Citric acid-based wood adhesive is considered a chemical-bonding wood adhesive. However, the detailed structures of the bonds between wood components and citric acid remain unknown. Here, we examine the chemical bonding structures between citric acid and wood by heteronuclear single quantum coherence-nuclear magnetic resonance (HSQC-NMR) analysis of wood-based molding using Japanese cedar (Cryptomeria japonica) and citric acid. In the HSQC-NMR spectrum of the wood molding, some esterified C/H correlation peaks appeared. The primary hydroxyl groups of polysaccharides, such as cellulose and galactoglucomannan, and the primary hydroxyl groups of the β-O-4 and β-5 substructures in lignin were found to be esterified with citric acid. In contrast, the secondary hydroxyl groups, except for xylan, barely reacted because of the steric hindrance. Additionally, the C/H correlation peak volumes of the reducing ends of mannan and xylan in the anomeric region increased after molding. It was clarified that the glycosidic bonds in the hemicelluloses were cleaved under the acidic molding condition with citric acid. The HSQC-NMR analysis revealed that the esterification of hemicellulose and lignin, and degradation of hemicellulose, proceeded under the molding condition. These results will promote understanding of the adhesive mechanism of citric acid-based wood adhesive and of the properties of the molding.
In sucrose/citric acid based wood adhesive, the detailed bonding mechanism has still been unknown. Here, we investigated the detailed chemical structures of this adhesive wood (Japanese cedar)-based molding by using heteronuclear single quantum coherence–nuclear magnetic resonance (HSQC-NMR). NMR peaks associated with the furan-type structure appeared, suggesting that the furan compound was formed from sucrose and converted to a furan polymer during the adhesive process and that some of the furan structures in the polymers were ester-bonded with citric acid. The secondary forces between the furan polymers and wood components were thought to contribute to the adhesive effect. In our analysis of the interphase structure, primary hydroxyl groups of both polysaccharides and of lignin substructures were found to be esterified with citric acid. Additionally, some of the glycosidic bonds in polysaccharides were cleaved during the acidic condition produced by citric acid. The above results provided evidence of the polymerization of sucrose-derived 5-HMF, the esterification of wood components, and the degradation of polysaccharides during the molding process. Citric acid functioned as a clamp between the obtained furan polymer and the wood components. The sucrose/citric acid based wood adhesive can be defined as a hybrid-type wood adhesive, involving both secondary forces and chemical bonding interactions.
scite is a Brooklyn-based startup that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
334 Leonard St
Brooklyn, NY 11211
Copyright © 2023 scite Inc. All rights reserved.
Made with 💙 for researchers