Grafting of cellulose by ring-opening polymerisation – A review

In this review, homogeneous and heterogeneous grafting from cellulose and cellulose derivatives by ring-opening polymerisation (ROP) are reported. Cellulose is biorenewable and biodegradable as well as a stiff material with a relatively low specific weight, foreseen to be an excellent replacement for synthetic materials. By utilising ROP of monomers such as ε-caprolactone or l-lactide from cellulose, composite materials with new and/or improved properties can be obtained. Grafting of solid cellulose substrates, such as cotton, microfibrillated cellulose (MFC) or cellulose nanocrystals, renders cellulose that can easily be dispersed into polymer matrices and may be used as reinforcing elements to improve mechanical and/or barrier properties of biocomposites. A surface grafted polymer can also tailor the interfacial properties between a matrix and the fibrillar structure of cellulose. When derivatives of cellulose are grafted with polymers in homogenous media, amphiphilic materials with interesting properties can be achieved, anticipated to be utilised for applications such as encapsulation and release.     

Interactions of Ionic Liquids with Polysaccharides – 2: Cellulose

Some general comments about ionic liquids (ILs) and carbohydrates are given. The main scope of the review is to discuss the present state of the art of chemical modification of cellulose applying IL as reaction media considering own research results. ILs, namely 1-butyl-3-methylimidazolium chloride (BMIMCl), 1-ethyl- 3-methylimidazolium chloride (EMIMCl), 1-butyl-2,3-dimethylimidazolium chloride (BDMIMCl), 1-allyl-2,3-dimethylimidazolium bromide (ADMIMBr) and 1-ethyl-3- methylimidazolium acetate (EMIMAc) are solvents for cellulose (even for high molecular bacterial synthesized cellulose) and can easily be applied as reaction media for cellulose modification. We investigated the homogeneous acylation, carbanilation and silylation of the biopolymer cellulose. Under mild conditions and within short reaction time at low temperature (65 °C to 80 °C) and low excess of reagent, various cellulose esters and carbanilates, dendronized cellulose and trimethylsilyl cellulose were obtained. The DS of the cellulose derivatives can be controlled by varying the reaction time, reaction temperature and the IL used as reaction medium.     

Mitigation of cellulose recalcitrance to enzymatic hydrolysis by ionic liquid pretreatment

Efficient hydrolysis of cellulose-to-glucose is critically important in producing fuels and chemicals from renewable feedstocks. Cellulose hydrolysis in aqueous media suffers from slow reaction rates because cellulose is a water-insoluble crystalline biopolymer. The high-crystallinity of cellulose fibrils renders the internal surface of cellulose inaccessible to the hydrolyzing enzymes (cellulases) as well as water. Pretreatment methods, which increase the surface area accessible to water and cellulases are vital to improving the hydrolysis kinetics and conversion of cellulose to glucose. In a novel technique, the microcrystalline cellulose was first subjected to an ionic liquid (IL) treatment and then recovered as essentially amorphous or as a mixture of amorphous and partially crystalline cellulose by rapidly quenching the solution with an antisolvent. Because of their extremely low-volatility, ILs are expected to have minimal environmental impact. Two different ILs, 1-n-butyl-3-methylimidazolium chloride (BMIMC1) and 1-allyl-3-methylimidazolium chloride (AMIMC1) were investigated. Hydrolysis kinetics of the IL-treated cellulose is significantly enhanced. With appropriate selection of IL treatment conditions and enzymes, the initial hydrolysis rates for IL-treated cellulose were up to 90 times greater than those of untreated cellulose. We infer that this drastic improvement in the "overall hydrolysis rates" with IL-treated cellulose is mainly because of a significant enhancement in the kinetics of the "primary hydrolysis step" (conversion of solid cellulose to soluble oligomers), which is the rate-limiting step for untreated cellulose. Thus, with IL-treated cellulose, primary hydrolysis rates increase and become comparable with the rates of inherently faster "secondary hydrolysis" (conversion of soluble oligomers to glucose).     

