Cellulose Esters Prepared by Wood Esterification

Trends in the yields and properties of cellulose esters are studied as a function of wood esterification conditions. The yield, total extent of cellulose ester substitution, and degree of conversion depend on the duration and acylation temperature     

Acetylation of Cellulose Nanowhiskers with Vinyl Acetate under Moderate Conditions

A novel and straightforward method for the surface acetylation of cellulose nanowhiskers by transesterification of vinyl acetate is proposed. The reaction of vinyl acetate with the hydroxyl groups of cellulose nanowhiskers obtained from cotton linters was examined with potassium carbonate as catalyst. Results indicate that during the first stage of the reaction, only the surface of the nanowhiskers was modified, while their dimensions and crystallinity remained unchanged. With increasing reaction time, diffusion mechanisms controlled the rate, leading to nanowhiskers with higher levels of acetylation, smaller dimensions, and lower crystallinity. In THF, a solvent of low polarity, the suspensions from modified nanowhiskers showed improved stability with increased acetylation.

     

Preparation of Phosphoric-Carboxylic Cation Exchangers from Wood Cellulose

Phosphorus-containing cellulose cation exchangers were synthesized by reaction of wood cellulose with orthophosphoric acid and the ternary polymer from glycidylmethacrylate, styrene, and maleic anhydride. The effects of the ratio of reactants, temperature, and duration of the reaction on the phosphorylation and exchange capacity of the modified cellulose material were studied.     

棉浆粨纤维素的超声波处理

氢键;结晶程度;棉浆粨纤维素的超声波处理     

Preparation and Characterization of Nanocomposites of Carboxymethyl Cellulose Reinforced with Cellulose Nanocrystals

Summary: Cellulose nanocrystals (CNC) were extracted from Kraft pulp of Eucalyptus urograndis. The CNC were isolated by acid hydrolysis with H₂SO₄ 64% (w/w) solution, for 20 minutes at 45 °C. The morphology and crystallinity of the CNC were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. The AFM image supports the evidence for the development of crystals of cellulose in nanometric scale. These nanoparticles were used as reinforcement material in carboxymethyl cellulose (CMC) matrix. Nanocomposites films were prepared by casting. The nanocomposites were characterized by thermal (TGA) and mechanical (DMA) analyses. A large reinforcing effect of the filler was observed. The tensile strength of nanocomposites was significantly improved by 107%, the elongation at break decreased by 48% and the thermal resistance increased slightly. The improvements in thermo-mechanical properties suggest a close association between filler and matrix.     

The Thermal Expansion of Wood Cellulose Crystals

We have investigated tension wood cellulose obtained from Populus maximowiczii using X-ray diffraction at temperatures from room temperature to 250 °C. Three equatorial and one meridional d-spacings showed a gradual linear increase with increasing temperature. For temperatures above 180 °C, however, the equatorial d-spacing increased dramatically. Thus, the linear and volume thermal expansion coefficients (TECs) below 180 °C were determined from the d-spacings. The linear TECs of the a-, b-, and c-axes were: α _a = 13.6 × 10⁻⁵ °C⁻¹, α _b = −3.0× 10⁻⁵ °C⁻¹, and α _c =0.6× 10⁻⁵ °C⁻¹, respectively, and the volume TEC was β = 11.1× 10⁻⁵ °C⁻¹. The anisotropic thermal expansion in the three coordinate directions was closely related to the crystal structure of the wood cellulose, and it governed the macroscopic thermal behavior of solid wood.     

Aerogels from Unaltered Bacterial Cellulose: Application of scCO2 Drying for the Preparation of Shaped,Ultra‐Lightweight Cellulosic Aerogels

Bacterial cellulose produced by the gram‐negative bacterium Gluconacetobacter xylinum was found to be an excellent native starting material for preparing shaped ultra‐lightweight cellulose aerogels. The procedure comprises thorough washing and sterilization of the aquogel, quantitative solvent exchange and subsequent drying with supercritical carbon dioxide at 40 °C and 100 bar. The average density of the obtained dry cellulose aerogels is only about 8 mg · cm^?3 which is comparable to the most lightweight silica aerogels and distinctly lower than all values for cellulosic aerogels obtained from plant cellulose so far. SEM, ESEM and nitrogen adsorption experiments at 77 K reveal an open‐porous network structure that consists of a comparatively high percentage of large mesopores and smaller macropores.

