超声波活化处理对微晶纤维素结构和氧化反应性能的影响

采用无污染的超声波技术预处理微晶纤维素, 研究了微晶纤维素在活化前后的超分子结构、形态结构和可及度的变化, 超声波活化对微晶纤维素选择性氧化性能的影响.     

Preparation and Properties of Enterosorbents Based on Carboxylated Microcrystalline Cellulose

Features of a non-traditional method of preparation of cellulose-based cation-exchange enterosorbents using nitrogen (IV) oxide are discussed. The proposed approach involves sequential use of oxidative and acid-hydrolyzing functions of nitrogen (IV) oxide to convert ordinary cellulose into carboxylated microcrystalline cellulose. X-ray phase analysis and transmission electron microscopy data show evidence of a topochemical character of cellulose microcrystal modification with carboxyl groups. Factors are indicated causing enhanced stability and whiteness of the samples thus obtained as compared with oxidized cellulose fibres, as well as the ease of stable tixotropic gel formation from the samples prepared in a salt form. Exemplified by methylene blue sorption, a comparative assessment of the sorptive ability of enterosorbent powders and hydrogels prepared in acid and salt forms. Results of clinical trials conducted with the gel enterosorbents in the areas of gastroenterology and detoxication therapy are presented. In view of compatibility of carboxylated microcrystalline cellulose in hydrogel form with many biologically active ingredients, prospective character of using the enterosorbents not only as such but also as a matrix for the development of new dosage forms of other medications is pointed out. Examples showing advantages of such combinations in specific sustained release drug forms (ointments and microgranules) are given.     

Effects of Microcrystalline Cellulose on Suspension Stability of Cocoa Beverage

The rheological properties and particle size distributions of cocoa beverage as well as aggregate structures of solid particles were studied to elucidate the effects of microcrystalline cellulose (MCC) on suspension stability of solid particles in cocoa beverage. Fluidity curve, dynamic viscoelasticity, particle size distribution, and SEM observation were made for beverage samples containing 0.1–0.5 wt% MCC and 11 model samples with various combinations of six ingredients. This revealed that cocoa and MCC particles are highly cohered into an aggregate and the aggregated particles further interact weakly with the milk component, leading to stabilization of the whole system of cocoa beverage.     

均相与非均相法合成的纤维素乙酸酯结构与性能的比较研究

研究了离子液体中均相反应制备纤维素乙酸酯(CA_(Homo))与非均相反应制备纤维素乙酸酯(CA_(Hete))的化学结构,进而比较了化学结构差别对纤维素乙酸酯性能的影响.均相与非均相法制备的CA化学结构存在显著差异,CA_(Homo)相比CA_(Hete)具有更好的均匀性,且CA_(Homo)和CA_(Hete)的取代基分布不同,CA_(Homo)的乙酰基取代顺序为C-6C-3C-2,CA_(Hete)的乙酰基取代顺序为C-3C-2C-6.同时对CA_(Homo)和CA_(Hete)的结晶行为、溶解性和热性能进行研究,结果表明,不同化学结构对CA的这些宏观性能影响较小,CA_(Homo)和CA_(Hete)均为无定型结构,可溶解于极性有机溶剂中,玻璃化转变温度和热稳定性相近.因此,通过离子液体均相制备的CA与现有非均相法制备的CA具有相似的物理性能,但均相法制备的CA结构均匀性更好.     

