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 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.     

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.     

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.     

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.     

UV grafting of methacrylic acid and acrylic acid on high‐density polyethylene in different solvents and the wettability of grafted high‐density polyethylene. II. Wettability

The wettability of high‐density polyethylene grafted with methacrylic acid is strongly influenced by the nature of the grafting solvent. Here, the wettability is expressed by the water contact angle and absorbency. The initial (10‐s) contact angle of polyethylene (PE) grafted in acetone/water solution decreased rapidly with the extent of grafting at low grafting levels and then remained independent of the grafting level at about 50°. When a water droplet was left on the surface for a longer time, its contact angle decreased to a very low value in the period of about 10 min. For the PE samples grafted in dichloromethane, petroleum ether, cyclohexane, and chloroform, there was only a small decrease (10°) in the contact angle of water from that observed on pure PE, even when the extent of grafting was very large. The PE films grafted in these organic solvents also took a much longer time than PE films grafted in acetone/ water solution to obtain equilibrium water absorbency. The water absorbency of PE films grafted in 30% acetone/water solution was about twice that of PE films grafted in the other solvents at the same extent of grafting. These results suggested that for the solvents other than acetone/water, the grafted layer is partially buried below the surface of PE. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 263–270, 2004     

Graft copolymers obtained by radiation grafting of methacrylic acid onto polypropylene films

Direct radiation grafting of methacrylic acid (MAA) onto polypropylene films (PP) was studied. The effect of different solvents such as benzene, distilled water, dimethyl formamide, isopropanol, isopropanol/water-mixture, on the swelling and the grafting process of MAA onto (PP) films was investigated. It was found that the grafting process was enhanced under vacuum irradiation in benzene as a diluent for MAA as compared with other solvents examined. The dependence of the grafting rate on such monomer concentrations was found to be 1.2 order. The relationship between the grafting rate and film thickness gave a negative first order dependence. This grafting system proceeded by a diffusion controlled process. Some selected properties of the grafted films such as mechanical and electrical properties, swelling behaviour, and gel determination, were also investigated.     

Reversible pH-controlled switching of poly(methacrylic acid) grafts for functional biointerfaces

Responsive polymeric brushes of poly(methacrylic acid) (PMAA) were grafted from silicon surfaces using controlled surface-initiated atom-transfer radical polymerization (SI-ATRP). The growth kinetics of PMAA was investigated with respect to the composition of the ATRP medium by grafting the polymer in mixtures of water and methanol with different ratios. The dissociation behavior of the polymer layers was characterized by FTIR titration after incubating the polymer-grafted substrates in PBS buffer solutions with different pH values. PMAA layers show a strong pH-dependent behavior with an effective pK(a) of the bulk polymer brush of 6.5 ± 0.2, which is independent of the polymer brush thickness and methanol content of the ATRP grafting medium. The pH-induced swelling and collapse of the grafted polymer layers were quantified in real time by in situ ellipsometry in liquid environment. Switching between polymer conformations at pH values of 4 and 8 is rapid and reversible, and it is characterized by swelling factors (maximum thickness/minimum thickness) that increase with decreasing the methanol content of the SI-ATRP medium.     

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.     

Radiation-Induced Grafting of Ethyl Vinyl Ether onto Polyvinyl Chloride)

The radiation-induced graft polymerization of ethyl vinyl ether (EVE) onto polyvinyl chloride) (PVC) was studied under a variety of conditions. Graft copolymer and homopoly(EVE) were formed in all cases. The presence of water reduced overall polymerization rates, percentage grafting, and homopoly(EVE) molecular weights. With “superdry” EVE, grafting reached 29% at a total dose of 6.9 Mrad. Grafting to PVC films was less efficient than grafting to PVC powder. Application of a relatively poor swelling agent for PVC resulted in an increase in the efficiency of grafting. From a comparison of studies of radiation-induced EVE homopolymerization and the present work, it was concluded that dry and superdry EVE are grafted to PVC by a cationic mechanism and wet EVE is grafted mainly by a free-radical mechanism.     

Effects of solvent in photo-induced graft copolymerization of vinyl monomers on cellulose

The effects of swelling of the sample and polymerization solvents were studied for photo-induced graft copolymerization of vinyl monomers on cellulose. The graft copolymerization of methyl methacrylate (MMA) was activated by swelling of the sample or organic solvent-water solutions within a certain range of their concentrations. Though each organic solvent gave a maximum in per cent grafting and the number of grafts at about 25 vol-% concentration, the initiation reaction scarcely took place at 100% concentration; thus, the solvent itself is considered to have a negative effect. The solvents used in the experiments were all hydrophilic, such as methanol, acetone, and dioxane. The average molecular weight of the grafted PMMA differed in each solvent, indicating a different characteristic effect of solvent on the growing grafted polymer radicals. The presence of ferric ion as a sensitizer stimulated further the contributions of the sample swelling and the organic solvents to the copolymerization reaction. A similar effect was observed for styrene as for MMA, but not for acrylic acid and methacrylic acid.     

