M. Netopilik et al., INFLUENCE OF CHEMICAL HETEROGENEITY OF COPOLYMERS ON THE SEPARATION PROCESS IN SIZE-EXCLUSION CHROMATOGRAPHY, Macromolecules, 29(18), 1996, pp. 6023-6030
The effect of the chemical-composition heterogeneity of flexible-chain
binary copolymers on their separation in size-exclusion chromatograph
y (SEC) was theoretically examined. The two parameter theory of polyme
r solutions was engaged to estimate the coil size. The variation in mo
lecular weight is shown for copolymer molecules which differ in the ra
tio of the two constituent monomeric units but have the same coil size
and, therefore, are eluted at the same elution volume. The result was
applied to a theoretical case of analysis of copolymers, the composit
ion and molecular-weight distributions of which are given by theoretic
al functions. If the refractive index increments of homopolymers whose
units constitute the copolymer are equal or close to each other, the
influence of the chemical heterogeneity on the experimental data is be
low the experimentally detectable limit. A significant error in the de
termination of the molecular-weight averages can occur only if the dif
ference in the refractive index increments exceeds physically reasonab
le limits.