Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives

Higginson, Cody J.; Malollari, Katerina G.; Xu, Yunqi; Kelleghan, Andrew V.; Ricapito, Nicole G.; Messersmith, Phillip B.

doi:10.1002/anie.201906008

Title: Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives

Journal Article · Wed Jul 24 00:00:00 EDT 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201906008· OSTI ID:1572038

^[1];

^[1]; Xu, Yunqi ^[1]; Kelleghan, Andrew V. ^[1];

^[2];

^[3]

Univ. of California, Berkeley, CA (United States)
Zymergen, Inc., Emeryville, CA (United States)
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1572038

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 35; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 62 works

Citation information provided by
Web of Science

References (54)

Polybenzoxazines: new players in the bio-based polymer arena Lligadas, Gerard; Tüzün, Alev; Ronda, Juan C. Polym. Chem., Vol. 5, Issue 23 https://doi.org/10.1039/C4PY00914B	journal	January 2014
Enzymatic polymerization of catechol under high-pressure homogenization for the green coloration of textiles Su, Jing; Noro, Jennifer; Fu, Jiajia Journal of Cleaner Production, Vol. 202 https://doi.org/10.1016/j.jclepro.2018.08.205	journal	November 2018
A simple surface treatment and characterization of AA 6061 aluminum alloy surface for adhesive bonding applications Saleema, N.; Sarkar, D. K.; Paynter, R. W. Applied Surface Science, Vol. 261 https://doi.org/10.1016/j.apsusc.2012.08.091	journal	November 2012
3,4-Dihydro-1,3,2H-Benzoxazines. Reaction of p -Substituted Phenols with N,N-Dimethylolamines Burke, W. J. Journal of the American Chemical Society, Vol. 71, Issue 2 https://doi.org/10.1021/ja01170a063	journal	February 1949
Study on benzoxazine-based film adhesive and its adhesion properties with CFPR composites Li, Hongfeng; Gu, Jiyou; Wang, Dezhi Journal of Adhesion Science and Technology, Vol. 31, Issue 16 https://doi.org/10.1080/01694243.2017.1283889	journal	January 2017
Smart chemical design incorporating umbelliferone as natural renewable resource toward the preparation of thermally stable thermosets materials based on benzoxazine chemistry Rodriguez Arza, Carlos; Froimowicz, Pablo; Ishida, Hatsuo RSC Advances, Vol. 5, Issue 118 https://doi.org/10.1039/C5RA18357J	journal	January 2015
Phenolic Naphthoxazines as Curing Promoters for Benzoxazines Kaya, Gizem; Kiskan, Baris; Yagci, Yusuf Macromolecules, Vol. 51, Issue 5 https://doi.org/10.1021/acs.macromol.8b00218	journal	February 2018
Hydroxyarginine-containing Polyphenolic Proteins in the Adhesive Plaques of the Marine Mussel Mytilus edulis Papov, Vladimir V.; Diamond, Thomas V.; Biemann, Klaus Journal of Biological Chemistry, Vol. 270, Issue 34 https://doi.org/10.1074/jbc.270.34.20183	journal	August 1995
Hydrothermal in-plane-shear strength of carbon fibre/benzoxazine laminates manufactured out-of-autoclave by liquid-resin-infusion Comer, A. J.; Ray, D.; Clancy, G. Composite Structures, Vol. 213 https://doi.org/10.1016/j.compstruct.2019.01.069	journal	April 2019
Silyl Ether as a Robust and Thermally Stable Dynamic Covalent Motif for Malleable Polymer Design Nishimura, Yoshio; Chung, Jaeyoon; Muradyan, Hurik Journal of the American Chemical Society, Vol. 139, Issue 42 https://doi.org/10.1021/jacs.7b08826	journal	October 2017
Mechanical characterization of copolymers based on benzoxazine and epoxy Ishida, Hatsuo; Allen, Douglas J. Polymer, Vol. 37, Issue 20 https://doi.org/10.1016/0032-3861(96)00303-5	journal	September 1996
Structural effects of phenols on the thermal and thermo-oxidative degradation of polybenzoxazines Yee Low, Hong; Ishida, Hatsuo Polymer, Vol. 40, Issue 15 https://doi.org/10.1016/S0032-3861(98)00656-9	journal	July 1999
Protection of hydroxyl groups as tert-butyldimethylsilyl derivatives Corey, E. J.; Venkateswarlu, A. Journal of the American Chemical Society, Vol. 94, Issue 17 https://doi.org/10.1021/ja00772a043	journal	August 1972
The biochemistry and control of enzymatic browning Martinez, M. Victoria; Whitaker, John R. Trends in Food Science & Technology, Vol. 6, Issue 6 https://doi.org/10.1016/S0924-2244(00)89054-8	journal	June 1995
Oxazine Ring-Related Vibrational Modes of Benzoxazine Monomers Using Fully Aromatically Substituted, Deuterated, ¹⁵ N Isotope Exchanged, and Oxazine-Ring-Substituted Compounds and Theoretical Calculations Han, Lu; Iguchi, Daniela; Gil, Phwey The Journal of Physical Chemistry A, Vol. 121, Issue 33 https://doi.org/10.1021/acs.jpca.7b05249	journal	August 2017
