New High Permeable Addition Poly(tricyclononenes) with Si(CH3)3 Side Groups. Synthesis, Gas Permeation Parameters, and Free Volume

• Published in: Macromolecules 2010-09, Vol.43 (17), p.7165-7172
• Main Authors: Gringolts, M, Bermeshev, M, Yampolskii, Yu, Starannikova, L, Shantarovich, V, Finkelshtein, E
• Format: Article
• Language: English
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma100656e

Addition polymerization of two tricyclononene monomers bearing one and two Si(CH3)3 groups was performed in the presence of Pd-containing catalysts. The polymers were obtained with high yields and were completely saturated. Good mechanical and film forming properties are observed for the polymers prepared in the presence of Pd(OAc)2/B(C6F5)3 catalyst. Their glass transition temperature was not observed until the onset of thermal decomposition (>370 °C) and the molecular weights are high (M w up to 7 × 105). Study of gas permeation parameters of the obtained poly[3-(trimethylsilyl)tricyclononene-7] and poly[3,4- bis(trimethylsilyl)tricyclononene-7] showed that both glassy polymers revealed substantially high gas permeability. Other transport characteristics (increase in permeability in the series C1−C4 alkanes and negative activation energies of permeation) indicate that these polymers reveal so-called solubility controlled permeation, which is typical for some extra-high permeability polymers. Positron annihilation lifetime spectroscopy indicated that both polymers are characterized by very large sizes of free volume elements.