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).     

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).     

Polyimide–silica hybrid coatings: morphological,mechanical, and thermal investigations

In this study, polyimide–silica (PI–silica) based hybrid coating compositions were prepared from tetraethoxysilane (TEOS), γ‐glycidyloxypropyl trimethoxy silane (GOTMS), and polyamic acid (PAA) via a combination of sol–gel and thermal imidization techniques. PAA was synthesized from 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) and 3,3'‐Diaminodiphenyl sulfone (DDS) in N‐Methyl‐2‐pyrrolidone (NMP). The silica content in the hybrid coatings was varied from 0 to 20 wt%. The structural characterization of the hybrid coatings was performed using FTIR and ²⁹Si‐NMR spectroscopies. Results from both pendulum hardness and micro indentation test show that the hardness of hybrid coatings improves with the increase in silica content. The tensile tests also demonstrated that the mechanical properties at low silica content are rather striking. Their surface morphologies were characterized by scanning electron microscopy (SEM). SEM studies revealed that inorganic particles were distributed homogenously through the PI matrix. It was also found that, incorporation of the silica domains increased the thermal stability of the hybrid coatings. Copyright © 2007 John Wiley & Sons, Ltd.     

Oligomeric Alkoxysilanes with Cagelike Hybrids as Cores: Designed Precursors of Nanohybrid Materials

Well‐defined alkoxysilane oligomers containing a cagelike carbosiloxane core were synthesized and used as novel building blocks for the formation of siloxane‐based hybrid networks. These oligomers were synthesized from the cagelike trimer derived from bis(triethoxysilyl)methane by silylation with mono‐, di‐, and triethoxychlorosilanes ((EtO)_nMe_3?nSiCl, n=1, 2, and 3). Hybrid xerogels were prepared by hydrolysis and polycondensation of these oligomers under acidic conditions. The structures of the products varied depending on the number of alkoxy groups (n). When n=2 and 3, microporous xerogels (BET surface areas of 820 and 510 m² g^?1, respectively) were obtained, whereas a nonporous xerogel was obtained when n=1. ²⁹Si NMR spectroscopic analysis suggested that partial rearrangement of the siloxane networks, which accompanied the cleavage of the Si–O–Si linkages, occurred during the polycondensation processes. By using an amphiphilic triblock copolymer surfactant as a structure‐directing agent, hybrid thin films with a 2D hexagonal mesostructure were obtained when n=2 and 3. These results provide important insight into the rational synthesis of molecularly designed hybrid materials by sol–gel chemistry.     

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).     

Influence of Alkylene Chain Length on the Morphology of Chiral Bridged Silsesquioxanes

Four chiral diureido derivatives of trans-(1R,2R)- and trans-(1S,2S)-diaminocyclohexane with different carbon chain lengths (n = 3, 4, 5, 10) were synthesized and were hydrolyzed in aqueous acidic conditions in order to examine the role of the carbon chain spacer on the resulting hybrid bridged silsesquioxanes. Solid state NMR (²⁹Si and ¹³C) studies demonstrated the presence of covalently bonded organo-bridged silica networks in these materials. Scanning electron microscopy (SEM) showed the materials obtained from the short chain derivatives to consist of fibers (n = 3 and 4). In contrast, plate-like shapes were formed from the longer chain precursors (n = 5 and 10). A lamellar structure was observed via transmission electron microscopy (TEM) for the hybrid obtained from the precursor with the longest chain (n = 10). This lamellar form was confirmed by powder X-ray diffraction (PXRD) measurement of the hybrid.     

A Designed 5‐Fluorouracil‐Based Bridged Silsesquioxane as an Autonomous Acid‐Triggered Drug‐Delivery System

Two new prodrugs, bearing two and three 5‐fluorouracil (5‐FU) units, respectively, have been synthesized and were shown to efficiently treat human breast cancer cells. In addition to 5‐FU, they were intended to form complexes through H‐bonds to an organo‐bridged silane prior to hydrolysis‐condensation through sol–gel processes to construct acid‐responsive bridged silsesquioxanes (BS). Whereas 5‐FU itself and the prodrug bearing two 5‐FU units completely leached out from the corresponding materials, the prodrug bearing three 5‐FU units was successfully maintained in the resulting BS. Solid‐state NMR (²⁹Si and ¹³C) spectroscopy show that the organic fragments of the organo‐bridged silane are retained in the hybrid through covalent bonding and the ¹H NMR spectroscopic analysis provides evidence for the hydrogen‐bonding interactions between the prodrug bearing three 5‐FU units and the triazine‐based hybrid matrix. The complex in the BS is not affected under neutral medium and operates under acidic conditions even under pH as high as 5 to deliver the drug as demonstrated by HPLC analysis and confirmed by FTIR and ¹³C NMR spectroscopic studies. Such functional BS are promising materials as carriers to avoid the side effects of the anticancer drug 5‐FU thanks to a controlled and targeted drug delivery.     

