Towards an Environmentally Acceptable Heterogeneous Catalytic Method of Producing Adipic Acid by the Oxidation of Hydrocarbons in Air

A survey is given of the catalytic methods potentially available for the production of adipic acid by the oxidation of readily available hydrocarbon precursors under environmentally benign conditions. Encouraging results are reported using H₂O₂ as oxidant and microporous FeAlPO-5 as catalyst at moderate temperatures.     

Mechanical and thermal properties of ceramic‐modified poly(amide imide)

Poly(amide imide)–epoxysilane (coupling agent) composites were reacted with silica, a condensation product of tetraethylorthosilicate (TEOS), by a sol–gel process and were then cast into films. After this procedure, the chemical characteristics and mechanical and thermal properties were measured. Fourier transform infrared showed that silica existed in the poly(amide imide) matrix. When a proper amount of silica was added to the poly(amide imide) matrix, the tensile strength, elongation, and toughness increased greatly. A poly(amide imide)/30 wt % epoxysilane composite with 20 wt % TEOS had the best mechanical properties. Thermogravimetric analysis under nitrogen and oxygen atmospheres indicated that the char contents increased with the amount of silica. The glass‐transition temperatures of the poly(amide imide)–silica nanocomposites were observed around 170–180°C with differential scanning calorimetry. This approach may be a new method for the low‐temperature thermal curing of poly(amide imide). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1780–1788, 2004     

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.     

Rearrangement of the main chain of the organocobalt polymers

The polymers 3 having pyridine moieties in the main chain were synthesized by the reaction of the organocobalt polymers 1 having cobaltacyclopentadiene moieties in the main chain with various nitriles 2. When brown colored 1 and excess 2 were heated in tetrahydrofuran at 80 °C for 24 h and then at 150 °C for 12 h in a sealed tube, the polymers 3 were obtained by the precipitation with methanol in good yields. From the spectroscopic measurements, the resulting polymers 3 were found to contain 35 – 90% of the pyridine moieties depending on the structures of 1. Received: 7 July 1997/Revised: 14 August 1997/Accepted: 25 August 1997     

Synthesis and properties of soluble polypyrrole doped with dodecylbenzenesulfonate and combined with polymeric additive poly(ethylene glycol)

Soluble polypyrrole (PPy) samples advanced in electrical conductivity σ were chemically synthesized with dodecylbenzenesulfonate (DBS) sodium salt as a dopant, with poly(ethylene glycol) (PEG) as an additive, and with ammonium persulfate as an oxidant. The PPy–DBS–PEG samples were soluble in organic solvents (N‐methylpyrrolinone and m‐cresol). The greater the molar percentage ratio was of DBS, the greater the solubility was of synthesized PPy composites (PPy–DBS–PEG). The maximum electrical conductivity at room temperature for PPy–DBS–PEG was 1.02 S/cm, which was in fact the true conductivity of 100/10 (mol %) PPy/DBS. The chemical composition and doping level of PPy–DBS–PEG were determined by elemental analysis. The results of Fourier transform infrared spectroscopy were used for the structural characterization of PPy–DBS–PEG. The scanning electron microscopy results showed that the electrical conductivity was related to the morphology of PPy–DBS–PEG. According to thermogravimetric analysis, PPy–DBS–PEG was more thermostable than PPy–DBS. Electron spin resonance measurements showed that the polaron and bipolaron acted as charge carriers of PPy–DBS–PEG. According to the temperature dependence of the electrical conductivity, PPy–DBS–PEG was a semiconductor and followed the three‐dimensional variable‐range hopping model. The improved electrical conductivity apparently resulted from the reduction of the crosslinking and structural defects of the PPy chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1170–1175, 2005     

Spectroscopic analysis of carbon dioxide and nitrogen mixed gas hydrates in silica gel for CO2 separation

In this study solid-state NMR spectroscopy was used to identify structure and guest distribution of the mixed N₂ + CO₂ hydrates. These results show that it is possible to recover CO₂ from flue gas by forming a mixed hydrate that removes CO₂ preferentially from CO₂/N₂ gas mixture. Hydrate phase equilibria for the ternary CO₂–N₂–water system in silica gel pores were measured, which show that the three-phase H–L_w–V equilibrium curves were shifted to higher pressures at a specific temperature when the concentration of CO₂ in the vapor phase decreased. ¹³C cross-polarization (CP) NMR spectra of the mixed hydrates at gas compositions of more than 10 mol% CO₂ with the balance N₂ identified that the crystal structure of mixed hydrates as structure I, and that the CO₂ molecules occupy mainly the abundant 5¹²6² cages. This makes it possible to achieve concentrations of more than 96 mol% CO₂ gas in the product after three cycles of hydrate formation and dissociation.     

