Synthesis and thermal crosslinking of oxazolidine‐functionalized polyurethanes

A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (M_w ～ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007     

Synthesis and properties of thermosetting polymers from a phosphorous‐containing fatty acid derivative

A new phosphorous‐containing fatty acid diepoxide was obtained from 10‐undecenoyl chloride and 10‐(2′,5′‐dihydroxyphenyl)‐9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide and crosslinked with 4,4′‐diaminodiphenylmethane and bis(m‐aminophenyl)methylphosphine oxide. The properties of the thermosetting materials were evaluated by differential scanning calorimetry, dynamic mechanical thermal analysis, thermogravimetric analysis, and limiting oxygen index (LOI). Thermal and thermooxidative degradation was studied by gas chromatography/mass spectrometry, FTIR, ³¹P magic angle spinning NMR spectroscopy, and scanning electron microscopy. LOI values indicate good flame‐retardant properties that are related to the formation of a protective phosphorous‐rich layer that slowed down the degradation and prevented it from being total. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5630–5644, 2006     

Efficient combination of task-specific ionic liquid and microwave dielectric heating applied to one-pot three component synthesis of a small library of 4-thiazolidinones

The first report of the use of task-specific ionic liquid as synthetic equivalent of ionic liquid-phase matrice for the preparation of a small library of 4-thiazolidinones is reported in this paper. The starting (ethyleneglycol)ionic liquid-phase is functionalized in good yields with 4-(formylphenoxy)butyric acid by using usual esterification reaction conditions (DCC/DMAP as catalyst). The synthesis of the ionic liquid-phase bound 4-thiazolidinones was performed by a one-pot three-component condensation under microwave dielectric heating. The final cleavage under microwave/catalysis strategy provides the expected 4-thiazolidinones in high purity after flash-chromatography purification. According to the ionic liquid-phase organic synthesis (IoLiPOS) methodology, it was found that optimized reaction conditions were performed by standard analytical methods (NMR, TLC). The ¹H, ¹³C NMR spectrum of some representative 4-thiazolidinones and ionic liquid-phase bound benzaldehyde are also reported.     

Spectrometrie de Masse D'ozonides Aliphatiques

A primary cleavage of aliphatic ozonides by electron-impact, implying O? O and C? C bond breaking, is described. This mode of degradation, which is not observed for aromatic ozonides, is fav oured by electron releasing substituents. For the cis and trans 4-methyl-2pentene ozonides, the ionization potentials are 8.81 and 8.86 (±0.5) eV, respectively. Two formation thresholds are observed for the [RCHO₂]⁺ion which are interpreted in terms of different modes of ozonide cleavage.     

Synthesis and characterization of polyurethanes from epoxidized methyl oleate based polyether polyols as renewable resources

Oligomeric polyether polyols were obtained through the acid‐catalyzed ring‐opening polymerization of epoxidized methyl oleate and the subsequent partial reduction of ester groups to give primary alcohols. The oligomers were characterized with titration, spectroscopic techniques (Fourier transform infrared and nuclear magnetic resonance), matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, size exclusion chromatography, and differential scanning calorimetry. Depending on the degree of reduction, polyols of different hydroxyl content values were obtained and were reacted with 4,4′‐methylenebis(phenyl isocyanate) to yield polyurethanes. These materials, which were characterized by differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical thermal analysis, could behave as hard rubbers or rigid plastics. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 634–645, 2006     

Recherches sur la structure électronique et les caractéristiques des différentes formes tautomères de la purine

Résumé Les caractéristiques électroniques (énergie, charges , géométrie, moment dipolaire, énergie de transition) des quatre formes tautomères de la purine et des phényl-8 N(1)H et N(3)H purines ont été déterminées par la méthode LCAO améliorée. La forme 9 est trouvée la plus stable à l'état isolé. Une interprétation nouvelle des bandes d'absorption est proposée.

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Researches on the electronic structure and the characteristics of various tautomer forms of Purine

The electronic characteristics (energy, charge , geometry, dipole moment, transition energy) of the four tautomeric forms of the purine and of the phenyl-8 N(1)H and N(3)H purines have been determined by the improved LCAO method. The form 9 is considered as the most stable at the isolated state. A new interpretation of the absorption bands is proposed.

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Zusammenfassung Die elektronischen Charakteristiken (Energie, Ladung , Geometrie, Dipolmoment, Übergangsenergie) der vier Tautomerformen des Purins und der Phenyl-8 N(1)H und N(3)H Purine sind durch die verbesserte LCAO-Methode bestimmt worden. Die Form 9 ist, zum isolierten Stand, als am meisten beständig zu betrachten. Eine neue Erklärung der Absorptionsbänder ist vorgeschlagen.

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Les auteurs remercient le Professeur B. Pullmann (Paris) de l'intérêt qu'il a porté à ce travail, ainsi que Madame H. Feilchenfeld (Jérusalem) pour les résultats inédits qu'elle a bien voulu leur communiquer.     

Fast solid-phase extraction-gas chromatography-mass spectrometry procedure for oil fingerprinting. Application to the Prestige oil spill

A rapid and simple fractionation procedure using solid-phase extraction (SPE) cartridges was developed for an accurate determination of aliphatic and polycyclic aromatic hydrocarbons in petroleum residues and further application in chemical fingerprinting of oil spills by gas chromatography-mass spectrometry (GC-MS). Among the adsorbents evaluated, SiO2/C3-CN exhibited the best selectivity, providing, by elution with n-hexane (4 ml) and n-hexane-CH2Cl2 (1:1) (5 ml), two well-resolved aliphatic and aromatic hydrocarbon fractions, with recoveries of 97 +/- 7.2 and 99.7 +/- 13.9%, respectively. The SPE fractionation procedure was compared with the conventional silica-alumina adsorption chromatography showing similar results but practical advantages in terms of reproducibility, analysis time, solvent reduction and cost. Moreover, is particularly suitable for routine analysis with a high sample throughput. The developed methodology was tested in the characterization of fuel-oil samples collected along the Spanish north-west coast, after the Prestige oil spill accident.     

Limit Cycles Bifurcating from a k-dimensional Isochronous Center Contained in ?n with k ? n

The goal of this paper is double. First, we illustrate a method for studying the bifurcation of limit cycles from the continuum periodic orbits of a k-dimensional isochronous center contained in ℝ ⁿ with n ⩾ k, when we perturb it in a class of differential systems. The method is based in the averaging theory. Second, we consider a particular polynomial differential system in the plane having a center and a non-rational first integral. Then we study the bifurcation of limit cycles from the periodic orbits of this center when we perturb it in the class of all polynomial differential systems of a given degree. As far as we know this is one of the first examples that this study can be made for a polynomial differential system having a center and a non-rational first integral. The first and third authors are partially supported by a MCYT/FEDER grant MTM2005-06098-C01, and by a CIRIT grant number 2005SGR-00550. The second author is partially supported by a FAPESP–BRAZIL grant 10246-2. The first two authors are also supported by the joint project CAPES–MECD grant HBP2003-0017.     

Nonlinear Coherent States and Ehrenfest Time for Schrödinger Equation

We consider the propagation of wave packets for the nonlinear Schrödinger equation, in the semi-classical limit. We establish the existence of a critical size for the initial data, in terms of the Planck constant: if the initial data are too small, the nonlinearity is negligible up to the Ehrenfest time. If the initial data have the critical size, then at leading order the wave function propagates like a coherent state whose envelope is given by a nonlinear equation, up to a time of the same order as the Ehrenfest time. We also prove a nonlinear superposition principle for these nonlinear wave packets.