γ-Ray-induced grafting of DMAEMA and AAc onto PP by two step method

Binary graft copolymerization of thermosensitive 2-(dimethylamino) ethyl methacrylate (DMAEMA) and pH sensitive acrylic acid (AAc) monomers onto polypropylene (PP) films was carried out by a two step method using a ⁶⁰Co gamma radiation source. The PP film was initially modified by grafting of DMAEMA through a direct method. The DMAEMA-g-PP film obtained was then subjected to radiation grafting of AAc by the pre-irradiation method to give (DMAEMA-g-PP)-g-AAc. The optimal conditions, such as reaction time, reaction temperature, monomer concentration, and dose were studied. The grafted samples were verified by the FTIR-ATR spectroscopy and swelling; thermal properties were analyzed by DSC and TGA.     

Radiation Synthesis of Superabsorbent Hydrogels Based on Chitosan and Acrylic Acid for Controlled Drug Release

Superabsorbent hydrogels based on the natural polymer chitosan and acrylic acid (CS/AAc) was prepared using ⁶⁰Co gamma radiation as a source of initiation and crosslinking. The factors, which affect the preparation of CS/AAc hydrogels such as irradiation dose, CS/AAc ratios, and acrylic acid monomer concentrations, to get the best optimum conditions, were investigated. The kinetic studies of the swelling of CS/AAc hydrogel showed that it follows a Fickian type of water diffusion. The Fickian constant value ‘n’ was more than 0.5 with a high swelling capacity of 300 g/g as superabsorbent hydrogel. In addition, the suitability of CS/AAc hydrogel as carrier material for the drug Chlortetracycline-HCl has been investigated by adsorption isotherm studies. The performance of drug release from hydrogel systems, influenced by acrylic acid ratio and the effect of pH of the medium was studied.     

Cu(II) immobilization in AAc/NIPAAm-based polymer systems synthesized using ionizing radiation

Polymer systems based on the pH-responsive monomer acrylic acid (AAc) and the thermosensitive monomer N-isopropylacrylamide (NIPAAm) were synthesized using gamma radiation. Three systems were synthesized: a comb-type hydrogel structure (grafting of NIPAAm onto crosslinked PAAc), a binary graft of both monomers onto a polypropylene (PP) film synthesized by a one-step method and a binary graft prepared by a two-step method. The binary graft systems were characterized by swelling behavior and the reversibility of water uptake. The three systems were compared with respect to their Cu(II) adsorption quantity, reversibility and time response. The binary graft system synthesized in one step exhibited the best adsorption response. The comb-type hydrogel required 150 h to reach its maximum swelling percentage, and the binary graft systems on polypropylene (PP) prepared by the one- and two-step irradiation-based methods required 10 and 30 min, respectively. The optimum pH range for Cu(II) immobilization was 5-6 in the binary graft system synthesized in one step. The maximum adsorption capacity for Cu(II) in the (PP-g-(AAc/NIPAAm)) (45% graft) was found to be 337 mg g⁻¹, and the adsorption followed the Freundlich model.     

Structure and swelling-release behaviour of poly(vinyl pyrrolidone) (PVP) and acrylic acid (AAc) copolymer hydrogels prepared by gamma irradiation

Copolymer network hydrogels were prepared by gamma irradiation of aqueous solutions of poly(vinyl pyrrolidone) (PVP) and acrylic acid monomer (AAc). The composition of the final hydrogels compared to the composition of the initial preparation solutions of hydrogels was determined. The chemical structure and nature of bonding was characterized by IR spectroscopy analysis, while the thermal durability of the prepared hydrogels was assessed by thermogravimetric analysis (TGA). The kinetic swelling in water and the pH-sensitivity of PVP/AAc copolymer hydrogels was studied. The drug release properties of PVP/AAc hydrogels taking methyl orange indicator as a drug model was investigated. The IR spectra indicate the formation of copolymer networks, whereas the TGA study showed that the PVP/AAc hydrogels possess higher thermal stability than pure PAAc and lower than PVP hydrogels. The kinetic swelling in water showed that all the hydrogels reached equilibrium after 24 h and that the degree of swelling increases with increasing the ratio of AAc in the initial feeding solutions. It was found that the degree of swelling of PVP/AAc hydrogels increases greatly within the pH range 4-7 depending on composition.     