Organic–inorganic hybrid materials. I. Characterization and degradation of poly(imide–silica) hybrids

Poly(imide–silica) hybrid materials with covalent bonds were prepared by (3-aminopropyl)methyldiethoxysilane (APrMDEOS) terminated amic acid, water, and tetramethoxysilane (TMOS) via a sol–gel technique. Infrared (IR), ²⁹Si and ¹³C CP/MAS nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA) were used to study hybrids containing various proportions of TMOS and hydrolysis ratios. The microstructure and chain mobility of hybrids were investigated by proton spin–spin relaxation T₂ measurements. The apparent activation energy E_a for degradation of hybrids in air was studied by the van Krevelen method. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2275–2284, 1999     

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).     

Polyimide–Silica Gel Hybrids Containing Metal Salts: Preparation via the Sol–Gel Reaction

A facile preparation of polyimide–silica gel hybrids by the simultaneous in-situ formation of polyimides during the hydrolysis–condensation of tetramethoxysilane (TMOS) is reported here. The hydrolysis and condensation of TMOS was carried out in a solution of DMAc containing 5% LiCl, CaCl₂ or ZnCl₂ and the seven-membered cyclic polyimide intermediate. The seven-membered cyclic intermediates, precursors of polyimides, were derived from the low-temperature polycondensation of dianhydrides [benzophenonetetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMDA), and 4,4-bis(hexafluoroisopropylidene)phthalic dianhydride (6FDA)] and di-isocyanates [isophorone di-isocyanate (IPDI), toluene di-isocyanate (TDI), hexamethylene di-isocyanate (HDI) and 4,4′-diphenylmethane di-isocyanate (MDI)]. These intermediates could readily be converted to the corresponding polyimides. Films were cast from the resulting mixtures and the solvent was gradually evaporated at 130 °C to result in the formation of clear, transparent, pale yellow or amber-colored hybrid films in which the salts were dispersed at the molecular level. Pyrolysis of polyimide–silica gel hybrids at 600 °C gave mesoporous silica. Silica gel obtained from hybrids HPI-8 (containing no salt) and HPI-11 (containing ZnCl₂) had a pore radius (BJH method) of 2.9 nm, while that from hybrid HPI-9 (containing LiCl) had a pore radius of 11.4 nm. The surface areas (BET method) obtained were 203 m² g⁻¹, 19 m² g⁻¹ and 285 m² g⁻¹, while the pore volumes were 0.373 cm³ g⁻¹, 0.158 cm³ g⁻¹ and 0.387 cm³ g⁻¹, respectively, for samples obtained from hybrids HPI-8, HPI-9 and HPI-11. © 1997 by John Wiley & Sons, Ltd.     

Effect of Processing Parameters on the Optical Properties of TiO<Subscript>2</Subscript>/Ormosil Planar Waveguide

Hybrid TiO₂/ormosil waveguiding films have been prepared by the sol-gel method at low thermal treatment temperature of 150C. The influence of processing parameters including the molar ratios of titanium butoxide (Ti(OBu)₄)/3-glycidoxypropyltrimethoxysilane (GLYMO) and H₂O/Ti(OBu)₄ (expressed as R), especially aging of sol on the optical properties was investigated. The optical properties of films were measured with scanning electron microscope (SEM), UV/VIS/NIR spectrophotometer (UV-Vis), m-line and the scattering-detection method. The results indicate that the film thickness increases with the increase of sol aging time, but the variation of refractive index as a function of sol aging time depends on the relative ratios of GLYMO to Ti(OBu)₄. Higher transmittance and lower attenuation of the planar waveguide can be obtained in the sol with lower Ti(OBu)₄ contents and shorter aging time.     

The synergistic effect of cobalt-dicarbollide anions on the extraction of M lanthanide cations by Calix[4]arenes: a molecular dynamics study at the water–‘oil’ interface

We report molecular dynamics studies on the effect of CCD^– (chlorinated cobalt-dicarbollide) anions on the Eu³⁺ lanthanide cation extraction by a calix[4]arene-CMPO ligand L, focusing on the water–‘oil’ interface, where ‘oil’ is modelled by chloroform. The free L ligand and its EuL³⁺ complex are found to adsorb and to concentrate at the interface, but are too hydrophilic to be extracted. Addition of CCD^– anions in diluted conditions (either covalent linked to L or as separated CCD^– H₃O⁺ ions) also leads to adsorption of these species at the interface. However, at high concentrations, CCD^– anions saturate the interface and promote the extraction of EuL³⁺ to the oil phase. Another important feature concerns the uncomplexed Eu(CCD)₃ salt: accumulation of CCD^– anions at the interface creates a negative potential which attracts the hydrated Eu³⁺ ions, therefore facilitating their complexation by interfacial ligands. These features allow us to better understand the synergistic effect of lipophilic anions in the assisted liquid-liquid extraction of trivalent M³⁺ lanthanide or actinide cations. To cite this article: B. Coupez, G. Wipf, C. R. Chimie 7 (2004).

