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51.
Kyoichiro Shibatani Kiyoshi Fujii 《Journal of polymer science. Part A, Polymer chemistry》1970,8(7):1647-1656
The reaction of stereoisomers of pentane-2, 4-diol and heptane-2, 4, 6-triol with formaldehyde was investigated as a model for the formalization reaction of poly(vinyl alcohol) in order to determine effect of the stereochemical configuration of the polyol molecules on the reaction. The isotactic (meso) diol portion reacted with formaldehyde to give cis-formal several times faster than did the syndiotactic (dl) diol portion to give trans-formal at 30–80°C. In the reaction of heterotactic (meso-dl) triol which provides both the isotactic and syndiotactic diol portions in a molecule, the proportion of trans-formal in the total formal decreased as the reaction proceeded. This shows that the formation of cis-formal is also favored thermodynamically to a greater extent, and hence the intramolecular migration of trans-formal to cis-formal did occur during the reaction. The rates of hydrolysis of formals of the diols were compared with those of the triols in order to see the effect of a hydroxyl group adjacent to the formal ring on the reaction. No appreciable rate difference was observed between the dimer and trimer models both in cis- and trans- formals. Therefore it was deduced from these results that the increase of the rate of hydrolysis of poly(vinyl formal) with the increase of hydroxyl groups along the polymer chain is a characteristic of macromolecules that is not observed in the low molecular weight models. 相似文献
52.
Doi H Sakai T Iguchi M Yamada K Tomioka K 《Journal of the American Chemical Society》2003,125(10):2886-2887
The external chiral ligand-controlled asymmetric conjugate addition reaction of lithium amides with alpha,beta-unsaturated esters provided beta-amino esters in high yields and high enantioselectivities. 相似文献
53.
Thermolysis of 2,5-diphenyl-1,4-dithiin-1-oxide afforded 2-formyl-2,4-diphenyl-1,3-dithiole, which was obtained also in photolysis along with another rearranged product, 2-benzoyl-4-phenyl-1,3-dithiole. 相似文献
54.
55.
Kazuto Inoue Yoshio Imai 《Journal of polymer science. Part A, Polymer chemistry》1976,14(7):1599-1607
Polyisophthalamides and polyterephthalamides were prepared by the solution polycondensation of the corresponding diacyl chlorides with 4,4′-diaminobibenzyl, trans-4,4′-diaminostilbene, and 4,4′-diaminotolan in N,N-dimethylacetamide (DMAc). Polypyromellitimides were synthesized in two steps by the ring-opening polyaddition of pyromellitic dianhydride with the aromatic diamines in DMAc, followed by thermal cyclodehydration. The amorphous polyisophthalamides were soluble in some amide solvents containing lithium chloride, while the polyterephthalamides having fair degree of crystallinity were insoluble in these solvents. The thermal stability of these aromatic polymers decreased in the order of the tolan-containing polymers > the stilbene-containing polymers > the bibenzyl-containing polymers, both in air and under nitrogen. 相似文献
56.
Kiyoshi Ozawa Yoshio Sakka Muneyuki Amano 《Journal of Sol-Gel Science and Technology》2000,19(1-3):595-598
Cubic antimonic acid (Sb2O5·nH2O) films were successfully prepared on stainless steel and Si(100) substrates by electrophoretic deposition (EPD) using two types of sols. The sols were prepared by reacting an H2O2 aqueous solution with Sb(O-i-C3H7)3 or metallic Sb powder. The resulting films were found to consist of fine particles of cubic Sb2O5·nH2O single crystals with uniform particle sizes of 30 nm and 150 nm. The weight of the Sb2O5·nH2O deposit on the anode Si(100) substrate by EPD increased linearly with the current density in the range of 0–0.67 mA cm–2, when the sol pH was over 7. The proton conductivity of the polycrystalline Sb2O5·nH2O discs, formed from the two types of sols, was evaluated by an ac impedance method at room temperature under controlled levels of relative humidity. 相似文献
57.
The effect of sucrose on the structure of molecular assemblies formed in an MO/H2O mixture has been studied using a small-angle X-ray scattering method. It was found that the phase transition Ia3d --> Pn3m --> H(II) occurs with increased sucrose concentration in the mixture with the composition 70 wt% MO at 20 degrees C. This structural change induced by sucrose addition would be ascribed to a cosmotropic property of sucrose, which leads to the dehydration of the MO head group and hence causes a decrease in the effective area occupied by the MO molecule at the polar/apolar interface, which facilitates the formation of molecular assemblies with a high curvature for the reversed liquid-crystal mesophase. 相似文献
58.
Keiichi Satoh Zhang Xiang-Yu Masashi Miya-iri Akiko Honma Kiyoshi Sawada 《Monatshefte für Chemie / Chemical Monthly》2006,137(11):1375-1383
Summary. The ion-pair solvent extraction behavior of ethylenediaminetetraacetate (EDTA) anion by various tetraalkylammonium ions was investigated at 25.0 ± 0.1°C. The extraction of EDTA exceeded 90% from the basic aqueous solution into the organic solvents such as n-hexane and benzene derivatives containing tri-n-octylmethylammonium chloride, but EDTA was hardly extracted from acidic solution. Among the chemical species of EDTA in aqueous solution, edta
4− is the most extractable one. On the other hand, the extraction of EDTA was less than 1% into chloroform and 1,2-dichloroethane even from the basic aqueous solution. The effect of the structure
of alkylammonium ion was also examined. Tetra-n-hexylammonium and tetra-n-octylammonium ions could not extract EDTA even from the basic aqueous solution, while the use of tri-n-octylmethylammonium and di-n-lauryldimethylammonium ions enhances the extraction of EDTA. These results suggest that the steric hindrance in the ion-pair of alkylammonium and EDTA anion in the organic phase affects the extractability of EDTA containing ion-pair. The solution structure of ion-pair in the organic phase was calculated by MMFF force field and the steric
effect in the ion-pair was also suggested. From the extraction constants obtained, the possibility of the extraction separation
of EDTA has been shown.
Present address: Chemistry Department, Heilongjiang University, Harbin, China 相似文献
59.
60.
Tanaka K Mori M Xu Q Helaleh MI Ikedo M Taoda H Hu W Hasebe K Fritz JS Haddad PR 《Journal of chromatography. A》2003,997(1-2):127-132
In this study, an aqueous solution consisting of benzoic acid with low background conductivity and beta-cyclodextrin (beta-CD) of hydrophilic nature and the inclusion effect to benzoic acid were used as eluent for the ion-exclusion chromatographic separation of aliphatic carboxylic acids with different pKa values and hydrophobicity on a polymethacrylate-based weakly acidic cation-exchange resin in the H+ form. With increasing concentration of beta-cyclodextrin in the eluent, the retention times of the carboxylic acids decreased due to the increased hydrophilicity of the polymethacrylate-based cation-exchange resin surface from the adsorption of OH groups of beta-cyclodextrin. Moreover, the eluent background conductivity decreased with increasing concentration of beta-cyclodextrin in 1 mM benzoic acid, which could result in higher sensitivity for conductimetric detection. The ion-exclusion chromatographic separation of carboxylic acids with high resolution and sensitivity was accomplished successfully by elution with a 1 mM benzoic acid-10 mM cyclodextrin solution without chemical suppression. 相似文献