Enthalpies of solution,partial molal heat capacities and apparent molal volumes of sugars and polyols in water

Integral enthalpies of solution of some sugars and polyols in water at low concentrations have been determined calorimetrically at 25 and 35°C. These data have been used to derive heat capacities of solution C°_p at 30°C. Partial molal heat capacities C°_p,2 have been obtained by combining C°_p with C _p,2 ^* , the heat capacity of pure solid compounds. Apparent molal volumes have been obtained from density data. The sugars as well as polyols show significantly high positive C°_p and C°_p,2 values. The results have been explained in terms of a specific hydration model. The effect of substitution of-OH by glycosidic-OCH₃ and of-CHOH by deoxy-CH₂ are also discussed.     

Isopiestic study of the interactions between calcium chloride and methyl glycofuranosides in aqueous solution

Osmotic coefficients have been determined for three isomeric methyl glycofuranosides, viz. methyl -D-lyxo-, -D-ribo-, and -D-ribofuranosides in aqueous solution by the isopiestic comparison method. The method was further applied to measure the osmotic coefficients for the ternary system consisting of calcium chloride, methyl glycofuranoside, and water. The results are analyzed in terms of an excess function from which the salting constants for the glycosides are derived. Relationships between the salting constants and the complexing of methyl glycofuranosides with calcium ion are discussed.     

Polyurethane/montmorillonite nanocomposites prepared from crystalline polyols, using 1,4-butanediol and organoclay hybrid as chain extenders

Polyurethane/montmorillonite (PU/MMT) nanocomposites were prepared via in situ polymerization from highly crystalline poly(butylene succinate)/poly(ethylene glycol) polyols and 4,4^′-dicyclohexylmethane diisocyanate, using both 1,4-butanediol and 1, 2, or 3 wt.% of a tris(hydroxymethyl)aminomethane-MMT hybrid, as chain extenders. The corresponding nanocomposites were designated PU-1MMT, PU-2MMT and PU-3MMT, respectively. The layered silicates were mostly intercalated in the nanocomposites. The distances between the individual silicate layers in the PU-1MMT and PU-2MMT were in the range of 2-10 nm, while those in the PU-3MMT were only about 2 nm. The inefficient exfoliation of the clay in this system was mainly due to the high crystallinity and polarity of the PBS polyol. There were no significant changes in the thermal properties of the pure PU and PU nanocomposites. However, the tensile modulus and elongation of the PU-2MMT at break were significantly greater than those of the pure PU and PU-3MMT.     

Freezing temperatures of aqueous solutions of mixtures of amides and polyols. Gibbs energy of interaction of the amide group with the hydroxyl group in aqueous solution

Freezing temperatures of dilute aqueous mixtures of: formamide with myo-inositol, d-mannitol, and cyclohexanol; N,N-dimethylformamide with inositol, mannitol, and cyclohexanol; and acetamide with inositol and mannitol have been measured. These data have been analyzed to yield the pairwise molecular Gibbs energies of interaction between the molecules in an aqueous solution. Using the group additivity principle, the results yield the pairwise functional group Gibbs energies of interaction of the amide group with the hydroxyl group, G _OH,CONH =–31 J-kg-mol^–2.     

Kinetic evaluation of hydrogenation of sucrose over ruthenium containing Y zeolites

Hydrogenation of sucrose over Ru/NaY, Ru/USY and Ru/CaY catalysts was carried out in a slurry reactor at 135°C and 12 atm. The catalysts were prepared by ion exchange followed by calcination and reduction. These were characterised as AA, TPR, DTA/TGA, H₂/Chemisorption, CO-FTIR, XRD and t-plot. To describe kinetic product distribution, the 4^th order Runge-Kutta method was used for determining the kinetic parameters.     

Synthesis and characterization of hyperbranched polyesters and polyurethane coatings

