纤维素在NaOH/硫脲/尿素水溶液中的流变性能研究

采用新型碱复合溶剂NaOH/硫脲/尿素水溶液作为溶剂溶解纤维素,对纤维素溶液的流变性能进行探索,从而为纤维素/NaOH/硫脲/尿素溶液纺丝提供理论依据。研究结果表明,纤维素溶液表现出非牛顿流体的性质,溶液的粘流活化能随纤维素质量分数以及剪切速率的不同而有所差异,纤维素溶液的结构黏度指数随着温度的升高、纤维素质量分数的增大而增大。5~25℃是所测的纤维素溶液纺丝的适宜温度范围,随着温度的升高,凝胶点开始出现,且凝胶点随着温度的升高向高频率的方向移动。随着纤维素质量分数的增大,纤维素溶液凝胶温度降低。     

X-ray studies of regenerated cellulose fibers wet spun from cotton linter pulp in NaOH/thiourea aqueous solutions

Regenerated cellulose fibers were fabricated by dissolution of cotton linter pulp in NaOH (9.5 wt%) and thiourea (4.5 wt%) aqueous solution followed by wet-spinning and multi-roller drawing. The multi-roller drawing process involved three stages: coagulation (I), coagulation (II) and post-treatment (III). The crystalline structure and morphology of regenerated cellulose fiber was investigated by synchrotron wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) techniques. Results indicated that only the cellulose II crystal structure was found in regenerated cellulose fibers, proving that the cellulose crystals were completely transformed from cellulose I to II structure during spinning from NaOH/thiourea aqueous solution. The crystallinity, orientation and crystal size at each stage were determined from the WAXD analysis. Drawing of cellulose fibers in the coagulation (II) bath (H₂SO₄/H₂O) was found to generate higher orientation and crystallinity than drawing in the post-treatment (III). Although the post-treatment process also increased crystal orientation, it led to a decrease in crystallinity with notable reduction in the anisotropic fraction. Compared with commercial rayon fibers fabricated by the viscose process, the regenerated cellulose fibers exhibited higher crystallinity but lower crystal orientation. SAXS results revealed a clear scattering maximum along the meridian direction in all regenerated cellulose fibers, indicating the formation of lamellar structure during spinning.     

咪唑类离子液体对微晶纤维素溶解性能的初步研究

合成了一种新的咪唑类离子液体——二氯二(3,3'-二甲基)咪唑基亚砜盐(Cl₂),并对该离子液体溶解微晶纤维素的溶解性能进行了初步研究。通过正交试验考察了不同因素对溶解性能的影响,最佳的试验条件为: 15% NaOH 溶液活化纤维素,离子液体溶解纤维素的温度为80℃,溶解时间60 min,离子液体在不含水条件下进行实验。结果表明,该离子液体对微晶纤维素具有一定的溶解性能。同时对溶解机理进行了初步讨论。     

水溶性改性细菌纤维素的制备及表征

将细菌纤维素再生后溶于NaOH/尿素/硫脲溶液,在碱性条件下与丙烯酰胺合成水溶液的改性细菌纤维素。红外光谱、元素分析和核磁共振谱图证实了改性细菌纤维素的存在。研究表明：当葡萄糖与丙烯酰胺摩尔比大于1：4.6时,反应产物是水溶性的;当葡萄糖与丙烯酰胺摩尔比为1：8时,产物的羟基总取代度约为0.412-0.502.     

超声波处理对纤维素碱脲体系溶解性能的影响

采用碱／尿素／水体系、碱／尿素／硫脲／水体系分别制备纤维素溶液,在溶解的不同阶段用超声波进行处理,并利用光学显微镜、偏光显微镜和X射线衍射对溶解效果进行表征。研究结果表明：溶解之前对纤维素原料的超声波处理主要是对纤维形态结构和超分子结构的破坏,略微增大溶解度;溶解过程中对纤维素溶液超声波处理则可以强化润胀,促进分散,显著增大纤维素的溶解度;在碱／尿素／水体系中超声波对溶解的促进作用强于在碱／尿素／硫脲,水体系中。     

Gelation behaviors of cellulose solution dissolved in aqueous NaOH/thiourea at low temperature