“一锅法”均相合成热塑性纤维素丙酸酯接枝聚乳酸共聚物

纤维素重复单元的羟基上引入足够数量的柔性分子链,有可能在破坏纤维素分子链间氢键的同时起到内增塑作用,从而赋予纤维素熔融流动性.由纤维素酯化反应得到的一些短链取代的纤维素酯[如纤维素醋酸酯(CA)、纤维素丙酸酯(CP)等]具有热塑性,但需要在外加大量增塑剂条件下才能熔融加工[1].接枝共聚合是改变纤维素物理化学性质的另一种有效方法[2～4]。     

Inverse temperature-dependent pathway of cellulose decrystallization in trifluoroacetic acid

An unusual inverse temperature-dependent pathway was observed during cellulose decrystallization in trifluoroacetic acid (TFA). Decreasing the TFA treatment temperature accelerated the cellulose decrystallization process. It took only 100 min to completely decrystallize cellulose at 0 degrees C in TFA, a result not achieved in 48 h at 25 degrees C in the same medium. There was neither cellulose esterification nor a change of cellulose macrofibril morphology by TFA treatment at 0 degrees C. Our IR data suggest that TFA molecules are present as cyclic dimers when they penetrate into crystalline cellulose regions, transforming crystalline cellulose to amorphous cellulose. On the other hand, the rate of TFA penetration into the cellulose matrix was greatly retarded at higher temperatures where monomeric TFA prevails. At elevated temperatures, esterification of TFA monomers on the external surface of crystalline cellulose, agglomeration of cellulose macrofibrils, as well as water released from the esterification reaction, inhibit the diffusion rate of TFA into the cellulose crystalline region and decrease the TFA swelling capability.     

Combination of oxidative and hydrolytic functions of nitric acid in production of enterosorbents based on carboxylated microcrystalline cellulose

A single-stage procedure was developed for preparing carboxylated microcrystalline cellulose from native cellulose in 45–55% nitric acid acting as a deposited form of catalyst of cellulose oxidation, nitrogen(IV) oxide, and as a selective reagent partially hydrolyzing cellulose.     

Influence of cellulose polymorphs on the polypropylene crystallization

Results of the hitherto research work on alkalisation of lignocellulosic materials have been much divergent. In view of the above, the subject of this study is mercerization of cellulose from pine wood. This choice of the subject permitted observation of transformation of cellulose I to cellulose II with no participation of other components of lignocellulosic materials. According to X-ray results, during mercerization the isolated cellulose was easily (completely) transformed into cellulose II variety, while the pine wood was converted more slowly to cellulose II polymorphs. Therefore, it could be concluded that the presence of lignin and hemicelluloses in wood prevented the transformation from cellulose I to II. The main objective of this research was to establish the effect of cellulose varieties on the nucleation ability of different fillers by using differential scanning calorimetry (DSC) and polarizing microscopy. The nucleating effect of the fillers occurs only in the presence of cellulose I variety. In contrast, the presence of cellulose II variety seems to practically eliminate the nucleating effect of the fillers. Moreover, nucleation of the mercerized wood (mixture of cellulose I and II) can be also observed, but this effect is not strong. It should be emphasised that as yet no correlation has been reported between the quantitative composition of cellulose polymorphic forms (appearing not only in wood, but in cellulose isolated from wood as well) and the nucleation ability of lignocellulosic fillers.     

