竹纤维素乙酰化改性及其纳米纤维的制备

竹纤维经一步碱纯化制得α-纤维素含量高于96%的碱处理竹纤维素,达到了商业合成醋酸纤维素对原料的要求;随后对提纯的竹纤维素进行乙酰化改性,以提高其用于静电纺丝技术制备纳米材料的溶解特性。采用相应的表征手段(SEM和NMR)分析了竹纤维纯化和乙酰化反应过程中产物形貌及结构的变化,结果表明:经Na OH溶液纯化后样品的纤维形貌得到了保持,粗糙的纤维表面印证了原料中杂质成分的脱除;乙酰反应使得纤维素分子上的羟基被取代转变为醋酸纤维素结构。并基于静电纺丝技术(纺丝工艺条件:电压22 k V,溶液流速为1 m L/h,接收距离15 cm,滚筒转速15.2 m/s)成功制得了形貌均匀、取向可控的竹纤维源纳米纤维。相关研究结论可为我国农业纤维性资源纳米化全新利用提供一定的理论基础,契合时下充分开发环境友好型可再生生物质资源的研究主题。     

芭蕉芋渣苯酚液化物制备酚醛发泡材料

以苯酚为液化剂对芭蕉芋渣进行液化,获得的液化产物树脂化后用于制备发泡材料。探讨液固比、温度、催化剂对芭蕉芋渣液化效果的影响,并分析芭蕉芋渣液化物的树脂化制备发泡材料的性能。结果表明,苯酚与芭蕉芋渣的质量比为6以上获得较好的液化效果;温度在120℃时,残渣率较低;用硫酸(98%)作催化剂比磷酸、盐酸的效果好。芭蕉芋渣液化的最佳工艺条件是液固比6,温度120℃,催化剂为硫酸(98%)、用量5%,液化时间是60 min。制备的芭蕉芋渣树脂的游离甲醛含量为1.09%,可在一定意义上取代酚醛树脂,既能减少成本,又有利于保护环境。     

液化条件对竹材废料醇液化产物得率的研究

以毛竹材为原料,浓硫酸为催化剂,加入PEG400/丙三醇制备液化物,研究了液固比（液化剂/竹材）、浓硫酸催化剂用量、液化温度、液化时间等对竹材废料多元醇液化物得率的影响。结果表明：随着液固比和液化时间的增加,竹材液化物的得率逐渐增加;随着浓硫酸催化剂用量和液化温度的增加,竹材液化物的得率呈现先增加后减小的趋势。当液固质量比3∶1、催化剂用量4%、液化温度130℃、液化时间70min时,竹材液化物的得率最高,为99.92%。     

木质纤维成分的乙酸分离方法及表征

研究了一种用含有少量硫酸的乙酸溶液分离杨木成分的方法。考察了反应时间、乙酸浓度、液比和催化剂浓度对木材成分分离的影响。对分离出的木材三种成分进行了表征。结果表明,分离杨木成分的较佳条件为:硫酸浓度0.3%,液比6,反应时间3h和乙酸浓度90%。残渣的主要成分是α-纤维素和半纤维素。水不溶沉淀物(乙酰化木质素)的重均分子量分布在341到253之间,分散性系数分布在1.1到1.2这一窄范围内。糖分析结果表明,可溶性成分主要来源于半纤维素,以单糖形式存在。     

微晶纤维素氰乙基化及其反应动力学研究

通过微晶纤维素的氰乙基化试验,研究了反应温度和反应时间对氰乙基化产物取代度(DS)的影响,表明在50℃以下,微晶纤维素的氰乙基化取代度随反应温度的升高和反应时间的延长而增加。傅里叶红外光谱分析显示微晶纤维素氰乙基化后羟基峰明显减弱,并形成了新的碳氮三键吸收峰,证明纤维素中的部分羟基氢被氰乙基所取代。X射线衍射分析显示微晶纤维素中原有的结晶结构被破坏。X4显微熔融温度测定仪、维卡软化点测定仪等的分析表明微晶纤维素氰乙基化产物的热塑性先随取代度的升高而提高,取代度超过1.43后,产物的热塑性又随取代度的升高而下降。确定了微晶纤维素氰乙基化在不同温度(30、35、40和45℃)下的反应速率常数(分别为1.30、1.61、1.94和2.26 s-1),计算出了微晶纤维素氰乙基化反应的表观活化能为29.8 kJ/mol。     

