纤维素基自愈合凝胶研究现状

纤维素是自然界丰富的天然有机高分子,具有价廉易得、环境友好、力学性能良好等优点,开发和利用空间非常广阔。传统水凝胶存在力学强度差、结构功能单一等问题,而引入纤维素及其衍生物是改善其性能的一种重要手段。因此通过物理或者化学方法对纤维素进行改性,制备具有自愈合性能的凝胶,受到科技工作者的广泛关注和研究。笔者以物理型和化学型自愈合凝胶为主线,综述了近年来采用纤维素制备自愈合材料的研究进展,为纤维素基自愈合凝胶的制备和应用提供参考。以纤维素基凝胶的自愈合机理进行分类,重点介绍了利用氢键、疏水相互作用、主-客体相互作用、金属配位作用和静电作用等物理作用,以及硼酸酯键、双硫键、酰腙键、烯胺键和Diels-Alder反应等化学作用构建的凝胶。分析了自愈合凝胶的设计思路,探讨了凝胶自愈合性能的影响因素,同时总结了基于纤维素制备的自愈合凝胶的结构特性及其在柔性电子、生物医疗、组织工程等方面的应用。最后,探讨了纤维素基自愈合凝胶所面临的问题,并展望了其研究前景。     

三肽纤维素酯的制备及应用研究

以微晶纤维素为原料,芴甲氧羰基-L-脯氨酸(FMOC-L-Pro-OH)、芴甲氧羰基-L-缬氨酰-L-苯丙氨酸(FMOC-L-Val-L-Phe-OH)和3,5-二硝基苯甲酸为衍生化试剂,经酰氯化、酯化、肽链的延长和氨基的修饰等反应,合成了末端氨基被修饰的三肽纤维素酯(TPC)。通过实验证实三肽若要与纤维素成酯,必须采用先酯化后肽链延长的方式,其中关键步骤为酯化反应,其反应条件为:纤维素在LiCl/DMAc溶液中的质量浓度为20 g/L,温度100℃,n(酰氯)∶n(纤维素中羟基总量)为3∶1,反应时间20 h。再通过肽链延长、氨基修饰反应,最终可得到取代度为2.15的三肽纤维素酯。经过FT-IR、TG、XRD和元素分析等多种分析手段测试可知,3,5-二硝基苯甲酸对肽链末端进行了成功的修饰,该反应路径可行。酯化反应的产物根据沉淀析出液不同,内部氢键产生也不相同,可得到功能不同的三肽纤维素酯。TPC的应用实验结果表明,以甲醇为沉淀析出液的纤维素酯,是良好的肠溶包衣材料,具有遮光性强崩解迅速的特点,但其生理毒性有待进一步研究;以水为沉淀析出液的纤维素酯,被制成手性涂敷柱后,综合了刷型固定相与纤维素固定相的两大优势,拆分能力强大高效,耐化学性极佳,适用范围比以往涂敷柱更广泛,尤其适用于四氢呋喃流动相体系。     

干法无胶纤维板粘合机理的研究Ⅱ．干法无胶纤维板的红外光谱分析

运用红外光谱分析法研究了干法无胶纤维板制造过程中木材组成成分官能团的变化，进而探讨了干法无胶纤维板的粘合机理。结果表明：（１）在热磨过程中，热磨制浆使木材中高聚物——纤维素、半纤维素、木素都有不同程度的降解。（２）在热压制板过程中，热磨降解后的木材成分经热压工艺能发生聚合反应，使木质纤维粘合成板。（３）热磨过程产生的活性羟基，热压后可以缔合形成氢键，增加了纤维之间的结合力，有利于木质纤维粘合成板。（４）热压成板后，憎水性羰基官能团增加，亲水性“自由的”羟基数量减少，增强了板的耐水性能     

硬脂酸/TiO_2/CNF超疏水复合材料的制备与表征

研究了一种利用硬脂酸对纳米二氧化钛(Nano-TiO_2)和纤维素纳米纤维(CNF)复合物进行有机表面修饰的新方法,主要包括纳米二氧化钛、纤维素纳米纤维的制备和利用硬脂酸对Nano-TiO_2/CNF复合体系进行有机表面修饰制得超疏水材料三个工艺过程。通过傅里叶变换红外光谱仪(FTIR)和场发射扫描电子镜(SEM)等对所得的样品进行表征,得出硬脂酸中的—COOH基团与TiO_2/CNF复合体系表面的—OH基团发生脱水反应,并将疏水性—CH_3基团引入复合体系中,复合体系表面构建的纳米级粗糙结构协同体系内引入的疏水基团使最终产物具有超疏水性。     

