Design of High-Performance Polybenzoxazines with Tunable Extended Networks Based on Resveratrol and Allyl Functional Benzoxazine

Abstract

A novel resveratrol-based bio-benzoxazine monomer (RES-al) containing an allyl group has been synthesized using resveratrol, allylamine, and paraformaldehyde via Mannich condensation reaction, and its chemical structures have been characterized by FT-IR spectroscopy and NMR techniques. The polymerization behavior of this benzoxazine resin has been investigated using in situ FT-IR and differential scanning calorimeter (DSC) measurements, and the thermal-mechanical properties of its corresponding polybenzoxazines are evaluated by DMA and TGA. We show that by controlling the curing process of the oxazine ring, the C=C bond in resveratrol, and the allyl group in RES-al, the cross-linking network of the polybenzoxazine can be manipulated, giving rise to tunable performance of thermosets. As all curable functionalities in RES-al are polymerized, the resulted polybenzoxazine exhibits a good thermal stability with a Tg temperature of 313 °C, a Td5 value of 352 °C, and char yield of 53% at 800 °C under N2.

Nanoporous Polybenzoxazine Aerogels for Thermally Insulating and Self-Extinguishing Materials in Aerospace Applications

“…The cold surface temperature of the sample above was only 36. 4 °C when the hot surface temperature was approximately 65.8 °C with heating for 400 s. In addition, excellent machinability into easily formed, uniquely shaped samples was also observed for PBO-AH. We demonstrated that PBO aerogels could be potential candidates for thermal protection materials in the space vehicle domain due to their excellent properties, including flame retardancy and thermal insulation in energy conservation.…”

“…Polybenzoxazine (PBO) is a new type of functional resin. − It has emerged as a thermal protection material in aerospace and has been favored by researchers because of its high charring yield and machinability, − showing potential ablative characteristics, superior mechanical strength, and resistance to high temperatures even in an oxygen atmosphere. However, PBO material exhibits a relatively high density and thermal conductivity due to the densified structure of the thermosetting PBO resin.…”

Investigation of thermal and mechanical properties of polybenzoxazine obtained in an in situ polymerization with surface‐modified montmorillonite clay

“…[21] Yunliang Xing et al described the synthesis and characteristics of a thermally stable polymer obtained from resveratrol, allyl amine and paraformaldehyde. [22] Ka Zeng et al studied the effect of pressure on curing benzoxazine monomer synthesized using aniline/ t-butyl amine with bisphenol-A and reported the decrease in thermal stability at high temperature curing. [23] Shvai Zhang et al prepared a nano composite using polybenzoxazine and modified graphene with trichlorophenylsilane that displays higher electromagnetic interference shielding property.…”

Highly Thermally Stable, Reversible, and Flexible Main Chain Type Benzoxazine Hybrid Incorporating Both Polydimethylsiloxane and Double‐Decker Shaped Polyhedral Silsesquioxane Units through Diels–Alder Reaction

“…Nevertheless, BZ resin has limited applicability at high temperature since C-N-C bond of molecule with no cross-links is readily broken at temperature >260 °C. [9] Attempts have been made to decrease chain mobility of BZ resin to improve its thermal and mechanical properties by incorporating unsaturated (such as allyl or alkynyl) groups, blending with high-performance polymers to form miscible blends, [10][11][12][13][14][15][16] and adding inorganic nanoparticles. [17][18][19][20][21][22] Many organic/inorganic polybenzoxazine (PBZ) hybrids (and other thermosetting resins) have been prepared by incorporating carbon-based materials (e.g., carbon nanotubes, [23][24][25] carbon black, [26] and graphene [27][28][29][30] ) and siliconbased materials [e.g., polydimethylsiloxane (PDMS), [5,[31][32][33] organic modified clay, [34,35] and polyhedral oligomeric silsesquioxane (POSS) [17][18][19][20][21][22][36][37][38][39][40] ].…”

“…Nevertheless, BZ resin has limited applicability at high temperature since C–N–C bond of molecule with no cross‐links is readily broken at temperature >260 °C. [ 9 ] Attempts have been made to decrease chain mobility of BZ resin to improve its thermal and mechanical properties by incorporating unsaturated (such as allyl or alkynyl) groups, blending with high‐performance polymers to form miscible blends, [ 10–16 ] and adding inorganic nanoparticles. [ 17–22 ]…”