Polyurethane (PU) coatings are widely used for variety of high‐performance applications in today's coating technology. The emerging hyperbranched polymers having three‐dimensional morphology have opened a new avenue to tailor the architecture of PU coatings. The methodology followed here is based on preparation of PU coatings from hyperbranched polyester. Initially, different hyperbranched polyester polyols (HPs) were synthesized by varying the hydroxyl‐terminated precursors that is, pentaerythritol, trimethylol propane or glycerol and keeping the diacid that is, adipic acid quantity constant at various mole ratios of 1:0.6, 1:0.8, 1:0.9, and 1:1, respectively. The obtained HPs were characterized by nuclear magnetic resonance (NMR) spectroscopy, matrix‐assisted laser desorption/ionization time‐of‐flight (MALDI‐TOF)‐mass spectrometry, and Fourier transform‐infrared (FTIR) spectroscopy. The degree of branching and the quantity of different structural units present in the various HPs were calculated by integrating the quaternary carbon and carbonyl zone in ¹³C NMR spectroscopy. The extent of condensation in different HPs was also calculated from ¹H NMR spectra. Later on, NCO‐terminated PU prepolymers (NCO‐PU) were synthesized by reacting HPs with isophorone diisocyanate (IPDI) at NCO/OH ratio of 1.6:1. In the third step, the excess NCO content in the NCO‐capped PU prepolymers were reacted with atmospheric moisture and hyperbranched polyurethane (HPU) coatings were formed. The coating films were analyzed by FTIR and dynamic mechanical thermal analysis instruments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2673–2688, 2007     

竹浆纤维素转化制低碳多元醇反应中有机氮对金属催化剂稳定性影响的研究

采用等体积浸渍法制备了一系列多孔竹炭负载的有机氮掺杂的镍钨催化剂,并将其应用于催化竹浆纤维氢解制C_2,3多元醇反应。有机氮源与催化剂前驱体中Ni²⁺络合,高温煅烧时载体表面碳、氮和金属离子相互作用后生成一定量的C₃N₄、氮化物和合金物相。通过XRD、XPS和TEM等表征手段分析了催化剂Ni-W/MBC表面物理化学性质与催化活性间的关系。结果表明,除了金属镍、氧化钨物相外,表面还含有Ni-W合金（NiWO₄为主）;金属粒子表面包围了一层石墨化C₃N₄物相。XPS分析表明,有机氮源高温分解反应后形成了C₃N₄物相。在反应条件下,15% Ni-20% W/MBC@M-0.25催化剂得到乙二醇收率为55.8%,而未添加有机氮源的催化剂15% Ni-20% W/MBC获得的乙二醇收率仅为36.9%。催化剂稳定性实验结果表明,Ni-W合金和C₃N₄物相的形成显著增强了Ni-W/MB催化剂的稳定性,延长了催化剂寿命。     

二氧化硅改性分子筛催化生物质基多元醇制备对二甲苯

本文证明了在二氧化硅改性的分子筛催化作用下,生物质基多元醇(如山梨醇、木糖醇、赤藓糖醇、甘油和乙二醇)可以经过催化裂解、烷基化和异构化等反应,生成高附加值的化学品(对二甲苯).与HZSM-5分子筛催化剂相比,二氧化硅改性的分子筛降低了分子筛催化剂的外表面酸和孔径,从而显著的提高对甲苯的选择性和产率.本文详细讨论了催化剂、甲醇添加剂、反应温度和不同类型多元醇原料对对二甲苯选择性和产率的影响.甲醇的添加促进多元醇催化裂解中的烷基化反应,提高了二甲苯的产率.在15%SiO_2/HZSM-5催化剂作用下,对二甲苯的产率最高可达到10.9 C-mol%,对二甲苯在二甲苯中选择性达到91.1%.本文通过研究相关重要反应和催化剂特性,揭示了生物质基多元醇催化裂解制备对二甲苯的反应路径.     

Optimization of media by evolutionary algorithms for production of polyols

Biotransformation of sucrose-based medium to polyols has been reported for the first time using osmophilic yeast, Hansenula anomala. A new, real coded evolutionary algorithm was developed for optimization of fermentation medium in parallel shake-flask experiments. By iteratively employing the nature-inspired techniques of selection, crossover, and mutation for a fixed number of generations, the algorithm obtains the optimal values of important process variables, namely, inoculum size and sugar, yeast extract, urea, and MgSO₄ concentrations. Maximum polyols yield of 76.43% has been achieved. The method is useful for reducing the overall development time to obtain an efficient fermentation process.     

Effects of polyols and sugars on the structure of water in concentrated gelatin gels as studied by low temperature differential scanning calorimetry

 Phase-transition temperatures, glass-transition temperatures, melting temperatures, gel–sol transition temperatures in differential scanning calorimetry heating curves of gelatin solutions with and without various sugars and polyols quenched by liquid nitrogen were studied. Both sugars and polyols added to concentrated gelatin solutions shifted the glass-transition temperatures to lower temperatures, and it was attributed to the increase of unfreezable water which acts as a plasticizer. The mechanisms of the increase in unfreezable water, however, seem to be different for sugars and polyols; sugars increase unfreezable water by increasing the number of junction zones which hold unfreezable water, while polyols by themselves increase the amount of unfreezable water. Received: 9 January 1997 Accepted: 1 July 1997