Effect of swelling on radiation-induced grafting of styrene to polyethylene

The radiation-induced grafting of low-density polyethylene in contact with styrene solution was studied. The effect of the degree of swelling of the polymer on the rate of grafting was investigated by diluting the styrene with methanol and with n-octane. For styrene-methanol solution, the rate of grafting was found to increase with degree of swelling, passing through a maximum when the sorbed solvent reaches 6.2 wt-% (70 vol-% methanol in the outside solution) and decreasing therafter. The methanol fraction of the sorbed liquid is far too small to cause precipitation of the grafted chains and inhibition of their termination rate. The dilution of styrene by octane has no effect on the swelling of polyethylene, but it decreases the grafting rate over the entire concentration range. The results are explained in terms of the concentration of sorbed monomer and the viscosity of the amorphous region of the polyethylene swollen by nonpolar liquids. Supporting evidence for the mechanism is presented in the form of grafting kinetic data as a function of dose rate (2.8 × 10²?9.5 × 10⁴ rad/hr), and post-irradiation grafting measurements for polyethylene in methanol-styrene (70/30, v/v). The data indicate that at the maximum grafting rate an optimum is achieved between a high concentration of sorbed monomer and a low viscosity for the poorly swelled polymer matrix.     

Controlled pore functionalization of poly(ethylene terephthalate) track-etched membranes via surface-initiated atom transfer radical polymerization

A new method for surface-initiated atom transfer radical polymerization (ATRP) on the technical polymer poly(ethylene terephthalate) (PET) has been developed which allows controlling and estimating the layer thickness of the grafted polymer in the isocylindrical pores of track-etched membranes. After PET surface treatment by oxidative hydrolysis, the bromoalkyl initiator was immobilized on the PET surface in a two-step solid-phase reaction; the isoporous membrane structure was preserved, and the pore diameter was increased from 760 to 790 nm. Poly(N-isopropylacrylamide) (PNIPAAm) was grafted under ATRP conditions from a methanol/water mixture at room temperature. Both monomer concentration and reaction time could be used as parameters to adjust the degree of grafting. Effective grafted layer thickness and its response to temperature were estimated from pure water permeability. All data, especially the high polymer densities (0.37 g/cm3) in the swollen layers at 25 degrees C, indicate that grafted PNIPAAm with a "brush" structure has been achieved. For dry PNIPAAm layer thicknesses on the PET pore walls of up to 80 nm, a temperature-induced swelling/deswelling ratio of approximately 3 had been observed. Reduction of the brush grafting density, via composition of the reaction mixture used in solid-phase synthesis for initiator immobilization, led to an increase of that swelling/deswelling ratio. Further, density and temperature response of the grafted PNIPAAm layers synthesized via ATRP were compared with those obtained in the same membranes by less controlled photografting, leading to lower grafting density and larger gradients in grafted layer density and, consequently, much higher swelling/deswelling ratios (>15).     

Copolymers of Starch and Polyacrylonitrile. Influence of Granule Swelling on Copolymer Composition under Various Reaction Conditions

Molecular weights and grafting frequencies of graft copolymers prepared with ferrous ammonium sulfate-hydrogen peroxide initiation showed a dependence on granule swelling similar to that found with ceric ammonium nitrate (increased swelling of starch granules decreased the number of grafted polyacrylonitrile chains and increased their average molecular weight). As with unswollen starch, the composition of the copolymer prepared from swollen starch was not influenced by granule size. Molecular weights of polyacrylonitrile branches grafted to swollen and unswollen starch were independent of reaction time; however, grafting frequencies with swollen and unswollen starch tended to converge toward a common value with increased reaction time and increased dilution. Data suggest that the influence of granule swelling on copolymer composition is due to a faster termination rate for growing polyacrylonitrile chains in unswollen starch.     

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.     

Heterogeneous grafting on polymers containing chlorine: Grafting of amide groups in water suspension and the reactivity of the new polymer towards epoxy resins

Heterogeneous grafting on polyvinylchloride suspended in water was carried out using N-butyl-3-mercaptopropionamide as nucleophile. Over 50% graft was obtained by using a small amount of solvent as a swelling agent and tricapryl methyl ammonium chloride as a phase transfer catalyst. Elemental analysis of the grafted polymer shows that the chlorine displaced from the polymers is replaced by the thio-amide group. The above conclusion is supported by NMR and IR analysis. The kinetics of the chlorine displacement from PVC by the thio amide group obeys the Shell progressive mechanism. The rate at which an individual spherical particle reacts depends on the diffusion through the reacted layer. The grafted polymer is soluble in tetrahydrofuran or nitrobenzene. The films obtained from the grafted material are brittle due to excessive internal hydrogen bonding. The electrostatic charge which is a characteristic surface phenomena in PVC is diminished in the grafted polymer which may be due to the existence of the amide group near the surface. The amide groups attached to the side chains on the polymer may participate in various reactions, e.g., with epoxy resins. IR analysis of the cured film indicates the disappearance of the oxiran band at 913 cm^?1 and an increase in the hydroxyl band around 3300 cm^?1. Thus, grafting of amide groups on PVC enables us to further modify PVC by epoxy resins.     

