Development of membranes by radiation grafting of acrylamide into polyethylene films: Properties and metal ion separation

Polyethylene‐g‐polyacrylamide membranes were prepared by graft polymerization of acrylamide into polyethylene films using a preirradiation technique. The membranes showed good swelling in water and a maximum of 232% swelling was achieved for a graft level of 590%. The electrical resistance of the membranes decreased with increase in the degree of grafting to 200% and then stabilized with a further increase in grafting to 590%. The membranes had an excellent binding capacity for mercury ions. Almost 99% mercury separation was achieved from a metal solution of 200 ppm. The metal binding capacity increased with increase in the degree of grafting in the membranes. A binding capacity as high as 6.2 mmol/g in a membrane with 590% grafting was achieved. The pH of the metal solution did not have any significant influence on the binding ability of the membranes. The mercury‐loaded membranes showed better thermal stability as compared to those without metal binding. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 282–291, 2002     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Characterization and thermal investigations

Polyethylene-g-polyacrylamide membranes were prepared by graft polymerization of acrylamide into polyethylene films by preirradiation technique. The characterization and thermal behavior of membranes with different degrees of grafting were evaluated by density, X-ray diffraction, thermogravimetric analysis, and differential scanning calorimetry measurements. Grafting led to considerable changes in the structure of polyethylene membranes. The density of the polyethylene film increased wtih the increase in the degree of grafting, although the increase beyond 100% grafting was less pronounced than at lower graft levels. The heat of fusion and the crystallinity of polyethylene decreased with the increase in the degree of grafting. The decrease in crystallinity is because of the cumulative effect of the dilution of inherent crystallinity by the incorporation of amorphous polyacrylamide grafts within the noncrystalline region of polyethylene (dilution effect) and partial disruption of the crystallites (crystal defects). X-ray diffraction measurements also revealed a decrease in the crystallinity in grafted films. Membranes behaved as a two-component system where polyethylene and polyacrylamide components underwent independent degradation irrespective of the graft levels. In general, the thermal stability of polyethylene in membranes was markedly improved by the grafting of acrylamide monomer as evident from the initial decomposition temperature increasing from 311°C for virgin PE to 390°C in grafted membranes. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2629–2635, 2001     

Surface modification of acrylonitrile copolymer membranes by grafting acrylamide. I. Initiation by ceric ions

Surface modification of membranes of an acrylonitrile copolymer (PAN) containing 5.5% methyl methacrylate (MMA) and 4.0% sodium methylpropylenesulfonate by grafting acrylamide (AAm) with cetric ammonium nitrate as initiator in the aqueous medium has been studied. Results showed that the extent of grafting was varied with some parameters, such as dimethyl formamide and Tween-20 amount in the reaction solution, concentration of AAm, and reaction time. The grafted copolymer was verified by infrared spectra and X-ray photoelectron spectroscopy. Both of these methods also showed that the ester group of MMA unit on the surface of PAN membranes may be partially hydrolyzed into carboxyl group in the copolymerization condition. Surface and pore structures of PAN membranes after grafting were viewed under a scanning electron microscope (SEM). From SEM photos we know that AAm homopolymer branches were grafted onto the surface of the membrane and the morphology of membrane did not change. Results of contact angle of isooctane on the membrane under water showed that the wettability of the modified membrane was improved. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1521–1529, 1997     

Surface modification of polyethylene terephthalate film by CO2 laser‐induced graft copolymerization of acrylamide

Graft copolymerization of acrylamide onto polyethylene terephthalate (PET) using a CO₂ pulsed laser was performed to improve water wettability. After laser irradiation in air, the films were placed in the aqueous solution of monomer and then heated to decompose peroxides formed onto the irradiated PET film. Peroxide density was determined spectrophotometrically by means of the iodide method. The grafted PET surfaces were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, and contact angle measurements. The electron micrographs showed that the grafting changed the surface morphology of the PET film, which is consistent with the infrared spectra of the grafted films. To evaluate the surface hydrophilicity, water drop contact angle was determined. The contact angle decreased as a result of graft polymerization. It was also found that the hydrophilicity is related to the surface morphology and grafting level. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 401–407, 2000     

Distribution of acrylic acid grafted chains introduced into polyethylene film by simultaneous radiation grafting with water and ethanol as solvents

