Abstract
AbstractThe effects of various alkylammonium thiocyanates (ethyl, butyl, hexyl, and octyl) on aqueous solutions of polyvinylpyrrolidone (PVP) and poly(vinyl alcohol–acetate) copolymer (PVA‐Ac) were studied and compared with the effects caused by the respective chlorides. Whereas the PVP solution was hardly affected by the chlorides, it was precipitated by n‐octylammonium thiocyanate (OASCN) at dilute concentrations and dissolved at higher concentrations. On taking the effects of ammonium chloride and thiocyanate on the solubility of PVA‐Ac as references, with increasing of alkyl chain length, alkylammonium chlorides raised the polymer solubility steadily; on the contrary, the thiocyanates at dilute concentrations, except for ethylammonium thiocyanate, lowered it, and OASCN at dilute concentrations, except for ethylammonium thiocyanate, lowered it, and OASCN at dilute concentrations was a particularly strong salting‐out agent. The amount of binding of OASCN to the polymers in the precipitated systems was measured. The precipitation was attributed to ion‐pair binding of OASCN to the polymers, and the mechanism was discussed in terms of the interaction between the water structure‐breaking SCN− and the water structure‐making hydrophobic groups.
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