Syntheses and characterizations of copolymers of dicyanoquinone methides with α-acetoxystyrenes

Summary 7,7-Dicyanoquinone methides (1a-b) copolymerized spontaneously with substituted -acetoxystyrenes (2a-b) in benzene at 60 °C to give alternating copolymers (poly(1a-b-co-2a-b)) with the molecular weights of 8–60×10⁴ in 42–66% yields. When these copolymers were heated under nitrogen, they eliminated acetic acid quantitatively at around 200 °C to be converted to the copolymers (poly(3a-d)) with olefinic bonds, which were characterized by infrared and nuclear magnetic resonance spectroscopy. Alternating copolymers and the corresponding copolymers with olefinic bonds were amorphous, and capable of being cast from their chloroform solutions into transparent, tough films.     

Solution and solid-state polymerizations of substituted p-quinodimethanes and p-quinone methides

This article describes the polymerization behavior of electron-accepting and electron-donating p-quinonoid monomers such as substituted p-quinodimethanes and p-quinone methides in solutions and solid states. In the solution polymerizations, the electron-accepting substituted p-quinodimethanes and p-quinone methides with same substituents such as cyano, ester, and sulfonyl groups at the exocyclic positions are not homopolymerizable, but copolymerizable with donor monomers like styrene in an alternating fashion. Their spontaneous polymerizations with donor monomers have been explained with the bond-forming initiation mechanism. The substituted p-quinodimethanes with ester groups are a first example to show an amphoteric behavior in alternating copolymerizations. Some electron-accepting substituted p-quinodimethanes and p-quinone methides with different substituents such as cyano, ester, acyl, alkylthio, and/or phenyl groups are homopolymerizable, and an anionic polymerization initiated with a butyllithium initiator proceeded in a living manner. Equilibrium polymerization behavior have been found in their radical homopolymerizations, and on the basis of the thermodynamic parameters determined for their polymerizations, it has been concluded that homopolymerizabilities of the electron-accepting substituted p-quinodimethanes and p-quinone methides are determined exclusively by a steric hindrance effect arising from the substituents at the exocyclic positions. A new concept for the radical alternating copolymerization have been proposed on the basis of the change in modes (random and alternating copolymerizations) for their copolymerizations with styrene and the cross-propagation step analysis by linear free energy relationship. The polymerizations of the electron-donating substituted p-quinodimethanes take place only in the presence of oxygen molecules. In the solid-state polymerizations, some electron-accepting substituted p-quinodimethanes with same ester substituents polymerized topochemically in vacuo, and the strict requirements of topochemical polymerization for substituted p-quinodimethane and p-quinone methide monomers have been determined on the basis of their crystallographic data. Topochemical alternating copolymerization with molecular oxygen in solid state was discovered for the first time.     

Synthesis and Polymerization of Novel Quinone Methide Ketals

Summary Novel quinone methide ketals, 8-[ 1'-cyano-1'-(ethoxycarbonyl)methylene]-l,4-dioxaspiro[4.5]deca-6,9-diene (1a) and 8-(1',l'-dicyanomethy1ene)-1,4-dioxaspiro[4.5]deca-6,9-diene (1b), were synthesized, and their polymerization behavior was investigated. Polymerizations of 1a and 1b initiated with BPO and BF₃·Et₂O gave corresponding novel ring-opening polymers, but no polymerization with BuLi. Copolymerization of 1a with St in the presence of AIBN at 60 °C gave the monomer reactivity ratios r₁(1a) = 0.50 ± 0.1 and r₂(St) = 0.1 ± 0.02, and Q and e values of 1a were 2.46 and +0.93, indicating that 1a is a highly conjugative, electron-accepting monomer. Homopolymers of 1a and 1b had better thermal stability than that of 7-cyano-7-(ethoxycarbonyl)- 1,4-benzoquinone methide. Received 23 January 2003/Revised version 28 February 2003/ Accepted 1 March 2003 Correspondence to Takahito Itoh     

Terpolymer films having semipolar structure: Preparation,wettability, and mechanical properties

A terpolymer, obtained by the free‐radical terpolymerization of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMMA), methyl methacrylate(MMA), and isobutyl methacrylate (IBMA), was allowed to react with hydrogen peroxide, chloroacetic acid, and diethyl sulfate to form the corresponding modified terpolymers: (1) N,N‐dimethyl‐N‐(2‐methacryloyloxyethyl)amine N‐oxide, MMA and IBMA (DMANO series); (2) N‐(carboxymethyl)‐N,N‐dimethyl‐ N‐(2‐methacryloyloxyethyl)ethyl ammonium, MMA and IBMA (CDME series); and (3) N‐(ethyl)‐N,N‐dimethyl‐N‐(2‐methacryloyloxyethyl)ethyl ammonium ethylsulfonate, MMA and IBMA (EDMEES series), respectively. The terpolymer compositions were determined using ¹³C NMR spectrometry. Surface free energies of the terpolymers were estimated by measuring the contact angles of water and methylene iodide on the three series films (DMANO, CDME, and EDMEES), and the effect of the N‐oxide group on wettability was discussed. It was found that the upper surface of the films for the DMANO and CDME series are more hydrophobic than that for the EDMEES series. Notably, elongation to break for the DMANO series was relatively larger than that for the CDME series because of the water bound to the N‐oxide functional group. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1235–1243, 2005     

