Departments of Materials Science and Engineering and Bioengineering, University of California, Berkeley, Berkeley, CA 9, 4720-1760, USA.
Department of Mechanical Engineering, University of California, Berkeley, USA.
Angew Chem Int Ed Engl. 2019 Aug 26;58(35):12271-12279. doi: 10.1002/anie.201906008. Epub 2019 Jul 24.
A synthetic strategy to incorporate catechol functional groups into benzoxazine thermoset monomers was developed, leading to a family of bioinspired small-molecule resins and main-chain polybenzoxazines derived from biologically available phenols. Lap-shear adhesive testing revealed a polybenzoxazine derivative with greater than 5 times improved shear strength on aluminum substrates compared to a widely studied commercial benzoxazine resin. Derivative synthesis identified the catechol moiety as an important design feature in the adhesive performance and curing behavior of this bioinspired thermoset. Favorable mechanical properties comparable to commercial resin were maintained, and glass transition temperature and char yield under nitrogen were improved. Blending of monomers with bioinspired main-chain polybenzoxazine derivatives provided formulations with enhanced shear adhesive strengths up to 16 MPa, while alloying with commercial core-shell particle-toughened epoxy resins led to shear strengths exceeding 20 MPa. These results highlight the utility of bioinspired design and the use of biomolecules in the preparation of high-performance thermoset resins and adhesives with potential utility in transportation and aerospace industries and applications in advanced composites synthesis.
开发了一种将儿茶酚官能团引入苯并恶嗪热固性单体中的合成策略，得到了一系列源自生物可利用酚类的仿生小分子树脂和主链型聚苯并恶嗪。搭接剪切胶接试验表明，与广泛研究的商业苯并恶嗪树脂相比，具有大于 5 倍改善的铝基剪切强度的聚苯并恶嗪衍生物。衍生物合成确定儿茶酚部分是这种仿生热固性在胶接性能和固化行为中的重要设计特征。保持了与商业树脂相当的有利机械性能，并且氮气下的玻璃化转变温度和产炭率得到了提高。将单体与仿生主链型聚苯并恶嗪衍生物共混提供了具有增强的剪切胶接强度高达 16 MPa 的配方，而与商业核壳粒子增韧环氧树脂合金化则导致剪切强度超过 20 MPa。这些结果突出了仿生设计和生物分子在制备高性能热固性树脂和胶黏剂方面的实用性，这些树脂和胶黏剂在运输和航空航天工业以及先进复合材料合成中的应用具有潜在的用途。
