Abstract
AbstractChemical heterogeneity can influence the properties of statistical copolymers. It is shown that any integral property of a copolymer will depend on the chemical heterogeneity if such a property is a non‐linear function of copolymer composition. This is illustrated by means of the conductivity of copolymers of aniline and 2‐bromoaniline. The monomer reactivity ratios of this monomer pair are rA (aniline) = 0.94 and rB (2‐bromoaniline) = 0.31. The dependence of conductivity on the copolymer composition is non‐linear. Consequently, the conductivity depends on the compositional distribution, ie on the extent of chemical heterogeneity. Heterogeneous high‐conversion copolymers have lower conductivity than corresponding relatively homogeneous low‐conversion copolymers. The change in the average copolymer composition with increasing conversion is demonstrated for a copolymerization mixture containing 30 mol% aniline. The conductivity decreases at the same time as the chemical heterogeneity of the copolymer develops. The change in the average copolymer composition alone cannot explain the observed conductivity decrease. The conductivity is dependent not only on average composition but also on the chemical composition distribution. Copyright © 2004 Society of Chemical Industry
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