Radiation synthesis of acrylic acid/polyethyleneimine interpenetrating polymer networks (IPNs) hydrogels and its application as a carrier of atorvastatin drug for controlling cholesterol

Gamma irradiation was used to form interpenetrating polymer networks structure (IPNs) hydrogels based on different ratios of acrylic acid monomer (AAc) and polyethyleneimine (PEI). The property-behavior was characterized by IR spectroscopy, gel content, thermogravimetric analysis (TGA) and swelling in water at room temperature and different pH values. The AAc/PEI hydrogels were used as a carrier for atorvastatin drug, in which the uptake-release character was studied. The results showed that the gel content of AAc/PEI hydrogels decreased greatly with increasing the ratio of PEI in the initial feeding solution. The AAc/PEI hydrogels displayed pH-sensitive character. The drug uptake-release study indicated that AAc/PEI hydrogels possessed controlled release behavior and that the release process depends on pH. In this respect, the release of atorvastatin drug was significant in acidic medium.     

Novel comb-type hydrogels of net-[PP-g-AAc]-g-4VP synthesized by gamma radiation,with possible application on Cu2+ immobilization

A novel comb-type grafted hydrogel system of net-[PP-g-AAc]-g-4VP was synthesized by gamma radiation in three steps. In the first step a pH sensitive graft copolymer of AAc onto PP film was obtained by radiation grafting of acrylic acid (AAc) onto polypropylene (PP) films in aqueous solution at radiation doses of 10 kGy with a ⁶⁰Co source. The grafted side chains of poly (acrylic acid) (PAAc) were then cross-linked with gamma radiation at different radiation doses to give net-[PP-g-AAc]. Finally, 4-vinylpyridine (4VP) was grafted into the net-[PP-g-AAc]. The comb-type grafted hydrogel obtained, net-[PP-g-AAc]-g-4VP, has been studied through determination of graft yield and swelling behavior at room temperature. Two critical pH values were found for net-[PP-g-AAc]-g-4VP at 4.5 and 7.2. Initial studies on the immobilization of Cu²⁺ ions from solution into net-[PP-g-AAc]-g-4VP films were performed.The comb-type grafted hydrogel, grafted onto PP was also characterized by differential scanning calorimetry (DSC), scanning electronic microscopy (SEM) and FTIR-ATR.     

The effect of concentration of acrylic acid,dose rates and temperature on preirradiated graft of natural rubber-based thermoplastic elastomer

Grafting acrylic acid (AAc) onto thermoplastic elastomer (TE) films, a kind of product from natural rubber latex block-grafted by methyl methacrylate monomer was investigated. The preirradiated dose from a gamma Co-60 source for TE at 75 kGy was considered to be useful. Significant concentration of AAc aqueous solution for the grafting process is 20% (vol%). Dose rate of about 3.4 kGy/h is more effective for the graft. The temperature of around 90°C is suitable for obtaining a higher degree of graft. It is observed that the rate of grafting of AAc onto TE is proportional to 0.48 power of dose rate and 1.9 power of AAc concentration. The rate of grafting can be expressed as R_g=k·I^0.48·M^1.9. On the other hand, overall activation energy of the graft is estimated about 7.2 Kcal/mol. The FTIR spectrum analysis of TE and TE-g-AAc films was proceeded.     

Gamma radiation synthesis of comb-type graft hydrogels based on poly(acrylic acid) and 4-vinylpyridine

A pH-sensitive comb-type hydrogel was obtained by gamma radiation polymerization and crosslinking of acrylic acid (AAc) in solution. The pH-sensitive 4-vinylpyridine (4VP) was then grafted to the poly acrylic acid (PAAc) hydrogel using gamma radiation from a ⁶⁰Co source. The comb type graft polymers obtained (net-PAAc)-g-4VP has been studied through determination of graft yield and swelling behavior. The critical pH value was found to be 5.6. The apparent mechanical properties appear to be qualitatively better than hydrogels of PAAc upon swelling. The new comb-type system presents faster swelling response (30 h) than the polyacrylic acid hydrogel (50 h). The increase in dose rate from 7.3 to 11.3 kGy h⁻¹, increase the radiation grafting percentage of 4VP in the system. Comb-type polymers were also characterized by DSC, TGA and FTIR-ATR.     

