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71.
V. V. Burlakov A. V. Letov P. Arndt W. Baumann A. Spannenberg Ch. Fischer L. I. Strunkina M. Kh. Minacheva Ya. S. Vygodskii U. Rosenthal V. B. Shur 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):63-67
Zwitterionic titanoxanes {Cp[η5-C5H4B(C6F5)3]Ti}2O (I) and {(η5-iPrC5H4)[η5-1,3-iPrC5H3B(C6F5)3]Ti}2O (II), which contain two positively charged Ti(IV) centres in the molecule, are able to catalyse the ring-opening polymerization of -caprolactone (-CL) in toluene solution and in bulk. The process proceeds with a noticeable rate even at room temperature and accelerates strongly on raising the temperature to 60 °C. The best results have been obtained on carrying out the reaction in bulk. Under these conditions, the use of I as a catalyst (-CL:I = 1000:1) gives at 60 °C close to quantitative yield of poly--CL with the molecular mass of 197 000. An increase in the -CL:I ratio to 6000:1 increases the molecular mass of poly--CL to 530 000. Tetrahydrofuran (THF) is also polymerized under the action of I albeit with a lesser rate. However, the molecular mass of the resulting poly-THF can reach rather big values under optimal conditions (up to 217 000 at 20 °C and the THF:I ratio of 770:1). A rise in the reaction temperature from 20 to 60 °C results here to a decrease in the efficiency of the process. Titanoxane II is close to I in its catalytic activity in the -CL polymerization but it is much less active in the polymerization of THF. Propylene oxide (PO), in contrast to -CL and THF, gives with I only liquid oligomers in wide temperature and PO:I molar ratio ranges (−30 to +20 °C, PO:I = 500–2000:1). γ-Butyrolactone and 1-methyl-2-pyrrolidone are not polymerized under the action of I at room temperature. The reactions found are the first examples of catalysis of the cationic ring-opening polymerization by zwitterionic metallocenes of the group IVB metals. 相似文献
72.
Thilo Berkenbusch Andy Ch. Laungani Reinhard Brückner Manfred Keller 《Tetrahedron letters》2004,45(52):9517-9520
4-tert-Butyl-2-cyclohexen-1-one dimerizes in THF solution via its kinetic enolate, leading to di-tert-butylditwistane 8 in up to 36% yield (−78 °C → room temp., protonolysis, flash chromatography). X-ray crystallography shows that 8 incorporates one R and one S enantiomer of the starting ketone; none of the diastereomeric ditwistanes epi-8, epi’-8 or iso-8 was isolated. This means that the formation of 8 proceeds with mutual kinetic resolution and 100% induced diastereoselectivity. 相似文献
73.
Chandrasekhar S Narsihmulu Ch Reddy NR Sultana SS 《Chemical communications (Cambridge, England)》2004,(21):2450-2451
We demonstrate for the first time, L-proline as a chiral catalyst for transfer aldol reaction between aldehydes and diacetone alcohol. 相似文献
74.
B. Roduit Ch. Borgeat B. Berger P. Folly B. Alonso J. N. Aebischer F. Stoessel 《Journal of Thermal Analysis and Calorimetry》2005,80(1):229-236
Summary An advanced kinetic study on the thermal behaviour of pyrotechnic ignition mixtures has been carried out by differential scanning calorimetry using different B/KNO3 mixtures (50:50, 30:70, 20:80) as a model reaction. The experimental conditions applied (isochoric conditions/closed crucibles and isobaric conditions/open crucibles) as well as the composition of the mixtures noticeably influences the relative thermal stabilities of the energetic materials. The kinetic study focused on the prediction of the thermal stability of the different mixtures both in extended temperature ranges and under temperature conditions at which ordinary investigation would be very difficult. Using advanced numerical tools [1], thermal ageing and influence of the complex thermal environment on the heat accumulation conditions were computed. This can be done for any surrounding temperature profile such as isothermal, non-isothermal, stepwise, modulated, shock, adiabatic conditions and additionally for temperature profiles reflecting real atmospheric temperature changes (yearly temperature profiles of different climates with daily minimal and maximal fluctuations). Applications of accurate decomposition kinetics enabled the determination of the time to maximum rate under adiabatic conditions (TMRad) with a precision given by the confidence interval of the predictions. This analysis can then be applied for the examination of the effects of the surrounding temperature for safe storage or transportation conditions (e.g. determination of the safe transport or storage temperatures). 相似文献
75.
A method has been developed for obtaining 3-vinylbenzoxazolinones and 3-vinylbenzoxazolinethione. It has been shown that it is also possible to obtain 3-methylbenzoxazolinethione by this method in good yield (76%). 相似文献
76.
