Plastisol gelation and fusion rheological aspects

This study deals with the rheological aspects of poly-vinyl chloride (PVC) plastisol gelation and fusion processes in foamable formulations. Here, such processes are simulated by temperature-programmed experiment (5 K min−1) in which complex viscosity components are continuously recorded. Nineteen samples based on a PVC-VAC (vinyl acetate 95/5) copolymer with 100 phr plasticizer have been studied, differing only by the plasticizer structure. The sample shear modulus increases continuously with temperature until a maximum, long time after the end of the dissolution process as characterized by DSC. The temperature at the maximum varies between 345 and 428 K with a clear tendency to increase almost linearly with the plasticizer molar mass, and to vary with the flexibility and the degree of branching of the plasticizer molecule. The shear modulus increase is interpreted in terms of progressive “welding” of swelled particles by polymer chain reptation. The plasticizer nature would mainly affect the friction parameter of chain diffusion.

Plastisol foaming process. Decomposition of the foaming agent, polymer behavior in the corresponding temperature range and resulting foam properties

The decomposition of azodicarbonamide, used as foaming agent in PVC—plasticizer (1/1) plastisols was studied by DSC. Nineteen different plasticizers, all belonging to the ester family, two being polymeric (polyadipates), were compared. The temperature of maximum decomposition rate (in anisothermal regime at 5 K min−1 scanning rate), ranges between 434 and 452 K. The heat of decomposition ranges between 8.7 and 12.5 J g−1. Some trends of variation of these parameters appear significant and are discussed in terms of solvent (matrix) and viscosity effects on the decomposition reactions. The shear modulus at 1 Hz frequency was determined at the temperature of maximum rate of foaming agent decomposition, and differs significantly from a sample to another. The foam density was determined at ambient temperature and the volume fraction of bubbles was used as criterion to judge the efficiency of the foaming process. The results reveal the existence of an optimal shear modulus of the order of 2 kPa that corresponds roughly to plasticizer molar masses of the order of 450 ± 50 g mol−1. Heavier plasticizers, especially polymeric ones are too difficult to deform. Lighter plasticizers such as diethyl phthalate (DEP) deform too easily and presumably facilitate bubble collapse.