Novel electrically conductive and ferromagnetic composites of poly(aniline‐co‐aminonaphthalenesulfonic acid) with iron oxide nanoparticles: Synthesis and characterization

Nanocomposites of iron oxide (Fe₃O₄) with a sulfonated polyaniline, poly(aniline‐co‐aminonaphthalenesulfonic acid) [SPAN(ANSA)], were synthesized through chemical oxidative copolymerization of aniline and 5‐amino‐2‐naphthalenesulfonic acid/1‐amino‐5‐naphthalenesulfonic acid in the presence of Fe₃O₄ nanoparticles. The nanocomposites [Fe₃O₄/SPAN(ANSA)‐NCs] were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, elemental analysis, UV–visible spectroscopy, thermogravimetric analysis (TGA), superconductor quantum interference device (SQUID), and electrical conductivity measurements. The TEM images reveal that nanocrystalline Fe₃O₄ particles were homogeneously incorporated within the polymer matrix with the sizes in the range of 10–15 nm. XRD pattern reveals that pure Fe₃O₄ particles are having spinel structure, and nanocomposites are more crystalline in comparison to pristine polymers. Differential thermogravimetric (DTG) curves obtained through TGA informs that polymer chains in the composites have better thermal stability than that of the pristine copolymers. FTIR spectra provide information on the structure of the composites. The conductivity of the nanocomposites (～ 0.5 S cm^?1) is higher than that of pristine PANI (～ 10^?3 S cm^?1). The charge transport behavior of the composites is explained through temperature difference of conductivity. The temperature dependence of conductivity fits with the quasi‐1D variable range hopping (quasi‐1D VRH) model. SQUID analysis reveals that the composites show ferromagnetic behavior at room temperature. The maximum saturation magnetization of the composite is 9.7 emu g^?1. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A resilience optimization approach for workforce-inventory control dynamics under uncertainty

The presence of uncertainties in manufacturing systems and supply chains can cause undesirable behavior. Failure to account for these in the design phase can further impair the capability of systems to respond to changes effectively. In this work, we consider a dynamic workforce-inventory control problem wherein inventory planning, production releases, and workforce hiring decisions need to be made. The objective is to develop planning rules to achieve important requirements related to dynamic transient behavior when system parameters are imprecisely known. To this end, we propose a resilience optimization model for the problem and develop a novel local search procedure that combines the strengths of recent developments in robust optimization technology and small signal stability analysis of dynamic systems. A numerical case study of the problem demonstrates significant improvements of the proposed solution in controlling fluctuations and high variability found in the system’s inventory, work-in-process, and workforce levels. Overall, the proposed model is shown to be computationally efficient and effective in hedging against model uncertainties.     

New fatty acid derivatives from <Emphasis Type="Italic">Homaxinella</Emphasis> sp., a marine sponge

Fractionation of the MeOH extract of Homaxinella sp., a marine sponge, led to the isolation of a sodium salt of a new brominated FA (1), two new MG (2 and 4), and a new lysoPC (6). The geometry of the double bonds in 1 and 2 was defined by comparison of the NMR chemical shifts of the allylic carbons, nuclear Overhauser effect spectroscopy correlations of the allylic protons, and coupling constants of the vinylic protons with those reported. Evidence mainly from NMR and MS analyses established the planar structures of the compounds. Compounds 1, 2, 4, and 6 were evaluated for cytotoxicity against a panel of five human solid tumor cell lines. Only compound 1 showed moderate activity.     

Synthesis and properties of cationic resins derived from aniline/benzylamine-modified epoxy resins and diethylamines

Aniline/benzylamine-modified epoxy resins with different molecular weights, which contain tertiary amines in the middle of the polymer chain, were synthesized by the reaction of aniline/benzylamine with epoxy resin at various molar ratios. The resulting aniline/benzylamine-modified epoxy resins were reacted with diethylamine and subsequently reacted with 2-ethylhexanol-blocked toluene diisocyanate to obtain thermally crosslinkable resins which contain tertiary amines at the end and in the middle of the polymer chain. These resins were partially neutralixed with acetic acid to give thermally crosslinkable cationic resins. The resulting cationic resins were dissolved in suitable solvents and mixed with deionized water to form various emulsions. The emulsion and electrodeposition properties of these resins were studied in some detail to compare the properties of these cationic resins. The results show that the deposition yields and throwing power of the emulsions prepared from benzylaminemodified epoxy resins are higher than those of the emulsions prepared from anilinemodified epoxy resins. The emulsion having proper pH values can give a high throwing power. High throwing power is the characteristic property of these modified cationic resins. Factors determining the throwing power and deposition yield of the emulsions were also investigated.