Abstract
Hyperbranched polycarbosilanes are investigated by the methods of molecular hydrodynamics and optics. Dependences of the hydrodynamic and conformational properties of these polymers on their molecular mass, the length of linear chains between branching points, and the chemical structure of end groups are analyzed. The hydrodynamic behavior of hyperbranched polycarbosilanes is explained by the fact that the dimensions of their macromolecules are compact and their shape is close to spherical. The convolution of chains between branching points becomes more pronounced with an increase in their length and a decrease in the molecular mass of the polymer. When end fluorinated groups are incorporated into the hyperbranched polycarbosilane, in thermodynamically good solvents and θ solvents, hydrodynamic characteristics change apparently owing to a change in the density of macromolecules in solution. In a poor solvent, the compaction of fluorinated macromolecules and a reduction in their shape asymmetry are observed. At a fixed branching degree, the hydrodynamic properties of hyperbranched polymers depend on the structural regularity of their macromolecules: In terms of hydrodynamic properties, the hyperbranched polycarbosilane with a degree of branching of 1 and a random distribution of branching points within the volume of a macro-molecule is appreciably different from a dendrimer of the same chemical nature and is close to polycarbosilanes with a degree of branching of 0.5.
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References
B. I. Voit and A. Lederer, Chem. Rev. 109, 5924 (2009).
Modification and Blending of Synthetic and Natural Macromolecules, Ed. by F. Ciardelli and S. Penczek (Kluwer Academic, Amsterdam, 2004).
K. Ishizu, K. Tsubaki, A. Mori, and S. Uchida, Prog. Polym. Sci. 28, 27 (2003).
C. R. Yates and W. Hayes, Eur. Polym. J. 40, 1257 (2004).
P.-G. De Gennes, Scaling Concepts in Polymer Physics (Cornell Univ. Press, Ithaca, 1979; Mir, Moscow, 1982).
B. Voit, J. Polym. Sci., Part A: Polym. Chem. 43, 2679 (2005).
K. Inoue, Prog. Polym. Sci. 25, 453 (2000).
Silicon-Containing Dendritic Polymers, Ed. by P. R. Dvornic and M. J. Owen (Springer, Amsterdam, 2009).
Y. H. Kim and O. W. Webster, Macromolecules 25, 5561 (1992).
M. Trollsas, M. A. Kelly, H. Claesson, et al., Macromolecules 32, 4917 (1999).
C. Drohmann, M. Moller, O. B. Gorbatsevich, and A. M. Muzafarov, J. Polym. Sci., Part A: Polym. Chem. 38, 741 (2000).
K. Ishizu and A. Mori, Polym. Int. 50, 906 (2001).
H. Mori, D. C. Seng, H. Lecher, et al., Macromolecules 35, 9270 (2002).
K. Ishizu, T. Shibuya, and A. Mori, Polym. Int. 51, 424 (2002).
K. Fang, Zh. Xu, X. Jiang, et al., Polym. Bull. (Berlin) 60, 533 (2008).
G. P. Vlasov, I. I. Tarasenko, G. A. Pankova, et al., Polymer Science, Ser. B 51, (2009) [Vysokomol. Soedin., Ser. B 51, 1559 (2009)].
E. De Luca and R. W. Richards, J. Polym. Sci., Part B: Polym. Phys. 41, 1339 (2003).
W. Burchard, Adv. Polym. Sci. 143, 113 (1999).
A. Lederer, D. Voigt, S. Clausnitzer, and B. Voit, J. Chromatogr., A 976, 171 (2002).
V. N. Tsvetkov, Rigid-Chain Polymers (Nauka, Leningrad, 1986; Plenum, New York, 1989).
A. M. Muzafarov, O. B. Gorbatsevich, E. A. Rebrov, et al., Polymer Science, Ser. A 35, 1575 (1993) [Vysokomol. Soedin., Ser. A 35, 1867 (1993)].
N. A. Belov, N. A. Sheremet’eva, Yu. P. Yampol’skii, and A. M. Muzafarov, Polymer Science, Ser. A 51, (2009 [Vysokomol. Soedin., Ser. A 51, 775 (2009)].
