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硫酸对单宁-蔗糖胶粘剂固化行为和粘结性能的影响

Effects of Sulfuric Acid on the Curing Behavior and Bonding Performance of Tannin⁻Sucrose Adhesive.

作者信息

Zhao Zhongyuan, Miao Yanfeng, Yang Ziqian, Wang Hua, Sang Ruijuan, Fu Yanchun, Huang Caoxing, Wu Zhihui, Zhang Min, Sun Shijing, Umemura Kenji, Yong Qiang

机构信息

Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China.

College of Furnishings and Industrial Design, Nanjing Forestry University, Nanjing 210037, China.

出版信息

Polymers (Basel). 2018 Jun 11;10(6):651. doi: 10.3390/polym10060651.

Abstract

The development of biomaterials-based adhesives is one of the main research directions for the wood-based material industry. In previous research, tannin and sucrose were used as adhesive to manufacture particleboard. However, the reaction conditions need to be optimized. In this study, sulfuric acid was added to the tannin⁻sucrose adhesive as a catalyst to improve the curing process. Thermal analysis, insoluble mass proportion, FT-IR, and solid state C NMR were used to investigate the effects of sulfuric acid on the curing behavior of tannin and sucrose. Thermal analysis showed weight loss and endotherm temperature reduced from 205 and 215 to 136 and 138 °C, respectively, by adding sulfuric acid. In case of the adhesive with pH = 1.0, the insoluble mass proportion achieved 81% at 160 °C, which was higher than the reference at 220 °C. FT-IR analysis of the uncured adhesives showed that adding sulfuric acid leads to hydrolysis of sucrose; then, glucose and fructose converted to 5-hydroxymehthylfurfural (HMF) and levulinic acid. Dimethylene ether bridges were observed by FT-IR analysis of the cured adhesives. The results of solid state C NMR spectrum indicated that 5-HMF participated in the curing process and formed methylene bridges with the C8 position of the resorcinol A-rings of tannin, whereas dimethylene ether bridges were detected as a major chemical chain of the polymer. Lab particleboards were produced using 20 wt % resin content at 180 °C and 10 min press time; the tannin⁻sucrose adhesive modified with sulfuric acid to pH = 1.0 exhibited better performance than the unmodified tannin⁻sucrose adhesive; the properties of the boards fulfilled the requirement of Japanese Industrial Standard (JIS) A5908 type 15.

摘要

基于生物材料的胶粘剂的开发是木质材料工业的主要研究方向之一。在先前的研究中,单宁和蔗糖被用作胶粘剂来制造刨花板。然而,反应条件需要优化。在本研究中,向单宁-蔗糖胶粘剂中添加硫酸作为催化剂以改善固化过程。采用热分析、不溶物质量比例、傅里叶变换红外光谱(FT-IR)和固态碳核磁共振(C NMR)来研究硫酸对单宁和蔗糖固化行为的影响。热分析表明,通过添加硫酸,失重和吸热温度分别从205和215℃降至136和138℃。对于pH = 1.0的胶粘剂,在160℃时不溶物质量比例达到81%,高于在220℃时的参比胶粘剂。对未固化胶粘剂的FT-IR分析表明,添加硫酸会导致蔗糖水解;然后,葡萄糖和果糖转化为5-羟甲基糠醛(HMF)和乙酰丙酸。对固化胶粘剂的FT-IR分析观察到了二亚甲基醚桥。固态C NMR光谱结果表明,5-HMF参与了固化过程,并与单宁间苯二酚A环的C8位形成了亚甲基桥,而二亚甲基醚桥被检测为聚合物的主要化学链。在180℃和10分钟的压制时间下,使用树脂含量为20 wt%制备实验室刨花板;用硫酸改性至pH = 1.0的单宁-蔗糖胶粘剂表现出比未改性的单宁-蔗糖胶粘剂更好的性能;板材性能满足日本工业标准(JIS)A5908 15型的要求。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d2c0/6404132/c8e5ad18d382/polymers-10-00651-g001.jpg

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