A unique transurf in styrene emulsion polymerization

The surface-active, chain transfer agent (‘transurf’) sodium ω-mercapto-decane sulfonate, SMDSo, was synthesized, purified, and its interfacial properties determined. The compound acted normally in styrene emulsion polymerization to produce extremely stable colloids containing only sulfonate ionic surface functional groups. It was then used to control the surface charge density of a model polystyrene colloid by means of seeded emulsion polymerization. Surface charge could thus be increased 16-fold over that of the seed particles, and was due solely to sulfonate groups introduced by the SMDSo. Unlike most conventional emulsion polymerizations, this technique allows one to control surface chemistry independently of particle size. To cite this article: C.C. Fifield, R.M. Fitch, C. R. Chimie 6 (2003).     

Cosurfactant effects on the microemulsion polymerization of styrene

The polymerization of styrene in o/w microemulsions stabilized with dodecyltrimethylammonium bromide (DTAB) with or without cosurfactant (n-butanol, n-hexanol or n-octanol) is examined here. The addition of a cosurfactant enhances the one-phase region in the order: n-butanol > n-hexanol > n-octanol. The kinetics of polymerization slows down in the presence of the alcohol. With the alcohol, the molar masses increase, but no particular trend was noticed on particle size of the lattices. However, by changing the surfactant counter-ion to chloride, alcohol effects on the kinetics almost vanish. Possible explanations to these results are given here. To cite this article: J.E. Puig et al., C. R. Chimie 6 (2003).     

Maleic diamide polymerizable surfactants. Applications in emulsion polymerization

A series of new polymerizable non-ionic and ionic surfactants (surfmers) with amides groups on both sides of the C=C double bonds have been prepared upon reaction of maleic isoimide carrying a long alkyl chain (or a benzyl group) with a hydrophilic amine derivative. Their critical micellar concentration (CMC) was measured with a surface tensiometer. They have been engaged in batch emulsion polymerization of styrene, and semi-batch seeded copolymerization of styrene and butyl acrylate, giving stable latexes during the polymerization process, and upon extraction with ethanol, showing a high rate of incorporation at the particle surface. However these surfmers do not confer good steric stabilization properties, which may be expected from the use of non-ionic surfactants. To cite this article: I. Klimenkovs et al., C. R. Chimie 6 (2003).     

Viscoelastic behaviour of butyl acrylate/styrene/2-hydroxyethyl methacrylate/acrylic acid latices thickened with associative thickeners

The rheological behaviour of butyl acrylate/styrene/acrylic acid latices thickened with a hydrophobically modified ethoxylated polyurethane (HEUR) or hydrophobically modified alkali-soluble polyacrylate emulsion (HASE) was investigated. While the pseudoplastic character of frequency dependence of complex viscosity was similar for both thickeners, viscoelastic behaviour, expressed as the ratio of loss and storage moduli, significantly differed, indicating that the HEUR molecules, unlike swollen HASE particles, create a viscoelastic space structure. The increase in hydrophilicity of the particle surface, achieved by incorporation of 2-hydroxyethyl methacrylate (HEMA) monomer into the latex copolymer reduced the viscoelasticity of latices thickened with HEUR, but not of those thickened with HASE. This confirms that adsorption of hydrophobic end-groups on particle surface is important for thickening of latices with HEUR and that a physical network of latex particles interconnected by the thickener macromolecules is formed. To cite this article: O. Quadrat et al., C. R. Chimie 6 (2003).     

Anionic surfmers in mini-emulsion polymerisation

Mini-emulsion polymerisation of styrene or methylmethacrylate, initiated with ammonium persulphate, have been carried out, in the presence of hexadecane or of polymethylmethacrylate as hydrophobic costabilizer, and the simple hemiester of linear dodecyl alcohol and maleic anhydride, or polymerisable surfactants (surfmers) derived from the condensation of succinic anhydride and either hydroxy propylmethacrylate (MAES), or hydroxyethylmethacrylate (ABS). While the pure surfmers have not so good surface activity, from surface tension measurements, stable mini-emulsion droplets are obtained using a mixture with low amounts of SDS, which have diameters of about 100–200 nm, which remain stable upon polymerisation. Most of the surfmers remain grafted onto the particle surface, thus conferring to these particles strong stability in the various tests. However, due to the high water solubility of the surfmers, another part remains in the serum as unconverted monomer or water-soluble polymers. To cite this article: A. Guyot et al., C.R. Chimie 6 (2003).     

