Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

Carbon-encapsulated Fe nanoparticles from detonation-induced pyrolysis of ferrocene

Carbon-encapsulated Fe nanoparticles with size between 5 and 20 nm were synthesized via a picric acid-detonation-induced pyrolysis of ferrocene, which is characterized by a self-heating and extremely fast process. The nanoparticles exhibit well-constructed core-shell structures, with bcc-Fe cores and graphitic shells. The graphitic shells can protect effectively the cores against the attack of HNO₃ solution. The formation of the core-shell nanoparticles can be selectively controlled by adjusting the composition of the picric acid-ferrocene mixture, which determines C/Fe atomic ratio of the reaction system. The core-shell nanoparticles are preferably formed at low C/Fe atomic ratios, while tubular structures are formed at high C/Fe ratio. The possible pathway for the carbon-encapsulated Fe nanoparticles formation is discussed briefly.     

含氟有机化合物氟化反应研究进展

介绍了含氟有机化合物的优点,一些常用的含氟有机化合物的分类和适用性,并介绍了主要的合成方法,按照合成物质的种类分为含氟非成环烷烃类、含氟环烷烃类及其衍生物和各自不同的应用.叙述了引入F原子或引入含氟端基的方法:电化学反应法、聚合反应法和其它反应法.     

Preparation and characterization of calcium carbonate/low‐density‐polyethylene nanocomposites

Calcium carbonate/low‐density‐polyethylene (LDPE) nanocomposites have been prepared by melting blend with twin‐screw extruder. The mechanical properties of composites and the dispersion of the nanoparticles were studied. The reinforcement mechanism was discussed. The results show that not only the tensile property but also the flexural modulus of the system have been evidently increased by the addition of calcium carbonate. The calcium carbonate particles have been dispersed in the matrix in the nanometer scale. The reinforcement mechanism of the calcium carbonate lies on that the calcium carbonate particles, acting as hetero‐nuclei, can induce higher crystallinity at the matrix‐particle interface compared to regions away from the interface. Consequently, in the process of the tensile test, the nanocomposites have better tensile yield strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of eugenol‐grafted chitosan hydrogels and their antioxidant activities

The hydrogels composed of chitosan and eugenol were prepared to enhance and sustain antioxidant activities. The vinyl groups of eugenol monomer were directly grafted on the amino groups of chitosan, using ceric ammonium nitrate. The graft of eugenol onto chitosan was confirmed by using Fourier‐transform infrared and proton nuclear magnetic resonance spectroscopies. Results from the swelling behavior, thermal stability, and wide‐angle X‐ray diffraction revealed that the equilibrium water content decreased with increase of graft yields, because of the hydrophobicity of eugenol, although the introduction of eugenol as a side chain disturbed the ordered arrangement of chitosan's crystalline structure. The eugenol‐grafted chitosan hydrogels showed lower pH sensitivity in comparison with chitosan alone, because the amino groups, which were pH sensitive, of chitosan were grafted with eugenol. The scavenging activity of the tested hydrogels increased with graft yield of eugenol, because phenolic groups in the eugenol could play a major role as potent free‐radical terminators, in the results of improved antioxidant activity in eugenol‐grafted chitosan hydrogel in comparison with chitosan alone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3500–3506, 2006     

Development of modified stokes expression to model the behavior of expanded beds containing polydisperse resins for protein adsorption

Expanded bed behavior was modeled by using the Richardson-Zaki correlation between the superficial velocity of the feed stream and the void fraction of the bed. A polydisperse material, Chelating excellose® (70-210 Μm in diameter, 1.21 g/cm³ in density), which has Ni²⁺ ions for the selective binding of histidine-tagged proteins, was used as the resin. A method to modify the Stokes expression to express the terminal settling velocity of the resins by introducing two empirical parameters, the effective diameter of the resins and an exponent for(ρ _p -ρ)/Μ term, was developed. Combined use of the Richardson-Zaki correlation and the modified Stokes expression was successful in modeling the bed expansion by incorporating physical properties of feed streams and the resins.     

Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization

Summary: Syndiotactic polystyrene (sPS)/organophilic clay nanocomposites were obtained by in situ coordination‐insertion polymerization of styrene. Two cationic surfactants (alkylammonium and alkylphosphonium) were used for the intercalation of montmorillonite (MMT). For each organically modified clay, three protocols were performed using an MAO‐activated hemi‐metallocene catalyst, in order to compare the influence of experimental conditions on the composite microstructure and on its thermal stability. The microstructures of nanocomposites were investigated by wide angle X‐ray scattering and DSC. Partially exfoliated or intercalated materials were obtained in all cases and a decrease of crystallinity is observed. Thermal properties were also studied by DSC and thermogravimetric analysis. The presence of clay does not have a strong influence on the sPS thermal transitions but the thermal decomposition process of the material was slowed down in the presence of few organoclay percents, particularly in the degradation beginning. The influence of these two organically modified clays on the thermal stability of the material is discussed.

Gel and suspension formed from the combination of cloisite with toluene (left) and styrene (right), respectively.     

Preparation of pH‐sensitive poly(vinyl alcohol‐g‐methacrylic acid) and poly(vinyl alcohol‐g‐acrylic acid) hydrogels by gamma ray irradiation and their insulin release behavior

A series of pH‐responsive hydrogels were studied as potential drug carriers for the protection of insulin from the acidic environment of the stomach before releasing in the small intestine. Hydrogels based on poly(vinyl alcohol) networks grafted with acrylic acid or methacrylic acid were prepared by a two‐step process. Poly(vinyl alcohol) hydrogels were prepared by gamma ray irradiation (50 kGy) and then followed by grafting either acrylic acid or methacrylic acid onto these poly(vinyl alcohol) hydrogels with subsequent irradiation (5–20 kGy). These graft hydrogels showed pH‐sensitive swelling behavior and were used as carriers for the controlled release of insulin. The in vitro release of insulin was observed for the insulin‐loaded hydrogels in a simulated intestinal fluid (pH 6.8) but not in a simulated gastric fluid (pH 1.2). The release behavior of insulin in vivo in a rat model confirmed the effectiveness of the oral delivery of insulin to control the level of glucose. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 636–643, 2004     

Solid extraction of caffeine and theophylline from green tea by molecular imprinted polymers

This paper involves a feasibility study on using molecular imprinted polymers as the sorbent materials in solid phase extraction for caffeine and theophylline from green tea. Two kinds of MIPs, with caffeine-theophylline mixture and pentoxifylline-theophylline mixture as the templates respectively, MAA as the monomer, EDMA as the crosslinker and ATBN as the initiator, were applied to this purpose. Mixture solution of caffeine and theophylline (1 Μg/ ml in acetonitrile) was applied to the solid extraction cartridges following a load, wash and elute procedure with acetonitrile, methanol, methanol-acetic acid (90/10, v/v) as the solvents, respectively. This solid phase extraction protocol was applied for extraction of caffeine and theophylline from green tea. Comparison between the results obtained with the MIPs cartridges and a traditional C₁₈ reversed-phase cartridge was made. It showed that the MIP-based sorbent on the solid phase extraction was comparable with that of C₁₈ material. HPLC analysis using a C₁₈ column (5 Μm, 250× 4.6 mm from Rstech corporation), methanol: water (60 :40, v/v) as the mobile phase at a flow rate of 0.6 ml/min was applied for the quantitative determination.     

改进β-紫罗兰酮的合成方法

以氢氧化锂/助催化剂为催化剂体系,柠檬醛为原料合成β-紫罗兰酮。此催化剂体系有良好选择性,用量少、成本低、对环境污染小。同时对反应溶剂、温度、反应时间等因素进行优化,使其适用于工业生产,最终摩尔收率可达86%以上。