Regenerated cellulose membrane prepared with ionic liquid 1‐butyl‐3‐methylimidazolium chloride as solvent using wheat straw

BACKGROUND: Currently, cellulose membranes are prepared by cellulose acetate hydrolysis or chemical derivatization dissolution and regeneration using cotton pulp or wood pulp. In this study, the concept ‘lignocelluloses biorefinery’ was used, and good quality long fiber was fractionated from wheat straw using clean technologies. The objective of this study is to develop wheat straw cellulose to prepare regenerated cellulose membrane with ionic liquid 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) as solvent. RESULTS: Wheat straw cellulose (WSC) fractionated from wheat straw contained 93.6% α‐cellulose and the degree of polymerization (DP) was 580. WSC was dissolved directly without derivatization in [BMIM]Cl. With increase in dissolving temperature, the DP of the regenerated cellulose dropped, which resulted in a decrease in the intensity of regenerated cellulose membrane. After regeneration in [BMIM]Cl, the WSC transformed from cellulose I to cellulose II, and the crystallinity of the regenerated cellulose was lower than the original cellulose. The regenerated WSC membrane had good mechanical performance and permeability, the tensile strength and breaking elongation were 170 MPa and 6.4%, respectively, the pure water flux was 238.9 L m^?2 h^?1 at 0.3 MPa pressure, and the rejection of BSA was stabilized at about 97%. CONCLUSION: Wheat straw cellulose fractionated from wheat straw satisfied the requirement to prepare regenerated cellulose membrane using ionic liquid [BMIM]Cl as solvent. Copyright © 2012 Society of Chemical Industry     

Morphology and ionic conductivity relationship in silk/cellulose biocomposites

The relationship between morphology and the ionic conductivity of polysaccharide–protein bio‐electrolyte membranes is explored in this study. Structural proteins and polysaccharides form hydrophobic and electrostatic interactions, and the resulting matrices can exhibit novel and useful properties. However, transforming these natural biomacromolecules from their native state to a more usable form is challenging. The structural, morphological, thermal, mechanical and electrical properties of biomaterials composed of microcrystalline cellulose and Bombyx mori silk when regenerated together using ionic liquids and various coagulation agents were investigated using a diverse set of techniques including Fourier transform infrared spectroscopy, SEM, TGA, DSC, X‐ray scattering, AFM‐based nanoindentation and dielectric relaxation spectroscopy. The surface topography of the films reveals morphological changes with varying coagulation agents and ionic liquids. It was found that the thermal and mechanical properties were dependent on intermolecular interactions dictated by the type of ionic liquid used during the coagulation process. X‐ray scattering provided information on how the cellulose crystallinity varied with coagulation agent. Specifically, samples coagulated with hydrogen peroxide showed an increase in cellulose crystallinity impacting properties such as elasticity, hardness and ionic conductivity of the biocomposites. In addition, the results revealed a strong correlation between β‐sheet content and ionic conductivity and cellulose crystallinity. The results provided evidence that the ionic conductivity is dependent on protein β‐sheet content and cellulose crystallinity. © 2019 Society of Chemical Industry     

Addition of 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl) imide to improve the thermal stability of regenerated cellulose

This article reports the influence of 1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl) imide (BMITFSI) addition on the thermal and mechanical properties of regenerated cellulose. Scanning electron microscopy, Young's modulus values, thermogravimetric analysis, glass‐transition temperature values, and ultraviolet–visible spectroscopy were used to assess the effect of BMITFSI addition on the properties of regenerated cellulose. The addition of a room‐temperature ionic liquid, BMITFSI, during the dissolution of cellulose was found to enhance the thermal stability of regenerated cellulose. Compared to other reported plasticizers for regenerated cellulose, such as glycerol, glycols, water, mineral oil, and α‐monoglycerides, the low vapor pressure of BMITFSI led to a long performance with the least evaporation or leaching. In addition, the immiscible nature of BMITFSI in water and its stability against moisture made BMITFSI an effective plasticizer for regenerated cellulose over a broad range of surrounding humidities and temperature conditions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

基于离子液体再生的纤维素热解特性

利用离子液体1-丁基-3-甲基咪唑氯([Bmim]Cl)溶解PH-101微晶纤维素,通过不同的再生方法获得两种再生的纤维素,并利用XRD确定其结晶度,场发射扫描电镜(SEM)获得其形貌特征,热重(TG)分析表征其热稳定性.采用Py-GC/MS 对不同结晶度纤维素进行快速热解,并对热解挥发分进行在线分析,观察结晶度对纤维素热解特性的影响.研究表明左旋葡聚糖产率随结晶度降低而减少,而小分子产物随结晶度降低而增多.     

