Cristian Petcu

Hybrid materials obtained in microemulsion from methyl methacrylate, methacryloxypropyltrimethoxysilane, tetraethoxysilane

Abstract Ternary diagrams for the methyl methacrylate (MMA) (methanol (MeOH)/water and tetraethoxysilane (TEOS)/MeOH/water systems were studied. The composition domains, where microemulsions form owing to the nanostructures developed by the MeOH–water system, were determined. Refractometric and conductometric studies showed that water-in-oil (w/o), bicontinuous or oil-in-water )(o/w) microemulsions may form. Hybrid materials were obtained by the sol–gel reaction of TEOS combined with the free-radical copolymerization of MMA and methacryloxypropyltrimethoxysilane (MPS). MPS was added in order to avoid phase separation. The change of the glass transition temperature and of the thermal stability of the organic network in the presence of the inorganic one, and the similar forming mechanisms and rates proved the formation of simultaneous interpenetrating polymer-inorganic networks.

Nanostructured Biomaterials with Controlled Properties Synthesis and Characterization

Magnetic nanoparticles were obtained using an adjusted Massart method and were covered in a layer-by-layer technique with hydrogel-type biocompatible shells, from chitosan and hyaluronic acid. The synthesized nanocomposites were characterized using dynamic light scattering, transmission electron microscopy, and Fourier transformed infrared spectroscopy. Biocompatibility of magnetic nanostructures was determined by MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide) cell proliferation assay, swelling tests, and degradation tests. In addition, interaction of hydrogel-magnetic nanoparticles with microorganisms was studied. The possibility of precise nanoparticles size control, as long as the availability of bio-compatible covering, makes them suitable for biomedical applications.

Ternary microemulsions of vinylic and acrylic monomers

Ternary systems consisting of sodium dodecyl sulfate (SDS) as surfactant, water and several vinyl and acrylic monomers [vinyl acetate (VAc), acrylonitrile (ACN), ethyl acrylate (EtA), butyl acrylate (BuA), 2-ethylhexyl acrylate (EHA), methyl methacrylate (MMA), butyl methacrylate (MMB) and styrene (St)] were studied. The solubilization of monomer in aqueous solutions of SDS was found to be dependent on its structure and concentration. The molar specific solubility was observed to decrease with hydrophobicity and increase with polarity of monomer, that is, it was lowest for St, EHA and highest for MMA, EtA. The NMR and fluorescence studies indicate that solubilization occurred at a different domain of the interfacial layer. The hydrophobic monomers are solubilized toward the hydrocarbon interior of the micelles whereas the hydrophilic ones, toward the hydrated tail of the surfactant. The penetration of monomers into the oil-in-water interface is limited because the screening of charged ions of emulsifier is not operative. A relationship between the persulfate initiator decomposition rate and the lability of the a-hydrogen linked to the substituted carbon of the double bond was established. The initiator productivity was the highest for MMA (lacking such a-hydrogen) and the lowest for VAc and St, the monomers in which the C–Ha bond is the most reactive. 2002 Elsevier Science Ltd. All rights reserved.

The Influence of Monomers upon Microemulsions with Short Chain Cosurfactant

Several monomers (i.e., acrylonitrile (ACN), ethyl acrylate (EtA), acrylate of 2 ethylhexyl (EHA), butyl acrylate (BuA), vinyl acetate (VAc), methyl methacrylate (MMA) and styrene (St)) were investigated in order to study their capacities to form microemulsions. The surfactant was nonyl phenol ethoxylate with 25 moles ethylene oxide and ethanol was used as the cosurfactant. The phase diagrams prove that the capacity for microemulsion formation varies in the following sequence: ACN = EtA > VAc > BuA > MMA > St > EHA. Conductometric and refractometric studies allowed us to evidence the formation of microemulsions with W/O, bicontinuous or O/W structure. Fluorescence studies give interesting informations on the stabilization capacity of the monomers dispersed by interaction with hydrophobic chain of the cosurfactant. H-NMR studies suggest that the monomers in microemulsions lie in regions with various polarities as function of their chemical nature. In polymerization initiated with benzoyl peroxide the minimum conversions were obtained in zones of composition where the initial microemulsions possess a bicontinuous microstructure. The reactions of degradative transfer of the increasing macroradicals account for these conversion modifications. For initiation with ammonium persulphate, its rate of decomposition depends on its ability to displace the proton bonded to the substituted vinylic carbon of the monomer. The productivity of this initiator varies within the sequence MMA > EtA > BuA > St > ACN > VAc. The consumption of the initiator, as induced by the monomer, depends on its chemical nature and on the solubilization site of the microemulsions.

The Influence of New Hydrophobic Silica Nanoparticles on the Surface Properties of the Films Obtained from Bilayer Hybrids

Ultra-hydrophobic bilayer coatings on a glass surface were fabricated by sol–gel process using hexadecyltrimethoxysilane (C16TMS) and tetramethoxysilane (TMOS) (1:4 molar ratio) as precursors. After coating, silica nanoparticles (SiO2 NPs) functionalized with different mono-alkoxy derivatives (methoxytrimethylsilane, TMeMS; ethoxydimethylvinylsilane, DMeVES; ethoxydimethylphenylsilane, DMePhES; and methoxydimethyloctylsilane, DMeC8MS) were added, assuring the microscale roughness on the glass surface. Influences of the functionalized SiO2 NPs and surface morphology on the hydrophobicity of the hybrid films were discussed. The successful functionalization of SiO2 NPs with hydrophobic alkyl groups were confirmed by Fourier transform infrared spectroscopy (FTIR). The thermal stability of hydrophobic SiO2 NPs showed that the degradation of the alkyl groups takes place in the 200–400 °C range. Bilayer coating with C16TMS/TMOS and SiO2 NPs modified with alkoxysilane substituted with C8 alkyl chain (SiO2 NP-C8) has micro/nano structure. Hydrophobicity of functionalized SiO2 NPs-C8 and its higher degree of nanometer-scale roughness gave rise to ultra-hydrophobicity performance for bilayer coating C16TMS/TMOS + SiO2 NPs-C8 (145°), compared to other similar hybrid structures. Our synthesis method for the functionalization of SiO2 NPs is useful for the modification of surface polarity and roughness.

