Influence de la temperature sur les manifestations de l' “effet de matrice” dans la polymerisation de l'acide acrylique en solution

This study is concerned with the influence of temperature on the kinetics of the polymerization of acrylic acid dissolved in dioxane or toluene and on the type of molecular association complexes present in these solutions. In dioxane solutions, an increase in temperature destroys the oligomeric auto-associations of acrylic acid and gives rise to monomer-solvent associations. Simultaneously, the consequences of the “matrix effect” (auto-acceleration and stéréospecificity) become less pronounced. In contrast, in toluene solutions, an increase in temperature converts the cyclodimeric auto-associations of the monomer into linear oligomers and the consequences of the matrix effect appear (or become more pronounced). The Arrhenius plots exhibit anomalies which conform with the above interpretation. The results obtained in dioxane and in toluene solutions are similar to earlier findings in methanol and n-hexane solutions respectively. This makes it possible to generalize the conclusions reached here to acrylic acid solutions in other solvents which may or may not associate with the monomer.     

Membranes permselectives obtenues par greffage radiochimique des acides acrylique et methacrylique sur des films de poly(chlorure de vinyle)

Membranes were prepared by subjecting to gamma-rays PVC films swollen in a mixture of acrylic acid and methylene chloride. The kinetics of the reaction were investigated as a function of monomer concentration, temperature and dose-rate. The swelling properties of the resulting membranes were studied as well as those of PVC films grafted with methacrylic acid. It was found that PVC films grafted with methacrylic acid only swell slightly in water even for high grafting ratios and the swelling is very slow. At elevated temperatures the films swell more quickly and reach a higher limiting swelling, but the effect is small. PVC films grafted with acrylic acid swell much more quickly and reach much higher swelling ratios. The extent of swelling markedly increases with temperature but this effect is not reversible: once the membranes have reached a high swelling ratio at elevated temperatures, they keep the same ratio when dipped in water at 20°. The Arrhenius plot of the swelling ratio exhibits a break at 50–60° apparently corresponding to a glass transition temperature. In methanol the swelling is significantly higher for PVC films grafted with methacrylic than with acrylic acid. Swelling of the membranes was also investigated in mixtures of water with methanol and methanol with methylene chloride. The results are interpreted by assuming a strong dipole-dipole interaction between the grafted branches and the trunk polymer resulting in a quasimolecular dispersion of the carboxylic chains in the PVC matrix. The latter acts as a barrier against the penetration of water. Heat treatment favours a segregation of the two polymeric species into microphases and this non-reversible transformation is assumed to be responsible for the unexpected behaviour of PVC films grafted with acrylic acid. The significant differences between the properties of PVC films grafted with either acrylic or methacrylic acid are attributed to the much higher hydrophobic character of the methacrylic chains.     

Greffage radiochimique de l'acide methacrylique sur des films de polytetrafluoroethylene

Methacrylic acid was grafted into the bulk of PTFE films 50 μm thick by irradiating the films in aqueous solutions of monomer containing CuCl₂. The influences of radiation dose-rate and of temperature were investigated. The swelling of the grafted films was studied in the following solvents for the grafted branches: water, methanol, DMF and their mixtures. In each case the molar ratios corresponding to the limiting swelling were determined. It was further found that the grafted films swell in carboxylic acids such as methacrylic, acrylic and acetic acids, which are non-solvents for the grafted branches. This swelling is much slower than the swelling in good solvents. It is suggested that it results from a molecular association of the carboxyl groups of the solvent with those of the polymer.     

Sur une exaltation de l'“effet de matrice” lors de la polymerisation de l'acide acrylique dans certains melanges ternaires

The polymerization of acrylic acid proceeds with an extremely high degree of auto-acceleration in certain ternary mixtures. The most drastic effects are observed when small amounts of methanol are added to a dilute solution of acrylic acid in n-hexane. In such systems the auto-acceleration index “β” may exceed 10. β Was found to exhibit a maximum over a fairly narrow range of concentrations. Moreover, the values of β are highest at temperatures between ?5 and + 10°, where a maximum of 16 is reached. The swelling of poly(acrylic acid) in the various reacting mixtures was measured and the molecular associations of the monomer with itself and with methanol were investigated. It was concluded that the “exaltation of the matrix effect” in some of the systems is caused by the complex [(Acrylic acid)₂, McOH]. This complex associates very rapidly with the polymer formed in the early stages of the reaction to produce a structure in which ultrafast propagation occurs. The swelling of the polymer favours the accessibility of the monomer to the polymeric chains during polymerization, leading to auto-acceleration which progresses with conversion and gives rise to a reaction with explosive character.     

