Biobased Bisbenzoxazine Resins Derived from Natural Renewable Monophenols and Diamine: Synthesis and Property Investigations

Abstract

Synthesizing biobased thermosetting resins with unique performance from renewable resources has attracted increasing attention because of the sustainable development aspirations from human beings. However, diamine-derived bio-bisbenzoxazine resins have rarely been reported because of the lack of naturally sourced diamines in nature. Here, we report a series of biobased bisbenzoxazine resins via green synthetic methods using various monophenols (guaiacol/sesamol/peterostilbene) and a diamine (Priamine 1074) as natural renewable raw materials. Chemical structural details of these bisbenzoxazines were characterized by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and size exclusion chromatography. Thermally activated polymerization behaviors were investigated by differential scanning calorimetry thermograms and in situ FT-IR analysis. Besides, surface properties of each resin were studied through the contact angle measurement, and surface-free-energy values without varying too much were achieved from this series of Priamine 1074-derived bioresin coatings before and after different polymerization cycles. Moreover, thermal stability of the fully polymerized bioresins was evaluated by dynamic mechanical analysis and thermogravimetry analyses. These bio-polybenzoxazines all showed good thermal properties with T d10 greater than 350 °C. Consequently, this new family of biobased bisbenzoxazine thermosetting resins and their corresponding polybenzoxazines exhibit outstanding surface and thermal performances, providing great potential applications for high-performance polymeric coating materials.

Facile and eco-friendly synthesis of hydrogen bonding-rich bio-based bisbenzoxazine resins with low surface free energy, strong adhesion strength and high thermal stability

“…Therefore, all the hydrogen bonding-rich bio-polybenzoxazine coatings exhibit low surface free energy values after curing, which are even much lower than those of our recently reported Priamine 1074 bio-based benzoxazine resins. 73…”

“…78 Poly(DcTa-fa) showed a very low degradation rate before 300 °C (0.082%/°C), which indicates the presence of degradation for the relatively small molecular chain ends and branches as compared to other recently reported high performance polybenzoxazines (both higher than 0.1%/°C). 73,79 As the temperature increased to 350 °C, poly(DcTa-sa) and poly(DcTa-da) showed a rapidly increasing degradation rate which may be owing to the evaporation of stearylamine, dehydroabietylamine and their derivatives. The whole degradation process of poly(DcTa-da) seemed more homogeneous, while it showed a lower degradation temperature for its main degradation stage, which can be owing to the unstable Mannich bridge in poly(DcTa-da).…”

Bio-Based Reprocessable and Degradable Epoxy Resins via Inverse Vulcanization

“…Eugenol is a natural phenolic compound from clove oil. Its unique chemical structure allows versatile modifications for fabricating high-performance materials such as low-dielectric materials, oil absorbents, fertilizer coating materials, etc. − Polymerization between eugenol allyl ether with sulfur was reported to produce polysulfide polymers for Li–S batteries . Here, an epoxy resin, eugenol glycidyl ether (EGE, Scheme ), is prepared from eugenol and polymerized with sulfur.…”

Solvent-free Synthesis of Alkynyl-Based Biobased Benzoxazine Resins with Excellent Heat Resistance

“…Benefiting from the broadness of synthetic raw materials, benzoxazine has unique advantages in the molecular structure and resin performance regulation. It has a wide range of applications in advanced industrial fields such as aerospace and electronic information. , In recent years, researchers have done a lot of work on the green preparation of benzoxazine resin, − but there are still some challenges in achieving high performance and greenization of benzoxazine resin.…”