生物基极性非质子溶剂/对甲苯磺酸耦合体系中竹粉定向解聚研究

以两种生物基极性非质子溶剂γ-戊内酯（GVL）和二氢左旋葡萄糖酮（Cyrene）,分别与对甲苯磺酸水溶液（TsOH aq）构成耦合体系，对竹粉定向解聚及其酶解过程开展了研究。实验结果表明：质量浓度为75 g/L的TsOH,溶剂体积比为4∶1的GVL/TsOH aq体系在130℃预处理毛竹60 min后，半纤维素和木质素分离效率更高，半纤维素分离率（S_H）和木质素分离率（S_L）分别达到98.5%和98.4%,同时纤维素保留率（R_C）为91.5%;而质量浓度为30 g/L的TsOH,溶剂体积比为0.8∶1的Cyrene/TsOH aq体系在120℃预处理毛竹60 min后，R_C达到87.3%,S_H和S_L仅为85.5%和79.4%。预处理后固体样品的表征结果表明：竹粉经GVL/TsOH aq预处理后的样品木质纤维致密结构被有效破坏，无定形的半纤维素和木质素绝大部分被分离，结晶度达68.27%,结构更接近于微晶纤维素，同时暴露出更多的游离羟基，有利于后续酶解。而酶...     

木质素样品的羟值测定方法

以聚醚多元醇羟值测定方法——邻苯二甲酸酐-吡啶法为基础建立了木质素样品中活性羟基官能团数目测定方法,针对木质素磺酸钠和玉米秸秆酶解木质素样品的特性,改进了羟值校正时酸值和碱值的测定方法:在确保酸值测定精确度的同时成功采用乙醇-水替代了高毒性吡啶溶剂,在碱值测定时率先采用邻苯二甲酸氢钾替代盐酸溶液,使测定碱值的相对标准偏差小于1%,精确度得以显著提高。     

脱木素木材衍生功能材料研究进展

木材是一种可再生和机械坚固的天然生物基模板,半纤维素和木质素基质结合纤维素原纤维在木材中分层排列。因此在不改变纤维素原纤维分级排列的情况下去除木材细胞壁中的木质素,可为具有对齐纤维素结构的生物模板功能材料领域带来更多可能性。基于脱木素木材提供的生物模板,可开发出不同的功能材料,并广泛应用于不同领域。文中总结脱木素木材的主要制备方法和功能材料的开发策略,展望脱木素木材衍生功能材料的发展潜力和趋势,旨在为木材功能化研究提供新思路。     

竹材酚醇液化及其应用研究进展

竹材酚醇液化是竹材综合利用的有效方法之一,通过溶剂反应破坏竹材纤维素的结晶结构、半纤维素和木质素高分子结构,使其分子链断裂,降解成带有反应活性的羟基化合物,可以用于制作胶黏剂、发泡材料和碳纤维等。文章分析了竹材液化原理、酚醇液化技术,以及竹材酚醇液化产物的应用研究现状,认为该领域今后需要加强基础理论和预处理技术的研究,尽快制定相关产品标准,实现竹材资源的高利用率和高附加值。     

松香及其衍生物在无机功能材料中的应用研究进展

松香是我国重要的生物质资源,其主要成分树脂酸含有三环菲骨架强疏水刚性基团和羧基弱亲水基团,可用于无机纳米材料的分散,降低无机纳米材料的聚集.通过对松香树脂酸双键和羧基等位点进行化学改性,增强亲水性能,可获得亲水亲油性能优异的表面活性剂,与无机材料具有更好的"融合性",作为模板剂和分散剂,可控辅助制备多种无机功能材料.而...     

Relation of chemical and mechanical properties of Eucalyptus nitens wood thermally modified in open and closed systems

ABSTRACT

In the present work, Eucalyptus nitens was thermally modified in an open (atmospheric pressure) and a closed (under pressure) reactor system. The effect of the changes of the chemical composition on the mechanical properties was investigated. Hemicelluloses, cellulose, lignin, extractives, acetic acid, formic acid, total phenols and the cellulose degree of polymerization (DP) as well as modulus of elasticity (MOE) and modulus of rupture (MOR) were measured for each modification. The results indicated that the closed system modification, particularly at high pressure, presented stronger variations on the chemical structure of the modified wood than the modifications in the open system. In both modifications, MOR showed a better correlation with the chemical changes than the MOE, especially xylose, cellulose DP, lignin and total phenols. These correlations suggest a tendency of a more brittle wood in the closed system modification at high pressure than in the modifications in the open system. Results can be used as a reference for future applications of thermally modified E. nitens wood.     

