Search results for "opolymerization"
showing 10 items of 56 documents
Two-Color Single Hybrid Plasmonic Nanoemitters with Real Time Switchable Dominant Emission Wavelength
2015
International audience; We demonstrate two-color nanoemitters that enable the selection of the dominant emitting wavelength by varying the polarization of excitation light. The nanoemitters were fabricated via surface plasmon-triggered two-photon polymerization. By using two polymerizable solutions with different quantum dots, emitters of different colors can be positioned selectively in different orientations in the close vicinity of the metal nanoparticles. The dominant emission wavelength of the metal/polymer anisotropic hybrid nanoemitter thus can be selected by altering the incident polarization.
Zirconium oxocluster/polymer hybrid nanoparticles prepared by photoactivated miniemulsion copolymerization
2017
The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate) 12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free …
Electrochemical reactivity of magnesium porphine : functionalization, oligo-polymerization and application to the synthesis of porphyrins and multi-p…
2012
This work deals with the redox reactivity of magnesium porphine, the study of its electropolymerization and resulting materials, of its functionalization by nucleophiles as well as the mechanistic investigation of the C-C oxidative coupling on a tris-meso-substituted porphyrin model.The electrochemical oxidation of magnesium porphine to its cation radical leads to oligomers in solution and polymers on the electrode, which molecular structure depends on the imposed potential. The reactivity of the cation radical has also been exploited by adding sufficient amount of nucleophiles (pyridine and triphenylphosphine) in the reactional in order to inhibit the oligomerization/polymerization process…
Structural and Thermal Properties of Ethylene-Norbornene Copolymers Obtained Using Vanadium Homogeneous and SIL Catalysts
2020
The series of ethylene-norbornene (E-NB) copolymers was obtained using different vanadium homogeneous and supported ionic liquid (SIL) catalyst systems. The 13C and 1H NMR (carbon and proton nuclear magnetic resonance spectroscopy) together with differential scanning calorimetry (DSC) were applied to determine the composition of copolymers such as comonomer incorporation (CNB), monomer dispersity (MD), monomer reactivity ratio (re), sequence length of ethylene (le) and tetrad microblock distributions. The relation between the type of catalyst, reaction conditions and on the other hand, the copolymer microstructure, chain termination reaction analyzed by the type of unsaturation are discusse…
Microstructure of ethylene-1-hexene and ethylene-1-octene copolymers obtained over Ziegler–Natta catalysts supported on MgCl 2 (THF) 2
2001
Abstract The ethylene copolymerizations with 1-hexene or 1-octene in the presence of hydrogen using three catalysts, MgCl 2 (THF) 2 /VOCl 3 /Et 2 AlCl, MgCl 2 (THF) 2 /VCl 4 /Et 2 AlCl, MgCl 2 (THF) 2 /TiCl 4 /Et 2 AlCl, were investigated. It was found that the addition of hydrogen into the copolymerization feed reduces the molecular weight of the copolymers produced and decreases the activity of all the studied catalysts. The microstructure of the copolymers obtained was determined on the basis of 13 C NMR investigations and the reactivity ratios of the comonomers were calculated. The lack of tendency of the olefin comonomers to the creation of the polymer block was confirmed. It was found…
Ethylene/1-olefin copolymerization behaviour of vanadium and titanium complexes bearing salen-type ligand
2013
Ethylene/1-olefin copolymerization using vanadium and titanium complexes bearing tetradentate [O,N,N,O]-type ligand and EtAlCl2 or MAO as a cocatalyst is carried out. In the presence of the vanadium complex activated with EtAlCl2 is observed (a) negative “comonomer effect”, (b) high comonomer incorporation and narrow chemical composition distribution (CCD), (c) unexpected copolymer microstructure, and (d) increased molecular weight of copolymers when compared with the homopolymer. In contrast, titanium catalyst gives copolymers with lower 1-olefin content and broad CCD. Supported complexes show higher activity, lower 1-olefins incorporation and give copolymers with ultra high molecular weig…
Synthesis of low density foam shells for inertial confinement fusion experiments
2011
This work deals with the fabrication process of low density foam shells and the sharp control of their shape (diameter, thickness, density, sphericity, non-concentricity). During this PhD we focused on the non-concentricity criterion which has to be lower than 1%. The shells are synthesized using a microencapsulation process leading to a double emulsion and followed by a thermal polymerization at 60°C. According to the literature, three major parameters, the density of the three phases, the deformations of the shells along the process and the kinetics of the polymerization have a direct influence on the shells non-concentricity. The results obtained showed that when the density gap between …
Multi-Alkenylsilsesquioxanes as Comonomers and Active Species Modifiers of Metallocene Catalyst in Copolymerization with Ethylene.
2018
The copolymers of ethylene (E) with open-caged iso-butyl-substituted tri-alkenyl-silsesquioxanes (POSS-6-3 and POSS-10-3) and phenyl-substituted tetra-alkenyl-silsesquioxane (POSS-10-4) were synthesized by copolymerization over the ansa-metallocene catalyst. The influence of the kind of silsesquioxane and of the copolymerization conditions on the reaction performance and on the properties of the copolymers was studied. In the case of copolymerization of E/POSS-6-3, the positive comonomer effect was observed, which was associated with the influence of POSS-6-3 on transformation of the bimetallic ion pair to the active catalytic species. Functionality of silsesquioxanes and polymerization par…
Olefin polymerization and copolymerization by complexes bearing [ONNO]-Type salan ligands: Effect of ligand structure and metal type (titanium, zirco…
2014
A series of novel titanium(IV) complexes bearing tetradentate [ONNO] salan type ligands: [Ti{2,2′-(OC6H3-5-t-Bu)2-NHRNH}Cl2] (Lig1TiCl2: R = C2H4; Lig2TiCl2: R = C4H8; Lig3TiCl2: R = C6H12) and [Ti{2,2′-(OC6H2-3,5-di-t-Bu)2-NHC6H12NH}Cl2] (Lig4TiCl2) were synthesized and used in the (co)polymerization of olefins. Vanadium and zirconium complexes: [M{2,2′-(OC6H3-3,5-di-t-Bu)2-NHC6H12NH}Cl2] (Lig4VCl2: M = V; Lig4ZrCl2: M = Zr) were also synthesized for comparative investigations. All the complexes turned out active in 1-octene polymerization after activation by MAO and/or Al(i-Bu)3/[Ph3C][B(C6F5)4]. The catalytic performance of titanium complexes was strictly dependent on their structures an…
Copolymerization of ethylene with 1‐hexene over metallocene catalyst supported on complex of magnesium chloride with tetrahydrofuran
2004
The study of ethylene/1-hexene copolymerization with the zirconocene catalyst, bis(cyclopentadienyl)zirconium dichloride (Cp 2 ZrCl 2 )/methylaluminoxane (MAO), anchored on a MgCl 2 (THF) 2 support was carried out. The influence of 1-hexene concentration in the feed on catalyst productivity and comonomer reactivity as well as other properties was investigated. Additionally, the effect of support modification by the organoaluminum compounds [(MAO, trimethylaluminum (AlMe 3 ), or diethylaluminum chloride (Et 2 AlCl)] on the behavior of the MgCl 2 (THF) 2 /Cp 2 ZrCl/MAO catalyst in the copolymerization process and on the properties of the copolymers was explored. Immobilization of the Cp 2 ZrC…