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101.
102.
Polymerization of allyl esters of unsaturated acids. V. Cyclopolymerization of methyl allyl fumarate
Kunio Urushido Akira Matsumoto Masayoshi Oiwa 《Journal of polymer science. Part A, Polymer chemistry》1980,18(6):1771-1785
The kinetics of radical polymerization of methyl allyl fumarate (MAF) is discussed in terms of cyclopolymerization and compared with the polymerization results of methyl allyl maleate (MAM) as a cis isomer. In the polymerization of MAF, the rate and degree of polymerization were quite enhanced compared with MAM, and gelation occurred at low conversion. The content of the unreacted allylic double bonds of the MAF polymer was quite large; whereas those of the unreacted fumaric double bonds and the cyclic structural units showed reverse tendencies. Only a slight presence of a five-membered ring was observed in the MAF polymer. The cyclization constants KA and KV, the ratios of the rate constants of the unimolecular cyclization reaction to those of the bimolecular propagation reaction of the uncyclized allylic and fumaric radicals, were estimated to be 2.73 and 1.48 mole/liter, respectively. These values suggest the great difference in the cyclopolymerization behavior between two isomeric monomers. These results are discussed in detail in connection with the high reactivity of the fumaric double bond compared to the maleic double bond. In addition, the formation mode and the sequence distribution of the structural units of the polymer produced are discussed on the basis of these analytical results. Thus, for the MAF polymer obtained in the bulk polymerization, about 60% of the cyclic structure can be formed via the intramolecular attack of the uncyclized fumaric radical on the allylic double bond, as opposed to the case of MAM via the predominant intramolecular attack (ca. 90%) of the uncyclized allylic radical on the maleic double bond; these results and the low probability for the succession of cyclic structures and the rather high probability of a vinyl-to-vinyl addition are presented. 相似文献
103.
Akikazu Matsumoto Katsuhiko Fukushima Takayuki Otsu 《Journal of polymer science. Part A, Polymer chemistry》1991,29(12):1697-1706
Radical polymerization of N,N,N′,N′-tetraalkylfumaramides (TRFAm) bearing methyl, ethyl, n-propyl, isopropyl, and isobutyl groups as N-substituents (TMFAm, TEFAm, TnPFAm, TIPFAm, and TIBFAm, respectively) was investigated. In the polymerization of TEFAm initiated with 1,1′-azobiscyclohexane-1-carbonitrile (ACN) in benzene, the polymerization rate (Rp) was expressed as follows: Rp = k [ACN]0.28 [TEFAm]1.26, and the overall activation energy was 102.1 kJ/mol. The introduction of a bulky alkyl group into N-substituent of TRFAm decreased the Rp in the following order: TMFAm > TEFAm > TnPFAm > TIBFAm > TIPFAm ~ 0. The relative reactivities of these monomers were also investigated in radical copolymerization with styrene (St) and methyl methacrylate (MMA). In copolymerization of TRFAm (M2) with St (M1), monomer reactivity ratios were determined to be r1 = 1.07 and r2 = 0.20 for St–TMFAm, and r1 = 1.88 and r2 = 0.11 for St–TEFAm, from which Q2 and e2 values were estimated to be 0.35 and 0.44 for TMFAm, and 0.19 and 0.47 for TEFAm, respectively. The other TRFAm were also copolymerized with St, but copolymerization with MMA gave polymers containing a small amount of TRFAm units. The polymer from TRFAm consists of a less-flexible poly(N,N-dialkylaminocarbonylmethylene) structure. The solubility and thermal property of the polymers were also investigated. 相似文献
104.
Carbon dioxide fixation by microalgae photosynthesis using actual flue gas discharged from a boiler 总被引:2,自引:0,他引:2
Matsumoto Hiroyo Shioji Norio Hamasaki Akihiro Ikuta Yoshiaki Fukuda Yoshinori Sato Minoru Endo Noriyoshi Tsukamoto Toshiaki 《Applied biochemistry and biotechnology》1995,(1):681-692
To mitigate CO2 discharged from thermal power plants, studies on CO2 fixation by the photosynthesis of microalgae using actual exhaust gas have been carried out. The results are as follows.
相似文献
1. | A method is proposed for evaluating the maximum photosynthesis rate in the raceway cultivator using only the algal physical properties; |
2. | Outdoor cultivation tests taking actual flue gas were performed with no trouble or break throughout 1 yr using the strain collected in the test; |
3. | The produced microalgae is effective as solid fuel; and |
4. | The feasibility studies of this system were performed. The system required large land area, but the area is smaller than that required for other biomass systems, such as tree farms. |
105.
Kaewsaiha P Matsumoto K Matsuoka H 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6754-6761
We synthesized an ionic amphiphilic diblock copolymer, poly(hydrogenated isoprene)-b-poly(styrenesulfonic acid) (PIp-h2-b-PSS), by living anionic polymerization, and the nanostructure of its monolayer spread on a water surface was directly investigated by the in situ X-ray reflectivity technique. The monolayer of the diblock copolymer on a water surface had a smooth hydrophobic PIp-h2 layer on water and a "carpet"/polymer brush double layer in a hydrophilic sodium polystyrene sulfonate (PSSNa) layer under the water. The surface pressure dependence and PSSNa chain length dependence of the PIp-h2 layer thickness and the brush nanostructure were quantitatively studied. The effect of salt concentration in the subphase was also investigated in aqueous solutions containing 0-2 M NaCl. The salt effect on monolayer structure occurred at around 0.2 M. The thickness of the PSS brush layer decreased at salt concentrations above 0.2 M, while no structural change was observed below 0.2 M. This critical salt concentration is thought to be related to the balance of ionic concentrations inside the brush and in bulk solution. 相似文献
106.
