静电纺丝法制备纤维素纳米纤维的研究进展

纤维素纳米纤维很好的结合了纤维素的重要属性和纳米材料的各项特性,但纤维素大分子之间存在大量氢键,使得纤维素较难溶于普通溶剂,导致通过静电纺丝法直接制备纤维素纳米纤维具有一定的难度.而先采用静电纺丝法制备纤维素衍生物纳米纤维,再对纤维素衍生物纳米纤维进行水解也是制备纤维素纳米纤维的一种有效方法.本文对近年来这两种纤维素纳米纤维制备方法的研究进行了综述,并对静电纺制备纤维素纳米纤维的发展前景做出了展望.     

静电纺丝法在制备改性醋酸纤维素中的应用

纤维素是一种天然存在于有机物或植物中储量巨大的可再生资源。醋酸纤维素是在催化剂的作用下,将纤维素的羟基酯化而得到的一种热塑性树脂。由于其具有稳定,易于加工,不易燃烧,生物可降解性等特点,常用来替代天然纤维素作为静电纺丝的原料。静电纺丝技术作为目前制备纳米纤维材料的一种简单有效的方法,近些年来一直备受关注。本文系统介绍了以醋酸纤维素为静电纺丝的基体材料, 通过添加纳米粒子、聚合物溶液、表面改性、同轴电纺等物理改性方法以及再生纤维处理和硝化反应等化学改性方法制备改性醋酸纤维素纤维, 讨论了改性后的新材料结构和性能等多方面的变化。综述了近几年来国内外关于以静电纺丝法制备改性醋酸纤维素纤维的研究进展以及其在生物医药、组织工程支架、过滤膜以及功能性织物等方面的应用前景。     

静电纺丝制备醋酸纤维素复合纳米纤维的研究进展

静电纺丝技术就是通过带电聚合物溶液或熔体的喷射来制备纳米纤维,是一种制备纳米纤维材料简单有效的技术。醋酸纤维素(CA)易溶于有机溶剂,常作为纤维素的替代材料应用于静电纺丝领域。本文总结了近年来国内外采用静电纺丝技术制备CA复合纳米纤维的研究新进展,重点介绍了CA/CNTs复合纳米纤维、CA/金属粒子复合纳米纤维、CA/金属氧化物复合纳米纤维、CA基载药复合纳米纤维、CA/PAN复合纳米纤维、CA/PVA复合纳米纤维、CA/CS复合纳米纤维等CA复合纳米纤维的研究进展以及潜在的应用领域。     

纤维素混合醚酯的制备与静电纺丝性能

研究了几种纤维素混合醚酯的制备及其高压静电场纺丝性能,分析了溶剂组成、溶液浓度、分子量、酯化基团对成纤性和纤维直径的影响。结果表明:在非均相条件下,经过碱化、醚化与酯化,得到不同结构的纤维素混合醚酯HPMCP、HPMCT与HPMCAS,均可实现静电纺丝;在甲醇/二氯甲烷=1∶4的溶剂体系中易得到表面光滑纤维;在溶剂组成一定条件下,溶液仅在一定浓度范围可纺,且浓度越低、纺丝电压越高,纺丝平均直径越小;当溶剂组成、溶液浓度一定时,分子量对其溶液纺丝的可纺性有直接影响,HPMCAS仅重均分子量达到7.2×104才能获得表面光滑纺丝纤维;在溶剂组成、溶液浓度和分子量一定的条件下,相邻酰基间距离越小,酸性越强,溶液电导率越大,丝越细。     

