氰乙基纤维素溶致性液晶的研究

氰乙基纤维素在二甲基甲酰胺、二甲基乙酰胺、二甲基亚砜、乙腈以及丙酮等溶剂中可以形成溶致性液晶。随浓度增加,溶液从各向同性状态经两相共存态转变成为完全的液晶态。升高温度到T_c,液晶相消失;降低温度到T′_c,液晶相再生成。T_c总大于T′_c。而且,浓度越高,过冷温度△T=T_c—T′_c越小。在各向同性,两相共存或完全的液晶状态,溶液平均折射率和消光度均与浓度呈线性关系。但在两相间相互转变时,即在C_1~*和C_2~*处,n-C和 A-C 曲线上出现转折点。高聚物与溶剂的相互作用参数X_(12)愈小,临界浓度C_1~*愈小。把描述大分子链柔顺性的参数f与X_(12)联系起来,可用 1956年 Flory的理论定性地解释溶剂对高聚物溶致性液晶形成的影响。     

氰乙基纤维素溶致性液晶折射率的研究

本文用折射率法研究了氰乙基纤维素在二甲基甲酰胺和二甲基亚砜中形成溶致性液晶的过程,测定了临界浓度C_1~*和C_2~*。对用该方法研究高聚物液晶溶液的有效性以及折射率与其浓度和溶液结构的关系进行了探讨。讨论了各种情况下的n—C曲线。     

乙基氰乙基纤维素/甲基丙烯酸酯液晶溶液的研究

乙基氰乙基纤维素/甲基丙烯酸酯在一定的浓度下可以形成溶致性液晶,从液晶相的双折射纹理结沟和小角光散射的Hν散射花样可知这类液晶是胆甾型的。同时,在液晶相开始出现时及各向同性相完全消失时的临界浓度C_1和C_2均随着甲基丙烯酸酯的酯基链增长而降低。     

乙基醋酸纤维素溶致性液晶的研究

非全取代的乙基纤维素在浓硫酸催化下与醋酸反应,生成乙基醋酸纤维素。乙基醋酸纤维素在适当的条件下可以形成溶致性液晶。随浓度的升高,溶液从各向同性态经两相共存,转变成完全的液晶态。在加热溶液时,可以看到两相共存状态的形成和液晶相的完全消失,降低温度,液晶相又可以再生成。在液晶相生成的过程中,存在过冷现象,液晶聚集的区域由许多微小的取向区域组成,它们的取向方向不相同。溶液的n—c曲线在各相同性、两相共存和液晶态区域内是直线,但在这些相态之间相互转变时出现转折点。溶液的双折射△n=ne—no在两相共存与液晶态相互转变时也会发生较大变化。乙基醋酸纤维素大分子链的刚性随有机酸溶剂体系的酸的强度增大而增大,使临界浓度C_1~*随溶剂酸的强度的增大而减小。     

新的液晶性壳聚糖衍生物——氰乙基壳聚糖的合成与表征

甲壳素是自然界蕴藏量最丰富的天然高分子化合物之一,但人们对它的了解却远不如纤维素和淀粉.仅就液晶领域而言,纤维素衍生物的液晶性早已为人们所认识,例如氰乙基纤维素的液晶性已有很多研究.     

纤维素及其衍生物液晶研究新进展

本文全面地综述了纤维素及其衍生物溶致性液晶和热致性液晶的形成, 液晶性与大分子链结构, 以及具有胆甾型液晶相结构的纤维素衍生物复合材料等方面的最新研究进展。     

聚己内酯分子量对乙基纤维素/聚己内酯共混体系的溶致性液晶织构的影响

利用偏光显微镜研究了乙基纤维素与聚己内酯共混物在二氯乙酸中的溶致性液晶形态。结果表明聚己内酯的分子量对共混体系的溶致性液晶结构有明显的影响。差示扫描量法测试显示含不同分子量聚己内酯的共混物,其混溶性及两组分间的相互作用无十分明显的差异。聚内酯分子量对共混体系溶致性液晶的形态和热稳定性的影响,可认为是由于分子量对体系的粘度贡献引起的。     

乙基氰乙基纤维素／聚丙烯酸复合物及大分子胆甾型液晶相的形态结构特征

对乙基氰乙基纤维素／丙烯酸胆甾型液晶溶液的液晶性，液晶态的织构特征，丙烯酸在液晶溶液中的聚合反应及在反应过程中胆甾型液晶相结构和性能的变化等方面进行了研究，     

羟乙基纤维素醋酸酯热致液晶性和相转变

本文研究了羟乙基纤维素醋酸酯的热致液晶和相转变过程。发现升温时,在130～185℃范围内羟乙基纤维素醋酸是各向异性的熔体,在温度高于185℃以后是各向同性的熔体。降温时,各向异性相在165℃时开始形成,进一步冷却到室温,形成液晶玻璃态。在降温过程中,相转变和液晶相织构的形成都很快,而且一旦液晶相的织构形成以后就不再随时间和温度降低而变化。羟乙基纤维素醋酸酯的热致液晶性还受其分子量影响,分子量越高,相转变温度越高。但是,在适当的分子量下,羟乙基纤维素醋酸酯才有最大的动力学相转变能力。     