Cellulose was dissolved rapidly in 9.5 wt% NaOH/4.5 wt% thiourea aqueous solution pre-cooled to −5 °C, as a result of the formation of an inclusion complex (IC) associated with cellulose, NaOH and thiourea, which could bring cellulose to the aqueous system. To clarify the rheological behaviors of the system dissolved at low temperature, this cellulose solution was investigated by dynamic viscoelastic measurement. The shear storage modulus (G′) and loss modulus (G″) as a function of the angular frequency (ω), concentration (c), temperature (T) and weight-average molecular weight (M_w) were analyzed and discussed. The results revealed that gels could form in the cellulose solution at either high temperature or low temperature, or for longer time. Interestingly, 4 wt% cellulose solution having cellulose M_w of 12.0 × 10⁴ remained at liquid state for longer time (12 days) at the temperature ranging from 0 to 5 °C. The gels already formed at elevated temperature were irreversible, i.e., after cooling to lower temperature including the temperature of cellulose dissolution (−5 °C), they could not be dissolved to become liquid. The Arrhenius analysis of the temperature dependence of viscosity in the cellulose solution indicated that a high apparent activation energy (E_a) occurred at 0 to −5 °C, suggesting the relatively stable IC structure. However, the viscosity of the cellulose solution increased slowly with an increase in the temperature at 0-40 °C, leading to the negative E_a values. The results suggested that the cellulose solution in NaOH/thiourea system is complex to differ from normal polymer systems.     

氢氧化钠/尿素/硫脲溶剂体系对纤维素溶解性能研究

通过设计正交实验,研究不同组成的氢氧化钠/尿素/硫脲溶剂体系对纤维素的溶解性能,确定了该溶剂体系中各组分的最佳含量,并通过X-射线衍射分析、红外光谱分析、热重分析等手段,表征了该溶剂体系获得的再生纤维素膜的结构和性能。结果表明:该溶剂体系对纤维素有良好的溶解性能,且溶解的纤维素再生后为纤维素Ⅱ,但其热稳定性低于原纤维素。     

Structure and physical properties of methylcellulose synthesized in NaOH/urea solution

Summary A series of methylcellulose (MC) samples were successfully synthesized using dimethyl sulphate (DMS) as a methylation reagent in 7 wt% NaOH/12 wt% urea aqueous solution through controlling the reaction conditions. The MC samples were characterized with ¹H and ¹³C NMR, gas chromatography (GC), ultraviolet spectroscopy, viscometry and solubility measurement. Analysis of GC showed that there were no unsubstituted anhydroglucose units (AGU) and few completely substituted AGU along the molecular chains of the MC samples, and there was a uniform distribution of methyl substitution along the MC molecular chains. The stability of 7 wt% NaOH/12 wt% urea solution for the methylation of cellulose was investigated for the first time. The results showed 2 wt% cellulose solution in the 7 wt% NaOH/12 wt% urea solvent was almost stable at room temperature, and little decomposition of the cellulose molecular chains occurred during the methylation reaction.     

Development of a fixed‐bed column with cellulose/chitin beads to remove heavy‐metal ions

Environmental friendly cellulose/chitin beads, having relatively high mechanical properties, were successfully prepared from a blend of cellulose and chitin in 6 wt % NaOH/5 wt % thiourea aqueous solution by coagulating with 5% H₂SO₄ aqueous solution. The ability of the beads to adsorb Pb²⁺ in an aqueous solution was measured with a fixed‐bed column. The effects of important parameters, to design an adsorption column of the cellulose/chitin beads for fixed‐bed columns, were investigated. The breakthrough curves for the adsorption behavior indicated that the column performance was improved with decreasing initial lead concentration, ionic strength, flow velocity or bead size, as well as increasing pH dependence and bed height. Column studies showed that constants, calculated from the experimental data, and the Bed Depth Service Time (BDST) model had a good correlation. The columns were easily regenerated by treating with 0.1 mol/L HCl aqueous solution after the adsorption of metals, providing a simple and economical method for removal and recovery of heavy metals. After four adsorption–desorption cycles, the efficiency of column for the removal of lead was not significantly reduced (not more than 5%). It is shown that heavy‐metal biosorption processes in fixed‐bed columns could give a broad range of potential industrial applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 684–691, 2004     

Preparation and properties of chemical cellulose from ascidian tunic and their regenerated cellulose fibers

Chemical cellulose (dissolving pulp) was prepared from ascidian tunic by modified paper‐pulp process (prehydrolysis with acidic aqueous solution of H₂SO₄, digestion with alkali aqueous solution of NaOH/Na₂S, bleaching with aqueous NaOCl solution, and washing with acetone/water). The α‐ cellulose content and the degree of polymerization (DPw) of the chemical cellulose was about 98 wt % and 918, respectively. The Japanese Industrial Standard (JIS) whiteness of the chemical cellulose was about 98%. From the X‐ray diffraction patterns and ¹³C‐NMR spectrum, it was found that the chemical cellulose obtained here has cellulose Iβ crystal structure. A new regenerated cellulose fiber was prepared from the chemical cellulose by dry–wet spinning using N‐methylmorpholine‐ N‐oxide (NMMO)/water (87/13 wt %) as solvent. The new regenerated cellulose fiber prepared in this study has a higher ratio of wet‐to‐dry strength (<0.97) than commercially regenerated cellulose fibers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1634–1643, 2002.     

