360
GRINGOL’TS et al.
study of the gas separation properties of addition
poly(5ꢀtrimethylsilylnorbornene) (APNBSi) and
REFERENCES
1. R. W. Baker, Ind. Eng. Chem. Res. 41, 1393 (2002).
2. R. W. Baker and K. Lokhandwala, Ind. Eng. Chem.
poly(3ꢀtrimethylsilyltricyclononene)
(APTCNSi)
(Table 5, runs 2, 3) synthesized on the Niꢀcontaining
catalysts has shown that their permeability coefficients
are almost two orders of magnitude above the permeꢀ
ability coefficient of unsubstituted addition polynorꢀ
bornene (Table 5, run 1) and are higher by a factor of
5–8 than those of the most permeable metathesis
polynorbornenes synthesized in this work (Table 4,
runs 2, 5). Thus, siliconꢀsubstituted addition polynorꢀ
bornenes can be grouped with highly permeable polyꢀ
mers, such as polyacetylenes (e.g., poly(trimethylsilylꢀ
propyne) and polymethylpentyne (PMP)). Monosubꢀ
stituted addition polytricyclononene APTCNSi has a
lower permeability coefficient than poly(trimethylsiꢀ
lylnorbornene) APNB. It is noteworthy that the glass
Res. 47, 2109 (2008).
3. P. Bernardo, E. Drioli, and G. Golemme, Ind. Eng.
Chem. Res. 48, 4638 (2009).
4. M. Freemantle, Ind. Eng. Chem. Res. 83, 49 (2005).
5. Materials Science of Membranes for Gas and Vapor Sepꢀ
aration Yu. Yampolskii, I. Pinnau, and B. D. Freeman,
Eds. (Wiley Chichester, 2006).
6. T.ꢀSh. Chung, L. Y. Jiang, Y. Li, and S. Kulprathipanja,
Prog. Polym. Sci. 32, 483 (2007).
7. N. B. McKeown, P. M. Budd, J. Kadhum, et al.,
Chem.ꢀEur. J. 11, 2610 (2005).
8. K. Nagai, T. Masuda, T. Nakagawa, et al., Prog. Polym.
Sci. 126, 721 (2001).
9. K. J. Ivin and J. C. Mol, Olefin Metathesis and Metatheꢀ
sis Polymerization (Academic,London, 1997).
transition temperature Tg for APTCNSi is 139–142°С,
whereas APNB does not experience the glass transiꢀ
tion but just begins to degrade (~350°C). This fact
suggests a lower chain rigidity of APTCNSi in which
the bulky Me3Si substituents have farther positions
from the main chain, thereby resulting in a decrease in
both the free volume and gas permeability. It may be
assumed that such a remote position of bulky substituꢀ
ents in rigidꢀchain addition polynorbornenes is more
significant for gas separation properties than in more
flexible metathesis polynorbornenes.
10. Handbook of Metathesis, R. H. Grubbs, Ed., (Wileyꢀ
VCH, Weinheim, 2003).
11. F. Blank and Ch. Janiak, Coord. Chem. Rev. 253, 827
(2009).
12. K. L. Makovetskii, Polym. Sci., Ser. C 50, 22 (2008).
13. V. V. Teplyakov, D. R. Paul, N. B. Bespalova, and
E. Sh. Finkel’shtein, Macromolecules 25, 4218 (1992).
14. E. Sh. Finkelshtein, N. B. Bespalova, E. B. Portnykh,
et al., Vysokomol. Soedin. 35, 489 (1993).
15. J. Vargas, A. A. Santiago, and M. A. Tlenkopatchev,
Macromolecules 40, 563 (2007).
We obtained interesting results in our study [36]
regarding the permeability of APNB films to С1–С4
hydrocarbons. It was found that the permeability coefꢀ
ficients increase with an increase in the penetrant size
(Table 5, run 2). Such an untypical behavior of conꢀ
ventional glassy polymers is observed only for highly
permeable polyacetylenes and indicates that the perꢀ
meability of APNB is controlled to a greater extent by
the solubility of gases in the polymer, rather than their
diffusion.
16. A. P. Contreras, M. A. Tlenkopatchev, M. M. Lo’pezꢀ
Gonza’lez, and E. Riande, Macromolecules 35, 4677
(2002).
17. K. Daz Vargas, L. F. Del Castillo, M. A. Tlenkopatchev,
and M. AguilarꢀVega, Macromol. Chem. Phys. 206
2316 (2005).
18. Y. Kawakami, H. Toda, M. Higashino, and Y. Yamashꢀ
ita, Polym. J. 20, 285 (1988).
19. T. Katsumata, M. Shiotsuki, F. Sanda, and T. Masuda,
,
Polymer 50, 1389 (2009).
In summary, using silylated norbornenes as an
example, we managed to show that the presence of
Me3Si substituent groups in the polymers is responsiꢀ
ble for their enhanced gas separation properties. The
effect of the introduction of Me3Si groups increases
with an increase in the chain rigidity. The authors are
currently continuing the intensive investigation into
the synthesis of siliconꢀsubstituted polynorbornenes
and polytricyclononenes and the examination of their
properties.
20. K. D. Dorkenoo, P. H. Pfromm, and M. E. Rezac, J.
Polym. Sci., Part B 36, 797 (1998).
21. C. Zhao, RibeiraM. Rosario, V. S. Subrahamnyam,
et al., Polymer 42, 2455 (2001).
22. B. R. Wilks, W. J. Chung, P. J. Ludovice, et al., J.
Polym. Sci., Part B 41, 2185 (2003).
23. H. Tetsuka, K. Isobe, and M. Hagiwara, Polym. J. 41
,
643 (2009).
24. N. A. Plate, S. G. Durgarjan, V. S. Khotimskii, et al., J.
Membr. Sci. 52, 289 (1990).
25. Materials Science of Membranes for Gas and Vapor Sepꢀ
aration, Yu. Yampolskii, I. Pinnau, and B. D. Freeman,
Eds. (Wiley, Chichester, 2006).
ACKNOWLEDGMENTS
26. N. S. Nametkin, V. M. Vdovin, V. I. Zavjalov, and P. L.
Grinberg, Izv. Akad. Nauk SSSR, Ser. Khim., 929
(1965).
27. R. F. Cunico, J. Org. Chem. 36, 929 (1971).
28. E. Sh. Finkelshtein, M. L. Gringolts, N. V. Ushakov,
This work was supported by the Russian Foundaꢀ
tion for Basic Research, project no. 09ꢀ03ꢀ00342a,
and the European Community’s Seventh Framework
Programme (FP7/2007ꢀ2013), project no. NMP3ꢀ
SLꢀ2009ꢀ228631, DoubkerNanoMem.
et al., Polymer 44, 2843 (2003).
PETROLEUM CHEMISTRY Vol. 50
No. 5
2010