Radiation synthesis of acrylic acid onto poly(tetraflouroethylene-perflourovinyl ether) film: Chemical modifications and electrical conductivity

Graft-polymerization of acrylic acid (AAc) monomer onto poly(tetraflouroethylene-perflouro vinyl ether) (PFA) copolymer film was carried out using gamma irradiation technique to synthesize grafted copolymer film PFA-g-PAAc (PFA-COOH). The effect of the dose on the degree of grafting of AAc onto PFA film was investigated. The results showed that the degree of grafting increases with increasing the irradiation dose. The grafted [PFA-COOH] film was chemically modified by reaction with aniline to produce modified [PFA-CO-NH-ph] film, followed by sulphonation reaction to introduce sulfonic acid (SO₃H) groups to get other modified [PFA-CO-NH-ph-SO₃H] film. The chemical structures of the grafted and modified films were identified by FT-IR, XRD, and SEM. It is of particular interest to measure the electrical conductivity of grafted and modified membranes as a function of degree of grafting. It was found that the conductivity of the grafted films increases with increasing the degree of grafting, however a slightly increase in conductivity was observed in [PFA-CO-NH-ph-SO₃H] sample. The electrical conductivity property of the modified PFA membranes suggests their possible use for fuel cell applications.     

Radiation-initiated emulsion copolymerization of styrene and carboxylic acid monomers

The emulsion Copolymerization of styrene and carboxylic acid monomers such as acrylic, methacrylic, and itaconic acids (AAc, MAAc, IAc) was studied by using ⁶⁰Co γ-rays as initiator and sodium do-decylsulfate as emulsifier. The polymerization behavior of these acid monomers was followed by simultaneous conductometric and potentiometric titrations for a latex sample taken in polymerization. The polymerization rate of these acid monomers increases in the following order of hydrophobicity: IAc < AAc < MAAc; this suggests that their polymerization sites are mainly the surface and/or subsurface regions of latex particles. The copolymerization rate of styrene and acid monomer increases with an increase in the acid monomer content for AAc and MAAc, whereas for IAc the rate decreases. The particle sizes determined by the stopped-flow method reveal that this variation of copolymerization rate cannot be explained by the number of growing particles and should be attributed to another factor; for instance, the transfer rate of styrene molecules from oil droplets to growing particles.     

Temperature- and pH-responsive behavior of a novel copolymer of (PP-g-DMAEMA)-g-AAc

Graft copolymers of 2-(dimethylamino)ethylmethacrylate (DMAEMA) and acrylic acid (AAc) onto polypropylene films were investigated for obtaining a pH- and thermo-sensitive material. DMAEMA and AAc were grafted by direct irradiation and pre-irradiation methods, respectively, using a ⁶⁰Co γ-source. Due to the acidic and basic nature of the monomers, this novel copolymer corresponds to the class of polyzwitterions. Their behavior was studied in presence of different buffer solutions from pH 2 to 12 for different grafting percentages (from 9 to 362%) of AAc and keeping the DMAEMA grafting percentage constant. These modified films showed the same critical pH point at 7.6 in a range of temperatures from 23 to 37 °C. The swelling percentage showed a dependence on AAc content and pH. The lower critical solution temperature was observed at 36 °C when AAc content was less than 30% of grafting. The grafted films were characterized by swelling behavior, FTIR-ATR and UV–Vis spectrometry for study of loading and release of vancomycin as a model drug at room temperature.     

Removal of Pb2+ and Cd2+ ions from aqueous solutions using guanidine modified hydrogels

In this study, experimental measurements have been made on the batch adsorption of cadmium and lead ions from aqueous solutions using poly(guanidine modified 2‐acrylamido‐2‐methylpropan sulfonic acid/acrylic acid/N‐vinylpyrrolidone/2‐Hydroxyethyl methacrylate), P(AMPSG/AAc/NVP/HEMA) hydrogels. The guanidyl end group bearing AMPSG monomer was synthesized from the reaction of AMPS and guanidine. The hydrogels were prepared by UV‐curing technique. The morphology of the dry H10‐hydrogel sample was examined by SEM. The influence of the uptake conditions, such as pH, functional monomer per cent, contact time, initial feed concentration, and foreign metal ions on the metal ion binding capacity of hydrogel, was also tested. The selectivity of the hydrogel toward the different metal ions tested was Hg(II) > Pb(II) > Au(III) > Cd(II). The adsorption isotherm models were applied to the experimental data, and it was seen that the Langmuir isotherm model was the best fit for the adsorption of Cd(II) and Pb(II) ions on P(AMPSG/AAc/NVP/HEMA) hydrogel. It was found that adsorbed lead and cadmium ions on P(AMPSG/AAc/NVP/HEMA) hydrogel can be effectively desorbed by acid leaching and the regenerated P(AMPSG/AAc/NVP/HEMA) hydrogel can be reused almost five times less without any loss of adsorption capacity. Copyright © 2009 John Wiley & Sons, Ltd.     