Understanding the surface properties of polybenzoxazines: Interaction of polybenzoxazine model compounds with metal ions and water Shen, D.; Liu, C.; Sebastián, R. M. Journal of Applied Polymer Science, Vol. 133, Issue 42 https://doi.org/10.1002/app.44099	journal	July 2016
Simple but Strong: A Mussel-Inspired Hot Curing Adhesive Based on Polyvinyl Alcohol Backbone Mu, Youbing; Wan, Xiaobo Macromolecular Rapid Communications, Vol. 37, Issue 6 https://doi.org/10.1002/marc.201500723	journal	January 2016
Polyphosphoprotein from the Adhesive Pads of Mytilus edulis ^† Waite, J. Herbert; Qin, Xiaoxia Biochemistry, Vol. 40, Issue 9 https://doi.org/10.1021/bi002718x	journal	March 2001
A comprehensive metabolic map for production of bio-based chemicals Lee, Sang Yup; Kim, Hyun Uk; Chae, Tong Un Nature Catalysis, Vol. 2, Issue 1 https://doi.org/10.1038/s41929-018-0212-4	journal	January 2019
The Chemistry Of Adrenochrome And Related Compounds Heacock, R. A. Chemical Reviews, Vol. 59, Issue 2 https://doi.org/10.1021/cr50026a001	journal	April 1959
Synthesis and properties of thermosetting resin based on urushiol Xu, Hongli; Lu, Zaijun; Zhang, Guangzhao RSC Advances, Vol. 2, Issue 7 https://doi.org/10.1039/c2ra00829g	journal	January 2012
Catechol oxidation: considerations in the design of wet adhesive materials Maier, Greg P.; Bernt, Christopher M.; Butler, Alison Biomaterials Science, Vol. 6, Issue 2 https://doi.org/10.1039/C7BM00884H	journal	January 2018
Intrinsic self-initiating thermal ring-opening polymerization of 1,3-benzoxazines without the influence of impurities using very high purity crystals Han, Lu; Salum, María Laura; Zhang, Kan Journal of Polymer Science Part A: Polymer Chemistry, Vol. 55, Issue 20 https://doi.org/10.1002/pola.28723	journal	July 2017
Selective cleavage of tert-butyldimethylsilyl ethers with neutral alumina Feixas, Joan; Capdevila, Anna; Camps, Francisco Journal of the Chemical Society, Chemical Communications, Issue 19 https://doi.org/10.1039/c39920001451	journal	January 1992
High-performance mussel-inspired adhesives of reduced complexity Ahn, B. Kollbe; Das, Saurabh; Linstadt, Roscoe Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9663	journal	October 2015
Jack of all trades: versatile catechol crosslinking mechanisms Yang, Juan; Cohen Stuart, Martien A.; Kamperman, Marleen Chem. Soc. Rev., Vol. 43, Issue 24 https://doi.org/10.1039/C4CS00185K	journal	January 2014
Hybrid polybenzoxazine with tunable properties Xu, Hongli; Zhang, Wenli; Lu, Zaijun RSC Advances, Vol. 3, Issue 11 https://doi.org/10.1039/c3ra22247k	journal	January 2013
Breaking the symmetry of dibenzoxazines: a paradigm to tailor the design of bio-based thermosets Puchot, L.; Verge, P.; Fouquet, T. Green Chemistry, Vol. 18, Issue 11 https://doi.org/10.1039/C5GC03102H	journal	January 2016
Enhancing the Adhesion of a Biomimetic Polymer Yields Performance Rivaling Commercial Glues Meredith, Heather J.; Jenkins, Courtney L.; Wilker, Jonathan J. Advanced Functional Materials, Vol. 24, Issue 21 https://doi.org/10.1002/adfm.201303536	journal	January 2014
Enhanced Thermal Property and Flame Retardancy via Intramolecular 5-Membered Ring Hydrogen Bond-Forming Amide Functional Benzoxazine Resins Liu, Jia; Safronava, Natallia; Lyon, Richard E. Macromolecules, Vol. 51, Issue 23 https://doi.org/10.1021/acs.macromol.8b02033	journal	November 2018
Thin-layer chromatography of gallic acid, methyl gallate, pyrogallol, phloroglucinol, catechol, resorcinol, hydroquinone, catechin, epicatechin, cinnamic acid, p-coumaric acid, ferulic acid and tannic acid Sharma, Om Prakash; Bhat, Tej Krishan; Singh, Bhupinder Journal of Chromatography A, Vol. 822, Issue 1 https://doi.org/10.1016/S0021-9673(98)00490-7	journal	September 1998
Cardanol benzoxazines – interplay of oxazine functionality (mono to tetra) and properties Shukla, Swapnil; Mahata, Arup; Pathak, Biswarup RSC Advances, Vol. 5, Issue 95 https://doi.org/10.1039/C5RA14214H	journal	January 2015
Mussel-Inspired Thiol–Ene Polymer Networks: Influencing Network Properties and Adhesion with Catechol Functionality Sparks, Bradley J.; Hoff, Ethan F. T.; Hayes, LaTonya P. Chemistry of Materials, Vol. 24, Issue 18 https://doi.org/10.1021/cm302301e	journal	September 2012
The Present and Future of Biologically Inspired Adhesive Interfaces and Materials Brubaker, Carrie E.; Messersmith, Phillip B. Langmuir, Vol. 28, Issue 4 https://doi.org/10.1021/la300044v	journal	December 2011
