Search results for "Radical polymerization"
showing 10 items of 184 documents
Half-sandwich molybdenum(III) compounds containing diazadiene ligands and their use in the controlled radical polymerization of styrene
2002
Abstract The reaction of CpMoCl2 with diazadiene ligands RNCHCHNR (R2dad) affords the corresponding paramagnetic complexes CpMoCl2(R2dad) (R=Ph, 1; p-Tol, 2; C6H3Pr2i-2,6, 3; and Pri, 4). All compounds have been characterized by EPR spectroscopy and have been investigated by cyclic voltammetry. They display one-electron oxidation and reduction processes, these being reversible or irreversible depending on the nature of R. The irreversibility of the reduction wave is due to a chemical follow-up process which consists of chloride loss from the reduced product. This phenomenon is suppressed in the presence of excess chloride in solution. An X-ray structure of 3 verifies the mononuclear na…
How the interplay of different control mechanisms affects the initiator efficiency factor in controlled radical polymerization: An investigation usin…
2007
International audience; Compound CpMoI2(iPr2dad) (iPr2dad = iPrNdouble bondCHsingle bondCHdouble bondNiPr), obtained by halide exchange from CpMoCl2(iPr2dad) and NaI, has been isolated and characterized by EPR spectroscopy, cyclic voltammetry, and X-ray crystallography. Its action as a catalyst in atom transfer radical polymerization (ATRP) and as a spin trap in organometallic radical polymerization (OMRP) of styrene and methyl acrylate (MA) monomers has been investigated and compared with that of the dichloro analogue. Compound CpMoCl2(iPr2dad) catalyzes the ATRP of styrene and MA with low efficiency factors f (as low as 0.37 for MA and ethyl 2-chloropropionate as initiator), while it irre…
Half-sandwich Mo(III) complexes with asymmetric diazadiene ligands
2006
The asymmetric 1,4-diazadiene ligands R ∗ N CHCH NR ∗ [R ∗ = ( S )-CH(CH 3 )Ph], R 2 ∗ dad , and 2,2′-bis(4-ethyloxazoline), as-ox, have been used to generate half-sandwich Mo III derivatives by addition to Cp 2 Mo 2 Cl 4 . Ligand R 2 ∗ dad affords a mononuclear, paramagnetic 17-electron product, CpMoCl 2 ( R 2 ∗ dad ) , whereas as-ox leads to the isolation of a dinuclear compound where only one molecule of ligand has been added per two Mo atoms, Cp 2 Mo 2 Cl 4 (as-ox). In the presence of free as-ox, this compound coexists with the paramagnetic mononuclear complex in solution. Both products are capable of controlling the radical polymerization of styrene under typical atom transfer radical…
Hybrid Magnetic Materials Based on Nitroxide Free Radicals and Extended Oxalato‐Bridged Bimetallic Networks
2005
A series of hybrid organic-inorganic magnets of formula p-rad[MIICr(ox)3] [M = Mn (1), Co (2), Ni (3), Zn (4)] and m-rad[MIICr(ox)3] [M = Mn (5), Co (6)], in which N-methylpyridinium cations bearing a nitronyl nitroxide moiety in positions 3 (m-rad) or 4 (p-rad) of the pyridine ring coexist with the 2D honeycomb-like oxalato-bridged bimetallic lattice, has been prepared and studied by AC and DC magnetic susceptibility measurements and EPR spectroscopy. In general, the physical properties of these magnets are not altered significantly by the insertion of the nitronyl nitroxide radicals although these paramagnetic molecules seem to interact weakly with the inorganic network as demonstrated by…
Heparin–polynitroxides: Synthesis and preliminary evaluation as cardiovascular EPR/MR imaging probes and extracellular space-targeted antioxidants
2011
We report here the synthesis of heparin-polynitroxide derivatives (HPNs) in which nitroxide moieties are linked either to uronic acid or glycosamine residues of the heparin macromolecule. HPNs have low anticoagulant activity, possess superoxide scavenging properties, bind to the vascular endothelium/extra-cellular matrix and can be detected by EPR and MRI techniques. As the vascular wall-targeted redox-active paramagnetic compounds, HPNs may have both diagnostic (molecular MRI) and therapeutic (ecSOD mimics) applications.
Preparation of pH sensitive poly(vinilydenefluoride) porous membranes by grafting of acrylic acid assisted by supercritical carbon dioxide
2012
Free radical grafting of acrylic acid (AA) on poly(vinilydenefluoride) (PVDF) porous membranes was studied at 65°C using supercritical carbon dioxide (scCO 2) as a solvent and delivery agent. The process was initiated by the thermal decomposition of benzoylperoxide (BPO). Spectroscopic analyses confirmed the presence of poly(AA) chains linked to treated membranes. The mass fraction of grafted AA increased with grafting time and BPO concentration while it decreased when the density of the fluid phase was enhanced. A not-monotonic trend was obtained when the effect of the initial AA concentration was studied. The grafting process was accompanied by a reduction of the crystallinity of the PVDF…
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 …
Novel poly (ionic liquid)-based anion exchange membranes for efficient and rapid acid recovery from industrial waste
2020
Abstract Owing to the less energy consumption, positive impact on the environment, and prospect of providing clean water resources, anion exchange membranes (AEMs) are promising materials for acid recovery from various industrial wastewater/effluent. Based on the diffusion dialysis process, AEMs selectively allow rapid proton permeation while efficiently retaining metal ions. To enhance the efficiency of the acid recovery process, precise control of macromolecular architecture and chemical composition that enables high hydrophilicity, proton conductivity through the membrane, and ion exchange capacity is required. In this direction, we report on the one-step fabrication of novel poly (ionic…
Leach-Proof Sol–Gel Microcapsules as Curing Agents for One-Pot Thermosetting Resins
2013
The sol-gel microencapsulation of free-radical initiator benzoyl peroxide in sol-gel methyl-modified silica microcapsules of core/shell geometry allows curing of acrylate-based polyurethane and polyester resin formulations sprayed from a pressurized can without the need to compartmentalize reactants from the initiator to cross-link. These results open the route to widespread application of sol-gel microcapsules to efficiently cure polymer and composite mixtures that are widely used as functional coatings, molding compounds, adhesives, and sealants.
Kinetic Analysis of “Living” Polymerization Systems Exhibiting Slow Equilibria. 3. “Associative” Mechanism of Group Transfer Polymerization and Ion P…
1996
The averages of the molecular weight distribution are derived for a “living” polymerization process which proceeds via active and “dormant” species and where the active species are formed by addition of a catalyst to a “dormant” species. Such a mechanism is applicable to group transfer and “living” cationic polymerizations (assuming that ion pairs are formed exclusively in the latter case). Both equilibrium and nonequilibrium initial conditions are used for the calculation. The results are very similar to those obtained for degenerative transfer (i.e., direct exchange of activity between active and “dormant” species). The dominating parameter is β = k2/(kpI0), where k2 and kp are the rate c…