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21.
Takuji Hirahara Takaaki Sugimura Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1970,8(10):2827-2837
Diphenylsulfone (DPSO2) was found to react with an equimolar amount of potassium in tetrahydrofuran (THF), dimethoxyethane (DME), or diglyme (DG) at reflux or an elevated temperature to yield a reddish-black solution, giving an electron spin resonance (ESR) signal. The signal was attributed to the formation of relatively labile DPSO2 anion radical. The apparent effects of solvents on the reactivity of DPSO2 with potassium depended on the polarities and the solvation powers: benzene ? toluene ? dioxane ? tetrahydrofuran < monoglyme < diglyme. The monopotassium complex was found to react further with another molecular amount of the metal to yield a dark blue solution giving no ESR signal. The monopotassium complex initiated the polymerization of acrylonitrile (AN). It did not, however, initiate the polymerization of methyl methacrylate (MMA), styrene (St), or isoprene (IP). The active species of the monopotassium complex that initiated the polymerization of AN was found from analyses of the reaction products and the infrared spectrum of oily oligomer of AN obtained by the complex to be potassium benzenesulfinate. The dipotassium complex was found to initiate the polymerization of MMA, St, IP and AN. The active species of the dipotassium complex that initiated the polymerization of MMA, St, or IP was found from analyses of the reaction products and the infrared spectrum of the oily oligomer of MMA obtained by the complex to be phenyl potassium. 相似文献
22.
Masahiro Tsunooka Shingo Tanaka Makoto Tanaka Hiroaki Egawa Takamasa Nonaka 《Journal of polymer science. Part A, Polymer chemistry》1985,23(9):2495-2505
In the photocrosslinking of poly(2,3-epithiopropyl methacrylate) (PETMA) films the effect of the pendant episulfide group's oxidation on the crosslinking of PETMA was investigated. Thermal crosslinking of PETMA is promoted by peroxides such as benzoyl peroxide and hydrogen peroxide. IR spectrum of the crosslinked PETMA showed that the reaction proceeded through the oxidation of episulfide groups by the peroxides. The anthracene (An) sensitized photocrosslinking of PETMA films also proceeded via the oxidation of episulfide groups by singlet oxygen. It was found that residual tetrahydrofuran (THF) in the films remarkably increased the rate of the photocrosslinking and/or reduced the induction period. From the further investigation concerning casting solvents it was found that residual CS2, CCl4, and CHCl3 in films increased the rate of the photocrosslinking and/or reduced the induction period of the photocrosslinking. The disappearance rate of An in the films was also increased by the presence of residual CS2, CCl4, and CHCl3, differring from the result of THF. These results were explained by a difference in lifetime of singlet oxygen in the films. From the results were explained by a difference in lifetime of singlet oxygen in the films. From the results concerning the effects of hydroperoxides such as THF hydroperoxide and t-butyl hydroperoxide on the photocrosslinking of PETMA films the acceleration effect of the residual THF was deduced to be due to the promotion of singlet oxygen-oxidation of sulfide groups by protic compounds such as THF hydroperoxide and H2O in the THF. 相似文献
23.
Yoshitsugu Kojima Takaaki Matsuoka Norio Sato Hideroh Takahashi 《Journal of polymer science. Part A, Polymer chemistry》1995,33(17):2935-2940
New conjugated oligomers were prepared by reacting phenylacetylene under high pressure of 0.11 to 0.92 GPa at 100–200°C for 0–5 h. The number-average molecular weight M?n, the weight-average molecular weight M?w, and the oligomer yield increased with pressure, tem-perature, and time. The average molecular weight of the oligomer showed the maximum value (M?n: 830, M?w: 2400) under 0.92 GPa, the maximum pressure, where phenylacetylene was oligomerized at a constant temperature. The structure of the oligomer was investigated from ESR, infrared, UV–VIS, field desorption mass (FDMS) spectra, and 13C NMR spec-trum. Analysis of the FDMS spectrum revealed that the molecular weight of the oligomer was multiple of the monomer. 13C NMR spectrum of the oligomer showed the absence of sp-carbon (? C?). We found that the oligomer had a cyclic structure. The cyclic oligomers of pentamer or more were new compounds. © 1995 John Wiley & Sons, Inc. 相似文献
24.
An(a, b)-n-fan means a union ofn internally disjoint paths. Menger's theorem states that a graphG has an(a, b)-n-fan if and only ifG isn-connected betweena andb. We show thatG contains edge-disjoint(a, b)-n-fans if and only if for anyk withk0min{n–1, |V(G)|–2} and for any subsetX ofV(G)-{a, b} with cardinalityk, G-X is (n-k)-edge-connected betweena andb. 相似文献
25.
