Kinetic study on the first stage during thermal degradation of polystyrene

The kinetic parameters of the first stage of polystyrene degradation have been investigated to elucidate the reaction mechanisms using the flow reactor system. The decrease in molecular weight of polystyrene was recorded at minute intervals over the temperature range 310°–390°C. Generally, the first and second stages were observed by thermogravimetric analysis (t.g.a.), however in the early stage of the degradation volatile yields of at least 5% occurred. Therefore, using t.g.a. analysis it is difficult to detect this earlier stage. It became evident that the first stage in the earlier part of the reaction could be detected by g.p.c. analysis. We have observed the hidden kinetic parameters of the nature of the first stage of the polystyrene degradation. The results indicate that the main chains were degraded randomly with the small quantitative volatile groups in the first stage and the rates of decrease in molecular weight in the first stage against reaction temperatures were evaluated as log k_s = 12.0 ? 41300/RT.     

Development of AAS resin by the emulsion–suspension polymerization method

In order to improve the weatherability of acryonitrile—styrene—butadiene rubber graft polymer (ABS resin), an attempt was made to develop a resin (AAS resin) in which acrylic rubber of good weatherability was used instead of butadiene rubber. First, by copolymerizing dicyclopentenyl-methacrylate (DCP-MA,3%) with butyl acrylate, crosslinked acrylic rubber was obtained. This also introduced grafting sites into the rubber. Next, methods of graft copolymerizing styrene and acrylonitrile with this rubber were examined. An emulsion–suspension polymerization method was developed in which the initial stage of the polymerization, emulsion polymerization, changed into suspension polymerization during the process. By this method of polymerization, rubber particles were combined and enlarged, bringing about a graft-type resin with high impact resistance. This polymerization method is industrially useful because particle-shaped resins are obtained without the need of a salting-out process. The AAS resin, obtained in this way, has much improved weatherability over ABS resin and shows strength equal to that of ABS resin. © 1992 John Wiley & Sons, Inc.     

Lysozyme requires fluctuation of the active site for the manifestation of activity

Mutations around His15 which lie far away from the active site,stimulated glycol chitin activity of lysozyme at physiologicaltemperature. Del-Argl4Hisl5 lysozyme, a mutant lysozyme whoseArgl4 and Hisl5 were deleted together, and has the highest activityamong these mutant lysozymes, had a similar binding abilityto a trimer of N-acetyl-glucosamine, a substrate analogue, relativeto native lysozyme. This suggests that the increased activitywas due to an increased k_cat in the catalysis reaction. TheH-D exchange rate of the N-1 proton in the Trp63 which is locatedin the active site cleft, was enhanced in the Del-Argl4Hisl5lysozyme, while 2-D proton NMR analysis revealed no conformationalchange around Trp63. We conclude that some sort of fluctuationat the active site might be required for the manifestation ofactivity. This theory is supported by the finding that the Del-Argl4Hisl5lysozyme showed a shift in temperature dependency of activityto lower temperatures compared with that of native lysozyme.     

Living cationic polymerization of vinyl monomers by organoaluminum halides

Summary Well-defined living polymers of isobutyl vinyl ether were obtained in the polymerization initiated with ethylaluminum dichloride (EtAlCl₂) in conjunction with a stoichiometric excess of dioxane (5–10 vol%) in n-hexane at 0°C. Under these conditions, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, while the molecular weight distribution stayed narrow (M_w/M_n = 1.1–1.25). In sharp contrast, the EtAlCl₂-initiated polymerization in the absence of dioxane led to non-living polymers with a broad molecular weight distribution. It was concluded that the propagating carbocation is stabilized not by the counteranion but by an externally added basic compound (dioxane) that strongly interacts with the active end.     

pH-controlled uphill transport of ammonium ions through polymer membranes with sulfonic acid groups

Uphill transport of ammonium ions through a membrane with sulfonic acid groups were investigated with pH-controllers which keep the solution at a constant pH. A membrane with sulfonic acid groups was prepared by casting an aqueous solution containing poly(styrenesulfonic acid) and poly(vinyl alcohol) on a glass plate. When a membrane with one side alkaline and the other acidic was fixed as a diaphragm in a cell, ammonium ions were transported from the alkaline side to the acidic side through the membrane against the concentration gradient of the adjacent solutions. Uphill transport of ammonium ions with pH-controllers was more efficient than without, thus keeping the pH difference between both sides of the membrane constant, which is a driving force for the uphill transport. Furthermore, the effect of pH of the acidic side on the uphill transport was investigated and the mechanism of the pH-controlled uphill transport is discussed.     

