细菌纤维素在LiCl/DMAc溶剂体系中的溶解性能研究

纤维素经过活化后可以溶解在LiCl/DMAc溶剂体系中,研究了乙二胺活化对细菌纤维素溶解性能的影响,得到最佳活化条件;研究了LiCl的浓度、溶解温度和搅拌时间对溶解性能的影响,得到最佳溶解条件;研究了细菌纤维素在LiCl/DMAc极性溶剂体系中的溶解机理。     

细菌纤维素在LiCI/DMAc溶剂体系中的溶解性能研究

纤维素经过活化后可以溶解在Lic1/DMAc溶剂体系中,研究了乙二胺活化对细菌纤维素溶解性能的影响,得到最佳活化条件;研究了LICl的浓度、溶解温度和搅拌时间对溶解性能的影响,得到最佳溶解条件;研究了细菌纤维素在LiCl/DMAc极性溶剂体系中的溶解机理。     

机械力与碱处理对不同木质纤维在LiCl/DMSO溶剂体系中溶解性能的影响比较

木质纤维素原料由于具有复杂的细胞壁结构,其组分的溶解和分离成了其高效转化和利用的难点和关键所在。Li Cl/DMSO溶剂体系作为木质纤维素的可全溶体系开发以来,在木质纤维素的转化和利用方面备受关注。木质纤维原料在应用于LiCl/DMSO溶剂体系之前,通常都是经过一定的机械力预处理的。鉴于木质纤维原料的粒径大小及化学组分对溶解性能影响很大,粒径越小,木质纤维原料的结晶度越低,越利于溶剂分子的渗透,本研究采用不同的球磨时间及不同的NaOH/Na_2S制浆工艺条件预处理杨木原料,制备粒径大小、化学结构及组成有很大差别的系列试样,在相同浓度的8%LiCl/DMSO溶剂体系下比较、探讨不同球磨时间及不同程度的化学制浆处理对杨木在LiCl/DMSO溶剂体系中的溶解性能的影响,同时探讨相似的预处理及溶解条件下杨木和麦草溶解性能的差异。     

在线红外跟踪碱活化纤维素在LiCl/DMAc中的溶解

LiCl/DMAc可作为纤维素的溶剂。笔者利用在线红外技术实时跟踪碱活化纤维素在LiCl/DMAc中的溶解过程。结果表明,LiCl/DMAc可以在一定程度上破坏纤维素中氢键,实现对纤维素的溶解,无中间衍生物产生,最终溶液中纤维素主要以多聚体形式存在。同时,检测出LiCl/DMAc对纤维素的高温预溶解与室温溶解过程,且此过程可逆。     

棉纤维在LiCl/DMAc极性溶液中的溶解性能研究

采用不同方法将棉纤维活化并溶解在LiCl/DMAc极性溶液中,研究了活化方法、溶解温度、时间及LiCl浓度对棉纤维素溶解性的影响。结果表明:DMAc热活化法为较好的活化方法;提高溶解温度,延长溶解时间及提高LiCl浓度均有利于棉纤维溶解;棉纤维在LiCl质量分数为12%的LiCl/DMAc溶液中,150℃下搅拌4h,溶解度可达3%。碱活化法使棉纤维素聚合度大幅度降低,可提高棉纤维溶解度至8%。通过扫描电镜和X射线衍射方法研究了棉纤维在前处理和溶解过程中的形态和结构变化,初步揭示了纤维素高温处理后在低温下发生溶解的机理。     

纤维素浆粕和Lyocell纤维在LiCl/DMAc中溶解差异的研究

为了研究Lyocell工艺中纤维素相对分子质量分布的变化,分析了纤维素浆粕和相应的由浆粕生产出的Lyocell纤维在LiCl/DMAc中的溶解情况,发现两者存在很大差异,分别从纤维素的晶型、取向和形态结构等方面分析原因。结果表明:由于Lyocell纤维(纤维素II)比纤维素浆粕(纤维素I)在热力学上更稳定,分子间的氢键更多,且Lyocell纤维的取向较纤维素浆粕高,纤维结构较致密,使得溶剂的渗透和氢键的破坏更加困难,因此Lyocell纤维在LiCl/DMAc中的溶解比纤维素浆粕差。     

纤维素在氯化锂—N,N二甲基乙酰胺溶剂系中溶胀与溶解的影响因素(摘)

在纤维素、氯化锂(LiCl)、N.N二甲基乙酰胺(DMAc)体系中,LiCl分子与纤维素分子中葡葡糖残基的摩尔比大于3左右,纤维素才可能形成真溶液。LiCl/DMAc溶剂体系中含少量水份,能加快纤维素在其中的溶解;溶剂体系中含过多的水分,便失去溶解纤维素的能力。适当升高纤     

