NAMS 2002 Workshop - ICOM 2008

poly(4) reached up to 17,900 barrers, which is even larger than that of the so far
most permeable PTMSP.
Poly(diphenylacetylene) [poly(DPA)] membrane was successfully prepared by
desilylation of poly(p-Me3Si-DPA) membrane catalyzed by trifluoroacetic acid.
This is quite interesting because poly(DPA) membrane cannot be fabricated
directly because of the insolubility of the polymer [9,10]. The membrane of
poly(DPA) is fairly permeable to oxygen (Po2 = ca. 1,000 barrers) in spite of the
absence of any spherical substituents.
It is impossible to directly obtain substituted polyacetylenes having polar groups
such as hydroxy groups because of catalyst deactivation during polymerization,
but this has been achieved by an indirect method. Namely, poly[1-p-(tbutyldimethylsiloxyphenyl)-2-phenylacetylene]
was at first synthesized, and then
its membrane was treated with CF3COOH/H2O to provide poly[1-(phydroxyphenyl)-2-phenylacetylene]
membrane. This oxygen-containing polymer
also shows fairly high oxygen permeability (250 barrers), and more interestingly it
shows large CO2 permselectivity (PCO2 110 barrers; PCO2/PN2 46) [11].
1. T. Masuda and K. Nagai, in ‘Materials Science of Membranes for Gas and Vapor Separation’,
Yu. Yampolskii, I. Pinnau, B. D. Freeman, Eds., Wiley, Chichester, Chapter 8 (2006).
2. T. Masuda, J. Polym. Sci., Part A: Polym. Chem., 45, 165 (2007).
3. K. Nagai, Y.-M. Lee, and T. Masuda, in ‘Macromolecular Engineering: Precise Synthesis,
Materials Properties, Applications’, K. Matyjaszewski, Y. Gnanou, and L. Leibler, Eds., Wiley-
VCH, Weinheim, Vol. 4, Chapter 12 (2007).
4. T. Masuda, E. Isobe, T. Higashimura, and K. Takada, J. Am. Chem. Soc., 105, 7473 (1983).
5. K. Nagai, T. Masuda, T. Nakagawa, B. D. Freeman, and I. Pinnau, Prog. Polym. Sci., 26, 721
(2001).
6. K. Tsuchihara, T. Masuda, and T. Higashimura, J. Am. Chem. Soc., 113, 8548 (1991).
7. Y. Hu, M. Shiotsuki, F. Sanda, and T. Masuda, Chem. Commun., 4269 (2007).
8. Y. Hu, M. Shiotsuki, F. Sanda, B. D. Freeman, and T. Masuda, J. Am. Chem. Soc., submitted.
9. M. Teraguchi and T. Masuda, Macromolecules, 35, 1149 (2002).
10. T. Sakaguchi, K. Yumoto, Y. Shida, M. Shiotsuki, F. Sanda, and T. Masuda, J. Polym. Sci,
Part A Polym. Chem., 44, 5028 (2006).
11. Y. Shida, T. Sakaguchi, M. Shiotsuki, and T. Masuda, Macromolecules, 38, 4096 (2005).