The effect of first-stage polymer Tg on the morphology and thermomechanical properties of structured polymer latex particles

A series of heterogeneous latexes having stage ratios of 40:60 between the first and second stage polymers were prepared by emulsion polymerization. The first-stage polymers were non-polar S-BuA with T_gs ranging from + 100 °C to + 20 °C and the second stage polymer was polar MMA–BuA–MAA having a T_g of 20 °C. The latex particle morphologies were studied using TEM and the thermomechanical properties of the resulting latex films were studied with DSC and DMA. Calculated diffusion rates for propagating species during the reactions were correlated to the observed morphologies and to the amount of interphase in the latex particles. To cite this article: O.J. Karlsson et al., C. R. Chimie 6 (2003).     

Hybrid copolymer latexes cross-linked with methacryloxy propyl trimethoxy silane. Film formation and mechanical properties

We describe in this work the copolymerization reaction of 3-trimethoxysilyl propyl methacrylate (MPS) with styrene (Styr.) and n-butyl acrylate (BuA) monomers through emulsion polymerization. The so-produced hybrid copolymer (P(BuA-co-MPS)) and terpolymer (P(Styr-co-BuA-co-MPS)) latexes were cast into films that displayed a good optical transparency. The copolymers microstructure in the films was characterized by FTIR, ¹³C and ²⁹Si solid state NMR spectroscopies, and was found to be highly dependent on parameters such as the monomer feed composition, the suspension pH and the silane addition profile. The films obtained from the hybrid latexes showed improved dynamic mechanical properties indicating that a reinforcing organo-mineral network had formed in the composite materials. The dynamic modulus of the hybrids increased with increasing silane contents while, concurrently, the tan δ peak shifted to higher temperatures, broadened and decreased in intensity. To cite this article: S. Vitry et al., C. R. Chimie 6 (2003).     

Monomer compartmentalisation in miniemulsion polymerisation studied by infrared spectroscopy

Miniemulsion polymerisations of styrene and butyl methacrylate were carried out in order to study mass transfer during the reaction. An in-line Attenuated Total Reflectance–Fourier Transform Infrared (ATR–FTIR) probe was used to follow the reactions, and the collected spectra were used to identify the different species that appeared and disappeared during polymerisation. The results show that the droplets were completely compartmentalized during the reaction, and that even when blends of droplets with different composition were polymerised together, no detectable levels of copolymer were formed. To cite this article: K. Ouzineb et al., C. R. Chimie 6 (2003).     

Poly(N-ethylmethacrylamide) thermally-sensitive microgel latexes: effect of the nature of the crosslinker on the polymerization kinetics and physicochemical properties

Thermally-sensitive crosslinked submicronic particles were prepared by an emulsion/precipitation process of N-ethylmethacrylamide (NEMAM), using potassium persulphate as initiator and four different crosslinkers; ethylene glycol dimethacrylate (EGDMA), 1,3-butanediol dimethacrylate (1,3-BDDMA), 1,4-butanediol dimethacrylate (1,4-BDDMA) and tetraethylene glycol dimethacrylate (TEGDMA). At first, polymerization kinetics was studied by NMR, revealing the negligible effect of the crosslinker nature. On the contrary, the water-soluble polymer amounts, the final hydrodynamic particle size, the swelling ability, the electrokinetic properties were found to be dependent upon the nature of crosslinker. The final latexes were found to be narrowly size distributed irrespective of the crosslinker agent’s chemical nature. In this study, the water solubility of the cross-linker was reported to be an important criterion, but other factors, such as diffusion and reactivity, have to be taken into consideration. To cite this article: P. Hazot et al., C. R. Chimie 6 (2003).     

