Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

Improvement of gas meter performance using polymer materials

The measuring elements of both dry‐ and wet‐type gas meters are composed of a diaphragm and rotary drum. In this article an explanation on the principle of measuring and the structure of the gas meter for each of these two types was discussed. Such applications were made as follows: synthetic rubber was used for the measuring diaphragm, engineering plastic was employed instead of metal for the measuring drum, and poly(butylene terephthalate) (PBT) was used for the casing, respectively. As a result, an improvement in the gas resistance performance and productivity, which led to a lighter weight, more compactness and a lower cost of productions was achieved. Also the influence of the solubility of the measured gas to the plastic on the measured valve was discussed. Copyright © 2003 John Wiley & Sons, Ltd.     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Electron beam induced modification of poly(ethylene terephthalate) films

Electron beam processing of poly(ethylene terephthalate) (PET) films is found to promote significant changes in the melting heat, intrinsic viscosity and polymer film-liquid (water, isooctane and toluene) boundary surface tension. These properties are featured with several maximums depending on the absorbed dose and correlating with the modification of PET surface functionality. Studies using adsorption of acid-base indicators and IR-spectroscopy revealed that the increase of PET surface hydrophilicity is determined by the oxidation of methylene and methyne groups. Electron beam treatment of PET films on the surface of N-vinylpyrrolidone aqueous solution provided graft copolymerization with this comonomer at optimum process parameters (energy 700 keV, current 1 mA, absorbed dose 50 kGy).     

Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Amending cultures of selenium-resistant bacteria with dimethyl selenone

A possible biological intermediate in the reduction and methylation of selenium oxyanions, dimethyl selenone, was synthesized, and the first experiments involving the amendment of selenium resistant bacterial cultures with this compound are reported. The amount of volatile, reduced selenium-containing species released from these cultures into the headspace is significantly more than that produced in analogous experiments involving sodium selenate amended cultures. Dimethyl selenone is reduced in the presence of dimethyl sulfide and dimethyl disulfide in a complex growth medium, trypticase soy broth with 0.1% nitrate. This reduction occurs whether or not the reduced sulfur compounds are biologically produced.     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Synthesis of new thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing epoxide pendant groups

A new class of thermosetting poly(2,6‐dimethyl‐1,4‐phenylene oxide)s containing pendant epoxide groups were synthesized and characterized. These new epoxy polymers were prepared through the bromination of poly(2,6‐dimethyl‐1,4‐phenylene oxide) in halogenated aromatic hydrocarbons followed by a Wittig reaction to yield vinyl‐substituted polymer derivatives. The treatment of the vinyl‐substituted polymers with m‐chloroperbenzoic acid led to the formation of epoxidized poly(2,6‐dimethyl‐1,4‐phenylene oxide) with variable pendant ratios, and the structures and properties were studied with nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The ratios of pendant functional groups were tailored for the polymer properties, and the results showed that the glass‐transition temperatures increased as the benzylic protons were replaced by bromo‐, vinyl‐, or epoxide‐functional groups, whereas the thermal stability decreased in comparison with the original polymer. Within a molar fraction of 20–50%, the degree of functionalization had little effect on the glass‐transition temperature; however, it correlated inversely with the thermal stability of each functionalized polymer. The thermal curing behavior of the epoxide‐functionalized polymer was enhanced by the increment of the pendant functionality, which resulted in a significant increase in the glass‐transition temperature as well as the thermal stability after the curing reaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5875–5886, 2006     

Calorimetric study of Diepoxide Chain-Extended Poly(Ethylene Terephthalate)

A series of chain-extended PET samples were obtained by the use of different amounts of a diepoxide as chain extender, which was prepared for this purpose. These samples exhibited different intrinsic viscosities and degrees of branching or cross-linking. The effects of this differentiation on the thermal properties were studied by differential scanning calorimetry. The thermal parameters studied were the glass transition temperature (T_g), the cold-crystallization temperature (T_cc), the melting temperature (T_m), the enthalpy (ΔH_m) and the degree of crystallinity. The data revealed that, the higher the quantity of chain extender or the chain extension time, the higher T_gand T_cc, but the lower T_mand ΔH_m, i.e. the more amorphous the chain-extended samples, as also shown by density measurements. This revised version was published online in July 2006 with corrections to the Cover Date.