Thermally assisted self-healing behavior of anhydride modified polybenzoxazines based on transesterification

Abstract

A self-healing polybenzoxazine is synthesized solely based on dynamic ester bonds. For this purpose, an anhydride (succinic anhydride) was added into bisphenol F derived benzoxazine monomer before thermocuring. Owing to the transesterification of newly formed ester bonds, the thermoset network behaves as a thermoplastic at 140 °C in the presence of Zn (Ac)2, and shows self-healing properties even after multiple damage-healing cycles. Furthermore, kinetics study indicates that the transesterification is a first-order reaction and the activation energy is about 135.4 kJ/mol. This study proposes a facile and economical way to prepare self-healing polybenzoxazine. It has promising applications in coating, adhesive, and other smart materials that rely on structurally dynamic polymers.

Development of a Strong, Recyclable Poly(dimethylsiloxane) Elastomer with Autonomic Self‐Healing Capabilities and Fluorescence Response Properties at Room Temperature

“…[9][10][11] In general, self-healing polymers can be fabricated using two fundamental approaches, either the extrinsic method, which involves microencapsulation, [12][13][14] or the intrinsic method, which applies various dynamic chemistries. The intrinsic strategy is also suitable for the fabrication of recyclable polymers because these types of materials possess similar design principles based on reversible covalent bonds (e.g., the Diels-Alder reaction, [15][16][17][18] reversible disulfide bonding, [19][20][21] imine bonds, [22][23][24] dynamic hydrazone bonds, [25] dynamic boronic ester bonds, [26][27][28] transesterification reactions, [29][30][31] or olefin metathesis [32,33] ) and reversible noncovalent bonds (e.g., hydrogen-bonding interactions, [34][35][36][37] host-guest interactions, [38,39] and metalligand interactions [40][41][42] ). It is well known that the reversible formation and cleavage of dynamic bonds and the mobility of polymer chains govern the healing capacity and mechanical properties of intrinsic self-healing polymer composites.…”

A Self-Healing System Based on Ester Crosslinks for Carbon Black-Filled Rubber Compounds

“…These interactions include polar-polar linkages, hydrogen bonding and ionic crosslinks. Importantly, a transesterification reaction of the ester crosslinks can also occur through the aid of ZAD and a thermally annealing treatment [17,20,44]. Figure 7 illustrates a graphical mechanism of the exchangeable bonds of ester crosslinks to auto-repair the broken network in the vulcanizate matrix.…”

Eco-Friendly Sustainable Poly(benzoxazine-co-urethane) with Room-Temperature-Assisted Self-Healing Based on Supramolecular Interactions

“… 15 Xiangdong Liu et al developed self-healing polybenzoxazine using succinic anhydride and bisphenol-F benzoxazine through trans-esterification at a temperature of 140 °C in the presence of zinc acetate as a catalyst. 28 The reported polybenzoxazine materials with self-healing ability almost always involved multiple and nontrivial steps. To the best of our knowledge, to date, there has been no report on eco-friendly bio-based polybenzoxazines with self-healing or self-repairing ability in the literature.…”