Effect of deprotection extent on swelling and dissolution regimes of thin polymer films

The response of unentangled polymer thin films to aqueous hydroxide solutions is measured as a function of increasing weakly acidic methacrylic acid comonomer content produced by an in situ reaction-diffusion process. Quartz crystal microbalance with energy dissipation and Fourier transform infrared spectroscopy measurements are used to identify four regimes: (I) nonswelling, (II) quasiequilibrium swelling, (III) swelling coupled with partial film dissolution, and (IV) film dissolution. These regimes result from chemical heterogeneity in local composition of the polymer film. The acid-catalyzed deprotection of a hydrophobic group to the methacrylic acid tends to increase the hydrophilic domain size within the film. This nanoscale structure swells in aqueous base by ionization of the methacrylic acid groups. The swollen film stability, however, is determined by the hydrophobic matrix that can act as physical cross-links to prevent dissolution of the polyelectrolyte chains. These observations challenge current models of photoresist film dissolution that do not include the effects of swelling and partial film dissolution on image quality.     

Relations entre la structure et les proprietes des membranes de polytetrafluoroethylene greffe—III. Membranes non-ionisables contenant de la poly-n-vinylpyrrolidone

Equilibrium properties (swelling) and transport phenomena (dialysis) of non-ionizable membranes, obtained by radiation grafting of N-vinylpyrrolidone onto thin PTFE films, were studied. Grafting was conducted by the direct method with monomer solutions in benzene. The overall activation energy of grafting determined between 20 and 50° is high (12.5 kcal mol^?1): the reaction is controlled by the monomer diffusion into PTFE film. The length of grafted chains increases with temperature.The molality of the membranes decreases when the temperature of grafting increases; for a given grafting ratio, the swelling is higher for membranes containing a small number of long grafts than for membranes with numerous short branches. The transfer of both ions and water is a function of the free volume in the films, it depends on the grafting ratio and is not influenced by the preparation conditions.     

Synthesis and characterization of 4‐vinyl pyridine‐grafted Teflon‐PFA film for water technologies

To get highly reactive polymeric materials for selective studies of enzyme immobilization, water purification, separation, and enrichment technologies, we attempted to graft 4‐vinyl pyridine (4‐VP) onto Teflon‐PFA by simultaneous γ‐ray initiation. The resulting graft copolymers were quaternized by treatment with some alkylating agents. Optimum conditions for grafting were evaluated through the variation of the total dose of radiation, the amount of water, and the monomer concentration. The effect of the solvent composition (H₂O/MeOH) was also studied. In the presence of MeOH, grafting occurred less often and was nonselective as 4‐VP was incorporated on both sides in comparison with highly selective grafting in an aqueous medium. The percentages of the grafting, total conversion, and grafting efficiency and the rates of the polymerization, grafting, and homopolymerization were also evaluated. Some other monomers such as methacrylic acid, methyl methacrylate, maleic acid, acrylonitrile, and vinyl imidazole were not incorporated onto the backbone film under the optimum grafting reaction conditions evaluated for the grafting of 4‐VP. Although some grafting occurred, the graft yield was too low to be considered of any significance. The grafted films were quaternized with benzyl chloride, and quaternized and unquaternized films were used for the immobilization of lipase. The former showed high activity with lipase and has potential for development as a bioreactor. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4506–4518, 2000     

Radiation-induced grafting of diallyldimethylammonium chloride onto acrylic acid grafted polyethylene

Diallyldimethylammonium chloride (DADMAC) was grafted onto polyethylene (PE) films by a double grafting procedure. The PE film was initially modified by grafting acrylic acid (AA), through a mutual irradiation method. AA-g-PE film, thus obtained was subjected to subsequent radiation grafting reaction of DADMAC, to give a DADMAC-g-AA-g-PE film having a comb-type structure. The influence of different conditions, such as the extent of AA grafting, DADMAC concentration, absorbed dose and dose rate, on the grafting yield of DADMAC was investigated. A maximum DADMAC grafting of 30% was achieved. The equilibrium degree of swelling (EDS) of the grafted films were gravimetrically determined. TGA and FT-IR techniques were employed to characterize the grafted PE films.