Influence des associations moleculaires sur la copolymerisation de l'acide acrylique avec l'acide methacrylique et avec l'acrylate de methyle

The copolymerization of acrylic acid with methacrylic acid in bulk is investigated at 40 and 60°. It is confirmed that a “matrix effect” occurs only for high contents of acrylic acid. The critical concentration beyond which the matrix effect disappears is shifted towards lower acrylic acid contents for higher temperatures. The copolymer composition is independent of temperature. The copolymerization of acrylic acid with methyl acrylate is investigated in a mixture which determines an “exaltation of the matrix effect” in the homopolymerization of acrylic acid (molar fractions: m_Monomers = 0.34; m_n-Hexane = 0.52; m_Methanol = 0.14). The resulting copolymers are found to contain a much larger fraction of acrylic acid residues than the copolymers formed in bulk or in toluene or DMF solutions.     

Influence de la conformation des polyions sur la fixation de colorants—III. Etude de la fixation de l'auramine o sur des polyacides synthetiques par equilibres de dialyse

The binding of auramine O (AuO), a cationic dye which does not dimerize, to poly(methacrylic acid) (PMA) and poly(acrylic acid) (PAA) has been measured by dialysis experiments. The effects of ionization, ionic strength and polymer to dye ratio (P/D) have been systematically investigated. At low ionization and P/D = 100, the bound fraction (q) of AuO is distinctly higher with PMA than with PAA at all ionic strength; this difference can be attributed to non-electrostatic interactions. Increase of ionic strength leads to displacement of the bound dye; on the other hand, high P/D ratio favours binding. We were able to describe the binding isotherms by an ion-exchange process at constant ionization and ionic strength. Water-methanol mixtures, known to destroy the coiled conformations of PMA, lead to a decrease in q; the same is observed in unionized acidic PMA solutions where ionic interactions are suppressed. These results indicate a strong binding due to the insertion of the dye into the polyion compact core and also a weak electrostatic one; they agree with the observations of spectrofluorescence; it must be emphasized that the bound fraction of dye is not, in itself, a significant parameter of conformational states.     

Effets des solvants sur le greffage radiochimique de la vinyl-4-pyridine dans des films de polytetrafluoroethylene

Grafting of 4-vinylpyridine into the depth of PTFE films was studied using the direct radiation chemical method and solutions of monomer in either methanol or pyridine. In methanol solutions, the grafting rate is maximum for monomer concentrations of 60–85 per cent. In pyridine solutions, the rate of grafting steadily increases with monomer content. The extent of swelling of the grafted films in water is greater the longer the grafted branches. These various results are discussed.     

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.     

Adsorption of polymers at the solution-solid interface. VI. Polyacids on nylon powder

The adsorption of some polyacids, principally poly(acrylic acid), on nylon powder has been studied. In aqueous solutions at low pH the adsorption behavior of poly(acrylic acid) is controlled by adsorbate coil dimensions rather than by electrostatic effects. Less adsorption takes place from methanol solutions but the process is much more rapid than from water. Above a critical value, increase of adsorbate molecular weight leads to a reduced adsorption, the effect being particularly evidenced by aqueous solutions. Model compounds (propionic and glutaric acids) are rapidly adsorbed from both methanol and water, but give low specific absorptions. Adsorption of poly(acrylic acids) and model compounds, is reduced, but not eliminated, by modification of the nylon adsorbent through acetylation or methoxymethylation. The adsorption of poly(acrylic acid) on nylon is not readily reversible; however, partial neutralization will release preadsorbed poly(acrylic acid) from nylon powder. The adsorption behavior of copolymers of acrylic acid with N-vinylpyrrolidone is reported, as are brief studies on some other homopolyacids. The results are generally interpreted on the basis of sorption of the macromolecules into a swollen, flexible adsorbent.     

