Thermodynamics of Mixing for Blends of Model Ethylene-Butene Copolymers

• Published in: Macromolecules 1994-07, Vol.27 (14), p.3896-3901
• Main Authors: Graessley, W. W, Krishnamoorti, R, Balsara, N. P, Butera, R. J, Fetters, L. J, Lohse, D. J, Schulz, D. N, Sissano, J. A
• Format: Article
• Language: English
• Subjects: 02 PETROLEUM; 020500 - Petroleum- Products & By-Products; 400201 - Chemical & Physicochemical Properties; Applied sciences; BINARY MIXTURES; COPOLYMERS; DATA; DIENES; DISPERSIONS; ENTHALPY; Exact sciences and technology; EXPERIMENTAL DATA; HYDROCARBONS; INFORMATION; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; MATHEMATICAL MODELS; MIXING HEAT; MIXTURES; MOLECULAR STRUCTURE; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC POLYMERS; PHYSICAL PROPERTIES; Physicochemistry of polymers; POLYENES; POLYMERS; Properties and characterization; SCATTERING; SMALL ANGLE SCATTERING; Thermal and thermodynamic properties; THERMODYNAMIC PROPERTIES
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma00092a033

This paper describes a study of thermodynamic interactions in binary blends of A[sub y]B[sub B[minus]y] copolymers. The blend components are hydrogenated polybutadienes, consisting of chains with branched C[sub 4] and linear C[sub 4] units and corresponding to model ethylene-butene copolymers. Overall compositions range from nearly polyethylene (y = 0) to nearly poly(butene-1) (y = 1) through a series of nearly random branched C[sub 4]-linear C[sub 4] copolymers. Values of the Flory-Huggins interaction parameter [chi] were determined by small-angle neutron scattering (SANS) from binary blends (one component deuterated) and then corrected for the effect of isotopic substitution. The reduced interaction parameter [chi]/(y[sub 2] [minus] y[sub 1]) was found to be a strong function of the average blend composition, contrary to classical copolymer theory. Higher order theories, based on diad or triad interactions, could be made to fit, but the physical significance of the fits was unclear. The same results were also expressed in terms of a relative solubility parameter, [delta]--[delta][sub ref], for each copolymer. These values were found to agree well with calculations based on PVT properties of the pure components. Thus, it seems clear that, for this system at least, departures from the copolymer equation are foretold in the pure component properties and have nothing to do with anomalies associated with mixing. More generally, inferences about the mixing process that are based on the temperature dependence of [chi] alone must be viewed with great caution.