纤维素衍生化手性固定相的制备和对噻吗洛尔拆分

用超声方法合成了三(3,5-二硝基苯甲酰基)纤维素(CTNB)、三(4-溴苯甲酰基)纤维素(CTBB)、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(CTPB).将此类衍生化纤维素作为薄层色谱的手性固定相,结合展开剂的优化,对噻吗洛尔对映体进行拆分研究,并对衍生化取代基对拆分效果的影响以及对映体在手性固定相上的拆分机理进行了详细的探讨.     

纤维素LiCl/DMAc体系的溶液特征

本文研究了纤维素LiCl／DMAc体系的溶液特征。实验结果证明该体系具有良好的时间稳定性和热稳定性，能在常温下近30天内没有明显的粘度降低；在100℃高温下，4h不降解。同时测定了溶液的特性粘数和Huggins常数，Huggins常数在0．4～0．6之间，对比纤维素的铜乙二胺（Cuen）溶液，发现特性粘数[η]LICI/DMAc＞[η]Cuen，无扰尺寸ALiCi／DMAc＞ACuen，可见在LiCl／DMAc体系中，溶剂与纤维素分子表现出更强的相互作用力，分子链充分伸展。该体系的特性粘数、粘度常数不仅与温度、溶剂有关，而且是LiCl浓度的函数，具有与聚电解质溶液相类似的性质。这可能是因为纤维素分子链上的H质子和溶液中的Cl-离子相互作用，而使纤维素分子带上部分电荷，相互排斥而引起的。因此利用M－H方程测分子量，粘度常数的确立必须考虑诸多因素的影响，否则会导致分子量的高估。     

Modification of cellulose fiber with silk sericin

Cellulose fiber surface was modified with silk sericin (or simply, sericin). Sericin fixation on cellulose was confirmed by environmental scanning electron microscopy (ESEM) and Fourier transform infrared spectrophotometry–attenuated total reflectance (FTIR‐ATR). Sericin content in finished samples was estimated by dyeing treated fabrics with an acid dye, Supranol Bordeaux B, and determining K/S and L values of the dyed fabrics. The treated fabrics were tested for free formaldehyde content, crease recovery, tensile strength, electrical resistance, water retention, and biocidal activity. From ESEM and FTIR‐ATR results, it was found that sericin coated onto cotton surfaces as a film. Increasing sericin content in the finishing solution increased the amount of coated sericin, and a greater depth of color in dyed samples and reduced free formaldehyde content in treated samples were observed. The sericin content in samples was found to have a negligible influence on tensile strength and crease recovery angle. With increasing sericin content, electrical resistivity of the samples dramatically decreased and water retention increased, indicating that sericin‐treated fabrics may be comfortable to wear because of its maintenance of moisture balance with respect to human skin. Because cotton textile coated with sericin exhibited low formaldehyde content and no biocidal activity against Klebsiella pneumoniae and Staphylococcus aureus, the fabric may reduce skin irritation and disturbance of physiological skin flora arising from textile contact. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1421–1428, 2005     

取代基及分子量对非离子型纤维素醚表面特性的影响

根据Washburn的浸渍理论(Penetration Theory)和van Oss-Good- Chaudhury的组合理论(Combining Theory)及应用柱状灯芯技术(Column Wicking Technique),对几种非离子型纤维素醚,如甲基纤维素、羟丙基纤维素和羟丙基甲基纤维素的表面特性进行了测试。由于这些纤维素醚的取代基、取代度和分子量不同,所以它们的表面能及其组成部分有着明显的差异。数据说明,非离子型纤维素醚Lewis碱大于Lewis酸,表面自由能的主要成分是Lifshitz-van der Waals力。羟丙基的表面能及其成分都大于羟甲基。而在相同取代基和取代度的前提下,羟丙基纤维素的表面自由能正比于分子量;而羟丙基甲基纤维素的表面自由能则正比于取代度,反比于分子量。实验还发现非离子型纤维素醚中的取代基羟丙基和羟丙基甲基的表面能似乎都大于纤维素的表面能,而实验证明所测试得出的纤维素的表面能及其成分的数据是与文献所吻合的。     

Rheological study on O−carboxymethylated chitosan/cellulose polyblends from LiCl/N,N‐dimethylacetamide solution