纳米纤维素的制备*

在纳米尺寸范围操控纤维素分子及其超分子聚集体,结构设计并组装出稳定的多重花样,由此创制出具有优异功能的新纳米精细化工品、新纳米材料,是纤维素科学的前沿领域和热点。为了研究当前制备纳米纤维素的现状和发展方向,简述了纳米纤维素化学基础,介绍了三类纳米纤维素：纳米纤维素晶体（晶须）、纳米纤维素复合物和纳米纤维素纤维,重点综述了纳米纤维素的五种制备方法：化学法制备纳米纤维素晶体和晶须、生物法制备细菌纤维素、物理法制备微纤化纳米纤维素、人工合成纳米纤维素和静电纺丝制备纤维素纤维,讨论了各种制备方法的优点和缺点,指出开展纳米纤维素超分子的可控结构设计、立体与位向选择性控制与制备、分子识别与位点识别等自组装过程机理、多尺度结构效应的形成机理等基础理论性研究是主要研究基础,新型的、绿色、低能耗、快速、高效的制备方法是纳米纤维素制备方法的发展方向。     

纤维素基聚合物液晶溶液的发展、现状及展望

使用液晶溶液纺丝可以制得高强度、高模量的纤维.经大量研究发现,作为环保可再生的资源,纤维素及其衍生物在一定浓度和一部分合适的溶剂体系中能够形成各向异性溶液.但目前,纤维素基聚合物的液晶溶液纺丝并没有成功实现工业化.文章综述了纤维素基聚合物的液晶理论,其液晶溶液的发展过程与现状及独特的流变行为,并展望在少数能直接溶解纤维素并形成液晶溶液的溶剂体系中,磷酸是一种合适的溶剂体系,有很大的发展和应用空间.     

静电纺丝技术制备无机纳米纤维材料的应用

高压静电纺丝技术是一种简单通用的制备聚合物及无机纳米纤维材料的方法. 本文综述了利用高压静电纺丝技术制备的无机纳米纤维材料在能源、 纳电子器件、 催化以及传感器等领域的研究进展, 并对其发展前景进行了展望.     

静电纺丝制备杯芳烃功能化纳米纤维的应用

静电纺丝技术是制备连续微纳米纤维的一种简单易行且高效的方法,所制备的纳米纤维因其独特的结构尺寸和广泛的应用领域而备受材料科学界的青睐。 作为第三代超分子主体化合物的杯芳烃及其衍生物因其独特的分子结构、优异的离子选择识别性和吸附性能而显示出广阔的应用前景。 本文简述了静电纺丝制备杯芳烃功能化纳米纤维的原理,系统地探讨了其作为吸附剂和催化剂载体的应用以及静电纺丝与杯芳烃相结合的优势。 讨论了目前静电纺丝制备杯芳烃功能化纳米纤维存在的问题,对未来的发展方向进行展望。     

微纳米纤维素功能膜在能源与环境领域的应用

探寻绿色清洁的资源与材料以维持高效的社会经济增长是未来数十年人们面临的最大挑战之一. 可持续资源与绿色材料的开发是降低传统化石能源与材料比重的最有前途的方案. 纤维素作为一种可持续发展、 可生物再生、 储量丰富且低成本的天然高分子聚合物, 在众多领域中具有广泛的应用, 并且纤维素可以加工成各种构型, 包括气凝胶、 泡沫、 海绵和薄膜等. 本文介绍了不同形态的纤维素及其衍生物组装而成的功能膜在能源与环境中的应用, 综述了微纳米纤维素及其衍生物在先进功能化储能器件方面的最新进展和制备方案, 以及在用于水处理的膜分离技术中的应用, 其中重点讨论了微纳米纤维素及其衍生物功能膜在电池、 电容器及水处理等领域中的作用, 如隔膜、 柔性电极膜和分离膜等. 此外, 还对纤维素及其衍生物功能膜的未来发展进行了总结和展望.     