羟丙基甲基纤维素溶致液晶的临界浓度与溶剂溶度参数关系的研究

羟丙基甲基纤维素溶致液晶的临界浓度与溶剂溶度参数关系的研究董炎明,洪肇昭（厦门大学化学系,厦门,３６１００５）关键词　羟丙基甲基纤维素,溶致性液晶,临界浓度,溶解度参数,链刚性溶致液晶的阀值或临界浓度是在一定温度下恰能形成液晶相的最低浓度,高分子链刚...     

乙基醋酸纤维素溶致性液晶的研究

乙基醋酸纤维素溶于三氟乙酸、二氯乙酸、醋酸中.在浓度大于临界浓度时,形成胆甾型液晶态.溶液随浓度的增加,从各向同性态经两相共存转变成液晶态.在加热液晶溶液时,溶液转变成各向同性态.降低温度,液晶相再生成.在形成液晶过程中,存在过冷现象.在一定的条件下,液晶相以球状的形式存在.溶液的双折射△n在两相共存与完全液晶态间相互转变时会发生较大变化.乙基醋酸纤维素大分子链的刚性随有机酸溶剂体系的酸强度的增大而增大,使临界浓度C_1~*随溶剂酸强度的增大而减小.     

气液色谱法研究醇类在芳烃中的缔合溶液热力学

用气液色谱法测量了不同温度下C~1-C~4醇类的各异构物在二苯甲烷、联苄、二苯乙炔、二苯甲酮及二苯亚砜中的无限稀活度系数γ~i、偏摩尔过量焓H^E~i及偏摩尔过量熵S^E~i。用Kretschmer-Wiebe 模型计算各醇类在二苯甲烷、联苄、二苯乙炔中的自身缔合常数K~A, 得到在同一溶剂中, C~1-C~4醇类, K~A减小次序。用同一模型计算各醇类在二苯甲酮、二苯亚砜中的交叉缔合常数K~A~B, 得到在同一溶剂中, K~A~B减小次序。     

Aqueous polymerization of methyl methacrylate initiated by Ce(IV)–alcohol redox systems: Effect of acid concentration and additives

Polymerization of methyl methacrylate (MMA) initiated by ceric ammonium nitrate in combination with alcohols, isopropyl and, isobutyl alcohol, has been studied in aqueous nitric acid. The effect of nitric acid and nitrate ion concentrations on the initial rate of polymerization as well as on that of ceric ion consumption and on polymer molecular weight has been investigated. The rate of polymerization initially rapidly to a maximum with increasing nitric acid concentration at constant nitrate ion concentration, and then, decreased at higher acid concentrations. The rate of ceric ion consumption increased on increasing the acid concentration. A fall in both the rates was observed as the nitrate ion concentration increased, and when acid concentration was kept constant. Average-molecular weights decreased with increasing the acid concentration; whereas they increased with increasing that of nitrate ion. The effect of certain water-miscible organic solvents has also been studied. Both the rates increased in their presence, whereas the molecular weight underwent a decrease     

小角激光散射法研究聚苯基喹 啉在稀溶液中的缔合现象

聚[2,2'-(1,4-苯撑)-6,6'-双(3-苯基喹 啉)](PPQ)是一种耐高温材料, 其合成方法, 机械性能及应用方面的研究已有很多报导, 但是有关其溶液性质和分子形态的研究还甚少。本文用小角激光散射法研究了PPQ的稀溶液性质, 并报导了PPQ在溶液中的缔合现象。     

导电聚吡咯膜电极的现场电化学-ESR研究

本文报导聚吡咯(PP)膜电极在水溶液中的电化学─ESR行为, 定性地探讨了电位,电量对PP膜中极化学形成与转化过程的影响, 并在PP膜/溶液界面存在电化学反应的情形下, 考察了PP膜中可能的电荷传输机理。     

有机溶剂/缓冲液双相体系中绿豆环氧化物水解酶催化环氧苯乙烯不对称水解反应

研究了有机溶剂/缓冲液双相体系中绿豆环氧化物水解酶高立体选择性地催化外消旋环氧苯乙烯水解生成(R)-苯基乙二醇反应.结果表明,与单水相反应体系相比,有机溶剂/缓冲液双相反应体系不仅有效地抑制环氧苯乙烯的非酶水解反应,而且明显提高底物的浓度,产物的收率和ee值更高.在所考察的不同有机溶剂中,正己烷不仅能较好地溶解底物,而...     

