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

Hamerton, I, McNamara, LT, Howlin, BJ, Smith, PA, Cross, P and Ward, S (2013) Examining the Initiation of the Polymerization Mechanism and Network Development in Aromatic Polybenzoxazines. Macromolecules, 46 (13). pp. 5117-5132.

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Abstract

Three bis-benzoxazine monomers based on the aniline derivatives of bisphenol A (BA-a), bisphenol F (BF-a), and 3,3'-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'-thiodiphenol (TDP) and 3,3'-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.

Item Type: Article
Divisions : Faculty of Engineering and Physical Sciences > Chemistry
Authors :
NameEmailORCID
Hamerton, IUNSPECIFIEDUNSPECIFIED
McNamara, LTUNSPECIFIEDUNSPECIFIED
Howlin, BJUNSPECIFIEDUNSPECIFIED
Smith, PAUNSPECIFIEDUNSPECIFIED
Cross, PUNSPECIFIEDUNSPECIFIED
Ward, SUNSPECIFIEDUNSPECIFIED
Date : 9 July 2013
Identification Number : 10.1021/ma401014h
Related URLs :
Depositing User : Symplectic Elements
Date Deposited : 01 May 2014 08:40
Last Modified : 31 Oct 2017 17:41
URI: http://epubs.surrey.ac.uk/id/eprint/804230

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