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Ozone and its reactions with diene rubbers

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PL
Reakcje ozonu z kauczukami dienowymi
Języki publikacji
EN
Abstrakty
EN
The reactions ofozone with l,4-cis-pofybutadiene (SKD); Diene 35NFA [having thefollowing linking of the butadiene units in the rubber macromolecules: 1,4-cis (47%), 1,4-trans (42%), 1,2- (11%)]; 1,4-cis-polyisoprene (Carom IR 2200), 1,4-trans-polychloroprene (Denka M 40), and l ,4-trans-polyiso-prene have been investigated in CC14 solutions. The changes ofthe viscosity of the polymer solutions dur-ing the ozonolysis have been characterized by the number of chain scissions per molecule of reacted ozone (cpj. The influence ofthe conditions of mass-transfer ofthe reagents in a bubble reactor on the re-spectwe cp values has been discussed. The basie functional groups-products from the rubbers ozonolysis have been identified and quantitatively characterized by means of IR-spectroscopy and 2H-NMR spec-troscopy. A reaction mechanism, that explains theformation ofall identified functional groups, has been proposed. It has been shown that the basie route ofthe reaction ofozone with elastomer double bonds -theformation ofnormal ozonides does not lead directly to a decrease in the molecular mass ofthe elastomer macromolecules, because the respectwe l,2,4-trioxolanes arę relatively stable at ambient temperaturę. The most favourable conditions for ozone degradation emerge when the cage interaction between Criegee intermediates and respectwe carbonyl groups does notproceed. The amounts ofmeasured different carbonyl groups have been used as an alternatwe wayfor evaluation ofthe intensity and efficiency ofthe ozone degradation. The thermal decomposition ofpartially ozonized diene rubbers has been investigated by DSC. The respectwe values ofthe enthalpy, the activation energy and the reaction order ofthe l,2,4-trioxolanes have been determined.
PL
Zbadano działanie ozonu na następujące kauczuki (w postaci roztworów w CCl^: 1,4-cis-polibutadien (SKD); Diene 35 NFA [o konfiguracjach merów butadienowych w makrocząsteczkach: 1,4-cis- (47%), 1,4-trans- (42%), 1,2- (11%)]; 1,4-cis-poliizopren (Carom IR 2200), 1,4-trans-polichloropren (Denka M40) i 1,4-trans-poliizopren. Zmiany lepkości roztworów polimerowych podczas ozonolizy powiązano z liczbą rozszczepień łańcucha przypadającą na cząsteczkę oddziaływującego ozonu (
Czasopismo
Rocznik
Strony
11--23
Opis fizyczny
Bibliogr. 43 poz., tab., rys.
Twórcy
autor
autor
Bibliografia
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  • 3. Jellinek H. H., Aspects of Degradation and Stabilisation of Polymers, Ed. H.HG. Jellinek, Elsevier, Amsterdam, Nederland, 1978, Chapter 9.
  • 4. Zaikov G. E. and Rakovsky S. K., Ozonation of Organie & Polymer Compounds, Smithres Rapra, UK, 2009, Chapter 3 and 4.
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  • 15. Montaudo G., Scamporrino E., Vitalini D. and Rapisardi R., Fast atom bombardment mass spectrometric analysis of the partial ozonolysis products of poly(isoprene) and poly(chloroprene), J. Polym. Sci: Part A, 30, 525(1992).
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  • 18. Somers A.K., Bastow T.J., BurgarM.L., Forsyth M., Hill.A.J., Quantifying rubber degradation using NMR, Polym. Deg. Stab., 70, 31 (2000).
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  • 20. Bunnelle W. H., Preparation, properties, and reactions of carbonyl oxides, Chem. Rev., 91, 335 (1991).
  • 21. McCullough K. J., Nojima M., „Peroxides from Ozonization", in: Organic Peroxides, Ando W., Chapter 13, Ed., John Wiley & Sons Ltd, 1992.
  • 22. Anachkov M. P., Rakovsky S. K., Shopov D. M., Razumovskii S. D., Kefely A. A. and Zaikov G. E., Study of the ozone degradation of polybutadiene, polyisoprene and polychloroprene in solution, Polym. Deg. Stab., 10 (1), 25 (1985).
  • 23. Razumovskii S. D., Rakovski S. K., Shopov D. M., Zaikov G. E, Ozone and Its Reactions with Organie Compounds (in Russian). Publ. House of Bulgarian Academy of Sciences, Sofia, 1983.
  • 24. Flory P. J., Principles of Pofymer Chemistry. N.Y., p.41 (1953).
  • 25. Rakovsky S. K., Zaikov G., Ozonolysis of pofydienes, J. Appl. Polym. Sci., 91 (3), 2048 (2004).
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  • 28. Razumovskii S. D., Zaikov G. E., Kinetics and mechanism of ozone reaction with double bonds, Uspekhi khimii, 49, 2344 (1980).
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  • 30. Rakovsky S. K., Cherneva D. R, Shopov D. M., Razumovskii S. D., Applying of barbotage method to investiga-tion the kinetic of ozone reactions with organic compounds., Izv. Khim. BAN, XI (4), 711 (1976).
  • 31. Anachkov M. P., Rakovsky S. K., Stefanova R. V. and Shopov D. M., Kinetics and mechanism of the ozone degradation of nitrile rubbers in soiution, Polym. Deg. Stab, 19 (2), 293 (1987).
  • 32. Anachkov M. P., Rakovsky S. K., Zaikov G. A., Ozonolysis of polybutadienes with different microstructure in solution, J. Appl. Polym. Sci, 104. (1), 427 (2007).
  • 33. The Sadtler Handbook of Proton NMR Spectra, Sadtler, Philadelphia, PA, 1978.
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  • 35. Nakanishi K., Infrared spectra and the structure of organie compounds, Mir, Moscow, 1965.
  • 36. Anachkov M. P., Rakovsky S. K., Stefanova R. V., Ozonolysis of 1,4-cis-polyisoprene and 1,4-trans-polyisoprene in solution, Polym. Deg. Stab., 67. (2), 355 (2000).
  • 37. Murray R. W., Kong W., Rajadhyaksha S. N., The ozonolysis of tetra methylethylene - concentration and temperaturę effects, J. Org. Chem., 58, 315 (1993).
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  • 39. Anachkov M. P., Rakovsky S. K., Stefanova R. V. and StoyanovA. K., Ozone degradation of polychloroprene rubber in solution, Polym. Deg. Stab., 41 (2), 185 (1993).
  • 40. Fotty F. K., Rakovsky S. K., Anachkov M. R., Ivanov S. K., Cumene oxidation in the presence of 1-decene-ozonide, Oxidation Commun., 20 (3), 411 (1997).
  • 41. Anachkov M. P., Rakovsky S. K., Stoyanov A. K. and Fotty R. K., DSC study of the thermal decomposition of 1-decene ozonide, Thermochim. Acta, 237, 213 (1994).
  • 42. Anachkov M. P., Rakovsky S. K. and Stoyanov A. K., DSC Study of the thermal decomposition of partially ozonized diene Rubbers, J. Appl. Polym. Sci., 61, 585 (1996).
  • 43. Anachkov M. P., Rakovsky S. K., Enthalphy of the thermal decomposition of functional groups of peroxide type, formed by ozonolysis of diene rubbers in solution, Bulg. Chem. Comm., 34 (3/4), 486 (2002).
Typ dokumentu
Bibliografia
Identyfikator YADDA
bwmeta1.element.baztech-article-BPS4-0001-0017
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