Synthesis and characterization of titanium and zirconium complexes with silicone-bridged phenoxycyclopentadienyl ligands

Dimethylsilyl(2,3,4,5-tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride (1a), a useful catalyst precursor for olefin copolymerization, was synthesized at high yield starting from allyl-protected phenolic ligand 3a,which was first treated with 2 equiv. of n-BuLi to selectively give the dilithium salt of 3a along with 1-heptene, a coupling product of a protected allyl ether moiety and butyl anion. Addition of TiCl₄ to the resulting dilithium salt of 3a in toluene afforded 1a in 50% isolated yield. This methodology could be applied to the preparation of related titanium and zirconoium complexes 1b-1d, 8 with silicone-bridged Cp-phenoxy ligands, whereas the reaction starting from methyl-protected precursor 2a did not produce the zirconium complex 8. Copolymerization of ethylene and 1-hexene with the newly prepared complexes was also investigated.     

Echo-intensity compensation in echolocating bats (Pipistrellus abramus) during flight measured by a telemetry microphone

An onboard microphone (Telemike) was developed to examine changes in the basic characteristics of echolocation sounds of small frequency-modulated echolocating bats, Pipistrellus abramus. Using a dual high-speed video camera system, spatiotemporal observations of echolocation characteristics were conducted on bats during a landing flight task in the laboratory. The Telemike allowed us to observe emitted pulses and returning echoes to which the flying bats listened during flight, and the acoustic parameters could be precisely measured without traditional problems such as the directional properties of the recording microphone and the emitted pulse, or traveling loss of the sound in the air. Pulse intensity in bats intending to land exhibited a marked decrease by 30 dB within 2 m of the target wall, and the reduction rate was approximately 6.5 dB per halving of distance. The intensity of echoes returning from the target wall indicated a nearly constant intensity (-42.6 +/- 5.5 dB weaker than the pulse emitted in search phase) within a target distance of 2 m. These findings provide direct evidence that bats adjust pulse intensity to compensate for changes in echo intensity to maintain a constant intensity of the echo returned from the approaching target at an optimal range.     

Throughput Measurement of a Multilayer-Coated Schwarzschild Objective Using Synchrotron Radiation

The throughput of a Schwarzschild objective using undulator synchrotron radiation was measured. Conventionally, the throughput was estimated from the squared reflectivity of one multilayer mirror and from the obstruction ratio. However, we evaluated the transmission ratio from the input and output photon flux using a precisely calibrated monochromatic beam from an undulator light source. It was found that the objective has a maximum throughput of 8.5% at a wavelength of 13.9 nm.     

A report on the 29th symposium on heteroatom chemistry of the chemical society of Japan

The 29th domestic Chemical Society of Japan Symposium on Heteroatom Chemistry was held in Hiroshima during the period of December 12–14, 2002, under the management of Tetsuo Otsubo of Hiroshima University. About 250 chemists from various academic institutes and industries enjoyed four plenary lectures, 44 oral presentations, and 53 poster presentations. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:387–398, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10186     

Organic hybrid of chlorinated polyethylene and hindered phenol. II. Influence of the chemical structure of small molecules on viscoelastic properties

The viscoelastic properties and stabilities of those properties of organic hybrids consisting of chlorinated polyethylene (CPE) and tetrakis[methylene‐3‐(3‐5‐di‐tert‐butyl‐4‐hydroxy phenyl)propionyloxy]methane (AO‐60) and triethylene glycol bis[3‐(3‐tert‐butyl‐4‐hydroxy‐5‐methyl phenyl)propionyloxy] (AO‐70) were investigated. The CPE/AO‐70 hybrids show only one transition, whereas for the CPE/AO‐60 hybrids, one novel relaxation appears above the glass‐transition temperature of CPE. This relaxation on the higher temperature side in the mechanical spectrum for CPE/AO‐60 is associated with the appearance of the AO‐60‐rich phase. Furthermore, the stabilities of the viscoelastic properties and microstructures of the organic hybrids consisting of CPE and multifunctional hindered phenols are dominated by the strength of the intermolecular interaction between CPE and phenols and the conformations of the middle skeletal parts of hindered phenols. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1496–1503, 2000     

Study of molecular size in ethylene-propene copolymerization with zirconocene and hafnocene catalysts

Ethylene-propene copolymerization was carried out with Cp₂MCl₂ (Cp = cyclopentadienyl), rac-Et(Ind)₂MCl₂, rac-Me₂Si(Ind)₂MCl₂ (Et = ethylene, Me₂Si = dimethylsilyl, Ind = indenyl, M = Zr or Hf)/methylaluminoxane. In the case of using ansa-hafnocenes, the minimum molecular size (extended chain length) of ethylene-propene copolymer was obtained at about 50 mol-% of propene content in the copolymer. The polymerization activity decreased with increase of propene feed ratio in non-bridged non-specific metallocenes. Higher polymerization activities were observed for the copolymerization compared to ethylene and propene homo-polymerization with ansa-isospecific metallocenes. The factor of molecular size lowering was studied by the chain propagation and chain transfer reaction.     

Numerical analysis of breaking waves using the moving particle semi-implicit method

The numerical method used in this study is the moving particle semi-implicit (MPS) method, which is based on particles and their interactions. The particle number density is implicitly required to be constant to satisfy incompressibility. A semi-implicit algorithm is used for two-dimensional incompressible non-viscous flow analysis. The particles whose particle number densities are below a set point are considered as on the free surface. Grids are not necessary in any calculation steps. It is estimated that most of computation time is used in generation of the list of neighboring particles in a large problem. An algorithm to enhance the computation speed is proposed. The MPS method is applied to numerical simulation of breaking waves on slopes. Two types of breaking waves, plunging and spilling breakers, are observed in the calculation results. The breaker types are classified by using the minimum angular momentum at the wave front. The surf similarity parameter which separates the types agrees well with references. Breaking waves are also calculated with a passively moving float which is modelled by particles. Artificial friction due to the disturbed motion of particles causes errors in the flow velocity distribution which is shown in comparison with the theoretical solution of a cnoidal wave. © 1998 John Wiley & Sons, Ltd.