静电纺丝纳米纤维膜固定化酶及其应用*

静电纺丝是一种简单有效的制备聚合物纳米纤维的技术,在组织工程、药物控释和传感器等方面具有广泛的应用。采用静电纺丝技术制备得到的纳米纤维膜具有比表面积大、孔隙率高和易于分离回收等优点,可以作为一种优良的酶固定化载体,目前在酶固定化领域受到了广泛的关注。本文综述了近年来静电纺丝纳米纤维膜固定化酶的研究进展,在阐述静电纺丝纳米纤维膜制备技术的基础上,详细介绍了纳米纤维膜表面担载法和包埋法固定化酶的原理和方法,分析了不同固定化方法的优缺点,并讨论了静电纺丝纳米纤维膜固定化酶的应用前景,对静电纺丝纳米纤维膜固定化酶的发展方向进行了展望。     

液晶纤维素及其衍生物的进展

本文讨论了纤维素及其衍生物形成液晶态的准则,综述了它们的溶致和热致液晶性能、流变性能、成型加工特性及纤维和薄膜的结构与力学性能,指出了进一步的研究方向。     

Unconventional Cellulose Products Through Nucleophilic Displacement Reactions

Summary: The paper highlights the synthesis of unconventionally functionalized cellulose derivatives obtained by nucleophilic displacement (S_N) reactions. The key intermediates, cellulose sulphonates, are discussed due to the fact that sulphonate groups play the major role as leaving group in S_N reactions with the biopolymer. A short overview about “classical” S_N reactions will be given. The main part of the review is focused on novel cellulose products in particular aminodeoxy cellulose derivatives showing monolayer formation, click chemistry with cellulose starting from deoxyazido (copper-catalyzed Huisgen reaction) yielding products with methylcarboxylate-, 2-aniline-, 3-thiophene moieties, e.g., and new selectively dendronized cellulose based materials. Structure characterization and typical applications are briefly reviewed as well.     

Studies on Non-natural Deoxyammonium Cellulose

Summary: Ammonium group containing cellulose derivatives are prepared from homogeneously synthesized cellulose p-toluenesulfonic acid esters (tosyl cellulose) by conversion with sodium azide and subsequent reduction of the azido moiety applying NaBH₄/CoBr₂/2,2′-bipyridine as reagent. Regarding the tosylation, cellulose samples of different degree of polymerization and hemicellulose content possess a different reactivity. The deoxyamino cellulose is water soluble in the protonated state. Elemental analysis, FTIR- and NMR spectroscopy were carried out to analyze the degree of substitution and functionalization pattern. It was also studied to synthesize deoxyazido celluloses without isolation of the tosyl cellulose. However, a predominant formation of deoxychloro moieties occurs.     

Pure Cellulose Nanoparticles from Trimethylsilyl Cellulose

Silyl ethers of cellulose are promising derivatives of the biopolymer because they exhibit thermoplastic behavior at higher functionalization, may be applied as intermediate in subsequent reactions and have a high tendency to form defined supramolecular structures. Trimethylsilylation can be carried out by applying ionic liquids (ILs) such as 1-ethyl-3-methylimidazolium acetate (EMIMAc) as reaction medium. Pure trimethylsilyl cellulose (TMSC) can be efficiently synthesized with 1,1,1,3,3,3-hexamethyldisilazane (HMDS) yielding products with degrees of substitution (DS) up to 2.89. During the synthesis of highly functionalized derivatives, precipitation of the TMSC occurred, which simplifies the recycling of the IL. The tendency of TMSC toward the formation of supermolecular structures was exploited for the formation of pure cellulose nanospheres by a simple dialysis process. FTIR spectroscopy confirmed the complete removal of the TMS functions during this process. Scanning electron microscopy, dynamic light scattering, atomic force microscopy, and particle size distribution analysis showed that cellulose particles with a size of 100 to 200 nm are accessible in this simple manner.     

离子液体在纤维素研究中的应用*

离子液体是一种新型的绿色溶剂,纤维素是一种可再生的生物资源,作为非衍生化纤维素溶剂,离子液体在纤维素研究中呈现出了良好的发展态势。本文综述了纤维素在离子液体溶解、再生、衍生化反应及其在生物酶催化等方面的一些研究成果。     

Cellulose/chitosan hybrid nanofibers from electrospinning of their ester derivatives