纤维素在离子液体溶剂中溶解性能的研究进展

离子液体以其熔点低、蒸气压小、酸性可调及良好的溶解性能、黏度、密度等优异的理化特性成为纤维素的新型溶剂。离子液体与传统的纤维素溶剂相比,具有低挥发性、可回收利用、热性质稳定的优点,避免了有机溶剂所造成的污染。介绍了纤维素在离子液体溶剂体系中的溶解、再生和衍生的研究进展。     

High‐strength regenerated cellulose fibers spun from 1‐butyl‐3‐methylimidazolium chloride solutions

High‐performance regenerated cellulose fibers were prepared from cellulose/1‐butyl‐3‐methylimidazolium chloride (BMIMCl) solutions via dry‐jet wet spinning. The spinnability of the solution was initially evaluated using the maximum winding speed of the solution spinning line under various ambient temperatures and relative humidities in the air gap. The subsequent spinning trials were conducted under various air gap conditions in a water coagulation bath. It was found that low temperature and low relative humidity in the air gap were important to obtain fibers with high tensile strength at a high draw ratio. From a 10 wt % cellulose/BMIMCl solution, regenerated fibers with tensile strength up to 886 MPa were prepared below 22 °C and relative humidity of 50%. High strengthening was also strongly linked with the fixation effect on fibers during washing and drying processes. Furthermore, an effective attempt to prepare higher performance fibers was conducted from a higher polymer concentration solution using a high molecular weight dissolving pulp. Eventually, fibers with a tensile strength of ～1 GPa and Young's modulus over 35 GPa were prepared. These tensile properties were ranked at the highest level for regenerated cellulose fibers prepared by an ionic liquid–based process. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45551.     

吡啶类离子液体的合成及对纤维素溶解性能的研究

采用一步法合成N-烯丙基吡啶氯盐离子液体([APy]Cl),测定其相溶性和吸水率,利用核磁共振氢谱(1H-NMR)、傅里叶变换红外光谱仪(FT-IR)、质谱(MS)和热分析系统(DSC-TGA)对其化学结构和热稳定性进行分析;并测定对纤维素的溶解能力。结果表明,[APy]Cl为纤维素的优良溶剂,在120℃时对棉浆粕纤维素(聚合度DP=556)的溶解度可达到19.71%,脱脂棉纤维素(DP=1971)可达15.29%。利用FT-IR、X射线衍射仪(XRD)和DSC-TGA对再生前后纤维素进行表征,结果表明该离子液体为纤维素的直接溶剂,可将晶型由Ⅰ型转变为Ⅱ型。     

Comparison of cellulose and chitin nanocrystals for reinforcing regenerated cellulose fibers

In this study, regenerated cellulose fibers reinforced by cellulose nanocrystals (CENC) and chitin nanocrystals (CHNC) were prepared by blending the nanocrystals suspensions with the cellulose solution in NaOH/urea/water solvent at room temperature. The effect of nanocrystals' addition on the properties of spinning dopes and regenerated fibers were investigated and compared. Results showed that the obtained CENC and CHNC had different dimensions, and both of them increased the viscosity and decreased the transparency of the spinning dopes. However, the dissolution state of cellulose was not changed. CHNC had a greater influence on the properties of spinning dopes, while CENC had more obvious effect on the performance of regenerated fibers. The CENC reinforced fibers showed a higher crystallinity index as compared to the CHNC reinforced fibers. The tensile strength of the regenerated fibers was evidently improved when 3 wt % CENC or 2 wt % CHNC were added, while the elongation at break of the fibers was slightly decreased with the increase of nanocrystals content. The morphology and thermal stability of the regenerated fibers was not affected by the addition of nanocrystals. This study suggested that the dimension, group and content of nanocrystals were important factors for the reinforcement of regenerated cellulose fibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44880.     