黑木相思木材化学性质株内变异研究

研究我国黑木相思木材化学性质的株内变异规律,为其加工利用提供基础数据。对广东韶关产28 a黑木相思木材进行化学组成测定,其综纤维素(α纤维素、半纤维素)、酸不溶木质素和抽出物(冷水、热水、1%氢氧化钠、苯醇)的含量在株内纵向上的变异规律不明显;相较于边材,心材的综纤维素含量略低,酸不溶木质素含量略高,抽出物含量更高,pH值更低。实际加工利用中需考虑其心材和边材比例对原料化学组成的影响。     

木薯淀粉苯酚液化产物的制备与表征

以苯酚和木薯淀粉为原材料、硫酸为催化剂,通过单因素对照试验,研究了苯酚与木薯淀粉的液固比、硫酸用量与液化时间对木薯淀粉苯酚液化产物的影响。采用傅里叶变换红外光谱(FT-IR)分析了木薯淀粉苯酚液化产物的化学官能团及化学反应,并通过X射线衍射法(XRD)分析研究了液化参数因素对液化产物结晶度及结晶形态的影响。结果表明:随着液固比、硫酸用量的增大,液化时间的延长,残渣率及液化产物结晶度降低,但结晶度在液化时间至3 h后不再下降;在酸性条件下木薯淀粉经苯酚液化后,残渣率均在0.32%以下,木薯淀粉液化产物在红外谱图中1 602、1 515 cm~(-1)附近有吸收峰,表明苯环上发生了取代反应;木薯淀粉在苯酚中液化后,X射线中有衍射峰消失,结晶度下降明显,结晶形态遭到破坏。     

杉木粉液化与液化产物树脂化的研究

以硫酸为催化剂、苯酚为液化剂采用溶剂热法对杉木粉进行液化,用杉木粉液化产物制备出酚醛树脂;考察了反应温度、反应时间、液比(苯酚-木粉的质量比)和催化剂用量对杉木粉液化效率的影响,并初步探讨了液化产物残渣率对所制酚醛树脂性能的影响。实验结果表明,杉木粉液化的最佳工艺条件是:反应温度160℃,液化时间12 h,液比值3,催化剂用量3%,在此条件下残渣率约为10%。液化产物残渣率的测定表明,升高反应温度、延长反应时间、增加液比和催化剂用量可以降低残渣率,提高液化效率;液比值为0.5~1.5时残渣率随液比增加而显著降低,催化剂用量为0.5%~2%时液化效率的变化明显。红外光谱结果表明,由液化产物所合成的酚醛树脂中羟甲基含量较高。液化产物残渣率低时制备的酚醛树脂残碳率较高。     

亚硫酸盐预处理对蔗渣酶解效率的影响

为了破坏蔗渣的抗降解性,获得高的酶解效率,采用亚硫酸盐法对蔗渣进行预处理,探讨亚硫酸氢钠用量对蔗渣理化性质、表面磺酸基含量(磺化度)及酶解效率的影响,并进一步分析了磺化度对酶解效率的影响。结果显示:不同亚硫酸氢钠用量蔗渣的结晶度(I_(Cr))变化不显著,但预处理后蔗渣纤维素结晶区相对含量上升,半纤维素含量减少。50 g蔗渣,按固液比1∶8(g∶m L)加入1.1%的稀硫酸,亚硫酸氢钠加入量(以绝干蔗渣计)为8%,在160℃条件下反应30 min时制得的蔗渣其表面磺酸基最多,达131.73μmol/g。在2%干蔗渣,7.5 FPU/g(以干蔗渣计),50℃,72 h酶解条件下,对不同磺化度的蔗渣进行酶解,结果显示酶解效率随底物的磺化度升高而升高,最高综纤维素水解效率可达83.76%。研究表明:蔗渣的酶解效率与磺酸基团的含量呈正相关,而与蔗渣中纤维素的结晶度关系不明显;酸性亚硫酸盐法可除去绝大部分半纤维素,破坏蔗渣抗降解性,促进酶解效率。     

