New benzoxazines containing polyhedral oligomeric silsesquioxane from eugenol, guaiacol and vanillin

Abstract

Polybenzoxazine-tethered polyhedral oligomeric silsesquioxane nanocomposites with well-defined architecture were prepared by the reaction of bio-phenols: eugenol, guaiacol, vanillin; poss-octaamine with paraformaldehyde. FT-IR measurements evidenced the 10 occurrence of Mannich reaction between phenolic group of bio-phenols and amino group of POSS molecule, with the consequent formation of a heterocyclic benzoxazine ring binding POSS in its backbone. Their chemical structures were proved by 1 H and 13 C-NMR analysis. Thermo-mechanical properties and thermal stability of the POSS-polybenzoxazine hybrid networks were determined by DSC, DMA and TGA. SEM, EDX, AFM and TEM micrographs show that POSS-Pbz nanocomposites exhibit featureless morphologies with no discernible phase separation, suggesting that the POSS nanoparticles are dispersed homogeneously throughout the matrix. The 15 homogeneity of these networks with octafunctional POSS is also indicated by their moduli in the range of 2.63 to 2.91 GPa. Moreover, their dielectric values [both dielectric constant (1.85) and dielectric loss (0.28)] and moisture absorption values are very low (<0.01%) which makes them suitable materials for use in microelectronics packaging.

Biobased Benzoxazine Derived from Daidzein and Furfurylamine: Microwave‐Assisted Synthesis and Thermal Properties Investigation

“…[15] Up to now,alarge quantity of biobased benzoxazines have already been prepared from the renewable cardanol, [16,17] diphenolic acid, [18,19] phloretic acid, [20] furfurylamine, [21,22] stearylamine, [23] coumarin, [24,25] umbelliferone, [26] and more recently the lignin derivatives (guaiacol, [27][28][29][30] vanillin, [31][32][33] and eugenol [34][35][36][37][38] ). [15] Up to now,alarge quantity of biobased benzoxazines have already been prepared from the renewable cardanol, [16,17] diphenolic acid, [18,19] phloretic acid, [20] furfurylamine, [21,22] stearylamine, [23] coumarin, [24,25] umbelliferone, [26] and more recently the lignin derivatives (guaiacol, [27][28][29][30] vanillin, [31][32][33] and eugenol [34][35][36]…”

“…In recent years,w ith the rapid development of biobasedm aterials,u sing renewable phenolic or amine derivatives to replace the petroleum-based raw materials for the synthesis of benzoxazine monomers has attracted considerable attention. [15] Up to now,alarge quantity of biobased benzoxazines have already been prepared from the renewable cardanol, [16,17] diphenolic acid, [18,19] phloretic acid, [20] furfurylamine, [21,22] stearylamine, [23] coumarin, [24,25] umbelliferone, [26] and more recently the lignin derivatives (guaiacol, [27][28][29][30] vanillin, [31][32][33] and eugenol [34][35][36][37][38] ). Similar to the petroleum-based polybenzoxazines, mosto f these biobased benzoxazinesa lso suffer from the same drawbacks (low crosslink density and high brittleness).…”

Functional Silica and Carbon Nanocomposites Based on Polybenzoxazines

“…Thus, this OBZ-POSS displayed a higher value of T g and a higher char yield than those of P-pa and BA-m, respectively. Muthusamy et al [66] synthesized three kinds of PBZ-tethered POSS derivatives through Mannich reactions of the bio-phenols eugenol (E), guaiacol (G), and vanillin (V) with octa(aminophenyl)silsesquioxane and formaldehyde to afford POSS-EBzo, POSS-GBzo, and POSS-VBzo, respectively. They used DMA to investigate the viscoelastic properties of these three POSS-PBZ nanocomposites.…”

Synthesis and characterization of bio‐based benzoxazines derived from thymol

“…However, petroleum‐based phenolics are nonrenewable resources and scarcity of these materials has heightened the need for novel benzoxazines that can be developed and commercialized to reduce the widespread dependence on fossil fuels . Recently, several naturally occurring phenolic compounds have been used for the synthesis of bio‐benzoxazines including cardanol, guiacol, urushiol, eugenol, vanillin, cardbisphenol, resorcinol, arbutin, lignin, chavicol, coumarin, rosin, and chalcone . These types of phenolic compounds are plant‐derived and widely found in variety of plants.…”