Particle size distribution in mini-emulsion polymerization

The particle size distribution polydispersities of a number of macro- and mini-emulsion latexes are reported. In cases where the macro-emulsion and mini-emulsions were produced under very nearly identical conditions, the mini-emulsion will have a polydispersity equal to, or only very slightly greater than, the equivalent macro-emulsion. To cite this article: K. Landfester et al., C. R. Chimie 6 (2003).     

Recent progress in nitroxide-mediated polymerizations in miniemulsion

Recent developments in nitroxide-mediated polymerizations conducted in emulsion and miniemulsion have advanced the field across a range of both experimental and theoretical fronts. This article reviews progress in bicomponent initiating systems (including use of camphorsulfonic acid to enhance rate), unimolecular initiating systems, miniemulsions not requiring the use of volatile costabilizers, polymerization of acrylates, mathematical modeling and simulation, and theoretical understanding with regards to issues such as compartmentalization, preservation of polymer chain livingness, the role of aqueous phase kinetics and phase partitioning. These topics are discussed and analyzed to present an integrated portrait of the current status of nitroxide-mediated polymerizations in emulsion/miniemulsion and to identify the most pressing concerns, issues, and opportunities. To cite this article: M.F. Cunningham, C. R. Chimie 6 (2003).     

Effect of the surfactant concentration on the kinetics of oil in water microemulsion polymerization: a case study with butyl acrylate

A comprehensive investigation of aqueous microemulsion polymerization of butyl acrylate at high surfactant concentrations by means of reaction calorimetry and dynamic light scattering revealed unexpected results with regard to polymerization kinetics and colloidal properties of the final latexes. Particularly, with increasing surfactant concentrations, a decrease in the overall rate of polymerization accompanied by an increasing incubation time of the polymerization and increasing average particle sizes in the final latexes has been observed. Based on reviewing former results on microemulsions and microemulsion polymerizations published in the open literature and the presentation of new experimental results an attempt is made to explain the experimental results consistently with a particle nucleation mechanism based on the classical nucleation theory. To cite this article: K. Tauer et al., C. R. Chimie 6 (2003).     

Synthesis and reactivity of new heterodinuclear iron/rhenium Cx complexes of the formula (η-C5Me5)Re(NO)(PPh3)(CC)n(η-dppe)Fe(η-C5Me5) (n = 3, 4): Redox properties and a dicobalt hexacarbonyl adduct

We report in this communication the synthesis and characterization of two Fe/Re heterodinuclear complexes 3_n of formula (η⁵-C₅Me₅)Re(NO)(PPh₃)(CC)_n(η²-dppe)Fe(η⁵-C₅Me₅) (n = 3, 4) as well as the hexacarbonyl dicobalt adduct (4) of the hexatriynediyl complex 3₃. We show by cyclic voltammetry that the “electronic communication” between the organometallic endgroups and thereby the thermodynamic stability of the corresponding mixed-valent (MV) parent 3_n⁺ is strongly influenced by bridge extension or by complexation of the [Co₂(CO)₆] fragment. In the case of the hexatriynediyl complex, the MV complex 3₃⁺ or 4 can be isolated by performing the chemical oxidation of 3₃ at low temperature. Spectroscopic studies of this compound and of other stable oxidized redox congeners should now help us to unravel how bridge extension modifies the electronic communication between the different redox-active endgroups in this family of unsymmetrically-substituted polyynediyl compounds.     

Synthesis and reactivity of neodymium(III) amido-tethered N-heterocyclic carbene complexes