沙柳与柠条混合原料碱性过氧化氢法分离的纤维素特性研究

分析了沙柳(Salix psamm ophila)与柠条(Caragana korshinskiiKom.)质量比为1∶1的混合原料的化学组成,在NaOH 18%(质量分数)、反应温度165℃、H2O23%(质量分数)、反应时间90 m in、液固比4∶1(mL∶g)的条件下降解木质素与半纤维素,分离纤维素,计算纤维素制备物的得率及粘度。采用GC、HPLC、FT-IR及13C NMR分析了纤维素制备物的特性,结果表明,碱性过氧化氢法能高效降解大部分木质素,得到的纤维素制备物中残余木质素含量较低(酚醛和酚酸总量为4.39%),纤维素纯度较高(葡萄糖含量84.68%),纤维素结晶度可能升高。     

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。     

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     

CNC负载ZnO纳米复合材料的吸附-光催化性能

以醋酸锌为原料、硫酸水解的纤维素纳米晶(CNC)为模板,通过沉淀法制备CNC负载ZnO纳米复合材料(CNC/ZnO),并进一步经550℃处理,得到CNC/ZnO的碳化产物(C CNC/ZnO)。采用透射电子显微镜(TEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FT IR)、紫外可见漫反射吸收光谱(UV Vis DRS)对其形貌结构、晶体结构、化学结构和光吸收性能进行表征,并测试其对亚甲基蓝(MB)染料的吸附 光催化性能。结果表明:CNC/ZnO纳米复合材料中,ZnO通过静电作用附着于CNC上,呈棒状及纵横交错排列,分散性得到显著提高;经550℃碳化后,ZnO仍以棒状排列方式沉积于碳化CNC上,排列方式未发生变化。引入CNC模板及碳化处理对ZnO晶体结构及光吸收性能产生重要影响,CNC/ZnO复合材料中,ZnO晶粒尺寸为8.4 nm,高于纯纳米ZnO(6.3 nm),其带隙能(Eg)为3.18 eV;C CNC/ZnO复合材料中,ZnO晶粒尺寸为7.8 nm,Eg值减小至1.75 eV。吸附 光催化性能测试表明:CNC/ZnO纳米复合材料对MB具有良好的吸附性能,黑暗条件下搅拌60 min,对MB的吸附去除率可达58%,开启光照60 min后,其对MB的吸附 光催化去除率增至88%;C CNC/ZnO复合材料对MB具有良好的吸附 光催化协同作用,黑暗下吸附60 min,对MB的吸附去除率为49%,光照60 min后,其对MB的吸附 光催化去除率可达99%。     

Hydrolysis of bamboo fiber cellulose in formic acid

Bamboo fiber dissolution and hydrolysis in formic acid were studied. After hydrolysis, formic acid can be recovered in a clean state and reused. Solid water-soluble sugars were obtained. After being dipped into the formic acid solution for 30 min, the bamboo fibers started to swell. After one hour, the bamboo fibers gradually started to dissolve in the formic acid solution. The color of the liquor/solution turned green and dark. In the end, the bamboo fibers became thoroughly dissolved in the liquor after four hours. There was a clear hierarchical tissue structure on the fiber surface, as observed by AFM before treatment. The differential structure disappeared after 30 min of treatment. The fiber surface became plump and glossy. After six hours reaction at 60°C, the solid sugar mixture recovered contained glucose, cellobiose, cellotriose, cellotetrose, cellopentose and cellohexaose. A significant fraction of the sugar products consisted of monomeric glucose. More than 54.5% of the bamboo fiber mass had been transformed into monomeric glucose. __________ Translated from Biomass Chemical Engineering, 2007, 41(2): 5–10 [译自: 生物质化学工程]     