N. A. Shumilkina, Candidate’s Dissertation in Chemistry (Moscow, 2006).
C. J. Hawker, R. Lee, and J. M. J. Frechet, J. Am. Chem. Soc. 113, 4583 (1991).
D. Hölter, A. Burgath, and H. Frey, Acta Polym. 48, 30 (1997).
E. B. Tarabukina, A. A. Shpyrkov, D. V. Potapova, et al., Polymer Science, Ser. A 47, 1304 (2005) [Vysokomol. Soedin., Ser. A 47, 2157 (2005)].
E. B. Tarabukina, A. A. Shpyrkov, D. V. Potapova, et al., Polymer Science, Ser. A 48, 974 (2006)] [Vysokomol. Soedin., Ser. A 48, 1655 (2006)].
E. B. Tarabukina, A. A. Shpyrkov, E. V. Tarasova, et al., Polymer Science, Ser. A 51, 150 (2009) [Vysokomol. Soedin., Ser. A 51, 196 (2009)].
A. I. Amirova, E. V. Belyaeva, E. B. Tarabukina, et al., Polymer Science, Ser. C 52, 70 (2010) [Vysokomol. Soedin., Ser. C 52, 1304 (2010)].
V. N. Tsvetkov, V. E. Eskin, and S. Ya. Frenkel’, The Structure of Macromolecules in Solutions (Nauka, Moscow, 1964) [in Russian].
Polymer Handbook, Ed. by J. Brandrup and E. H. Immergut (Wiley, New York, 1975).
G.-B. Zhang, J. Kong, X.-G. Fan, et al., Appl. Organomet. Chem. 29, 277 (2009).
E. A. Tatarinova, E. A. Rebrov, V. D. Myakushev, et al., Izv. Akad. Nauk, Ser. Khim., No. 11, 2484 (2004).
R. Scherrenberg, B. Coussens, P. Vliet, et al., Macro-molecules 31, 456 (1998).
A. V. Lezov, A. B. Mel’nikov, G. E. Polushina, et al., Dokl. Akad. Nauk 381, 69 (2001).
I. B. Rietveld and J. A. M. Smith, Macromolecules 32, 4608 (1999).
T. H. Mourey, S. R. Turner, M. Rubinstein, et al., Macromolecules 25, 2401 (1992).
V. N. Tsvetkov and S. I. Klenin, Dokl. Akad. Nauk SSSR 88, 49 (1953).
V. N. Tsvetkov, P. N. Lavrenko, and S. V. Bushin, Usp. Khim. 51, 1698 (1982).
A. A. Shpyrkov, I. I. Tarasenko, G. A. Pankova, et al., Polymer Science, Ser. A 51, 250 (2009) [Vysokomol. Soedin., Ser. A 51, 377 (2009)].
G. M. Pavlov, E. V. Korneeva, S. A. Nepogod’ev, et al., Polymer Science, Ser. A 40, 1282 (1998)] [Vysokomol. Soedin., Ser. A 40, 2056 (1998)].
E. A. Antonov, Candidate’s Dissertation in Mathematics and Physics (St. Petersburg, 2004).
A. M. Muzafarov and E. A. Rebrov, Polymer Science, Ser. C 42, (2001) [Vysokomol. Soedin., Ser. C 42, 2015 (2000)].
K. Johns and G. Stead, J. Fluorine Chem. 104, 5 (2000).
B. G. Willonghly and R. E. Banks, in Encyclopedia of Advanced Materials, Ed. by D. Bloor, R. J. Brook, M. C. Flemings, and S. Mahajan (Pergamon, Oxford, 1994).
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Original Russian Text © A.P. Filippov, E.V. Belyaeva, E.B. Tarabukina, A.I. Amirova, 2011, published in Vysokomolekulyarnye Soedineniya, Ser. C, 2011, Vol. 53, No. 7, pp. 1281–1292.
This work was supported by the Russian Foundation for Basic Research (project no. 08-03-00421) and the Program of Basic Research of the Division of Chemistry and Materials Sciences, Russian Academy of Sciences, “Creation and Study of Macromolecules and Macromolecular Structures of New Generations.”
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Filippov, A.P., Belyaeva, E.V., Tarabukina, E.B. et al. Behavior of hyperbranched polymers in solutions. Polym. Sci. Ser. C 53, 107–117 (2011). https://doi.org/10.1134/S1811238211060014
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DOI: https://doi.org/10.1134/S1811238211060014