The graft copolymerization of acrylic acid onto low‐density polyethylene films by simultaneous γ‐ray irradiation was carried out. The effect of water and ethanol as grafting solvents on the distribution of grafted poly (acrylic acid) in the low‐density polyethylene films was studied with optical microscopy observations of dyed and sliced samples and attenuated total reflection/Fourier infrared spectroscopy analysis. When no vigorous homopolymerization occurred, both polyethylene and poly(acrylic acid) existed in the grafted layer, and the thickness of the grafted layer and the poly(acrylic acid) concentration in the grafted layer increased with an increasing degree of grafting, regardless of the grafting conditions, the former increasing faster than the latter. In comparison with water as the solvent, in the absence of the inhibitor, homopolymerization could be suppressed to a certain degree in the ethanol solvent system, whereas in the presence of the inhibitor, obvious homopolymerization occurred at a lower monomer concentration, and both the degree of grafting and the thickness of the grafted layer were lower. Such differences could be explained by the chain transfer and the relatively low solubility of poly(acrylic acid) in ethanol. In addition, an experimental scheme using optical microscopy to observe the dyed and sliced polymers was optimized. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1570–1577, 2007     

Dialysis membranes from polyethylene films grafted with acrylic acid

Low‐density polyethylene‐g‐poly(acrylic acid) membranes were prepared by the direct radiation grafting of aqueous acrylic acid solutions (containing Mohr's salt) onto low‐density polyethylene films and were irradiated at two different irradiation doses (2 and 3 Mrad) at a dose rate of 0.02 Mrad/h. Two series of polyethylene‐g‐poly(acrylic acid) membranes with 100 and 150% grafting were obtained. The free carboxylic acid groups in the grafted films were converted into the corresponding acrylates by reactions with different metal salts. The swelling (water uptake) and dialysis permeability of glucose and urea through the grafted membranes in different metal‐ion forms were investigated. The prepared membranes showed good permeability to both solutes, which increased as the hydrophilicity of the membrane increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 10–14, 2004     

Reactive extrusion process for the grafting of maleic anhydride onto linear low‐density polyethylene with ultraviolet radiation

In this work, we chemically modified linear low‐density polyethylene with maleic anhydride in the molten state using, in a first step, different doses of ultraviolet irradiation to generate hydroperoxide groups, which were highly reactive at the processing temperature. Then, in a second reactive extrusion step, maleic anhydride was grafted to the linear low‐density polyethylene under different processing conditions. Characterization of the modified and unmodified linear low‐density polyethylene material was performed with Fourier transform infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Maleic acid grafting on low density polyethylene

Grafting of maleic acid (MAc) on low density polyethylene (LDPE) was carried out using γ‐irradiation technique. Preactivation method was used for grafting and a maximum grafting of 2.4% was obtained. Grafted polymer(LDPE‐g‐MAc) was characterized by chemical method, Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Thermo‐Gravimetric Analysis (TGA), Melt Flow Index (MFI), Tensile Property Measurement, Particle Size Analysis, and Hot Stage Optical Microscopy. Presence of carbonyl peak of high intensity, high acid value, and low melt flow index value confirmed grafting of MAc on LDPE. A marginal change in thermal and mechanical properties of LDPE was observed after grafting. Change in crystallization behavior of LDPE has been noticed after grafting. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2802–2807, 2004     

羧甲基甲壳素与丙烯酰胺接枝聚合反应研究

制备了羧甲基甲壳素接枝丙烯酰胺共聚物,讨论了反映温度、时间、引发剂用量、溶剂用量、单体用量对接枝反应的影响。最佳反应条件为：羧甲基甲壳素0．4g,溶济水50mL,引发剂60mg,单体1．6g,反应温度50℃,反应时间3．0h。     

Enzyme‐mediated grafting of acrylamide to ultrahigh molecular weight polyethylene fiber: A novel radical initiation system

The enzyme‐mediated grafting of acrylamide (AM) to ultrahigh molecular weight polyethylene (UHMWPE) fibers using horseradish peroxidase (HRP) was demonstrated. To optimize the reaction condition, the concentrations of monomer, H₂O₂, the initiator, and time were varied. The grafting results were discussed and a reaction mechanism was proposed. Function groups and structural change of the graft copolymer were determined by FTIR spectroscopic and scanning electron microscopy micrographs for proof of grafting and the results were discussed. Results show that the surface of treated fiber becomes rougher than the untreated surface. Compared to unmodified fiber, modified fiber surface had significantly increased the interfacial shear strength, and carbonyl‐stretching regions in the IR spectra. The interfacial shear strength of the UHMWPE fiber increased, clearly indicating that enzymatic‐grafted acrylamide could significantly increase the hydrophilicity of the surfaces of UHMWPE fibers. Moreover, the hydrophilicity of treated fiber depends on the monomer concentration, the initiator concentration, and oxidizing agent concentration as well as the time of the reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1011–1016, 2005     

