Abstract
Addition and ring-opening metathesis polymerizations of new monomers (Me3Si- and Me3Ge-substituted tricyclononene and tricyclononadienes) were studied. Addition polymerization was carried out on Pd- and Ni-catalyst systems activated by B(C6F5)3 and/or methylalumoxane. New addition polymers were obtained with good yields up to 70% and with molecular weights (Mw) up to 5.6 × 105. Metathesis polymerization was performed using the first-generation Grubbs catalyst. The yields of the first obtained metathesis polymers were higher than 80%, and the Mw values were up to 8.8 × 105. It was revealed that the cyclobutene double bond in the studied tricyclononadienes is inactive in both metathesis and addition polymerizations. The relative activities of the substituted tricyclononene-7 and the corresponding tricyclononadiene-3,7 in the metathesis copolymerization were defined using 1H NMR spectroscopy. It was found that the novel addition polymer poly[(3-trimethylgermyl)tricyclononene-7] possesses high gas-transport parameters (for example, P(O2)=660 Barrers, P(CO2)=3850 Barrers) and solubility-controlled permeation of gaseous hydrocarbons (α (n-C4H10/CH4)=17.3).
Similar content being viewed by others
Log in or create a free account to read this content
Gain free access to this article, as well as selected content from this journal and more on nature.com
or
References
Haselwander, T. F. A., Heitz, W., Krugel, S. A. & Wendorff, J. H. Polynorbornene: synthesis, properties and simulations. Marcomol. Chem. Phys. 197, 3435–3453 (1996).
Haselwander, Th. F. A., Heitz, W., Krugel, S. A. & Wendorff, J. H. Rigid random coils: rotationally confined chain molecules. Marcomolecules 30, 5345–5353 (1997).
Ivin, K. J. & Mol, J. C. Olefin Metathesis and Metathesis Polymerization 472 (Academic Press, London, 1997).
Hennis, A. D., Polley, J. D., Long, G. S., Sen, A., Yandulov, D., Lipian, J., Benedict, G. M., Rhodes, L. F. & Huffman, J. Novel, efficient, palladium-based system for the polymerization of norbornene derivatives: scope and mechanism. Organometallics 20, 2802–2812 (2001).
Kagan, H. B. & Riant, O. Catalytic asymmetric Diels-Alder reactions. Chem. Rev. 92, 1007–1019 (1992).
Tabushi, I., Yamamura, K. & Yoshida, Z. Regio- and stereospecific [2.pi.+2.sigma.+2.sigma.] cycloaddition reaction of quadricyclane. J. Am. Chem. Soc. 94, 787–792 (1972).
Petrov, V. A. & Vasil’ev, N. V. Synthetic chemistry of quadricyclane. Curr. Org. Synth. 3, 175–213 (2006).
Finkelshtein, E. Sh., Bermeshev, M. V., Grongolts, M. L., Starannikova, L. E. & Yampolskii, Yu. P. Substituted polynorbornenes as promising materials for gas separation membranes. Russ. Chem. Rev. 80, 341–361 (2011).
Gringolts, M. L., Bermeshev, M. V., Makovetsky, K. L. & Finkelshtein, E. Sh. Effect of substituents on addition polymerization of norbornene derivatives with two Me3Si-groups using Ni(II)/MAO catalyst. Eur. Polym. J. 45, 2142–2149 (2009).
Gringolts, M., Bermeshev, M., Yampolskii, Yu., Starannikova, L., Shantarovich, V. & Finkelshtein, E. New high permeable addition poly(tricyclononenes) with Si(CH3)3 side groups. synthesis, gas permeation parameters, and free volume. Macromolecules 43, 7165–7172 (2010).
Feiring, A. E., Crawford, M. K., Farnham, W. B., French, R. H., Leffew, K. W., Petrov, V. A., Schadt, F. L., Tran, H. V. & Zumsteg, F. C. Bis(fluoroalcohol) monomers and polymers: improved transparency fluoropolymer photoresists for semiconductor photolithography at 157 nm. Macromolecules 39, 1443–1448 (2006).
Feiring, A. E., Crawford, M. K., Farnham, W. B., Feldman, J., French, R. H., Junk, C. P., Leffew, K. W., Petrov, V. A., Qiu, Weiming, Schadt, F. L., Tran, H. V. & Zumsteg, F. C. New amorphous fluoropolymers of tetrafluoroethylene with fluorinated and non-fluorinated tricyclononenes. Semiconductor photoresists for imaging at 157 and 193 nm. Macromolecules 39, 3252–3261 (2006).
