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Metathesis polytricyclononenes were synthesized via ROMP polymerization in the presence of the 1‐st generation Grubbs catalyst and their gas‐transport properties were studied for the first time. The aim of this work was to evaluate the influence of Me3E‐groups (E = C, Si, Ge) on gas permeation parameters of ROMP materials. New metathesis poly(3‐tert‐butyltricyclononene‐7) and poly(3‐trimethylgermyltricyclononene‐7) were obtained with high yields (up to 95%) and high‐molecular weights (Mw∼3–7×105 g mol−1). The glass transition temperatures of the ROMP polytricyclononenes with Me3E‐groups decreased when E was changed from C to Si and then to Ge. It was shown that the polytricyclononene containing Me3Si‐groups has the highest gas permeability while the polytricyclononene containing Me3C‐substituents has the lowest gas permeability. In addition, the gas permeation parameters were estimated for ROMP Me3Si‐ and Me3Ge‐substituted polytricyclonona‐3,7‐dienes. So the influence of the second double bond in the monomer units on the permeability of the polymers obtained was studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41395.

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