Wpływ budowy polimerowych katalizatorów utleniania na ich aktywność katalityczną

B. Kolarz; A. Jakubiak; J. Jezierska

Published : 2022-08-30

Vol. 51 No. 7-8 (2006)

Effect of the structure of polymeric catalysts of the oxidation on their catalytic activity

B. Kolarz A. Jakubiak J. Jezierska

Abstract

The effect of the structure of particular group of polymeric catalysts of the oxidation process on their catalytic activity, in the model reaction of hydroquinone oxidation to p-benzoquinone with hydrogen peroxide, was investigated. Two series of terpolymers of acrylonitril (AN) and vinyl acetate (VA) crosslinked with either divinylbenzene (DVB) or trihydroxymethylpropane triacrylate (TMPA) or trihydroxymethylpropane trimethacrylate (TMPMA) (Table 2) were obtained in suspension polymerization. Dependently on the type of crosslinking monomer the products showed either the gel structure or porous one. In two-stage process the nitrile groups of terpolymer were subjected to aminolysis with hydrazine and amino groups obtained in this way were modified with thiourea in the presence of alkyl iodide (Scheme A). The supports containing aminoguanidyl, carboxyl or hydroxyl groups were obtained (Table 1 and 3) and their structures were characterized using FT-IR method. The proper catalysts were prepared via sorption of Cu(II) ions on these supports. Some parameters of these catalysts and of the catalysts prepared in one-stage aminolysis of terpolymers with guanidine carbonate or aminoguanidine carbonate were compared. They were: hydroquinone conversion degree (LH2Q), yield of quinone (YQ) as a main product and selectivity of the catalysts calculated on this basis (Table 4 and 5, Fig. 5 and 6). The catalysts crosslinked with DVB and subjected to one-stage modification showed the highest activity and selectivity (close to 100 %). In all cases the catalysts with aminoguanidyl groups were more active than those with hydrazine groups not subjected further modification. The results obtained show that the conditions encouraging the formation of N2O2 complexes as well as advantageous microenvironment formed by uncomplexed functional groups determine the activity and selectivity of the catalysts investigated.

Keywords

usieciowane terpolimery akrylonitrylu ; aminoliza hydrazyną ; nośniki z grupami aminoguanidynowymi ; katalizatory utleniania ; aktywność ; selektywność crosslinked acrylonitrile terpolymers ; aminolysis with hydrazine ; supports with aminoguanidyl groups ; oxidation catalysts ; activity ; selectivity

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Kolarz, B., Jakubiak, A., & Jezierska, J. (2022). Effect of the structure of polymeric catalysts of the oxidation on their catalytic activity. Polimery, 51(7-8), 561–570. Retrieved from https://polimery.ichp.vot.pl/index.php/p/article/view/1557

References

Owsik I., Kolarz B. N.: Wiad. Chem. 2003, 57,20.

2. Praca zbiorowa: „Synthesis and Separation using Functional Polymers" (red. Sherrington D. C., Hodge P.), Wiley, Chichester 1988.

3. Bekturov E. A., Kudaibergenov S. E,: „Catalysis by Polymers", Huthing & Wepf. 1996.

4. Praca zbiorowa: „Polymeric Materials in Organic Synthesis and Catalysis" (red. Buchmeister M. R.), Wiley, VCH 2003.

5. Cavani E, Trifiro E: Catal Today 1997, 34, 269.

6. Kopylova V. D.: Sofo. Extr. łon Exch. 1998,16,267.

7. Kaliyappan T., Kaannan P: Prog. Polym. Sci. 2000, 25,343.

8. Owsik L: „Anionity z ligandami guanidynowymi kompleksowanymi metalem jako katalizatory reakcji utleniania", Praca doktorska, Wydział Chemiczny Politechniki Wrocławskiej 2003.

9. Owsik L, Kolarz B. N.: J. Mol Catal, A; Chem. 2002,178,63.

10. Owsik L, Kolarz B. N.: Catal. Today 2004, 91—92,199.

11. Kolarz B. N., Jezierska J., Bartkowiak D., Gontarczyk A.: React. Polym. 1994, 23,53.

12. Jakubiak A., Owsik L, Kolarz B. N.: Ann. Pol. Chem. Soc. 2004, 3, 955.

13. Kolarz B. N., Jermakowicz-Bartkowiak D., Owsik L, Jezierska J.: React. Funct. Polym. 2004, 61,335.

14. Kolarz B. N., Jakubiak A.: w pracy zbiorowej „Modyfikacja polimerów" (red. Żuchowska D., Steller R.), Oficyna Wydawnicza Politechniki Wrocławskiej, Wrocław 2005, str. 81—84.

15. Ishtchenko V. V, Huddersman K. D., Vitkovskaya R. E: Appl Catal A: General 2003, 242,123.

16. Ishtchenko V. V., Vitkovskaya R. E, Huddersman K. D.: Appl Catal A: General 2003, 242, 221.

17. Kolarz B. N., Wojaczyńska M., Trochimczuk A.: Makromol. Chem. 1993,194,1299.

18. Jermakowicz-Bartkowiak D., Kolarz B. N., Tylus W.: Polymer 2003, 44, 5797.

19. Zhang B. W., Fischer K., Bieniek D., Kettrup A.: React. Polym. 1994, 24, 49.

20. Bunia L, Cascaval C. N., Rosu D., Ciobanu C., Popa M.: Polym. Degrad. Stab. 2000, 70,205.

21. Santa Maria L. C., Amorim M. C. V., Aguiar M. R. M. P. i współ.: React. Funct. Polym. 2001,49,133.

22. Pouchert C. J.: „The Aldrich Library of Infrared Spectra", Aldrich Chem. Corp. 1978.

23. Boca M., Naligura D., Linert W.: Tetrahedron 2000, 56,441.

24. Sucharda-Sobczyk A.: Prace Naukowe Instytutu Chemii Organicznej i Fizycznej Politechniki Wrocławskiej, Nr 21, Seria: Monografie 7, Wrocław 1981.

25. Kolarz B. N., Trochimczuk A., Wojaczyńska M. i współpr.: React. Polym. 1992,17,31.

26. Kolarz B. N., Bryjak J., Wojaczyńska M., Pawłów B.: Polymer 1996, 37,2445.

27. Boudakgy A., Jezierska J., Kolarz B. N.: Makromol. Chem. Macromol. Symp. 1992, 59,343.

28. Jakubiak A., Kolarz B. N., Jezierska J.: e-Polymer (przyjęto do druku).

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B. Kolarz kolarz@pwr.wroc.pl

Affiliation
Politechnika Wrocławska, Wydział Chemiczny, Wybrzeże Wyspiańskiego 27, 50-370 Wrocław

A. Jakubiak

J. Jezierska