All-cellulose composites prepared by partially dissolving cellulose using NaOH/thiourea aqueous solution

All-cellulose composites (ACCs) were prepared by partially dissolving cellulose in the filter paper using NaOH/thiourea aqueous solution. The effects of dissolution time, thiourea ratio, and temperature on the properties of ACCs were investigated. ACCs were characterized by scanning electron microscope, attenuated total reflectance Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and tensile tests. The results revealed that the fibers in ACCs were tightly intertwined. The crystalline form of cellulose in ACCs was transformed from type I to type I/II mixture, and the crystallinity decreased from 77.32 to 51.40%. The tensile strength of ACCs was remarkably improved to 23.16 MPa. The results confirmed ACCs had a high potential for practical applications in the packaging field.     

纤维素氨基甲酸酯溶液的制备及稳定性研究

研究了制备纤维素纤维的新型原料——纤维素氨基甲酸酯(CC)溶液的制备工艺及其稳定性。结果表明:在-5~10℃条件下,用聚合度为350~612的纤维素浆粕(棉浆粕、木浆粕)合成的氮含量(酯化度)为2.34%~3.56%的CC能很好地溶解在质量百分比浓度为8%~11%的NaOH溶液中,形成淡黄色透明溶液,该溶液稳定性良好,可用于纺丝。另外,尿素、AlCl3及ZnCl2在一定范围内对CC有助溶作用。     

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。     

Solution of cellulose xanthate at elevated alkali contents

Conclusions A method has been developed for dissolving cellulose xanthate at a higher NaOH content in the first period of solution. The optimum NaOH content for this purpose is 9–9.6%.All-Union Synthetic Fibre Research Institute (VNIIV). Translated from Khimicheskie Volokna, No.2, pp. 60–61, March–April, 1969.     

Solubility of bacterial cellulose and its structural properties

Based on experiments conducted, it has been found that bacterial cellulose, like spruce cellulose, is soluble in an aqueous NaOH solution with the concentration of 8.5% at a temperature of −5°C if the polymerization degree of the cellulose does not exceed 400. When 1% of urea is added to the NaOH solution, the solubility of cellulose increases; and, in this solvent, bacterial cellulose may be dissolved so long as its polymerization degree is below 560. The results of these experiments are of great practical importance since they point to the possibility of the preparation of cellulose spinning solutions suitable for fiber formation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1871–1876, 1998     

Ozone treatment for improving the solubility of cellulose extracted from palm fiber

We investigated effects of ozone treatment on solubility of cellulose and chemical composition in cellulose extracted from palm fiber. The initial holocellulose, α-cellulose, and lignin contents of the extracted cellulose were 88.0, 81.9, and 8.75%, respectively. The extracted cellulose was treated with ozone and NaOH solution. Ozone treatment for 5 hr at 40°C using 3% citric acid decreased the lignin content from 8.75 to 2.71%. Under these conditions, the degree of polymerization (DP) of the cellulose decreased to 29 from 160 and the carboxyl content increased to 2.05 mmol/g. When the solid phase was treated with NaOH after ozone treatment, the mass of the solid phase decreased as the ozone treatment time increased. The lowest mass was 0.43 g. Additionally, the mass of cellulose regenerated from the liquid phase increased with increasing treatment time. The highest mass of regenerated cellulose was 0.54 g. The masses of the solid phase and regenerated cellulose obtained without ozone treatment under the same conditions were 0.76 and 0.18 g, respectively. These results suggest that ozone treatment improves the solubility of cellulose by converting hydroxyl groups in the cellulose to carboxyl groups and reducing the DP.     

