Scion, Te Papa Tipu Innovation Park, 49 Sala Street, Rotorua 3046, New Zealand.
Scion, Te Papa Tipu Innovation Park, 49 Sala Street, Rotorua 3046, New Zealand.
Carbohydr Polym. 2016 Jan 20;136:1238-50. doi: 10.1016/j.carbpol.2015.10.033. Epub 2015 Oct 22.
A large volume of wood waste is produced in timber processing industry which traditionally used in low value applications. Here, value addition to the wood waste (Sander dust) and cellulose, hemicellulose isolated thereof by functionalisation using cyclic anhydrides in a solvent-free and green reactive extrusion process is reported. The effect of extrusion temperature, catalyst and different weight ratios of Sander dust (SD):succinic anhydride (SA) on the esterification reaction is evaluated. The esterified products were characterised by the acid value, degree of substitution (DS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), solid state (13)C NMR and thermo-gravimetric analysis (TGA). Under optimum extrusion conditions, mixed esters are formed, with highest acid value obtained for succinylation of cellulose (0.122 g/g at DS of 0.350) which is two times higher compared to succinylated SD (0.059 g/g at a weight gain of 0.452) and hemicellulose (0.043 g/g at DS of 0.290). The reactivity trend for individual anhydride was: (1) SA-Cellulose>SD>hemicellulose; (2) maleic anhydride (MA)-SD>hemicellulose>cellulose and (3) dodecenyl succinic anhydride (DDSA)-SD ≈ cellulose ≫ hemicellulose. The pendant free carboxyl groups generated through functionalisation of wood waste, cellulose and hemicellulose without the presence of polymeric carriers will allow more tailored or targeted modification of wood-plastic composites.
大量的木屑废料产生于木材加工行业,这些木屑废料传统上应用于低附加值领域。本研究采用无溶剂、绿色的反应挤出法,利用环状酸酐对木屑(桑德粉)和分离出的纤维素、半纤维素进行功能化,实现了对木屑废料附加值的提升。考察了挤出温度、催化剂以及不同重量比的桑德粉(SD):琥珀酸酐(SA)对酯化反应的影响。通过酸值、取代度(DS)、傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、固态(13)C NMR 和热重分析(TGA)对酯化产物进行了表征。在最佳挤出条件下,形成了混合酯,其中纤维素琥珀酸酯化产物的酸值最高(DS 为 0.350 时,酸值为 0.122 g/g),比 SD(增重 0.452 时,酸值为 0.059 g/g)和半纤维素(DS 为 0.290 时,酸值为 0.043 g/g)的琥珀酸酯化产物高两倍。各酸酐的反应活性趋势为:(1)SA-纤维素>SD>半纤维素;(2)马来酸酐(MA)-SD>半纤维素>纤维素;(3)十二烯基琥珀酸酐(DDSA)-SD≈纤维素>半纤维素。通过对木屑、纤维素和半纤维素进行功能化,生成了无聚合物载体的悬垂游离羧基基团,这将允许对木塑复合材料进行更有针对性的修饰或改性。