Zhang Shengming, Fang Guizhen, Chen Haitao, Lang Qian
College of Engineering, Northeast Agricultural University, Harbin 150030, China.
Agricultural Engineering Postdoctoral Research Station, Northeast Agricultural University, Harbin 150030, China.
Polymers (Basel). 2019 Jul 21;11(7):1218. doi: 10.3390/polym11071218.
To the value-added application of the soda lignin by improving its reactivity and antioxidant activity, a self-made Pd/SO/ZrO catalyst was used to catalyze the degradation reaction of soda lignin. The catalyst was loaded with the palladium of 1.47 wt.% while retaining the super acidity of SO/ZrO. The reaction condition was determined as follows: the dioxane-water solution was selected as the reaction solution, the addition amount of the catalyst was 5 wt.% of the soda lignin, the system was heated at 100 °C for 4 h under a hydrogen pressure of 3 MPa. The reactivity of the catalyzed-soda lignin compared to the soda lignin before the reaction was significantly improved: the values of phenolic hydroxyl groups and total hydroxyl groups were increased by 35.3% and 97.1%, respectively, and the value of methoxy groups was decreased by 13%. Approximately 63.3% of the β-O-4 bonds were cleaved, which resulted in a reduction of the weight average molecular weight from 8200 g·mol to 4900 g·mol. At the same time, the EC values of the catalyzed-soda lignin on DPPH (1,1-diphenyl-2-picrylhydrazyl) and ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) radicals scavenging were decreased by 20.6% and 32.6%, respectively, and the reducing power of catalyzed-soda lignin at the absorption value of 0.5 was increased by 10.5%. The Pd/SO/ZrO catalyst works by breaking the β-O-4 linkages and degrading the methoxy groups. The catalyzed-soda lignin exhibits the possibility of being used as the antioxidants, grafting precursors, adhesive additives, and raw materials for lignin/polymer composites.
为了通过提高碱木质素的反应活性和抗氧化活性来实现其增值应用,使用自制的Pd/SO/ZrO催化剂催化碱木质素的降解反应。该催化剂负载了1.47 wt.%的钯,同时保留了SO/ZrO的超强酸性。反应条件确定如下:选择二氧六环 - 水溶液作为反应溶液,催化剂的添加量为碱木质素的5 wt.%,体系在3 MPa氢气压力下于100 °C加热4 h。与反应前的碱木质素相比,催化后的碱木质素的反应活性显著提高:酚羟基和总羟基的值分别增加了35.3%和97.1%,甲氧基的值降低了13%。约63.3%的β-O-4键被裂解,导致重均分子量从8200 g·mol降至4900 g·mol。同时,催化后的碱木质素对DPPH(1,1-二苯基-2-苦基肼)和ABTS(2,2'-联氮-双-(3-乙基苯并噻唑啉-6-磺酸))自由基的清除能力的EC值分别降低了20.6%和32.6%,在吸光度为0.5时催化后的碱木质素的还原能力提高了10.5%。Pd/SO/ZrO催化剂通过断裂β-O-4键和降解甲氧基起作用。催化后的碱木质素显示出用作抗氧化剂、接枝前体、粘合剂添加剂以及木质素/聚合物复合材料原料的可能性。