Visible-light-active titanium oxide photocatalyst realized by an oxygen-deficient structure and by nitrogen doping

A visible-light (vis)-active titanium oxide photocatalyst was prepared by a simple wet process: the calcination of the hydrolysis product of Ti(SO₄)₂ with ammonia using an ordinary electric furnace in dry air at 400 °C. The color of this photocatalyst was vivid yellow and absorbed light in the blue (400 nm) to bluish-green (550 nm) region exclusively. Its structure was characterized to anatase with oxygen-deficient stoichiometry by XRD and X-ray photoelectron spectroscopy. Nitrogen was also detected, but only in trace amounts. Using blue-light-emitting diodes as a light source, 540 ppm of acetone was decomposed within 36 h and a stoichiometric yield of CO₂ was obtained. From the results of the crystalline size D, it was found that vis-activity could be realized on polycrystalline particles and the grain-boundaries (GBs) are thought to be important, since oxygen vacancies are easily created in GBs, which could form a GB state. Finally, we concluded that oxygen-deficient sites formed in GBs are important to emerge vis-activity, and nitrogen doped in the part of oxygen-deficient sites are important as a blocker for reoxidation.     

Decomposition of CCl2F2 over metal sulfate catalysts

Activity for hydrolysis of CCl₂F₂ (CFC12) on various metal sulfate was investigated. Zr(SO₄)₂ was found to be the most active while FeSO₄, Cr₂(SO₄)₃, Al₂(SO₄)₃, La₂(SO₄)₃ and Ce₂(SO₄)₃ had intermediate activity. MnSO₄, CoSO₄, and MgSO₄ showed low activity and SrSO₄, CaSO₄, and BaSO₄ had even less activity. The major carbon containing product was CO₂ and small amount of CClF₃ and CO were formed over several sulfates. The crystal structure of the sulfates was stable during decomposition of CCl₂F₂, and the conversion reached a steady state after initial decrease at 275 °C over Zr(SO₄)₂ catalyst. The concentration of surface hydroxyl was larger than that over AlPO₄-based catalysts and a reaction mechanism similar to that over AlPO₄-based catalysts was proposed.     

Effect of glass transition temperature on heat‐responsive gas bubbles formation from polymers containing tert‐butoxycarbonyl moiety

Various types of polymers containing tert‐butoxycarbonyl (BOC) moiety as the typical protecting group of functional moieties have been used for the design of stimuli‐responsive polymer materials. In this study, we investigated the heat‐responsive deprotection behavior of BOC‐containing polymers obtained by radical polymerization of 4‐(tert‐butoxycarbonyloxy)styrene (BSt) and copolymerizations of BSt with styrene and methyl acrylate. The deprotection of BOC groups accompanying the evolution of isobutene and carbon dioxide as gaseous products was monitored by thermogravimetric analyses at different temperature circumstances; that is, on heating at a rate of 10 °C/min and under isothermal conditions at various temperatures. The deprotection resulted in a significant decrease in the transmittance of visible light due to the formation of a large number of gas bubbles, that is, foaming, in the polymer films when a heating temperature was close to the glass transition temperature of the used polymer. The potential of BOC‐containing polymers was also evaluated as the heat‐responsive adhesive polymers for dismantlable adhesion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46252.     

Cationic polymerization behavior of β‐methylglycidyl ether derivatives and physical properties of their cationically cured materials

β‐Methylglycidyl ethers have been applied to Electrical and Electronic adhesives. However, there is no report about the detailed polymerization behavior and physical properties of their cured products. Hence, we investigated cationic polymerization behavior of bisphenol A di(β‐methylglycidyl) ether (Me‐BADGE) and physical properties of the cured products containing Me‐BADGE. DSC analysis suggested that Me‐BADGE could be cured completely at lower temperature than bisphenol A diglycidyl ether (BADGE). Physical properties were analyzed by dynamic viscoelastic analysis. Glass transition temperature (T_g) of BADGE homopolymer was 194°C. In contrast, the copolymer of BADGE (50 wt %) with Me‐BADGE (50 wt %) showed T_g at 124°C. According to the data of E’ and tan δ, crosslink density of the cured products decreased with increasing the Me‐BADGE content. The analysis of cationic polymerization of monofunctional β‐methylglycidyl ether suggested that the cationic polymerization proceeded not only through oxonium cation but also through carbocation formed by ring‐opening reaction of oxonium cation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42377.     

Absolute Configuration of β- and α-Asymmetric Carbons within β-O-4-Structures in Hardwood Lignin

In this study, we investigated the proportion of erythro- and threo-forms of β-O-4-ether structures and their enantiomeric compositions in hardwood lignin by applying the ozonation method to birch wood meal. Optical activity was not substantially observed in either the erythronic or threonic acids obtained as the ozonation products of β-O-4-structures in birch wood meal. The proportions of the four stereoisomeric forms {(αS,βR)-erythro, (αR,βR)-threo, (αS,βS)-threo, and (αR,βS)-erythro forms} were estimated to be 37-38%, 13-14%, 12-13%, and 36-37% based on the yields of erythronic and threonic acids, and on their optical activities. The proportions suggest that the entire components of β-O-4-ether structures in birch wood lignin have R- and S-configurations at the β-carbon in approximately the same quantities {(βR)-β-O-4-structure: (βS)-β-O-4-structure = 50–52:48–50}; i.e., that the β-ether structures are essentially racemic. This estimation implies that, during lignin biosynthesis, an equal number of enantiomeric forms of β-O-4-bonded quinone methides were formed by radical coupling reactions.     

