Influence of carboxyl group on the acid hydrolysis of cellulose

Cellulose isolated from wood is more susceptible than cotton cellulose to homogeneous hydrolysis in phosphoric acid. The influence of carboxyl group introduction at the C6 position on the hydrolysis rate of cellulose in 82.5% phosphoric acid was studied as a model of the oxidation of cellulose during pulping. The rate constant of hydrolysis for dissolving pulp was larger than that of cotton cellulose at temperatures of 25°–35°C. Mercerized cotton cellulose was partially oxidized regioselectively at the C6 position by a free radical system using 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO). The oxidized cellulose was obtained at a range of 1.7–12.7 mEq carboxyl content per 100 g of cellulose. The hydrolysis rate of the oxidized cellulose samples accelerated with increasing carboxyl content in the samples.Part of this work was presented at the 5th Annual Meeting of the Cellulose Society of Japan, Kyoto, July 1998     

的催化作用

采用以多元羧酸为酯化剂，无机盐为催化剂的交联体系。这一体系是水溶的、无毒害的纤维素交联反应的非甲醛系试剂的交联体系。作者采用傅立叶转换红外光谱(ITIR)分析了多元羧酸与纤维素交联反应过程中催化剂次磷酸盐(NaH2PO2)的作用机理。结果表明：催化剂NaH2PO2对多元羧酸与纤维素酯化反应的两个过程都有催化作用，其两个过程为：1)多元羧酸脱水形成五元环酸酐中间体，NaH2PO2可以降低五元环酸酐中间体形成的温度，加速五元环酸酐的形成；2)五元环酸酐与纤维素亲核取代形成酯，NaH2PO2提高了酯化产物转化率，具有明显的催化作用。     

Preparation and characterization of electroless nickel-coated cellulose fibres

The aim of this project was to fabricate electroless nickel-coated cellulose fibres. Ultimately, these nickel-coated cellulose fibres will be used to develop a cost-effective polymer composite for electromagnetic interference (EMI) shielding and/or electrostatic discharge (ESD) applications. An attempt has been made to impart electrical conductivity onto cellulose fibres via an electroless nickel plating process. The aim was to achieve a homogeneous, continuous layer of Ni on the cellulose fibres, and the plating conditions were optimized to achieve this. The relationship between the coating morphology and the performance of the coated fibre was also of interest. Testing was carried out using cellulose filter paper and then loose cellulose fibres. Scanning electron microscopic (SEM) images of nickel-coated filter paper showed that nickel particles are bonded to the cellulose fibres. The coating appeared more compacted and continuous as plating time increased, corresponding to lower surface resistivity. This observation suggested a correlation between morphology and electrical conductivity of the coating. For nickel-coated cellulose fibres, after optimization of plating conditions, a uniform deposition of nickel particles around the cellulose surfaces was confirmed by SEM images. EDS and XRD results confirmed similar coating could be produced on filter paper and cellulose fibres. SEM images of cross-sectioned nickel-coated cellulose fibres illustrated nickel particles had penetrated into the inner walls of the cellulose fibres. This impregnation of the fibres should act to increase the bonding between nickel coating and cellulose fibres. These nickel-impregnated cellulose fibres could now be incorporated into a polymer matrix to create an electrically conducting composite with the right processing parameters.     

纤维素溶解机理研究述评

纤维素是植物细胞壁的主要组分之一,是由葡萄糖通过1,4-β糖苷键连接而成的均一聚糖,广泛应用于生产酯类、醚类等纤维素基化工产品。纤维素基产品的制备及应用与其溶解程度密切相关,探究纤维素溶解机理,寻找一种绿色高效的纤维素溶剂至关重要。综述了当前国内外学者们对纤维素溶解机理的解释(氢键破坏理论)以及可能影响溶解的因素(化学热力学、化学动力学、结晶度、纤维素两亲性、电荷数和温度),在此基础上探讨了导致纤维素水溶性差的原因,提出了在复杂体系中除了氢键作用以外,还需要综合考虑范德华力、疏水性相互作用的影响。同时,总结了纤维素在离子液体中溶解机理方面存在的争议,其中关于氢键理论还存在一定问题,动力学控制理论尚不明确,阳离子在溶解过程所起的作用被忽视,指出离子液体阳离子的两亲性是纤维素溶解的关键因素。基于纤维素的两亲性及两亲性溶剂促进纤维素溶解的重要理论,提出了应重点寻找新型两亲性溶剂的观点,为未来寻求高效、环境友好、成本低廉的纤维素溶剂指明了方向。     

