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32.
Asymmetric addition of thiol to diene polymer in the presence of optically active amines as catalyst
The asymmetric addition reaction of thiolacetic acid or benzylmercaptan to diene polymer (natural rubber, cis- and trans-1,4-polyisoprene, cis-1,4-polybutadiene, various styrenebutadiene copolymers and alternating acrylonitrile-butadiene copolymer) by optically active catalysts such as d-bornylamine ([α]d?45.2°), l-aspartic diethyl ester (?11.2°), l-aspartic dibutyl ester (?5.3°) were carried out in benzene at room temperature to 90°C. The optically active polymers were obtained from natural rubber and cis-1,4- and trans-1,4-polyisoprene, but were not obtained from cis-1,4-polybutadiene, styrene-butadiene copolymers, and butadiene-acrylonitrile copolymer. The [α]25D value of optically active derivatives was ?0.1° ~ ?1.0° (in benzene), and the optical rotatory dispersion curves were found to fit the simple Drude equation. 相似文献
33.
The hydrogenation of cis-1,4-polyisoprene with diimide generated in situ from p-toluenesulphonylhydrazide (TSH), was investigated under various conditions. In aromatic solvents at 100–140°C, the rate of hydrogenation was increased with increase in concentration of polyisoprene and of TSH. Part of the polymer was depolymerized and cyclized during the reaction. Increasing the hydrogenation tended to decrease the rate of sulphur vulcanization, of the compounded rubber and the physical properties of vulcanizates were poor. The reaction of polyisoprene rubber with TSH, was also carried out in a solid state at 140°C for 20–60 min. It was found that by using a large amount of TSH hydrogenation and cyclization of rubber occurred. The quantity of TSH used as a blowing agent, for rubber in the manufacture of sponge rubber, i.e. 5–10 phr, did not cause hydrogenation. 相似文献
34.
The Williams-Landel-Ferry (W-L-F) equation was shown to describe the temperature dependence of the viscosity of a sulfonium accelerated, amine cured epoxy resin that had been formulated for pultrusion. The reference temperature and the viscosity at the reference temperature of the W-L-F equation were found to be simple functions of the resin advancement as determined by isothermal differential scanning calorimetry, A method is described of constructing the baseline for temperature-programmed differential scanning calorimetry analyses in which the heat capacity is changing due to reaction. 相似文献
35.
Naoto Kimbara Akio Nishijima Toshio Sato Yuji Yoshimura Hiromichi Shimada Nobuyuki Matsubayashi Akinori Yukimura 《Catalysis Letters》1990,6(3-6):409-415
TiN supported molybdenum sulfide catalysts showed much higher activity for cleavage of C-C bonds than oxide supported molybdenum sulfide catalysts, indicating the possibility of a new generation of supports for hydroprocessing catalysts. 相似文献
36.
Yuji Shimada Akio Sugihara Yumi Minamigawa Kenichi Higashiyama Kengo Akimoto Shigeaki Fujikawa Sadao Komemushi Yoshio Tominaga 《Journal of the American Oil Chemists' Society》1998,75(9):1213-1217
An attempt was made to enrich arachidonic acid (AA) from Mortierella single-cell oil, which had an AA content of 25%. The first step involved the hydrolysis of the oil with Pseudomonas sp. lipase. A mixture of 2.5 g oil, 2.5 g water, and 4000 units (U) Pseudomonas lipase was incubated at 40°C for 40 h with stirring at 500 rpm. The hydrolysis was 90% complete after 40 h, and the resulting free fatty acids (FFA) were extracted with n-hexane (AA content, 25%; recovery of AA, 91%). The second step involved the selective esterification of the fatty acids with lauryl alcohol and Candida rugosa lipase. A mixture of 3.5 g fatty acids/lauryl alcohol (1:1, mol/mol), 1.5 g water, and 1000 U Candida lipase was incubated at 30°C for 16 h with stirring at 500 rpm. Under these conditions, 55% of the fatty acids were esterified, and the AA content in the FFA fraction was raised to 51% with a 92% yield. The long-chain saturated fatty acids in the FFA fraction were eliminated as urea adducts. This procedure raised the AA content to 63%. To further elevate the AA content, the fatty acids were esterified again in the same manner with Candida lipase. The repeated esterification raised the AA content to 75% with a recovery of 71% of its initial content. 相似文献
37.
Microbial synthesis of copolymers of [R]-3-hydroxybutyrate (3HB) and 4-hydroxybutyrate (4HB), P(3HB-co-4HB), by Alcaligenes eutrophus, Alcaligenes latus, and Comamonas acidovorans from various carbon sources has been studied. The copolyester compositions varied from 0 to 100 mol% 4HB, depending on the microorganism and the combination of carbon substrates supplied. The thermal and physical properties of compositions with 0–100 mol% 4HB were investigated. The copolyesters represented a wide variety of polymeric materials, from hard crystalline plastic to very elastic rubbers, depending on composition. The copolyester films with high 4HB fractions (64–100 mol% 4HB) exhibited the characteristics of a thermoplastic elastomer, and the tensile strength increased from 17 to 104 MPa as the 4HB fraction increased. The enzymatic degradation of P(3HB-co-4HB) films was studied in an aqueous solution of extracellular polyhydroxybutyrate (PHB) depolymerase from Alcaligenes faecalis or lipase from Rhizopus delemer. The erosion rate of P(3HB-co-4HB) films was strongly dependent on the copolymer composition. In addition, environmental degradation of P(3HB-co-4HB) films in sea water was investigated. 相似文献
38.
Yuji A. Tajima 《Polymer Composites》1982,3(3):162-169
Viscosity is an important process variable that should be monitored and controlled to ensure the consistent and reliable production of graphite-fiber-reinforced composite parts by the autoclave/vacuum bag process. Unfortunately, no technique is currently known for the direct measurement of viscosity in this process. However, d.c. conductivity and a.c. phase lag appear to correlate quite well with viscosity, and either electrical property may be followed in order to indirectly monitor viscosity. As the method of measuring d.c. conductivity is so inexpensive, simple, and almost free of electrical interference compared to the method of measuring a.c. phase lag, it appears to be the method of first choice for application in an autoclave environment. 相似文献
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