     

Preparation and Characterization of Niobium Oxide Coated Cellulose Fiber

The Nb₂O₅/cellulose composite was prepared by reacting α-cellulose with NbCl_5-n(OC₂H₅)_n, in nonaqueous solvent, under nitrogen atmosphere and submitting the obtained material to hydrolysis. An increase in the crystallinity degree is observed in the composite material because the precursor reagent reacts with the amorphous phase of the cellulose fibers. Loadings between 4.5 and 16.0% of the oxide were achieved and in every case the oxide particles uniformly cover the fiber surface. Lewis and Brønsted acid sites were determined by using pyridine as the basic molecular probe.     

Synthesis and Characterization of Cellulose Triacetate Obtained from Date Palm (Phoenix dactylifera L.) Trunk Mesh-Derived Cellulose

Cellulosic polysaccharides have increasingly been recognized as a viable substitute for the depleting petro-based feedstock due to numerous modification options for obtaining a plethora of bio-based materials. In this study, cellulose triacetate was synthesized from pure cellulose obtained from the waste lignocellulosic part of date palm (Phoenix dactylifera L.). To achieve a degree of substitution (DS) of the hydroxyl group of 2.9, a heterogeneous acetylation reaction was carried out with acetic anhydride as an acetyl donor. The obtained cellulose ester was compared with a commercially available derivative and characterized using various analytical methods. This cellulose triacetate contains approximately 43.9% acetyl and has a molecular weight of 205,102 g·mol⁻¹. The maximum thermal decomposition temperature of acetate was found to be 380 °C, similar to that of a reference sample. Thus, the synthesized ester derivate can be suitable for fabricating biodegradable and “all cellulose” biocomposite systems.     

Cellulose Nanofibers from Schinus molle: Preparation and Characterization

Schinus molle (SM) was investigated as a primary source of cellulose with the aim of discovering resources to generate cellulose nanofibers (CNF). The SM was put through a soda pulping process to purify the cellulose, and then, the fiber was treated with an enzymatic treatment. Then, a twin-screw extruder and/or masuko were utilized to help with fiber delamination during the nanofibrillation process. After the enzymatic treatment, the twin-screw extruder and masuko treatment give a yield of 49.6 and 50.2%, respectively. The optical and atomic force microscopy, morfi, and polymerization degrees of prepared cellulosic materials were established. The pulp fibers, collected following each treatment stage, demonstrated that fiber characteristics such as length and crystallinity varied according to the used treatment (mechanical or enzymatic treatment). Obviously, the enzymic treatment resulted in shorter fibers and an increased degree of polymerization. However, the CNF obtained after enzymatic and extrusion treatment was achieved, and it gave 19 nm as the arithmetic width and a Young’s modulus of 8.63 GPa.     

Interpretation of Strengthening Mechanism of Densified Wood from Supramolecular Structures

In this study, densified wood was prepared by hot pressing after partial lignin and hemicellulose were removed through alkaline solution cooking. The tensile strength and elastic modulus of densified wood were improved up to 398.5 MPa and 22.5 GPa as compared with the original wood, and the characterization of its supramolecular structures showed that the crystal plane spacing of the densified wood decreased, the crystallite size increased, and the maximum crystallinity (CI) of cellulose increased by 15.05%; outstandingly, the content of O(6)H⋯O(3′) intermolecular H-bonds increased by approximately one-fold at most. It was found that the intermolecular H-bond content was significantly positively correlated with the tensile strength and elastic modulus, and accordingly, their Pearson correlation coefficients were 0.952 (p < 0.01) and 0.822 (p < 0.05), respectively. This work provides a supramolecular explanation for the enhancement of tensile strength of densified wood.     

Selectively Dendronized Cellulose: Synthesis and Characterization

Selectively dendronized cellulose at C‐6 was synthesized homogeneously (in DMSO) and heterogeneously (in methanol) by the conversion of 6‐azido‐6‐deoxy cellulose (degree of substitution, DS 0.75) with polyamidoamine (PAMAM) dendrons possessing an ethynyl focal moiety via the copper‐catalyzed Huisgen reaction (click reaction) under mild conditions. First to third generation of PAMAM‐triazolo cellulose derivatives with DS values of up to 0.69 could be prepared, which are soluble in organic solvents (DMSO, DMF) and in water. The novel biopolymer derivatives were characterized by elemental analysis, FTIR, and NMR spectroscopic methods, showing no impurities and no conversion at the secondary positions.

