Examining the Initiation of the Polymerization Mechanism and Network Development in Aromatic Polybenzoxazines

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• 作者：Ian Hamerton ; Lisa T. McNamara ; Brendan J. Howlin ; Paul A. Smith ; Paul Cross ; Steven Ward
• 刊名：Macromolecules
• 出版年：2013
• 出版时间：July 9, 2013
• 年：2013
• 卷：46
• 期：13
• 页码：5117-5132
• 全文大小：727K
• 年卷期：v.46,no.13(July 9, 2013)
• ISSN：1520-5835

文摘

Three bis-benzoxazine monomers based on the aniline derivatives of bisphenol A (BA-a), bisphenol F (BF-a), and 3,3鈥?thiodiphenol (BT-a) are examined using a variety of spectroscopic, chromatographic, and thermomechanical techniques. The effect on the polymerization of the monomers is compared using two common compounds, 3,3鈥?thiodiphenol (TDP) and 3,3鈥?thiodipropionic acid (TDA), at a variety of loadings. It is found that the diacid has a greater effect on reducing the onset of polymerization and increasing cross-link density and T_g for a given benzoxazine. However, the addition of >5 wt % of the diacid had a detrimental effect on the cross-link density, T_g, and thermal stability of the polymer. The kinetics of the polymerization of BA-a were found to be well described using an autocatalytic model for which values of n = 1.64 and m = 2.31 were obtained for the early and later stages of reaction (activation energy = 81 kJ/mol). Following recrystallization the same monomer yielded values n = 1.89, m = 0.89, and E_a = 94 kJ/mol (confirming the influence of higher oligomers on reactivity). The choice of additive (in particular the magnitude of its pK_a) appears to influence the nature of the network formation from a linear toward a more clusterlike growth mechanism.