细菌纤维素在氢氧化钠―尿素水溶液体系中的溶解性能研究

纤维素经过活化、再生后可以溶解在氢氧化钠/尿素体系中。本文研究了乙二胺活化对细菌纤维素结晶度的影响规律,得到最佳活化条件;然后将活化后的细菌纤维素在LiCl/DMAc体系中溶解再生,得到再生细菌纤维素。最后,使用氢氧化钠/尿素溶液作为再生细菌纤维素的复合溶剂,得到的细菌纤维素的水溶液。通过红外光谱、X射线衍射仪、热重分析仪等分析了细菌纤维素不同处理阶段得到产物的性能。溶解与再生并没有发生化学变化,纤维素的结构基本保持不变,但结晶度有所降低,热稳定性有所提高。     

离子液体溶剂法制备再生纤维素纤维

离子液体是纤维素的有效溶剂,可以实现快速溶解.以离子液体生产的再生纤维素纤维较多地保留了纤维素的天然特性,易于生物降解,产品性能优于传统的粘胶工艺.介绍了离子液体的物性、作为纤维素溶剂的优点、对纤维素的溶解机理、纺丝原液制备及纺丝工艺.     

聚丙烯腈/棉纤维素薄膜的制备与性能研究

以N,N二甲基乙酰胺/无水氯化锂（DMAc/LiCl）为溶剂配置聚丙烯腈（PAN）和棉纤维素溶液,采用旋涂法制备不同比例的PAN/棉纤维素薄膜。通过旋转黏度计对PAN/棉纤维素共混溶液的表观黏度进行研究,采用X射线衍射仪、傅里叶红外光谱仪、电子万能试验机以及吸水性能测试对PAN/棉纤维素薄膜的结构和性能进行了研究。结果表明,共混溶液的表观黏度随着纤维素含量的增加逐渐增大;DMAc/LiCl溶剂对PAN和棉纤维素的溶解为直接溶解,没有发生衍生化反应;PAN和棉纤维素均保持各自结晶结构不变;当棉纤维素含量为2.0 %（质量分数,下同）时,复合薄膜的拉伸强度和断裂伸长率达到最大值;棉纤维素含量越高,复合薄膜的吸水性越好。     

Cellulose in lithium chloride/N,N-dimethylacetamide, optimisation of a dissolution method using paper substrates and stability of the solutions

Activation and dissolution in lithium chloride/N,N-dimethylacetamide (LiCl/DMAc) of cellulose from paper substrates are studied. The importance of the multiple parameters involved such as salt concentration, sample source and preparation is shown in a literature review. The experiments are carried out in order to perfect the method of activation and dissolution of paper containing different kinds of additives, typically found in historic papers. The suitability and efficiency obtained in the different trials are evaluated. The final procedure involves the activation by solvent exchange, with a water/methanol/DMAc sequence, followed by dissolution in 8% LiCl/DMAc at 4 °C. A study of the stability of the cellulose solutions in the experimental conditions showed that no degradation nor aggregation occurred during the solvation process and even after several months and confirmed the non-aggressiveness of LiCl/DMAc.     

不同预处理条件下纤维素的结构变化及其在DMAc/LiCl中的溶解

介绍了乙二胺、氢氧化钠和高温等三种不同的纤维素预处理方法。研究预处理后纤维素的结构变化,讨论预处理过程中的转化机理,并通过X射线衍射对纤维素结晶度的变化进行表征,证明乙二胺预处理后纤维素的结晶度下降最大。纤维素经过预处理后可以溶解在DMAc/L iC l中,讨论其溶解机理,通过对比三种预处理纤维素的溶解性能,表明经过乙二胺预处理之后的纤维素在DMAc/L iC l中溶解性能最好,氢氧化钠预处理的纤维素次之,高温预处理的纤维素溶解性能相对较差。     

Effect of solvent exchange on the pore structure and dissolution behavior of cellulose

Effect of solvent exchange, i.e., the sequential immersion in water, acetone, and DMAc on the pore structure of cellulose and its dissolution behavior in lithium chloride/N,N‐dimethylacetamide (LiCl/DMAc) was investigated by using size exclusion liquid chromatography (SEC), dynamic light scattering (DLS), and small‐angle X‐ray scattering (SAXS). In the SEC experiment, poly(styrene)s, diethyl phthalate, and acetone were used as probe solutes and 2‐butanone was used as an eluent. Capacity factor of these solutes in the solvent‐exchanged cellulose were larger than those in the untreated one. This was remarkable when diethyl phthalate and acetone were used as solutes. Since the molecular radii of these solutes were estimated to be less than 1 nm, it was shown that the solvent exchange increases the amount of pores within cellulose with the radii of less than 1 nm. In the SAXS experiment, structural difference between the solvent exchanged and the untreated celluloses was observed when the celluloses were immersed in acetone. Values of specific inner surface and average chord length calculated from SAXS profile showed that the amount of small pores was increased in the solvent exchanged cellulose. Considering the results from SEC, DLS, and SAXS measurements, facilitated dissolution of the solvent exchanged cellulose in LiCl/DMAc was attributed to the increase in the pores with the radii of less than 1 nm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3976–3984, 2007     

Recycling of waste cotton fabrics into regenerated cellulose films through three solvent systems: A comparison study