Grafting onto Wool. IX. Graft Copolymerization of Vinyl Monomers by Use of Vanadium Oxyacetylacetonate as Initiator

Methyl methacrylate (MMA), acrylic acid (AAc), and vinyl acetate (VAc) were graft copolymerized onto Himachali wool in an aqueous medium by using vanadium oxyacetyl acetonate as initiator. Graft copolymerization was studied at 45, 55, 65, and 75°C for various reaction periods. The percentage of grafting was determined as functions of concentration of monomers, concentration of initiator, time, and temperature. The maximum percentage of grafting with each monomer occurred at 55°. Several grafting experiments were carried out in the presence of various additives which include HNO3, DMSO, and pyridine. Nitric acid was found to promote grafting of MMA. All these additives had adverse effects on grafting of VAc and AAc. MMA, VAc, and AAc were found to differ in reactivity toward grafting and followed the order MMA > AAc > VAc.     

Graft copolymerization kinetics of acrylic acid onto the poly(ethylene terephthalate) surface by atmospheric pressure plasma inducement

After one atmospheric pressure plasma treatment of poly(ethylene terephthalate) (PET) film, acrylic acid (AAc) in aqueous solution was successfully graft‐copolymerized onto PET films. The effects of reaction time, AAc monomer concentration and reaction temperature on grafting behavior of AAc were systematically studied. Possible reaction kinetics of plasma‐induced graft copolymerization, starting from initial hydroperoxide decomposition, were proposed. Through the Arrhenius analysis about graft copolymerization kinetics of AAc monomers on PET surface, it was revealed that the activation energies of decomposition, propagation and termination were 98.4, 63.5, and 17.5 kJ/mol, respectively. The temperature around 80 °C was favorable not only for the formation of oxide radicals through the thermal decomposition of hydroperoxide on PET surface but also for the extension of graft copolymer chain through direct polymer grafting. Poly(acrylic acid) (PAAc) grains grafted onto PET surfaces possessed relatively uniform size and both PAAc grain size and surface roughness increased with increasing the grafting degree of AAc. The increase of grain size with increasing grafting degree results from the possibility of forming long chain graft copolymers and their shielding of reactive sites. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1594–1601, 2008     

Gradual phase transition of poly(N-isopropylacrylamide-co-acrylic acid) gel induced by electric current

The copolymer gels showing gradual phase transition induced by temperature were synthesized by redox random copolymerization of N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) monomer under a constant electric current. The behavior of gradual phase transition induced by temperature was examined by measuring the thermal properties, pKa values and swelling ratio. The experimental results indicate that temperature-induced gradual phase transitions of poly(NIPAAm-co-AAc) gel are mainly driven by transport before polymerization and protonation/ionization of the AAc, caused by the electric current.     

Grafting polymerization of acrylic acid onto preirradiated polypropylene fabric

Acrylic acid (AAc) was grafted onto polypropylene (PP) fabric by a preirradiation method using a Co-60 gamma ray. The effect of absorbed dose, AAc concentration, reaction temperature, reaction time, storage time, as well as the effect of ferrous ion and sulfuric acid on the degree of grafting were determined. It has been shown that the synergistic effect of sulfuric acid with the ferrous sulfate can not only increase the grafting yield, but also decrease the apparent activation energy for the grafting. It leads to the possibility of getting a particular grafting yield at a lower absorbed dose. In this experiment, It has also been shown that the grafting activity of preirradiated PP fabric in AAc aqueous solution could be well kept at room temperature for a long period.     

Characterization of Starch/Acrylic Acid Super‐Absorbent Hydrogels Prepared by Ionizing Radiation

Copolymerization of acrylic acid (AAc) and gelatinized maize starch in aqueous medium using γ‐irradiation, followed by neutralization with alkali solution was carried out. The preparation conditions, such as irradiation dose and starch/AAc compositions were investigated. The higher the irradiation dose, as well as the AAc content in the feed solution, the higher the gel content. The copolymers were characterized by FTIR spectroscopy, thermo‐gravimetric analysis (TGA) and scanning electron microscopy (SEM). SEM revealed that the higher the dose, the lower the copolymer pore size. Starch/AAc copolymers have thermal stability higher than that for starch and poly acrylic acid individually. The swelling of starch/AAc hydrogels reduced as the gel content increases. The maximum water absorption obtained for starch/AAc hydrogels in distilled water was 200 g/g, and for neutralized starch/AAc hydrogels was 350 g/g. The swelling ratio of starch/AAc hydrogels of different compositions in NaCl solution is lower than that obtained in distilled water. The results suggest that the neutralized starch/AAc hydrogels have a high swelling property, and can be used in a variety of commercial applications.     

