Ren Jun-Li, Xu Feng, Sun Run-Cang, Peng Bai, Sun Jin-Xia
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou, China.
J Agric Food Chem. 2008 Feb 27;56(4):1251-8. doi: 10.1021/jf072983q. Epub 2008 Feb 1.
Lauroylation of wheat straw hemicelluloses in the N, N-dimethylformamide/lithium chloride system under microwave irradiation was studied. The parameters optimized included lauroyl chloride concentration as the molar ratio of xylose unit in hemicelluloses/lauroyl chloride (1:1-1:4), 4-dimethylaminopyridine concentration (2-10%), reaction time (1-8 min), molar ratio of xylose unit in hemicelluloses/triethylamine (1:2), and reaction temperature (78 degrees C). The reaction efficiency was measured by the yield and degree of substitution (DS). Under an optimum reaction condition (molar ratio of xylose unit in hemicelluloses/lauroyl chloride 1:3, molar ratio of xylose unit in hemicelluloses/triethylamine 1:2, 5% 4-dimethylaminopyridine, 78 degrees C, 5 min), a DS of 1.63 was obtained. Changes in the structure of hemicelluloses were verified by FT-IR and 1H and 13C NMR spectroscopy. The results showed that the lauroylation occurred preferentially at the C-3 position of the xylose unit in hemicelluloses. The behavior of the lauroylated hemicelluloses was monitored by means of thermogravimetric (TG) and differential thermogravimetric (DTG) analysis. It was found that the product with low DS had a lower thermal stability than the native hemicelluloses, whereas the lauroylated polymers with high DS showed a higher thermal stability than the unmodified hemicelluloses.
研究了在微波辐射下,麦秸半纤维素在N,N - 二甲基甲酰胺/氯化锂体系中的月桂酰化反应。优化的参数包括月桂酰氯浓度(以半纤维素中木糖单元与月桂酰氯的摩尔比计,1:1 - 1:4)、4 - 二甲基氨基吡啶浓度(2 - 10%)、反应时间(1 - 8分钟)、半纤维素中木糖单元与三乙胺的摩尔比(1:2)以及反应温度(78℃)。通过产率和取代度(DS)来衡量反应效率。在最佳反应条件下(半纤维素中木糖单元与月桂酰氯的摩尔比为1:3、半纤维素中木糖单元与三乙胺的摩尔比为1:2、4 - 二甲基氨基吡啶为5%、78℃、5分钟),得到的取代度为1.63。通过傅里叶变换红外光谱(FT - IR)、1H和13C核磁共振光谱验证了半纤维素结构的变化。结果表明,月桂酰化优先发生在半纤维素木糖单元的C - 3位。通过热重(TG)和微商热重(DTG)分析监测月桂酰化半纤维素的行为。发现低取代度的产物热稳定性低于天然半纤维素,而高取代度的月桂酰化聚合物热稳定性高于未改性的半纤维素。