Free-radical-induced polymerization of epoxides in the presence of maleic anhydride

The free-radical-induced reactions of cyclohexene oxide in the presence of maleic anhydride have been found to lead to polyether in presence of AIBN and to a mixture of polyether, ester, and maleic anhydride adduct of polyether with di-tert-butyl peroxide (DTBP), the amounts of the mixture components depending on the concentration of DTBP and the temperature. Analogous reactions in the presence of succinic anhydride lead to no polyether. The obtained polyether has no hydroxyl group. The reaction appears to consist of three different steps, radical initiation, cationic propagation, and radical termination.     

On the space curves with the same image under the gauss maps

From an irreducible complete immersed curveX in a projective space ? other than a line, one obtains a curveX ^′ in a Graasmann manifoldG of lines in ? that is the image ofX under the Gauss map, which is defined by the embedded tangents ofX. The main result of this article clarifies in case of positive characteristic what curvesX have the sameX′: It is shown thatX is uniquely determined byX′ ifX, or equivalentlyX′, has geometric genus at least two, and that for curvesX ₁ andX ₂ withX ₁ ≠X ₂ in ?, ifX′₁ =X′₂ inG and eitherX ₁ orX ₂ is reflexive, then bothX ₁ andX ₂ are rational or supersingular elliptic; moreover, examples of smoothX ₁ andX ₂ in that case are given.     

Distribution of the iron(III)-ethyl acetoacetate complex between aqueous solution and benzene

Summary Studies have been made on the distribution of iron(III)-ethyl acetoacetate complex between aqueous solution and benzene. Effect of pH, concentration of ethyl acetoacetate and shaking conditions were chosen as experimental parameters. Iron(III) can be well extracted from aqueous solution of pH 4.4–9.8 into benzene with constant extractability (97%), if the concentration of ethyl acetoacetate is kept in excess over that of iron(III). The applicability of the complex ( _max: 452 nm) to the spectrophotometric determination of iron is also discussed.

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Verteilung des Eisen(III)-Acetessigester-Komplexes zwischen wä\riger Lösung und Benzol

Zusammenfassung Zur Untersuchung der Verteilung wurden der pH-Wert, die Konzentration an Acetessigester und die Ausschüttelungsbedingungen variiert. Eisen(III) kann bei pH 4.4–9.8 mit Benzol mit einer konstanten Extrahierbarkeit von 97% ausgeschüttelt werden, wenn die Konzentration an Acetessigester größer ist als die an Eisen(III). Die Anwendbarkeit des Komplexes ( _max: 452 nm) zur spektralphotometrischen Eisenbestimmung wird diskutiert.

     

Determination of a polymeric hindered amine light stabilizer in polypropylene formulated with magnesium hydroxide flame retardant by reactive thermal desorption-gas chromatography.

A polymeric hindered amine light stabilizer (HALS), Tinuvin 622 (MW [symbol: see text] 4000), in PP materials formulated with a magnesium hydroxide flame retardant was determined by reactive thermal desorption (RTD) gas chromatography (GC). Two kinds of the HALS components that were formed through the RTD in the presence of tetramethylammonium hydroxide [(CH3)4NOH, TMAH] were clearly observed in the chromatograms of the PP samples, with negligible interference from the other additives and the PP substrate. Here, the coexisting flame retardant was proved to affect significantly the RTD process of the occluded HALS. As a result, the recovery of the HALS components in the RTD-GC chromatograms of the PP samples increased with increase in the content of the flame retardant. This enhancement of the HALS recovery is attributed mainly to the preferential exposure of the HALS on the surface of the ground PP sample through the interaction between the polymeric HALS and the flame retardant in the molten PP during kneading. In spite of such a considerable action of the flame retardant, the observed intensities of the characteristic peaks of HALS by RTD-GC showed a good linear relationship with the HALS content in the PP samples with constant content of the flame retardant (50 phr); this relationship could be used as the calibration line for the determination of the polymeric HALS in the PP materials containing the flame retardant.     

Volumetric study on the inclusion complex formation of α- and β-cyclodextrin with 1-alkanols at different temperatures

The partial molar volumes (V_a) of 1-alkanols (carbon number, m=5, 6, 7) in - and -cyclodextrin (CD) solutions at 5.00 mmol kg^–1 have been determined as a function of alkanol concentration (C_a) between 293.2 and 308.2 K by using a dilatometer. It has been observed that with an increase in C_a, V_a increased in -CD solution but decreased in -CD solution, asymptotically to a value of V_a in CD-free water. The dependence of V_a on C_a provided the binding constant (K) of 1:1 complex, the volume change in complex formation, and the partial molar volume of complex itself. The complex formation mechanism has been discussed on the basis of these values and their carbon number dependences in the respect of geometric behavior, hydrophobic interaction, and van der Waals interaction. It is concluded that the CD cavity in water is not rigid but flexible for fitting in nicely with guest molecule.     

