New ring-opening polymerization via a π-allylpalladium complex

Summary A binary system of a palladium complex as catalyst and zinc alkoxide as initiator conducted a novel ring-opening polymerization of cyclic carbonate, i. e., 5,5-dimethyl-4-ethenyl-1,3-dioxan-2-one. The polymerization proceeded along with releasing carbon dioxide to produce the corresponding polyether. The -allylpalladium complex generated from the monomer with the catalyst is the key intermediate for this new polymerization. The propagating end is zinc alkoxide, which nucleophilically attacks the monomer activated as the -allylpalladium complex in the propagation.     

Examination of acetolysis products of phosphatidylcholine by gas chromatography-mass spectrometry

A comparison of monoacetyldiglycerides obtained from authentic phosphatidylcholines by acetolysis with those obtained by phospholipase C-acetylation was made to examine the intermolecular acyl migration, the intramolecular acyl migration between C-1 and C-2, and the formation of 1,3-isomer in the acetolysis reaction. Egg yolk phosphatidylcholine also was used. It was revealed that is acetolysis, the intermolecular acyl migration and selective degradation of polyunsaturated fatty acids did not take place at all. The intramolecular acyl migration, including the formation of 1,3-isomer, occurred to a small extent. Appreciable difference was not found in comparison of molecular species compositions of monoacetyldiglycerides derived by both methods from egg yolk phosphatidylcholine, except small differences found in the contents of two kinds of molecular species.     

Properties of aqueous solutions of several salts of α,ω-alkanediol disulfates

Several salts of α,ω-sulfates, MO₃SO(CH₂)_n OSO₃M(n=12, 14, 16, 18, and M=Li, Na, and K) were prepared from the corresponding α,ω-alkane diols. The Krafft points of these α,ω-sulfates with common counterion as estimated by electroconductivity measurements increased with the increase of the hydrocarbon chain length, and the effect of the counterions on the Krafft points of the α,ω-sulfates with the same hydrocarbon chain length was in the order : Li<Na<K. Solutions of the α,ω-sulfates, except disodium dodecanediol disulfate, showed two break points corresponding to the first and second critical micelle concentration in each plot of the electroconductivity as a function of the concentration. The existence of the second break point suggested that another aggregation of rearrangement of the existing aggregates occurs in α,ω-sulfate solutions in addition to the usual micelle formation. The first and second break points of α,ω-sulfates with sodium counterion decreased logarithmically with increasing total number of methylene groups. The relationships were given as follows: log(first break point)=−0.138Nc−0.095; log(second break point)=−0.104Nc−0.251. The effect of the counterions upon the break points of α,ω-sulfates with the same hydrocarbon chain length was in accordance with their positions in the lyotropic series.     

Dynamic moduli for short fiber-CR composites

The dynamic moduli, E′ and E″, and tan δ for nylon–CR and PET–CR composites with unidirectional short fibers were studied as a function of temperature by using a Rheovibron. The temperature dependence of tan δ showed two dispersion peaks for nylon–CR composite. The peak at ?28°C corresponded to the main dispersion of CR and the peak at 100°C to the α-dispersion of nylon 6. For a PET-CR composite, in addition to the individual dispersion of CR and PET, a small and broad peak was observed at about 90°C. The angular dependence of E′ indicated that the short fibers assumed good orientation. The storage modulus for the composites was given by the parallel model as E′ = V_f′E_f + V_mE′_m., where E′_c, E′_f and E′_m were the storage modulus for the composite, fiber, and matrix and V_f and V_m were the volume fraction of fiber and matrix, respectively. In the transverse direction of fiber, the peak values of tan δ at ?28°C were given by the following equation; tan δ_c = tan δ_m ? δV_f, where tan δ_c and tan δ_m are the loss tangent for the composite and matrix, respectively, and α is coefficient depending on fiber type. The results indicated that a region with strong interaction was formed between fibers and CR matrix.     

An ergonomics study of thumb movements on smartphone touch screen

This study investigated the relationships between thumb muscle activity and thumb operating tasks on a smartphone touch screen with one-hand posture. Six muscles in the right thumb and forearm were targeted in this study, namely adductor pollicis, flexor pollicis brevis, abductor pollicis brevis (APB), abductor pollicis longus, first dorsal interosseous (FDI) and extensor digitorum. The performance measures showed that the thumb developed fatigue rapidly when tapping on smaller buttons (diameter: 9 mm compared with 3 mm), and moved more slowly in flexion–extension than in adduction–abduction orientation. Meanwhile, the electromyography and perceived exertion values of FDI significantly increased in small button and flexion–extension tasks, while those of APB were greater in the adduction–abduction task. This study reveals that muscle effort among thumb muscles on a touch screen smartphone varies according to the task, and suggests that the use of small touch buttons should be minimised for better thumb performance.     

Polymerization of epoxide with aluminum complex/silanol catalyst. VII. Thermal and electrical properties of epoxy resin cured with the new catalyst

Curing catalyst for epoxy resins was newly found. The catalyst consists of aluminum complex and silanol. Lack of one component of the pair does not cure epoxy resins. The epoxy resins cured with the catalyst are characterized by excellent electrical properties, especially at high temperature, due to the absence of strong acid species in the cured epoxy resin matrix. Heat-resistant property of the resin was also excellent. These properties were compared with those of epoxy resin cured with commonly used BF₃ complex.     

Electrochemical reduction of nitrate on Pt(S)[n(1 1 1) × (1 1 1)] electrodes in perchloric acid solution

The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO₄ + 10 mM KNO₃. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO₃⁻ species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as H_nt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO₄ in the absence of nitrate.     

Isotactic polypropylene hollow microfibers prepared by CO2 laser‐thinning

An isotactic polypropylene hollow microfiber was continuously produced by using a carbon dioxide (CO₂) laser‐thinning method. To prepare the hollow microfiber continuously, the apparatus used for the thinning of the solid fiber was improved so that the laser can circularly irradiate to the hollow fiber. Original hollow fiber with an outside diameter (OD) of 450 μm and an internal diameter (ID) of 250 μm was spun by using a melt spinning machine with a specially designed spinneret to produce the hollow fiber. An as‐spun hollow fiber was laser‐heated under various conditions, and the OD and the ID decreased with increasing the winding speed. For example, when the hollow microfiber obtained by irradiating the CO₂ laser to the original hollow fiber supplied at 0.30 m min^?1 was wound up at 800 m min^?1, the obtained hollow microfiber had an OD of 6.3 μm and an ID of 2.2 μm. The draw ratio calculated from the supplying and the winding speeds was 2667‐fold. The hollow microfibers obtained under various conditions had the hollowness in the range of 20–30%. The wide‐angle X‐ray diffraction patterns of the hollow microfibers showed the existence of the highly oriented crystallites. Further, the OD and ID decreased, and the hollowness increased by drawing hollow microfiber obtained with the laser‐thinning. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2600–2607, 2006     

Mechanical Properties of Alumina/Silicon Carbide Whisker Composites

The improvement of mechanical properties of Al₂O₃/SiC whisker composites has been studied with emphasis on the effects of the whisker content and of the hot-pressing temperature. Mechanical properties such as fracture toughness and fracture strength increased with increasing whisker content up to 40 wt%. In the case of the high SiC whisker content of 40 wt%, fracture toughness of the sample hot-pressed at 1900° decreased significantly, in spite of densification, compared with one hot-pressed at 1850°. Fracture toughness strongly depended on the microstructure, especially the distribution of SiC whiskers rather than the grain size of the Al₂O₃ matrix.