Evaluation for the curing characteristics of phenolic molding compounds by rockwell hardness test at an elevated temperature

Rockwell hardness measurement at an elevated temperature has been proposed as an evaluation method for the curing characteristics of thermosetting molding compounds. This method is convenient and has a high accuracy over a wide range of curing, Using a cone indenter, the following advantages are brought about: a good correspondence with acetone extraction test, in showing the degree of cure of the internal part of a molding rather than that of the skin layer, and a higher sensitivity in measuring higher degrees of cure. On examining curing behavior of commercial phenolic molding compounds by this method, an inflection point was observed on a plot of the hardness vs log curing time. This critical point has been called “the minimum cure time”, beyond which the molding exhibits good physical properties.     

Iodine reaction of vinyl acetate/vinyl propionate copolymers. III. Iodine affinities of the radically polymerized copolymers and the copolymers derived from partially saponified polyvinyl acetate

The minimum sequence lengths (n_c) of vinyl acetate (VAc) units necessary to form a colored iodine complex were determined to be 4 and 17 for radically polymerized VAc/vinyl propionate (VPr) and VAc/isopropenyl acetate (IPAc) copolymers, respectively. The iodine affinities (I/VAc) of VAc/VPr copolymers (SP-series) obtained by propionylation of partially saponified polyvinyl acetate (PVAc) were remarkably affected by the saponification conditions. An increase of the water content in acetone/water mixture as saponification solvent brought about a decrease of the iodine affinities of the SP-series. The dependence of the iodine affinity on the saponification of monomer units in the SP-series was compared with that in the radically polymerized VAc/VPr copolymers by taking the sequence probability as the measure of monomer unit distribution. The results strongly supported an occurence of the slide fastener reaction at high degrees of saponification, which was well-known in the saponification of PVAc. Furthermore, it was found that the saponification mode of PVAc at low degrees of saponification was influenced uniquely by the water content in saponification solvents and the saponification temperature.     

High oleic acid oil suppresses lung tumorigenesis in mice through the modulation of extracellular signal-regulated kinase cascade

This study was undertaken to estimate the effect of dietary high oleic acid oil (OA) on 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK)-induced lung tumorigenesis in mice. Diet containing 10% oil was fed to mice through experimental periods. On day 30 after NNK injection (100 mg/kg body weight, i.p.), the treatment increased the level of prostaglandin E₂ (PGE₂) as well as proliferating cell nuclear antigen, a marker of cell proliferation in a high linoleic acid oil (LA)-fed group but not in an OA-fed group. The NNK treatment also induced the activation of an extracellular signal-regulated kinase (Erk) cascade (Erk, Mek and Raf-1) in an LA-fed group. On the other hand, OA feeding abolished the NNK-induced activation of the Erk cascade. In conjugation with these events, OA feeding reduced lung tumor incidence and tumor multiplicity (percentage of mice with tumors) in mice compared with LA feeding at the 20th experimental week. These results suggest that OA suppresses lung tumorigenesis and that this suppression is correlated with the inhibition of PGE₂ production and inactivation of the Erk cascade.     

Syntheses and conformational studies of poly(S-menthyloxycarbonylmethyl l- and d-cysteines)

S-menthyloxycarbonylmethyl l- and d-cysteines were prepared by the reaction of l- or d-cysteine and (?)-menthyl chloroacetate in liquid ammonia and were then polymerized to poly(S-menthyloxycarbonylmethyll- and d-cysteines) by the N-carboxyanhydride (NCA) method. From the results obtained by means of infra-red spectra, X-ray diffractions, optical rotatory dispersions (o.r.d.), and circular dichroisms (c.d.), $\text{poly}\text{(S-}\text{menthyloxycarbonylmethyl-}\text{l}\text{-cysteine}\text{)}$ was found to be a right-handed α-helix in the solid state and in ethyl ether/chloroform and chloroform solutions. Similarly, $\text{poly}\text{(S-}\text{menthyloxycarbonylmethyl-}\text{d}\text{-cysteine}\text{)}$ was a left-handed α-helix. The helix-coil transition of these polymers was observed in the vicinity of 3–4% trifluoroacetic acid (TFA) in chloroform/TFA mixtures.     