纤维素苯甲酸酯接枝二乙二醇十六烷基醚的制备及性能

分别以1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)和1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)/N,N-二甲基乙酰胺(DMAc)为溶剂体系,以微晶纤维素(聚合度为220)和苯甲酰氯(BC)为原料制备纤维素苯甲酸酯(CB).探索了溶剂体系、反应温度和投料比对产物取代度、溶解性和熔融性能的影响.结果表明,以[Amim]Cl为溶剂时,随着反应温度的升高(60~80℃)或体系中苯甲酰氯与葡萄糖单元环(AGU)投料量的增加(3∶1~9∶1),产物的溶解性和熔融性能均提高,取代度也随之升高(0.13~2.98);以[Emim]Ac/DMAc为溶剂时,产物中苯甲酰基的接枝度较低,且共聚物中引入乙酰基不适合制备纤维素-g-苯甲酰氯.初步探讨了在[Amim]Cl中合成纤维素苯甲酸酯接枝二乙二醇十六烷基醚(CB-g-E_2C_(16))固-固相变材料的性能,研究结果表明,CB-g-E_2C_(16)相变材料的相变温度为12.7~29.1℃,相变焓为12~24 J/g,在294℃仍能保持热稳定性,为该类纤维素基固-固相变材料的可熔融加工奠定了理论基础.     

消臭抗菌纤维素纤维的制备、结构和性能

采用一种制备消臭、抗菌纤维素纤维的新方法，即先将纤维素纤维用多元羧酸进行化学修饰，然后在铜溶液中处理，生成铜螯合纤维素纤维，用红外光谱、电子自旋波谱表征了该纤维的配位结构，消臭和抗菌实验结果显示，这种功能性纤维对硫化氢，氢气、三甲胺的消臭率分别达到100％，92．1％和80．4％，对金黄色葡萄球菌，大肠杆菌和白色念珠菌的抑菌率分别为79．14％，93．59％和82．50％，用X射线衍射，电子自旋波谱分析了该纤维吸附硫化氢，氨气、三甲胺的机理。     

Preparation of Cellulose Oligomers from Cellulose Triacetate (Standard Procedure)

This communication reports the detailed procedure for the cleavage of cellulose triacetate (30 g scale) with pivalic anhydride and boron trifluoride etherate in dichloromethane (pivaloylysis). With this mild and efficient method the cellulose oligomers up to the octasaccharide can be obtained in gram scale. Full characteristic data of this compounds are given.     

纤维素/壳聚糖共混透明膜的制备及阻隔抗菌性能研究

利用壳聚糖溶液包覆法制备了具有高气体阻隔性及抗菌性的透明纤维素膜,其扫描电镜照片证明壳聚糖厚度在1.31 ～4.07 μm之间.通过红外光谱、紫外光谱、热重分析仪、电子万能试验机和接触角测试仪对纤维素/壳聚糖共混膜的结构和性能进行了详细研究,结果表明由于壳聚糖和纤维素之间具有一定的氢键相互作用,使得纤维素/壳聚糖共混膜较好地保持了纯纤维素膜的机械强度,其拉伸强度都大于110 MPa.此外,壳聚糖的包覆对纤维素膜的透明性没有影响,它在600 ～ 800 nm处的透光率仍维持在80％左右,并且提高了纤维素膜的疏水性,其水接触角从纤维素膜的70°提高到了100°.利用气体渗透仪进一步研究了纤维素/壳聚糖共混膜的氧气阻隔性,结果表明该膜具有很好的氧气阻隔性,其氧气渗透系数甚至低于市场上理想的氧气阻隔材料乙烯-乙烯醇共聚物(EVA).金黄色葡萄球菌抗菌测试表明,通过壳聚糖包覆法改性纤维素能够明显提高纤维素膜的抗菌性.     

水可分散体羧甲基纤维素醋酸丁酸酯结构与性能研究

采用大浴比碱化、醚化与半均相酯化的合成方式,制备出纤维素混合醚酯——羧甲基纤维素醋酸丁酸酯（CMCAB）。利用^1H—NMR、FTIR、XRD、TG和DSC等技术对CMCAB结构与热性能进行分析与表征,并对其溶液表面性能、水分散体流变性能进行了研究。结果表明,CMCAB分子链上亲水性羧基分布均匀;CMCAB结晶度低、热...     

Preparation,Characterization and Properties of Cellulose Acetate-Grafted-Poly(glycidyl methacrylate) Copolymers

The cellulose acetate-grafted-poly(glycidyl methacrylate) copolymers were synthesized successfully by free radical polymerization. The resulting copolymer was characterized by proton nuclear magnetic resonance (¹H-NMR), solid-state ¹³C-NMR, Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The crystallization behavior, thermal properties, specific particle surface area, moisture sorption behavior of the modified cellulose acetate were investigated by wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) method and Dynamic Vapor Sorption (DVS) instrument. It was found that the poly(glycidyl methacrylate) (PGMA) grafting was effective in improving the water adsorption of cellulose acetate (CA) changing the specific surface area, and reducing the T_g of copolymers.     

