以离子液体为介质的纤维素加工与功能化

纤维素作为自然界中储量最大的天然高分子,被认为是未来世界能源与化工的主要原料.但由于分子链间存在丰富氢键网络以及高度结晶的聚集态结构特点,天然纤维素不熔化、难溶解,造成纤维素的加工极其困难,纤维素材料的传统生产工艺复杂且污染严重,极大限制了纤维素材料的广泛应用.近年来,人们发现一些特定结构的离子液体能够高效溶解纤维素,为纤维素的加工和功能化提供了新的多用途平台.本文从"溶解纤维素的离子液体、纤维素溶解机理与溶液性质、以离子液体制备再生纤维素材料和以离子液体为介质合成纤维素衍生物"4个方面详细介绍了本课题组在此领域的研究进展.     

菌类多糖链构象及其表征方法研究进展

概述了菌类多糖在溶液中链构象及其表征方法的研究进展.主要报道从各种真菌(香菇、茯苓、灵芝、木耳、黄单胞菌、裂褶菌等)中提取的多糖在溶液中的分子量、分子形态和尺寸,即链构象.同时介绍多糖链构象对生物活性的影响,并且指出多糖刚性链带电基团及适量分子量有利于促进它与免疫细胞上受体结合,从而抑制肿瘤细胞增殖.由此表明,多糖链构象的研究对弄清其生物功能和推动生命科学发展十分重要.多糖在溶液中主要以无规线团、双螺旋、三螺旋、蠕虫状、棒状链以及聚集体构象存在,它取决于单糖组成、糖苷键、支链结构以及分子内和分子间作用力.测定链构象的方法主要包括光散射、黏度、显微技术(透射电镜,扫描电镜以及原子力显微镜)、微量热法和小角X-射线散射等.此外,介绍了多糖溶液理论以及计算链构象参数的表达式.     

菌类多糖链构象及其表征方法研究进展 （专题报道）

 概述了菌类多糖在溶液中链构象及其表征方法的研究进展.主要报道从各种真菌（香菇、茯苓、灵芝、木耳、黄单胞菌、裂褶菌等）中提取的多糖在溶液中的分子量、分子形态和尺寸,即链构象.同时介绍多糖链构象对生物活性的影响,并且指出多糖刚性链带电基团及适量分子量有利于促进它与免疫细胞上受体结合,从而抑制肿瘤细胞增殖.由此表明,多糖链构象的研究对弄清其生物功能和推动生命科学发展十分重要.多糖在溶液中主要以无规线团、双螺旋、三螺旋、蠕虫状、棒状链以及聚集体构象存在,它取决于单糖组成、糖苷键、支链结构以及分子内和分子间作用力.测定链构象的方法主要包括光散射、黏度、显微技术（透射电镜,扫描电镜以及原子力显微镜）、微量热法和小角X-射线散射等.此外,介绍了多糖溶液理论以及计算链构象参数的表达式.     

界面层中模型高分子链构象的统计理论

高分子自由链在溶液、熔体或固体中的构象有完整的理论和实验工作 ,已是成熟的知识[1～ 4] .近年来 ,受限大分子构象的探索已成为新的热点[5] .界面是一种最简单的限制 ,将对其附近的高分子产生显著的影响 .除理论家的重视以外 ,界面附近高分子构象问题还与许多应用领域相关 .例如 ,液体高分子的表面张力 ,固体高分子的粘附 ,滑移 ,磨蚀等力学特性 ,甚至它们的光学和电学性质都与界面上的组成和分子构象相关[6] .ｄｅＧｅｎｎｅｓ[7] 最早强调界面附近的分子链构象问题的重要性 .他首先从理论上猜测长链的链端若与界面有强吸引作用 ,则它们…     

高分子平衡熔点的统计热力学及相关分子能量参数的估算

高分子晶体普遍存在于塑料和合成纤维等合成高分子以及纤维素、淀粉、蚕丝和蜘蛛丝等天然高分子之中.高分子晶体的平衡熔点是我们了解其热力学性质的基本参数之一.在本文中我们首先介绍如何藉助格子模型和平均场假定来统计计算可结晶高分子溶液的配分函数,接着推导出微观分子间相互作用参数(即链单元间局部的平行排列相互作用)与高分子本体平衡熔点之间的关系.最后,我们由平衡熔点的实验数据来推算几种高分子的微观平行排列相互作用参数.     

