Polímeros: Ciência e Tecnologia
Polímeros: Ciência e Tecnologia
Scientific & Technical Article

Synthesis and photostabilizing performance of a polymeric HALS based on 1,2,2,6,6-pentamethylpiperidine and vinyl acetate

Chinelatto, Marcelo Aparecido; Agnelli, José Augusto M.; Canevarolo, Sebastião V.

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Polymeric hindered amine light stabilizers (polymeric HALS) have been extensively studied because they combine a high ability to protect the polymers against harmful effects of weathering with minimum physical loss. In this study a new polymeric N-methylated HALS was synthesized by the radical copolymerization of a cyclic tertiary amine with vinyl acetate (VAc). 4-Acryloyloxy-1,2,2,6,6-pentamethylpiperidine (APP), the cyclic tertiary amine, was prepared by the initial conversion of 2,2,6,6-tetramethyl-4-piperidinol derivatives via two different routes. The APP/VAc copolymer synthesized was characterized by size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR) and carbon-13 nuclear magnetic resonance (13C NMR). The photostabilizing performance, particularly the induction period of polypropylene (PP) films containing different concentrations of APP/VAc copolymer, when exposed to accelerated aging, was comparable to that of PP films compounded with commercial polymeric HALS.


degradation, HALS, hindered amines, photo-oxidation, photostabilizer.


1. Andrady, A. L., Hamid, S. H., Hu, X., & Torikai, A. (1998). Effects of increased solar ultraviolet radiation on materials. Journal of Photochemistry and Photobiology. B, Biology, 46(1-3), 96-103. http://dx.doi.org/10.1016/S1011-1344(98)00188-2. PMid:9894353.

2. Feldman, D. (2002). Polymer weathering: photo-oxidation. Journal of Polymers and the Environment, 10(4), 163-173. http://dx.doi.org/10.1023/A:1021148205366.

3. Rabek, J. F. (1995). Polymer photodegradation: mechanisms and experimental methods. London: Chapman & Hall.

4. Ammala, A., Bateman, S., Dean, K., Petinakis, E., Sangwan, P., Wong, S., Yuan, Q., Yu, L., Patrick, C., & Leong, K. H. (2011). An overview of degradable and biodegradable polyolefins. Progress in Polymer Science, 36(8), 1015-1049. http://dx.doi.org/10.1016/j.progpolymsci.2010.12.002.

5. Cáceres, C. A., Zborowski, L., & Canevarolo, S. V. (2011). Thermo-mechanical degradation and voc emission of unstabilized and stabilized polypropylene copolymer during multiple extrusion. Materials Research, 14(4), 569-575. http://dx.doi.org/10.1590/S1516-14392011005000081.

6. Minagawa, M. (1989). New developments in polymer stabilization. Polymer Degradation & Stability, 25(2-4), 121-141. http://dx.doi.org/10.1016/S0141-3910(89)81004-3.

7. Smoliak, L. Y., & Prokopchuk, N. R. (2003). Estimation of parameters that correlate molecular structure of hindered amines with their stabilizing efficiency. Polymer Degradation & Stability, 82(2), 169-172. http://dx.doi.org/10.1016/S0141-3910(03)00180-0.

8. Malík, J., Hrivík, A., & Alexyová, D. (1992). Physical loss of hindered amine light stabilizers from polyethylene. Polymer Degradation & Stability, 35(2), 125-130. http://dx.doi.org/10.1016/0141-3910(92)90103-C.

9. Pan, J. (2001). Synthesis and characterization of new stabilizers with optimal molecular weight. Chinese Journal of Polymer Science, 19(4), 341-350.

10. Jiangqing, P., Cheng, W., Song, Y., & Hu, X. (1993). Preparation and characterization of new copolymers containing hindered amine. Polymer Degradation & Stability, 39(1), 85-91. http://dx.doi.org/10.1016/0141-3910(93)90128-6.

11. Sun, G. J., Jang, H. J., Kaang, S., & Chae, K. H. (2002). A new polymeric hals: preparation of an addition polymer of dgeba-hals and its photostabilizing effect. Polymer, 43(22), 5855-5863. http://dx.doi.org/10.1016/S0032-3861(02)00514-1.

12. Wang, H., & Chen, W. (2006). Radiation-induced grafting of binary monomers containing hals onto polymers. Radiation Physics and Chemistry, 75(1), 138-148. http://dx.doi.org/10.1016/j.radphyschem.2005.04.022.

13. Wang, H. (2005). Radiation-induced grafting of pentamethyl hindered amine light stabilizer 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate onto polypropylene. Journal of Applied Polymer Science, 98(5), 2157-2164. http://dx.doi.org/10.1002/app.22388.

14. Cicogna, F., Coiai, S., Passaglia, E., Tucci, I., Ricci, L., Ciardelli, F., & Batistini, A. (2011). Grafting of functional nitroxyl free radicals to polyolefins as a tool to postreactor modification of polyethylene-based materials with control of macromolecular architecture. Journal of Polymer Science. Part A, Polymer Chemistry, 49(3), 781-795. http://dx.doi.org/10.1002/pola.24493.