Chemical analysis of the product in acid-catalyzed solvolysis of cellulose using polyethylene glycol and ethylene carbonate

Degradation and decomposition of cellulose were studied in an acid-catalyzed solvolysis treatment of biomass using polyethylene glycol (PEG) and ethylene carbonate (EC). The solvolysis reaction was followed by a typical reaction system of wood liquefaction that uses sulfuric acid catalyst at 140° or 150°C at atmospheric pressure. The methods of fractionation and chemical analysis of the degraded cellulose in the solvolyzed product are discussed. The solvolyzed product was separated into several fractions, and they were hydrolyzed to release glucose and levulinic acid to determine the quantity of glucosides and levulinates in the solvolysis product. The data clearly showed that the solvolysis reaction had the same mechanism when using PEG or EC. Degradation of cellulose leads to the formation of glucosides, which then decompose, resulting in a levulinic acid structure, and producing a water-insoluble fraction. The conversion rates of both glucosides and levulinates strongly depend on the reaction conditions of the solvolysis. In particular, EC promotes faster conversion of the reactions. The method discussed here is a chemical analytical technique for characterization of the products of wood liquefaction.     

Mixed acylation of Scots pine sawdust and impact on hydrophobicity

Abstract

Acetic–fatty esters of Scots pine sawdust (SPS) were obtained by reaction of SPS with mixtures containing acetic–fatty anhydrides and no solvent or catalyst. Such mixtures were synthesized by reaction between a carboxylic acid and acetic anhydride. The global reaction of acetic anhydride and a fatty acid yields at equilibrium a mixture of five compounds: acetic–fatty anhydride, acetic anhydride, fatty acid, acetic acid and fatty anhydride. The influence of temperature, molar ratio, reaction time and length of the fatty chain on the esterification and on the ratio of grafted acetyl/fatty acyl was investigated. Static contact angles (CAs) with water were measured over 5 min. CA values were dependent on the fatty acyl content and independent of the acetyl content. The minimum ester content of the oleoyl group required to obtain permanent water repellency was 25 mmol kg^?1. Water vapour adsorption measurements indicated that in contrast to water repellency, hydrophobicity to water vapour was correlated with the total mass acyl content.     

Crystals of cellulose grown from TFA solution

Summary Crystallization experiments starting from highly concentrated solutions of cellulose in trifluoroacetic acid (TFA) resulted in white crystalline particles with diameters of as much as 0.5 mm. The plate-like particles consist of lamellae arranged perpendicular to the surface. The lamellae are grown from thin scale-like platelets showing clear diffraction reflexes and an internal parallel structure. Parallel structures were also detected in partially hydrolyzed cellulose. It is concluded that cellulose chains of low DP tend to rearrange themselves by a side by side accumulation of extended molecules.     

超疏水纤维素复合气凝胶的制备及其油水分离

纤维素气凝胶因具有强亲水性和低油水选择性,且目前纤维素气凝胶表面的疏水化处理过程较冗长,限制了其在油水分离领域的应用。为了解决上述问题,笔者以硫酸水解微晶纤维素制备得到的纳米纤维素(CNC)为原料,利用甲基三甲氧基硅烷(MTMS)在水相中对其进行硅烷化改性,通过冷冻干燥得到了硅烷化纤维素复合气凝胶。结果表明:所制备的纤维素复合气凝胶具有轻质、多孔特性,随着MTMS添加量的增加,密度逐渐升高(≤0.012 0 g/cm^3),孔隙率略有下降; MTMS的加入对纤维素复合气凝胶的微观形貌影响不大,其骨架结构以二维片层形貌为主,聚甲基硅氧烷均匀地包覆在纤维素片层表面; MTMS的加入使纤维素复合气凝胶的热稳定性明显提高,且未改变纤维素气凝胶的晶型结构,但导致其结晶度逐渐下降。纤维素复合气凝胶的表面接触角随着MTMS添加量的增加而升高,最高达到153.7°,表现出优异的超亲油/超疏水性能。作为吸油材料,超疏水纤维素复合气凝胶不仅可以吸附多种油类和有机溶剂(吸附容量达到52～121 g/g),而且表现出很好的循环使用性能。     

Characterization of the products resulting from ethylene glycol liquefaction of cellulose

The composition of liquefied cellulose in the presence of ethylene glycol (EG) was studied. The liquefied products were fractionated and analyzed with highperformance liquid chromatography and nuclear magnetic resonance. EG-glucosides were detected as the only saccharides and 2-hydroxyethyl levulinate as the highly decomposed compound derived from cellulose. Quantitative analysis of the EG-glucosides and levulinic acid that comes from the levulinate shows the presence of the following mechanism in the EG-liquefaction of cellulose. First, cellulose is degraded and produces considerable amounts of EG-glucosides during the early stage of liquefaction. Then, when liquefaction is prolonged, the glucosides are decomposed, leading to a large quantity of levulinates.     