The reaction of the heteroleptic Nd(III) iodide, [Nd(L′)(N″)(μ-I)] with the potassium salts of primary aryl amides [KN(H)Ar′] or [KN(H)Ar^*] affords heteroleptic, structurally characterised, low-coordinate neodymium amides [Nd(L′)(N″)(N(H)Ar′)] and [Nd(L′)(N″)(N(H)Ar^*)] cleanly (L′ = t-BuNCH₂CH₂[C{NC(SiMe₃)CHNt-Bu}], N″ = N(SiMe₃)₂, Ar′ = 2,6-Dipp₂C₆H₃, Dipp = 2,6-Prⁱ₂C₆H₃, Ar^* = 2,6-(2,4,6-Prⁱ₃C₆H₂)₂C₆H₃). The potassium terphenyl primary amide [KN(H)Ar^*] is readily prepared and isolated, and structurally characterised. Treatment of these primary amide-containing compounds with alkali metal alkyl salts results in ligand exchange to give alkali metal primary amides and intractable heteroleptic Nd(III) alkyl compounds of the form [Nd(L′)(N″)(R)] (R = CH₂SiMe₃, Me). Attempted deprotonation of the Nd-bound primary amide in [Nd(L′)(N″)(N(H)Ar^*)] with the less nucleophilic phosphazene superbase Bu^tNP{NP(NMe₂)₃}₃ resulted in indiscriminate deprotonations of peripheral ligand CH groups.     

Effect of gleysation on remobilization of radionuclides in waterlogged soils

Joint leaching of iron and other macro- and microelements including radionuclides from radioactively contaminated floodplain soil of the Yenisei River is studied on miniecosystems. In developing anaerobic conditions, the redox potential E_h decreased to +140 mV, causing partial reduction of iron and solubilisation of iron hydrous oxide and organomineral films of the soil. Leaching of stable elements and radionuclides with water proceeds parallel to that of iron. To accelerate reductive mobilization of iron, 0.4% aqueous ascorbic acid was used instead of water as the leaching liquid phase. In this case, E_h approached –60 mV, and the leaching of stable and radioactive elements considerably increased, the effect being most pronounced for plutonium. To cite this article: E.K. Legin et al., C. R. Chimie 7 (2004).

Résumé

Effet du passage en milieu anaérobie sur la mobilisation des radionucléides dans les sols humides. La lixiviation simultanée du fer et d’autres éléments de sols contaminés de la vallée de la rivière Yénései a été étudiée. En imposant des conditions anaérobies, le potentiel redox chute à 140 mV, causant une réduction partielle du fer trivalent et la solubilisation de l’hydroxyde de fer et du film organominéral du sol. Les lixiviations du fer, des autres éléments et, par conséquent, des radionucléides contaminant le sol vont de pair. Pour accélérer la mobilisation réductive du fer, une solution d’acide ascorbique à 0,4% a été utilisée à la place de l’eau. Dans ces conditions, la valeur de E_h approche –60 mV et la lixiviation des éléments augmente considérablement, cet effet étant plus prononcé pour le plutonium. Pour citer cet article : E.K. Legin et al., C. R. Chimie 7 (2004).     

Substituent Effects on Binding Constants of Carotenoids to n-Heptane/AOT Reverse Micelles

The absorption spectra of 6′-apo-β-caroten-6′-ol (1), 6′-apo-β-caroten-6′-oic acid (2), and ethyl 6′-apo-β-caroten-6′-oate (3) were analyzed in homogeneous media and in reversed micelles of AOT (sodium 1,4-bis(2-ethylhexyl) sulfosuccinate) in n-heptane. The possible solute–solvent interactions of these compounds were analyzed in pure solvents by Taft and Kamlet's solvatochromic comparison method. These carotenoids show sensitivity similar to that of medium polarity-polarizability as measured by π*. Moreover, the absorption spectra of carotenoid 3 and to much less extent carotenoid 2 display broadening of the visible bands induced by polar solvents characteristic of carotenoids that contain a carbonyl functional group in conjugation with the carbon–carbon π-electron system. They are also sensitive to the ability of the solvent to accept protons in a hydrogen bond interaction measured by β. This sensitivity follows the expected order: 2>1>3. In the reverse micellar system, while the spectra for 3 remain unchanged, the intensity of the absorption band characteristic of n-heptane for 1 and 2 decreases as the AOT concentration increases, and a new band develops. This new band is attributed to the solute bound to the micelle interface. These changes allowed us to determine the binding constant (K_b) between these compounds and AOT. At W₀=[H₂O]/[AOT]=0 the values of K_b of 326±5 and 6.2±0.3 were found for the acid 2 and the alcohol 1, respectively. The strength of binding is interpreted considering their hydrogen-bond donor ability and the solubility in the organic pseudophase. For 1K_bdecreases as W₀ is increased, while for 2 no variation was observed. These effects are discussed in terms of carotenoid–water competition for interfacial binding sites.     

