A novel strategy to obtain sulfur-rich polybenzoxazine copolymers by reacting allyl functional benzoxazine (BA-ala) and elemental sulfur was described. Simultaneous inverse vulcanization and ring-opening reactions of benzoxazine generated soluble copolymers in specific feed ratios. Parameters such as monomer structure and feed ratios on the polymerization were studied. The thermal stability of the copolymers was investigated and compared to that of polybenzoxazines derived from neat BA-ala by using thermogravimetric analysis and differential scanning calorimetry. The surface properties of the materials as examined by scanning electron microscopy confirmed that elemental sulfur and benzoxazine copolymers can be produced without a phase separation at the micrometer level. Moreover, a sponge-like insoluble macroporous polybenzoxazine networks was obtained at the 20 wt % feed ratio of sulfur.
In this work, a recycling and self-healing strategy for polybenzoxazines through both S-S bond cleavage-reformation reaction and supramolecular attractions is described. Both recyclable and selfhealable polybenzoxazines can be prepared from low cost chemicals with a simple procedure in only 30 minutes. For this purpose, inverse vulcanization of poly(propylene oxide)benzoxazine (PPOB) and diallybenzoxazine (B-al) with elemental sulfur was performed at 185 °C. The obtained cross-linked polymer films exhibited thermally driven recycling ability up to 5 cycles. Moreover, the self-healing ability of a test specimen was shown. Spectral characterizations, thermal stability and fracture toughness of the films were investigated after each recycling.In the past few decades, polybenzoxazines (PBZs), also known as benzoxazine resins, emerged as a superior alternative to classical resol and novolac type phenolic resins. The main structural difference of PBZs from classical phenolics is the tertiary amine groups in each repeating unit, which generates immense effect especially on hydrogen bonding types and strength. Due to these unique structural characteristics, PBZs exhibit high tensile strength and modulus (100-125 MPa, and 3.8-4.5 GPa, respectively), and high glass transition temperatures (T g ) (170-340 °C). Accordingly, these materials, particularly rigid ones or those admixed with transition metals, have high service temperatures, char yields, and are stable under acidic/alkali conditions. Unlike the general nature of phenolics, PBZs have low water adsorption stemming from strong intra-molecular hydrogen bonding. Another important aspect is related to their dimensional stability during synthesis. These resins are obtained by ring-opening polymerization of benzoxazine monomers at temperatures between 160-250 °C, sometimes higher, without any additive (Scheme 1) [1][2][3][4][5][6] . It should be emphasized that 1,3-isomers are the only active benzoxazines to undergo such polymerization. According to mechanistic studies, polymerization proceeds via the cationic pathway as oxazine rings have N and O atoms, which are capable of stabilizing cations during polymerization 7-9 .The other appealing side of PBZs is the synthesis of corresponding benzoxazine monomers, which can be accomplished using any suitable phenol, a primary amine, and formaldehyde; therefore, the number of possible benzoxazines is large (Fig. 1) [10][11][12][13][14][15][16] . Apparently, this design flexibility brings about a huge molecular diversity and control of structure and properties of PBZs. For example, crosslinking density of the resins can be increased by introducing dimerizable or polymerizable functionalities on benzoxazines 17,18 . The toughness of PBZs can be manipulated by using long chain amines and other soft or conversely rigid groups [19][20][21][22] . Gas forming moieties can be attached to benzoxazines causing macroporosity to occur during curing; thus, sponge-like materials can be obtained, etc 23,24 . Such suppleness in the properties ...
A self-healing strategy for poly(propylene oxide)s bearing benzoxazine units (PPO-Benz) through supramolecular attractions is described. Poly(propylene oxide) bisamine (PPO) with a molecular wieght of 2000 Da was reacted with formaldehyde and bisphenol A to yield desired PPO-Benz with 12 360 Da. The cross-linked polymer films were then prepared by solvent casting of suitable compositions of PPO-Benz and carboxlic acid containing benzoxazine monomer (Carb-Benz) in chloroform followed by thermal ring-opening reaction of benzoxazine groups at 200 °C. Thermal curing and thermal stability of the film and final products were investigated. It was demonstrated that the self-healing capacity of the films was improved by employing Carb-Benz in the formulation.
A novel approach is reported for self-healing of polybenzoxazine thermosets based on both supramolecular attractions and metal–ligand interactions. The relating smart material was synthesized by using bis(3-aminopropyl)-terminated polydimethylsiloxane, formaldehyde, and bisphenol A. The films of the obtained main-chain polybenzoxazine precursor (Poly(Si-Bz)) containing 2% FeCl3 were prepared and cured at low temperatures (100–120 °C). The structures of the precursors and final products were characterized by spectral analysis. The curing and thermal stability of the related materials were investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Self-healing efficiency was studied by stress–strain measurements. Potential shape recovery (SR) behavior was also demonstrated by preparing curled or spiral fixed shapes, and the transformation of temporary shapes to these fixed shapes was verified.
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