Measurement of High-Temperature Elastic Properties of Ceramics Using a Laser Ultrasonic Method

Young's modulus and Poisson's ratio of SiC ceramics at temperatures >1400°C were obtained using a laser ultrasonics method that included a Fabry-Pérot interferometer (LUFP). At temperatures <1000°C, Young's modulus and Poisson's ratio measured using the LUFP method agreed well with those measured using standard contact methods, such as the resonance method and the ultrasonic pulse method. These results showed that the LUFP method is a powerful tool for measuring high-temperature elastic properties of advanced ceramics in a noncontact manner.     

Photoelectric properties of ABA‐type triblock copolymers designed using fluorine‐containing polyimide macroinitiators with polyhedral oligomeric silsesquioxane

4,4′‐(Hexafluoro‐isopropylidene) diphthalic anhydride‐2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (6FDA‐TeMPD) was synthesized and reacted with polyhedral oligomeric silsesquioxane (POSS) to form an ABA‐type triblock copolymer by atom transfer radical polymerization. The solid‐state and optical properties of the resulting copolymers were systematically investigated, and their electronic states were analyzed. As the POSS concentration increased, the transparency across the entire wavelength range increased. In the ABA‐type triblock copolymers, a new transition was observed between the highest occupied molecular orbital in POSS and the lowest unoccupied molecular orbital in 6FDA‐TeMPD because of their high molecular size dispersion. Since the refractive index of 6FDA‐TeMPD decreased linearly as the POSS concentration increased, the refractive index of the ABA‐type triblock copolymers of 6FDA‐TeMPD with POSS could be easily controlled. POLYM. ENG. SCI., 57:1207–1213, 2017. © 2017 Society of Plastics Engineers     

Crosslinking of poly(vinyl alcohol) and poly(vinyl acetate) using poly(maleic anhydride‐alt−2,4‐dimethyl‐1,3‐pentadiene) as polyfunctional crosslinker and decrosslinking by ozone degradation

Crosslinking and decrosslinking reactions of poly(vinyl alcohol) (PVA) and poly(vinyl acetate) (PVAc) using an alternating copolymer of maleic anhydride and 2,4‐dimethyl‐1,3‐pentadiene (PMAD) as the polyfunctional crosslinker and subsequent ozone degradation are reported. PVA and PVAc are heated at 200 °C for 0.5 to 3 h in the presence of 5 to 30 wt % of PMAD in the solid state to obtain the corresponding crosslinked polymers. The reactions of a hydroxy group of PVA and an acetate group of PVAc with an anhydride group of PMAD slowly proceed to give insoluble polymers with a loose crosslinking structure. Almost no change in the thermal decomposition temperatures and the IR spectra is observed during the crosslinking reactions. The crosslinked PVA produces hydrogels with a high swelling ratio of 500 to 1700%, which are readily degradable during a reaction with ozone in water at 0 °C. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44229.     

Poly(N‐isopropylacrylamide) gel‐based macroporous monolith for continuous‐flow recovery of palladium(II) ions

Macroporous monoliths, composed of thermoresponsive, tertiary‐aminated, and crosslinking monomers, were prepared for continuous‐flow separation of palladium(II) ions. N ‐Isopropylacrylamide was required to form the porous structure in the monoliths, indicating that the mechanism of porous structure formation involved polymerization‐induced phase separation of the poly(N ‐isopropylacrylamide) gel. Tertiary‐aminated monoliths showed adsorption selectivity for palladium(II) ions in hydrochloric media, compared with copper(II) ions. The maximum capacities of the monoliths with tertiary amine contents of 10, 20, 30, and 70 mol % for palladium(II) ions were 0.6, 1.1, 1.3, and 2.3 mmol/g, respectively. Darcy's permeabilities of water through the macroporous monolith were 10^?14 to 10^?13 m², and those were comparable to that through a commercially available membrane filter with a pore size of several micrometers. In the continuous‐flow process, the macroporous monolith with tertiary amine selectively adsorbed palladium(II) ions in the coexistence of copper(II) ions with 10 times higher concentration than the palladium(II) ions. The palladium(II) ions were eluted from the macroporous monolith, and the concentration of palladium(II) ions in the eluate was up to 45 times of that in the feed solution. The average enrichment factor and total recovery percentage of palladium(II) ions were 8.7 times and 95%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44385.     

Stereo-Preference in the degradation of the erythro and threo isomers of β-O-4-type lignin model compounds in oxidation processes. part 2: In the reaction with hydroxyl and oxyl anion radicals under hydrogen peroxide bleaching conditions

We examined which isomer, the erythro or threo, of non-phenolic β-O-4-type lignin model compounds is stereo-preferentially attacked by hydroxyl radical and its conjugate base, oxyl anion radical, generated by the decomposition of hydrogen peroxide in the presence of ferric ion and its precipitates under hydrogen peroxide bleaching conditions. The intrinsic stereo-preference of oxyl anion radical was slightly toward the erythro isomer, while hydroxyl radical had a further smaller stereo-preference. These stereo-preferences can be explained by our prior knowledge that oxyl anion radical preferentially attacks the side-chain of the lignin model compounds rather than the aromatic nucleus. The amount of the degraded lignin model compounds became less great with decreasing pH, but reversely and intensively greater in the pH range below 10. This phenomenon can be attributed to the change in the decomposition mechanism of hydrogen peroxide accompanying the pH variation.