Microencapsulated mycelium-bound tannase from Aspergillus niger

Microencapsulated Aspergillus niger with mycelium-bound tannase activity was employed to investigate the esterification of propyl gallate from gallic acid and propanol in organic solvents. The effects of various organic solvents (log P:−1.0 to 6.6) on the enzymatic reactions showed that benzene (log P:2.0) was the suitable solvent, for which the conversion reached 26.8%. The optimum catalyst concentration and water concentration was found at 25 capsules in 10 mL of benzene and 0.04 g of water/capsule. The external mass transfer effect could be eliminated at stirring speeds of 180 rpm or higher. Both substrates 1-propanol and gallic acid had significant inhibition effects on the tannase activity. Maximum molar conversion (36.2%) was achieved with 9.1% (v/v) 1-propanol and 8 mM gallic acid and decreased with increasing amounts of substrates.     

Unique role of water content in enzymatic synthesis of ethyl lactate using ionic liquid as solvent

Enzymatic synthesis of ethyl lactate was studied in organic solvents and in ionic liquids to determine optimal media for the reaction, and to investigate the effect of water content on the ester yield. Experiments proved that Cyphos 202 ionic liquid is the best solvent affording the highest ethyl lactate yields. Furthermore, 20 times less enzyme sufficed to carry out the reaction in this ionic liquid compared to organic solvents; ionic liquid could be applied as solvent. Using water removal, the ester yield decreased since a side reaction, dimerization of lactic acid, occurred as well. In contrast to these results, without water removal, the produced water was partly consumed by the decomposition of lactoyllactic acid to free lactic acid, increasing thus the substrate concentration of the mixture and enhancing the ester yield.     

Spectroscopic studies of charge transfer complexes of meso‐tetra‐p‐tolylporphyrin and its zinc complex with some aromatic nitro acceptors in different organic solvents

The charge transfer complex (CTC) formation of 5,10,15,20‐tetra(p‐tolyl)porphyrin (TTP) and zinc 5,10,15,20‐tetra(p‐tolyl)porphyrin with some aromatic nitro acceptors such as 2,4,6‐trinitrophenol (picric acid), 3,5‐dinitrosalicylic acid, 3,5‐dinitrobenzoic acid (DNB) and 2,4‐dinitrophenol (DNP) was studied spectrophotometrically in different organic solvents at different temperatures. The spectrophotometric titration, Job's and straight line methods indicated the formation of 1:1 CTCs. The values of the equilibrium constant (K_CT) and molar extinction coefficient (ε_CT) were calculated for each complex. The ionization potential of the donors and the dissociation energy of the charge transfer excited state for the CTC in different solvents was also determined and was found to be constant. The spectroscopic and thermodynamic properties were observed to be sensitive to the electron affinity of the acceptors and the nature of the solvent. No CT band was observed between Zn‐TTP as donor and DNP or DNB as acceptors in various organic solvents at different temperature. Bimolecular reactions between singlet excited TTP (¹TTP*) and the acceptors were investigated in solvents with various polarities. A new emission band was observed. The fluorescence intensity of the donor band decreased with increasing the concentration of the acceptor accompanied by an increase in the intensity of the new emission. The new emission of the CTCs can be interpreted as a CT excited complex (exciplex). Copyright © 2007 John Wiley & Sons, Ltd.     

Swelling behavior of chemically crosslinked PVA gels in mixed solvents

We report the swelling behavior of chemically crosslinked polyvinyl alcohol (PVA) gels with different degrees of hydrolysis in water, several organic solvents, and their mixed solvents. The gels were dried after gelation and were put into their respective solvents. The gel volume in pure water decreased with increasing temperatures, and the total changes increased with decreasing degrees of hydrolysis. The swelling ratio depends on the solvent and its concentration. In the cases of mixed solvents of methanol–water, ethanol–water, and acetone–water, the gels shrank continuously with increasing concentrations of solvents and reached the collapsed state in the pure organic solvent. In the case of dimethyl sulfoxide (DMSO), on the other hand, the gels shrunk, swelled, and finally reached the swollen state in pure DMSO. Results of measurements using Fourier Transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD) suggested that crosslinks and microcrystallites were formed due to hydrogen bonds during the drying process after gelation. The hydrogen bonds were partly destroyed in a rich solvent, but the residual hydrogen bonds had an essential role in determining the swelling behavior in a poor solvent. The swelling behavior and the possible phase transition of the present system are discussed in terms of the solubility of polymers with different degrees of hydrolysis in given mixed solvents and in terms of the formation and destruction of physical crosslinks in the chemical PVA gels. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1978–1986, 2010