Radiation synthesis of a thermo-pH responsive binary graft copolymer (PP-g-DMAEMA)-g-NIPAAm by a two step method

Summary  (PP-g-DMAEMA)-g-NIPAAm was synthesized using gamma radiation from a ⁶⁰Co source. Graft polymerization of N,N’-dimethylaminoethylmethacrylate (DMAEMA) onto polypropylene (PP) was accomplished in about 100 percent yield by the mutual irradiation technique at a dose of 10 kGy. Grafting of N-isopropylacrylamide (NIPAAm) onto PP-g-DMAEMA was carried out by the pre-irradiation method with doses from 20 to 100 kGy. The influence of temperature, reaction time, and monomer concentration on grafting yield was studied. Grafting processes were confirmed by infrared spectroscopy (FTIR-ATR). (PP-g-DMAEMA)-g-NIPAAm films were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The lower critical solution temperature (LCST) and critical pH point of the films were obtained by water contact angle and percent swelling measurements. The LCST was also determined by DSC. We report here hare a new binary graft copolymer which shows two LCST values, synthesized in two steps.     

Graft copolymerization of 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method

An attempt has been made to graft copolymerize 4-vinyl pyridine onto isotactic polypropylene hydroperoxide by mutual irradiation method in an aqueous medium. Polypropylene hydroperoxide has been prepared by irradiating recrystallized polypropylene beads from a Co⁶⁰ source in the presence of air. The resulting polypropylene hydroperoxide beads have been used as the backbone polymer and grafting of 4-vinyl pyridine has been studied as a function of various reaction parameters. Optimum conditions for maximum percentage of grafting have been evaluated. Rate of grafting (R_g) has been determined as a function of preirradiation dose and initial monomer concentration. Water has been found to affect percentage of grafting. The graft copolymers have been characterized by spectroscopic method and isolation of the grafted poly(4-VP) from the graft copolymer. A plausible mechanism is proposed to explain the mutual grafting of 4-vinyl pyridine onto polypropylene hydroperoxide. © 1993 John Wiley & Sons, Inc.     

Investigation of radiation grafting of vinyl acetate onto (tetrafluoroethylene–perfluorovinyl ether) copolymer films

A study has been made of radiation-induced grafting of vinyl acetate (VAc) on to (tetrafluoroethylene–perfluorovinyl ether) copolymer (PFA). Effects of grafting conditions such as inhibitor and monomer concentrations and irradiation dose on the grafting yield were investigated. In this grafting system, ammonium ferrous sulphate (Mohr′s salt) was added to the monomer-solvent mixture to minimize the homopolymerization of VAc and the most suitable concentration was found to be 2.0 wt%. It was found that the dependence of the initial grafting rate on monomer concentration is of the order 1.5. The degree of grafting tends to level off at high irradiation doses due to the recombination of formed free radicals without initiating graft polymerization. Some properties of the prepared graft copolymer such as swelling behaviour, electrical conductivity, thermal and mechanical properties were also investigated. The electrical conductivity was improved by hydrolysis of poly(vinyl acetate) in the grafted chains to their respective vinyl alcohols. The tensile properties were improved by grafting; however, the elongation percent decreased. The DTA data showed thermal stability of such graft copolymers for temperatures up to 300°C, but stability decreased at higher temperatures.     

Temperature Sensitive Behavior of Poly(N‐isopropylacrylamide) Grafted Onto Electron Beam‐Irradiated Poly(propylene)

Summary: N‐Isopropylacrylamide (NIPAAm) was graft‐polymerized from its acetone solution onto poly(propylene) (PP) films, after electron‐beam irradiation in the presence of air oxygen. The effects of pre‐irradiation dose as well as monomer concentration, reaction temperature and reaction time on the grafting efficiency were investigated. Typical conditions for achieving maximum grafting yield were observed for 1 M monomer concentration, after PP pre‐irradiation with a 300 kGy dose and a reaction temperature of 50 °C. The location of the graft polymerization was examined by different methods including measurements of dimensional variations, calorimetry, SEM and AFM. The temperature‐responsive behavior of grafted copolymer was studied by swelling and contact angle measurements at different temperatures.

