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低共熔溶剂体系预处理制备纤维素纳米纤丝及其性能研究

Preparation of Cellulose Nanofibril by the Pretreatment with Deep Eutectic Solvent System

  • 摘要: 采用氯化胆碱-尿素低共熔溶剂(DES)体系预处理,结合纳米均质化机械处理将漂白硫酸盐杨木浆纤维制备成纤维素纳米纤丝(CNF),并利用元素分析、扫描电子显微镜、红外光谱、热重分析和X射线衍射对CNF的性能进行了分析表征,还计算了CNF的聚合度(DP)和制备能耗。研究结果表明:DES预处理可以促进纸浆纤维的润胀,有利于纳米均质化过程中纤维的纤丝化。在均质处理15次下,与未经过DES预处理的纤维原料均质化处理能耗(4.35×107 kW·h/t)相比,DES预处理的纤维原料均质化处理能耗(2.44×107 kW·h/t)降低了43.91%。DES预处理可降低纤维原料的结晶度(ICr),均质处理15次后,未经过和经过DES处理制备所得CNF的结晶度分别为54%与44%;DES预处理还降低了CNF的热稳定性,但对纤维原料的聚合度没有明显影响。均质次数的增加可以促进纤维的纤丝化,同时降低纤维的结晶度和聚合度。红外光谱分析表明DES预处理过程中胆碱阳离子通过静电与纤维素纤维的阴离子基团产生相互作用,元素分析表明CNF中仍存在含氮残留物。

     

    Abstract: A choline chloride-urea(molar ratio of 1:2) based deep eutectic solvent(DES) system was used as a non-hydrolytic pretreatment media to prepare the cellulose nanofibrils(CNF) from bleached kraft poplar pulp by using microfluidizer. The properties of CNF were characterized by elemental analysis, scanning electron microscope(SEM), Fourier transform infrared spectroscopy(FT-IR), thermogravimetric analysis and X-ray diffraction analysis. Furthermore, the polymerization degree(DP) of CNF and the energy consumption were calculated. The results showed that DES pretreatment could promote the swelling of pulp fibers, which was beneficial to fibrillation during the microfluidization process. The microfluidization treatment, was performed 15 times. It was found that compared with the energy consumption(4.35×107 kW·h/t) of raw materials without DES pretreatment, the energy consumption(2.44×107 kW·h/t) of raw materials with DES pretreatment decreased by 43.91%. whereas the crystallinity indexes(ICr) of CNF prepared before and after pretreatment were 54% and 44%, respectively. However, DES pretreatment had no obvious effect on the polymerization degree of fiber raw materials. DES pretreatment also reduced the thermal stability of CNF. The increase of homogenization times could promote the fibrillation of fibers, and reduce the crystallinity and polymerization degree of cellulose at the same time. FT-IR analysis showed that choline cations interacted with anionic groups of cellulose fibers through static electricity during DES pretreatment. Elemental analysis showed that nitrogen-containing residues remained in CNFs.

     

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