A three-component coupling was used to prepare a series of 1,4-disubstituted-1,2,3-triazoles from the corresponding acetylated Baylis-Hillman adducts, sodium azide and terminal alkynes. This one-pot reaction further increases the efficacy of ‘Click’ synthesis and diversifies the preparation of multi-functional 1,4-disubstituted-1,2,3-triazoles. 相似文献
77.
V. V. Anisovich B. Ch. Metsch H. R. Petry A. V. Sarantsev 《Zeitschrift für Physik A Hadrons and Nuclei》1995,351(4):417-433
We investigate a special concept of quarkhadron duality in meson physics at low and intermediate energies. With a relativistic propagator for confined quarks, we calculated masses and widths of the mesons which areS- andP-wave states ofq¯q (J P=0?, 1?, 0+, 1+c, 2+) as well as meson-meson scattering amplitudes at energies up totrs ≤ 1.3 GeV by including light pseudoscalar and vector mesons into the interaction dynamics. Our investigation shows that the influence of the light meson dynamics resutls in:
- a contribution to the constituent quark mass of approximately 200 MeV.
- the appearance of a new soft confinement force barrier responsible for the formation of the highly excited meson states.
78.
The quantum density of states of the Henon-Heiles potential displays a pronounced beating pattern. This has been explained by the interference of three isolated classical periodic orbits with nearby actions and periods. A singular magnetic flux line, passing through the origin, drastically alters the beats even though the classical Lagrangian equations of motion remain unchanged. Some of the changes can be easily understood in terms of the Aharonov-Bohm effect. However, we find that the standard periodic orbit theory does not reproduce the diffraction-like quantum effects on those classical orbits which intersect the singular flux line, and argue that corrections of relative order variant Planck's over 2pi are necessary to describe these effects. We also discuss the changes in the distribution of nearest-neighbor spacings in the eigenvalue spectrum, brought about by the flux line. (c) 1995 American Institute of Physics. 相似文献
79.
Th. Schalkhammer Ch. Lobmaier F. Pittner A. Leitner H. Brunner F. R. Aussenegg 《Mikrochimica acta》1995,121(1-4):259-268
A new optical sensor is presented, based on the analyte reaction resulting in swelling and shrinking of a thin polymer layer. Changing the concentration of ions in a new bisazide photo-cross-linked poly(vinylpyrrolidone) polymer results in a concentration-dependent volume change of the hydrated gel. The volume response of the sensor induced by different ions is fully reversible over more than 250 cycles. The response of the device depends on the type, the charge and the concentration of the ions. The sensor material is part of an optical thin film system which transforms the variations in volume of the polymer into spectral information. The steady state of the sensor response is obtained within 60 s. The response time is mainly limited by the pump rate, the back pressure and the total volume of the system but not by the swelling of the sensor polymer. A comparative study of ion effects has demonstrated a fundamental correlation of the polymer swelling properties with the Hofmeister series of chaotropic agents. Thus it is concluded that the photopolymer, which is solubilized in aqueous solutions by the interaction of its amide structure with the solvent, behaves like the backbone amide structure of proteins. 相似文献
80.
H. Weisen F. Hofmann M. J. Dutch J. -M. Moret J. B. Lister A. Pochelon R. A. Pitts M. Anton R. Behn S. Bernel F. Bühlmann R. Chavan B. P. Duval D. Fasel A. Favre S. Franke A. Heym Ch. Hollenstein P. Isoz B. Joye X. Llobet B. Marletaz Ph. Marmillod Y. Martin Ch. Nieswand P. J. Paris A. Perez Z. A. Pietrzyk O. Sauter W. Van Toledo G. Tonetti M. Q. Tran F. Troyon D. J. Ward 《Czechoslovak Journal of Physics》1995,45(12):1095-1110
During the first two years of operation, the TCV tokamak has produced a large variety of plasma shapes and magnetic configurations, with 1.0B
tor1.46T,I
p800kA,k2.05, –0.71. A new shape control algorithm, based on a finite element reconstruction of the plasma current in real time, has been implemented. Vertical growth rates up to 1000s–1 have been stabilized using the external coil system. Ohmic H-modes with Troyon factors (
tor
aB/I
p) up to two and densities up to 2.25×1020m–3, corresponding to the Greenwald limit, have been obtained in diverted discharges. Limiter H-modes with line averaged electron densities up to 1.7×1020m–3 have been obtained in elongated D-shaped plasmas with 360 kAI
P600 kA.Presented at 17th Symposium Plasma Physics and Technology, Prague, June 13–16, 1995.This work was partly supported by the Fonds National Suisse de la Recherche Scientifique. 相似文献