Beyond Flory-Huggins Theory: New Classes of Blend Miscibility Associated with Monomer Structural Asymmetry

Flory-Huggins (FH) theory is restricted to polymer mixtures whose monomers are structurally identical, a situation limited to isotopic blends and computer simulations. We investigate the influence of monomer structure on blend miscibility and scattering properties using the lattice cluster theory generalization of the FH model. Monomer structural asymmetry is shown to profoundly affect blend miscibility $(T_c,{\phi }_c)$, chain swelling $\left(T_{\theta }\right)$, and the scale $\left(\xi \right)$ and intensity [ $S\left(0\right)$] of composition fluctuations. Four distinct blend miscibility classes are identified and experimental evidence for these classes is discussed.