纤维素在NMMO水溶液中的溶解机理研究进展

被称之为绿色纤维的Lyocell纤维,其成功开发的基础在于纤维素溶剂N-甲基吗啉-N-氧化物(NMMO)的发现。尽管在发现初期,就有人根据溶解现象和实验证实纤维素在NMMO水溶液中的溶解过程是一个大分子间氢键被破坏的物理过程,但人们对其溶解机理的认识还是经历了一个长期的过程。以往的实验方法局限于纤维素分子与溶剂分子间弱相互作用的研究,随着计算机技术的发展,分子模拟的方法填补了这一空白,使纤维素的溶解机理得到了新的认识,例如纤维素分子和NMMO分子的两亲性,以及疏水缔合相互作用。纤维素溶解机理的深入认识不仅可以促进Lyocell过程稳定性、溶剂回收效率的提升,还会为新溶剂的开发奠定理论基础。本文从NMMO的认识过程、纤维素在NMMO水溶液中溶解过程的实验发现和分子模拟计算等方面,全面总结和理解纤维素在NMMO水溶液中的溶解机理。     

尿素/己内酰胺/氢氧化钠/水溶剂体系对纤维素的溶解和再生性能

探讨了尿素/己内酰胺/氢氧化钠/水溶剂体系对纤维素的溶解和再生情况.利用正交试验确定了该体系各组分的最佳组成(质量分数):尿素10%,己内酰胺4%,氢氧化钠8%.采用红外光谱(FTIR)、热重失重(TGA)分析和X射线衍射(XRD)等手段对再生前后的纤维素进行了表征.结果表明,该溶剂体系对纤维素具有良好的溶解性能,并且是纤维素的直接溶剂;低温有利于纤维素的溶解;溶解再生后的纤维素晶型发生了变化,热稳定性有所降低.     

尿素/己内酞胺/氢氧化钠/水溶剂体系对纤维素的溶解和再生性能

探讨了尿素/己内酞胺/氢氧化钠/水溶剂体系对纤维素的溶解和再生情况.利用正交试验确定了该体系各组分的最佳组成(质量分数):尿素10%,己内酞胺4%,氢氧化钠8%.采用红外光谱(MR)、热重失重(TGA)分析和X射线衍射(XRD)等手段对再生前后的纤维素进行了表征.结果表明,该溶剂体系对纤维素具有良好的溶解性能,并且是纤...     

纤维素在离子液体中的溶解性能及机理研究进展

综述了纤维素在离子液体中的溶解性能和机理的研究进展,总结了纤维素在离子液体中发生溶胀、溶解的物化特性;指出纤维素在离子液体中的溶解属于直接溶解,溶解温度、溶解时间、加热方式、离子液体结构及是否含水等均可影响纤维素的溶解性能;分析了离子液体体系中纤维素应用方面存在的问题,即用于溶解纤维素的离子液体种类有限,溶解机理尚无成熟和完整的理论模型,有待于进一步研究.     

离子液体溶解纤维素的研究

纤维素是一种可生物降解的天然高分子材料,由于纤维素含有大量的分子间和分子内氢键,导致纤维素难溶于水和一般的有机溶剂。现有的溶剂存在稳定性差、具有毒性、难以回收等缺点,对纤维素的加工、利用造成困难,因此,寻找新型绿色溶剂成为纤维素开发的热点和难点。离子液体是一种新型高效绿色溶剂,在一定条件下可以溶解纤维素、角蛋白等生物大分子,离子液体的出现为纤维素的溶解提供了一种环境友好、可生物降解的溶剂体系,具有广阔的应用前景。本文就不同种类离子液体溶解纤维素的溶解度以及影响溶解度的几种因素进行了综述,总结了离子液体与纤维素作用机理以及离子液体的回收方法,为纤维素的加工利用提供了理论依据和工业指导。     

纤维素在碱/尿素复合溶剂中的低温溶解及纺丝研究进展

低温碱/尿素复合溶剂体系对纤维素具有独特的溶解性能,为再生纤维素纤维的制备提供了新方法.这种新型的纤维素纤维制备工艺具有生产流程短、生产成本低、对环境无污染等优点,发展前景十分广阔.但低温碱/尿素溶剂体系溶解纤维素的溶解机理复杂,溶解条件苛刻,纤维素溶解度低,纺丝液的稳定性差,成品纤维的强度还有待提高.本文综述了纤维素...     

