High-frequency alpha transition response of some plasticized poly(vinyl chloride) compositions

A high-frequency alpha transition of some plasticized poly (vinyl chloride) compositions was measured at 4 MHz employing an ultrasonic pulse technique. The material property used to determine the transition region was the intrinsic loss, which is indicative of changes in both the storage and loss moduli. Four dicarboxylic esters were used as plasticizing agents. These were (1) butyl benzyl phthalate, (2) di-(2-ethylhexyl) phthalate, (3) dibenzyl sebacate, and (4) di-(2-ethylhexyl) sebacate. Compositions were prepared using 10, 20, and 30 parts by weight of plasticizer per hundred of polymer. A small quantity of thermal stabilizer was added to prevent degradation. Samples were produced by an extrusion process to promote a high degree of fusion and consolidation. Comparison of the data showed the usual decrease in the transition temperature with increasing concentration of the plasticizing agent. However, it was shown that the controlling factor of the transition response was the molecular structure of the plasticizer. Both the structure of the parent dicarboxylic acid and the ester side groups were controlling factors. This relationship was supported when a high-frequency storage and loss modulus (dilatational) was compared at 25°C to the molecular weight of the side chain. The dimethyl ester was included for both series for comparative purposes. These data showed that the storage modulus increased and the loss modulus decreased with increasing chain length and complexity. However, the factor contributing most was the complexity (steric hindrance) of the plasticizing molecule.