纤维素/全硫化弹性纳米粒子复合膜的制备与性能

利用碱脲溶剂低温溶解纤维素,在该体系中掺杂一定比例的全硫化羧基丁苯弹性纳米粒子,制备了纤维素/全硫化弹性纳米粒子复合膜.通过透射电镜、扫描电镜、WAXD、固体核磁共振、热分析和力学性能测试等对该复合膜的结构和性能进行了表征.结果表明,全硫化羧基丁苯弹性纳米粒子(CSB ENP)均匀的分散在具有微纳孔洞结构的纤维素基体中.CSB ENP的引入对纤维素再生过程中的结晶性影响不大.纤维素/全硫化弹性纳米粒子复合膜具有良好的透光性,并且热稳定性也有所提高.加入少量的CSB ENP可以增韧纤维素膜,且能保持良好的力学性能.当CSB ENP的含量为5 wt%时复合膜的断裂拉伸强度和断裂伸长率同时得到了提高.     

Preparation and Properties of Cellulose/Waste Leather Buff Biocomposites

The aim of the present work was to utilize waste leather buff (WLB) as filler in cellulose and make biocomposites for packaging applications such as wrappers. Cellulose was dissolved in the environmentally friendly ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl). To this solution, WLB was added in amounts of 5 to 25 wt.% of cellulose. The cellulose and cellulose/WLB composite films were prepared by regenerating the corresponding cast solutions in a water coagulation bath followed by washing and drying. These films were tested for their tensile properties, thermal stability, and morphology. The tensile modulus and strength of the composite films were lower than those of the matrix. The lowering of the tensile modulus and strength with increasing WLB loading was attributed to the random orientation of the leather fibers of WLB in the composites. However, the % elongation at break of the composite films was found to be higher than that of the matrix and increased with increasing WLB content. The possible interaction between the matrix and WLB filler was probed using FT-IR analysis. The thermal stability of the composite films was higher than that of the matrix. The increase in thermal stability of the composite films was attributed to cross-linked collagen protein leather fibers in WLB. The fractographs of the composite films indicated good interfacial bonding between cellulose and leather fibers of WLB. These composite films may be considered for packaging and wrapping applications.     

微晶萘固相反射散射分光光度法测定钼的研究

研究了微晶萘萃取钼与吡咯烷基二硫代甲酸铵配合物的条件,并设计了固相反射散射分光光度法直接测定萘相中钼的含量。方法有较好的选择性,可以在钨存在下直接测定地质样品中钼的含量,方法检出限为０．０２３μｇ／ｍｌ相对标准偏差为４．２％。     

A Review of Cellulose and Cellulose Blends for Preparation of Bio-derived and Conventional Membranes,Nanostructured Thin Films,and Composites

Cellulose has been used as a raw material for the manufacture of membranes and fibers for many years. This review gives the background of the most recent methods of treating or dissolving cellulose, and its derivatives to form polymer films or membranes for a variety of applications. Indeed, some potential applications of bacterial cellulose, nanofibrillar cellulose (NFC) for films showing enhanced barrier characteristics are reviewed as well as the utilization of cellulose nanonocrystals (CNC) for production of highly oriented super strong films or thin films is discussed. Because of the success of the Lyocell process as well as the amine/metal thiocyanate solvent blends of cellulose and other polysaccharides like starch, chitosan, and other natural polymers. Consequently, the use of cellulose (or its derivatives) and another polysaccharide dissolved as a blend is also elaborated. It is our hope that the reader will want to follow up and investigate these new systems and use them to develop end use materials for all sorts of applications, from medical to water filtration, or electrogels for use in batteries.     

