Abstract
Experimental methods for fractionating polyisobutylene and for determining osmotic pressures have been described. The ratio π/c of osmotic pressure to concentration has been found in the case of cyclohexane solutions of polyisobutylene to vary nonlinearly with concentration, contrary to recent theories advanced by Huggins and the writer. The slope of this relationship appears to be independent of molecular weight. Reliable methods for extrapolating π/c to c=0 have been established, enabling the determination of absolute molecular weights with satisfactory precision up to values of about 1,000,000. Molecular weights of polyisobutylenes calculated from Staudinger's equation are too low; the discrepancy is more than ten-fold at high molecular weights. On the basis of data for carefully fractionated samples covering a two-hundred-fold molecular weight range, the intrinsic viscosity is found to be proportional to the 0.64 power of the molecular weight. This decided deviation from Staudinger's “law”cannot in this instance be attributed to nonlinear chain structure, as Staudinger has sought to do in other cases. This dependence of molecular weight on intrinsic viscosity leads to the definition of a “viscosity average”molecular weight which is obtained when the relationship is applied to heterogeneous polymers. The viscosity average is less than the weight average molecular weight, which would be obtained if Staudinger's equation were applicable, and greater than the number average obtained by osmotic or cryoscopic methods.
Correct determination of intrinsic viscosity