15. Kaci, M., Touati, N., Setnescu, R., Zaharescu, T., Setnescu, T., & Jipa, S. (2005). Grafting of hindered amine stabilizer in poly(propylene) films under γ-irradiation. Macromolecular Materials and Engineering, 290(8), 802-808. http://dx.doi.org/10.1002/mame.200500096.

16. Singh, R. P., Patwa, A. N., Desai, S. M., Pandey, J. K., Solanky, S. S., & Vishwa Prasad, A. (2003). Synthesis of new polymeric hindered amine light stabilizers: performance evaluation in styrenic polymers. Journal of Applied Polymer Science, 90(4), 1126-1138. http://dx.doi.org/10.1002/app.12672.

17. Yang, H., & Lü, Q. (1997). Copolymerization of propylene with hindered piperidine monomer over a high activity supported ziegler-natta catalyst. Chinese Journal of Polymer Science, 15(2), 146-153.

18. Wilén, C. E., Auer, M., Strandén, J., Näsman, J. H., Rotzinger, B., Steinmann, A., King, R. E., Zweifel, H., & Drewes, R. (2000). (20002). Synthesis of novel hindered amine ligh stabilizers (hals) and their copolymerization with ethylene or propylene over both soluble and supported metallocene catalyst systems. Macromolecules, 33(14), 5011-5026. http://dx.doi.org/10.1021/ma0000780.

19. Auer, M., Nicolas, R., Vesterinen, A., Luttikhedde, H., & Wilén, C. E. (2004). Facile synthetic route to polymerizable hindered amine light stabilizers for transition-metal-catalyzed olefin copolymerization. Journal of Polymer Science. Part A, Polymer Chemistry, 42(6), 1350-1355. http://dx.doi.org/10.1002/pola.11082.

20. Chinelatto, M. A., Agnelli, J. A. M., & Canevarolo, S. V. (2014). Synthesis and characterization of copolymers from hindered amines and vinyl monomers. Polímeros, 24(1), 30-36. http://dx.doi.org/10.4322/polimeros.2014.046.

21. Gugumus, F. (1991). Mechanisms and kinetics of photostabilization of polyolefins with n-methylated hals. Polymer Degradation & Stability, 34(1-3), 205-241. http://dx.doi.org/10.1016/0141-3910(91)90120-G.

22. Gugumus, F. (1993). Current trends in mode of action of hindered amine light stabilizers. Polymer Degradation & Stability, 40(2), 167-215. http://dx.doi.org/10.1016/0141-3910(93)90208-Z.

23. Kurumada, T., Ohsawa, H., Oda, O., Fujita, T., Toda, T., & Yoshioka, T. (1985). Photostabilizing activity of tertiary hindered amines. Journal of Polymer Science: Polymer Chemistry Edition, 23(5), 1477-1491. http://dx.doi.org/10.1002/pol.1985.170230520.

24. Gijsman, P. (2010). Photostabilization of polymer materials. In N. S. Allen (Ed.), Photochemistry and photophysics of polymer materials (pp. 627-679). New Jersey: John Wiley & Sons.

25. Pospíšil, J., Pilař, J., & Nešpůrek, S. (2007). Exploitation of the complex chemistry of hindered amine stabilizers in effective plastics stabilization. Journal of Vinyl and Additive Technology, 13(3), 119-132. http://dx.doi.org/10.1002/vnl.20113.

26. Al-Malaika, S., Scott, G., & Wirjosentono, B. (1993). Mechanisms of antioxidant action: polymer-bound hindered amines by reactive processing, part III effect of reactive antioxidant structure. Polymer Degradation & Stability, 40(2), 233-238. http://dx.doi.org/10.1016/0141-3910(93)90210-A.

27. Al-Malaika, S., Ibrahim, A. Q., & Scott, G. (1988). Mechanisms of antioxidant action: photo-antioxidant activity of polymer-bound hindered amines. part I-bismaleate esters. Polymer Degradation & Stability, 22(3), 233-239. http://dx.doi.org/10.1016/0141-3910(88)90013-4.

28. Pan, J., Yang, Z., Zhang, T., Lau, W. W. Y., & Lee, C. S. (1994). A comparative study of monomer, homopolymer and copolymer hals. Polymer Degradation & Stability, 44(1), 85-91. http://dx.doi.org/10.1016/0141-3910(94)90037-X.

29. Gijsman, P., Smelt, H. J., & Schumann, D. (2010). Hindered amine light stabilizers: an alternative for radiation cross-linked uhmwpe implants. Biomaterials, 31(26), 6685-6691. http://dx.doi.org/10.1016/j.biomaterials.2010.05.053. PMid:20619782.

30. Gugumus, F. (2000). Aspects of the impact of stabilizer mass on performance in polymers 2. Effect of increasing molecular mass of polymeric HALS in pp. Polymer Degradation & Stability, 67(2), 299-311. http://dx.doi.org/10.1016/S0141-3910(99)00131-7.

31. Philippart, J. L., Sinturel, C., & Gardette, J. L. (1997). Influence of light intensity on the photooxidation of polypropylene. Polymer Degradation & Stability, 58(3), 261-268. http://dx.doi.org/10.1016/S0141-3910(97)00056-6.
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