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1.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex
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Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
2.
Enrique Fernández-Cara Sergio Guerrero Oleg Yurievich Imanuvilov Jean-Pierre Puel 《Comptes Rendus Mathematique》2004,338(5):375-380
This Note deals with the controllability of Stokes and Navier–Stokes systems with distributed controls with support in possibly small subdomains. We first present a new global Carleman inequality for the solutions to Stokes-like systems that leads to the null controllability at any time T>0. Then, we present a local result concerning exact controllability to trajectories of the Navier–Stokes system. To cite this article: E. Fernández-Cara et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004). 相似文献
3.
Reaction of acetylene dicarboxaldehyde monoacetal with substituted Meldrum’s acid leads good yields in 2-pyranones-4-carboxaldehydes substituted in position 3. 相似文献
4.
Alexey Yurasov Alexander Granovsky Sergey Tarapov Jean-Pierre Clerc 《Journal of magnetism and magnetic materials》2006
The transmission of millimeter-range electromagnetic waves (30–50 GHz) through a magnetic nanocomposite thin film exhibiting tunnel magnetoresistance (TMR) is calculated. The relative change of transmission coefficient in an applied magnetic field due to the magnetorefractive effect is approximately linear with TMR and strongly depends on nanocomposite resistivity and film thickness. The obtained results are in a good agreement with experiment. 相似文献
5.
Particle filters are presently among the most powerful tools for filtering discrete time non linear systems. However the presence of unknown parameters in the system equations makes their use more complex and can even impair their convergence properties. This Note shows how an on-line consistent estimation of these parameters can be obtained simultaneously to that of the state variables to be filtered. This approach relies upon a kernel-based non parametric estimation of conditional probability densities from successive Monte Carlo generations of system particles. To cite this article: V. Rossi, J.-P. Vila, C. R. Acad. Sci. Paris, Ser. I 340 (2005). 相似文献
6.
Jean-Pierre Dedieu Gregorio Malajovich Mike Shub 《Foundations of Computational Mathematics》2005,5(2):145-171
We prove a linear bound on the average total curvature of the
central path of linear programming theory in terms of the number
of independent variables of the primal problem, and independent of
the number of constraints. 相似文献
7.
Jin Cheng Ching-Lung Lin Gen Nakamura 《Proceedings of the American Mathematical Society》2005,133(8):2359-2367
In this paper we prove the following kind of unique continuation property. That is, the zero on each geodesic of the solution in a real analytic hypersurface for second order anisotropic hyperbolic systems with real analytic coefficients can be continued along this curve.
8.
Jean-Pierre Changeux Alain Connes M. B. DeBevoise Jean Petitot Mark Anspach 《Mathematical Intelligencer》2005,27(4):48-56
Conclusion The debate between Jean-Pierre Changeux and Alain Connes is one of the most, interesting to take place in recent years. It
re-frames in a very up-to-date context a whole series of traditional and difficult questions from the standpoint of the knowledge
and experience of two of the leading protagonists of contemporary science. To the choice presented by the neurobiologist between
a Platonist ontology and a neurocognitive psychology of mathematical activity, the mathematician replies with a conception
that is objective (neither ontological nor psychological) of the thoroughly consistent universe of mathematical idealities.
It is indeed in this three-sided arena that the major difficulties play themselves out. One of the great virtues of the book
is to cast a spotlight on this confrontation. 相似文献
9.
Zhen‐Feng Chen Hong‐Li Zhou Hong Liang Yan Li Ren‐Gen Xiong Xiao‐Zeng You 《应用有机金属化学》2003,17(11):883-884
The centrosymmetric binuclear structure of [Pb2(H‐Norf)2(ONO2)4]shows the geometry around each lead(II) atom to be distorted trigonal bipyramidal with Pb–O distances ranging from 2.357(3) to 2.769(4) Å. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
10.
Jean-Pierre Demailly 《Mathematische Zeitschrift》1987,194(4):519-564
Sans résumé 相似文献