Résumé

Synergie due aux anions dicarbollides lors de l’extraction d’ions lanthanides M³⁺ par des calix[4]arènes : simulations de dynamique moléculaire à l’interface eau–« huile ». Nous étudions par simulations de dynamique moléculaire l’effet de synergie dû aux anions CCD^– (cobalt-dicarbollides) lors de l’extraction de Eu³⁺ par un calix [4]arène L, en se focalisant sur l’interface eau–« huile », l’huile étant modélisée par du chloroforme. On montre que le ligand L et son complexe EuL³⁺ s’adsorbent à l’interface, mais sont trop hydrophiles pour être extraits. L’addition d’anions CCD^– (qu’ils soient sous la forme d’ions CCD^– H₃O⁺ séparés ou greffés de façon covalente au calixarène) conduit aussi à l’adsorption de ces espèces à l’interface. Cependant, aux plus fortes concentrations, les anions CCD^– saturent l’interface et induisent l’extraction du complexe EuL³⁺ vers l’huile. Un autre résultat remarquable concerne les sels Eu(CCD)₃ : l’accumulation des anions CCD^– à l’interface y crée un potentiel négatif, ce qui attire les cations Eu³⁺ et facilite ainsi leur complexation par des ligands à l’interface. Ces résultats permettent de mieux comprendre l’effet de synergie dû aux anions CCD^– lors de l’extraction d’ions lanthanides ou actinides M³⁺ et, d’une manière générale, ce qui se passe à l’interface entre l’eau et des liquides non miscibles. Pour citer cet article : B. Coupez, G. Wipf, C. R. Chimie 7 (2004).     

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.     

Preparation of stable second‐order nonlinear optical films by sol–gel technique

A stable nonlinear optical (NLO) film containing “T” type alkoxysilane dye was prepared by sol–gel technology. This crosslinked “T” type alkoxysilane dye was synthesized and fully characterized by FTIR, UV–Vis spectra, and ¹H‐NMR. Followed by hydrolysis and copolymerization processes of the alkoxysilane with γ‐glycidoxypropyl trimethoxysilane (KH560) and tetraethoxysilane (TEOS), high quality inorganic–organic hybrid second‐order NLO films were obtained by spin coating. The “T” type structure of the alkoxysilane was found to be effective for improving the temporal stability of the optical nonlinearity due to the reduction in the relaxation of the chromophore in the film materials. Copyright © 2009 John Wiley & Sons, Ltd.     

Polymer–filler interactions in sol–gel derived polymer/silica hybrid nanocomposites

The effect of polymer–filler interaction on solvent swelling and dynamic mechanical properties of the sol–gel derived acrylic rubber (ACM)/silica, epoxidized natural rubber (ENR)/silica, and poly (vinyl alcohol) (PVA)/silica hybrid nanocomposites has been described for the first time. Tetraethoxysilane (TEOS) at three different concentrations (10, 30, and 50 wt %) was used as the precursor for in situ silica generation. Equilibrium swelling of the hybrid nanocomposites in respective solvents at ambient condition showed highest volume fraction of the polymer in the swollen gel in PVA/silica system and least in ACM/silica, with ENR/silica recording an intermediate value. The Kraus constant (C) also followed a similar trend. In dynamic mechanical analysis, the storage modulus dropped at higher strain (>1%), which indicated disengagement of polymer segments from the filler surfaces. This drop was maximum in ACM/silica, intermediate in ENR/silica, and minimum in PVA/silica, both at 50 and 70 °C. The drop in modulus with theoretical volume fraction of silica (ϕ) was interpreted with the help of a Power law model ΔE′ = a₁ϕ, where a₁ was a constant and b₁ was primarily a filler attachment parameter. Strain dependence of loss modulus was observed in ACM/silica hybrid nanocomposites, while ENR/silica and PVA/silica nanocomposites showed almost strain‐independent behavior. The storage modulus showed sharp increase with increasing frequency in ACM/silica system, while that was lower in both ENR/silica (at higher frequency) and PVA/silica systems (in the entire frequency spectrum). The increase in modulus with ϕ also followed similar model ΔE′ = a₂ϕ proposed in the strain sweep mode. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2399–2412, 2005     

Design of In Vitro Bioactive Hybrid Materials from the First Generation of Amine Dendrimers as Nanobuilding Blocks