Temperature dependence of the swelling ratio in water as a function of temperature.     

Study of electron beam preirradiation-induced graft copolymerization of acrylic acid onto powdered isotactic polypropylene

In order to obtain required polymer materials, acrylic acid was grafted onto powdered isotactic polypropylene by an electron beam preirradiation technique. All processes (including irradiation, storage of the samples, and grafting polymerization) were carried out in air. The effects of irradiation dose, storage time, reaction temperature, morh's salt, acid, and monomer concentration were investigated and discussed in detail. The results show that the grafting can be achieved well without purging oxygen, and morh's salt is indispensable for initiating grafting reaction and decreasing the homopolymerization. Optimal reaction conditions can be generalized for large-scale production of the desired polymer materials. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1357–1362, 1999     

Preparation and properties of cationic membranes obtained by radiation grafting of methacrylic acid onto PTFE films

Cationic membranes were prepared by direct radiation grafting of methacrylic acid (MAA) onto poly(tetrafluoroethylene) (PTFE) films followed by alkaline treatment to confer ionic character in the graft copolymer. The complete inhibition of homopolymerization of MAA by using ammonium ferreous sulfate (Mohr's salt) failed. However, the addition of 0.5 wt % FeCl₃ to the monomer solution effectively inhibited the homopolymerization process and higher grafting yield was obtained. It was found that the graft polymerization proceeded successfully in presence of methanol/water mixture (30/70 wt %), and much higher degrees of grafting were obtained as compared with those in the presence of other diluents used here. The influence of irradiation atmosphere (air, N₂ gas, and vacuum) on the grafting process was investigated. The dependence of the grafting rate on MAA concentration was found to be of orders 2.9 and 0.72 in the presence of 0.5 wt % Mohr's salt or 0.5 wt % FeCl₃, respectively. This grafting system proceeds by the front mechanism. Investigation of mechanical properties, electrical conductivity, and swelling behavior of the grafted films revealed that such a copolymer could be acceptable in practical use as a cation-exchange membrane.     

Radiation Grafting of N-Isopropylacrylamide onto Poly(vinyl chloride) tubes by Gamma Irradiation

Summary Grafted copolymer of poly(vinyl chloride) (PVC) with N-isopropylacrylamide (NIPAAm) was prepared by radiation-grafting method using γ-ray source. NIPAAm was graft polymerized from its aqueous solution onto PVC tubes by preirradiation method, all samples were exposed in the presence of air at room temperature to ⁶⁰Co. Conditions for achieving maximum grafting yield were observed between 0.5 and 1 moldm^-3 of monomer concentration, pre-irradiation dose of PVC from 5 to 110 kGy, and reaction temperature of 323 and 333 K. Characterization of the grafted copolymer was conducted by various methods: FTIR-ATR, TGA, and SEM. The temperature-responsive behavior of grafted copolymer was studied by swelling at various temperatures and pH 6.8.     

Graft Copolymers of Polypropylene Films. 1. Radiation-induced Grafting of Mixed Monomers

Radiation graft copolymerization of comonomer mixtures of acrylic acid (AAc) and styrene (S) onto polypropylene (PP) films by the mutual method has been investigated. The effect of different factors that may affect the grafting yield, such as inhibitor concentration (Mohr’s salt), solvent composition (MeOH and H₂O), radiation dose and dose rate, was studied. It was found that Mohr’s salt was very effective when the content of AAc in the comonomer mixtures was low. However, the addition of 1·25wt% of Mohr’s salt reduced homopolymer formation and enhanced the grafting process. Graft copolymerization in the presence of a solvent mixture composed of methanol and water was found to afford a higher grafting yield than in pure methanol, regardless of the composition of the comonomer mixture used. However, the highest degree of grafting was obtained at a solvent composition of 20% H₂O: 80% MeOH and a comonomer mixture of 20% AAc: 80% S. An attempt was made to determine each PAAc and PS fraction by different methods in the graft copolymer obtained. Elemental analysis indicated that the PAAc fraction with respect to PS in the graft copolymer decreased with increasing AAc ratio in the comonomer feed solution. The rough assessment of these fractions by IR spectroscopy showed similar trends. The reactivity ratios of AAc and S monomers determined in the present graft copolymerization system were found to be 0·45 and 1·3, respectively. © of SCI.     