壳核型磁性纳米纤维素微球的超声制备及表征

A kind of cellulose magnetic nanoparticle with a core / shell structure has been prepared by ultrasonic irradiation. Cellulose acts as the shell while Fe3O4 magnetic nanoparticles take the role as the core. Magnetic force microscopy（MFM）with atomic force microscopy（AFM）measurement showed that the size of the magnetic nanoparticles is about 30-50 nm in diameter,while the Fe3O4 core is about 20-30 nm. FT-IR,XRD and MFM was used to provide the chemical and magnetic information of the nanoparticles. The MFM image showed that the nanoparticles separate very well with each other,indicating the cellulose shell produces a good prevention from the aggregation of the Fe3O4 particles. MFM studies also showed two magnetic nanoparticles can form particle-pairs,indicating a weak magneto-dipole interaction between magnetic nanoparticles. It is also found that the average sizes of magnetic nanoparticles have relation to the power of ultrasonic irradiation,and the possible mechanism is discussed.     

纤维素纳米晶模板法制备多级孔炭材料及其电化学性能

以纤维素纳米晶(CNC)为模板,酚醛树脂为碳源,KOH为活化剂,通过高温碳化制备了多级孔炭材料.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段对合成的一系列炭材料进行了表征.结果表明,前驱体中CNC的降解会形成与CNC直径相当的介孔,KOH活化则会导致炭材料产生大量的微孔和大孔,以及部分4 nm左右较小尺度的介孔,所制备炭材料呈现明显的多级孔特性,其比表面积达554.7 m²/g,总孔体积为0.323 cm³/g.以CNC为模板,KOH活化的炭材料作为电极材料时,在1.0 A/g电流密度下其比电容达202.8 F/g,当电流密度升高至40.0 A/g时,其电容保持率仍达69%,表明该炭材料具有优异的倍率性能;由该电极材料组装的超级电容器在10000次充放电循环后,电容保持率达95%以上,具有良好的循环稳定性.     

水溶性微晶壳聚糖的制备及结构

采用HCl和H3PO4的水／醇溶液为反应介质降解壳聚糖,并用无水乙醇沉淀和洗涤,制备出收率超过95％的水溶性的微晶壳聚糖,其晶体尺寸为400－800mm,晶型完全不同于固体粉末聚糖,这两种微晶的红外光谱酰胺峰（1650,1600cm^-1）已完全消失,而在1620,1520cm^-1附近出现了－NH3^ 的反对称变形振动和对称变形振动双峰,并发现用HCl制得的微晶壳聚糖溶于冷水,用H3PO4制得的微晶壳聚糖可以均匀分散于冷水而溶于60℃热水。     

薄层色谱用纤维素苯甲酸酯类手性固定相的制备及色谱性能

用超声方法合成了3种纤维素苯甲酸酯类手性固定相，三（苯甲酰基）纤维素（CTB）、三（4－甲基苯甲酰基）纤维素（CTMB）、三（4－硝基苯甲酰基）纤维素（CTPNB）；该类手性固定相（CSP）用于薄层色谱分离手性药物对映体，采用合适的展开剂系统，共有6对含氮手性药物获得了安全分离；比较了3种手性固定相的拆分性能，表明CTB和CTMB对手性药物显示出良好的拆分性能，而CTPNB的拆分性能较差。     

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.     

离子液体溶解纤维素的研究

纤维素是一种可生物降解的天然高分子材料,由于纤维素含有大量的分子间和分子内氢键,导致纤维素难溶于水和一般的有机溶剂。现有的溶剂存在稳定性差、具有毒性、难以回收等缺点,对纤维素的加工、利用造成困难,因此,寻找新型绿色溶剂成为纤维素开发的热点和难点。离子液体是一种新型高效绿色溶剂,在一定条件下可以溶解纤维素、角蛋白等生物大分子,离子液体的出现为纤维素的溶解提供了一种环境友好、可生物降解的溶剂体系,具有广阔的应用前景。本文就不同种类离子液体溶解纤维素的溶解度以及影响溶解度的几种因素进行了综述,总结了离子液体与纤维素作用机理以及离子液体的回收方法,为纤维素的加工利用提供了理论依据和工业指导。