Enhancement of the reaction between pulp components and hydroxyl radical produced by the decomposition of hydrogen peroxide under alkaline conditions

Experiments on alkaline hydrogen peroxide treatments with stepwise addition and oxygen pressurization were performed to determine whether they enhance the reaction between pulp components and hydroxyl radicals produced by the decomposition of hydrogen peroxide. In this study the degradation of methyl-dglucopyranoside (MGP), a model compound of pulp components, was an indicator of the progression of the reaction between pulp components and hydroxyl radicals. When comparing the degradation of MGP in the stepwise and one-time addition systems, MGP was degraded more in the stepwise addition system than in the one-time addition system when Fe³⁺ was added. This result indicates that the hydroxyl radical produced by the decomposition of hydrogen peroxide efficiently attacks MGP in the stepwise addition system. MGP was degraded to the same degree in the stepwise addition system as in the one-time addition system when Fe²⁺ or Mn²⁺ was added. Aggregation and precipitation of metal ions might affect their catalysis. Oxygen-pressurized hydrogen peroxide treatment caused almost no enhancement of the degradation of MGP compared to the treatment under atmospheric pressure. Instead, high stability of hydrogen peroxide was produced by oxygen-pressurized hydrogen peroxide treatment. Such high stability can result in frequent attacks of the hydroperoxide anion, the conjugate base of hydrogen peroxide, against some chromophores and quinones.Part of this paper was presented at the 1998 International Pulp Bleaching Conference, Helsinki, Finland     

Chemical structural elucidation of total lignins in woods I: fractionation of the lignin in residual wood meal after extraction of milled wood lignin

Residual wood meal after extraction of milled wood lignin (WMEM) ofEucalyptus globulus was extracted with alkali and LiCl/N,N-Dimethylacetamide (DMAc). These agents dissolve mainly hemicellulose and cellulose, respectively. The extractability of WMEM in alkali solutions was influenced by the degree of swelling of the cellulose. Under good swelling conditions, considerable amounts of cellulose and lignin were extracted with the hemicellulose. Maximum extractability was about 60% of the WMEM under optimum conditions (3 M or 5 M LiOH or 3M NaOH solution). Some portion of cellulose was extracted with LiCl/DMAc at room temperature. Thus, lignin inE. globulus WMEM was divided into three fractions: hemicellulose-lignin fraction, cellulose-lignin fraction, and insoluble-lignin fraction.Part of this work was presented at the 49th annual meeting of the Japan Wood Research Society, Tokyo, April 1999; and at the 50th annual meeting of the Japan Wood Research Society, Kyoto, April 2000     

LiCl/DMSO再生大豆秸秆纤维凝胶的制备及其性能研究

经乙二胺预处理后大豆秸秆先溶解于8%LiCl/DMSO木质纤维全溶体系,然后于乙醇中凝胶化制备多孔吸液木质纤维凝胶。研究发现:木质纤维原料脱木质素程度会影响凝胶的多孔结构、热稳定性及溶胀性能。随着脱木质素程度加强,木质纤维原料中纤维素、半纤维素和木质素之间解离程度加强,凝胶热稳定性提高,残炭量减少,可形成小孔径、高比表面积的致密多孔网络结构并影响其溶胀性能。当大豆秸秆经2 h脱木质素处理时,该秸秆原料所制备的凝胶热分解温度、残炭量、比表面积和平均孔径分别为230℃、15%、64.29 m~2/g和17.813 nm,在15℃下平衡溶胀率为2 126.79%,与未脱木质素的大豆秸秆制备的凝胶相比,热分解温度提高了30℃,残炭量降低了47.7%,比表面积增加11.02 m~2/g,平均孔径减小了2.468 nm,而平衡溶胀率降低了16.6%。     

微波等离子体处理木材表面光电子能谱分析

XPS是固体木材表面组成分析最有效和最灵敏的工具之一。本研究使用XPS研究木材微波等离子体处理前后表面化学组成的变化。经微波等离子体处理后 ,C1的含量降低而C2 、C3含量增加 ,并伴随C4生成 ,表明纤维素和 /或木素上羟基含量的增加。微波等离子体处理还在木材表面引入了N元素 ,推测有亲水的 -NH2 生成。比较了相同工作条件下 ,N2 、O2 及空气等离子体对木材表面化学组成影响 ,结果表明 :O2的影响最显著而N2 最弱 ,氧的影响还存在其特殊性。     

Condensation reactions of phenolic resins VII: catalytic effect of sodium bicarbonate for the condensation of hydroxymethylphenols