Kasai HF Tsubuki M Matsumoto Y Shirao M Takahashi K Honda T Ueda H 《Chemical & pharmaceutical bulletin》2004,52(3):311-315
Gas chromatographic separations of the stereoisomers of menthol derivatives, important intermediates in the synthesis of physiologically active natural products, were carried out on several substituted beta-cyclodextrin (CD) columns, including per-O-methyl-beta-cyclodextrin (PME-beta-CD), heptakis(2,3-di-O-acetyl-6-tert-butyldimethylsilyl)-beta-CD (DIAC-6-TBDS-beta-CD), and heptakis(2,3-di-O-methyl-6-tert-butyldimethylsilyl)-beta-CD (DIME-6-TBDS-beta-CD) as chiral stationary phases (CSPs). With the DIME-6-TBDS-beta-CD column, a separation of the Z- and E-isomers of methylidenementhol was accomplished; no separation was achieved with the other columns. The stereoisomers of methylidenementhol and the corresponding tert-butyldimethylsilyl (TBS) ether were separated on both the beta-CD and the heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TME-beta-CD) columns by high-performance liquid chromatography (HPLC) with a mobile phase involving acetonitrile and H(2)O. For the separation of the Z- and E-isomers of methylidenementhol, the TME-beta-CD column was superior. In contrast, the beta-CD column was preferable in the case of the corresponding TBS ether. 相似文献
107.
Ishikawa Y Matsumoto Y Nishida Y Taniguchi S Watanabe J 《Journal of the American Chemical Society》2003,125(21):6558-6562
Silicon carbide (SiC) and diamond were decomposed to CO(2)(g) by the photocatalysis with TiO(2) at room temperature, although the decomposition rate of diamond was very slow. According to the XPS spectra of Si2p on the SiC surface, SiO(2) was simultaneously formed on the surface by the TiO(2) photocatalysis. The thickness of the SiO(2) formed on the SiC surface during the photocatalytic oxidation for 1 h was estimated to be about 40 A from the depth profile of the XPS spectra using Ar etching. The SiC surface was oxidized by the TiO(2) photocatalysis even under the condition without a direct contact with the TiO(2). This indicates that the photocatalytic oxidation of the SiC occurs due to active oxygen species photogenerated on the TiO(2) surface, but not by hole produced in the valence band of the TiO(2). Moreover, a remote surface treatment system using the quartz beads coated with TiO(2) was developed for the SiC surface oxidation. Consequently, the TiO(2) photocatalysis will be very useful for the surface treatment of SiC such as photopatterning without defects and damage to the substrate because the photocatalytic reaction is carried out under mild conditions. 相似文献
108.
A method for the quantification of total d-gluconate by flow-injection analysis was developed using an immobilized-enzyme reactor and fluorescence detection. d-Gluconate was quantified using co-immobilized gluconate kinase (GK) and 6-phosphogluconate dehydrogenase (PGDH) reactor. d-Gluconate was phosphorylated to 6-phospho-d-gluconate by GK in the presence of ATP, and then the 6-phospho-d-gluconate produced was oxidized by PGDH with NADP+. The NADPH produced by the GK-PGDH reactor was monitored fluorometrically at 455 nm (excitation at 340 nm). A linear relationship between the responses and concentrations of d-gluconate was obtained in the ranges of 1.0 × 10−6–1.6 × 10−4 M. The relative standard deviation for 10 successive injections was 0.57% at the 0.1 mM level. This analytical method was applied to the quantification of d-gluconate in honeys, vinegars and noble rot wines, and the results showed good agreement with those obtained using the conventional F-kit method. 相似文献
109.
Kaoru Suzuki Iwao Nishiyama Yasushi Ozaki Kozo Kuchitsu 《Chemical physics letters》1978,58(1):145-148
Light emission from Cl(5p) atoms (near 440 nm) produced in the reaction of HCl in a discharged flow of argon was investigated with a flowing-afterglow apparatus. Ionic species, most probably argon ions in metastable states, Ar+M, were found to be responsible for the Cl(5p) production in the dissociative excitation of HCl. 相似文献
110.
Noboru Yamazaki Makoto Matsumoto Fukuji Higashi 《Journal of polymer science. Part A, Polymer chemistry》1975,13(6):1373-1380
Poly-p-benzamide of high molecular weight (ηinh = ~ in H2SO4) was obtained by the direct polycondensation reaction of p-aminobenzoic acid (p-ABA) by means of diphenyl and triaryl phosphites in N-methylpyrrolidone (NMP)-pyridine solution containing lithium and calcium chlorides. Molecular weight of polymer varied with the amount of these salts, showing maximum values at the concentration of about 4 wt-% of LiCl or about 8 wt-% of CaCl2 in the reaction mixture. The reaction temperature at around 80°C gave a polymer of the highest viscosity. The polycondensation reaction was also affected by monomer concentration, solvents, and tertiary amines like pyridine. Similarly, aromatic polyamides with high molecular weight (ηinh values up to 1.34 in H2SO4) were prepared from isophthalic acid and aromatic diamines, whereas terephthalic acid gave only low-viscosity polymers. 相似文献