Azowe inicjatory funkcyjne - rozpad termiczny w mieszaninach akrylonitryl/N,N-dimetyloformamid

E. Wiśniewska; B. Pabin-Szafko

Published : 2022-08-26

Vol. 52 No. 7-8 (2007)

Functional azo-initiators - thermal decomposition in acrylonitrile/N,N-dimethylformamide mixtures

E. Wiśniewska B. Pabin-Szafko

Abstract

The elementary reaction in radical polymerization process i.e. thermal decomposition of series of azo-initiators - 4,4’-azobis(4-cyanopentanoic) acid (ACPA) and 2,2’-azobisisobutyronitrile (AIBN) derivatives (Scheme A) - in the mixtures of acrylonitrile (AN)/N,N-dimethylformamide (DMF), in relation to monomer concentration (xM) at temp. 60°C, was investigated. It was found unambiguously that the reaction order equaled 1 for all initiators tested (Fig. 2). Experimentally determined courses of kd=f(xM) dependence are nonlinear (Fig. 3), their plots differ what can be connected with diverse chemical structures of azo-initiators, and they can be described by a model of initiator solvation by monomer (M) and solvent (S). The solvated forms occurring in the system were determined. Their relative stability constants and thermal decomposition rate constants were calculated (applying Marquardt’s algorithm) as well as relative parts in the mixture (Table 3). At low AN concentrations in DMF solutions the double solvates with solvent SIS and mixed MIS (monomer + solvent) predominate whereas in the concentrated solutions, when xM > 0.5, the contribution of double solvated forms with monomer MIM, characterized with the highest decomposition rate constant, increases.

Keywords

polimeryzacja rodnikowa akrylonitrylu ; rozpad termiczny azoinicjatorów ; rzędowość reakcji rozpadu termicznego ; stała szybkości rozpadu termicznego ; solwatacja inicjatora radical polymerization of acrylonitrile ; thermal decomposition of azo-initiators ; order of thermal decomposition reaction ; thermal decomposition rate constant ; initiator solvation

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Wiśniewska, E., & Pabin-Szafko, B. (2022). Functional azo-initiators - thermal decomposition in acrylonitrile/N,N-dimethylformamide mixtures. Polimery, 52(7-8), 562–570. Retrieved from https://ichp.vot.pl/index.php/p/article/view/1450

References

Matyjaszewski K.: w "Handbook of radical polymerization" (red. Davis T. P.), Wiley-Interscience 2002.

2. Scott G. E., Senogles E.: J. Macromol. Chem.: Rev. Macromol. Chem. 1973, 10, 49.

3. Moad G., Solomon D. H.: "The Chemistry of Radical Polymerization", Pergamon, Elsevier Science Ltd. 1995.

4. Overberger C. G., O'Shaughnessy M. T., Shalit H.: J. Am. Chem. Soc. 1949, 71, 2661.

5. Moroni A. F.: Makromol. Chem. 1967, 105, 43.

6. Schildknecht C. E.: "Polymerization Processes", J. Willey&Sons, New York-London-Sydney-Toronto 1977.

7. Idage B. B., Vernekar S. P., Ghatge N. D.: J. Polym. Sci.: Polym. Chem. Ed. 1983, 21, 2145.

8. Cheikhalard T., Tighzert L., Pascault J. P.: Angew. Makromol.Chem. 1998, 256, 49.

9. Fernandez-Garcia M., Martinez I. I., Madruga E. L.: Polymer 1998, 39, 991.

10. Miller A., Szafko J.: J. Polym. Sci.: Polym. Chem. Ed. 1980, 18, 1177.

11. Szafko J. Feist W.: J. Polym. Sci. Part A: Polym. Chem. 1995, 33, 1637.

12. Szafko J., Feist W.: J. Polym. Sci. Part A.: Polym. Chem. 1995, 33, 1643.

13. Szafko J., Feist W., Pabin-Szafko B.: J. Polym. Sci. Part A: Polym. Chem. 1996, 34, 613.

14. Szafko J. Feist W., Pabin-Szafko B.: J. Polym. Sci. Part A.: Polym. Chem. 2000, 38, 2156.

15. Bartoň J., Borsig E.: "Complexes in Free-Radical Polymerization", Elsevier, Amsterdam 1988.

16. Szafko J., Pabin-Szafko B.: Fibres&Textiles in EE 2002, 10 (nr 1), 66.

17. Szafko J., Pabin-Szafko B.: Fibres&Textiles in EE 2002, 10 (nr 4), 11.

18. Szafko J., Pabin-Szafko B.: Polimery 2002, 47, 822.

19. Walz R., Bömer B., Heitz W.: Makromol. Chem. 1977, 178, 2527.

20. Pabin-Szafko B., Wiśniewska E., Szafko J.: Polimery 2005, 50, 271.

21. Walling C.: "Free Radicals in Solution", Wiley, New York 1957.

22. Szafko J., Onderko K., Pabin-Szafko B.: Polimery 2003, 48, 329.

23. Szafko J., Wiśniewska E., Pabin-Szafko B.: Polimery 2002, 47, 563.

24. Szafko J., Pabin-Szafko B., Onderko K., Wiśniewska E.: Polimery 2002, 47, 22.

25. Eroglu M. S., Hazer B., Güven O., Baysal B.M.: J. Appl. Polym. Sci. 1996, 60, 2141.

26. Simionescu C. I., i in.: J. Polym. Sci. Part A.: Polym. Chem. 1994, 32, 3123.

27. Wódka T.: J. Appl. Polym. Sci. 1993, 47, 407.

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