Novel full bio-based phloroglucinol benzoxazine resin: Synthesis, curing reaction and thermal stability. (18th June 2020)

• Record Type: Journal Article
• Authors: Zhan, Zuomin; Yan, Hongqiang; Wang, Huaqing; Cheng, Jie; Ran, Shiya; Fang, Zhengping
• Is Part Of: Polymer. Volume 200(2020)
• Publication Date: 2020-06-18
• Subjects: Full bio-based benzoxazine -- Synthesis -- Low-temperature curing performance -- Thermal stability; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; 547.7
• DOI: 10.1016/j.polymer.2020.122534
• Languages: English
• ISSNs: 0032-3861

Abstract

Abstract: The present work demonstrates an approach to develop full bio-based polybenzoxazines with excellent low-temperature curing performance. In order to achieve this goal, biomass-derived phloroglucinol (P) as phenol source, furfurylamine (FA) or P-aminobenzoic acid (PABA) as amine source and paraformaldehyde were selected to synthesize two novel full bio-based benzoxazine resin (3, 7, 11-tris(furan-2-ylmethyl)-3, 4, 7, 8, 11, 12-hexahydro-2H, 6H, 10H-benzol[1, 2-e:3, 4-e′:5, 6-e″]tris([1, 3]oxazine) (P-fa) and 4, 4′, 4″-(2H, 6H, 10H-benzo[1, 2-e:3, 4-e′:5, 6-e″]tris([1, 3]oxazine)-3, 7, 11(4H, 8H, 12H)-triyl)tribenzonic acid (P-paba)). Their structures and curing reactions had been characterized by Fourier transform infrared spectroscopy (FTIR), proton and carbon nuclear magnetic spectroscopy ( 1 H NMR and 13 C NMR) and differential scanning calorimetry (DSC). Compared with bisphenol A/aniline benzoxazine (BA-a), P-fa and P-paba monomers showed a different curing reaction process and excellent low temperature curing performance, especially P-paba monomer, whose exothermic peak was in a temperature range of 140–170 °C. The obtained full bio-based polybenzoxazines presented a low degradation rate (−3.58 wt%/min), high char yield (53.0%), low heat release capacity (37 J/g·K), and low total heat release (8.3 kJ/g). Meanwhile, P-paba monomer had an excellent promoting effect on the curing reaction of P-fa monomer. These findings have highly significant implications for the design of new full bio-based polybenzoxazines with excellent low-temperature curing performance and high residual char. Graphical abstract: Image 1 Highlights: Two novel full bio-based P-fa and P-paba have been successfully synthesized. P-fa and P-paba behave as excellent low-temperature curing bio-based benzoxazine resins with high char yield. P-paba monomer is a good accelerator and enables PHG-F-Boz monomer to cure completely below 200 °C.