Nonsolvent Annealing Polymer Films with Ionic Liquids

Neutron reflectometry has been used to determine the interface structure and swelling of thin polymer films, when annealed in contact with a series of 1-alkyl-3-methylimidazolium ionic liquids (ILs). By choosing immiscible polymer/IL combinations, we have established that thin polymer films can be annealed for several hours in contact with ILs at temperatures well above the glass transition temperature and that this nonsolvent annealing environment can be exploited to direct self-assembly in polymer films. The ingress of IL into polymer films was quantified in terms of the swelling up to 10%. The polymer/IL interfacial width generally also increased from 0.9 nm up to similar to 3 nm, but there was remarkably little correlation between interfacial width and swelling. For one combination of polymer and IL (deuterated PM MA and Bmim-BF4) the interfacial width decreased slightly with increasing temperature, consistent with LCST behavior for this system. All of the ILs tested had a profound influence the distribution of carboxy-end-functionalized deuterated polystyrene, "dPS-COOH", in blended films with polystyrene homopolymers. The ILs promoted dPS-COOH adsorption at the film/IL interface and the simultaneous rapid desorption at the film silicon oxide interface. The rate of desorption was found to correlate with the swelling behavior of the polymer with respect to the IL anion species: PF6- < Br- < Cl < BF4-, suggesting that the polymer films are plasticized by the IL as it penetrates the film.