Structure and Properties of CdS/Regenerated Cellulose Nanocomposites

Summary: Novel inorganic‐organic hybrid materials composed of cadmium sulfide (CdS) semiconducting nanocrystals and regenerated cellulose (RC) were prepared by using in situ synthesizing method. Cellulose was dissolved in a 6 wt.‐% NaOH/4 wt.‐% urea/thiourea aqueous solution at low temperature followed by addition of cadmium chloride (CdCl₂), resulting that the CdS nanocrystals were successfully grown in situ in the cellulose solution. Nanocomposite films containing homogeneous CdS nanoparticles were obtained by casting the resulting solution. Their structure and optical properties were characterized by X‐ray photoelectron spectroscopy, wide‐angle X‐ray diffraction, thermogravimetry analysis, dynamic mechanical analysis, atomic force microscopy, transmittance electronic microscope, UV‐vis spectroscopy, and photoluminescence spectroscopy. The experimental results confirmed that the CdS nanocrystalline existed in the composite films, and cellulose matrix provided a confined medium for CdS particle growth in uniform size. The CdS/RC composites showed narrow emission in photoluminescence spectra, and their optical absorbance in the UV range was higher than that of the cellulose film without CdS. This work provided a simple method to prepare cellulose functional materials in NaOH/urea aqueous solution.

Photoluminescence of CdS/RC nanocomposites and TEM image of CdS nanocrystals dispersed in RC matrix.     

Novel nanoporous membranes from regenerated bacterial cellulose

Bacterial cellulose (BC) in an NaOH/urea aqueous solution was used as a substrate material for thefabrication of a novel regenerated cellulose membrane. The dissolution of BC involved swelling BC in a 4 wt % NaOH/3 wt % urea solution followed by a freeze–thaw process. The BC solution was cast onto a Teflon plate, coagulated in a 5 wt % CaCl₂ aqueous solution, and then treated with a 1 wt % HCl solution. Supercritical carbon dioxide drying was then applied to the formation of a nanoporous structure. The physical properties and morphology of the regenerated bacterial cellulose (RBC) films were characterized. The tensile strength, elongation at break, and water absorption of the RBC membranes were 4.32 MPa, 35.20%, and 49.67%, respectively. The average pore size of the RBC membrane was 1.26 nm with a 17.57 m²/g surface area. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Office waste paper as cellulose nanocrystal source

Cellulose nanocrystals (CNC) are isolated from office waste paper using an alkali solution and a subsequent acid hydrolysis process. The Fourier transform infrared spectroscopy and X‐ray diffraction (XRD) results demonstrate that ink and fillers used in the papermaking industry are almost totally removed after alkali treatments. The XRD results show that CNCs obtained after 2 wt % NaOH solution treatment and a subsequent hydrolysis process exhibit only a cellulose I crystalline structure, and the crystallinity index value increases around 42% with respect to initial office waste paper. Nevertheless, CNCs obtained after 7.5 wt % NaOH solution treatment and a subsequent acid hydrolysis process show a mixture of cellulose I and cellulose II polymorphs. The thermal analysis shows that the CNCs obtained after 7.5 wt % NaOH solution treatment and a subsequent acid hydrolysis process are thermally less stable than other samples, suggesting that the cellulose chains could depolymerize into low molecular weight sugar compounds. Even though the atomic force microscopy images confirm the presence of CNCs, the optical images show that some cellulose microfibers still maintain their structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45257.     

A novel method for vinyl grafting onto cotton fabric using ceric-cellulose thiocarbonate redox system

Treatment of cotton fabric with carbon disulphide in presence of NaOH resulted in cellulose thiocarbonate. The latter formed a complex when treated with ceric ammonium nitrate (CAN). After being thoroughly washed, the Ce^IV cellulose thiocarbonate was capable of initiating vinyl graft polymerization onto cotton fabric without homopolymer formation. The graft yield obtained with methyl methacrylate was found to increase by increasing CAN from zero to 50 mmol/l at temperatures from 60 to 80°C. Grafting was greatly favoured at pH 2; alkaline pH offset grafting. Incorporation of up to 7% of methanol, ethanol, or isopropanol in the aqueous polymerization medium enhanced grafting significantly with the certainty that the highest graft yield was obtained with isopropanol; using higher alcohol percentages decreased grafting. The rate of grafting showed an initial fast rate followed by a slower rate; 60 minutes reaction time proved appropriate for grafting irrespective of the condition used. In addition to methyl methacrylate the ability of Ce^IV-cellulose thiocarbonate to induce grafting of acrylonitrile and acrylamide was also examined. The rate of grafting followed the order methyl methacrylate > acrylonitrile > acrylamide.