Abstract
Temperature dependences of the specific heats, characteristic temperatures, and enthalpies of physical transformations of the first to fifth generations of carbosilane dendrimers with allyl terminal groups were studied using an adiabatic vacuum calorimeter in the temperature range 6—340 K. The error of measurements was, as a rule, about 0.2%. Thermodynamic characteristics of physical transformations of the dendrimers were determined and their thermodynamic functions C p°(T), H°(T)—H°(0), S°(T)—S°(0), and G°(T)—H°(0) were calculated for the temperature range 0—340 K. The thermodynamic functions of the dendrimers are linearly related to their molecular weights, the number of allyl groups on their outer spheres, and the number of moles of diallylmethylsilane per mole of the dendrimers formed. Additive dependence of the properties of the dendrimers on their chemical composition and structure indicates that the energy of interaction between structural fragments of the dendrimers is independent of the dendrimer generation number. The fractal dimensions, D, of all dendrimers studied in this work are 1.2—1.3 in the temperature range 30—50 K, thus indicating a chain-layered structure of the dendrimer glasses.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
A. M. Muzafarov and E. A. Rebrov, Vysokomol. Soedin., C, 2000, 42, 2015 [Polym. Sci., Ser. C, 2000, 42 (Engl. Transl.)].
D. A. Tomalia, Macromol. Symp., 1996, 101, 243.
S. A. Ponomarenko, N. I. Boiko, and V. P. Shibaev, Vysokomol. Soedin., C, 2001, 43, 1601 [Polym. Sci., Ser. C, 2001, 43 (Engl. Transl.)].
C. Gormon, Adv. Maer., 1998, 10, 235.
J.P. Majoral and A.M. Laminad, Chem. Rev., 1999, 99, 1989.
A. M. Muzafarov, E. A. Rebrov, and V. S. Papkov, Usp. Khim., 1991, 60, 1596 [Russ. Chem. Rev., 1991, 60 (Engl. Transl.)].
M. N. Bochkarev and M. A. Katkova, Usp. Khim., 1995, 64, 1106 [Russ. Chem. Rev., 1995, 64 (Engl. Transl.)].
B. V. Lebedev, N. N. Smirnova, V. G. Vasilév, and M. N. Bochkarev, Vysokomol. Soedin., A, 1996, 38, 999 [Polym. Sci., Ser. A, 1996, 38 (Engl. Transl.)].
N. N. Smirnova, B. V. Lebedev, and V. G. Vasilév, Zh. Obshch. Khim., 1996, 66, 199 [Russ. J. Gen. Chem., 1996, 66 (Engl. Transl.)].
K. V. Kir´yanov. B. V. Lebedev, and M. N. Bochkarev. Vysokomol. Soedin., A, 1999, 41, 1739 [Polym. Sci., Ser. A, 1999, 41 (Engl. Transl.)].
B. V. Lebedev, N. N. Smirnova, M. V. Ryabkov, S. A. Ponomarenko, V. A. Makeev, N. I. Boiko, and V. P. Shibaev, Vysokomol. oedin., A, 2001, 43, 514 [Polym. Sci., Ser. A, 2001, 43 (Engl. Transl.)].
M. V. Ryabkov, T. G. Kulagina, and B. V. Lebedev, Zh. Fiz. Khim., 2001, 75, 2165 [Russ. J. Phys. Chem., 2001, 75 (Engl. Transl.)].
B. V. Lebedev, T. G. Kulagina, M. V. Ryabkov, S. A. Ponomarenko, E. A. Makeev, N. I. Boiko, V. P. Shibaev, E. A. Rebrov, and A. M. Muzafarov, J. Thermal Analysis and Calorimetry, 2003, 71, 481.
S. A. Ponomarenko, E. A. Rebrov, N. I. Boiko, A. M. Muzafarov, and V. P. Shibaev, Vysokomol. Soedin., A, 1998, 40, 1253 [Polym. Sci., Ser. A, 1998, 40 (Engl. Transl.)].
V. M. Malyshev, G. A. Mil´ner, E. L. Sorkin, and V. F. Shibakin, Pribory i tekhnika eksperimenta [Instruments and Experimental Techniques], 1985, 6, 195 (in Russian).
R. M. Varushenko, A. I. Druzhinina, and E. A. Sorkin, J. Chem. Thermodynamics, 1997, 29, 623.
T. S. Yakubov, Dokl. Akad. Nauk SSSR, 1990, 310, 145 [Dokl. Chem., 1990 (Engl. Transl.)].
A. D. Izotov, O. V. Shebershneva, and K. S. Gavrichev, Abstrs. All_Russia Conf. on Thermal Analysis and Calorimetry, Kazan, 1996, 200 (in Russian).
V. V. Tarasov, Zh. Fiz. Khim., 1953, 27, 1430 [J. Phys. Chem. USSR, 1953, 27 (Engl. Transl.)].
B. V. Lebedev and N. N. Smirnova, Khimicheskaya termodinamika polialkanov i polialkenov [Chemical Thermodynamics of Polyalkanes and Polyalkenes], Izd_vo Nizhegorodskogo GU, Nizhny Novgorod, 1999, 274 pp. (in Russian).
G. Adam and J. U. Gibbs, J. Chem. Phys., 1965, 43, 139.
W. Kauzman, Chem. Rev., 1948, 43, 218.
A. Bestul and S. S. Chang, J. Chem. Phys., 1964, 40, 3731.
B. V. Lebedev, Termodinamika polimerov [Thermodynamics of Polymers], Izd_vo GGU, Gor´kij, 1989, 112 pp. (in Russian).
E. M. M. de Brabandervan den Berg and E. W. Meijer, Angew. Chem., Int. Ed., 1993, 32, 1308.
B. Wunderlich and U. Gaur, Pure Appl. Chem., 1980, 52, 445.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Lebedev, B.V., Ryabkov, M.V., Tatarinova, E.A. et al. Thermodynamic properties of the first to fifth generations of carbosilane dendrimers with allyl terminal groups. Russian Chemical Bulletin 52, 545–551 (2003). https://doi.org/10.1023/A:1023977916394
Issue Date:
DOI: https://doi.org/10.1023/A:1023977916394