The Compatibility, Efficiency and Permanence of Plasticizers

Abstract

This paper attempts to interrelate three important aspects of plasticizer behavior: compatibility or how much plasticizer can be added without causing phase separation; efficiency, or how much a given amount of plasticizer lowers the brittle temperature; and permanence, or how well a plasticizer is retained by the polymer on heat aging or solvent treatment. Compatibility is discussed in terms of the Flory-Huggins theory of the thermodynamics of polymer solutions, which relates the activity of the plasticizer to its concentration in the polymer. Efficiency is measured by how the plasticizer lowers the melt viscosity of the polymer. An empirical relationship between efficiency and μ (the Huggins polymer-solvent interaction constant) is shown. Loss of plasticizer at elevated temperatures depends in part on the effective vapor pressure of the plasticizer, and in part on how rapidly diffusion of plasticizer from the interior of the sample replenishes that lost from the surface. From the fact that diffusion constant times viscosity is a constant, it is possible to correlate measured diffusion rates with plasticizer content and with plasticizer efficiency. A linear relationship is predicted and found experimentally between logarithm of the diffusion constant and the brittle temperature. In this sense, the more efficient a plasticizer is, the more rapidly it can diffuse out of the polymer and be lost. Consideration is given to the effect of plasticizer on electrical resistance and tensile strength. A preliminary discussion of polymeric plasticizers is presented.