Efficiency of plasticization of PVC by higher-order di-alkyl phthalates and survey of mathematical models for prediction of polymer/diluent blend Tg's

Presently, a suitable theory to predict the T_g vs. composition relationship for a given polymer-plasticizer blend, based on detailed molecular structure and molecular energitics considerations, is not available. In particular, the plasticizer efficiency parameter, k, which is uniquely defined at low-to-moderate diluent concentrations, and is an essential variable in the Mauritz-Storey theory of the diffusion of large molecules in amorphous polymers in the rubbery state, must always be determined by experiment. In this work, k was determined by DSC for PVC that was plasticized over a range of concentrations with a number of higher branched and linear di-alkyl phthalates. The results will be used in our plasticizer diffusion theory as well as provide guidance in the future development of a general mathematical model for predicting k. It was seen that k decreased with increasing molecular weight for both the linear and branched phthalates. For a given molecular weight, the branched phthalates have higher k values than the linear structures. These results have been rationalized in terms of the additional free volume created by the inefficiency of packing polymer chains about these large penetrant molecules. The DSC scans also implied an increasing degree of microstructural heterogeneity with increasing plasticizer concentration. Finally, relationships between plasticizer diffusion coefficient in the rubbery state and the plasticized T_g were established for low-to-moderate diluent concentration for three of the plasticizers studied by utilizing experimental diffusion data from our earlier work on these systems.