CP/MAS ~(13)C NMR技术对木浆纤维微观结构的研究

利用交叉极化结合魔角旋转技术~(13)C核磁共振法(CP/MAS ~(13)C NMR)对桉木浆纤维的微观结构进行研究,为进一步研究木质纤维素材料开发过程中反应障碍特征奠定基础.通过对NMR光谱C1区(δ 102～108)进行洛仑兹拟合,得到桉木浆纤维中纤维素Iα的相对含量为26.92%,纤维素Iβ的相对含量为52.04%,主要以纤维素Iβ晶体形式为主.通过计算纤维素C4结晶区(δ 86～92)和非结晶区(δ 80～86)的相对含量得到桉木浆的纤维素结晶度为47%.通过洛仑兹和高斯函数的混合模型对NMR光谱C4区(δ 80～92)进行拟合得到基原纤尺寸和微原纤横向尺寸分别为4.0与17.9 nm,并通过计算不同形态的结晶纤维素的相对含量得到纤维素结晶度为51%,证实了在微原纤内部次晶纤维素的存在.     

Utilizing Polymer Blends to Prepare Ultrathin Films with Diverse Cellulose Textures

This paper presents an overview of the recent work on ultrathin polymer blend films containing cellulose. Three systems prepared via trimethylsilyl cellulose derivative, which is subsequently hydrolyzed to cellulose, are presented: polystyrene/cellulose, poly(methyl methacrylate)/cellulose and polystyrene-block-polyethyleneoxide/cellulose. Diverse textures emerge within the films depending on the interactions between the polymers and their interactions with the substrate as well as on different solubilities of the polymers. Furthermore, an ultrathin film containing a cellulose/xylan blend is presented. This film was deposited directly from a common solvent (dimethylacetamide/lithium chloride) and it did not exhibit distinct morphological patterns comparable to the blends with synthetic polymers.     

Green and combinational method towards clickable alkynylated cellulose fibers (ACFs)

This paper presents an environmentally friendly strategy to obtain alkynylated cellulose fibers (ACFs), a versatile platform for tailoring cellulose by robust click reaction. This strategy is based on the integration of two efficient reactions: selective oxidation of cellulose fibers by sodium periodate (NaIO₄) generating dialdehyde cellulose fibers and subsequent Schiff base reaction with 3-ethynylaniline yielding alkynylated cellulose fibers (ACFs). The alkynyl moieties introduced into ACFs were simply transferred with azido compounds under Cu(I) catalysis and mild conditions. The content of alkynyl groups of ACFs was found to be as high as 3.0 mmol/g. Fourier transform infrared spectroscopy (FTIR) showed that the selective oxidation of cellulose fibers generated aldehyde groups and the Schiff base reaction resulted in the incorporation of ethynyl groups and benzene rings into cellulose fibers. FTIR and X-ray photoelectron spectroscopy results confirmed the successful click reaction between ACFs and 4-azidobenzoic acid. This clickable platform would serve as a versatile starting precursor for finely tuning cellulose fibers for advanced applications.     

Synthese et etude de celluloses echangeuses d'ions. Leur emploi dans l'epuration des eaux residuaires de l'industrie textile—1: Synthese d'une cellulose greffee par des chaines poly (acide acrylique) et d'une cellulose renfermant des fonctions ammonium quaternaire

For use as ion exchangers and particularly as purification agents for textile industrial effluents, cellulose grafted with polyacrylic acid and cellulose substituted by quaternary ammonium functions have been prepared. For both syntheses, the influences of experimental parameters have been studied in detail and the optimum conditions for large-scale preparation have been determined. Large amounts of modified cellulose have been obtained and tested in industry (cf. part III). The grafting by acrylic acid has been carried out by the ceric-ion method; the quaternary ammonium cellulose has been obtained by condensation of cellulose with epoxy propyl triethyl ammonium chloride. Synthesis of this salt in the presence of cellulose has been achieved so that the quaternary ammonium cellulose can be obtained from cellulose and epichlorhydrin in one step.     

