Analytic PRISM theory of structurally asymmetric polymer blends and copolymers

• Published in: Macromolecules Vol. 26; no. 22; pp. 6050 - 6067
• Main Author: Schweizer, Kenneth S
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 25.10.1993
• Subjects: 360602 - Other Materials- Structure & Phase Studies; Applied sciences; COPOLYMERS; Exact sciences and technology; MATERIALS SCIENCE; MATHEMATICAL MODELS; MICROSTRUCTURE; ORGANIC COMPOUNDS; ORGANIC POLYMERS; PHASE STUDIES; Physicochemistry of polymers; POLYMERS; Properties and characterization; Thermal and thermodynamic properties; Deuterium; Isotope effect; Molten state; Thermodynamic model; Phase diagram; Spinodal decomposition; Theoretical study; Copolymer; Homopolymer; Mixture; Interaction parameter
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma00074a029

Analytic PRISM theory with the new molecular closures is applied to determine the effective chi -parameters and spinodal instability curves for structurally asymmetric polymer alloys. Compressibility effects are found to be very important, and the use of a literal incompressible RPA-like approximation is shown to incur qualitative errors in most cases. A rich and nonadditive dependence of phase transition temperatures and apparent SANS chi -parameters on backbone stiffness asymmetry, attractive interaction potential asymmetry, and thermodynamic variables is found for binary homopolymer blends. A novel strategy for designing miscible mixtures based on a cancellation, or "compensation", of the relevant asymmetries is identified. The influence of chain stiffness asymmetry in blends characterized by specific interactions is also studied. Generalization of the analytic PRISM theory to mixtures of random copolymers and periodic block copolymer melts is presented. All the rich behavior predicted for phase-separating homopolymer mixtures is again found for these systems, plus addition non-mean field effects associated with random copolymer composition and block architecture. The theory is applied semiquantitatively to interpret recent experiments on polyolefin blends, diblock copolymers, and random copolymer alloys. Theoretical predictions are made which qualitatively account for recent experimental observations of a stong influence of stiffness asymmetry on phase separation temperatures, and the breakdown of the mean field random copolymer approach. Anomalous behavior is also predicted for deuterated mixtures due to an interference between the consequences of stiffness asymmetry and enthalpic interactions. The physical mechanism for the many non-Flory--Huggins effects predicted by the compressible PRISM theory is local, scalar density correlations, which appears to be different than the "nematic fluctuation" mechanism suggested by recent field theoretic work.