Chemical modification of poly(substituted-acetylene). VI, Introduction of fluoroalkyl group into poly(1-trimethylsilyl-1-propyne) and the improved ethanol permselectivity at pervaporation

In order to improve the separation characteristics of membranes for pervaporation, the introduction of fluoroalkyl groups into poly(1-trimethylsilyl-1-propyne) (PTMSP) was achieved by two methods. First, 3,3,3-trifluoropropyldimethylsilylated PTMSP was prepared via metalation of PTMSP followed by treating with 3,3,3-trifluoropropyldimethylchlorosilane. About 6 mol % of 3,3,3-trifluoropropyldimethylsilyl group was introduced by the polymer reaction. Second, the copolymerizations of 1-trimethylsilyl-1-propyne (TMSP) with 1- (3,3,3-trifluoropropyldimethylsilyl)-1-propyne (FPDSP) or 1- (1H,1H,2H,2H-tridecafluorooctyldimethylsilyl)-1-propyne (FODSP) were carried out to afford TMSP/FPDSP or TMSP/FODSP random copolymers. The ratio of TMSP monomer unit and the comonomer unit, x/y, was in the range of 99/1-85/15. All the chemically modified PTMSP membranes showed ethanol permselectivity for pervaporation of aqueous ethanol solution. In particular, the introduction of less than about 5 mol % of fluoroalkylsilylated units into PTMSP effectively enhanced the selectivity. However, excess introduction of FODSP comonomer unit caused a decrease of the selectivity, with the value being smaller than that of PTMSP membrane. Furthermore, tetrahydrofuran, acetone, acetonitrile, dioxane, and isopropanol were efficiently separated from their dilute aqueous solutions using a TMSP/FPDSP copolymer membrane.