Smart chemical design incorporating umbelliferone as natural renewable resource toward the preparation of thermally stable thermosets materials based on benzoxazine chemistry

Abstract

A smart synthetic chemical design incorporating a natural renewable resource, umbelliferone, is presented to synthesize thermoset materials with good thermal properties.

Tailor-made and chemically designed synthesis of coumarin-containing benzoxazines and their reactivity study toward their thermosets

“…Having this motivation, the present work aims to uncover the contribution of each substituent on coumarin‐based benzoxazines and correlate them to the thermal properties. This article supplements our earlier report on the synthesis and characterization of a coumarin‐functional benzoxazine monomer and its cross‐linked material …”

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]…”

High‐Performance Bio‐Based Benzoxazines from Enzymatic Synthesis of Diphenols

“…Although the synthesis of 1,3‐benzoxazine monomers was first reported in 1944 by Holly and Cope, benzoxazine resins only enter the field of thermosetting materials in the 90s thanks to Ning and Ishida who popularized their synthesis by a solventless process . These resins present a combination of properties such as high thermal stability, mechanical strength, low flammability, low water absorption, and high chemical resistance that make them of high interest for the preparation of high‐performance materials and it is worth highlighting that they appear as one of the rare new polymers which have undergone commercialization in the last decades . Overall, the attractiveness of benzoxazine resins probably lies on two main additional features: the great flexibility of monomer molecular design and related chemical functionality and the great versatility of their synthetic process though in the industry, only the manufacture in solvent is considered at the present time.…”

“…As benzoxazine precursors are readily synthesized by a Mannich‐like condensation of an amine, a phenol, and formaldehyde, both the diverse and large number of phenolic derivatives and amine derivatives commercially available allows the preparation of a very wide range of monomers, which can be used in order to tailor or reach specific properties . The number of newly synthesized monomers is thus constantly increasing with a particular interest for those based on renewable or sustainable organic materials as the development of environmentally compatible and sustainable polymers is one of the current challenges in polymer science …”

“…As aromatic compounds including phenolic derivates are the second most abundant class of organic compounds in nature representing about 25% of the earth's biomass, quite a large number of renewable phenol derivatives have been tested in recent years to synthesize benzoxazine precursors such as diphenolic acid, cardanol, vanillin, eugenol, chavicol, guaiacol, “lignin‐like” naturally occurring phenolic compounds (coumaric acid, ferulic acid, and phloretic acid), umbelliferone, arbutin, urushiol, catechol, etc. A special interest is focused on difunctional benzoxazine structure because it leads to cross‐linking.…”