ArticlePolymers2026
Structure-Property Relationships of Aryl Ether Diamine-Based Benzoxazines: Role of Aromatic Substitution and Molecular Weight Between Crosslinks.
Article in Polymers, 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
A systematic evaluation of meta-substitution and backbone molecular weight in diamine-based benzoxazines was conducted to investigate the impact on melt processability, network development, and the structure-property relationships in polybenzoxazines. Six benzoxazine monomers derived from aryl ether diamines were synthesized, with controlled levels of meta-substitution and varying numbers of ether-bridged phenyl rings in the monomer backbone. Meta-substitution was found to suppress crystallinity in high-purity benzoxazine monomers and lower onsets of polymerization were observed due to meta-positioning of the terminal diamine rings. Terminal diamine meta-substitution also led to higher polymerization enthalpies, attributed to the emergence of an additional polymerization mechanism that increased the glass transition temperature up to 60 °C and delayed the onset of mass loss degradation. Benzoxazines with glass transition temperatures approaching 200 °C are susceptible to Mannich bridge degradation during polymerization, and this additional polymerization pathway both illustrates the nuanced complexities of benzoxazine structure-property relationships as well as provides a potential design strategy for benzoxazines with high glass transition temperatures approaching 250 °C.
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