Swelling-shrinking behavior of a polyampholyte gel composed of positively charged networks with immobilized polyanions

Polyampholyte gels were prepared by free radical polymerization of aqueous monomer solutions with the following composition: 69% N-isopropylacrylamide (thermosensitive neutral monomer), 1% N,N'-methylenebisacrylamide (cross-linker), 15% 1-vinylimidazole (cationic monomer), and either 15% acrylic acid (AAc, anionic monomer) or poly(acrylic acid) (PAAc, polyanion). We thus obtained two sorts of polyampholyte gels; that is, G1 with immobilized PAAc and G2 with randomly copolymerized AAc. The equilibrium swelling ratio (Qe) was studied as a function of the pH, NaCl concentration, and temperature. Also studied was the kinetics of swelling and shrinking in response to a sudden pH change. The significant results obtained were as follows: (i) A fully collapsed state was observed at pH 4.5-9.0 for G1 and at pH 4.5-7.0 for G2. (ii) Below and above these pH ranges, both gels were in a swollen state; therefore, an isoelectric point (pI) appeared in a wide pH range. (iii) At alkaline pH regions where a hysteresis was observed in the Qe versus pH curves of G1 and G2 as the pH was first increased then decreased, G1 exhibited very slow swelling-shrinking kinetics. (iv) An increase in the NaCl concentration allowed the gel to swell at pH approximately pI (antipolyelectrolyte behavior) but to shrink at pHs below and above the pI range (polyelectrolyte behavior). (v) The magnitude of the salt-induced shrinking of G1 is smaller than that of G2 at pH 10 and at NaCl concentrations > 0.01 M. (vi) At pH 10, an increase in the temperature from 35 to 50 degrees C led to a shrinking change of G1 but not of G2. These results were found to be explicable in terms of a different distribution of negative charges within the polyampholyte gel network.     

Charged polystyrene nanoparticles: role of ionic comonomers structures

Emulsion copolymerizations of styrene were carried out with four structurally different ionic comonomers namely acrylic acid (AAc), methacrylic acid (MAA), 2-hydroxyethyl methacrylate (HEMA), and sodium styrene sulfonate (NaSS) to study the effect of monomer structure on the copolymerization kinetics and size, morphology, charge density, and the self-assembly of the particles. The copolymerization kinetics was found to be highly dependent upon the ionic comonomer structure, and the nature of this dependence altered from homogeneous to micellar nucleation regime. The decrease in particle size (D) with increasing surfactant concentration (S) was observed in all the cases; however, the exponents of D vs. S were not similar for all the cases. In the homogeneous nucleation regime, exponents followed the order as AAc (0.446) > MAA (0.396) > NaSS (0.252) > HEMA (0.241), whereas the order was almost reversed in the micellar nucleation regime as NaSS (0.406) > HEMA (0.228) > AAc (0.206) > MAA (0.172). The hydrophobic/hydrophilic character and the steric factors were found to be the driving force for the variation in D vs. S exponents with ionic comonomer structure. The presence of charges on the particle surface contributed by the ionic comonomers triggered the self-assembly of the particles upon sedimentation and diffracted visible light obeying Bragg's law.     

Effect of synthesis method and buffer composition on the LCST of a smart copolymer of N‐isopropylacrylamide and acrylic acid

Responsive polymers have been the focus of many studies during the past decade because of their ability to change according to environmental stimuli. In this paper, we report on the development of a method to synthesize a pH/temperature‐sensitive linear copolymer, poly(N‐isopropylacrylamide‐ co‐acrylic acid)(poly(NIPAAm‐co‐AAc)), with a molecular weight of about 10⁶–10⁵ Da in water using azobisisobutyronitrile (AIBN) as the initiator. The effects of the following on the lower critical solution temperature (LCST) of the copolymer and homopolymer of NIPAAm were investigated: the type of buffer salts and pH changes of test solutions, molecular weight and concentration of homopolymer/copolymer solutions, and AAc monomer molar feed ratio (mol%). The effects of different synthesis methods on the molecular weight and on the AAc content were also evaluated. The mechanism of action in environments with different pH values is discussed. Copyright © 2007 John Wiley & Sons, Ltd.