细菌纤维素在室温离子液体中的溶解性能

研究了细菌纤维素(BC)在绿色溶剂1-烯丙基-3-甲基氯代咪唑室温离子液体中的溶解行为,通过偏光显微镜观察了BC在此离子液体中的溶解过程,热失重(TGA)和红外光谱(FT-IR)测试了再生前后BC的性能,探索了BC在离子液体中溶解、再生的可能性和可行性.结果表明:离子液体是BC的优良溶剂,对BC的溶解属于直接溶解,不发生其他的衍生化反应;再生后BC的热稳定性变好,且离子液体可回收利用.     

纤维素的绿色溶解体系

纤维素是一种天然的可再生资源,将其溶解是对其有效利用的关键。本文从溶解机理的角度对环境友好的非反应型纤维素溶剂,包括无机溶剂和有机溶剂体系,进行了重点介绍。无机溶剂体系包括碱/尿素/水体系、碱/硫脲/水体系等,其是在低温下通过尿素或硫脲小分子形成稳定的氢键网络包裹自由的纤维素大分子,使之不能相互结合,从而使碱不断打开纤维素分子间、分子内氢键获得更多的自由纤维素分子,并最终使其溶解。有机溶剂体系包括胺氧化物和离子液体,其是通过电子给予体和电子接受体与纤维素羟基作用实现纤维素的溶解。     

高力学强度细菌纤维素气凝胶纤维的连续化制备

气凝胶纤维因其高外表面积和高柔韧性在能量管理系统中具有潜在应用而引起了广泛关注.但是,目前制备的气凝胶纤维力学强度较低,限制了其实际应用.为提高气凝胶纤维力学性能,在始终保持细菌纤维素(BC)纳米纤维处于湿态下,利用NaOH/尿素/硫脲复合溶剂直接低温溶解原生BC,获得透明的BC纺丝原液;通过湿法纺丝制备了BC水凝胶纤维,经过水洗和冷冻干燥后处理,制得BC气凝胶纤维.采用偏光显微镜(POM)、13C核磁共振(13C-NMR)和高级旋转流变仪研究BC在复合溶剂中的溶解过程与状态;利用全反射傅里叶变换红外吸收光谱(ATR-FTIR)、X射线衍射(XRD)和热失重(TG)研究BC溶解前后结构与性能变化;利用场发射扫描电镜(FESEM)、全自动比表面积和孔径分布分析仪、单丝强力仪对获得的BC气凝胶纤维结构与性能进行表征.结果表明,复合溶剂在?15℃条件下可以直接溶解原生湿态BC,最高溶解浓度为3 wt%;采用湿法纺丝制得高度多孔的连续BC气凝胶纤维,比表面积高达192 m^2/g且具有优异的力学性能,断裂强度和杨氏模量高达(9.36±1.68)MPa和(176±17.55)MPa,如0.4 mg BC气凝胶纤维可以支撑高于其本身质量5×10^4倍的重物.     

纤维素在新型绿色溶剂离子液体中的溶解及其应用*

近年来,离子液体作为一种极具应用前景的绿色溶剂受到越来越多的关注。纤维素是自然界中含量最丰富的可再生资源,必将成为未来最重要的工业原料之一。离子液体在纤维素化学领域的应用遵循了绿色化学中开发环境友好溶剂和利用生物可再生资源为原料这两个基本原则,大大拓展了纤维素的工业应用前景,为纤维素资源的绿色应用提供了一个崭新的平台。本文对纤维素在离子液体中溶解的研究进展及其在制备再生纤维素材料、纤维素衍生物及生物乙醇等方面的应用进行了综述。纤维素大分子的降解机理及其控制途径、纤维素晶态结构变化规律及其调控途径、纤维素与固体反应试剂的均相衍生化体系的建立及提高衍生化效率的途径等基础问题仍需要进一步深入研究。     

Novel Fibers Prepared from Cellulose in NaOH/Urea Aqueous Solution

Summary: Novel regenerated cellulose fibers have been successfully spun from the cellulose dope in NaOH/urea aqueous solution, which could rapidly dissolve cellulose. The fibers possess circular cross‐sections as well as relatively high molecular weight, and a crystallinity index with cellulose II family crystal structure, leading to good mechanical properties. This technology is simple, cheap, and environmentally friendly, promising to substitute for viscose rayon production having hazardous byproducts.