Emission from Silica Hybrid Containing RGB Fluorescent Conjugated Polymers

Summary Red, green and blue fluorescent poly(arylene vinylene)s were prepared by Wittig reaction. Polycondensation of tetraethoxysilane (TEOS) was carried out in the presence of a mixed solution of these polymers to give a silica hybrid in which RGB fluorescent polymers were immobilized without phase separation. White light emission was observed from the ternary polymer blend/silica hybrid.     

THE INFLUENCE OF CRACK-FACE FLUID PRESSURE ON THE FATIGUE CRACK PROPAGATION DUE TO ROLLING CONTACT WITH FRICTIONAL HEAT

A three-dimensional surface planar crack problem in a half-space is considered under rolling/sliding contact with frictional heat and hydraulic pressure by the entrapped fluid within the crack. Rolling contact is simulated as a line load with both normal and shear components, moving with constant velocity over the surface of the half-space. The body force method for three-dimensional fracture mechanics is utilized to determine the three modes of stress intensity factors along the crack contour. To account for mixed-mode propagation, the modified Paris power law is used. Numerical results for the stress intensity factors and the simulations of fatigue crack propagation are given for 30-degree inclined planar surface cracks of semicircular shape. The effects of the frictional coefficient, sliding/rolling ratio, and the crack-face fluid pressure on the crack propagation life are considered for a high carbon-chromium bearing steel.     

Synthesis and Polymerization of 7,7-Bromo-8,8-dicyano-quinodimethane

Summary 7,7-Dibromo-8,8-dicyanoquinodimethane (1) was synthesized successfully as orange needles. Its homopolymerization and copolymerization with styrene were investigated. 1 polymerized with AIBN and triethylamine, but not with BF₃·Et₂O. 1 copolymerized with styrene in a random fashion and Q and e values were estimated to be 336 and +1.45, indicating a highly conjugative, electron-accepting monomer. Received: 29 March 2001 / Accepted: 12 April 2001     

Development of optimization model for power system operation,outline of model design and verification of output

Osaka Gas Co., Ltd., jointly with NTT DATA Mathematical Systems Inc., has developed unit‐commitment model for optimizing dispatch of power generation units. Main purpose of this development is to simulate the future world of electric power system in accordance with national energy policy aiming to introduce large amount of renewable energy as well as vitalized cross‐border power exchange via PX market to enhance economically‐efficient power system operation. The model incorporates not only constraints of supply‐demand balance but also constraints of operating reserves, regulation reserves, maximum CO2‐emissions, etc.     

Plasticity initiation and subsequent deformation behavior in the vicinity of single grain boundary investigated through nanoindentation technique

The initiation of plasticity and the subsequent state in the vicinity of a single grain boundary during indentation-induced deformation were investigated to understand an elementary step of a stress-strain behavior of polycrystalline materials. Nanoindentation measurements on several points on a single grain boundary and the grain interior of an interstitial-free steel and an analysis on the pop-in behavior and the plastic nanohardness were carried out. The pop-in load P ^c that was obtained on the loading curve is different for each measurement. However, the loading curves overlap one another and the unloading curves coincide as well after the pop-in event. The nanohardness Hn has no dependence on the P ^c in the range of 150–550 μN. The relation between P ^c and Δh can be expressed as a simple cubic polynomial function based on a geometrically necessary dislocation loop model. The fitted function differed for various grains with different crystallographic orientations.     

Anhydrous proton-conducting electrolyte membranes based on hyperbranched polymer with phosphonic acid groups for high-temperature fuel cells

The two different molecular weight hyperbranched polymers (HBP(L)-PA-Ac and HBP(H)-PA-Ac) with both phosphonic acid group as a functional group and acryloyl group as a cross-linker at the chain ends were successfully synthesized as a new thermally stable proton-conducting electrolyte. The cross-linked electrolyte membranes (CL-HBP-PA) were prepared by their thermal polymerizations using benzoyl peroxide and their ionic conductivities under dry condition and thermal properties were investigated. The ionic conductivities of the low molecular weight CL-HBP(L)-PA membrane and the high molecular weight CL-HBP(H)-PA membrane were found to be 1.2 × 10⁻⁵ and 2.6 × 10⁻⁶ S cm⁻¹, respectively, at 150 °C under dry condition, and showed the Vogel–Tamman–Fulcher (VTF) type temperature dependence. Both membranes were thermally stable up to 300 °C, and they had suitable thermal stability as electrolyte membranes for the high-temperature fuel cells under dry condition. Fuel cell measurements using a single membrane electrode assembly cell with both cross-linked membranes were successfully performed.