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木质素基呋喃树脂的结构分析

Structural Analysis of Lignin-Based Furan Resin.

作者信息

Zhu Xuhai, Bruijnaers Bardo, Lourençon Tainise V, Balakshin Mikhail

机构信息

Department of Bioproducts and Biosystems, School of Chemical Engineering, Aalto University, Vuorimiehentie 1, 02150 Espoo, Finland.

Cellulose-Resin Composite Group, Nemho R&D Group, Trespa International B.V., Wetering 20, 6002 SM Weert, The Netherlands.

出版信息

Materials (Basel). 2022 Jan 4;15(1):350. doi: 10.3390/ma15010350.

Abstract

The global "carbon emission peak" and "carbon neutrality" strategic goals promote us to replace current petroleum-based resin products with biomass-based resins. The use of technical lignins and hemicellulose-derived furfuryl alcohol in the production of biomass-based resins are among the most promising ways. Deep understanding of the resulting resin structure is a prerequisite for the optimization of biomass-based resins. Herein, a semiquantitative 2D HSQC NMR technique supplemented by the quantitative P NMR and methoxyl group wet chemistry analysis were employed for the structural elucidation of softwood kraft lignin-based furfuryl alcohol resin (LFA). The LFA was fractionated into water-insoluble (LFA-I) and soluble (LFA-S) parts. The analysis of methoxyl groups showed that the amount of lignin was 85 wt% and 44 wt% in LFA-I and LFA-S fractions, respectively. The HSQC spectra revealed the high diversity of linkages formed between lignin and poly FA (pFA). The HSQC and P results indicated the formation of new condensed structures, particularly at the 5-position of the aromatic ring. Esterification reactions between carboxyl groups of lignin and hydroxyl groups of pFA could also occur. Furthermore, it was suggested that lignin phenolic hydroxyl oxygen could attack an opened furan ring to form several aryl ethers structures. Therefore, the LFA resin was produced through crosslinking between lignin fragments and pFA chains.

摘要

全球“碳排放峰值”和“碳中和”战略目标促使我们用生物质基树脂替代当前的石油基树脂产品。在生物质基树脂生产中使用工业木质素和半纤维素衍生的糠醇是最具前景的方法之一。深入了解所得树脂的结构是优化生物质基树脂的前提条件。在此,采用定量³¹P NMR和甲氧基湿化学分析辅助的半定量二维HSQC NMR技术对针叶木硫酸盐木质素基糠醇树脂(LFA)进行结构解析。将LFA分离为水不溶性部分(LFA-I)和可溶性部分(LFA-S)。甲氧基分析表明,LFA-I和LFA-S组分中木质素的含量分别为85 wt%和44 wt%。HSQC光谱揭示了木质素与聚糠醇(pFA)之间形成的连接具有高度多样性。HSQC和³¹P结果表明形成了新的缩合结构,特别是在芳环的5位。木质素羧基与pFA羟基之间也可能发生酯化反应。此外,有人认为木质素酚羟基氧可能攻击开环的呋喃环形成几种芳基醚结构。因此,LFA树脂是通过木质素片段与pFA链之间的交联产生的。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ba03/8746157/30f399ff7efc/materials-15-00350-g001.jpg

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