聚乙烯醇调控水溶性共轭聚噻吩的光学性质

针对发光共轭聚合物稀溶液在干燥形成固体时的荧光淬灭问题, 通过高分子聚乙烯醇(PVA)的氢键网络调控水溶性共轭聚噻吩在溶液中的聚集行为和构象, 并采用不同的干燥方式实现了调控其固体光学性质的目的. 紫外-可见光吸收、荧光发射光谱测试表明, 在水溶液中PVA可以分散共轭聚合物链, 并增强其共平面性; 高温干燥后, 聚噻吩薄膜与无PVA添加的聚噻吩溶液的荧光性质相似; 而采用冷冻干燥法, 薄膜则保留了添加PVA后混合溶液的发光特性. 该结果表明, PVA对聚噻吩在溶液状态下的聚集/分子构象的调控行为随干燥方式的不同得到了不同程度的保留——高温加热干燥仅维持了PVA对聚噻吩的分散作用; 而冷冻干燥则完整保留了PVA与聚噻吩的分子间相互作用, 将溶液中分子的分散状态和构象同时固定. 本研究从干燥方式的角度为固态共轭聚合物聚集行为及发光性质的调控提供了新的策略.     

溶剂沸点对聚(3-己基噻吩)薄膜内链结构与分子取向的影响

以聚(3-己基噻吩)(P3HT)为研究对象,借助荧光相关光谱、紫外-可见光谱和掠角红外光谱考察了溶剂性质对旋涂膜内P3HT的链结构与分子取向的影响。结果表明:溶液中P3HT的分子链构象受溶解度的影响,当P3HT溶解在溶解性好的良溶剂中时,链构象更伸展;固体薄膜内P3HT的物理结构却不受其在溶剂中溶解度大小的影响而具有沸点依赖性,溶解在高沸点溶剂中的P3HT旋涂后,薄膜内P3HT主链平面性与π-π相互作用均得到提高;此外,溶剂沸点的增加导致分子取向由"面朝上"方式转变为"边朝上"方式。     

1-烯丙基,3-甲基咪唑室温离子液体的合成及其对纤维素溶解性能的初步研究

随着不可再生资源 (如石油、天然气、煤矿和金属矿藏等 )的急剧耗竭 ,天然高分子的开发与利用日益引起世人的关注 .纤维素作为自然界中最丰富的天然高分子材料 ,其开发与利用一直备受关注[1] .但由于天然纤维素较高的结晶度和分子间和分子内存在大量的氢键 ,使其具有不熔化、在大多数溶剂中不溶解的特点 ,这成为纤维素在应用开发中的最大障碍 .开发有效的纤维素溶剂体系是解决这一难题的关键 .研究较多的纤维素溶剂主要有铜氨溶液、Ｎ 甲基吗啉 Ｎ 氧化物(ＮＭＭＯ)溶剂体系 ,氯化锂 二甲基乙酰胺 (ＬｉＣｌ ＤＭＡＣ)溶剂体系等[2 ] ,而这…     

甲壳素和壳聚糖作为天然生物高分子材料的研究进展

甲壳素是自然界中含量仅次于纤维素的天然高分子,壳聚糖是甲壳素脱乙酰化后带有阳离子的多糖.壳聚糖中的自由氨基以及它的高结晶性,使得它能溶于酸,而不溶于碱和绝大数的有机溶剂.同时壳聚糖具有无毒性、无刺激性、良好的生物相容性、生物可溶解性, 以及高的电荷密度,因而被作为一种新型的天然生物材料得到广泛应用.文章介绍了甲壳素和壳聚糖的结构和性质,综述分析了甲壳素和壳聚糖在制备微球和作为支架材料中的应用, 并总结了甲壳素和壳聚糖在这两个方面存在的问题和发展前景.     

基于“多链超分子柱”的侧链液晶高分子柱状相

一些具有伸展构象的侧链液晶高分子,如甲壳型液晶高分子或树枝化高分子,可以经由分子链的平行排列而呈现柱状液晶相.一般认为,该类柱状相的基本结构单元是单根高分子链所形成的超分子柱.而以几根链组装形成的超分子柱,即"多链超分子柱",也可作为侧链液晶高分子柱状相的基本结构单元,但多年以来这一现象并未引起人们的重视.近期,我们以hemiphasmid型侧链液晶高分子为研究对象,阐明了"多链超分子柱"是侧链液晶高分子柱状相微相分离的一种重要形式.本文从hemiphasmid型侧链液晶高分子的柱状相结构分析、化学结构对"多链超分子柱"的影响、"多链超分子柱"模型的理论分析与预测、"多链超分子柱"的"柱内缠结"以及hemiphasmid型侧链液晶聚降冰片烯的功能性等若干方面,对基于"多链超分子柱"的侧链液晶高分子柱状相进行了介绍.我们认为,深入研究"多链超分子柱"性质,将拓展侧链液晶高分子的应用领域,加深对高分子物理基本问题的认识.     

