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71.
Tatsuro Ouchi Kazuhiro Nomoto Yoshifumi Hosaka Minoru Imoto Tadao Nakaya Tsutomu Iwamoto 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6-7):859-866
Abstract Three kinds of betaine-type polymers, which are macromolecular amphoteric electrolytes, were found to be able to polymerize vinyl monomers in aqueous solution through a radical mechanism without any further initiator. Betain-type polymers form hydrophobic areas (HA) in water. Vinyl polymerization commenced in the HA. The effect of the pH of the aqueous solution on polymerization was investigated. 相似文献
72.
Using p,p'-dimethoxydiphenyldiazomethane (DMDM) as initiator, the polymerization of methyl methacrylate (MMA) in benzene or in bulk was carried out. The initial rate of polymerization, Rp, was found to be expressed by the following equation: Rp = k[DMDM]0.53 [MMA]0.84 The polymerization was confirmed to proceed by a radical mechanism. The over-all activation energy for the polymerization in benzene was calculated as 19.3 kcal/mole. The rate of thermal decomposition of DMDM was also measured in benzene and the rate equation was obtained as follows: kd (sec?1) = 1.0 × 1015 exp (?29.1 kcal/RT) (for 50-80°C) Explanations of these observations are discussed in connection with those of the preceding papers. 相似文献
73.
The polymerization of acrylonitrile (AN) initiated by 1,4-dimethyl-1,4-bis(p-nitrophenyl)-2-tetrazene (Ie) was studied in dimethylformamide (DMF) at high temperature. The polymerization proceeds by a radical mechanism. The rate of polymerization is proportional to [Ie]0.64 and [AN]1.36. The overall activation energy for the polymerization is 21.5 kcal/mole within the temperature range of 115-130°C. The chain transfer of Ie was also undertaken over the temperature range of 120-135°C. The activation parameters for the decomposition of Ie at 120°C are kd = 2.78 × 10?6 sec?1, ΔH? = 40.8 kcal/mole, and ΔS? = 19.5 cal/mole-deg, respectively. 相似文献
74.
Abstract The binary system of tetramethyl tetrazene (TMT) and Co(II) chloride was used as initiator of acrylonitrile (AN) in dimethylformamide. The initial rate of polymerization (Rp) was found to be expressed by Rp = k[TMT]0.62[Co(II) chloride]0.57 [AN]2.00 The polymerization was confirmed to proceed via a radical mechanism. The over-all activation energy for the polymerization was estimated as 15.1 kcal/mole. On the basis of these results and the product analysis of the reaction between the catalyst components in the absence of monomer, the initiation mechanism of the polymerization is discussed. 相似文献
75.
Synthesis of Substituted Phenyl Esters of Amino Acids and Polycondensation in Langmuirblodgett Films
Kenji Hanabusa Takekazu Oumi Toshiki Koyama Hirofusa Shirai Tadao Hayakawa Akio Kurose 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1397-1413
Long-alkyl-chain phenyl esters of β-alanine, glycine, and L-valine were prepared, and their monolayer properties were correlated with their molecular structures. These compounds formed stable monolayers on acidic subphases. In particular, the p-hexadecylphenyl esters of β-alanine and glycine were remarkably stable, and their monolayers could be deposited on calcium fluoride plates as Y-type film by Blodgett's technique. The polycondensation of multilayers under an atmosphere saturated with triethylamine was investigated by changes in the IR spectra. It was determined that the polycondensation proceeded by a first-order reaction mechanism in the initial stage and that the rate in multilayers was faster than that in the bulk crystalline powder. These results suggest that the polycondensation is accelerated by a regular arrangement of the monomer in the multilayers, where the active sites are concentrated and located better for the polycondensation. In the case of the polycondensation in multilayers of the glycine ester, two kinds of condensation proceeded to afford poly(glycine) and 2,5-piperazinedione. 相似文献
76.
Several polyurethanes based on bis-(p-oxymethylphenyl) terephthalate (BOPT) were synthesized and studied with respect to some of their thermal properties. BOPT exhibits a mesomorphic phase at 252–264°C. Polymerization was carried out by equimolar reaction with hexamethyl-ene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate (H12MDI) α,α'-diisocyanate-1,3-dimethylcyclohexane (H6 XDI), 4,4′-diphenylmeth-ane diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and phenylene diisocyanate (PDI). It became clear that polyurethanes obtained from BOPT with HDI, H12MDI, H6XDI, and TDI have mesomorphic phases at 243–291, 214–250, 172–229, and 180–234°C, respectively, as determined by DSC and polarized microscopy, and that all polyurethanes are crystalline as evidenced by x-ray diffraction. 相似文献
77.
Mitsunori Oda Takanori Kajioka Kazuya Ikeshima Ryuta Miyatake Shigeyasu Kuroda 《合成通讯》2013,43(13):2335-2343
The trimethylsilyl enol ether of l-acetylcyclohepta-1,3,5-triene was transformed to 3,3-dialkyl-1,2,3,8-tetrahydroazulen-1-one by a two-step sequence involving the Mukaiyama aldol reaction with ketones and the subsequent Nazarov cyclization. 相似文献
78.
The pigment, tecophilin, in blue flowers of Tecophilaea cyanocrocus was isolated and the structure was determined to be 3-O-(6-O-α-l-rhamnopyranosyl-β-d-glucopyranosyl)-7-O-(6-O-(4-O-(2-O-(4-O-β-d-glucopyranosyl-(E)-caffeoyl)-6-O-(4-O-β-d-glucopyranosyl-(E)-caffeoyl)-β-d-glucopyranosyl)-(E)-caffeoyl)-β-d-glucopyranosyl)delphinidin. The reproduction experiment of the same color as petals according to the results of chemical analysis and measurement of vacuolar pH of blue cells clarified that the blue color solely develops by tecophilin without interaction of metal ions nor co-pigments. 1H NMR analysis and CD spectrum indicate the co-existence of clockwise intermolecular self-association of the delphinidin nuclei and intramolecular π–π stacking between the chromophore and caffeoyl residues to derive bathochromic shift of the absorption spectrum and stabilize the color by preventing hydration reaction. 相似文献
79.
Simultaneous high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis of cyanide and thiocyanate from swine plasma 总被引:1,自引:0,他引:1
Raj K. Bhandari Erica Manandhar Robert P. Oda Gary A. Rockwood Brian A. Logue 《Analytical and bioanalytical chemistry》2014,406(3):727-734
An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na13C15N and NaS13C15N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted 1-cyano[f]benzoisoindole, while thiocyanate was chemically modified with monobromobimane to form an SCN-bimane product. The method produced dynamic ranges of 0.1–50 and 0.2–50 μM for cyanide and thiocyanate, respectively, with limits of detection of 10 nM for cyanide and 50 nM for thiocyanate. For quality control standards, the precision, as measured by percent relative standard deviation, was below 8 %, and the accuracy was within ±10 % of the nominal concentration. Following validation, the analytical procedure successfully detected cyanide and thiocyanate simultaneously from the plasma of cyanide-exposed swine. 相似文献
80.