Direct measurements of HOx radicals in the marine boundary layer: testing the current tropospheric chemistry mechanism

OH and HO(2) radicals, atmospheric detergents, and the reservoir thereof, play central roles in tropospheric chemistry. In spite of their importance, we had no choice but to trust their concentrations predicted by modeling studies based on known chemical processes. However, recent direct measurements of these radicals have enabled us to test and revise our knowledge of the processes by comparing the predicted and observed values of the radical concentrations. We developed a laser-induced fluorescence (LIF) instrument and successfully observed OH and HO(2) at three remote islands of Japan (Oki Island, Okinawa Island, and Rishiri Island). At Okinawa Island, the observed daytime level of HO(2) agreed closely with the model estimates, suggesting that the photochemistry at Okinawa is well described by the current chemistry mechanism. At Rishiri Island, in contrast, the observed daytime level of HO(2) was consistently much lower than the calculated values. We proposed that iodine chemistry, usually not incorporated into the mechanism, is at least partly responsible for the discrepancy in the results. At night, HO(2) was detected at levels greater than 1 pptv at all three islands, suggesting the presence of processes in the dark that produce radicals. We showed that ozone reactions with unsaturated hydrocarbons, including monoterpenes, could significantly contribute to radical production.     

Fluorination of 2-alkyl-substituted oxanes. The synthesis and purification of perfluoro(2-alkyl-substituted oxane)s

Five kinds of 2-alkyl-substituted oxanes like 2-ethyloxane, 2-n-propyloxane, 2-iso-propyloxane, 2-n-butyloxane and 2-n-amyloxane were fluorinated electrochemically to give the corresponding perfluoro(2-alkyloxane)s. The perfluoro(2-alkyloxane)s were obtained in good yields from these starting materials together with isomeric perfluoro(2-alkyloxolane)s, perfluoro(2-alkyl-5-methyloxolane)s and perfluoro(dialkyl ether)s. The purification of the perfluoro(2-alkyloxane)s which contained small amounts of isomeric perfluoro(2-alkyloxolane)s was successfully achieved by recovering the former unreacted after treating these mixture with anhydrous aluminum chloride at 150 /sR 160 °C during /sR 48 hrs in order to convert the latter into the easy-separable perfluoro(2,5,5- trichloro-2-alkyloxolane)s. Small quantities of new perfluoro(5,5-dichloroalkanoyl chloride)s were also among the chlorination products. The spectroscopic data as well as the physical properties of these new fluorination products, and perfluoro(2,5,5-trichloro-2-alkyloxolane)s and perfluoro(5,5-dichloroalkanoyl chloride)s are presented.     

Synthesis of poly (ethylene oxide)-b-polysilane by anionic polymerization of masked disilenes using a macroinitiator method

Poly(ethylene oxide-)-poly(1, 1-dimethyl-2, 2-dihexyldisilene) block copolymers (PEO-b-PMHS) were synthesized by the anionic polymerization of masked disilenes initiated with the potassium alkoxide of poly(ethylene glycol). The block copolymer self-assembled into polymer micelles in water accompanied by a transition in the polysilane conformation.     

Simple preparation and catalytic activity of Pd particles dispersed mesoporous carbons from poly(VDC/MA) containing Pd and Y compounds

We report a simple preparation of Pd particles dispersed mesoporous carbons. The carbons were prepared by steam activation of carbonized vinylidene chloride/methyl acrylate copolymer (poly(VDC/MA)) containing yttrium acetylacetonate (Y(acac)(3)) and palladium acetylacetonate (Pd(acac)(2)). The resulting carbons consist of high contents of mesopore and uniformly dispersed fine Pd particles. We measured the catalytic activities of the carbons obtained for hydrogenation of methyl linoleate. The Pd particles dispersed in mesoporous activated carbons obtained from poly(VDC/MA) containing both Y(acac)(3) and Pd(acac)(2) showed high catalytic activities, compared with the microporous activated carbon obtained from poly(VDC/MA) containing only Pd(acac)(2). Especially Pd particles dispersed in mesoporous carbons exhibited excellent selectivity for hydrogenation of diene (methyl linoleate) to monoene (methyl oleate).     

Sub-Doppler rotationally resolved spectroscopy of lower vibronic bands of benzene with Zeeman effects

Sub-Doppler high-resolution excitation spectra and the Zeeman effects of the 6(0)(1), 1(0)(1)6(0)(1), and 1(0)(2)6(0)(1) bands of the S1(1)B2u<--S(0)(1)A1g transition of benzene were measured by crossing laser beam perpendicular to a collimated molecular beam. 1593 rotational lines of the 1(0) (1)6(0) (1) band and 928 lines of the 1(0)(2)6(0)(1) band were assigned, and the molecular constants of the excited states were determined. Energy shifts were observed for the S1(1)B2u(v1=1,v6=1,J,Kl=-11) levels, and those were identified as originating from a perpendicular Coriolis interaction. Many energy shifts were observed for the S1(1)B2u(v1=2,v6=1,J,Kl) levels. The Zeeman splitting of a given J level was observed to increase with K and reach the maximum at K=J, which demonstrates that the magnetic moment lies perpendicular to the molecular plane. The Zeeman splittings of the K=J levels were observed to increase linearly with J. From the analysis, the magnetic moment is shown to be originating mostly from mixing of the S1(1)B2u and S2(1)B1u states by the J-L coupling (electronic Coriolis interaction). The number of perturbations was observed to increase as the excess energy increases, and all the perturbing levels were found to be a singlet state from the Zeeman spectra.