Effect of reaction kinetics of polymer electrolyte on the ion‐conductive behavior for poly(oligo oxyethylene methacrylate)–LiTFSI mixtures

The effect of the reaction kinetics on the ionic conductivity for a comblike‐type polyether (MEO) electrolyte with lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) was characterized by DSC, complex impedance measurements, and ¹H pulse NMR spectroscopy. The ionic conductivity of these electrolytes was affected by the reaction condition of the methacrylate monomer and revealed by the glass transition temperature (T_g), spin–spin relaxation time (T₂), steric effects of the terminal groups, and the number of charge carriers indicated by the VTF kinetic parameter. In this system, the electrolytes prepared by the reaction heating rate of 10°C/min of MEO–H and 15°C/min of MEO–CH₃ showed maximum ionic conductivity, σ_i, two to three times higher in magnitude than that of the σ_i of the others at room temperature. As experimental results, the reaction kinetic rate affected the degree of conversion, the ionic conductivity, and the relaxation behaviors of polyether electrolytes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2149–2156, 2003     

Environmentally benign precipitation copolymerization of methacrylate ester and styrene to make polymeric microspheres in supercritical carbon dioxide

The polymeric microspheres were synthesized by the precipitation copolymerization of glycidyl methacrylate (GMA) with methacrylic acid(MAA) or 2‐hydoxyethyl methacrylate (2‐HEMA) containing styrene (ST) in SC‐CO₂. Scanning electron microscopy (SEM) showed that the products were spherical microparticles, with the addition of MAA and/or 2‐HEMA as the monomer, with diameter of 0.2–2 μm. The effects of copolymerization pressure, temperature, and ratios of GMA/MAA, ST, and/or GMA/2‐HEMA, on the particle size and morphology were investigated in detail. A new experiment setup is proposed for the large amount of production, based on the rule of lower monomer concentration, more stable system, and better use of the present polymerization apparatus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2425–2431, 2007     

High-strength–high-modulus polyimide fibers II. Spinning and properties of fibers

The polyimides based on 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) described in Part I of this series were dissolved in p-chlorophenol and spun into fibers using a coagulating bath of ethanol. The fibers as spun had in general low tenacities and low moduli, but a heat treatment at 300–500°C under tension produced a remarkable increase in strength and modulus, and fibers with a tensile strength of 26 g/den (3.1 GPa) and an initial modulus higher than 1,000 g/den (120 GPa) could be obtained. Thus, the annealed fibers of polyimides are comparable to aramid fibers in mechanical properties. To heating in air and in the saturated steam, the polyimide fibers showed higher resistance than the aramid fibers. The polyimide fibers surpassed the aramid fibers in resistance to acid treatment and ultraviolet (UV) irradiation, but were inferior in resistance to alkali treatment. The annealed fibers of polyimides displayed distinct X-ray diffraction patterns. The chain repeat distance of 20.5 Å determined on the fibers of polyimide prepared from BPDA and o-tolidine, and 20.6 Å determined on the fibers of polyimide derived from BPDA and 3,4′-diaminodiphenyl ether are reasonable when the dimensions of monomeric units and the shapes of the molecular chains are considered. The X-ray reflections of both polyimide fibers were indexed satisfactorily on the basis of postulated unit cells.     

Toughening of cycloaliphatic epoxy resins by poly(ethylene phthalate) and related copolyesters

Poly(ethylene phthalate) (PEP) and poly(ethylene phthalate–co‐ethylene terephthalate) were used to improve the brittleness of the cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl 3,4‐epoxycyclohexane carboxylate (Celoxide 2021?), cured with methyl hexahydrophthalic anhydride. The aromatic polyesters used were soluble in the epoxy resin without solvents and effective as modifiers for toughening the cured epoxy resin. For example, the inclusion of 20 wt % PEP (MW, 7400) led to a 130% increase in the fracture toughness (K_IC) of the cured resin with no loss of mechanical and thermal properties. The toughening mechanism is discussed in terms of the morphological and dynamic viscoelastic behaviors of the modified epoxy resin system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 388–399, 2002; DOI 10.1002/app.10363     

Synthesis and photo-induced solution properties of new rigid-rod polyimides

A series of new, substituted pyromellitic dianhydrides were synthesized from 1,2,4,5-tetramethylbenzene. New soluble rigid-rod polyimides were obtained from the dianhydrides and 2,2′-bis(trifluoromethyl)-4,4′-biphenyl (PFMB) in phenolic solvents in the presence of isoquinoline as a catalyst. The polyimides are soluble in N-methyl-2-pyrrolidone (NMP), N,N-dimethylacetamide (DMAc), m-cresol and other solvents, in spite of having no bending in their rigid structures.

UV irradiation changed color of the polyimide solutions and also their viscosity. We observed new absorbance in the 700-nm region and an ESR signal by UV irradiation. The new visible absorbance and the ESR signal are derived from the same origin. They are attributed to the anion radical of the diimide moiety in the polyimide as deduced from the hyper fine structure of the ESR signal. In addition, UV irradiation diminishes the solution viscosity.