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1 Polish Journal of Chemistry

1 2001

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Lattice Cluster Theory for Copolymer Blends : General Theory in the Incompressible System, Long Chain Limit

Dudowicz J., Freed K. F.

Polish Journal of Chemistry

2001

Vol. 75, nr 4

527-545

The lattice cluster theory is developed for binary blends of two structured monomer copolymers in the simplifying limit of an incompressible system and high molecular weights. The major advance in the present theory is the inclusion of nonrandom mixing effects that lead to a monomer sequence dependence of the Helmholtz free energy without the introduction of new adjustable parameters beyond those present in descriptions of binary homopolymer blends formed from the constituent monomers. Equivalently, the sequence dependent contributions are shown to emerge from a proper determination of the "surface fractions" in individual copolymer chains. The general theory applies to blends of random copolymer, diblock copolymers, alternating copolymers, as well as of copolymers with kinetically controlled monomer sequences. The theory is illustrated for purely random copolymer blends of deuterated and hydrogenated polybutadienes, where the computed phase boundaries depart qualitatively from those predicted by random copolymer Flory-Huggins theory.