Relation empirique entre la viscosite intrinseque et la masse moleculaire d'un polymere dissout dans un bon solvant

We propose the following empirical relationship between the intrinsic viscosity of a polymer and its molecular weight M.

$\text{{[η]?[η]}{}_{\mathrm{\theta }}\text{/[η][η]}{}_{\mathrm{\theta }}\text{=?Δρ}{}_{\mathrm{\infty }}\text{+}\text{A′}\text{M}\text{1}\text{2}$

[η] and [η]₀ are the intrinsic viscosities in a good solvent and in θ conditions respectively. Δ?, and A′ are constants characteristic of a system polymer-solvent. This relationship is valid for PS and PMMA in various good solvents and for a range of molecular weight from 3000 to 250,000. It is in this range that the Mark-Houwink-Sakurada equation is least applicable.     

Comportement sous impact electronique d'allenes ω-fonctionnels et des acetyleniques isomeres. Mise en evidence du transfert d'un chlore et d'un hydroxyle par un rearrangement de type mclafferty a l'aide de la spectrometrie cid-mike.

This paper describes the use of collision induced dissociation spectra in structural elucidation of C₄H₅X^+. ions, formed by chlorine or hydroxyl group migration in a McLafferty type rearrangement of the molecular ion of (ω-functionnalized allenes and their isomeric acetylenes.     

Spectres de vibration et structure d'un cristal d'amidogallate de sodium

Raman spectra (4000-150 cm^?1) of a single crystal of NaGa(NH₂)₄ and infrared spectra (4000-200 cm^?1 ) of a polycrystalline sample have been studied at different temperatures. An assignment of the bands is given. The spectra are discussed assuming S₄ and T_d point group symmetry of the Ga(NH₂)^?₄ ion at low temperature and at room temperature respectively. Metal-ligand and N-H stretching frequencies are compared to those of some other amido metalates.     

Determination de la constante d'acidite intrinseque d'un echangeur d'ions carboxylique

To obtain the intrinsic acidity constant of a carboxylic ion-exchanger, we propose a method of graphical double extrapolation. The results for an ion-exchanger made of polyvinyl alcohol grafted with acrylic acid are close to those published for the corresponding linear polyacid.     

Etude du mecanisme de la cyclotrimerisation catalytique de l'hexyne-3 par l'intermediaire d'un complexe cyclobutadienique du nickel

The reduction of nickel halide by metals in low oxidation states, in a boiling solution of 3-hexyne in tetrahydrofuran leads to catalytic and quantitative cyclotrimerisation of the unsaturated compound. During the reaction, tetraethylcyclobutadienenickel(II) dibromide can be isolated in appreciable yield. A mechanism is proposed for the cyclotrimerisation.     

Etude de la reactivite d'ylures de sulfonium et de pyridinium stabilises par un groupement cyanoformyle

The sulfonium and pyridinium ylides stabilized by a cyanoformyl group, in an acidic medium, lead to sulfonium and pyridinium salts which are equivalents of pyridinium or sulfonium ketene salts. This originality has been used to prepare new stabilized ylides, or derivatives of substituted arylacetic acids or 4-hydroxy thiazoles.     

Reactivite du tetraallyletain et d'allyltrialkyletains vis a vis d'aldehydes,de cetones et d'epoxydes

Tetraallytin reacts readily with non activated ketones and exothermically with aldehydes contrary to other allylic organotins such as allytributyltin. Homoallylic alcohols are obtained after acidolysis of the adducts. Upon extended heating, allylic organotins and epoxides form products which correspond to additon products of isomeric carbonyl compounds. However, starting from cis- and trans-1-phenyl-1,2-epoxypropanes, direct regiospecific but non-stereospecific ring opening is observed with poor yields.     

Theorie approachee de la permittivite dielectrique d'un melange

After a general survey of the relations, proposed by several authors, to calculate the mean dielectric permittivity of a mixture versus the volume concentration and the permitivity of the components, we propose a formula and charts deduced from it. Experimental measures have been made on polystyrene-based mixtures and allow the checking of this formula.     

Structure de l'echitamidine,d'un stereoisomere et de deux regioisomeres

The relative configuration of echitamidine is established by spectral and X-ray crystallographic techniques. Three other isomers are described and a structure is proposed for them.     

Stereochimie de la deprotonation et de la reaction d'aldolisation des dithioesters

Cis lithium thioenolates are preferentially formed by deprotonation of dithiopropanoates with lithium diisopropylamide in tetrahydro-furan at -78°C. The cis selectivity observed, is unproved by increasing the alkylthio group size or by the ability of this group to chelate the lithium cation. When more bulkier bases such as lithium 2,2,6,6-tetramethylpiperi-dide or lithium hexamethyldisilazane are used, the selectivity is lowered. This lowering of selectivity is suppressed when the deprotonation is performed in presence of 12-crown-4. Addition of hexamethyl phosphoramide to the base does not invert the selectivity as it uas reported for the deprotonation of esters ; a rather better cis selectivity is reached in the case of methoxymethyl dithiopropanoate. These original results are well understood in terms of an open transition state model. Preformed lithium thioenolates are reacted uith a variety of aldehydes and afford stereo-specifically syn aldols. The influence of hexamethylphosphoramide and reaction time is also examined.     

Etude cinetique de la copolymerisation alternee de l'indene et du methacrylate de methyle en presence de sesquichlorure d'ethylaluminium

The copolymerization of indene with methyl methacrylate (MAM) initiated by u.v. irradiation, in the presence of ethylaluminium sesquichloride (SCEA) as a complexing agent, yields alternating copolymers when [Indene] ≥ [MAM] ≥ [SCEA]. Values of $\text{M}$_n of the copolymers range from 32,000 to 900,000, depending on the concentrations of the reagents, reaction temperature and intensity of u.v. light. The kinetics can be explained simply by assuming a statistical copolymerization of indene with a MAM-SCEA binary complex, but intervention of a ternary complex SCEA-MAM-indene cannot be discarded. At high MAM concentrations, the free MAM becomes involved in the copolymerization.     

Etude de la protolyse du cryptate d'iode positif

The diprotonated cryptand ∣2.2.2 H₂∣²⁺ is formed by the addition in nitromethane 1 of two equivalent of trifluoroacetic acid (or hydroiodic acid) to the cryptate ∣2.2.2 I∣⁺, I^?; the reaction is accompanied by the release of molecular iodine. Upon adding only one equivalent of trifluoroacetic acid, no release of iodine is observed and the formation of complex ∣H - 2.2.2- I∣²⁺ is deduced from NMR, UV and conductance measurements.     

Étude de la synthése,la structure et la réactivité d'un nouveau réactif organométallique résultant d'une réaction de dimérisation du bromure d'allyl-zinc

When heated for several hours in refluxing solvent, allylzinc bromide forms a new organometallic compound with a bis-1,3-organozinc structure. This compound reacts with different compounds leading in most cases to attachment of the structural group:

     

Mecanisme de la fixation du fer ferrique sur un copolymere d'ester carboxylique—II. Etude des coefficients de distribution et de la permeation du fer(III)

Experimental determination of distribution coefficients and diffusivity through the Hycar 4021 copolymer of macro-amounts of iron(III) in ethanolic hydrochloric acid lead to the knowledge of the processes involving ethanol. Micro-amounts of iron(III) are fixed on the copolymer by a different process.