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。     

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。     

超声波处理纤维素的结构变化及其在多聚磷酸中的溶解

研究了超声波预处理方法对纤维素在磷酸体系中溶解的影响。利用偏光显微镜跟踪观测纤维素的过程;通过X射线衍射,红外光谱分析,电子显微镜研究预处理前后纤维素的结构变化。实验证明,用超声波处理后,纤维素晶体类型无变化,仍为纤维素I晶体,但纤维素表面积增加,可及度增加。通过对原纤维素和超声波处理条件下的纤维素用磷酸进行溶解,溶解过程和溶解结果说明用超声波对纤维素进行预处理,可以加快纤维素的溶解速度。     

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。     

纤维素在离子液体中的溶解及再生纤维素的结晶结构的研究

介绍了离子液体的特点、纤维素在离子液体中的溶解机理和溶解过程,分析了温度、时间、浓度对纤维素溶解的影响,对再生纤维素的结晶结构进行了表征。     

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。     

再生纤维素颗粒的制备及其在水热条件下的结构变化

文章以醋化级木浆为纤维素原料,65%Zn Cl_2水溶液为溶剂,水为析出剂得到纤维素凝胶后,水热处理制备了颗粒状再生纤维素。考察了水热p H以及水热温度对再生纤维素颗粒性质的影响,并对孔结构、晶型、热稳定性和形貌等进行了表征。研究结果表明:水热p H为8时,水热后再生纤维素颗粒的孔容和比表面积均大于其他水热p H下的再生纤维素颗粒,且结晶度较高,含有少量纯度较高的Zn O。水热温度为170℃时,孔容大,孔径小,比表面积最大,达72.24 m~2/g。但是在水热温度为160℃时,再生纤维素颗粒的结晶度和热分解温度高于170℃和180℃得到的再生纤维素,且热稳定性较好,残余的Zn O的量较少。     

纤维素在离子液体中的溶解特性研究

测定了纤维素在不同结构的离子液体——1-烯丙基-3-甲基咪唑氯化物([AMIM]Cl)和1-丁基-3-甲基咪唑氯化物([BMIM]Cl)中的溶解度和溶解速率。结果发现:相同条件下,纤维素在[AMIM]Cl中具有较大的溶解度和较快的溶解速率;随着纤维素聚合度的增大,相同条件下,纤维素在离子液体中的溶解度降低。进一步通过WXRD、FT-IR、13C NMR和黏度法分析了溶解前后纤维素的化学结构、结晶结构和聚合度,结果表明:纤维素在离子液体中的溶解属于直接溶解,纤维素经离子液体溶解和再生后,晶型由纤维素I转变为纤维素II;溶解时间和温度对再生纤维素的聚合度有较大的影响,随着溶解时间的延长和溶解温度的提高,再生纤维素聚合度降低。     

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。     

纤维素在离子液体中的溶解与降解

离子液体是一种新型的绿色溶剂,纤维素是一种可再生的生物资源。离子液体以其优异的理化特性成为纤维素的新型溶剂,并呈现出良好的发展态势。本文综述了离子液体的物理特性及纤维素在离子液体中溶解、降解方面的一些研究成果。     

Enzymatic saccharification of dissolution pretreated waste cellulosic fabrics for bacterial cellulose production by Gluconacetobacter xylinus

BACKGROUND: Waste textiles, such as dyed cellulosic and/or polyester blended fabrics have the potential to serve as an alternative feedstock for the production of biological products via microbial fermentation. Dissolution pretreatment was employed to enhance the enzymatic saccharification of dyed and synthetic fiber blended cellulosic fabrics. The fermentable reducing sugars obtained from waste cellulosic fabrics were used to culture Gluconobacter xylinus for value‐added bacterial cellulose (BC) production. RESULTS: Concentrated phosphoric acid was the ultimate cellulose solvent for dissolution pretreatment since 5% w/w cellulosic fabric can be completed dissolved at 50 °C. After regeneration in water, the cellulosic precipitate was subjected to cellulase hydrolysis, resulting in at least 4‐fold enhancement of saccharification rate and reducing sugars yield. The colored saccharification products can be utilized by G. xylinus to produce BC, approximately 1.8 g L^?1 BC pellicle was obtained after 7 days static cultivation. CONCLUSION: Dyed and blended waste fabric can be pretreated effectively by dissolution to produce fermentable sugars by cellulase hydrolysis. Dissolution pretreatment can expose the dyed or polyester fiber covered digestible cellulosic fibers to cellulase and leads to a significant enhancement of saccharification yield. The colored saccharification products have no significant inhibiting effect on the fermentation activity of G. xylinus for BC production. Copyright © 2010 Society of Chemical Industry     

