Compared to other glassy polymers, poly (1-trimethylsilyl-1-propyne) [PMSP] has an extraordinarily large unrelaxed free volume, making PMSP the most permeable polymer known. In this paper, the gas permeabilities of PMSP films filled with polydimethylsiloxane [PDMS] and polyethylene glycol [PEG] are discussed. PMSP films were filled with PDMS and PEG by immersing the films in PDMS/ methyl ethyl ketone and PEG/1, 1, 2-trichloroethane solutions, respectively. The PDMS and PEG used were PDMS1000cs (Mw=3×104), PDMS100cs (Mw=6×103), PDMS10cs (Mw=1×103), and PEG6000 (Mw=6×103). Macro domains of PDMS and PEG oligomers are not formed in the filled PMSP films because no peaks appear in the DSC curves for the filled films. As PEG or PDMS content in the filled PMSP films increases, both the permeability coefficient and the equilibrium sorption concentration of carbon dioxide in these films decrease, while the separation factor for carbon dioxide over nitrogen increases. Compared to the carbon dioxide permeability of PDMS-filled PMSP films, the permeability of carbon dioxide is higher for PMSP films containing less than 20 wt% PEG and lower for films containing more than 20 wt% PEG. These results suggest that the gas sorption, diffusion, and permeation properties of filled PMSP films depend on oligomer content and morphology of the filled films.

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