Fabrication of Regenerated Cellulose Fibers with Good Strength and Biocompatibility from Green Spinning Process of Ionic Liquid

In this study, 1-ethyl-3-methylimidazolium diethyl phosphate, having the advantages of regulating the performance of cellulose dissolution and degradation, simplicity in synthesis, is chosen as solvent to dissolve wood pulp cellulose for regenerated cellulose fibers (RCFs) manufacture using dry-jet wet spinning equipment. The effect of draw ratios on RCFs’ mechanical properties in three bathes, including coagulation bath, stretch bath, and washing bath is investigated and a series of RCFs with high strength are obtained. The morphology, crystallinity, thermal stability, and dyeing behavior of the prepared RCFs are analyzed and discussed. More importantly, the biocompatibility of the RCFs, which is first performed, demonstrated that the toxicity of RCFs is as low as the viscose fibers. These RCFs could be easily dyed by natural turmeric and antibacterial fibers are obtained finally. In conclusion, this work provides tools for achievement of RCFs with good strength and environmental friendliness by changing the draw ratios, and also further develops a new green process for fabricating RCFs based on ionic liquids.     

Effects of plasticization conditions on the structures and properties of cellulose packaging films from ionic liquid [BMIM]Cl

By using natural softwood pulp with higher degree of polymerization (DP = 1460) as cellulose source, 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) ionic liquid as solvent and glycerol as plasticizer, a novel cellulose packaging film was prepared. The effects of plasticization conditions on the structures, mechanical properties, permeability for oxygen and water vapor were measured by Wide-angle X-ray scattering, thermogravimetric analysis, scanning electron microscopy (SEM), and other techniques. The investigations suggested that the glycerol concentration and plasticizing time had great effect on the properties of the regenerated cellulose films. The crystal transformation of cellulose I to cellulose II occurred during the dissolution and regeneration process, combining with the decrease of thermal stability. The tensile strength decreased rapidly with the addition of glycerol and prolongation of plasticizing time. However, elongation at break of the regenerated cellulose films increased at first and then decreased with increasing of glycerol concentration and plasticizing time. The morphologies for the fracture surface obtained from SEM images showed transformation of typical brittle fracture to plastic deformation with increasing of glycerol concentrations. It was also found that both water vapor permeability and oxygen permeability of the regenerated cellulose films decreased slowly with increasing of glycerol concentrations and plasticizing time, but water vapor permeability and oxygen permeability presented an almost opposite trend. The films prepared by using ionic liquid technology would be used in food packaging or other fields as a kind of green packaging material. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

凝固浴温度对再生细菌纤维素纤维结构与性能的影响

以细菌纤维素为原料,N-甲基吗啉-N-氧化物为溶剂制得纺丝原液,在不同的凝固浴温度条件下,制备再生细菌纤维素纤维,对其形貌、结晶度、取向度、力学性能、吸湿保湿性等进行了研究.结果表明:随着凝固浴温度的提高,再生细菌纤维素纤维表面逐渐趋于光滑,且结晶度提高、取向度和断裂强度降低;凝固浴温度为0～45℃,再生细菌纤维素纤维...     

蔗渣纤维素在离子液体中的溶解与再生

以蔗渣纤维素为原料,在1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)离子液体中,制备出蔗渣纤维素再生膜。通过偏光显微镜观察了蔗渣纤维素的溶解过程,采用红外光谱、扫描电镜、X射线衍射、热重及力学性能等分析测试手段,对蔗渣纤维素及再生膜进行表征,结果表明:未经活化的蔗渣纤维素可快速、直接溶解在离子液体中,再生前后蔗渣纤维素发生了从纤维素Ⅰ到纤维素Ⅱ的晶型转变,蔗渣纤维素再生膜具有致密的结构,热力学稳定性达到292℃,拉伸强度高达144MPa。     

Drawing of self‐reinforced cellulose films

Self‐reinforced cellulose films were prepared by incomplete dissolution of commercial microcrystalline cellulose in LiCl/DMAc solvent and subsequent coagulation of regenerated cellulose in the presence of undissolved microcrystalline cellulose. By drawing in wet conditions and subsequent drying, preferred orientation was introduced into the self‐reinforced cellulose films, resulting in significantly improved tensile strength of up to 430 MPa and modulus of elasticity of up to 33 GPa. A linear relationship was observed between applied draw, and the orientation of cellulose in the films, and the measured elastic modulus and tensile strength, respectively. The optically transparent drawn films significantly surpass the strength and modulus of elasticity of current all‐bio‐based planar materials and may therefore present a bio‐degradable alternative to nonbio‐based materials with similar performance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2703–2708, 2007     

Preparation and characterization of transparent cellulose films using an improved cellulose dissolution process