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     

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     

Electrospinning of cellulose nanofibers from ionic liquids: The effect of different cosolvents

Cellulose was electrospun with various concentrations of ionic liquid and cosolvent. Three different cosolvents were used in this study; dimethylacetamide (DMAc), dimethyl formamide (DMF), and dimethyl sulfoxide (DMSO). The cosolvents were added to modify the viscosity, electrical conductivity, and surface tension of the solutions. The solubility of cellulose in ionic liquids is highly affected by changes in solvent properties on the molecular level in the binary solvent systems. The difference in molecular structure of the cosolvents and the interactions between cosolvent and ionic liquid can explain the difference in dissolution power of the cosolvents. Scanning electron microscope (SEM) was used to characterize electrospun cellulose fibers. For the systems tested the importance of having a rather high viscosity and high surface tension, and some degree of shear thinning to produce fibers is shown. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

新型溶剂法制备再生纤维素纤维研究进展

再生纤维素纤维以可再生、可生物降解的天然纤维素为原料,它的研究和开发对充分利用纤维素资源和促进纤维行业的可持续发展具有重要意义.离子液体和碱溶液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.这种新型的再生纤维素纤维具有制备过程简单、对环境无污染、纤维力学性能优异或生产成本低等优点,发展前景十分广阔.综述了离子液体法和碱溶液法再生纤维素纤维的最新研究进展,包括溶剂种类及其溶解能力、纤维素原料的性质与选择、纤维的制备方法和力学性能等,同时归纳和对比了各因素对新型再生纤维素纤维力学性能的影响.最后展望了两种新型再生纤维素纤维存在的挑战、未来发展趋势和工业化前景.     

Influence of polymerization on the cholesteric structure in ethyl-cyanoethyl cellulose/acrylic acid solutions

Ethyl-cyanoethyl cellulose ((E-CE)C) forms cholesteric liquid crystals in acrylic acid (AA) and the cholesteric order in the solutions can be frozen when the AA is quickly polymerized but the cholesteric structure is changed after the polymerization though the property of the selective reflection is reserved. The maximum wavelength of the selective reflection of the cholesteric phase λ_max is shifted to the shorter wavelength direction and the selectivity and the intensity of the reflection are decreased after the AA polymerization. It is found that the shift of the reflection wavelength results from the decrease of the cholesteric pitch after the polymerization and the variation of the cholesteric pitch is decreased with increasing the (E-CE)C concentration. The decrease of the pitch after the AA polymerization is due to the volume shrinkage of the solvent monomer during the polymerization and it depends on the polymerization temperature.     

Structural changes of regenerated cellulose dissolved in FeTNa,NaOH/thiourea,and NMMO systems

Regenerated cellulose was prepared from microcrystalline cellulose (MCC) via dissolution in three well‐known nonderivatizing systems: ferric chloride/sodium tartarate/sodium hydroxide (FeTNa), sodium hydroxide/thiourea (NaOH/thiourea), and N‐methylmorpholine‐N‐oxide (NMMO) systems. The effect of regeneration using the different systems on the supramolecular structure of the regenerated celluloses was studied using X‐ray diffraction and Fourier transform infrared (FTIR). The effect of regeneration on supermolecular structure, morphology, and thermal stability of regenerated celluloses were studied using scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The effect of regeneration systems used on the chemical reactivity of cellulose toward carboxymethylation, acetylation, and cyanoethylation reactions was briefly studied. The results showed dependence of all the aforementioned properties on the dissolution reagent used in spite of that all studied reagents cause the same change in cellulose crystalline structure (from cellulose I to cellulose II). The degree of polymerization, crystallinity, and thermal stability of the regenerated cellulose (RC) samples were in the following order: NaOH/thiourea RC > FeTNa RC > NMMO RC. SEM micrograph showed unique surface for the NMMO RC sample. The reactivity of the different regenerated cellulose samples toward carboxymethylation, cyanoethylation, and acetylation depended mainly on the reaction system and conditions used rather than on crystallinity of regenerated cellulose. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

NMMO/DMSO溶剂体系对纤维素溶解作用的研究

借助X－射线衍射和核磁共振技术研究了纤维素在N－甲基氧化吗啉／二甲基亚砜（NMMO／DMSO）溶剂体系中的溶解机理．虽然DM－SO可以溶胀纤维素，并使少量部分取向性差或不完整的微晶体溶化，但不能溶解纤维素。NMMO浸入高度溶胀的纤维素分子之间，与纤维素发生某种形式的相互作用，加速了纤维素的非晶化和DMSO的溶剂化作用，最终使体系成为均匀的溶液。