Preparation and properties of polyimide/silica hybrid composites based on polymer‐modified colloidal silica

A new type of polyimide/silica (PI/SiO₂) hybrid composite films was prepared by blending polymer‐modified colloidal silica with the semiflexible polyimide. Polyimide was solution‐imidized at higher temperature than the glass transition temperature (T_g) using 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA) and 4,4′‐diaminodiphenyl ether (ODA). The morphological observation on the prepared hybrid films by scanning electron microscopy (SEM) pointed to the existence of miscible organic–inorganic phase, which resulted in improved mechanical properties compared with pure PI. The incorporation of the silica structures in the PI matrix also increased both T_g and thermal stability of the resulting films. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2053–2061, 2006     

Rheological characteristics of mesophase pitch

Rheological characteristics of two pretreated petroleum pitches, during their transformation to mesophase, have been studied by using rotalional viscometer. Simultaneously, the formation, growth, coalescence of mesuphase spheres, and the alignment of coalesced mesophase were observed by Hot-Stage-Cinema-Microscope, discussed with the results of viscosity change and the Q.I. content. It is found that both pretreated pitches were Newtonian fluids at low temperature, but behaved pseudoplastics as increase of mesophase content above 390C. Shear thinning behaviour was also apparent in the shear rate range of 1.9–20 sec⁻¹ at temperature above 390C. The apparent viscosity-temperature curves of this pyrolysed pitches were much affected by the pretreatment conditions.     

Blends of chlorinated isotactic polypropylene with poly(ethylene-co-vinyl acetate) I. Effect of component polymers composition on the blend miscibility

Chlorinated isotactic polypropylenes (CPP) having various chlorine contents were blended with poly(ethylene-co-vinyl acetate)s (EVA) having various vinyl acetate (VA) contents. The blends were made by casting films from dilute THF solutions and miscibility of the blends was identified by single glass transition temperature, which was confirmed by DSC and dynamic mechanical measurements. Based on the miscibility data from a large number of CPP/EVA combinations, a miscibility map was depicted where CO equivalent weight (CO-EQW) of EVA was plotted against chlorine equivalent weight (Cl-EQW) of CPP. Though an attractive interaction between CPP and EVA could be detected in all the miscible and immiscible blend pairs, miscibility of the CPP/EVA blends could solely be observed in a relatively narrow range of Cl-EQW ca. 65–100 and CO-EQW ca. 170–230.     

Rheological properties of hyperbranched polymer/poly(ethylene terephthalate) reactive blends

The rheological properties in solution, in shear and in uniaxial elongation of poly(ethylene terephthalate) (PET) reacted together with hyperbranched polymers (HBPs) were investigated. Two different PET grades, of low and high molecular weights, were compounded with sub‐ to over‐stoichiometric concentrations of HBPs of second and fourth pseudo‐generation, and subsequently subjected to a solid‐state polycondensation (SSP). The formation of microgels, which occurs at high HBP concentration, gave rise to a large increase in melt elasticity and a related decrease in melt strength. At low HBP concentrations, the complex viscosity of the unreacted HBP/PET was considerably reduced, thus demonstrating a lubrication effect of the HBP molecules. During SSP, the intrinsic and shear viscosities exhibited a gradual increase, which was similar for both PET and HBP/PET blends, and was correlated to an increase in molecular weight, through linear‐chain extension and branching reactions. The elongational viscosity of the reactive blends was also increased as a function of reaction time, and this increase was much larger in the case of the HBP/PET blends. A 400% increase in melt strength of the PET was obtained by combining SSP and trace amounts of an HBP of second generation, without any decrease in drawability.     

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     

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.     

Mobile phase composition for resolving whey proteins in reversed-phase high performance liquid chromatography

Reversed-phase high-performance liquid chromatography was successfully developed for the simultaneous and rapid separation for the main whey proteins, α-Lactalbumin and β-Lactoglobulin. This method consisted of a linear gradient of the two mobile phases of 0.1% trifluoroacetic acid in water and 0.1% trifluoroacetic acid in acetonitrile. The total run time for this separation was approximately 30 min, and α-Lactalbumin was eluted followed byβ- Lactoglobulin. The injection volume was fixed at 20 μl and the flow rate was 1 ml 1/min. The optimum mobile phase composition and gradient conditions to separate α-Lactalbumin and β-Lactoglobulin (A+B) were experimentally obtained at the 15 μm particle with a pore size of 300 Å on the linear-gradient mode.     

Fabrication of SiO2-ZrO2 composite fiber mats via electrospinning

(1 − x)SiO₂-(x)ZrO₂ (x = 0.1, 0.2) composite fiber mats were prepared by electrospinning their sol-gel precursors of zirconium acetate and tetraethyl orthosilicate (TEOS) without using a polymer binder. The electrospun composite fibers were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and mercury porosimetry. The composite fibers having a tetragonal crystalline ZrO₂ were obtained by calcining the electrospun composite fibers at high temperatures. The results show that the structure and crystallization of ZrO₂ in the composite fibers can be controlled by sintering temperature, while the porosity and morphology of the fiber mats did not depend on the sintering temperature.     

Synthesis and properties of acrylonitrile-CR-methyl methacrylate graft copolymer

Graft copolymerization of acrylonitrile (AN) and methyl methacrylate (MMA) onto polychloroprene (CR) was carried out using benzoyl peroxide as initiator. The effects of mole ratio of AN to MMA, reaction temperature, reaction time, solvent, and initiator concentration on the graft copolymerization were examined. It was found that the thermal stability and weatherability of the AN—CR—MMA graft copolymer (ACM) were considerably better than those of CR.     

A porous mixed-valent iron MOF exhibiting the acs net: Synthesis, characterization and sorption behavior of Fe3O(F4BDC)3(H2O)3·(DMF)3.5

A new mixed-valent iron MOF, formulated as Fe₃O(F₄BDC)₃(H₂O)₃·(DMF)_3.5 (1), has been synthesized by using a perfluorinated linear dicarboxylate to link trigonal prismatic Fe₃(μ³-O)(O₂C–)₆ clusters. The structure refinement based on single crystal X-ray diffraction data collected from 1 reveals the material exhibits the acs topology with large channels along the crystallographic c-axis. Due to the presence of fluorine atoms the organic link, 2,3,5,6-tetrafluorobenzene-1,4-dicarboxylate (F₄BDC), has a 63° torsion angle between the carboxylate and aromatic planes, resulting in larger channels compared to those in the isoreticular material MOF-235. While few iron-based MOFs have demonstrated porosity, nitrogen and hydrogen sorption experiments carried out at 77 K proved the porosity of outgassed 1, which has a Langmuir surface are of 635 m²/g and a gravimetric capacity of 0.9 wt% of hydrogen at 1 bar.