     

Characterization of Highly Porous Materials from Cellulose Carbamate

Highly porous cellulose was formed by gelation of cellulose carbamate solutions in caustic soda. Two methods for gel preparation were optimized for the formation of beads and bulky materials – the chemical precipitation from dilute sulfuric acid and the thermal gelation by annealing at elevated temperatures. Various methods were used for characterizing of the pores of low density materials: scanning electron microscopy, small angle X-ray scattering, mercury intrusion and nitrogen sorption. These methods were optimized and used for characterizing the complete pore system from micro to macro pores. The effects of different preparation (cellulose carbamate concentration in caustic soda) and processing (precipitation, drying and pyrolysis) on the pore structure were studied by the set of complementary methods. Aerocell samples with a minimum density of 0.06 g/cm³ were prepared from cellulose carbamate. They are characterized by a broad pore size distribution ranging from 0.5 nm to 1 mm, specific internal surfaces of up to 660 m²/g and total pore volumes of up to 18 cm³/g.     

纳米纤维素晶须的表面醋酸酯化改性及复合材料的力学性能

采用硫酸水解法制备纳米纤维素晶须, 再以冰醋酸为分散介质, 浓硫酸为催化剂, 醋酸酐为酯化剂对纳米纤维素晶须进行不同程度醋酸酯化改性, 得到醋酸酯化的纳米纤维素. 采用红外光谱(FTIR)、 X射线光衍射(XRD)、 透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对改性产物进行分析和表征. 结果表明, 改性纳米纤维素晶须中醋酸酯基的平均取代度过小或过大时均不适宜用作复合材料的增强相. 当改性纳米纤维素晶须中醋酸酯基的平均取代度为0.05时, 醋酸酯化反应只发生在纳米纤维素晶须的表面. 此时, 晶须能在丙酮中稳定悬浮, 表现出流动双折射现象, 并保持了改性前纳米纤维素晶须的棒状形态和高结晶度. 将这种改性后的纳米纤维素晶须作为增强相与醋酸纤维素通过溶液浇铸法制成纳米复合膜, 结果显示, 与空白醋酸纤维素膜相比, 添加改性纳米纤维素晶须后, 纳米复合膜的拉伸强度、 杨氏模量和断裂伸长率都得到了提高. 在玻璃化转变区间纳米复合膜储能模量的降低幅度小于空白膜.     

纤维素及其衍生物的高压静电纺丝

高压静电纺丝作为一种制备纳米纤维的先进技术,近年来受到普遍关注。而纤维素和纤维素衍生物由于其优越的性质已应用于各个领域。运用高压静电纺丝技术对纤维素及其衍生物进行研究,开拓了新的研究领域和发展方向。本文介绍了高压静电纺丝技术的研究背景和原理,总结了近几年研究者们在纤维素以及纤维素衍生物高压静电纺丝方面的工作进展,尤其对不同溶剂体系溶解纤维素用于静电纺丝的优缺点进行了比较,评述了这方面的前沿性探索研究,并对未来的发展进行了展望。     

Extraction and Characterization of Natural Cellulose Fibers from Maize Tassel

This article reports on the extraction and characterization of novel natural cellulose fibers obtained from the maize (tassel) plant. Cellulose was extracted from the agricultural residue (waste biomaterial) of maize tassel. The maize tassel fibers were obtained after treatment with NaOH and were carefully characterized while the chemical composition was determined. The chemical composition of the maize tassel fibers showed that the cellulose content increased from 41% to 56%, following alkali treatment. FT-IR spectroscopic analysis of maize tassel fibers confirmed that this chemical treatment also shows the way to partial elimination of hemicelluloses and lignin from the structure of the maize tassel fibers. X-ray diffraction results indicated that this process resulted in enhanced crystallinity of the maize tassel fibers. The thermal properties of the maize tassel fibers were studied by the TGA technique and were found to have improved significantly. The degradation temperature of the alkali-treated maize tassel fiber is higher than that of the untreated maize tassel fibers. This value convincingly showed the potential of maize tassel fibers for use in reinforced biocomposites and waste water treatment.     

Peroxide-Ammonia Delignification of Pine Wood

Oxidative delignification of pine wood by hydrogen peroxide in aqueous ammonia was studied. A new method for producing cellulose and N-containing organic fertilizers was developed. It was demonstrated that a solution of hydrogen peroxide (3-9%) in aqueous ammonia delignified extensively wood to produce cellulose in yields up to 54.6% with a residual lignin content up to 1.1%. The process of pine-wood delignification by hydrogen peroxide in aqueous ammonia was described satisfactorily by a first-order kinetic equation.     

Controlled Synthesis and Electrochemical Behavior of Single-crystal MoO2 Nanowhiskers by a Facile Precursor-reduction Route

Among the transition-metal oxides, molybdenum oxides are the focus of much attention owing to its numerous applications in catalysts, additives, sensors, photochromic and electrochromic materials1. Especially, the applications of MoO2 in optical propertie…