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Title: Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives

Abstract

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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of California, Berkeley, CA (United States)
  2. Zymergen, Inc., Emeryville, CA (United States)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1572038
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 35; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; adhesives; bioinspired materials; polybenzoxazines; polymers; surfacechemistry

Citation Formats

Higginson, Cody J., Malollari, Katerina G., Xu, Yunqi, Kelleghan, Andrew V., Ricapito, Nicole G., and Messersmith, Phillip B. Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives. United States: N. p., 2019. Web. doi:10.1002/anie.201906008.
Higginson, Cody J., Malollari, Katerina G., Xu, Yunqi, Kelleghan, Andrew V., Ricapito, Nicole G., & Messersmith, Phillip B. Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives. United States. doi:10.1002/anie.201906008.
Higginson, Cody J., Malollari, Katerina G., Xu, Yunqi, Kelleghan, Andrew V., Ricapito, Nicole G., and Messersmith, Phillip B. Wed . "Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives". United States. doi:10.1002/anie.201906008. https://www.osti.gov/servlets/purl/1572038.
@article{osti_1572038,
title = {Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives},
author = {Higginson, Cody J. and Malollari, Katerina G. and Xu, Yunqi and Kelleghan, Andrew V. and Ricapito, Nicole G. and Messersmith, Phillip B.},
abstractNote = {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.},
doi = {10.1002/anie.201906008},
journal = {Angewandte Chemie (International Edition)},
number = 35,
volume = 58,
place = {United States},
year = {2019},
month = {7}
}

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