Suzuki N Aihara N Takahara H Watanabe T Iwasaki M Saburi M Hashizume D Chihara T 《Journal of the American Chemical Society》2004,126(1):60-61
Five-membered metallacyclic alkynes that have no substituents adjacent to the triple bond have been synthesized, isolated, and structurally characterized. Zirconocene dichlorides, Cp'2ZrCl2 (Cp' = C5H5, C5H4-t-Bu), reacted with 1,4-dichlorobut-2-yne in the presence of magnesium to give 1-zirconacyclopent-3-yne compounds (5 (a) Cp' = C5H5, (b) Cp' = C5H4-t-Bu) that have a -CH2CCCH2- moiety in good yields. They are stable enough to be isolated in a pure form, despite the absence of substituents. 5a reacted with an equimolar amount of Cp2Zr(but-1-ene)(PMe3) to produce a bimetallic complex in which the zirconacyclopentyne coordinates to the other zirconocene moiety as an alkyne. 相似文献
26.
We demonstrate band gap control of CdTe nanocrystals by selective surface modification using alkanethiol molecules. Both absorption and emission wavelengths can be tuned simply by mixing a dispersion of the nanocrystals with alkanethiol at room temperature, resulting in blue shifts in the optical spectra during reaction. The degree of blue shift depends on both the concentration of alkanethiols and the reaction time, thereby providing kinetic control over the emission peak wavelength of the nanocrystals in mild conditions. The observed spectral changes are suggested to be caused by a decrease in the size of the CdTe core through formation of CdTe1-x(SC10)x shells because of specific exchange of Te with alkanethiolates. The results reported herein provide a new band gap engineering scheme for semiconductor nanocrystals and offer opportunities for the design of ligand-stabilized semiconductor nanocrystals with tunable composition and optical properties. 相似文献
27.
We estimated the energy barriers of proton transfers in the systems of (CF3SO3/H/SO3CF3)− and (CF3SO3/H/H2O/SO3CF3)− as models of a water-swollen Nafion membrane by an ab initio density functional quantum calculation method with consideration of the hydration effect. As a result, the proton transfer between the SO sites, which is accompanied by one water molecule, was found to be one of the proton-transfer mechanisms in the water-swollen Nafion membrane; that is, the surface diffusion mechanism was found to be important for the proton transfer in that membrane. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1905–1914, 2004 相似文献
28.
Jun-Ichi Asakura Masakuni Yoshihara Takaaki Shindo Yoshio Matsubara Toshihisa Maeshima 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):371-377
The radical copolymerization of vinylidene chloride (Vc, M1) with 3(2-methyl)-6-methylpyridazinone (I, M2) was carried out in benzene, ethanol, phenol, and acetic acid at 60 and 80°C. The monomer reactivity ratios were found to vary with the reaction conditions. The linear correlationships were obtained by plotting the values of log r1 against those of V C[dbnd]O and V C[dbnd]C of monomers determined in the solvents. 相似文献
29.
Hideaki Takahashi Shin-ichiro Kurimoto Junichi Kobayashi Takaaki Kubota 《Tetrahedron letters》2018,59(51):4500-4502
A new indole alkaloid with the canthin-6-one skeleton, ishigadine A, has been isolated from an Okinawan marine sponge Hyrtios sp. The structure of ishigadine A was elucidated on the basis of spectroscopic analyses. Ishigadine A is a new canthin-6-one alkaloid possessing a hydroxy group, a 1,3-dimethyl-4-methylthioimidazolium, and a 1-propylguanidine. Ishigadine A is the third canthin-6-one alkaloid from sponges. Ishigadine A might be generated from l-arginine, l-histidine, and l-tryptophan. Ishigadine A exhibited moderate cytotoxicity against L1210 murine leukemia cells. 相似文献
30.
Susumu Takigawa Masanori Koshimizu Takio Noguchi Tsutomu Aida Seiichi Takami Tadafumi Adschiri Yutaka Fujimoto Akira Yoko Gimyeong Seong Takaaki Tomai Keisuke Asai 《Journal of Radioanalytical and Nuclear Chemistry》2017,314(2):611-615
We synthesized liquid scintillators incorporating ZrO2 nanoparticles for application in neutrinoless double beta decay experiments. ZrO2 nanoparticles of less than 10 nm in size were synthesized with sub- and supercritical hydrothermal methods. The Zr concentrations in the liquid scintillators were determined to be up to 1.4 wt% with inductively coupled plasma analysis, and the liquid scintillators were transparent to scintillation. These results indicate that these methods are applicable for the preparation of liquid scintillators for neutrinoless double beta decay experiments. 相似文献