New rheological developments for reactive processing of poly(ε-caprolactone)

This short review aims to show how an integrated activity on reactive processing have been developed these last years in our laboratory. We can say that the originality of this approach is based on combining developments in chemistry, in line instrumentation, and rheology aspects. Our rheological works can be divided into four important contributions: rheo-physics, rheo-chemistry, rheo-mixing and rheo-processing. These different parts are illustrated from the ε-caprolactone polymerisation in bulk and dispersed media. Rheo-physics studies allowed us to calculate the molecular weight distribution and chain structures of in situ polymerised poly(ε-caprolactone) samples. From rheo-chemistry works, we are now able to predict the variation of the complex shear modulus versus the extent of the polymerisation. The developments of new rheological tools such as rheo-mixer enable us to investigate complex mixing situations encountered in reactive polymer blends and formulations. Lastly, a rheo-processing approach based on the in-line measurement of the viscosity in a slit rheometer at the die exit of the extruder allows us to envisage its application to the experimental control of the reactive processing in extruder. To cite this article: P. Cassagnau et al., C. R. Chimie 9 (2006).     

Synthesis of polydimethylsiloxane microemulsions by self-catalyzed hydrolysis/condensation of dichlorodimethylsilane

The preparation of PDMS microemulsions was carried out by adding at controlled rate dichlorodimethylsilane (DCMS) in a solution of sodium dodecylpolyoxyethylene(8) sulphate. The instantaneous hydrolysis of DCMS and subsequent condensation of the corresponding dihydroxysilane generate dispersions of cyclosiloxanes of small lengths (4 to 6 D units). The high load of chloride ions released during the hydrolysis step requires the presence of the above-mentioned electrosteric surfactant to avoid rapid coagulation of the dispersion. In addition, its sulphate end-group captures a proton that catalyses the ring-opening polymerization of cyclosiloxane as well as the polycondensation of disilanol PDMS chains. Final particles exhibit a diameter of about 50 nm for a polydispersity index of less than 1.1. They are constituted of PDMS chains exclusively linear ( ; ) and of small cycles in low contents (less than 5 wt% in the best conditions). To cite this article: G. Palaprat, F. Ganachaud, C. R. Chimie 6 (2003).     

Polymer phase separation in composite latex particles. 1. Considerations for the nucleation and growth mechanism

This study addresses the question of how polymer phase separation takes place during polymerization reactions within composite latex particles. Experiments resulted in acrylic/styrene latices with two-phase structures that were analyzed via TEM. Those that resulted from the use of semi-batch reactions allowed us to observe domains that likely did not undergo phase rearrangement after they were formed within the particles. We computed the critical size of the phase-separated domains by assuming that the nucleation and growth mechanism applied to such experiments. We also computed how much these domains would increase in size by subsequent polymerization within those domains. Comparisons of predicted and experimental domain sizes and distributions showed quite reasonable agreement. The domains formed in latex particles of about 350 nm were in the 30–50-nm range. Despite the close agreement between theory and experiment, we are not convinced that phase separation occurs by nucleation and growth, as it appears to us that given the relative rates of reaction and polymer diffusion, phase separation events will often be forced to occur within the spinodal region of the phase diagram. To cite this article: J.M. Stubbs, C. R. Chimie 6 (2003).     

On the optimal surfmer addition profile in emulsion polymerisation

In this work, the optimal surfmer feeding profile for stabilizing a high-solid-content acrylic latex with a non-ionic alkenyl functional ^TMMaxemul 5011 was calculated. For this purpose, the model developed by de la Cal and Asua (J. Polym. Sci., Part A: Polym. Chem. 39 (2001) 585) was used. It was observed that, in spite of the low reactivity of the surfmer, it was possible to increase substantially the surfmer conversion using an optimal surfmer addition policy. To cite this article: E. Aramendia et al., C. R. Chimie 6 (2003).