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

doi:10.3969/j.issn.0253-2417.2021.04.010

摘要/Abstract

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（D_P）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（I_Cr），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。

关键词: 纤维素纳米纤丝, 氯化胆碱-尿素, 低共熔溶剂, 预处理, 性能

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(D_P) 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(I_Cr) 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.

Key words: cellulose nanofibril, choline chloride-urea, deep eutectic solvents, pretreatment, properties

中图分类号:

TQ35
TK6

马光瑞, 和铭, 杨桂花, 李伟栋, 吉兴香, 陈嘉川. 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[J]. 林产化学与工业, 2021, 41(4): 69-76.

Guangrui MA, Ming HE, Guihua YANG, Weidong LI, Xingxiang JI, Jiachuan CHEN. Preparation of Cellulose Nanofibril by the Pretreatment with Deep Eutectic Solvent System[J]. Chemistry and Industry of Forest Products, 2021, 41(4): 69-76.

图/表 6

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样品 sample	聚合度 D_P	结晶度/% I_Cr	样品 sample	聚合度 D_P	结晶度/% I_Cr
杨木浆料 poplar pulp	1216	63	DES预处理后浆料 DES treated pulp	1193	62
CNF-5p	1191	62	DES-CNF-5p	877	59
CNF-10p	803	57	DES-CNF-10p	793	47
CNF-15p	657	54	DES-CNF-15p	647	44

均质次数/次 microfluidization	能耗energy consumption/(kW·h·t^-1)
均质次数/次 microfluidization	未DES预处理 without DES treatment	DES预处理 DES treatment
5	2.87×10⁷	1.76×10⁷
10	3.80×10⁷	2.26×10⁷
15	4.35×10⁷	2.44×10⁷

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