Abstract
Heat capacities at constant pressure and volume for solid, branched macromolecules were calculated from 0 to 1000K from approximated frequency data and compared, when possible, with experimental data. The polymers analysed were: polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly-1-heptene, poly-1-octene, polyisobutylene, polyacrylonitrile, poly(methyl methacrylate), poly(ethyl methacrylate), poly(n-butyl methacrylate), poly(methacrylic acid), poly(methyl acrylate), poly(ethyl acrylate), poly(n-butyl acrylate) and poly(octadecyl acrylate). It was found that the group vibrations are strictly additive and that the skeletal vibrations can be fitted to an empirical distribution which reaches the polyethylene spectrum at a side-chain length of about six chain atoms.
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