The characteristic parameters for three different equation-of-state (EOS) theories have been determined for polystyrene and low-molecular weight polyisoprene using pressure-volume-temperature (PVT) data. Basically two procedures for the calculation of characteristic parameters were applied. The characteristic parameters were calculated, firstly, from coeficients of expansion, compressibilities and densities, and secondly, by fitting the corresponding EOS to PVT data minimizing the sum of the squares of the differences between experimental and calculated pressures. The characteristic parameters obtained by the two methods are compared with regard to their ability to describe PVTdata.Acomparison ofthe three different EOS theories reveals that, for describing polymeric liquids, the modified cell model of Dee and Walsh is superior to the theory of Flory, Orwoll and Vrij as well as to the lattice fluid theory of Sanchez and Lacombe. Finally, formulae are given to convert the characteristic parameters from one theory into those of another.
Pressure, volume, temperature (PVT) measurements reveal that during the intramolecular cyclization reaction of poly(acrylonitri1e) (PAN) and poly(styrene-co-acrylonitrile) (SAN) the volume decreases. This volume contraction becomes smaller with increasing styrene content in the random copolymers and should be related to the simultaneous decrease of longer acrylonitrile homo-sequences. The onset temperature of the cyclization reaction is raised with higher styrene contents in the random copolymers. Thus, it can be excluded that the cyclization reaction has a major influence on the discoloration process of SAN samples having relatively small acrylonitrile contents (less than 50 mol-Yo) during thermal annealing below 300 "C.
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