Permeation and sorption in polynorbornenes with organosilicon substituents

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Abstract
Gas sorption properties, permeability coefficients, and diffusion coefficients of a series of norbornene polymers are presented. Introduction of the Si(CH3)3 group into the polynorbornene (PNB) backbone chain results in significant increases in glass transition temperature, permeability, and diffusion coefficient for a number of gases (H2, O2, N2, CO2, CH4, C2H6). The transport properties and sorption isotherms for poly(5‐trimethylsilyl norbornene) (PTMSNB) are very similar to those for poly(vinyltrimethyl silane) (PVTMS), which contains the same side‐chain group but differs from PTMSNB by the structure of its main chain. For another silicon‐containing polymer poly[5‐(1,1,3,3‐tetramethyl‐1,3‐disilabutyl) norbornene] (PDSNB) having a bulkier side‐chain group, the glass‐transition temperature is decreased in comparison with that of PNB, presumably owing to self‐plasticization. Both silicon‐containing norbornene polymers (PTMSNB and PDSNB) have permeability coefficients for “rapid” gases like H2 or CO2 of about 102 Barrer. The high values of the Langmuir sorption capacity C′H for PTMSNB and PVTMS, as well as the high diffusivity and mobility of spin probes in these polymers, were attributed to a large free volume related to the bulky Si(CH3)3 groups attached directly to the main chain. © 1993 John Wiley & Sons, Inc.

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