Polymerisation de l'acide methacrylique en masse et en solution

In spite of the fact that the bulk polymerization of methacrylic acid proceeds under precipitating conditions, all conversion curves are linear and start from the origin. The overall activation energy of the gamma ray initiated reaction is very small: 1.3 kcal/mol. Methanol and water are solvents for the polymer but also form monomer-solvent complexes through H-bonds. It was found that, over a limited concentration range in these solvents, the reaction becomes auto-accelerating both in precipitating and homogeneous reaction media. Non-polar solvents (hydrocarbons) lead to a significant reduction in the polymerization rate but this effect is not as pronounced as for acrylic acid. Chlorinated derivatives reduce the polymerization rate of acrylic acid to the same extent as hydrocarbons but, for methacrylic acid, chlorinated derivatives lead to sensitization. By analogy with earlier results for acrylic acid, it is assumed that the auto-acceleration observed in water and methanol solutions is caused by a “matrix effect”. In bulk, the monomer undoubtly also associates with the polymer but, in view of the bulky methyl groups, the regularly oriented structure which favours propagation presumably never arises. The very small activation energy of the polymerization suggests that chain termination requires a significant activation energy. The mechanism of this process is not clear.     

Influence des solvants sur la copolymérisation de l'acrylamide avec l'acrylonitrile

The copolymerization of acrylamide with acrylonitrile was investigated in various solvents, which can be put into three groups according to their influence on molecular associations; (1) solvents autoassociated by hydrogen- bonds (acetic acid, methanol, water, dimethylformamide); (2) polar solvents which can associate with the NH group of acrylamide (acetonitrile, dioxane, acetone); (3) inert solvents (toluene, benzene, hexane). The reaction kinetics and the compositions of the copolymers are different for each group of solvents. The composition of copolymers formed in solvents of group 1 vary widely, depend- ing on the solvent. Copolymers formed in all solvents of group 2 have the same composition which is that of copolymers formed in bulk. The amount of acrylamide is highest in copolymers formed in inert solvents of group 3. Such parameters as the degree of conversion, the reaction temperature, the mode of initiation and the extent of dilution only slightly affect the composition of copolymers. Homopolymerizations of acrylamide and acrylonitrile were investigated in all solvent used.The results suggest that the effects of solvents on the copolymerization of acrylamide with acrylonitrile are consequences of the various modes of molecular association of acrylamide. The solvents affect the equilibrium between auto- association of acrylamide and its association with solvent and thereby affect the reactivity of the monomer.     

Polymerisation radiochimique de l'acide acrylique en solution dans l'alcool isopropylique et le dimethylformamide

The radiation-induced polymerization of acrylic acid in isopropyl alcohol and dimethylformamide solutions was investigated between?196°and40°. Mixtures which form glasses at low temperatures exhibit a maximum in the rate of polymerization at 30° and 50° above the glass transition temperature (T_g). The difference between the most favourable temperature for polymerization and T_g is larger than in systems studied previously. This fact could be due to the presence of H-bonded aggregates.The study of the polymerization of acrylic acid in dimethylformamide solution at 20° led to a correlation between this reaction and the presence of plurimolecular aggregates. The very high polymerization rate and the syndiotacticity of the resulting poly(acrylic acid) confirm the earlier assumption of a favourable orientation for propagation of the molecules of acrylic acid in these aggregates.     

Polymerisation radiochimique de l''acide methacrylique en solution

The polymerization of methacrylic acid was investigated in various solvents under the action of gamma-rays. It was found that, as in the case of acrylic acid, solvents could be divided into groups according to the observed effects. The addition of methanol or dioxane up to 50 per cent does not significantly alter the polymerization rate. These two solvents do not dissociate the plurimolecular aggregates of methacrylic acid, the presence of which is demonstrated by the high viscosity of the medium. In the presence of either toluene or n-hexane, the rate gradually decreases and the aggregates are dissociated. Chloroform and CCl₄ also dissociate the aggregates but lead to acceleration of the reaction. This effect which was not observed with acrylic acid presumably results from an energy transfer process. The polymerization of methacrylic acid in bulk and in solution has a very small overall activation energy, 1·0–1·5 kcal/mole between 16 and 60°. All conversion curves are linear in contrast to the case of acrylic acid where auto-accelerated conversion curves were observed in most mixtures. A comparison of these results shows that the initial rates of polymerization of acrylic acid follow relationships similar to those observed for methacrylic acid except for the chlorinated solvents. It is concluded that the molecular aggregates produce the same influence on the polymerization of methacrylic acid as on the initial stages of the reaction for acrylic acid, but the “matrix effect” of poly(acrylic acid) does not appear in the case of poly(methacrylic acid).     

L'influence de la temperature sur l'echange anionique

The influence of temperature on the distribution coefficients of Zn ions in systems ethanol or acetone, hydrochloric acid and Dowex 1×8 ion exchange resin (100–200 mesh) was studied. TheK _d-values increase a little with the temperature. The thermodynamic constants for some systems were calculated.      