Effective dissolution of cellulosic macromolecules is the first predominant step to prepare functional bio‐based materials with desirable properties. In this study, we developed an improved dissolution process using a freeze‐drying pretreatment to promote the dissolution of cellulose. Rheological measurements of cellulose solutions and physicochemical characterization of regenerated cellulose films (scanning electron microscopy, Fourier transform infrared spectroscopy, X‐ray diffraction, and thermogravimetric analysis) were performed. Cellulose solution prepared from 5% microcrystalline cellulose (w:v) in the solvent exhibits a Newtonian fluid character while cellulose solutions at higher concentrations show a pseudo‐plastic fluid behavior. Results from physicochemical characterization indicate that a freeze‐drying pretreatment step of cellulose leads to a complete dissolution at 5% concentration while only part of cellulose is dissolved at 10% and 15% concentrations. The results obtained indicated that the use of a freeze‐drying pretreatment step under mild conditions lead to a complete dissolution of cellulose at 5% concentration. The cellulose films prepared from 5% concentration exhibited desirable properties such as good optical transparency, crystallinity, and thermal stability. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44871.     

Characteristics of cellulose isolated by a totally chlorine‐free method from Caragana korshinskii

The chemical composition and fiber morphology of Caragana korshinskii were investigated in this study. Isolation of cellulose was performed in a nonsulfur acetic acid/nitric acid system under various conditions. The influence of three factors, i.e., nitric acid concentration (0, 2, 4, 6, 8, or 10%), temperature (95, 100, 110, 115, 120, or 130°C), and reaction time (30, 40, 50, 60, or 90 min) on the cellulose properties (viscosity, yield, and molecular weight) was studied. The cellulose isolated was characterized by using Fourier transform infrared, gas chromatography, high performance liquid chromatography, solid‐state cross‐polarization magic angle spinning carbon‐13 nuclear magnetic resonance, wide‐angle X‐ray diffraction, and thermogravimetric analysis/differential scanning calorimetry techniques. The results showed that the treatment using 80% acetic acid and nitric acid as a catalyst under the given conditions resulted in slight acetylation of the cellulose and increased the degree of crystallinity of cellulose except for significant degradation of lignin and hemicellulosic polymers. The thermal stability of the cellulose declined with an increase in nitric acid concentration. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3251–3263, 2006     

Decrement of cellulose recalcitrance by treatment with ionic liquid (1‐ethyl‐3‐methylimidazolium acetate) as a strategy to enhance enzymatic hydrolysis

BACKGROUND: The high crystallinity of cellulose underlies the recalcitrance that this polymer presents in enzymatic degradation. Thus, a pre‐treatment step is applied in most bioconversion processes. Treatments with ionic liquids are considered an emerging pre‐treatment technology, owing to their high efficiency in solvating cellulose, over molecular solvent systems. RESULTS: Crystalline cellulose with and without ionic liquid (1‐ethyl‐3‐methylimidazolium acetate) treatment, both commercially available, were used as substrates in enzymatic hydrolysis reactions using the earlier evaluated cellulolytic system of Fusarium oxysporum. The in situ removal of the hydrolysate during reactions enhanced the reaction rate as well as the overall glucose production. Ionic liquid treatment significantly decreased cellulose crystallinity and enhanced bioconversion yields and rates. The effects of cellulose structural changes during treatment on hydrolysis rate were investigated and the recalcitrance constants were determined. CONCLUSION: The study showed that ionic liquid‐treated cellulose became more homogeneous and more easily degradable than the untreated cellulose, a conclusion that was expressed mathematically by the difference in the recalcitrance constants for the two substrates. It was concluded that glucose production from ionic liquid‐treated cellulose could achieve very high conversion yields in consolidated bioprocesses or during simultaneous saccharification and fermentation. Copyright © 2012 Society of Chemical Industry     

离子液体法制备再生细菌纤维素纤维

以离子液体(氯化1-甲基-3-正丁基咪唑)溶解高聚合度细菌纤维素(BC),采用湿法纺丝制备再生细菌纤维素(RBC)初生纤维;通过红外光谱分析(FTIR)、广角X射线衍射(WAXD)分析、热失重(TG)分析、扫描电镜( SEM)、单丝强度拉伸等表征了RBC初生纤维的结构和性能.结果表明:该溶剂体系通过10 h的快速搅拌溶...     

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.     

离子液体法纤维素纤维的制备及性能研究进展

对纤维素在离子液体中的溶解、溶解机理、纺丝原液的性质、纺丝工艺及纤维性能等进行了综述,认为离子液体作为一种新型纤维素溶剂,具有溶解速度快、溶解度大、对纤维素降解程度小、溶剂回收简单、回收率高等特点,且再生的纤维素具有良好的光泽和力学性能。