Effect of tree age on the cellulose structure of Nalita wood (Trema orientalis)

The change of crystalline structure of Nalita cellulose with tree age has been studied using X-ray diffraction and FT-IR spectroscopy. The proportion of crystallinity and crystal size were increased with tree age. FT-IR spectroscopy showed that the Nalita cellulose was a monoclinic unit cell structure (I_β). The proportion of crystallinity and crystal size of the 30-month-old Nalita wood was higher as compared to aspen wood. The degree of polymerization (DP) of Nalita cellulose of different ages has also been studied. The DP of cellulose increased with tree age. The DP of Nalita cellulose was lower than that of aspen cellulose. The percentage of glucose in Nalita wood increased with tree age.     

Improved method for evaluation of cellulose degradation

 Use of a fundamental concept, henceforth referred to as the scission fraction of cellulose unit (SFCU), was suggested to clarify the cleavage reactivity of cellulose during oxygen delignification (OD). According to the SFCU theory, the cleavage activity of pulp cellulose remains relatively undisturbed provided the experimental conditions are maintained regardless of pulp origin. SCFU is a universal variable for evaluating how processes and additives affect the degree of pulp cellulose degradation. Specifically in this study, the effects of the protector additives MgSO₄ and phenol on the oxygen delignification (OD) process were investigated. Both phenol and MgSO₄ retard the cleavage rate of the cellulose chain, but the retarding effect of MgSO₄ is greater than that of phenol. Phenol alone cannot significantly improve the selectivity of the OD process, whereas MgSO₄ can decrease the cleavage rate of cellulose and increase the selectivity of OD. Moreover, synergistic selectivity enhancement for pulp using a combination of MgSO₄ and phenol was observed. The protective effect of various chemical protectors was additive, whereas the retarding effect on delignification was not. Received: December 21, 2001 / Accepted: July 22, 2002 Acknowledgments We acknowledge the member companies of the Institute of Paper Science and Technology whose interest drives most of our research efforts. Additionally, we gratefully acknowledge the Department of Energy (grant DE-FC07-02ID14261) whose support has made part of this work possible.     

Estimation of the sulfur ester content of cellulose nanocrystals prepared by sulfuric acid hydrolysis: a reproducible and fast infrared method

A fast and reproducible method for estimating the sulfur ester content of cellulose nanocrystals (CNCs) prepared by a pilot plant (Alberta Innovates Technology Futures—Alberta, Canada) is discussed. CNCs from sulfuric acid hydrolysis form electrostatically stabilized suspensions because of the introduction of sulfate ester groups onto the surface of the crystallites during the chemical production. The surface charge of the crystals and indirectly the sulfur ester content has implications when considering several applications. In the past, tedious and time-consuming methods such as X-ray photoelectron spectroscopy, X-ray diffraction, and elemental analysis have been used to estimate the sulfur content of CNCs. As of late, conductometric titrations have surpassed these techniques for estimating the sulfur content of CNC. In this communication, a technique is explored that is specific, fast, and reproducible across a number of samples for determining the quantity of C–O–S linkages in CNC samples. The method is based on integrating key peaks characteristic of sulfur functionalities obtained via Fourier transform infrared spectroscopy. The samples were analyzed as obtained, and no time was needed for extra sample cleanup prior to analysis. Finally, good correlation was obtained between the results obtained for the different samples and comparable to the results obtained from the widely used conductometric method.     