Advanced chemically induced phase separation in thermosets: Polybenzoxazines toughened with multifunctional thermoplastic main-chain benzoxazine prepolymers Sawaryn, Christian; Landfester, Katharina; Taden, Andreas Polymer, Vol. 52, Issue 15 https://doi.org/10.1016/j.polymer.2011.04.064	journal	July 2011
Natural monomers: A mine for functional and sustainable materials – Occurrence, chemical modification and polymerization John, George; Nagarajan, Subbiah; Vemula, Praveen Kumar Progress in Polymer Science, Vol. 92 https://doi.org/10.1016/j.progpolymsci.2019.02.008	journal	May 2019
Development of Fully Biobased High-Performance Bis-Benzoxazine under Environmentally Friendly Conditions Kotzebue, Lloyd R. V.; de Oliveira, Jéssica R.; da Silva, Joane B. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 4 https://doi.org/10.1021/acssuschemeng.8b00340	journal	March 2018
Surface Roughness and Bond Strength of Adhesives Jennings, C. W. The Journal of Adhesion, Vol. 4, Issue 1 https://doi.org/10.1080/00218467208072208	journal	May 1972
Mussel-Inspired Adhesives and Coatings Lee, Bruce P.; Messersmith, P. B.; Israelachvili, J. N. Annual Review of Materials Research, Vol. 41, Issue 1 https://doi.org/10.1146/annurev-matsci-062910-100429	journal	August 2011
A mussel-inspired polybenzoxazine containing catechol groups He, Youjun; Gao, Sheng; Lu, Zaijun Polymer, Vol. 158 https://doi.org/10.1016/j.polymer.2018.10.046	journal	December 2018
Synthetic Biomaterials from Metabolically Derived Synthons Ricapito, Nicole G.; Ghobril, Cynthia; Zhang, Heng Chemical Reviews, Vol. 116, Issue 4 https://doi.org/10.1021/acs.chemrev.5b00465	journal	January 2016
Tough, Bio-Inspired Hybrid Materials Munch, E.; Launey, M. E.; Alsem, D. H. Science, Vol. 322, Issue 5907 https://doi.org/10.1126/science.1164865	journal	December 2008
Heterogeneous Oxidation of Catechol Pillar, Elizabeth A.; Zhou, Ruixin; Guzman, Marcelo I. The Journal of Physical Chemistry A, Vol. 119, Issue 41 https://doi.org/10.1021/acs.jpca.5b07914	journal	October 2015
Physical and mechanical characterization of near-zero shrinkage polybenzoxazines Ishida, Hatsuo; Allen, Douglas J. Journal of Polymer Science Part B: Polymer Physics, Vol. 34, Issue 6 https://doi.org/10.1002/(SICI)1099-0488(19960430)34:6<1019::AID-POLB1>3.0.CO;2-T	journal	April 1996
A Study on Hydrogen-Bonded Network Structure of Polybenzoxazines ^† Kim, Ho-Dong; Ishida, Hatsuo The Journal of Physical Chemistry A, Vol. 106, Issue 14 https://doi.org/10.1021/jp010606p	journal	April 2002
Mussel adhesion – essential footwork Waite, J. Herbert The Journal of Experimental Biology, Vol. 220, Issue 4 https://doi.org/10.1242/jeb.134056	journal	February 2017
Primary Amine-Functional Benzoxazine Monomers and Their Use for Amide-Containing Monomeric Benzoxazines Agag, Tarek; Arza, Carlos R.; Maurer, Frans H. J. Macromolecules, Vol. 43, Issue 6 https://doi.org/10.1021/ma902556k	journal	March 2010
Physical and mechanical properties of flexible polybenzoxazine resins: Effect of aliphatic diamine chain length Allen, Douglas J.; Ishida, Hatsuo Journal of Applied Polymer Science, Vol. 101, Issue 5 https://doi.org/10.1002/app.22501	journal	January 2006
The efficiency of various toughening agents in novel phenolic type thermoset resin systems Dipl. -Ing. Gietl, T.; Dr. -Ing. Lengsfeld, H.; Dr. -Ing. Altstädt, V. Journal of Materials Science, Vol. 41, Issue 24 https://doi.org/10.1007/s10853-006-0879-9	journal	October 2006
High-Performance Bio-Based Benzoxazines from Enzymatic Synthesis of Diphenols Bonnaud, Leïla; Chollet, Benjamin; Dumas, Ludovic Macromolecular Chemistry and Physics, Vol. 220, Issue 1 https://doi.org/10.1002/macp.201800312	journal	November 2018
Nanoparticles as curing and adhesive aid for biobased and petrobased polybenzoxazines Green Materials, Vol. 5, Issue 2 https://doi.org/10.1680/jgrma.17.00004	journal	June 2017
Phenolic materials via ring-opening polymerization of benzoxazines: Effect of molecular structure on mechanical and dynamic mechanical properties Ning, Xin; Ishida, Hatsuo Journal of Polymer Science Part B: Polymer Physics, Vol. 32, Issue 5 https://doi.org/10.1002/polb.1994.090320515	journal	April 1994
Bioinspired polymeric woods Yu, Zhi-Long; Yang, Ning; Zhou, Li-Chuan Science Advances, Vol. 4, Issue 8 https://doi.org/10.1126/sciadv.aat7223	journal	August 2018
Bioinspired structural materials Wegst, Ulrike G. K.; Bai, Hao; Saiz, Eduardo Nature Materials, Vol. 14, Issue 1 https://doi.org/10.1038/nmat4089	journal	October 2014

