Vapor-liquid equilibria for copolymer+solvent systems: Effect of intramolecular repulsion
Role of intramolecular interactions in blend miscibility is well documented for polymer+copolymer mixtures. Some copolymer+polymer mixtures are miscible although their corresponding homopolymers are not miscible; for example, over a range of acrylonitrile content, styrene/acrylonitrile copolymers are miscible with poly(methyl methacrylate) but neither polystyrene nor polyacrylonitrile is miscible with poly(methyl methacrylate). Similarly, over a composition range, butadiene/acrylonitrile copolymers are miscible with poly(vinyl chloride) while none of the binary combinations of the homopolymers [polybutadiene, polyacrylonitrile, and poly(vinyl chloride)] are miscible. This behavior has been attributed to ``intramolecular repulsion`` between unlike copolymer segments. We have observed similar behavior in vapor-liquid equilibria (VLE) of copolymer+solvent systems. We find that acrylonitrile/butadiene copolymers have higher affinity for acetonitrile solvent than do polyacrylonitrile or polybutadiene. We attribute this non-intuitive behavior to ``intramolecular repulsion`` between unlike segments of the copolymer. This repulsive interaction is weakened when acetonitrile molecules are in the vicinity of unlike copolymer segments, favoring copolymer+solvent miscibility. We find similar behavior when acetonitrile is replaced by methyl ethyl ketone. To best knowledge, this effect has not been reported previously for VLE. We have obtained VLE data for mixtures containing a solvent and a copolymer as a function of copolymer composition. It appears that, at a given solvent partial pressure, there may be copolymer composition that yields maximum absorption of the solvent. This highly non-ideal VLE phase behavior may be useful for optimum design of a membrane for a separation process.
- Research Organization:
- Lawrence Berkeley Lab., CA (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States); American Chemical Society, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
- DOE Contract Number:
- AC03-76SF00098
- OSTI ID:
- 101234
- Report Number(s):
- LBL--36964; CONF-9506220--1; ON: DE95014781
- Country of Publication:
- United States
- Language:
- English
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