Análise Térmica da Poliacrilonitrila Plastificada com Glicerol em Extrusora
Thermal Analysis of Extruded Polyacrylonitrile Plasticized by Glycerol
Junior, Carlos A. R. Brito; Fleming, Robson R.; Pardini, Luiz C.; Alves, Nilton P.
http://dx.doi.org/10.1590/S0104-14282012005000055
Polímeros: Ciência e Tecnologia, vol.22, n4, p.364-368, 2012
Resumo
Neste trabalho são apresentados resultados de análise térmica para poliacrilonitrila (PAN) plastificada com glicerina. Foram observados os efeitos da glicerina de alta pureza (glicerol) e demais aditivos à base de glicóis na fusão e degradação térmica da PAN pela técnica de DSC sob alta taxa de aquecimento (90 °C/min) e atmosfera inerte. Foi constatado que o glicerol reduziu a temperatura de fusão da PAN de 290 °C para 217 °C. Em uma etapa preliminar foi empregado o método de Kissinger para verificar o efeito da composição química da PAN sob sua degradação térmica. A energia de ativação aparente para o copolímero de PAN foi calculada em 149 kJ.mol–1. Sugeriu-se que a presença do comonômero acetato de vinila (AV) na composição química da PAN proporcionou menor entalpia de degradação (353 J.g–1) em comparação com outros comonômeros constituintes de uma PAN precursora de fibras de carbono (988 J.g–1).
Palavras-chave
Poliacrilonitrila, glicerina, análise térmica, método de Kissinger
Abstract
This paper presents results from thermal analysis of polyacrylonitrile (PAN) plasticized with glycerin, where effects from the high purity glycerin (glycerol) and other additives to glycol were studied. Using differential scanning calorimetry (DSC) at high heating rate (90 °C/min) and inert atmosphere, we observed a decrease in the melting temperature of PAN (from 290 °C to 217 °C) owing to the presence of glycerol. The Kissinger’s method was used to investigate the kinetics of thermal degradation for acrylonitrile (AN) with vinyl acetate (AV). The apparent activation energy for the copolymer AN/AV was calculated as 149 kJ.mol–1. The AV comonomer resulted in a lower degradation enthalpy for the copolymer AN/AV (353 J.g–1) compared with the comonomers comprising a precursor PAN for carbon fibers (988 J.g–1).
Keywords
Polyacrylonitrile, glycerin, thermal analysis, Kissinger’s method
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20. DeMaria, F. & Young, C. C. - “Process for melt spinning acrylonitrile polymer fiber using hot water as stretching aid”, US Patent 4303607 (1981).
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28. Yoon, H. S. et al. - “Unspun acrylic staple fibers”, US Patent 5589264, n.446, 287 (1996).
29. Smierciak, R. C.; Wardlow, J. E. & Ball, L. E. - “A process for making a high nitrile multipolymer prepared from acrylonitrile and olefinically unsaturated monomers”, WO Patent 1996/02/6968 (1996).
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35. Wu, G. P. - Polym. Bull., 62, p.667 (2009). http://dx.doi.org/10.1007/ s00289-009-0039-x
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39. Lee, J. S.; Hsu, C. K. & Chang, C. L. - Thermochim. Acta, 173, p.392 (1973).
40. Hou, C.; Qu, R.; Qun, W.; Ying, L. & Wang, C. - J. Appl. Polym. Sci., 98, p.1708 (2005). http://dx.doi.org/10.1002/app.22343
41. Ouyang, Q.; Cheng, L.; Wang, H. & Li, K. - Polym. Degrad. Stab., 93, p.1415 (2008). http://dx.doi.org/10.1016/j. polymdegradstab.2008.05.021
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43. Han, N.; Zhang, X.-X. & Wang, X-C. - Iran. Polym. J., 19, p.243 (2010).
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