Influence de la temperature sur les associations moleculaires et sur la polymerisation de l'acide acrylique en solution

Infra-red spectra of pure acrylic acid and solutions of monomer in toluene indicate that increasing the temperature from 20 to 60° displaces the equilibrium of H-bonded species from cyclic dimer to open oligomer. Viscosity measurements on the same solutions confirm this conclusion. In methanol solutions. alcohol-alcohol and alcohol-acid associations are found together with the acid-acid associations and the interpretation of the results is extremely difficult. Polymerization kinetics are directly influenced by the shift of association equilibria. In hexane, an increase in temperature results in a sudden increase in reaction rate as the linear oligomeric structures appear in the solution. In methanol increase in temperature reduces the kinetic anomalies observed at 20 and the polymerization no longer exhibits any stereospecificity. At the same time, a chain transfer process sets in. These various results confirm the earlier assumption of an assisted propagation step occurring in auto-associated aggregates of acrylic acid.     

Influence des solvants sur les associations moleculaires et sur la cinetique de polymerisation de l'acrylonitrile. Precisions supplementaires sur l'“effet de matrice”

The polymerization of acrylonitrile is auto-accelerating in bulk and in solvents which do not dissolve the polymer. The “auto-acceleration indexes” remain almost constant in these systems. Trichloracetic acid, a very polar solvent, leads however to linear conversion curves. An earlier assumption is confirmed according to which auto-acceleration is not caused by non-stationary conditions but by an oriented association complex between the monomer and the polymer arising at the beginning of the reaction (“matrix effect”). DMF, a solvent for polyacrylonitrile, seems to produce a similar effect. The disappearance of auto-acceleration in DMF solutions was explained until now by the disappearance of the perturbation of the reaction connected with polymer precipitation (“occlusion effect”). Linear conversion curves were obtained, however, in 60% DMF solutions in which the polymer still precipitates. A detailed study of post-polymerization confirms the above interpretation. It is shown that auto-acceleration remains unaltered in the presence of solvents which swell polyacrylonitrile, such as acetonitrile or small amounts of DMF, whereas post-polymerization (caused by occluded chains) is strongly reduced. Moreover, a marked post-polymerization is observed in the presence of trichloracetic acid, demonstrating the presence of long-living chains in a system which gives rise to linear conversion curves. The association of acrylonitrile with numerous solvents is investigated; it is shown by swelling measurements that polyacrylonitrile associates with its monomer.     

Sur un “effet de matrice” dans la polymerisation de l'acrylonitrile en masse

The kinetics of the radiation initiated polymerization of acrylonitrile at 20° have been investigated in the presence of a highly divided polyacrylonitrile obtained by polymerizing the crystalline monomer. This polymer catalyses the reaction to a much larger extent than polymer formed at 20°. The analogy between the kinetic features of the polymerizations of acrylic acid and acrylonitrile in bulk leads to extending to this last monomer the assumption of a “matrix effect” in its polymerization. This effect is believed to result from the dipole interaction of the nitrile groups which lead to the formation of a complex in which the double bonds are favourably oriented for the propagation. If the matrix-polymer is produced with a pre-irradiation dose at low temperature exceeding a critical value, inhibition occurs perhaps resulting from the addition of growing chains to the CN double bonds present in the matrix-polymer.     

Copolymerization de l'acenaphtylene avec le n-vinylcarbazole

The copolymerization of acenaphthylene (ANA) with N-vinylcarbazole (NVC) was investigated at 60° in the melt with 1% AIBN and in benzene solution at 20° with gamma ray initiation. In the melt at 60°, the polymerization rate gradually decreases with the amount of NVC in the mixture. The following reactivity ratios were determined: r_NVC = 0.12; r_ANA = 7.0. The copolymers have a fairly narrow distribution of compositions but contain small amounts of poly NVC. Gamma ray initiation at 20° gives rise to the free radical copolymer together with significant amounts of poly NVC which results from a cationic mechanism. In addition, acenaphthylene cyclodimerizes in the process.     

