Cross-linking of poly[1-(trimethylsilyl)-1-propyne] membranes using bis(aryl azides)

Cross-linkable poly[1-(trimethylsilyl)-1-propyne] (PTMSP) films were cast from toluene solutions containing PTMSP and either 4,4'-diazidobenzophenone or 4,4'-(hexafluoroisopropylidene)diphenyl azide. The composite films were clear and homogeneous and were cross-linked by UV irradiation at room temperature or thermal annealing at 180 degrees C. Low levels of the bis(aryl azide) (1-5 wt%) were effective in rendering the films insoluble in toluene and THF, both good solvents for PTMSP. The process is simple and effective, and thus PTMSP can be readily converted to mechanically stable membranes with permeabilities and separation factors comparable or higher than those of poly(dimethylsiloxane). The films were characterized by measuring their density, their permeability toward O-2 and N-2, and their spectroscopic properties. Compared to PTMSP, films containing bis(aryl azide) cross-linkers had lower permeabilities and higher separation factors, consistent with a reduction in free volume. When the films were cross-linked photochemically, the permeabilities declined further and the separation factor increased. Films cross-linked thermally had permeabilities comparable to their PTMSP/azide precursors, and density and swelling measurements suggest that higher free volumes are obtained in thermally cross-linked films. All films stored in air suffered from a slow decline in permeability which may reflect slow surface oxidation of the films. When stored in vacuum, cross-linked films were stable and showed no loss in permeability, but the permeability of uncross-linked PTMSP films stored under the same conditions fell to 70% of their original value in 1 month. We attribute the permeability decline to densification accelerated by impurities and solvents. (C) 1998 John Wiley & Sons, Inc.