Large amounts of textile waste are generated every year and disposed of through landfill or incineration, leading to numerous environmental and social issues. In this work, the dissolution of three typical waste cotton fabrics (t-shirts, bed sheets and jeans) in NaOH/urea aqueous solution, H₂SO₄ aqueous solution, and LiCl/DMAc solution was investigated. Compared to different types of cotton fabrics, the effects of three solvents on the dissolution of fabrics were more obvious, leading to the significant changes in the structure and properties of regenerated cellulose films. Cotton fabrics (about 2%–5%) were rapidly dissolved (8 min) in H₂SO₄ and NaOH/urea solvents after acid pretreatment, while the dissolution in LiCl/DMAc solvent did not need any pretreatment, but a lower cellulose concentration (1%), higher dissolution temperature (80°C), and longer dissolution time (24 h) were required. The films produced from bed sheets in NaOH/urea solution exhibited the highest tensile strength, thermal stability, and water vapor barrier property. It was because of the stronger cellulose chain entanglement and hydrogen bonds induced by the higher cellulose concentration in NaOH/urea solution. Therefore, this work proves the feasibility to recycle waste cotton fabrics into biodegradable cellulose films, which can be potentially used in various food and agricultural applications.     

Shear‐induced morphology changes in N,N′‐dimethylacetamide/lithium chloride pretreated cellulose

A new mechanochemical treatment was performed on cellulose with the objective of modifying its morphology, reducing its crystallinity, and enabling better dissolution. Cellulose treated with N,N′‐dimethylacetamide (DMAc)/lithium chloride (LiCl) was subjected to shear with natural rubber as the carrier and shear‐transfer medium. When cellulose was subjected to such a mechanochemical treatment, significant changes in its surface morphology and a decrease in crystalline index were observed. The dissolution of the mechanochemically treated cellulose samples in DMAc/LiCl was found to be better compared with the dissolution of samples subjected to either mechanical shear or the chemical action of DMAc/LiCl independently. Chemical interactions between DMAc/LiCl and cellulose were enhanced synergistically under shear‐induced deformation. When shear alone was used in the absence of a DMAc/LiCl treatment, changes in the morphology, crystalline index, and dissolution were found to be negligible. The shear‐induced cellulose samples were characterized with Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and thermogravimetric analysis. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44809.     

Application of optical microscopy as a screening technique for cellulose and lignin solvent systems

Rapid and facile screening techniques to determine the effectiveness of solvents for cellulose or biomass dissolution can advance biomass processing research. Here, we report the use of a simple optical microscopy method to screen potential cellulose and lignin solvents. The described methodology was used to screen the dissolution of cellulose and lignin in two imidazolium‐based ionic liquids (ILs), two phosphonium‐based ILs, as well as a N,N‐dimethylacetamide/lithium chloride (DMAc/LiCl) solution in less time than other techniques. The imidazolium‐based ILs and the DMAc/LiCl were found to dissolve both cellulose and lignin. Also, it was observed that one of the phosphonium‐based ILs dissolved lignin and not cellulose, demonstrating a potential for biomass fractionation applications. © 2011 Canadian Society for Chemical Engineering     

Effect of solvent exchange on the structure and rheological properties of cellulose in LiCl/DMAc

Effect of solvent exchange on the structure of cellulose was investigated by Fourier transform infrared spectroscopy, wide angle X‐ray diffraction, and scanning electron microscopy analysis. The solvent exchange facilitated the dissolution of cellulose in LiCl/DMAc with no change of the crystalline structure of cellulose. In contrast, solvent exchange led to the fibrillation on the treated fiber surface and the trimmed rod‐like particles, further confirming the occurrence of particle disintegration. The rheological properties of three cellulose samples with different degrees of polymerization (DP) and different concentrations were investigated. Results indicated that the cellulose LiCl/DMAc solutions were non‐Newtonian fluids. At low deformation rates the cellulose solution behaved like a viscous liquid (loss modulus G″ being larger than storage modulus G′), but elastic properties developed at high angular frequency. The two domains of viscoelastic behavior were separated by the so‐called crossover point for G′ and G″, which was slightly shifted to lower frequencies as the testing temperature increased from 50 to 80°C. As the concentration and the average molecular weight (or DP) increased, the angular frequency at the crossover point increased also under the experimental conditions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

基于金属盐溶液的纤维素溶解及其应用研究进展

纤维素是自然界储量最丰富的可再生生物质资源，其绿色高值化利用在实现“双碳”和“循环经济”目标中起到重要作用。纤维素的绿色高效溶解是实现其高值化利用重要途径之一。众多纤维素溶剂体系存在价格昂贵、毒性和环境威胁、溶解工艺复杂、溶解效率低、溶剂回收困难和能耗高等问题。金属盐溶液体系具有稳定性高、价格便宜，同时溶解纤维素速度快、溶解工艺简单等特点，是更具应用前景的低成本绿色溶剂。该文综述了不同金属盐溶液溶解纤维素的溶解机理，总结了影响溶解性能的关键因素，并进一步介绍了基于不同金属盐溶液溶解纤维素在薄膜材料、凝胶材料以及复合材料等领域的应用研究进展，总结并展望了金属盐溶液在纤维素溶解及功能化应用方面的优势、不足及发展方向。