Mercerization and acid hydrolysis of bacterial cellulose

Structural changes in never- dried, disintegrated bacteria l cellulose by treatment with aqueous NaOH were examined by electron microscopy, X-ray diffractometry and acid hydrolysis behaviour and compared with those of cotton cellulose. The microfibril kept its fibrillar morphology after treatment with NaOH solutions of less than 9% (w/w), but changed into irregular aggregates when treated with NaOH above 12% (w/w), corresponding to the crystal conversion to cellulose II. The crystallinity of the resulting cellulose II was very low after a brief alkali treatment, but was increased significantly by elongated treatment (up to 10 days). In contrast, cotton cellulose was converted to cellulose II of fairly high crystallinity by alkali treatment of as little as 3 min duration, and the crystallinity did not change with longer treatments. The leveling-off degree of polymerization (LODP) of bacterial cellulose was decreased from 150 to 50 by 18% (w/w) NaOH treatment, while that of cotton linter decreased from 260 to 70. These characteristic differences between cotton linter cellulose and bacterial cellulose can be ascribed to a basic difference in microfibrillar organization in these materials: the microfibrils in cotton cellulose are in close contact with neighbouring microfibrils having opposite polarity, and in bacterial cellulose are isolated from each other and require chain folding to form the antiparallel cellulose II crystal     

Direct Electrochemical Oxidation of Cellulose: A Cellulose‐Based Fuel Cell System

Direct electricity generation from cellulose without saccharification and fermentation processes was achieved on gold electrode under the alkaline conditions. We (i) overcame problems with the insolubility of cellulose, and captured its electrochemical potential, and (ii) showed that cellulose was converted to cellulose derivatives due to electrochemical oxidation. In addition, we (iii) constructed a cellulose‐based fuel cell, demonstrating that cellulose can be direct electrical based fuel source. The presented fuel cell system overcomes the enormous distribution challenges encountered with other alternative bioenergy sources such as hydrogen.     

介质和力场协同作用对纳米纤维素形貌结构的调控

纤维素是一种由直链多聚糖通过糖苷键连接而成的巨型线性高分子,纤维素分子链通过氢键紧密排列形成纤维素晶体.由于纤维素晶体具有优良的化学可修饰性和机械性能等优点,纳米化加工的纤维素可广泛应用于日常生活和工业生产的各个领域.本文主要介绍了本课题组在机械剪切力作用下,实现纤维素纳米化并同时进行亲水或疏水改性的研究进展,重点介绍了介质极性对纤维素分子链之间相互作用的影响,并通过改变分子链之间的相互作用来调控纳米化纤维素的形貌和亲、疏水性.提出机械外力和环境极性协同作用下,晶面导向剥离纤维素的理论.     

Effect of crystallinity on radiation-induced graft copolymerization on cellulose

With vinyl monomers, viz., styrene, butyl methacrylate, dimethylaminoethyl methacrylate, and ethyl acrylate, it was noted that higher per cent grafting was obtained with “recrystallized” cellulose than with “amorphous” cellulose. The possibility of the production of a porous structure in cellulose as a result of γ-irradiation followed by the dissolution of the reactive regions is suggested. DTA and DTG data of irradiated cellulose triacetate (CTA) reveal lowering of the melting point on irradiation, indicating a decrease in crystallinity. Decrease in density of cellulose on irradiation by γ-rays also indicates loosening of the structure of cellulose. It is postulated that grafting occurs in those regions of cellulose which were crystalline before irradiation, as well as in less crystallinie regions.     

Resolution of enantiomers by HPLC on cellulose derivatives

Summary Various polysaccharide derivatives, particularly cellulose derivatives, were synthesized and used as chiral stationary phases for optical resolution by HPLC after being adsorbed on macroporous silica gel. Cellulose triacetate (CTA-II), which was synthesized under homogeneous conditions, showed a chiral recognition ability for many racemates. Other cellulose derivatives such as cellulose tribenzoate (OB), cellulose-trisphenylcarbamate (OC), cellulose tribenzyl ether (OE), and cellulose tricinnamate (OK) also showed unique chiral recognition. Among other polysaccharide derivatives, curdlan triacetate was also exhibited an effective chiral recognition. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Thermal decomposition and burning behavior of cellulose treated with ethyl ester phosphoramidates: Effect of alkyl substituent on nitrogen atom

