In
this study, a fully biobased composite reinforced by cotton
fabrics was successfully fabricated by copolymerizing a bioderived
unsaturated polyester (PEOI) with a green diluent, dimethyl itaconate
(DI). The PEOI prepolymer was synthesized from itaconic acid (IA),
oxalic acid (OA), and ethylene glycol (EG) via a simple polycondensation
process and was characterized by Fourier transform infrared spectroscopy
(FTIR), nuclear magnetic resonance (NMR), and viscosity measurements.
Subsequently, the prepolymer was dissolved in DI to prepare a polymerizable
unsaturated polyester resin (UPE) with low viscosity, excellent reactivity
for free radical polymerization, and good compatibility with cotton
fibers. After being reinforced by cotton fabrics, the resulting composites
showed satisfactory material performance, including a strong tensile
strength at break of approximately 34 MPa, a glass transition temperature
(T
g) of approximately 108 °C, and
thermal decomposition temperatures (T
d5%) ranging from 224 to 276 °C. These green composites derived
from renewable resources are hopeful candidates for replacing petroleum-based
UPE resins, and the family of IA derivatives may play promising roles
in fabricating fully biobased composites.
To improve processability of benzoxazine monomer in preparation of composites, a water-slurry strategy was examined using several laboratory-scale instances. The water slurries were fabricated by mixing solid resin powder of 3-furfury-8-methoxy-3,4-dihydro-2H-1,3-benzoxazine with water and one type of filler particle, i.e., calcium carbonate, montmorillonite, or hollow glass beads. Experimental data show that approving liquidity can be achieved when more than 180 phr of water was mixed in the solid mixtures containing the resin powder and 100 phr of solid filler. The biobased composite prepared using the optimized condition exhibits outstanding mechanical properties and antifatigue performance as the composites prepared via solvent method. This water-slurry approach provides an environmentally friendly strategy to manuscript benzoxazine composites, offering benzoxazine with more promising applications in many industries such as building, wind energy, aircraft, and automobile.
Ring-opening polymerization of bifunctional benzoxazine has long been thought to produce a permanent network structure without reprocessing ability. Here, we demonstrate that surprising healability can be achieved by a controlled polymerization of an ortho-blocked bifunctional benzoxazine poly(oC-hda). The cured resin possesses a crosslinked structure, but can be deformed, remolded from crushed pieces or healed from mechanical damage. Based on a series of intensive experiments, we show that the healability can be explained by a dynamic bonding exchange mechanism between the phenoxy structures existing during the curing process. Moreover, we verify the possibility to heal the fatigue damaged poly(oC-hda) based composite to extend its service life. Our study provides another dynamic covalent bond to synthesize healable polymers, offering a broad platform for combining healability and desired thermosetting features together.
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