Polymer-clay nanocomposites obtained by solution polymerization of vinyl benzyl triammonium chloride in the presence of advanced functionalized clay

AbstractPolymer-clay nanocomposites were synthesized by solution polymerization method using advanced functionalized clay and vinyl benzyl trimethyl ammonium chloride as monomer. First stage consisted in the silylation of a commercial organo-modified clay-Cl 20A using alkoxysilanes with different chain lengths. In the second step, the synthesis and characterization of polymer-nanocomposites were followed. To evaluate the clay functionalization process as well as the final polymer-clay products, thermogravimetric, X-ray diffraction, dynamic light scattering, Fourier transform infrared spectroscopy and three test liquid contact angles analyses were used. The loss of ammonium ions from commercial clay, the grafting degree, the lengths and the nature of alkyl chain influence the dispersion of the advanced modified clay into the polymer solution and, furthermore, the properties of the final polymer-clay nanocomposite film. Graphical AbstractPolymer-clay nanocomposites were obtained by solution polymerization using advanced functionalized clay and a water soluble monomer. The loss of ammonium ions, the grafting degree, the lengths and the nature of alkyl chain influenced the dispersion of the modified clay into the polymer solution and the properties of the final hybrid film.

HOMOPOLYMERIZATION AND COPOLYMERIZATION OF VINYL ACETATE IN NON-IONIC ICROEMULSIONS. I. A STUDY OF HOMOGENEITY DOMAINS

Abstract The homogeneity ranges of the systems consisting of the monomer (vinyl acetate or vinyl acetate + di-2-ethyl hexil maleate), cosurfactant (ethanol, n-propanol, n-butanol), surfactant (nonylphenol ethoxylate with 25 moles of ethylene oxide) and water were studied. Addition of the more hydrophobic comonomer requires utilization of a more hydrophobic cosurfactant. The increase of surfactant concentration entails the widening of the homogeneity range. The effect of the cosurfactants mentioned is accounted for by the modification of the cluster structure of water. Therefore the refractive indexes and the signals of protons in NMR spectra vary non-linearly with the composition of homogeneous systems. DSC analysis of the systems obtained has come out with two crystallization temperatures of water undercooled to −60°C in systems of concentrations close to those of organic and aqueous phases. The results plead for the existence of a structure which differs from that of the ideal solutions of the systems s...

Polymer-Titanium hybrids obtained by radical polymerization and Sol-Gel process

The possibility to prepare hybrids made by poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA) and/or poly(ethyl acrylate) (PEtA) with TiO2 was studied. The processes of polymer formation-radical polymerization and sol-gel process for inorganic network —were achieved simultaneously. Due to a high reactivity of titanium isopropoxide (TIP) in the sol-gel process, a complexant comonomer, allyl acetoacetate (AlAcAc), was used. Covalent bonds between polymer and inorganic chains were obtained by addition of trialkoxysilane derivates with vinyl (VTES) or methacryloyl (MPTS) groups. The presence of TIP inhibits the radical polymerization of vinyl acetate (VAc). The PVAc-TiO2 hybrids were produced by the sol-gel process of TIP in the presence of pre-obtained PVAc. Except for VTES and MPTS, trialkoxysilane derivates with methyl (MeTES), octyl (OTES) and phenyl (PTES) groups were used. The thermal stability of hybrids is strongly affected by TiO2 presence and by the type of trialkoxysilane derivates. The thermal stability of PVAc hybrids decreases in the presence of TiO2 inorganic network. The glass transition temperature of polymers increases in the presence of the inorganic network.

DISPERSION POLYMERIZATION OF STYRENE STARTING FROM MICROEMULSIONS

ABSTRACT The domains of homogeneity for the systems containing styrene - alcohol (methanol, isopropanol, t-butanol) - water are investigated. These ones represent the reaction medium of dispersion polymerization The domains of homogeneity increase with increasing the hydrocarbon chain of the cosurfactant and in the presence of surfactants. Conductometric and refractometric studies have established that the homogeneous systems obtained in the presence of monomaleate of nonylphenol ethoxylated with 25 moles ethylene oxide, in a concentration of 10% based on the above-mentioned mixture, are microemulsions with oil-in-water (o/ w) bicontinuous or water-in-oil (w/ o) structure. In the presence of 10% bismethacrylate of PEG 1500 or 5% bismethacrylate of PEG 1500 and 5% acrylic acid, based on styrene, the domains of homogeneity are smaller, but the character of microemulsion is preserved. The latexes prepared by polymerizing styrene dispersed in microemulsions display larger particle diameter in case of isopropa...

Notes: Polymer-Water Interaction in Emulsion Copolymerization of Vinyl Acetate

Abstract In the case of copolymer latexes of vinyl acetate with maleic diesters, the amount of water bound to particles decreases with the increase of comonomer hydrophobicity. Increasing the concentration of bound water for more polar polymers determines a decrease of free water concentration. Therefore, the concentration of free surfactant and initiator in free water is higher and results in an increase of decomposition rate of potassium persulfate initiator. The increase of more polar copolymers hydration results in the increase of latex particle size. Abstract published in “Proc-Working Party on Polymer Reaction Engineering”, Thessaloniki, September 1996.