Comparison of cellulose extraction methods for analysis of stable-isotope ratios of carbon and oxygen in plant material

The Jayme-Wise and diglyme-HCl methods for extracting cellulose from plant material for stable-isotope analysis differ considerably in ease of use, with the latter requiring significantly less time and specialized equipment. However, the diglyme-HCl method leaves a small lignin residue in the crude cellulose that may affect stable-isotope values, whereas alpha-cellulose produced by the Jayme-Wise method is relatively pure. We examined whether adding a bleaching step to the diglyme-HCl method could produce cellulose of comparable purity to alpha-cellulose by comparing the yield, percent carbon, and carbon (delta13C) and oxygen (delta18O) stable isotope ratios of the two celluloses. We tested each method on the wood of five species that differ in ease of delignification, Eucalyptus maculata Hook., E. botryoides Sm., E. resinifera Sm., Pinus pinaster Ait. and Callitris glaucophylla J. Thompson & L.A.S. Johnson, as well as the foliage of C. glaucophylla. For hardwoods such as the eucalypts, the diglyme-HCl method without bleaching produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. For the softwood, C. glaucophylla, 3 h of bleaching with acidified chlorite following treatment with diglyme-HCl produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. Bleached and unbleached crude celluloses and alpha-cellulose of P. pinaster were similar in delta18O, but not delta13C. Both types of crude cellulose produced from the foliage of C. glaucophylla had significantly different isotope ratios from alpha-cellulose. Overall, the diglyme-HCl method, with or without bleaching, appears to be a simple, fast method for extracting alpha-cellulose from hardwoods for stable-isotope analyses, but its suitability for softwoods and foliage needs to be evaluated depending on the species.     

A rapid and simple method for processing wood to crude cellulose for analysis of stable carbon isotopes in tree rings

For analysis of carbon isotope discrimination in wood, cellulose or holocellulose is often preferred to whole tissue because of the variability in isotopic composition of different wood components and the relative immobility of cellulose. Most currently used methods for the preparation of wood components for stable isotope analysis (e.g., the Jayme-Wise method) produce a residue of holocellulose. The Jayme-Wise method was initially developed to extract holocellulose from small (~1 g) samples of wood, and, despite subsequent modifications, the method requires specialized glassware, considerable time and entails the risk of sample loss. For carbon isotope analysis, we adapted an acid-catalyzed solvolytic method for preparing crude cellulose by treating wood meal with acidified di-glycol methyl ether (diglyme). The one-step process requires no special glassware, is complete within 24 hours and enables over 100 samples to be processed in a day. This method gives similar delta(13)C values to the Jayme-Wise method for wood of Eucalyptus globulus Labill., Pinus radiata D. Don and Pinus pinaster Ait. The relationship between delta(13)C of wood and crude cellulose is as strong as that observed between wood and alpha-cellulose and stronger than that observed between wood and holocellulose in other species. These relationships suggest that variation in delta(13)C of wood may result from hemicellulose and that analysis of stable carbon isotopes in crude cellulose is preferable. If the consistent -0.3 bias in the value of delta(13)C of cellulose resulting from residual lignin is corrected for, then the relationship between delta(13)C of wood and crude cellulose may be used to predict delta(13)C of cellulose from a small sub-sample. The method is well suited to species with low concentrations of extractives, but further testing is needed to assess its general applicability.     

NaClO添加量对TEMPO氧化纳米微纤丝结构与性能的影响

以毛竹粉为原料,采用TEMPO催化氧化联合超声处理制备纳米微纤丝,通过改变Na Cl O与纤维素的质量比,研究了Na Cl O添加量对纳米纤维素的长径比、纤维形态以及羧基含量等特性的影响。结果表明:随着Na Cl O添加量的增加,纳米纤维素羧基含量逐渐提高,长径比增大;当Na Cl O添加量为15 mmol/g时,纳米纤维素羧基含量可高达1.646 mmol/g,横截面直径可达6～10 nm,长径比为273～455;随着纳米纤维素羧基含量的增加,纳米纤维素悬浮液的透光率和剪切黏度不断增大。虽然TEMPO催化氧化程度不断加深,但纳米纤维素的晶型并未遭到破坏,仍然呈现出典型的纤维素I晶体结构,而随着羧基含量的增加,纳米纤维素的结晶度和热稳定性有一定程度的下降。     

Fundamental studies on wood/cellulose-plastic composites: effects of composition and cellulose dimension on the properties of cellulose/PP composite

Although wood/cellulose-plastic composites (WPC) of low wood/cellulose content have been more accepted worldwide and are promoted as low-maintenance, high-durability building products, composites containing high wood/cellulose content are not yet developed on an industrial scale. In this study, flow properties, mechanical properties, and water absorption properties of the compounds of cellulose microfiber/polypropylene (PP) and maleic anhydride-grafted polypropylene (MAPP) were investigated to understand effects of the high cellulose content and the dimensions of the cellulose microfiber. The molding processes studied included compression, injection, and extrusion. It was found that fluidity is not only dependent on resin content but also on the dimension of the filler; fluidity of the compound declined with increased fiber length with the same resin content. Dispersion of the composite was monitored by charge-coupled device (CCD) microscope. Increasing the plastic content in the cellulose-plastic formulation improved the strength of mold in addition to the bond development between resin and filler, and the tangle of fibers. The processing mode affected the physicomechanical properties of the cellulosic plastic. Compression-molded samples exhibited the lowest modulus of rupture (MOR) and modulus of elasticity (MOE) and the highest water absorption, while samples that were injection-molded exhibited the highest MOR (70 MPa) and MOE (7 GPa) and low water absorption (2%).     

