Biobased polybenzoxazines incorporate
natural phenolic structures
to produce polymers with near-zero shrinkage, high char yields, and
high chemical and thermal resistances, garnering great interest as
sustainable high-performance polymers. Herein, difunctional and trifunctional
benzoxazine monomers, bisguaiacol-furfurylamine (BG-f) and triguaiacol-furfurylamine
(TG-f), respectively, were synthesized from renewable guaiacol, vanillin,
and furfurylamine using solventless procedures. Benzoxazines were
blended with varying weights of epoxy resin and thermally cured to
produce benzoxazine-epoxy (BG-f-E and TG-f-E) polymers. These polymers
displayed glass transition temperatures ranging from 130 to 157 °C
(peak of the loss modulus), thermal stabilities from 299 to 329 °C
in both N2 and air, and char yields ranging from 35% to
58%. BG-f-E and TG-f-E with greater benzoxazine content produced stiffer
materials exhibiting glassy storage moduli values upward of 3.48 and
3.69 GPa, respectively. BG-f-E polymers displayed higher molecular
weight between cross-link values (646 g mol–1 to
981 g mol–1) compared to TG-f-E polymers (316 g
mol–1 to 465 g mol–1) and exhibited
fracture energies upward of 404 J m–2. These investigations
demonstrate the utility of incorporating biobased benzoxazines into
benzoxazine-epoxy resin formulations to design sustainable polybenzoxazines
with tunable thermal and mechanical properties for high-performance
polymer applications.
The development of operationally simple and cost-effective methods for CC bond formation reactions are highly important in pharmaceutical, agrochemical and material research. In this article we describe the first copper-catalyzed cross-coupling reaction of thioamides with acceptor/acceptor-substituted and acceptor-only substituted α-diazocarbonyl compounds to yield enaminones. The reaction shows broad substrate scope in terms of thioamides and diazocarbonyl compounds. Primary, secondary and tertiary thioamides all give enanminones when reacted with α-diazodiesters, α-diazoketoesters, α-diazodiketones, α-diazoketoamides, α-diazoesteramides, αdiazoketosulfones and α-diazomonoketones.
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