Bio-based epoxy monomers from divanillyl alcohol were successfully synthesized and fully characterized. Diglycidylether of divanillyl alcohol (DiGEDVA), triglycidylether of divanillyl alcohol (TriGEDVA) and tetraglycidyl of divanillyl alcohol (TetraGEDVA) were cured with cyclo-aliphatic diamine (IPDA) a common diamine hardener. Main properties of these vanillin-based epoxy resins were determined by DSC, TGA, DMA, tensile tests and compared to DGEBA-based reference. These bio-based systems displayed phase transition Tα from 140 to 200 °C and exhibited thermal degradation comparable to the DGEBA-based network with high char residue. Such bio-based aromatic monomers are promising substitutes to the DGEBA and can be used in high performance epoxy resin applications as bio-based aromatic polyglycidylethers.
Bulk nitroxide-mediated polymerization (NMP) of bmyrcene (My)/glycidyl methacrylate (GMA) mixtures with varying GMA molar feed fraction (f GMA,0 5 0.10-0.91) was accomplished at 120 8C, initiated by SG1-based alkoxyamine bearing a N-succinimidyl ester group (NHS-BlocBuilder). Low dispersity My/GMA copolymers ( -D < 1.56) with slight number-average molecular weights (M n s) deviations from predicted values (M n,theo with M n /M n,theo > 70%) were obtained. The copolymerization was revealed to be statistical, confirmed via Fineman-Ross (r My 5 0.80 6 0.31 and r GMA 5 0.71 6 0.15) and Kelen-T€ ud€ os (r My 5 0.48 6 0.12 and r GMA 5 0.53 6 0.18) approaches. Glass transition temperature (T g ) of the statistical P(My-stat-GMA)s increased from 277 to 143 8C as the GMA molar fraction incorporated (F GMA ) increased from 0.10 to 0.90. High SG1 chain-end fidelity for My-rich and GMA-rich P(My-stat-GMA)s was assessed by phosphorus nuclear magnetic resonance ( 31 P NMR, SG1 fraction >69 mol %) and chain-extensions in toluene with My, GMA and styrene (S) (monomodal shift in M n ). Last, diblock P(My-b-GMA) was made and treated with morpholine to produce amphiphilic copolymer able to self-organize into micelles.
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