Polymerization of Isoprene in Ethylacetate in the Presence of Hydrogen Peroxide

Vitaly Boiko
Affiliation: 
Institute of Macromolecular Chemistry of National Academy of Sciences of Ukraine 48, Kharkivske Sh., 02160 Kyiv, Ukraine; boikovita@bigmir.net
DOI: 
https://doi.org/10.23939/chcht04.01.057
AttachmentSize
PDF icon full_text.pdf82.32 KB
Abstract: 
Orders by monomer and initiator at polymerization of isoprene in solution of ethylacetate under the action of hydrogen peroxide have been determined. The order by monomer is equal to 1.49 ± 0.03, by initiator – 0.46 ± 0.05. Unlike polymerization in solution of isopropyl alcohol, a process in ethylacetate proceeds in homogeneous solution. The value of order by monomer differs from the one for ideal polymerization, pointing to the specific mechanism of polymerization in the given system, while the value of order by initiator points to the quadratic termination of macroradicals, typical for ideal polymerization. These data as well as the literature lead to the conclusion that initiation takes place through decomposition of monomer-initiator complex.
References: 

[1] Get'manchuk Yu. and Bratychak M.: Khimiya Vysokomolekulyarnyh Spoluk. NU "Lvivska politekhnika", Lviv 2008.

[2] Moad G. and Solomon D.: The Chemistry of Radical Polymerization. Elsevier 2006.
https://doi.org/10.1016/B978-008044288-4/50028-5

[3] Kabanov V., Zubov V. and Semchikov Yu.: Kompleksno-Radikalnaya Polymerizacia. Khimiya, Moskwa 1987.

[4] Spirin Yu.: Reakcii Polymerizacii. Naukova dumka, Kyiv 1977.

[5] Oudian G.: Osnovy Khimii Polimerov. Mir, Moskwa 1974.

[6] Valuev V., Dmitrieva T., Shlyahter R. et al.: Vysokomol. Soed. A, 1982, 24, 1168.

[7] Grishchenko V., Boiko V., Svistova E. et al.: J. Appl. Polym. Sci., 1992, 46, 2081.
https://doi.org/10.1002/app.1992.070461203

[8] Karaputadze T., Shumskiy V., Skurlatov Yu. and Kirsh Yu.: Vysokomol. Soed. B, 1982, 24, 305.

[9] Panarin E., Kalninsh C. and Azanova V.: Vysokomol. Soed. A, 2007, 49, 438.
https://doi.org/10.1134/S0965545X07030078

[10] Boiko V.: Vysokomol. Soed. A, 2005, 47, 2081.

[11] Grishchenko V., Pakirbaeva L., Tkach V. et al.: Ukr. Khim. Zh., 1987, 53, 768.

[12] Grishchenko V. and Spirin Yu.: Vysokomol. Soed. A, 1969, 11, 980.
https://doi.org/10.1016/0032-3950(69)90377-3

[13] Spirin Yu., Grishchenko V. and Kochetova G.: Teor. Eksper. Khimiya, 1972, 8, 532.

[14] Boiko V.: Dopovidi Nats. Acad. Nauk Ukrainy, 2008, 2, 140.

[15] Keil B. (ed.): Laboratornaya Tekhnika Organicheskoy Khimii. Mir, Moskwa 1966.

[16] Marcus Y.: Chem. Soc. Rev., 1993, 22, 409.
https://doi.org/10.1039/cs9932200409

[17] Denisov E.: Zh. Phyz. Khimii, 1994, 68, 29.

[18] Pinazzi C., Legeaу G. and Brosse J.: Makromol. Chem., 1975, 176, 2509.
https://doi.org/10.1002/macp.1975.021760904