The sorption of water vapour by anhydride modified softwood

A comprehensive investigation into the effect of molecular size of the substituent group of softwood modified with linear chain carboxylic acid anhydrides, namely acetic, propionic, butyric, valeric, hexanoic, upon the sorption of water vapour has been performed. The sorption isotherms for untreated and chemically modified wood were analysed using the Hailwood–Horrobin model. The experimental analysis of the sorption isotherms showed that esterification affects the total, polymolecular and monomolecular sorption. The effect of molecular size of the substituent group on site accessibility was addressed by comparing the effect on water vapour sorption produced by adducts with differences in molecular size. Similar levels of cell-wall bulking were produced at different levels of hydroxyl substitution. Analysis of the sorption isotherms at comparable weight percentage gain revealed that the five anhydrides used show similar effectiveness in both total, polymolecular and monomolecular sorption, despite the substantial difference in the proportion of hydroxyl groups reacted. It is concluded that the reduction in total, polymolecular and monomolecular sorption produced by the linear chain anhydrides is primarily determined by the volume of adduct deposited in the cell wall (bulking) rather than by the number of hydroxyl groups that have been substituted. The validity of the Hailwood–Horrobin model is questioned.     

抗菌剂改性纤维素物料及其抗菌性能(Ⅱ)--改性纤维素物料抗菌素的释出及其抗菌性能

抗菌剂(CA)改性棉纱布(CM)和漂白棉布(CC)系经CA与CM和CC相互吸附作用而制成.本文研究了在不同pH值溶液中抗菌素释出状况.试验结果证明,在pH＝7.0时抗菌素释出量最大.改性纤维素物料的微生物试验表明其具有抗菌性能,作为重要医疗包扎物品,具有实际应用价值.     

The ultrastructure of cellulose from wood

Summary Since in these studies wood is used as basic material for the isolation of cellulose the structure and the composition of this planty substance were considered in greater detail. New measurements of the fiber dimensions and the thickness of the cell wall layers of typical springwood and summerwood tracheids in combination with data obtained from literature led to a model showing the most probable distribution of cellulose, polyoses, and lignin within the cell wall. The ultrastructural composition of the wood cell wall has been deduced from the properties and the behaviour of the cell wall components. The described model will be the basis for subsequent considerations.

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Zusammenfassung Da bei diesen Untersuchungen Holz das Ausgangsmaterial zur Isolierung von Cellulose bildet, wurden die Struktur und die Zusammensetzung dieser pflanzlichen Substanz näher betrachtet. Neue Messungen der Faserdimensionen und der Dicke der einzelnen Wandschichten typischer Früh- und Spätholztracheiden in Verbindung mit Literaturwerten führten zu einem Modell, das die wahrscheinlichste Verteilung von Cellulose, Polyosen und Lignin innerhalb der Zellwand zeigt. Die ultrastrukturelle Zusammensetzung der verholzten Zellwand wurde aus den Eigenschaften und dem Verhalten der Zellwandkomponenten abgeleitet. Das beschriebene Modell wird die Grundlage für nachfolgende Betrachtungen bilden.

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Dedicated in appreciation to my esteemed teacher Prof. Dr.-Ing. Georg Jayme, on the occasion of his 70th birthday.     

Effect of nitrogen and carbon sources on lignin and cellulose degradation by Armillaria ostoyae

Lignin has been hypothesized to be the primary mechanism of resistance to fungal pathogens in plant tissue. Degradation of lignin and cellulose by Armillaria ostoyae cultured for six weeks in Melin-Norkrans medium containing various nitrogen and carbon sources was measured radiometrically. No consistent pattern of lignin or cellulose degradation was found, regardless of A. ostoyae isolate, nitrogen source and concentration, or carbon concentration. More lignin was degraded as the concentration of glucose and fructose increased but not when the concentration of sucrose increased.