Effect of intermittent heat treatment on crystallinity in wood cellulose

The effect of intermittent heat treatment on cellulose crystallites in wood was studied to evaluate quantitatively the changes of crystallinity induced by intermittent and continuous heating. The changes in crystallinity were found to be strongly affected by the intermittent heat treatment. The increased crystallinity, the width of the crystals, and the piezoelectric properties were the same for the first intermittent heating as for continuous heating. Further intermittent heating for the same time duration and temperature had no effect on the above properties, probably due to the stopping of the thermal reaction during the interval. Our results suggested that intermittent heat treatment has certain critical cooling temperatures that stop the thermal reaction and are closely related to the duration of the interval. Samples once exposed to a certain duration of heat treatment and then cooled need more time, about twice that of the first duration of intermittent heating compared with continuous heating, to reach maximum crystallinity in wood cellulose.     

Graft copolymerization of cellulose and 2-hydroxyethyl methacrylate in an ionic liquid

Dissolution and homogeneous graft copolymerization of cellulose were performed in an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) with 2-hydroxyethyl methacrylate. The synthesized AmimCl and cellulose graft copolymers were characterized by FTIR, 1 H-NMR and XRD spectroscopy. The results show that AmimCl dissolved cellulose directly by destroying intermolecular and intramolecular hydrogen bonds in cellulose and the crystalline form of cellulose was transformed from cellulose I to cellulose II after regeneration from AmimCl. The best synthetic condition of the cellulose-graft-P (2-hydroxyethyl methacrylate) was that cellulose 0.5 g, 2-hydroxyethyl methacrylate 3.00 g and initiator ammonium persulfate 0.05 g reacted for 180 min at 60°C; the rate of grafting reached 77.3%.     

Study of crystalline behavior of heat-treated wood cellulose during treatments in water

The crystalline behavior of heat-treated wood cellulose treated at 85% relative humidity (RH), in water, or boiled in water after heat treatment was investigated. The normal increased crystallinity was significantly depressed for samples that were oven-dried and then treated in 85% RH or in water. In the case of boiling-water treatment, a more pronounced increased in crystallinity was initially observed, which then decreased gradually. The crystallinity decreased more than untreated wood for samples that were heat treated for long periods and was slightly higher than the decreased crystallinity from the beginning of the above two treatments. On the other hand, no significant change in crystallinity was observed for samples of increased crystallinity or decreased crystallinity that were treated under high-moisture conditions, for all three treatments. The results show that the crystalline state of wood cellulose heat treated under oven dry or high-moisture conditions behave differently if treated in water after heat treatment. Results suggested that the mechanism of crystallization might be different for samples that are subjected to heat treatment under oven-dry and high-moisture conditions.     

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。     

Canopy cover effects on cellulose decomposition in oak and pine stands

Cellulose mass loss was measured for four levels of canopy cover,i.e., clearcut, 25%, 75%, and uncut, in northern red oak (Quercus rubra) and red pine (Pinus resinosa) stands in northern Lower Michigan, USA. Cellulose mass loss was more rapid in the clearcut and 25% canopy cover treatments than in the 75% canopy cover and uncut treatments. After 4 month incubation of cellulose filter papers, mass loss rates averaged 75.2% in the clearcut, 56.3% in the 25% canopy cover, 46.9% in the 75% canopy cover, and 45.7% in the uncut stands. For the clearcut and the 25% canopy cover treatments, cellulose mass loss in the mineral soil layer was significantly higher than in the forest floor after 2 and 4 months of incubation, while cellulose mass loss of the uncut treatment was significantly lower in the soil layer than in the forest floor after 4 months of incubation. Cellulose mass loss was not significantly different between the oak and the pine stands (p > 0.05), but cellulose mass loss rates in other canopy cover treatments except for the clearcut were generally higher in red oak stands than in red pine stands. These results suggest that canopy manipulation increases cellulose decomposition and may stimulate nutrient cycling process in canopy removal stands. This study was supported in part by USDA Forest Service and Michigan Technological University.     

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.