Structure and properties of polypropylene crystallized from the glassy state

Glassy isotactic propylene (PP) films of thickness up to 0.3 mm were obtained by an ultraquenching technique. The structure and properties of the as-quenched and subsequently crystallized samples were characterized by various techniques. Electron microscopy indicates the glass has no structure larger than 25 Å. X-ray diffraction shows PP crystallizes from the glass into a smectic structure at ca. ?20°C and then transforms to monoclinic microcrystals at ca. 40°C; a nodular structure (80 to 100 Å in diameter) was observed on the surface. The transformation temperature increases with the film thickness. Annealing above the α-relaxation temperature results in an increase in the nodule size. A correspondence was found between the diameter of the nodules observed on the surface and long spacings obtained by small-angle X-ray scattering from the bulk. Dynamic mechanical spectra show the presence of two relaxation-like peaks at ca. ?10°C and 10°C for the as-ultraquenched samples. X-ray scattering, differential scanning calorimetry (DSC), and torsion pendulum measurements show PP crystallizes from the glass at a temperature, depending on the rate of heating, that corresponds to the lower relaxation peak temperature.     

Cyclooxygenase inhibitors derived from thalidomide

Several N-3,5-dimethylphenylphthalimide analogs possessing more potent cyclooxygenase-inhibiting activity than that of aspirin were prepared during structural development studies based on thalidomide. Substituent effects on the activity were investigated.     

Experimental Study on Light Scattering of High Concentration Suspension

To understand the optical properties of living tissue in the NIR range, it appeared informative to investigate the scattering properties of high concentration particle suspension. We measured the angular light scattering of aqueous suspension of 3.5 μmφ polystyrene particles contained in a 60 μm thick cuvette up to 50% volume concentration at 805 nm wavelength using a goniophotometer. We found that the discrepancy between the measurement and the Monte Carlo simulation becomes larger with increased concentration, which is attributable to the phase function change as well as the scattering coefficient change.     

Anisotropy of dielectric relaxation in crystal form II of poly(vinylidene fluoride)

The anisotropy of the crystalline relaxation (α relaxation) in oriented poly(vinylidene fluoride) in crystal form II has been studied. The dielectric increment Δε is analyzed on the basis of the two-site model. A linear relation between Δε/χξ and cos²θ is obtained, where χ is the degree of crystallinity, ξ is the ratio of the internal field to the applied field, and θ is the angle between the applied electric field and the molecular axis. The dipole moment changes direction only along the molecular axis in the relaxation in crystal form II; the molecular motion cannot be explained by chain rotation around the molecular axis. Possible models for the α relaxation are proposed: change in conformation with internal rotation can occur in the crystalline chains, and defects in the crystalline regions play an important role in the α relaxation.     

Inclusion Behavior of 4-Nonylphenol into Cyclodextrin Derivatives

The solubilities of 4-nonylphenol in five kinds of hydroxypropyl-cyclodextrin (HP-CDs) solutions were investigated in order to evaluate them for soil remediation. The relative aqueous-phase concentration of 4-nonylphenol linearly increased with the increasing HP-CD concentration. The addition of HP-beta-CD (degree of substitution, D.S.=0.6) produced the largest change because the inner core of HP-beta-CD is the most hydrophobic. The solubility of 4-nonylphenol in the HP-CD solutions depended upon the cavity diameter and the degree of HP-CD substitution. Both ozone and activated carbon treatments have been using for removing organic compounds and foul odor compounds from tap water. As the inclusion complexes moved into the groundwater, the ozone degradation of the inclusion complexes was estimated. The 4-nonylphenol-HP-CD inclusion complexes were easily degraded by ozone. The degree of degradation increased with the increasing ozonization time. Weakly acidic compounds were produced from the 4-nonylphenol-HP-CD inclusion complexes by ozonization. HP-CDs could be used for the removal of 4-nonylphenol from soil. Copyright 2001 Academic Press.     

Mono Halogen Substituted Calix[4]pyrroles: Fine-tuning the Anion Binding Properties of Calix[4]pyrrole

Abstract

Single halogen atom (i. e. I, Br, Cl and F) substituted calix[4]pyrroles, compounds 2, 3, 4 and 5, were synthesized. Studies of these systems reveal that replacement of a single β-pyrrolic hydrogen atom can increase the anion binding ability of calix[4]pyrroles for a variety of anions (e. g. Cl^?, Br^?, H₂PO₄ ^? and HSO^? ₄) relative to normal non-halogen substituted calix[4]pyrrole 1. In the case of chloride anion, the expected relative affinity sequence of 5 > 4 > 3 > 2 was observed. This was not found to be true for Br^?, H²PO^? ₄, and HSO^? ₄. Here, the chlorine substituted calix[4]pyrrole 4 was found to display a slightly higher affinity in the case of each anion than the fluorine-bearing derivative 5. This was rationalized in terms of intermolecular NH … F hydrogen bonding interactions being present in CD₂Cl₂ solutions of 5. Support for this latter conclusion came from concentration and temperature-dependent NMR spectroscopic studies.

A matched set of mono halogen substituted calix[4]pyrroles was used to study in detail, the extent to which halogen substituents may be used to fine-tune the anion binding properties of calix[4]pyrroles.     

Extra meridional reflections of drawn polyoxymethylene

Extra meridional reflections (00l: l = 3, 5, 13, 15, 21) were observed in drawn polyoxymethylene (POM). The 003, 0015, and 0021 x-ray diffraction intensities increase on annealing, while the 005 and 0013 intensities decrease. It is concluded that crystalline regions are of two kinds: in the first, which generates the 003, 0015, and 0021 reflections, the molecular conformation is slightly distorted from the uniform helix by intermolecular steric hindrance between the CH₂ groups; and in the second, which generates 005 and 0013 reflections, the molecular conformation is distorted in another way. The second form is converted into the first by annealing. The displacements in the c direction of the CH₂ groups and the oxygen atoms from the uniform helix in the first form are about 1.0% and 0.75% of the interval between a CH₂ group and an oxygen atom along helix axis of the POM crystal; thus the correct conformation in the stable state is known. The nature of distortion in the second region is not clarified but several characteristics are offered.