A facile approach has been established to generate cellulose/chitosan hybrid nanofibers with full range of compositions by electrospinning of their ester derivatives, cellulose acetate (CA) and dibutyryl chitin (DBC), followed by alkaline hydrolysis to cellulose (Cell) and chitosan (CS). DBC was synthesized by acid-catalyzed acylation of chitin (CHI) with butyric anhydride and the newly formed butyl groups on C3 and C6 were confirmed by FT-IR and ¹HNMR. DBC had robust solubility in acetone, DMAc, DMF, ethanol, and acetic acid, all except ethanol were also solvents for CA, allowing mixing of these ester derivatives. Fiber formation by electrospinning of either DBC or CA alone and together in these common solvents and their mixtures were studied. The 1/1 acetone/acetic acid was found to be the optimal solvent system to generate fibers from either DBC or CA as well as their mixtures at all CA/DBC ratios, resulting in hybrid fibers with diameters ranging from 30 to 350 nm. DBC and CA were well mixed and showed no phase separate in the hybrid fibers. Alkaline hydrolysis (NaOH) of the equal mass CA/DBC nanofibers regenerated Cell and CHI readily via O-deacylation, then proceeded to further deacetylate CHI to CS via N-deacetylation at higher alkaline concentrations and/or temperatures. Under conditions studied, hydrolysis with 5N NaOH at 100 °C for 3 h was optimal to regenerate cellulose/chitosan hybrid nanofibers.     

Analyse Thermique de la Cellulose et de Quelques Derives Etherifies et Esterifies

The cellulose and its derivatives are used more and more, especially like excipients in pharmaceutical industry.The identification of cellulose and some of its derivatives: cellulose acetophthalate, hydroxy-propylmethylcellulose acetosuccinate, sodium carboxymethylcellulose, hydroxysthylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose, hydroxypropylmethyl-cellulose phthalate, is possible by thermal analysis (simultaneous DTA-TG). For that reason, one consider the temperature of the DTA maximum peaks and the DTG minimum peaks. This identification is easy when these products are a majority in pharmaceutical specialities.

     

Regioselectively Functionalized Cellulose Derivatives: A Mini Review

Summary: The paper reviews recent developments in synthesis and characterization of regioselectively functionalized cellulose derivatives. It demonstrates the importance of protecting groups like triphenylmethyl- and thexyldimethylsilyl (TDMS) ethers in cellulose chemistry. The protected cellulose derivatives can be used for the preparation of 2,3-O-functionalized polymers. Moreover, the TDMS group opens up the synthesis of 3-O-ethers of cellulose that possess interesting properties in terms of structure in solution, water-solubility, and thermoreversible gelation.     

Functionalized Cellulose Based Microcomposites

Summary: A technique has been developed that allows the production of cellulosic micro composites by immobilizing super-ground functionalised materials in the cellulose matrix. For this purpose, the well-established ALCERU® process has been a subject of technological modification. Depending on the degree of filling, several types of composites are accessible. At lower concentrations, the fibres maintain their textile-physical parameters and may be used in applications, where a textile appearance is required. The increasing concentration of the functional additives influences increasingly the overall properties of the composite and leads to composites with special functions such as water retention, electric conductivity, and specific absorption ability for organics or heat storage functions. In addition, loads exceeding the cellulose portion are useful as green shapes for ceramics.     

Properties and Applications of Cellulose Acetate

Cellulose acetate is one of the most important esters of cellulose. Depending on the way it has been processed cellulose acetate can be used for great varies of applications (e.g. for films, membranes or fibers). The properties of the applied cellulose acetates are very important for these applications. A special field for using cellulose acetate is the synthesis of porous, spherical particles, so called cellulose beads. Different types of technical cellulose acetates were used and their ability to form such cellulose beads was characterized. First the different types of cellulose acetates were characterized by means of solubility; turbidity and degree of substitution. In addition the molar mass and the distribution of substituents along the polymeric chain were analyzed. Next, the cellulose beads were synthesized within an emulsion process using these different cellulose acetates. Then the properties (particle size, porosity, morphology) of the cellulose beads were determined. Finally, the relationship between the characteristic of cellulose acetates and properties of cellulose beads was investigated.