This article describes the catalytic effect of NaHCO₃ on condensation reactions of monomeric hydroxymethylphenols (HMPs) to elucidate the cure-acceleration mechanism. By comparison of the kinetics of self-condensations of HMPs, NaHCO₃ was proved to increase the reactivity of para-hydroxymethyl groups. The changes of ¹³C nuclear magnetic resonance (NMR) chemical shifts on each HMP system with the additive indicated that the addition of NaHCO₃ enhanced some molecular interactions between HMPs and NaHCO₃, facilitating a resonance effect that might play a similar role in dissociation of the phenolic hydroxyl groups of HMPs. In addition, computational modeling by molecular orbital calculations elucidated that hydrogen carbonate anion (HCO ₃ ⁻ ) forms an interaction between either the para-hydroxymethyl group and the phenolic hydroxyl group or between the two para-hydroxymethyl groups of HMPs by hydrogen bonds. From the experimental results, the authors proposed the mechanism of the catalytic action of NaHCO₃: it appears to be due to the delocalization of an electron initiated by the interaction of the para-hydroxymethyl groups and the phenolic hydroxyl of HMPs with HCO ₃ ⁻ through hydrogen bonds, which results in facilitating the formation of active species.     

Preparation of novel reagents 4-alkoxytrityl chlorides and their reaction with methyl Α-d-glucoside

A series of novel 4-O-alkoxytrityl chlorides (1) with different chain lengths was synthesized as a novel reagent for obtaining 6-O-alkylated cellulose with high regioselectivity via trityl groups in one reaction step without the use of any protective groups. These chlorides were reacted with methyl -d-glucoside, which was used as a model compound, to examine the reactivities toward the primary hydroxyl groups of cellulose to afford a series of 6-O-alkylated methyl -d-glucosides in high yields. The product compounds were found to have interesting solubilities and thermal properties. Thus, newly prepared trityl chloride derivatives were found to be useful regioselective derivatization reagents on the primary hydroxyl group in carbohydrates, especially in cellulose.     

Newly developed nanocomposites from cellulose acetate/layered silicate/poly(ε-caprolactone): Synthesis and morphological characterization

New biodegradable cellulose acetate/layered silicate grafted poly(ε-caprolactone) [(CA/layered silicate)-g-PCL] nanocomposites were prepared by in situ polymerization of ε-caprolactone in the presence of cellulose acetate (CA) and organically modified layered silicate (OMLS). The structures of the resulting composites were investigated. X-ray diffractometry was carried out to survey general structural features of (CA/OMLS)-g-PCL nanocomposites, and revealed that OMLSs having hydroxyl groups in the organic modifiers greatly altered the layered silicate structure by monomer intercalation and successive exfoliation through its polymerization. Two of the representative cases were characterized by wide-angle and small-angle X-ray scattering analyses with a synchrotron source. The morphology of these nanocomposites was further examined by transmission electron microscopy. When SPN, one of OMLSs having one hydroxyl group in its modifier, was used, the silicate layers could not be dispersed thoroughly, but existed as aggregates consisting of several silicate layers. Among them, the crystal growth of PCL developed by transcrystallization, where the crystal growth was restricted in the confined space. When Cloisite 30B, having two hydroxyl groups within the modifier, was used, the silicate layers forming the clay were dispersed completely in the composite and random orientation of the OMLS was observed.     

超声波一步法制备纤维素氯化锂/二甲基乙酰胺溶液

运用超声波一步法制备了纤维素氯化锂/二甲基乙酰胺的离子溶液。通过调节超声波功率和处理时间,对纤维素、氯化锂和二甲基乙酰胺混合物超声波处理5~7 min,并于室温下搅拌3~5 h,即可获得纤维素均匀溶液;研究了超声波处理对纤维素分子及形态结构的影响,并对纤维素溶液的流变性能进行了考察。结果表明,超声波一步法具有工艺简单、易操作以及溶解时间短的特点,所得到的纤维素溶液具有高分子溶液的一般特征。     

Effects of side-chain hydroxyl groups on pyrolytic <Emphasis Type="Italic">β</Emphasis>-ether cleavage of phenolic lignin model dimer

Effects of side chain hydroxyl groups on pyrolytic β-ether cleavage of phenolic model dimers were studied with various deoxygenated dimers under pyrolysis conditions of N₂/400°C/1 min. Although phenolic dimer with hydroxyl groups at the C _α ⁻ and C _γ ⁻positions was much more reactive than the corresponding nonphenolic type, deoxygenation at the C _γ -position substantially reduced the reactivity up to the level of the nonphenolic type. These results are discussed with the cleavage mechanism via quinone methide intermediate formation, which is activated through intramolecular hydrogen bonds between C _α ⁻ and C _γ ⁻ hydroxyl groups.     

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。