Thermally induced conformation transition of triple-helical lentinan in NaCl aqueous solution

Lentinan, a beta-(1-->3)-D-glucan, was isolated from Lentinus edodes by using an improved extraction and purification method to show good water solubility and high yield. The results from 13C NMR, size-exclusion chromatography combined with multiangle laser light scattering (SEC-MALLS), dynamic light scattering (DLS), and optical rotation revealed that lentinan existed in a triple-helical conformation in the aqueous solution at 25 degrees C, whereas the thermally induced conformation transition from triple helix to single flexible chains occurred at elevated temperatures. The dependences of the weight-average molecular weight (Mw), radius of gyration (z1/2), hydrodynamic radius (Rh), intrinsic viscosity ([eta]), and specific optical rotation of lentinan on temperature in 0.9% NaCl aqueous solution showed an abrupt drop at 130-145 degrees C. It was confirmed that the conformation transitions from triple strand to single chain and from extended chains to winding chains for lentinan were completed rapidly at 130-145 degrees C, as a result of the simultaneous destruction of the intra- and intermolecular hydrogen bonds in lentinan. The thermally induced conformational transition was irreversible. The results from atomic force microscopy (AFM) and DLS demonstrated the existence of intrachain entanglement for the triple-helical chains, leading to the wormlike linear, circular, and crossover species for lentinan having high Mw (1.71x10(6)) in aqueous solution at 25 degrees C.     

Dissolution of chitin in aqueous KOH

Our NMR experiments show that chitin can dissolve well in aqueous KOH through a freeze-thawing process, and the dissolution power of the alkali solvent systems is in the order of KOH > NaOH > LiOH aqueous solution, which is totally contrary to that of cellulose in the alkali aqueous solution (i.e., LiOH > NaOH ? KOH). In this work, we systematically study the dissolution process in KOH and KOH/urea aqueous solutions. Chitin has good solubility (solubility ~80 %) in 8.4–25 wt% KOH aqueous solution at ?30 °C. The role of urea also has been investigated: unlike aqueous chitin-NaOH solutions, urea indeed enhances the solubility of chitin in KOH aqueous solutions, but the increased degree becomes unobtrusive with decreasing temperature and increasing dissolution time; the DA decline curves of chitin-KOH and chitin-KOH/urea aqueous solutions are nearly overlapping, indicating that the effect of the urea on the degree of acetylation of chitin in KOH aqueous solutions is small, similar to the NaOH/urea solvent.     

Interaction between –OH groups of methylcellulose and solvent in NaOH/urea aqueous system at low temperature

To clarify the interaction between the –OH groups of cellulose and NaOH/urea in aqueous solutions, methylcellulose (MC) was used as solute to study its solution properties at low temperature. Dynamic light scattering, ¹³C NMR spectroscopy, differential scanning calorimetry, and transmission electron microscopy (TEM) were used to characterize the MC macromolecular size and intermolecular interactions between MC and solvent molecules. The results revealed that MC existed mainly as individual molecules in the NaOH/urea aqueous solution prepared by freeze-thawing process, whereas aggregates occurred in the MC solution prepared at room temperature. DLS further confirmed that MC existed mainly as individual flexible chains in the solution treated at low temperature. TEM images showed the sphere-like coil appearance of the MC macromolecules in the solution prepared at low temperature. Therefore, the strong interaction between –OH groups of MC and solvent occurred at low temperature, leading to the formation of the imperfect inclusion complex through hydrogen bonding network between MC, NaOH, urea and water.     

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.     

Dilute solution properties of cellulose in LiOH/urea aqueous system

Cellulose was dissolved rapidly in 4.6 wt % LiOH/15 wt % urea aqueous solution and precooled to –10 °C to create a colorless transparent solution. ¹³C‐NMR spectrum proved that it is a direct solvent for cellulose rather than a derivative aqueous solution system. The result from transmission electron microscope showed a good dispersion of the cellulose molecules in the dilute solution at molecular level. Weight‐average molecular weight (M_w), root mean square radius of gyration (〈s²〉_z^1/2), and intrinsic viscosity ([η]) of cellulose in LiOH/urea aqueous solution were examined with laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 4.6 wt % LiOH/15 wt % urea aqueous solution was established to be [η] = 3.72 × 10^?2 M in the M_w region from 2.7 × 10⁴ to 4.12 × 10⁵. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were given as 6.1 nm, 358 nm^?1, and 20.8, respectively. The experimental data of the molecular parameters of cellulose agreed with the Yamakawa–Fujii theory of the worm‐like chain, indicating that the LiOH/urea aqueous solution was a desirable solvent system of cellulose. The results revealed that the cellulose exists as semistiff‐chains in the LiOH/urea aqueous solution. The cellulose solution was stable during measurement and storage stage. This work provided a new colorless, easy‐to‐prepare, and nontoxic solvent system that can be used with facilities to investigate the chain conformation and molecular weight of cellulose. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3093–3101, 2006     

Hydrogen-bond-induced inclusion complex in aqueous cellulose/LiOH/urea solution at low temperature.

