Abstract
The kinetics of the polymer cross-metathesis reaction in a mixture of polynorbornene and polycyclooctene catalyzed by the Grubbs first-generation ruthenium catalyst at room temperature is studied. The structure of the reaction product, a multiblock copolymer of norbornene and cyclooctene, is determined by a number of factors typical for a mixture of polymers reacting with each other via the interchange reaction with the participation of terminal groups. The addition of 5 mol % catalyst transforms the mixture into an almost random copolymer over a day. At a lower content of the catalyst, the maximum conversion is reached in a mixture enriched with polynorbornene. The interchain exchange results in an increase in the fraction of trans C=C bonds in polycyclooctene and cyclooctene–norbornene copolymers to 80%.
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References
Transreaction in Condensation Polymers, Ed. by S. Fakirov (Wiley, Weinheim, 1999).
H. R. Kricheldorf, Polycondensation: History and New Results (Springer, Berlin; Heidelberg, 2014).
N. A. Platé, A. D. Litmanovich, and Y. V. Kudryavtsev, Polym. Sci., Ser. A 46 11, 1108 (2004).
L. B. Krentsel, G. D. Markova, Y. V. Kudryavtsev, M. P. Filatova, V. A. Vasnev, A. D. Litmanovich, and N. A. Platé, Macromol. Chem. Phys. 206 21, 2206 (2005).
L. B. Krentsel, V. V. Makarova, Y. V. Kudryavtsev, E. N. Govorun, A. D. Litmanovich, G. D. Markova, V. A. Vasnev, and V. G. Kulichikhin, Polym. Sci., Ser. A 51 (11–12), 1241 (2009).
J. H. Youk and W. H. Jo, J. Polym. Sci., Polym. Phys. 39 12, 1337 (2001).
A. V. Chertovich, D. V. Guseva, Y. V. Kudryavtsev, and A. D. Litmanovich, Polym. Sci., Ser. A 50 4, 451 (2008).
R. Szymanski and S. Sosnowski, Macromol. Theory Simul. 21 6, 411 (2012).
Y. Mohammadi, H. A. Khonakdar, S. H. Jafari, M. R. Saeb, M. Golriz, U. Wagenknecht, G. Heinrich, S. Sosnowski, and R. Szymanski, Macromol. Theory Simul. 24 2, 152 (2015).
K. J. Ivin and J. C. Mol, Olefin Metathesis and Metathesis Polymerization (Acad. Press, London, 1997).
A. Bertrand and M. A. Hillmyer, J. Am. Chem. Soc. 135 30, 10918 (2013).
S. Monfette and D. E. Fogg, Chem. Rev. 109 8, 3783 (2009).
Y.-X. Lu, F. Tournilhac, L. Leibler, and Z. Guan, J. Am. Chem. Soc. 134 20, 8424 (2012).
Y.-X. Lu and Z. Guan, J. Am. Chem. Soc. 134 34, 14226 (2012).
H. Otsuka, T. Muta, M. Sakada, T. Maeda, and A. Takahara, Chem. Commun., No. 9, 1073 (2009).
T. Maeda, S. Kamimura, T. Ohishi, A. Takahara, and H. Otsuka, Polymer 55 24, 6245 (2014).
T. Ohishi, K. Suyama, S. Kamimura, M. Sakada, K. Imato, S. Kawahara, A. Takahara, and H. Otsuka, Polymer 78, 145 (2015).
M. L. Gringolts, Yu. I. Denisova, G. A. Shandryuk, L. B. Krentsel, A. D. Litmanovich, E. S. Finkelshtein, and Y. V. Kudryavtsev, RSC Adv. 5 1, 316 (2015).
Yu. I. Denisova, M. L. Gringolts, A. S. Peregudov, L. B. Krentsel, E. A. Litmanovich, A. D. Litmanovich, E. Sh. Finkelshtein, and Y. V. Kudryavtsev, Beilstein J. Org. Chem. 11, 1796 (2015).
M. Bornand and P. Chen, Angew. Chem., Int. Ed. 44 48, 7909 (2005).
R. M. E. Greene, J. G. Hamilton, K. J. Ivin, and J. J. Rooney, Makromol. Chem. 187 3, 619 (1986).
P. Dounis, W. J. Feast, and A. M. Kenwright, Polymer 36 14, 2787 (1995).
K. Vehlow, D. Wang, M. R. Buchmeiser, and S. Blechert, Angew. Chem., Int. Ed. 47 14, 2615 (2008).
W. A. Schneider and M. F. Müller, Makromol. Chem. 189 12, 2823 (1988).
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Original Russian Text © Yu.I. Denisova, M.L. Gringolts, L.B. Krentsel’, G.A. Shandryuk, A.D. Litmanovich, E.Sh. Finkelshtein, Ya.V. Kudryavtsev, 2016, published in Vysokomolekulyarnye Soedineniya. Ser. B, 2016, Vol. 58, No. 3, pp. 246–251.
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Denisova, Y.I., Gringolts, M.L., Krentsel’, L.B. et al. Regulation of the degree of blockiness of the norbornene–cyclooctene copolymer synthesized via the cross-metathesis reaction. Polym. Sci. Ser. B 58, 292–297 (2016). https://doi.org/10.1134/S1560090416030040
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DOI: https://doi.org/10.1134/S1560090416030040