Modification irréversible de la morphologie de films de poly(chlorure de vinyle) greffés d'acide acrylique sous l'action de solvants et de la température

PVC films grafted with acrylic acid were prepared with grafting ratios as high as 160% and their swelling in N/10 KOH, was measured. An earlier observation was confirmed showing that, when the films are heated in the swollen state, they undergo an irreversible transformation which leads to an increase of their swelling ratio. A study with scanning and transmission electron microscopes showed that rigid PVC as well as PVC grafted with acrylic acid up to 27% did not exhibit any specific microstructure. At high magnifications, fibrils characteristic of fragile fractures clearly appeared on the SEM pictures. For grafting ratios of 67% or more, segregated microphases of PVC and poly(acrylic acid) are clearly seen. The size of these microphases increases after the grafted films are swollen in KOH at 60°. A systematic study with PVC films grafted to 160% showed a steady evolution of the size of the microdomains during swelling in KOH. The results explain the variations of a macroscopic property of the film (its extent of swelling) by a modification of their microstructure.     

Etude de l'action de la pression sur la pression osmotique des solutions de polymeres

Osmotic pressures of solutions of polymers were measured as a function of pressure. The measurements were made at room temperature at pressures up to 500 bars. The results are as follows:

•

-the effect of pressure depends upon the polymer-solvent pair. Depending upon the particular case the effects can be positive, negative or zero. We have given examples for each case.     

强酸性阳离子交换树脂催化酯化丙烯酸和甲醇合成丙烯酸甲酯的反应动力学

以丙烯酸和甲醇为原料,强酸性阳离子交换树脂Amberlyst-15为催化剂,对苯二酚为阻聚剂,合成丙烯酸甲酯。 考察了醇酸摩尔比、催化剂用量和温度对反应过程的影响,在实验范围内,随着温度或者催化剂用量的增加,反应速率加快,丙烯酸的转化率也不断提高。 醇酸摩尔比的增加能提高丙烯酸的转化率,反应速率出现先增加后减缓的现象。 与此同时,建立该催化酯化反应的Pseudo-Homogeneous（PH）的理想和非理想以及Langmuir-Hinshelwood（LH）反应动力学模型,辨识得到相应反应动力学方程。 经比较,采用活度替代物质的量浓度的LH模型的平均相对偏差(MRD)最小,计算值为1.466%,最适合实际反应。     

Preparation de membranes hydrophiles obtenues par le greffage de la n-vinylpyrrolidone dans le poly(chlorure de vinyle)

PVC films were radiation-grafted in NVP-methanol solutions. Unusual kinetics relations were observed: an increase in monomer concentration or in temperature decreased the reaction rate. These effects are attributed to a higher mobility of the growing chains leading to faster chain termination and resulting in a drop of the overall rate and shortening of grafted chains. The graft copolymers swell homogeneously in water and in methanol. The swelling rate and limiting swelling ratio increase linearly with the grafting ratio. The swelling ratio was found to depend on chain length, being higher for short chains. An irreversible increase of the swelling ratio was found by raising the temperature. These unusual swelling properties of the grafted films are attributed to strong interactions between pyrrolidone groups and the Cl atoms of the PVC.     

Synthesis of comb type and semi-interpenetrating networks of acryloyl-l-proline methyl ester and poly (acrylic acid) for Cu (II) immobilization

Graft copolymer hydrogels and semi-interpenetrating networks (s-IPN) of acryloyl-l-proline methyl ester (A-ProOMe) and poly (acrylic acid) (PAAc) were synthesized in methanol solutions, by ionizing radiation (γ rays from a Co⁶⁰ source at room temperature). These systems are thermo and pH-sensitive and the pH sensitivity increases from acidic to basic solutions. The Lower Critical Solution Temperature (LCST), due to presence of poly (acryloyl-l-proline methyl ester) (PA-ProOMe) has been found between 18 and 20 °C and an unexpected Upper Critical Solution Temperature (UCST) due to poly acrylic acid (PAAc) has been found between 21 and 22 °C. Preliminary studies on the immobilization of Cu²⁺ for both hydrogels were done at several pH values at room temperature. Other techniques employed to characterize the comb type hydrogels and sIPN included scanning electronic microscopy (SEM) and infrared (FTIR-ATR).     

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.