This research explores the structural effect of phosphoramidates as flame retardants (FRs) for cotton cellulose. Flame retardant (FR) and thermal decomposition actions of phosphate such as triethyl phosphate (TEP), primary phosphoramidate such as diethyl phosphoramidate (DEPA) and secondary phosphoramidates such as phosphoramidic acid, N(2-hydroxy ethyl) diethylester (PAHEDE), diethyl ethyl phosphoramidate (DEEP) and diethyl 2-methoxyethylphosphoramidate (DEMEP) on cotton cellulose were investigated. Limiting oxygen index (LOI) of treated cotton cellulose showed that all phosphoramidates exhibited better flame retardant properties as compared to TEP. Secondary phosphoramidate PAHEDE had better flame retardant properties as compared to DEMEP and DEEP which indicate that flame retardancy of secondary phosphoramidates is structure related. Test performed on pyrolysis combustion flow calorimeter (PCFC) for treated cellulose showed higher reduction in heat of combustion for efficient FRs (PAHEDE, DEPA). Evolved gas analysis using thermogravimetric analyzer-Fourier transform infrared spectroscopy (TGA-FTIR) and thermogravimetric analyzer-mass spectrometer (TGA-MS) of treated cellulose showed that phosphoramidates could catalyze the dehydration and char formation of cellulose at a lower temperature. The enhanced flame retardant action of phosphoramidate may be due to the catalytic thermal decomposition of the phosphoramidate structure to produce acidic intermediates which could react with cellulose to alter its thermal decomposition.     

纤维素溶剂研究进展

概述了纤维素溶剂的重要研究进展,主要包括N-甲基吗啉-N-氧化物(NMMO)在85℃以上高温可破坏纤维素分子间氢键,导致溶解;氯化锂/二甲基乙酰胺(LiCl/DMAc)在100℃以上可溶解纤维素;1-丁基-3-甲基咪唑盐酸盐([BMIM]Cl)和1-烯丙基-3-甲基咪唑盐酸盐([AMIM]Cl)离子液体,含强氢键受体Cl-离子,通过它们与纤维素羟基作用而引起溶解.氨基甲酸酯体系则是通过尿素与纤维素在100℃以上反应转变为纤维素氨基甲酸酯,然后再溶解于NaOH水溶液中;氢氧化钠/水体系,只能溶解结晶度和聚合度较低的纤维素;NaOH/尿素、NaOH/硫脲和LiOH/尿素水溶液体系,它们预冷至-5~-12℃后可迅速溶解纤维素.主要是通过低温产生小分子和大分子间新的氢键网络结构,导致纤维素分子内和分子间氢键的破坏而溶解,同时尿素或者硫脲作为包合物客体阻止纤维素分子自聚集使纤维素溶液较稳定.低温溶解技术不仅突破了加热溶解的传统方法,而且可推进化学"绿色化"进程.共引用参考文献50篇.     

Removal of boron(III) by N-methylglucamine-type cellulose derivatives with higher adsorption rate

To obtain adsorbents for boron(III) derived from a natural polymer, two forms (powder and fiber) of N-methylglucamine-type cellulose derivatives were newly synthesized. After the graft polymerization of two forms of cellulose with vinyl monomer having epoxy groups, the N-methylglucamine-type cellulose derivatives were obtained by the reaction of the grafted cellulose with N-methylglucamine. The adsorption capacities of the cellulose derivatives for boron(III) were the same levels as that of a commercially available N-methylglucamine-type polystyrene resin. However, the cellulose derivatives adsorbed boron(III) more quickly than the polystyrene resin. The adsorption and desorption of boron(III) with a column method using the cellulose fiber were achieved at a higher flow rate than that using the polystyrene resin. In addition, the boron(III), adsorbed on the cellulose fiber column, was quantitatively recovered with dilute hydrochloric acid in 20- and 200-fold increased concentrations. Consequently, it was found that the cellulose derivatives were superior to the polystyrene resin as adsorbents for boron(III) for treatment of a large quantity of wastewater.