An O?carboxymethylated chitosan (O? CMCh) water solution (I) and N,N‐dimethylacetamide (DMAc) emulsion (II) were blended with a cellulose LiCl/DMAc solution, and corresponding polyblends (Polyblends I and II) were obtained. The rheology of the three fluids, that is, the cellulose solution and Polyblends I and II, was investigated. The cellulose solution was characterized by a power‐law fluid. When an O‐CMCh water solution or DMAc emulsion was added to the cellulose solution, the power‐law curve was preserved. The power‐law indexes (n) of all three fluids increased along with the temperature. Polyblend I displays an n close to but a little higher than that of the cellulose solution, while Polyblend II shows a much higher power index than those of the other two fluids. The values of the apparent viscosity (η_a) for all the three fluids are close and decrease along with an increase in the temperature. Adding O‐CMCh microparticles into Polyblends I and II results in a decrease in the structural viscosity index (Δη) in comparison to that of the cellulose solution, and this effect is very obvious for Polyblend I. A cellulose solution's Δη declines with the augmentation of temperature, while the Δη's of both Polyblends I and II show minimum values at about 323 K. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1719–1725, 2003     

不同预处理条件下纤维素的结构变化及其在DMAc／LiCI中的溶解

介绍了乙二胺、氢氧化钠和高温等三种不同的纤维素预处理方法。研究预处理后纤维素的结构变化，讨论预处理过程中的转化机理，并通过X射线衍射对纤维素结晶度的变化进行表征，证明乙二胺预处理后纤维素的结晶度下降最大。纤维素经过预处理后可以溶解在DMAc／LiCI中，讨论其溶解机理，通过对比三种预处理纤维素的溶解性能，表明经过乙二胺预处理之后的纤维素在DMAc／LiCI中溶解性能最好，氢氧化钠预处理的纤维素次之，高温预处理的纤维素溶解性能相对较差。     

乙羧氟草醚的合成

以间羟基苯甲酸和3,4-二氯三氟甲苯为原料,经过成盐、醚化、硝化、缩合4步反应得到乙羧氟草醚,所得产物化学结构经红外光谱、核磁共振谱及质谱等确证。反应总收率在75.0%以上,含量(HPLC)达89.0%。     

Living cationic polymerization of isobutyl vinyl ether (II): Photoinduced living cationic polymerization in a mixed solvent of toluene and diethyl ether

A new method of preparation of living cationic polymer of isobutyl vinyl ether via photoinduced polymerization in the presence of diphenyliodonium iodide (DPII, initiator) and zinc iodide in a mixed solvent of toluene/diethyl ether, which was irradiated at ?78°C for short period, was completed within 15 min. The reaction was allowed for further reaction in the dark until monomer was fully consumed. It was found that increase in the conversion of monomer to polymer during the irradiation is very limited. Confirmation of the linear dependence of number‐average molar mass of resulting polymer on % conversion together with the fact that polymerization proceeds until monomer consumption, and controllability of number‐average molar mass of resulting polymer, depending on the molar ratio of monomer and initiator, strongly suggests the living nature of this polymerization, unless reaction temperature becomes higher than 0°C, i.e., the absence of chain breaking process. The narrow molar mass distribution, whose polydispersity index values are less than 1.2, reveals that the rate of initiation where irradiation is usually completed within 15 min is much faster than that of propagation in cationic nature in this system. Effect of some major factors, such as solvent polarity and temperature, on the living nature of the polymerization was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3581–3586, 2006     

纤维素科学与技术研究进展

本文综述纤维素科学与技术的研究进展。阐述了纤维素结构、纤维素的合成、纤维素液晶、功能纤维素、纤维素溶剂、纤维素裂解和纤维素的废物利用等的最新动态。     

纤维素LiCl/DMAc溶液流变性能研究

本文研究了9％LICI／DMAC纤维素溶液的流变性能。在该体系中纤维素溶液是非牛顿流体，属于假塑性流体，具有典型的幂律性。通过幂律方程拟合计算，其稠度系数为60～135，流动特性指数为0.62～0．70。随着浓度增大，稠度系数增大和流动特性指数降低；温度的变化对流动特性指数的影响不大，温度升高，流动特性指数略有减小，而稠度系数相对增大。溶液的粘度随着剪切速率的增大，开始时粘度迅速降低，后趋于稳定，这可能与纤维素分子在溶液中的取向有关。在不同剪切速率下，其流动活化能为23～30kJ．