN PARTICLES FORMED DURING SYNTHESIS

Isothermal crystallization kinetics for random copolymers of vinyliden e chloride (VDC) with methyl acrylate (MA) is reported. Syntheses of m any semicrystalline polymers follow heterogeneous reaction paths in wh ich the macromolecule chains phase separate from the reaction mixtures . The internal particle morphology (the internal structure of the resi n bead) from this type of reaction is granular and porous, as a result of the demixing processes accompanying polymer formation. Demixing in these polymers involves either liquid-liquid (L-L) phase separation f ollowed by liquid-solid (L-S) transformation (crystallization) or L-S transformation alone. Crystallization (L-S transformation) must be an indispensable part of the process if a porous granular structure is to be expected. This is because L-S transformation is the most probable means by which the demixed structure can be stabilized against complet e coalescence or agglomeration, which would lead to totally fused bead internal structure. This is particularly true if the glass transition temperature (T-g) is lower than the polymerization temperatures, as i s the case with the VDC-MA copolymers. Copolymers that crystallize the fastest will have the finest (most porous) resin bead morphology. The result of this work is consistent with expectation. The homopolymer ( PVDC) that crystallizes the fastest has the finest resin bead internal morphology. The copolymers show slower crystallization rates with inc reasing noncrystallizable MA content. Correspondingly, resin morpholog y measured by specific surface area decreased with increasing amounts of the noncrystallizable (MA) comonomer unit in the copolymer. This is clearly seen in SEM photographs of the internal bead structures of th ese copolymers. (C) 1995 John Wiley & Sons, Inc.