纤维素LiCl/DMAc溶液流变性能研究

本文研究了9％LICI／DMAC纤维素溶液的流变性能。在该体系中纤维素溶液是非牛顿流体，属于假塑性流体，具有典型的幂律性。通过幂律方程拟合计算，其稠度系数为60～135，流动特性指数为0.62～0．70。随着浓度增大，稠度系数增大和流动特性指数降低；温度的变化对流动特性指数的影响不大，温度升高，流动特性指数略有减小，而稠度系数相对增大。溶液的粘度随着剪切速率的增大，开始时粘度迅速降低，后趋于稳定，这可能与纤维素分子在溶液中的取向有关。在不同剪切速率下，其流动活化能为23～30kJ．     

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。     

纤维素在LiCl/DMAc中的GPC研究的现状及进展

综述了以 LiCl/DMAc 为流动相,用 GPC 分析纤维素分子量分布的样品制备、校准及色谱分析条件,并就其应用及存在的问题进行了总结。     

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。     

蔗渣/LiCl/DMAc溶液体系及其纤维素接枝聚丙烯酰胺的制备

为了发展利用植物生物质资源,采用将蔗渣溶于LiCl/DMAc体系并利用溶解于其中的物质与丙烯酰胺进行均相接枝反应以制备蔗渣接枝聚丙烯酰胺。结果表明蔗渣在160℃活化1h,烘干后与100g/L的LiCl/DMAc体系以固液比1∶50混合,然后在160℃加热4h的条件下可以取得81.3%的溶解率。溶液中不但含有纤维素,而且含有半纤维素和木质素。该溶液在30℃、N2环境且丙烯酰胺分两次投料的条件下进行共聚的接枝率达到62.86%。进一步的实验表明蔗渣接枝物的主要成分是纤维素-g-聚丙烯酰胺。这为植物生物质的高值化利用提供了新的途径。     

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。     

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。     

细菌纤维素/LiCl/DMAC溶液体系流变性的研究

采用锥板式旋转黏度计测定细菌纤维素溶液的流变行为。结果表明,细菌纤维素溶液为非牛顿流体,随着剪切速率的增大,溶液呈现切力变稀现象。溶液中纤维素含量和温度影响纤维素溶液的流变行为,剪切黏度随温度的上升及纤维素含量的减少而下降,结构化程度随温度上升和纤维素含量减少而降低。     

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     

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.     

天然纤维素的溶解技术及其进展

本文系统介绍了近年来天然纤维素的溶解技术及其进展。内容包括天然纤维素的制备与分离、天然纤维素的溶解机理及所用的溶剂、天然纤维素溶解技术的发展趋势等。     

纤维素/磷酸纺丝溶液的制备

相对于粘胶法溶解纤维素,以磷酸为溶剂溶解纤维素具有操作简单、价格低廉、溶解温度较低、溶解速度较快,而且对环境污染较小等优势。通过混合多聚磷酸和磷酸制备了无水的混合磷酸溶剂体系,分析了P2O5含量、温度和搅拌速率对溶剂平衡时间的影响,并对纤维素在该溶剂体系中的溶解性能进行了研究,探讨了P2O5含量、固含量和温度对纤维素溶解性能的影响。从纺丝溶液的稳定性、均一性和可纺性方面考虑,最佳的溶解条件为:混合磷酸溶剂体系中的P2O5含量为74%,纤维素固含量为18%,溶解温度为0℃。     

Structopendant unsaturated cellulose esters via acylation in homogeneous lithium chloride/N,N-dimethylacetamide solutions

Novel acylation reactions of cellulose were accomplished with a series of unsaturated carboxylic acids or their respective anhydrides including crotonic acid (CRA), methacrylic acid (MAA), vinyl acetic acid (VAA), fumaric acid monoethyl ester (FAME), and cinnamic acid (CINA) in lithium chloride (LiCl)/dimethylacetamide (DMAc) homogeneous solutions. The acylation reactions were conducted at room temperature using dicyclohexylcarbodiimide (DCC) as a condensation agent and 4-dialkyl-aminopyridine (4-[N,N-dimethylamino-] or 4-pyrrolidino-pyridine, DMAP or PP) as a catalyst. A reaction mechanism is proposed based on experimental evidence. The acylated cellulose derivatives obtained from CRA, MAA, or their anhydrides exhibit poor solubility in organic solvents. Side reactions, e.g., the Michael addition, likely occur at the high temperatures required for reaction of these acyl groups. However, acylation of cellulose with VAA, FAME, and CINA is facile with derivatives readily soluble in DMSO. The structures of these derivatized celluloses were characterized with FTIR and ¹H-NMR spectroscopy and degrees of substitution were calculated. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 293–305, 1997