Design and function of lignin-based recyclable composites

Through the phase-separation system composed of phenols and concentrated acid, the phenol components are selectively hybridized into C1-positions of phenylpropane units of native lignin to give 1,1-bis(aryl)propane-type linear polymers (lignophenols) quantitatively. Lignophenols have unique properties such as high phenolic activity and obvious phase transition. Furthermore, the functionality of lignophenols was able to be controlled using the intramolecular switching function: Under alkaline condition, C1-phenols in lignophenols nucleophilically attack adjacent C2 as switching devices, followed by the cleavage of aryl ether linkages. In ligno-p-cresol and ligno-2,4dimethylphenol with similar switching functionality and structural characteristics, ligno-p-cresol was highly hydroxymethylated (HM) on the cresolic nucleus to give network-living pre-polymer. On the other hand, ligno-2,4dimethylphenol having reactive sites mainly on the terminal unit gave linear-living pre-polymers. The structures of polymerized lignophenols were controlled by mixing ratio of HM-ligno-p-cresol and HM-ligno-2,4-dimethylphenol or by the hybridization ratio of p-cresol and 2,4-dimethylphenol in lignophenols followed by hydoxymethylation. The resulting polymer chains were cleaved at the switching points to give low molecular weight subunits by the switching function. Recyclable composites were prepared by the combination of cellulose and HM-lignophenol (the mixing ratio of HM-ligno-p-cresol to HM-ligno-2,4-dimethylphenol was 1:0, 1:1, 0:1, respectively). The composites had glossy surfaces and looked like wood. The dimensional stability of composites was improved significantly with increasing mixing ratio of HM-ligno-p-cresol to HM-ligno-2,4-dimethylphenol. Using the switching functionality of lignophenol, the composites were re-separated into lignophenols with low molecular weight and cellulose.