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DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
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
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Facile fabrication of fast recyclable and multiple self‐healing epoxy materials through diels‐alder adduct cross‐linker 下载免费PDF全文
Xiao Kuang Guoming Liu Xia Dong Xianggui Liu Jianjun Xu Dujin Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(18):2094-2103
A reversibly cross‐linked epoxy resin with efficient reprocessing and intrinsic self‐healing was prepared from a diamine Diels‐Alder (DA) adduct cross‐linker and a commercial epoxy oligomer. The newly synthesized diamine cross‐linker, comprising a DA adduct of furan and maleimide moieties, can cure epoxy monomer/oligomer with thermal reversibility. The reversible transition between cross‐linked state and linear architecture endows the cured epoxy with rapid recyclability and repeated healability. The reversibly cross‐linked epoxy fundamentally behaves as typical thermosets at ambient conditions yet can be fast reprocessed at elevated temperature like thermoplastics. As a potential reversible adhesive, the epoxy polymer with adhesive strength values about 3 MPa showed full recovery after repeated fracture‐thermal healing processes. The methodology explored in this contribution provides new insights in modification of conventional engineering plastics as functional materials. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2094–2103 相似文献
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Understanding and control of the surface properties such as molecular orientations are of great importance in numerous applications of ionic liquids. However, there remain discrepancies among the previous experimental and theoretical studies on the surface orientation and structures of room temperature ionic liquids(RTIL) systems. In this article, the orientation of 1-butyl-3-methylimidazolium([bmin]) cation at the air/liquid interface of a characteristic RTIL, 1-butyl-3-methylimidazolium hexafluorophosphate([bmim][PF6]), was investigated by the sum frequency generation vibrational spectroscopy(SFG-VS). Detailed polarization and experimental configuration analyses of the SFG-VS spectra showed the possibility of a small spectral splitting in the CH3 symmetric stretching region, which can be further attributed to the probable existence of multiple orientations for the interfacial [bmim] cations. In addition, the(N)–CH3 vibrations were absent, ruling out the prediction by several recent molecular dynamics simulations which state that portions of the [bmim] cations orient with a standing-up(N)–CH3 group at the ionic liquid surface. Hence, new realistic theoretical models have to be developed to reflect the complex nature of the ionic liquid surface. 相似文献
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Probing the Catalytic Activity of Reduced Graphene Oxide Decorated with Au Nanoparticles Triggered by Visible Light 下载免费PDF全文
Dr. Jiale Wang Dr. Fabiane J. Trindade Caroline B. de Aquino Joana C. Pieretti Prof. Dr. Sergio H. Domingues Prof. Dr. Romulo A. Ando Prof. Dr. Pedro H. C. Camargo 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9889-9894
Hybrid materials in which reduced graphene oxide (rGO) is decorated with Au nanoparticles (rGO–Au NPs) were obtained by the in situ reduction of GO and AuCl4?(aq) by ascorbic acid. On laser excitation, rGO could be oxidized as a result of the surface plasmon resonance (SPR) excitation in the Au NPs, which generates activated O2 through the transfer of SPR‐excited hot electrons to O2 molecules adsorbed from air. The SPR‐mediated catalytic oxidation of p‐aminothiophenol (PATP) to p,p′‐dimercaptoazobenzene (DMAB) was then employed as a model reaction to probe the effect of rGO as a support for Au NPs on their SPR‐mediated catalytic activities. The increased conversion of PATP to DMAB relative to individual Au NPs indicated that charge‐transfer processes from rGO to Au took place and contributed to improved SPR‐mediated activity. Since the transfer of electrons from Au to adsorbed O2 molecules is the crucial step for PATP oxidation, in addition to the SPR‐excited hot electrons of Au NPs, the transfer of electrons from rGO to Au contributed to increasing the electron density of Au above the Fermi level and thus the Au‐to‐O2 charge‐transfer process. 相似文献