γ辐射硅橡胶固相接枝甲基丙烯酸甲酯的研究

利用60Coγ射线,研究了硅橡胶(SR)与甲基丙烯酸甲酯(MMA)固相接枝反应,考察了接枝单体浓度、辐射剂量和剂量率等因素对接枝反应的影响,用红外光谱(FT-IR)、热重分析(TG)、和接触角测定仪等分析手段对接枝产物的结构和性能进行了表征分析。实验结果表明:辐射剂量和单体浓度分别为30kGy和m(MMA)/m(SR)=0.1左右时,接枝效果较好,接枝后的硅橡胶的热性能和亲水性能得到改善。     

Amination of glycidyl methacrylate-grafted polystyrene particles and their adsorption capacity for Nd3+ and Cd2+

A new chelating adsorbent was prepared by grafting glycidyl methacrylate (GMA) onto polystyrene (PS) particles using simultaneous radiation technique and amination of graft copolymers by reacting with diethylenetriamine. The effects of various parameters such as, irradiation doses, inhibitor concentrations, amination temperature, and reaction time were investigated. The grafting yield increased with irradiation dose to reach its maximum value at 15 kGy. The accelerative effect of solvent medium on the grafting yield was higher in THF than DMF. The addition of 0.001 % (wt) inhibitor to the reaction medium led to a sharp increase of grafting yield. The best conversion ratio was obtained at 115 °C during 24 h. By using a column separation technique, the adsorption behaviors of the adsorbent toward Cd²⁺ and Nd³⁺ in aqueous solution were examined. The adsorption amount of both Cd²⁺ and Nd³⁺ increased with initial ions concentration. The maximum equilibrium of Cd²⁺ and Nd³⁺ adsorbed ions were 18.1 and 17.58 mg/g, respectively. It was observed that the functionalized GMA-g-PS was reusable by desorbing with 0.1 M nitric acid almost without losing their adsorption capacity. FTIR test indicates that epoxide and amine groups were introduced onto GMA-g-PS and aminated GMA-g-PS, respectively. The T _g of graft copolymer slightly decreased, and that of aminated GMA-g-PS was higher than graft copolymer.     

Tailoring bulk and surface grafting of poly(acrylic acid) in electron-irradiated PVDF

Endowing conventional hydrophobic poly(vinylidene fluoride) (PVDF) films with hydrophilic properties was conducted using electron beam irradiation. Grafting of acrylic acid (AA) in/onto pre-irradiated PVDF films was investigated. Reaction parameters, monomer concentration and inhibitor concentration were examined. Radiation grafted films (PVDF-g-PAA) were synthesized with various grafting yields ranging from 12 to 130 wt % in presence of Mohr's salt (25 wt %). Below 80 wt % of monomer concentration, the degree of swelling was found to increase with the grafting yield. The PAA was arranged randomly in all PVDF matrix (grafting through). Above 80 wt % of monomer concentration, the PAA was grafted only onto the surface of PVDF films leading to a highly dense layer of PAA. Grafting through or surface grafting processes were achieved by varying the water fraction in the initial monomer solution. Water molecule acts not only as a carrier for the monomer but also as a plasticizer expanding the film in the three dimensions. Evidences of grafting through and surface grafting were produced using FTIR in ATR mode, SEM coupled to X-ray detection and XPS. An accurate quantification of AA units was possible up to the micromole via a Cu²⁺–EDTA complex analyzed by UV–vis spectroscopy.     

Functionalization of crosslinked polystyrene by radiation-induced grafting

γ-ray irradiated beads of poly(styrene-divinylbenzene) (PS-DVB) have been graft copoly-merized with polyacrylic acid. Preirradiated PS-DVB beads were refluxed with acrylic acid in water, benzene, or toluene. Percentage of grafting was studied under various reaction parameters like total dose, reaction time, and molar concentration. Effects of reaction media, temperature of reaction, and presence of Mohr salt on the percentage of grafting were also studied. From the swelling property of PS-DVB beads in DMF and dichloro-methane, it appeared that no appreciable cross-linking had occurred in the process of grafting. © 1996 John Wiley & Sons, Inc.     