Graft copolymer–lanthanide complexes obtained by radiation grafting on polyethylene film

Radiation‐induced grafting of acrylic acid (AAc) onto polyethylene (PE) film was investigated. The grafted films rapidly adsorbed Eu, Gd, Tb, and Dy ions at high efficiency. The carboxylic acid groups on the AAc‐grafted PE film acted as a chelating site for the selected lanthanide ions. Complex formation of lanthanide ions and the carboxylic acid group on PE film was investigated by IR, FT–Raman, and X‐ray photoelectron spectroscopy (XPS). Photoluminescence (PL) spectra and the thermal properties of the graft copolymer–lanthanide complexes onto PE film were also investigated. The application of such prepared graft copolymer–lanthanide complexes in the field of fluorescence emission displays (FEDs) may be interest. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 328–336, 2003     

玉米淀粉/丙烯酰胺接枝型高吸水性树脂的合成

本文以硝酸铈铵为引发剂 ,研究了单体浓度、引发剂浓度、反应温度和反应时间等因素对玉米淀粉与丙烯酰胺接枝共聚制备高吸水性树脂的影响 ,通过反应条件和正交试验 ,确定了最适宜的反应条件和工艺路线 ,制备出了吸水率在 4 5 0～ 70 0g·g-1的玉米淀粉接枝型高吸水性树脂。     

Recent developments in the radiation grafting of N‐vinyl‐2‐pyrrolidone onto low‐density polyethylene with cinnamonitrile derivatives

The radiation‐induced graft polymerization of N‐vinyl‐2‐pyrrolidone onto low‐density polyethylene films was conducted with γ radiation by a simultaneous technique. The grafted copolymer was modified with cinnamonitrile or benzylidene malononitrile. The modified and grafted films were amidoximated with hydroxylamine hydrochloride in a basic medium. However, during amidoximation, the benzylidene malononitrile was cyclized to yield isoxazole ring through an addition to the nitrile group in its structure, whereas the nitrile groups of cinnamonitrile were converted into amidoxime groups. The swelling behavior of the grafted copolymers and copolymers grafted and modified either with cinnamonitrile or benzylidene malononitrile was studied. Amidoximated and grafted films and copolymer–metal complexes of Cu(II) were prepared and characterized. The effect of the isoxazole ring on polymeric materials was also investigated. These films were characterized with different analysis techniques, such as infrared, ultraviolet (UV), elemental analysis, energy‐dispersive spectroscopy, and electron spin resonance (ESR). The UV and ESR analyses revealed that the geometric structure of Cu(II) was square‐planar. Scanning electron microscopy was used to examine the grafted and modified films to determine the changes in the surface morphology. Morphological changes clearly appeared for both complexed and isoxazole films because of the increase in their crystallinity. The thermal stability of different films was investigated with thermogravimetric analysis. The improvement of the copolymer by modification with cinnamonitrile derivatives showed great promise for some practical applications, such as metal recovery by complexation or the use of isoxazole in medicine. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1189–1197, 2005     

Gamma radiation induced graft copolymerization of acrylamide onto poly(vinyl chloride) films

Grafting of acrylamide (AAm) onto poly(vinyl chloride) (PVC) films using gamma radiation has been carried out. The effects of different parameters on the graft yield have been investigated. These parameters include radiation dose, monomer concentration, solvent composition, types of inhibitors and acidity of the medium. In addition, the effects of the multifunctional monomers N,N′-methylene allyl amide (MAAm) and 2,4,6-triallyloxy-1,3,5 triazine (TARA) on the graft yield have been investigated. It has been found that methanol/water mixture in the ratio (1:1) is the proper diluent mixture for enhancing the graft copolymerization process. The presence of sulphuric acid in the reaction medium adversely affects the graft yield more than acetic acid. The presence of MAAm in the reaction medium markedly increases the graft yield, while TARA has practically no effect on the grafting process. Grafted films have been characterized and evidence of grafting has been obtained using thermal and spectroscopic analysis together with swelling measurements in water. © 1998 SCI.     