In this work, the first generation of poly(propyleneimine) dendrimers were functionalized with alkoxysilane terminal groups and subjected to one of two different sol–gel process that followed two different catalytic pathways, that is base‐ or acid‐catalyzed pathways. Thus, two series of new organic–inorganic hybrid materials were obtained in the form of monolithic pieces with differences in terms of both morphology and silanol content, which originated from the different sol–gel pathway that was followed. Moreover, calcium ions were added into the hybrid composition to promote in vitro bioactivity and phosphorous sources were used during the sol–gel step to obtain an earlier bioactive response. Characterization of these organic–inorganic hybrid materials was performed by means of thermogravimetric and elemental analyses, Fourier transform infrared spectroscopy (FTIR), solid state ¹³C, ²⁹Si and ³¹P magic‐angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, N₂‐adsorption isotherms, mercury‐intrusion porosimetry, and ζ‐potential measurements. The in vitro bioactivity of the dendritic hybrid networks was evaluated by soaking the materials in simulated body fluid and the results were explained in terms of the composition of the hybrids and the sol–gel route that was followed to prepare them.     

Development of Photochromic Coatings on Polycarbonate

New photochromic materials based on heteropolyoxometallates (HPOM) incorporated into a hybrid organic-inorganic binder were prepared and coated onto polycarbonate (PC) substrates. The hybrid binder was formed through the controlled hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and bisphenol A (BPA) by the sol–gel technique. The photochromic behavior of the materials was investigated by using ultraviolet-visible (UV-Vis) absorption spectroscopy and color index values. The results indicated that the films were reduced photochemically to yield a blue species under UV irradiation, with the film color changing to deep blue with increasing time, and HPOM and BPA content. The photosensitivity of several films with molybdenum HPOM showed faster coloration and much slower bleaching than the tungsten HPOM. A photochromic mechanism involving electron transfer between the GPTMS matrix with BPA, and PWO is proposed. After UV irradiation, the O–H and bonds decomposed gradually and W^{6 +} was reduced gradually with increasing time. The photochromic coatings on PC substrate showed reversible transmittance change before and after UV irradiation, making then efficient light protectors under UV irradiation.     

The maleimide modified epoxy resins for the preparation of UV‐curable hybrid coatings

In the present study, maleimide‐modified epoxide resin containing UV‐curable hybrid coating materials were prepared and coated on polycarbonate substrates in order to improve their surface properties. UV‐curable, bismaleimide‐modified aliphatic epoxy resin was prepared from N‐(p‐carboxyphenyl) maleimide (p‐CPMI) and cycloaliphatic epoxy (Cyracure‐6107) resin. The structure of the bismaleimide modified aliphatic epoxy resin was analyzed by FTIR and the characteristic absorption band for maleimide ring was clearly observed at 3100 cm^?1. Silica sol was prepared from tetraethylorthosilicate (TEOS) and methacryloxy propyl trimethoxysilane (MAPTMS) by sol–gel method. The coating formulations with different compositions were prepared from UV‐curable bismaleimide‐based epoxy oligomer and sol–gel mixture. The molecular structure of the hybrid coating material was analyzed by ²⁹Si‐CP/MAS NMR spectroscopy techniques. In the ²⁹Si CP/MAS NMR spectrum of the hybrid coating, mainly two kinds of signals were observed at ?68 and ?110 ppm that correspond to T³ and Q⁴ peaks, respectively. This result shows that a fully condensed structure was obtained. The thermal and morphological properties of these coatings materials were investigated by using TGA and SEM techniques. Hardness and abrasion resistance properties of coating materials were examined and both were found to increase with sol–gel precursor content of the coating. The photopolymerization kinetics was investigated by using RT‐IR. 70% conversion was attained with the addition of 15 wt% of BMI resin into the acrylate‐based coating formulation. It was found that the UV‐curable organic–inorganic hybrid coatings improved the surface properties of polycarbonate. Copyright © 2009 John Wiley & Sons, Ltd.     

Proton-Conducting Phosphosilicate Films Prepared Using Template for Pore Structure

Ordered mesoporous glass films were prepared using an interfacial silica-surfactant self-assembly technique and their porous and proton conducting properties were investigated. Gel films were deposited on substrates by dip-coating of the mixed-solution of hydrolyzed-alkoxide and non-ionic surfactant C₁₆H₃₃(OCH₂CH₂)₁₀OH. Cubic-orderd mesostructure was formed by dipping the solution, the ordered structure of which decayed gradually with increasing the aging period of the solution and disappeared after aging of 120 h. The resulting ordered mesoporous films obtained following heating at 400°C exhibited surface area and average pore diameters of 1030 m²/g and 2.5 nm, respectively. The obtained glass films exhibited proton conductivity of 10^{– 3} S/cm at 80°C in 70% RH.     

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).