1973 Articles

Thermodynamic Properties of Poly(trans 1,4-butadiene) Crystals. Relationship to Molecular Structure

Stellman, Jeanne M.; Woodward, Arthur E.; Stellman, Steven D.

Heat capacity measurements of melt crystallized poly( trans-1,4-butadiene) (PTBD) were carried out in the 50-130" region and the entropy change from 73" to the melting point, 139", was calculated. A value of the entropy change obtained using the rotational isomeric state approximation is found to underestimate the experimental entropy change. Theoretical energy calculations were carried out using empirical potential energy functions for a single PTBD chain, a unit cell and a lattice of cells. Minimization of the lattice energy with respect to two of the monoclinic cell constants for the low-temperature crystal form gave results in good agreement with X-ray diffraction data. The energy of transition from the low-temperature form was calculated and a theoretical heat capacity curve was obtained.