SEM micrograph of the cross‐section of the novel cellulose fibers generated here.     

Dissolving of cellulose in PEG/NaOH aqueous solution

Here, a new solvent system for cellulose is reported. The solvent is a mixed aqueous solution of 1.0 wt.% poly(ethylene glycol) (PEG) and 9.0 wt.% of NaOH. Cellulose powder was added into the mixture at room temperature at first, and freezing it at −15 °C for 12 h following a thaw of the mixture at room temperature under strong stirring. There formed a clean solution of cellulose, and the optical microscopy was used to record the dissolving process. ¹³C-NMR, FT-IR, XRD, and intrinsic viscosity measurements revealed that there forms a homogeneous solution of cellulose in the new solvent system. The maximum solubility of cellulose with average molecular weight of 1.32 × 10⁵ g mol⁻¹ in the solvent system is 13 wt.%. The cellulose solution in the new solvent system is stable, even for 30 days storage at room temperature.     

A Rapid Process for Producing Cellulose Multi‐Filament Fibers from a NaOH/Thiourea Solvent System

Summary: Cellulose was dissolved rapidly in 9.5 wt.‐% NaOH and 4.5 wt.‐% thiourea aqueous solution pre‐cooled to −5 °C to prepare a transparent solution. Novel cellulose multi‐filament fibers were spun successfully, for the first time, from the cellulose dope on an extended laboratory scale. The results from ¹³C NMR, scanning electron microscopy and wide angle X‐ray diffraction (WAXD) patterns indicated that the fibers exhibited cellulose II character and possessed a circular cross‐section and smooth surface. The tensile strength of the novel fibers reached 1.9–2.2 cN · dtex⁻¹. 2D WAXD and SAXS patterns revealed that, with a drawing progress, the orientation factor increased and mechanical properties were improved.

SEM micrographs of the novel multi‐filament fibers spun from cellulose solution in a NaOH/thiourea aqueous system pre‐cooled to −5 °C on an extended laboratory scale.     

Dissolution of Cellulose in Aqueous NaOH Solutions

Dissolution of a number of cellulose samples in aqueous NaOH was investigated with respect to the influence of molecular weight, crystalline form and the degree of crystallinity of the source samples. A procedure for dissolving microcrystalline cellulose was developed and optimized, and then applied to other cellulose samples of different crystalline forms, crystallinity indices and molecular weights. The optimum conditions involved swelling cellulose in 8–9 wt % NaOH and then freezing it into a solid mass by holding it at –20°C. This was followed by thawing the frozen mass at room temperature and diluting with water to 5% NaOH. All samples prepared from microcrystalline cellulose were completely dissolved in the NaOH solution by this procedure. All regenerated celluloses having either cellulose II or an amorphous structure prepared from linter cellulose and kraft pulps were also essentially dissolved in the aqueous NaOH by this process. The original linter cellulose, its mercerized form and cellulose III samples prepared from it had limited solubility values of only 26–37%, when the same procedure was applied. The differences in the solubility of the celluloses investigated have been interpreted in terms of the degrees to which some long-range orders present in solid cellulose samples have been disrupted in the course of pre- treatments.     

Influence of finishing oil on structure and properties of multi-filament fibers from cellulose dope in NaOH/urea aqueous solution

Cellulose multi-filament fibers have been spun successfully on a pilot plant scale, from a cellulose dope in 7 wt% NaOH/12 wt% urea aqueous solution pre-cooled to −12 °C. Coagulation was accomplished in a bath with 10 wt% H₂SO₄/12 wt% Na₂SO₄ and then 5 wt% H₂SO₄ aqueous solution. By using different finishing oil, including H₂O, 4% glycerol aqueous solution, 2% polyvinyl alcohol (PVA) aqueous solution, 2% polyethylene glycol octyl phenylether (OP) aqueous solution, mobol and 2%glycerol/1%PVA/1%OP aqueous solution (PGO), we prepared six kinds of the cellulose multi-filaments, with tensile strength of 1.7–2.1 cN/dtex. Their structure and properties were investigated with scanning electron microscope (SEM), ¹³C NMR solid state, wide-angle X-ray diffraction (WAXD) and tensile testing. The cellulose fibers treated with PGO possessed higher mechanical properties and better surface structure than others. Interestingly, although the orientation of the cellulose multi-filaments is relatively low, the tensile strength of the single-fiber was similar to that of Lyocell. It was worth noting that the dyeability of the multi-filament fibers was superior to viscose rayon.     