Studies on syntheses and permeabilities of special polymer membranes

Summary The permeabilities of various cellulose ester membranes and cellulose membranes were investigated using pure water and aqueous solution of glycerol as feed. In all membranes, the permeation rate for aqueous solution of glycerol was greater than for pure water. The permeation rates of cellulose ester membranes increased with an increase in number of carbon atoms of the substituent group in cellulose ester.     

Hydrothermal Formation of Hydroxyapatite Layers on the Surface of Type-A Zeolite

Type-A zeolite evenly covered with hydroxyapatite thin layers was prepared using hydrothermal treatment at 120°C for 8 h under autogenous pressure. The hydroxyapatite needlelike nanocrystals, 100–200 nm in diameter and 30 nm in thickness, were grown under the reaction between discharged Ca²⁺ ions from type-A zeolite and PO₄³⁻ ions in (NH₄)₃PO₄ solution. The preferential orientations of the c -axis of hydroxyapatite crystals perpendicular to a zeolite surface were observed using transmission electron microscopy. The crystal structure of type-A zeolite was not destroyed under the reaction, but the surface morphology was changed only with complete covering of scaly hydroxyapatite particles.     

Effective renaturation of reduced lysozyme by gentle removal of urea

To increase the folding yield of concentrated reduced lysozyme,we developed a renaturation method by means of dialysis fromconcentrated urea with redox agents. After lysozyme was incubatedin the reducing buffer (8 M urea solution) with oxidized glutathione,renaturation of reduced lysozyme was started by dialysis againstthe dialyzing buffer containing 8 M urea with redox agents.The urea concentration of the dialyzing bottle was graduallydiluted with dialyzing buffer without urea at a flow rate of0.1 ml/min by high pressure pump. Using this systematic dialysis,a concentration as high as 5 mg/ml of reduced lysozyme couldbe renaturated in 80% yield, while the folding yield was <5%even at a concentration of 1 mg/ml using a conventional rapiddilution method [Goldberg et al. (1991) Biochemistry, 30, 2790–2797].Therefore, it was concluded that gentle removal of urea fromdenatured proteins, dissolved in concentrated urea solution,by means of dialysis should be useful to renature denaturedproteins effectively.     

Self-assembled monolayers of p-toluene and p-hydroxymethylbenzene moieties adsorbed on iron by the formation of covalent bonds between carbon and iron atoms for protection of iron from corrosion

An iron electrode was modified by electrolytic reduction in deaerated acetonitrile solution of p-toluenediazonium tetrafluoroborate CH₃C₆H₄N₂BF₄ (TDFB) or p-hydroxymethylbenzenediazonium tetrafluoroborate HOCH₂C₆H₄N₂BF₄ (HOTDFB) below 10 °C to form a self-assembled monolayer (SAM) of toluene CH₃C₆H₄- or hydroxymethylbenzene HOCH₂C₆H₄- (HOMB) moiety, probably adsorbed on the electrode by the formation of a covalent bond between carbon and iron atoms, as shown in references. The protective ability of the layer was examined by polarization measurement of the electrode in an aerated 0.5 M NaCl solution. The protective efficiencies of these two SAMs were not high, around 30%, a little higher than that of the toluenethiol CH₃C₆H₄SH SAM which was anchored on iron via a coordinate bond between sulfur and iron atoms. The iron surfaces modified with TDFB and HOTDFB were characterized by contact angle measurement, FTIR reflection spectroscopy and X-ray photoelectron spectroscopy. The persistence in protection of iron against corrosion by coverage with the HOMB SAM was confirmed by polarization measurements after immersion in 0.5 M NaCl for a long period of the time.