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991.
Atom transfer radical polymerization conditions with copper(I) bromide/2,2′-bipyridine (Cu/2,2′-bpy) as the catalyst system were employed for the homopolymerization and random copolymerization of 1-phenoxycarbonyl ethyl methacrylate (PCMA) with methyl methacrylate (MMA). Temperature studies indicated that the polymerizations occurred smoothly in bulk at 110 °C. Poly(PCMA)(polydispersity index=1.27) homopolymer was characterized and then used as macroinitiator for increasing its molecular weight. The homopolymerization of PCMA was also carried out under free radical conditions using 2,2′-azobisisobutyronitrile as an initiator.The monomer and polymers were characterized by FT-IR and 1H and 13C-NMR techniques. The glass transition temperatures, the solubility parameters and average-molecular weights of the polymers were determined. Thermal stabilities of the polymers were given as compared with each other by using TGA curves. Thermal degradation products of poly(PCMA)s obtained by ATRP and free radical polymerization were compared with each other by using 1H-NMR technique. 相似文献
992.
The triplet nature of rare long-lived states of d0 metallocenes formed upon ligand-to-metal energy transfer was confirmed by studies of triplet-triplet charge transfer in biscyclopentadienyl
complexes Cp2MCl2 (M = Zr (1), Hf (2)). The interaction between precatalysts and substrates of catalytic polymerization systems, viz., complexes 1 and 2 and unsaturated hydrocarbons (alkenes and dienes), was studied in the region of concentrations close to catalytic values.
For organometallic π-complexes, it has been shown for the first time that, in the case of the unsaturated hydrocarbons, the
efficiency of energy transfer obeys the Perrin equation. The process occurs at distances R
0 close to the diameter of the interacting molecules and is well described by the exchange-resonant mechanism of interaction.
In the case of the cyclopentadiene-Cp2MCl2 (M = Zr, Hf) systems, R
0 = 14.6 Å. A linear relationship between the critical radius of the quenching sphere R
0 and the number of carbon atoms in a linear α-olefin has been revealed for the first time and evidences the formation of a
π-complex between the precatalyst and substrate molecules.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 35–39, January, 2007. 相似文献
993.
研究了水溶性钌-膦配合物催化肉桂醛选择加氢反应中,相转移剂和表面活性剂对反应转化率和选择性的影响,考察了表面活性剂CTAB(十六烷基三甲溴化铵)浓度以及影响两相界面性质的因素—水相和有机相体积比、有机溶剂的改变等的影响.结果表明,相转移剂可以促进反应进行,其中以季铵盐相转移剂最好;表面活性剂能够显著地加快反应,其中以阳离子表面活性剂的效果最佳,且分子中含有长链烷基者(如CTAB)效果更好,非离子和阴离子表面活性剂的效果较差;对于CTAB,其浓度的增加导致反应速度的明显加快,但CTAB浓度达到1.65×10-2mol/L之后,反应体系乳化严重,反应完成后,两相分离变得困难.而增加水相体积和加入适当的有机溶剂,有利于转化率和选择性的提高. 相似文献
994.
Kaster Jeffrey A. Michelsen Donald L. Velander William H. 《Applied biochemistry and biotechnology》1990,(1):469-484
A microbubble dispersion (MBD) was used to supply oxygen for aerobic fermentations in a standard 2 L stirred tank fermenter.
The microbubble dispersion was formed using only surfactants produced naturally. Growth rates ofSaccharomyces cerevisiae cultures were found to be equal or greater with MBD sparging than with gas sparging. The oxygen transfer coefficent with
MBD sparging was found to be 190/h and independent of impeller speed from 100–580 rpm. The oxygen transfer coefficient with
air sparging rose from 55 to 132/h over the same range of impeller speeds. Power requirements for the fermenter systems were
estimated. 相似文献
995.
Martyn A. Brown Bruce R. McGarvey Andrzej Ozarowski Dennis G. Tuck 《Journal of organometallic chemistry》1998,550(1-2)
The primary process in the reaction of hexaphenylditin with various substituted orthoquinones (Q) is shown to involve attack by the quinone at a phenyl ligand. The intermediate thus formed decomposes to yield Ph3Sn(SQ·), where S(Q·−) is the corresponding semiquinonate. Rearrangement of these species in solution gives rise to biradicals, while intramolecular electron transfer may lead to the formation and precipitation of Ph2Sn(CAT), where CAT2− is the corresponding substituted catecholate. The identification of these processes depends in part on electron paramagnetic resonance spectroscopy. The reaction of Ph3SnCl or Ph2SnCl2 with Na(TBSQ·) (TBSQ·−=3,5-di-tert-butyl-orthobenzosemiquinonate) results in the formation of Ph2Sn(TBSQ·), which can undergo redistribution and intramolecular electron transfer, so that the solution chemistry of these latter systems is similar to that of the products of the Sn2Ph6+Q reaction. 相似文献
996.
Diclobutrazol的合成及其生物活性研究张洪奎,廖联安,陈明德,叶向阳,郭奇珍(厦门大学化学系厦门361005)关键词:Diclobutrazol,相转移催化,合成,生物活性Diclobutrazol(1)俗名粉锈清,是一种广谱内吸性杀菌剂,... 相似文献
997.
998.
999.
The effect of vibrational excitation of HBr on the H+HBrH2+Br and H+HBrH+HBr reactions has been investigated on the extended LEPS surface (ELEPS) constructed on the basis of quantum chemically calculated points of PES. Together with this surface the LEPS surface of Sudhakaran and Raff [1] was used for comparison at two relative translational energies. A quasiclassical trajectory method was used to study the abstraction and exchange reaction dynamics. The reactive cross section was calculated as a function of the relative collision energy and the vibrational state of HBr. The following conclusions can be drawn from the results of the study: (i) vibrational excitation v=0 v=2 more than doubles the reaction cross section, (ii) the increase in the collision energy is most effectively channelled into the product translational energy.Dedicated to Professor J. Koutecký on the occasion of his 65th birthday 相似文献
1000.