取代基及分子量对非离子型纤维素醚表面特性的影响

根据Washburn的浸渍理论(Penetration Theory)和van Oss-Good- Chaudhury的组合理论(Combining Theory)及应用柱状灯芯技术(Column Wicking Technique),对几种非离子型纤维素醚,如甲基纤维素、羟丙基纤维素和羟丙基甲基纤维素的表面特性进行了测试。由于这些纤维素醚的取代基、取代度和分子量不同,所以它们的表面能及其组成部分有着明显的差异。数据说明,非离子型纤维素醚Lewis碱大于Lewis酸,表面自由能的主要成分是Lifshitz-van der Waals力。羟丙基的表面能及其成分都大于羟甲基。而在相同取代基和取代度的前提下,羟丙基纤维素的表面自由能正比于分子量;而羟丙基甲基纤维素的表面自由能则正比于取代度,反比于分子量。实验还发现非离子型纤维素醚中的取代基羟丙基和羟丙基甲基的表面能似乎都大于纤维素的表面能,而实验证明所测试得出的纤维素的表面能及其成分的数据是与文献所吻合的。     

Rheological study on O−carboxymethylated chitosan/cellulose polyblends from LiCl/N,N‐dimethylacetamide solution

An O?carboxymethylated chitosan (O? CMCh) water solution (I) and N,N‐dimethylacetamide (DMAc) emulsion (II) were blended with a cellulose LiCl/DMAc solution, and corresponding polyblends (Polyblends I and II) were obtained. The rheology of the three fluids, that is, the cellulose solution and Polyblends I and II, was investigated. The cellulose solution was characterized by a power‐law fluid. When an O‐CMCh water solution or DMAc emulsion was added to the cellulose solution, the power‐law curve was preserved. The power‐law indexes (n) of all three fluids increased along with the temperature. Polyblend I displays an n close to but a little higher than that of the cellulose solution, while Polyblend II shows a much higher power index than those of the other two fluids. The values of the apparent viscosity (η_a) for all the three fluids are close and decrease along with an increase in the temperature. Adding O‐CMCh microparticles into Polyblends I and II results in a decrease in the structural viscosity index (Δη) in comparison to that of the cellulose solution, and this effect is very obvious for Polyblend I. A cellulose solution's Δη declines with the augmentation of temperature, while the Δη's of both Polyblends I and II show minimum values at about 323 K. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1719–1725, 2003     

不同预处理条件下纤维素的结构变化及其在DMAc／LiCI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／LiCI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／LiCI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。     

纤维素科学与技术研究进展

本文综述纤维素科学与技术的研究进展。阐述了纤维素结构、纤维素的合成、纤维素液晶、功能纤维素、纤维素溶剂、纤维素裂解和纤维素的废物利用等的最新动态。     

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．     

Recoverable shear strain of liquid crystal‐forming concentrated hydroxypropyl cellulose solutions

The recoverable shear strain (S_R) for the liquid crystal‐forming hydroxypropyl cellulose solutions was determined by means of a concentric cylinder rotational apparatus as functions of shear stress prior to recovery and concentration of the solutions at 30°C. S_R greatly depended on shear stress and concentration; the phase of the solution (the single phase or biphase) governed the dependences of S_R on stress and concentration. S_R increased with increasing stress for the single phase and decreased for the biphase. S_R seemed to be related to the die swell (B): S_R ∝ Bⁿ. S_R exhibited a maximum and a minimum with respect to concentration. S_R for the cellulosic cholesteric liquid crystalline solutions was greater than that for the isotropic solutions. A model was proposed for explaining the greater S_R. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 865–872, 2002     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

生物转化植物纤维产酒精的研究进展

植物纤维是潜在的可再生资源，利用微生物对其进行降解、转化以实现工业化低成本生产，已成为研究的热点。从生物方法角度对植物纤维为原料产酒精的3个阶段：原料预处理、纤维素酶糖化和发酵进行全面的阐述，包括微生物及其作用机理和处理工艺等方面的内容。     

聚丁二酸丁二醇酯/纤维素纳米晶复合纤维增强机制

采用熔融纺丝法制备了聚丁二酸丁二醇酯(PBS)/纤维素纳米晶(CNC)复合纤维,重点研究了CNC的分散性、PBS与CNC间氢键作用、PBS分子取向、CNC沿轴向排布以及PBS相结晶度对复合纤维强度的影响。通过光学显微镜和场发射扫描电镜观察发现:高牵伸倍率下的复合纤维较低牵伸倍率下的复合纤维侧面更加平整、光滑,且高牵伸倍率下CNC列。红外光谱图证实了PBS与CNC用力。此外,在提高牵伸倍率时,PBS复合纤维结晶度增大,并且其声速值也明显提高。多因素协同导致PBS/CNC(质量比99/1)复合纤维经4倍牵伸后断裂强度达3.59 cN/dtex,远高于相同处理条件下的纯PBS纤维。     

Viscoelastic properties of cellulose derivatives: 1. Cellulose acetate

The dynamic mechanical spectrum of cellulose acetate (CA) from −130°C to 240°C has been determined at different frequencies (from 0.1 to 30 Hz). Three relaxations, designated , β and γ in order of decreasing temperature, and one shoulder (β*) above room temperature were found. Comparison with calorimetric and thermogravimetric measurements yields the conclusion that the relaxation (197°C at 3 Hz) is related to the glass-to-rubber transition and the β* shoulder (50°C–100°C) is due to loss of moisture. The β relaxation (−38°C at 3 Hz, ΔH = 100 kJ mol⁻¹) is tentatively assigned to local motions of the main chain (glucopyranose rings). The low-temperature γ relaxation (−88°C at 3 Hz, ΔH = 46 kJ mol⁻¹), is humidity-dependent: its intensity decreases when the samples are dried to moisture contents lower than that obtained by normal room conditioning (about 3%). Higher water contents shift the relaxation to lower temperatures without increasing the intensity of the mechanical loss. It is suggested that water associated with the unesterified methylol groups of cellulose acetate is responsible of the dynamic mechanical γ dispersion.