Copolymerisation radiochimique du styrene avec l'acrylonitrile en solution

The radiation-initiated copolymerization of styrene and acrylonitrile was investigated at 20° in dimethylformamide (DMF) and in benzylalcohol solutions. The compositions of the copolymers were only slightly affected by these polar solvents. The influence of temperature on the copolymerization in DMF solutions was studied in greater detail. It was found that the acrylonitrile content in the copolymer obtained at -78° drastically increased as a result of an anionic polymerization of acrylonitrile. Fractional precipitation of the products obtained at -78° showed that they were not mixtures of polymers but were block copolymers containing long sequences of acrylonitrile units. This copolymer is assumed to arise as a result of the simultaneous growing of the two ends of a primary radical-ion, acrylonitrile adding to one end by an anionic mechanism while the free radical end initiates a random copolymerization of styrene and acrylonitrile. The anionic contribution to the over-all process was established. The anionic homopolymerization of acrylonitrile was studied in DMF, toluene and their mixtures. The rate was found to exhibit a maximum for 20% acrylonitrile in DMF. It was further noticed that significant amounts of DMF could be replaced by toluene or styrene without affecting the rate. The reduction in rate in more concentrated monomer solutions was attributed to an autoinhibition of acrylonitrile in its anionic polymerization.     

Greffage de l'acide methacrylique sur des films de poly(chlorure de vinyle) par la methode radiochimique directe

Since PVC films do not swell in pure methacrylic acid (MAA) the films were subjected to gamma-rays while dipped in various mixtures MAACHCl₂. Under such conditions, the grafting proceeds smoothly and its rate exhibits a flat maximum for the mixture containing ca. 50% (molar) monomer. The rate satisfies the relationship Rate = KI^0.6 and the over-all activation energy of the process is 4 kcal/mole. MAA grafted PVC films do not swell in solvents for PMAA (such as water or methanol) even for high grafting ratios. This result is unexpected since PTFE films grafted with either acrylic or methacrylic acid swell to a large extent in water and are excellent membranes. The swelling of the grafted PVC films was investigated in mixtures 1,2-dichloroethylene -methanol. It was found that the extent of swelling was highest in the mixture containing 35% methanol. The unusual swelling properties of these grafted films are attributed to strong polar interactions between PVC and PMAA chains.     

Preparation de membranes mosaiques par greffage radiochimique dans des films de polytetrafluoroethylene

Mosaic membranes were prepared by two successive grafting steps of acrylic acid and 4-vinyl-pyridine into well localized domains of polytetrafluoroethylene films. The films were subjected to X-rays through a grid-shaped shield which activated linear zones of the film 0.5 mm wide, separated by 0.5 mm of unactivated film. The films were then grafted with acrylic acid, neutralized and subjected to a second irradiation through a shield which protected the grafted zones. 4-Vinylpyridine was then grafted into the stripes left unchanged after the first treatment. The following properties of the resulting mosaic membranes were examined: swelling in water, electric conductivity and ion-pair diffusion. The coefficients of ion-pair diffusion were found to be 100–1000 times higher for the mosaic membranes than for carboxylic membranes of the same grafting ratio.     

Double template electrochemical deposition and characterization of NiCo and NiCu alloys nanoparticles and nanofilms

The principle of double template deposition technique was developed to prepare NiCo and NiCu alloy nanomaterials. Ordered particles of about 800 nm high were obtained by reduction of ions from aqueous solution into the pores of anodic aluminum oxide (AAO) membrane with intact barrier layer. The size of the nanoparticles was significantly reduced by combination of AAO and the hexagonal phase of a lyotropic liquid crystal. The scanning tunneling microscopy (STM) micrograph of the material prepared in the presence of liquid crystal reveals the hexagonal array of cylindrical pores. The corrosion potential of the alloy nanofilm shifted to more negative values when the sizes of the particles decrease. The anodic linear sweep voltammetry shows, in each case, various current peaks characteristic of the dissolution of chemical elements in the film.     

EM Heating-Stimulated Water Flooding for Medium–Heavy Oil Recovery

We report a study of heavy oil recovery by combined water flooding and electromagnetic (EM) heating at a frequency of 2.45 GHz used in domestic microwave ovens. A mathematical model describing this process was developed. Model equations were solved, and the solution is presented in an integral form for the one-dimensional case. Experiments consisting of water injection into Bentheimer sandstone cores, either fully water saturated or containing a model heavy oil, were also conducted, with and without EM heating. Model prediction was found to be in rather good agreement with experiments. EM energy was efficiently absorbed by water and, under dynamic conditions, was transported deep into the porous medium. The amount of EM energy absorbed increases with water saturation. Oil recovery by water flooding combined with EM heating was up to \(37.0\%\) larger than for cold water flooding. These observations indicate that EM heating induces an overall improvement in the mobility ratio between the displacing water and the displaced heavy oil.