Wood Science and Technology

, Volume 52, Issue 4, pp 1133–1151 | Cite as

Comparison of the structural characterization of lignophenols and alkaline lignins before and after methylolation

  • Hao Ren
  • Lulu Zhu


This study reports on the isolation of bamboo lignophenols (LPs) and alkaline lignins (ALs) followed by their subsequent modification by methylolation. Methylolated lignins are quite useful and in high demand in wood–plastics composites or phenolic resin. The structural characterizations of the two lignin samples both before and after methylolation were compared by gel permeation chromatography, Fourier transform infrared spectroscopy, and 1H–13C heteronuclear single quantum coherence nuclear magnetic resonance spectroscopy (2D HSQC NMR). It was found that after methylolation, the weight average molecular weight (Mw) and polydispersity (D = Mw/Mn) of the LPs varied to a greater extent than those of the ALs (c.f., Mw: from 1167 (D = 1.96) to 8267 (D = 5.47) for the LPs and Mw: from 917 (D = 1.45) to 1580 (D = 1.62) for the ALs). These results indicated that the LPs have more functional groups prone to methylolation compared to ALs. Quantitative 13C and 2D-HSQC NMR analysis demonstrated that both LPs and ALs were hydroxyl phenol, guaiacyl, syringyl-type (HGS-type), and that the esterified p-coumarate groups in the native bamboo lignins were cleaved under alkaline cooking conditions but were not cleaved in the phase separation system. In addition, the 1,1-bis(aryl)propane-2-O-aryl ether unit was confirmed to be the basic unit of the LPs, and both the introduced and unreacted p-cresol moieties were observed by 2D HSQC NMR spectroscopy. Finally, the higher ratio of syringyl unit to guaiacyl unit (S/G ratio) and methoxy group content of the ALs compared to the LPs explained the poorer reactivity of the ALs toward methylolation.



The authors are grateful to the National Key Basic Research Program of China (Project No. 2017YFD0601005), and the National Natural Science Foundation of China (Project No. 31470599). The work was also supported by the Nanjing Forestry University Outstanding Youth Fund (NLJQ2015-5) and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), China.


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© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Jiangsu Co-Innovation Center for Efficient Processing and Utilization of Forest Resources, Jiangsu Provincial Key Lab of Pulp and Paper Science and TechnologyNanjing Forestry UniversityNanjingChina

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