It was puzzling that cellulose could be dissolved rapidly in 4.6 wt % LiOH/15 wt % urea aqueous solution precooled to -12 degrees C, whereas it could not be dissolved in the same solvent without prior cooling. To clarify this important phenomenon, the structure and physical properties of LiOH and urea in water as well as of cellulose in the aqueous LiOH/urea solution at different temperatures were investigated by means of laser light scattering, 13C NMR spectroscopy, differential scanning calorimetry, Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, and transmission electron microscopy (TEM). The results reveal that a hydrogen-bonded network structure between LiOH, urea, and water can occur, and that it becomes more stable with decreasing temperature. The LiOH hydrates cleave the chain packing of cellulose through the formation of new hydrogen bonds at low temperatures, which result in a relatively stable complex associated with LiOH, water clusters, and cellulose. A channel inclusion complex (IC) hosted by urea could encage the cellulose macromolecule in LiOH/urea solution with prior cooling and therefore provide a rationale for forming a good dispersion of cellulose. TEM observations, for the first time, showed the channel IC in dry form. The low-temperature step played an important role in shifting hydrogen bonds between cellulose and small molecules, leading to the dissolution of macromolecules in the aqueous solution.     

Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions

Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions was studied systematically. The dissolution behavior and solubility of cellulose were evaluated by using (13)C NMR, optical microscopy, wide-angle X-ray diffraction (WAXD), FT-IR spectroscopy, DSC, and viscometry. The experiment results revealed that cellulose having viscosity-average molecular weight ((overline) M eta) of 11.4 x 104 and 37.2 x 104 could be dissolved, respectively, in 7% NaOH/12% urea and 4.2% LiOH/12% urea aqueous solutions pre-cooled to -10 degrees C within 2 min, whereas all of them could not be dissolved in KOH/urea aqueous solution. The dissolution power of the solvent systems was in the order of LiOH/urea > NaOH/urea > KOH/urea aqueous solution. The results from DSC and (13)C NMR indicated that LiOH/urea and NaOH/urea aqueous solutions as non-derivatizing solvents broke the intra- and inter-molecular hydrogen bonding of cellulose and prevented the approach toward each other of the cellulose molecules, leading to the good dispersion of cellulose to form an actual solution.     

The dissolution of cellulose in NaOH-based aqueous system by two-step process

A new dissolution method, a two-step process, for cellulose in NaOH/urea aqueous system was investigated with ¹³C NMR, wide X-ray diffraction (WXRD), and solubility test. The two steps were as follows: (1) formation and swelling of a cellulose–NaOH complex and (2) dissolution of the cellulose–NaOH complex in aqueous urea solution. The dissolution mechanism could be described as strong interaction between cellulose and NaOH occurring in the aqueous system to disrupt the chain packing of original cellulose through the formation of new hydrogen bonds between cellulose and NaOH hydrates, and surrounding the cellulose–NaOH complex with urea hydrates to reduce the aggregation of the cellulose molecules. This leads to the improvement in solubility of the polymer and stability of the cellulose solutions. By using this two-step process, cellulose can be dissolved at 0–5 °C in contrast to the known process that requires −12 °C. Regenerated cellulose (RC) films with good mechanical properties and excellent optical transmittance were prepared successfully from the cellulose solution.     

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.     

Room temperature dissolution of cellulose in tetra-butylammonium hydroxide aqueous solvent through adjustment of solvent amphiphilicity

The amphiphilicity of solvent systems is realized for adjusting the dissolution of natural cellulose by making use of tetra-butylammonium hydroxide (TBAH) as an example. TBAH aqueous solution is found to have an obvious effect on adjusting its amphiphilicity, along with a flexible concentration ranging from 40 to 60 wt% for dissolving cellulose. With a suitable amphiphilic property, cellulose can be dissolved by a TBAH aqueous system . The experimental results demonstrate that with the introduction of urea (more than 0.2:1, w:v) into a TBAH aqueous system, the dissolution process of cellulose can be dramatically promoted, leading to a transparent solution of cellulose. Herein, a complex solvent of TBAH/urea has been proposed for mild and effective dissolution of cellulose under ambient conditions. In the TBAH/urea complex solvent, the structure of the hybrid hydrate of TBAH and urea formed. Urea served as a hydrophobic contributor adjusting the amphiphilicity of the solvent system, allowing interfacial resistance between the amphiphilic crystal surfaces of the natural cellulose and solvent to be reduced. After that, the crystal of natural cellulose could be fully infiltrated and subsequently dissolved by the TBAH/urea aqueous solvent. The performances of the aqueous solvent and ambient temperature dissolution make aqueous TBAH/urea a potential and green solvent of cellulose for broad applications, such as composites, films or wet spinning of cellulose, in laboratories or industries.