Cited By (3)

Smart and sustainable design of latent catalyst-containing benzoxazine-bio-resins and application studies Zhang, Kan; Liu, Yuqi; Han, Mengchao Green Chemistry, Vol. 22, Issue 4 https://doi.org/10.1039/c9gc03504d	journal	January 2020
A reversible underwater glue based on photo- and thermo-responsive dynamic covalent bonds Wang, Zhao; Guo, Lifeng; Xiao, Hongyan Materials Horizons, Vol. 7, Issue 1 https://doi.org/10.1039/c9mh01148j	journal	January 2020
The molecular mechanisms underlying mussel adhesion Li, Yiran; Cao, Yi Nanoscale Advances, Vol. 1, Issue 11 https://doi.org/10.1039/c9na00582j	journal	January 2019

Similar Records

Acrylonitrile‐butadiene‐lignin thermoplastic rubber adhesive for enhanced metal‐to‐metal joining

Journal Article · Wed Mar 06 00:00:00 EST 2024 · Polymer Composites · OSTI ID:1572038

Yu, Zeyang; Kanbargi, Nihal; Gupta, Sumit; +6 more

Recent Progress of High Performance Thermosets Based on Norbornene Functional Benzoxazine Resins

Journal Article · Tue Apr 27 00:00:00 EDT 2021 · Polymers · OSTI ID:1572038

Lu, Yin; Yu, Xinye; Han, Lu; +1 more

IACMI Project 4.2: Thermoplastic Composite Development for Wind Turbine Blades

Technical Report · Tue Dec 07 00:00:00 EST 2021 · OSTI ID:1572038

Snowberg, David; Berry, Derek; Swan, Dana; +6 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
adhesives
bioinspired materials
polybenzoxazines
polymers
surfacechemistry

Title: Bioinspired Design Provides High-Strength Benzoxazine Structural Adhesives

Citation Formats

References (54)

Cited By (3)

Similar Records

Related Subjects