Search results for "olefin"
showing 10 items of 147 documents
Grafting of Hindered Phenol Groups onto Ethylene/α-Olefin Copolymer by Nitroxide Radical Coupling
2017
The covalent immobilization of hindered phenol groups, with potential antioxidant activity, onto an ethylene/α-olefin (EOC) copolymer was carried out by the nitroxide radical coupling (NRC) reaction performed in the melt with a peroxide and the 3,5-di-tert-butyl-4-hydroxybenzoyl-2,2,6,6-tetramethylpiperidine-1-oxyl radical (BHB-T). Functionalized EOC (EOC-g-(BHB-T)) was exposed to photo- and thermo-oxidation. By comparison with some model compounds bearing the (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO) moiety or the hindered phenol unit, it was observed that the grafted BHB-T could effectively help the stabilization of the polymer matrix both under photo- and thermo-oxidation. In addit…
Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues
2013
The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric…
Dichlorovanadium(IV) diamine-bis(phenolate) complexes for ethylene (co)polymerization and 1-olefin isospecific polymerization
2018
Abstract Two vanadium complexes bearing amine-bis(phenolate) ligands with the amino side-arm donor, [V{Me2NCH2CH2N(CH2-2-O-3,5-tBu2-C6H2)2}Cl2] (1) and [V{Me2NCH2CH2N(CH2-2-O-3,5-tBu2-C6H2)(CH2-2-O-C6H4)}Cl2] (2), were synthesised and characterized by FTIR and 1H NMR spectroscopy. Upon activation with Al(iBu)3/Ph3CB(C6F5)4, these complexes became active catalysts for 1-octene polymerization giving highly stereoregular polymers (mmmm ∼ 90%) having regioirregularly arranged units. The catalytic activity of the catalysts in ethylene homo- and copolymerization, and their ability to incorporate a comonomer were highly dependent on both the activator type and the complex structure. 1/EtAlCl2 exhi…
Reactive melt blending of functionalized-MW/CNTs with polyolefin
2012
Adding nanotube adding into a polymeric matrix leads to the formulation of nanocomposites with enhanced macroscopical performances, and, moreover, the use of functionalized MW-CNTs leads to the nanocomposite formulation with even better properties. Furthermore, the reactive melt blending can be considered as a powerful processing method, i.e. reasonably simple and ecologically friendly, in order to formulate polymer based nanocomposite with good performance. In this work, the reactive melt blending between an ethylene-acrylic acid co-polymer, bis-oxazoline and functionalized MW-CNTs was performed and the rheological properties of the formulated systems were investigated.
Counter anion binding in the phenoxyimine, salan and metallocene olefin polymerization catalysts activated with perfluorophenylborate
2012
Abstract Ion pair separation is a process that may influence the activity of homogeneous catalysts of olefin polymerization. We have studied the energy of separation for selected titanium and zirconium metallocene and post-metallocene catalytic ion pairs by means of DFT, dispersion-corrected DFT and Paired Interacting Orbitals method (PIO). Unusually weak cation–anion interactions in the bis(phenoxyimine) systems were attributed to strong electron-donating properties of the phenoxyimine ligands. Energy decomposition analysis (EDA) revealed that almost 70% of the counter ion binding energy results from electrostatic interactions. The PIO method made it possible to analyze the nature of the c…
Structural flexibility of bis(phenoxyimine) titanium complexes in the early stages of olefin polymerization process: a DFT study
2010
The behaviors of three structurally similar salan- and phenoxyimine-based catalysts activated by perfluorophenylborate were compared in the early stages of ethylene polymerization. It was found that moderate modification of the ligand structure can dramatically reduce the interactions between the cationic active site and the counteranion and, as a result, decrease the theoretically calculated upper bound to the ion separation barrier from 15 to 2 kcal/mol. The interactions between the ions in the ion pair have further repercussions on the structure of the active sites (octahedral vs square pyramid), transition states and thus the insertion barriers.
The consequences of physical post-treatments (microwave and electron-beam) on food/packaging interactions: A physicochemical and toxicological approa…
2016
IF 4.052; The safety of microwave and electron-beam treatments has been demonstrated, in regards to the formation of reaction products that could endanger human health. An integrated approach was used combining the potential toxicity of all the substances likely to migrate to their chemical characterizations. This approach was applied to polypropylene (PP) films prepared with a selection of additives. Components were identified by liquid and gas chromatography using a mass selective detector system. Their potential toxicity was assessed using three in vitro short-term bioassays and their migrations were carried out using a standards-based approach. After the electron-beam treatment some add…
The role of pore topology on the behaviour of FCC zeolite additives
1999
Abstract A large variety of zeolite topologies including: large pore tridirectional (Beta), large pore unidirectional (Mordenite, SSZ-24), bidirectional 10 member ring pores (MRP) (ZSM-5), bidirectional 10 × 8 MRP (Ferrierite), tridirectional with connected 12 and 10 MRP (CIT-1), bidirectional with 12 MRP connected by 10 MRP (NU-87), tridirectional with 10 × 11 × 12 MRP (NU-86), and finally 10 MRP, and independent 12 MR cavities connected by 10 MR windows (MCM-22), have been studied as catalysts for the cracking of a gasoline range model molecule ( n -heptane). Kinetic and decay constants as well as selectivity parameters such as paraffin/olefin, i -C 4 / n -C 4 , i -C 5 / n -C 5 , C 3 /C 4…
Understanding C C bond formation in polar reactions. An ELF analysis of the Friedel Crafts reaction between indoles and nitroolefins
2013
[EN] The Friedel-Crafts (FC) reaction of N-methyl indole 1 with nitroethylene 2 has been studied using DFT methods at the B3LYP/6-31+G** level in order to characterize the bonding changes along the C-C bond-formation process in polar reactions. For this FC reaction a two-step mechanism has been found. The first step is associated with the C-C bond formation between the most electrophilic centre of nitroethylene and the most nucleophilic centre of N-methyl indole, to yield a zwitterionic intermediate IN. The second step corresponds to an intramolecular proton transfer process at IN, regenerating the aromatic system present at the indole. Despite the high electrophilic character shown by nitr…