Homogenous synthesis of hydroxyethylcellulose in NaOH/urea aqueous solution

Hydroxyethylcellulose (HEC) was synthesized by a fully homogenous method from cellulose in 7.5 wt.-% NaOH/11 wt.-% urea aqueous solutions under mild conditions. HEC samples were characterized with NMR, SEC-LLS, solubility, and viscosity measurements. The MS and DS values of the obtained HEC samples are in the range from 0.54 to 1.44 and 0.45 to 1.14, respectively, and the relative DS values at C-2 and C-6 hydroxyl groups are slightly higher than those at C-3 hydroxyl groups. HEC samples are soluble in water starting from a MS of 0.57 and DS of 0.49, which display high viscosity in aqueous solutions. Moreover, a NaOH/urea aqueous solution is a stable system for cellulose etherification. In this way, we could provide a simple, pollution-free, and homogeneous aqueous solution system for synthesizing cellulose ethers.     

Dissolution and regeneration of cellulose in NaOH/thiourea aqueous solution

A novel cellulose solvent, 1.5 M NaOH/0.65 M thiourea aqueous solution, was used to dissolve cotton linters having a molecular weight of 10.1 × 10⁴ to prepare cellulose solution. Regenerated cellulose (RC) films were obtained from the cellulose solution by coagulating with sulfuric acid (H₂SO₄) aqueous solution with a concentration from 2 to 30 wt %. Solubility of cellulose, structure, and mechanical properties of the RC films were examined by infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, ¹³C NMR, and tensile tests. ¹³C NMR analysis indicated that the novel solvent of cellulose is a nonderivative aqueous solution system. The presence of thiourea enhanced significantly the solubility of cellulose in NaOH aqueous solution and reduced the formation of cellulose gel; as a result, thiourea prevented the association between cellulose molecules, leading to the solvation of cellulose. The RC film obtained by coagulating with 5 wt % H₂SO₄ aqueous solution for 5 min exhibited higher mechanical properties than that with other H₂SO₄ concentrations and a homogenous porous structure with a mean pore size of 186 nm for free surface in the wet state. The RC film plasticized with 10% glycerin for 5 min had a tensile strength of 107 MPa and breaking elongation of 10%, and about 1% glycerin in the RC film plays an important role in the enhancement of the mechanical properties. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1521–1529, 2002     

Hydrogels prepared from unsubstituted cellulose in NaOH/urea aqueous solution

Novel cellulose hydrogels were synthesized through a "one-step" method from cellulose, which was dissolved directly in NaOH/urea aqueous solution, by using epichlorohydrin as crosslinker. Structure and properties of the hydrogels were characterized by using SEM, NMR, and water absorption testing. The hydrogels are fully transparent and display macroporous inner structure. The equilibrium swelling ratios of the hydrogels in distilled water at 25 degrees C are in the range from 30 to 60 g H(2)O/g dry hydrogel. Moreover, the reswelling water uptake of the hydrogels could be achieved to more than 70% compared with their initial swelling states. This work provided a simple and fast method for preparing eco-friendly hydrogels from unsubstituted cellulose.     

氢氧化钠水溶液体系中金属铬的电化学氧化过程

铬铁电氧化溶出技术是一种全新的制备铬酸钠的方法,具有反应条件温和、过程可控、工艺环保等优点,然而金属铬在NaOH水溶液中的电化学氧化过程尚不明确. 本文采用循环伏安法（CV）和阳极极化法（LSV）对金属铬在NaOH水溶液中的电化学氧化过程进行研究. 使用EDS、SEM、XRD和XPS对电解前后的金属铬表征,判断中间物的产生,使用紫外可见分光光度计验证电解液中生成了铬酸钠. 结果表明,金属铬和中间产物Cr(OH)₃可能依次发生电化学氧化直接生成Na₂CrO₄,阳极极化为金属铬的活化. 随着NaOH溶液浓度的增加,Cr(OH)₃和Na₂CrO₄的生成量在增加,金属铬电化学氧化制备铬酸钠的适宜条件为碱浓度≥ 2 mol·L^-1,阳极电势≥ 1.6 V（vs. SCE）.