黄原胶与丙烯酰胺接枝共聚反应的研究

以过硫酸铵为引发剂,在氮气保护下,研究了黄原胶与丙烯酰胺的接枝共聚反应。考察了单体浓度、引发剂浓度、反应温度和反应时间等因素对接枝率及接枝效率的影响,探讨了过硫酸铵引发黄原胶接枝丙烯酰胺共聚反应的基本规律。采用红外光谱、X射线粉末衍射对接枝共聚物的结构进行研究,用热重分析法表征了产物的热性能,并初步探讨了接枝机理。结果表明,过硫酸铵能有效地引发黄原胶与丙烯酰胺的接枝共聚反应,并且接枝率和接枝效率随单体浓度、引发剂浓度、反应温度的变化出现极大值,随反应时间的延长不断上升,直至基本不变。     

PE膜表面接枝间苯二酚

Low density polyethylene film surface-grafted process. Firstly, acrylic acid was grafted to the surface grafting. Secondly, the carboxylic groups in poly （acrylic resorcinol was prepared by a sequential of low density polyethylene by UV photoacid） chains were transferred to acyl chloride groups by the reaction of carboxylic groups with thionyl chloride. The stability of acyl chloride groups in several solvents （alcohol, water, acetone, aqueous NaOH and in N2 atmosphere） was investigated, and N2 atmosphere and acetone were appropriate media to protect acyl chloride groups from side reaction. Finally, resorcinol monomer reacted with acyl chloride to append to the poly（acrylic acid） chains at room temperature. FT-IR ATR was used to characterize the change of carbonyl groups during each step of the grafting process. Furthermore, by the experimental data of gravimetric analysis the grafted resorcinol monomer on the surface of low density polyethylene film was verified to have undergone condensation with acetone further in the resorcinol/acetone solution at 56℃, which might be a useful feature for synthesizing a thermoplastic/thermosetting composition.     

Graft copolymerization of 4-vinylpyridine and methyl acrylate onto polyethylene film by radiochemical method

Graft copolymerization of 4-vinyl pyridine (4-VP) and methyl acrylate (MA) onto polyethylene (PE) was studied in aqueous medium in air by the mutual irradiation method. The percentage of grafting was determined as a function of the (i) total dose, (ii) monomer concentration, and (iii) amount of water. The effect of different alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and pentanol on the percentage of grafting of 4-VP and MA was studied. The effects of different amines on the percentage of grafting of 4-VP were also studied. The graft copolymers were characterized by IR spectroscopy and thermal analysis and by identifying the isolated polymer from the grafted film. Grafted PE film was tested for permeability behavior and was found to be permeable to a 0.5% aqueous sodium chloride solution. A plausible mechanism is suggested to explain the grafting of 4-VP and MA onto PE film. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 599–610, 1998     

超细纤维素胶体和丙烯酰胺的接枝共聚

本文用纤维素材料经酸分解制备具有平衡聚合度（LODP）的微晶纤维素，再分散成超细纤维素胶体（准均相纤维素体系）。用扫描电镜（SEM）观察处理前后的纤维素颗粒尺寸，并比较它们和丙烯酰胺接枝共聚的反应速率、聚合转化率、接枝率、接技效率、聚丙烯酰胺支链的分子量及其分布的情况。     

Influence of the radiation grafting conditions on the cross‐sectional distribution of poly(vinylbenzyl chloride) grafted polymer onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) films

Poly(vinylbenzyl chloride) (PVBC)‐grafted poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films were prepared as precursors for ion‐exchange membranes with a radiation grafting technique. A scanning electron microscopy–energy dispersive X‐ray spectroscopy (SEM‐EDX) instrument was used to investigate the effects of the radiation grafting conditions on the distribution profiles of the grafts in the FEP‐g‐PVBC films because the properties of the ion‐exchange membranes were largely affected not only by the degree of grafting (DOG) but also by the distribution of the graft chain. These results indicate that the distribution profile of the grafts largely depended on the grafting parameters, such as the solvent, monomer concentration, film thickness, and irradiation dose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

木薯淀粉接枝AA／AM高吸水树脂合成工艺的影响因素及优化

以过硫酸铵、亚硫酸氢钠作为引发剂，N，N’-亚甲基双丙烯酰胺作为交联荆，将木薯淀粉与丙烯酰胺、丙烯酸在水溶液中接枝共聚，合成了高吸水性树脂。单因素实验结果表明，反应温度、引发剂用量、交联剂用量、丙烯酸中和度．丙烯酰胺用量对产品的吸水倍率影响较大。正交实验结果表明：适宜的接枝共聚条件为反应温度50℃，引发剂用量0．6％，交联剂用量0．04％，丙烯酸中和度85％，丙烯酰胺用量20％。