Graft copolymerization of itaconic acid onto sodium alginate using ceric ammonium nitrate as initiator

Graft copolymers of sodium alginate (NaAlg) with itaconic acid (IA) were prepared in aqueous solution using ceric ammonium nitrate (CAN) as the redox initiator under N₂ atmosphere. The carboxylic acid groups of IA were neutralized with sodium hydroxide before grafting process. Grafted copolymers as sodium salts (NaAlg‐g‐PIA) were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, intrinsic viscosity measurement, differential scanning calorimetry, and thermogravimetric analysis. The graft yield (GY %) of the graft copolymer and the grafting efficiency (GE %) of the reaction were evaluated comparatively. The effects of the reaction variables such as the reaction time, temperature, percentage of NaAlg, monomer and initiator concentrations on these parameters were studied. It was observed that GY% and GE% increased and then decreased with increasing concentrations of IA and polymerization temperature. The optimum grafting conditions for maximum GY were obtained with a reaction time of 5 h, reaction temperature of 30°C, IA concentration of 0.23 M, CAN concentration of 9.12 × 10^?2 M and percentage of NaAlg 0.5 g/dL. The overall activation energy for the grafting was also calculated to be 1135 cal/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of Grafted Hydrogels as Mono-Divalent Cation Exchange for Drug Delivery

pH-sensitive acrylic acid grafted polyvinylalcohol (AAc-g-PVA) hydrogels has been prepared by gamma irradiation. The maximum grafting yield was at monomer concentration 50% and dose 50 kGy. The swelling, network parameters, thermogravimetric analysis, activation energy and scanning electron microscope of the grafted hydrogels were evaluated. Hydrogel demonstrate high swelling at pH 6.8. The deswelling of the swollen gel in Ni²⁺ and Cu²⁺ cations solution was explained on the basis of mono-divalent cation exchange. The release of antihistaminic chlorphenamine maleate hydrochloride (CPM) was faster in gastric fluid (SGF) of pH 1.1 than in intestinal fluid (SIF) of pH 6.8.     

Preparation of poly(vinyl alcohol) grafted with acrylic acid/styrene binary monomers for selective permeation of heavy metals

A study was made to modify water‐soluble poly(vinyl alcohol) (PVA) by grafting acrylic acid and styrene (AAc/Sty) comonomers using gamma rays as an initiator. The factors that affect the preparation process and grafting yield were studied and more economical grafts under the most favorable reaction conditions were obtained. It was found that the high degree of grafting in such systems was obtained in the presence of an ethanol–water mixture in which water plays a significant role in enhancing the graft copolymerization. The critical amount of water to afford the maximum grafting yield was evaluated. The effect of the comonomer composition on the grafting yield was also investigated and it was observed that using a mixture of AAc/Sty monomers influences the extent of grafting of each monomer onto the PVA substrate and the phenomenon of synergism occurs during such a reaction. Also, the degree of grafting increases as the content of the solvent decreases in the reaction medium. However, the grafting yield increased as the total dose increased. The graft copolymer was characterized by IR and UV spectroscopic methods. The permeation of heavy metals such as Ni and Co through the grafted membranes was investigated and the efficiency of the separation process was also determined. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 806–815, 1999     

Radiation induced graft copolymerization of vinyl monomers and their binary mixture onto rayon fibre

Ethyl acrylate (EA), Vinyl imidazole (VI), and their binary mixture have been copolymerized onto rayon in aqueous medium by mutual method using γ-radiation. The graft yield has been determined as a function of different reaction parameters such as total dose, concentration of vinyl monomers, and amount of water. Effect of surfactant (1-octane sulfonic acid, sodium salt) has been studied on the percentage of grafting of EA, VI, and (EA + VI). A plausible mechanism has been suggested to explain the observed behavior of the surfactant on grafting. Water retention and moisture regain of the grafted film was determined at appropriate relative humidity. The graft copolymers have been characterized by IR spectroscopy and scanning electron microscopic methods. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Gamma preirradiation and grafting of 2N-morpholino ethyl methacrylate onto polypropylene fabric