Sanders, D. P., Connor, E. F., Grubbs, R. H., Hung, R. J., Osborn, B. P., MacDonald, S. A., Willson, C. G. & Conley, W. Metal-catalyzed addition polymers for 157 nm resist applications. synthesis and polymerization of partially fluorinated, ester-functionalized tricyclo[4.2.1.02,5]non-7-enes. Macromolecules 36, 1534–1542 (2003).
Saunders, R. S. New polymers from ring-opening metathesis polymerization of quadricyclane adducts. Macromolecules 28, 4347–4349 (1995).
Gringol’ts, M. L., Bermeshev, M. V., Syromolotov, A. V., Starannikova, L. E., Filatova, M. P., Makovetskii, K. L. & Finkel’shtein, E. Sh. Highly permeable polymer materials based on silicon-substituted norbornenes. Petrol. Chem. 50, 352–361 (2010).
Gringolts, M. L., Bermeshev, M. V., Starannikova, L. E., Rogan, Yu. V., Yampol’skii, Yu. P. & Finkel’shtein, E.Sh Synthesis and gas separation properties of metathesis polynorbornenes with different positions of one or two SiMe3 groups in a monomer unit. Polym. Sci. Ser. A 51, 1233–1240 (2009).
Bermeshev, M. V., Syromolotov, A. V., Gringolts, M. L., Starannikova, L. E., Yampolskii, Y. P. & Finkelshtein, E. Sh. Synthesis of high molecular weight poly[3-{tris(trimethylsiloxy)silyl}tricyclononenes-7] and their gas permeation properties. Macromolecules 44, 6637–6640 (2011).
Bulgakov, B. A., Bermeshev, M. V., Demchuk, D. V., Lakhtin, V. G., Kazmin, A. G. & Finkelshtein, E. Sh. Synthesis of tricyclononenes and tricyclononadienes containing MX3-groups (M=C, Si, Ge; X=Cl, Me). Tetrahedron 68, 2166–2171 (2012).
Finkelshtein, ESh., Makovetskii, K. L., Gringolts, M. L., Rogan, Y. V., Golenko, T. G., Lakhtin, V. G. & Filatova, M. P. Addition polymerization of silyl-containing norbornenes in the presence of Ni-based catalysts. J. Mol. Catal. A Chem. 257, 9–13 (2006).
Finkelshtein, E. S., Portnykh, E. B., Ushakov, N. V., Gringolts, M. L. & Yampolsky, Yu. P. Synthesis of a new polymer — polycyclopentylenevinylene bearing Ge-containing group. Macromol. Chem. Phys. 198, 1085–1090 (1997).
Pixton, M. R. & Paul, D. R. in Polymeric Gas Separation Membranes (eds Paul D. R., Yampolskii Y. P.,) 83 (CRC Press, Boca Raton, FL, 1994).
Khanarian, G., Hoechst Celanese Optical properties of cyclic olefin copolymers. Opt. Eng. 40, 1024–1029 (2001).
Nagai, K., Masuda, T., Nakagawa, T., Freeman, B. D. & Pinnau, I. Poly[1-(trimethylsilyl)-1-propyne] and related polymers: synthesis, properties and functions. Progr. Polym. Sci. 26, 721–798 (2001).
Acknowledgements
We are grateful for support from the Ministry of Education and Science of the Russian Federation (GK No. 16.120.11.3056-MK, 16.740.11.338) and the Russian Foundation for Basic Research (Grant No. 12–08–00648-a). We thank Dr Boris Shklyaruk for the registration of WAXS and Professor Yuri Yampolskii for useful discussions on the gas-permeability study.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Bermeshev, M., Bulgakov, B., Demchuk, D. et al. Metathesis and addition polymerization of novel Me3Si- and Me3Ge-substituted tricyclononenes. Polym J 45, 718–726 (2013). https://doi.org/10.1038/pj.2012.211
Received:
Revised:
Accepted:
Published:
Issue date:
DOI: https://doi.org/10.1038/pj.2012.211
Keywords
This article is cited by
-
Metathesis and additive poly(tricyclononenes) with geminal trimethylsilyl side groups: chain rigidity, molecular and thin film properties
Journal of Polymer Research (2018)
-
Experimental and Theoretical Study of [2σ + 2σ + 2π]–Cycloaddition of Quadricyclane and Ethylenes Containing Three Silyl-Groups
Silicon (2015)
-
Structure-Sensitive Maxima in the Absorption Spectra of Polymers in the Terahertz Frequency Range
Radiophysics and Quantum Electronics (2015)