The radiation-induced grafting of 2N-morpholino ethyl methacrylate (MEMA) in aqueous solution onto polypropylene fabric by a preirradiation technique has been investigated. Among the most important factors affecting the graft yield are monomer concentration, irradiation dose, reaction temperature, and time. It was found that the graft yield increased with increasing monomer concentration, grafting temperature, and preirradiation dose. The kinetic studies showed that the dependence of the grafting rate on monomer concentration is of 1.1 order. Moreover, the calculated overall activation energy was 14.2 kcal/mol. The grafted PP fabric shows an increase in moisture regain with increasing graft yield. Also, the dyeability with acid dye was significantly increased due to grafting with MEMA. © 1995 John Wiley & Sons, Inc.     

Chemical modification of polypropylene fibers grafted vinyl imidazole/acrylonitrile copolymer prepared by gamma radiation and its possible use for the removal of some heavy metal ions

The chemical modification of polypropylene (PP) fibers by graft copolymerization with vinylimidazole (VIm) and acrylonitrile (AN) was carried out using γ‐radiation. Preparation conditions, such as irradiation dose, comonomer concentration and composition and type of solvent, affecting the degree of grafting were investigated. The suitable diluent for obtaining reasonable graft VIm/AN copolymer yield was acetone. The higher grafted yield was achieved by increasing the amount of vinylimidazole in comonomer feed solution as well as irradiation dose. The derivatives of PP‐g‐P(VIm/AN) grafted fibers of different functional groups were obtained by treating the grafted fibers with various organic reagents containing reactive amino groups, such as sulpha‐drug compounds, aliphatic‐ and aromatic amines. Characterization of the obtained graft copolymers and their chemical treatments with different amines was also investigated. It was observed that the nitrile group in PP‐g‐P(VIm/AN) polymer undergoes simple addition reaction via nucleophilic interaction mechanism to produce the corresponding PP‐graft‐P(vinylimidazole/acrylomidine) derivatives. The ability of the grafted fibers and their treated forms to absorb some metal ions as Cd, Hg, and Pb from their individual and mixture solutions was evaluated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009.     

Novel fishnet fibers with anti‐adhesion of seaweeds obtained by UV‐irradiation technique

A novel Nylon‐6 fishnet fiber with the antiadhesion of seaweeds was prepared by UV radiation‐initiated grafting of acrylic acid (AA) onto Nylon‐6 fibers, and its structure was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The influences of grafting conditions, such as irradiation dose, temperature, concentration of monomer, inorganic acid, and inhibitor etc., on grafting rate were studied, and the antiadhesion of seaweeds was evaluated with Dunaliella. The results showed that the grafting amount of Nylon‐g‐AA was increased with the increase of irradiation time. With the increase of concentration of AA, temperature, reaction time, inorganic acid, and inhibitor, the grafting amount increased firstly and then decreased, respectively. Nylon‐6 fibers modified by Poly(acrylic acid) (PAA) had a strong effect on the adhesion of Dunaliella, and the antiadhesion was improved with the increase of the grafting amount. Results from the mechanical analysis revealed that the tensile strength of the UV‐irradiation fibers decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1252–1256, 2007     

Microwave‐initiated synthesis of polyacrylamide grafted sodium alginate: Synthesis and characterization

Microwave‐initiated synthesis of polyacrylamide‐grafted sodium alginate, a graft copolymer with wide variety of applications has been reported in this study. The effect of reaction parameters (i.e., irradiation time and monomer concentration) onto the percentage grafting has been investigated. The resulting polymer has been characterized by a variety of characterization techniques such as intrinsic viscosity measurement, Fourier transform infrared spectra, ¹³C NMR spectra, elemental analysis, thermogravimetric analysis, molecular weight determination using static light scattering analysis, and scanning electron micrographs. Further, the flocculation efficiency of this graft copolymer has been investigated in coal suspension. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010