Hydrophilicity and surface energy of polyethylene modified by radiation grafting of acrylamide

Summary LDPE films were modified via direct γ-radiation grafting of acrylamide (AAm) from its 30% aqueous solution. Equilibrium swelling of the grafted samples in water, and a water/PAAm molar ratio in the swelled films were determined as a function of PAAm content. Contact angles formed by sessile drops of water or diiodomethane on the starting and modified LDPE were measured with following calculation of a surface energy in these samples. A gradual filling of LDPE surface with PAAm as well as changes in hydrophilic-hydrophobic properties of the composition during the grafting process was discussed. It has been found an essential increase in surface energy of the modified LDPE up to ∼15% of the grafted PAAm content with a further stabilization of the energy value. Received: 12 March 2001/Revised version: 26 June 2001/Accepted: 27 June 2001     

Photoinduced grafting of acrylamide onto polyethylene film by means of two-step method

Benzophenone-coated low-density polyethylene (LDPE) was grafted with acrylic acid (AA), methacrylic acid (MA), acrylonitrile (AN), and methyl methacrylate (MMA) in an aqueous medium by photoirradiation. The first-step graft samples thus prepared with a grafting of about 50% were subjected to second-step photografting with acrylamide (AAm). On AA- and MA-grafted LDPE samples, the second-step grafting of AAm was very smooth, and a high level of grafting up to 800% was attained with ease. On the other hand, grafted LDPE samples employing hydrophobic monomers, AN and MMA, had a lower percent of grafting than those with hydrophilic monomers, AA and MA. By ESR study, a thermally stable radical was found in the first-step graft sample irradiated with light of λ > 330 nm. Mechanisms for the formation of such a radical in the first-step graft sample are proposed, and the contribution of the radical to the second-step grafting is discussed.     

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     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Influence of synthesis conditions

SYNOPSIS: The graft copolymerization of acrylamide monomer into polyethylene films was carried out by the preirradiation method. The influence of synthesis conditions, such as monomer concentration, preirradiation dose, reaction temperature, Mohr's salt, and pregrafting storage was investigated. The order of dependence of the rate of grafting on preirradiation dose and monomer concentration was found to be 0.87 and 1.86, respectively. An activation energy of 22.9 kJ/mol for the grafting reaction was obtained. The storage of preirradiated polyethylene film at −4°C prior to the reaction showed a decrease in the degree of grafting up to 10 days, beyond which the degree of grafting remained constant. The addition of FeSO₄ in the grafting medium not only inhibits the homopolymerization of the monomer but also decreases the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1331–1337, 2000     

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     

淀粉接枝丙烯酰胺的应用研究

淀粉接枝丙烯酰胺聚合物既保留有天然淀粉特性,又兼具丙烯酰胺的优点,综合性质也得到了较大提升,应用领域得到了极大的拓展,独特的刚柔结合的空间网状大分子结构,表现出较强的絮凝性能,目前,广泛应用于印染、采矿和石油化工等方面。综述了淀粉接枝丙烯酰胺聚合物在各方面的应用,并对未来的发展进行了展望。     

淀粉接枝丙烯酰胺的应用研究

淀粉接枝丙烯酰胺聚合物既保留有天然淀粉特性,又兼具丙烯酰胺的优点,综合性质也得到了较大提升,应用领域得到了极大的拓展,独特的刚柔结合的空间网状大分子结构,表现出较强的絮凝性能,目前,广泛应用于印染、采矿和石油化工等方面。综述了淀粉接枝丙烯酰胺聚合物在各方面的应用,并对未来的发展进行了展望。     

Radiation-induced grafting of sulfonates on polyethylene

Indirect methods for introducing sulfonate groups into polyethylene, using the preirradiation technique, were studied. One of the methods involved graft polymerization of 2,3-epoxypropyl acrylate into polyethylene followed by sulfonation of the epoxy ring with bisulfite. The hydroxy sulfonate thus obtained was unstable in an acid or base environment and hydrolyzed at the esteric bond. The second method involved hydrophylization of the polyethylene by forming a pregraft of polyacrylic acid or polyvinyl alcohol, followed by preirradiation grafting with sodium styrene sulfonate or, less successfully, with sodium vinyl sulfonate. The sulfonates thus obtained were resistant to acids and bases. The acid capacity, water absorption, and water permeability of the grafted films were determined.     

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     

Grafting polythiophene on polyethylene surfaces

Polythiophene (PT) was grafted on PE film using three reaction steps. First, PE films were brominated in the gas phase, yielding PE–Br; second, a substitution reaction of PE–Br with 2‐thiophene thiolate anion gave the thiophene‐functionalized PE; finally PT was grafted on the PE surface using chemical oxidative polymerization to give PE–PT. The polymerization was carried out in a suspension solution of anhydrous FeCl₃ in CHCl₃, yielding a reddish PE–PT film after dedoping with ethanol. ATR‐FTIR shows that the PT was grafted on PE in the 2,5‐position. SEM imaging revealed islands of PT on the PE film. AFM analysis found the thickness of islands to be in the range of 120–145 nm. The conductivity of these thin films was in the range of 10^?6 S cm^?1, a significant increase from the value of ～10^?14 S cm^?1 measured for PE film. © 2003 Society of Chemical Industry     

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     

Chemical reactions on plasma-treated polyethylene surfaces

Oxygen plasma treatment as a surface functionalization technique is discussed. Oxygen-containing functionalities were introduced on the surface of high- (HDPE) and low-density polyethylene (LDPE) by glow discharge. The number of surface hydroxyl groups was increased by a post-discharge wet treatment in a reducing solution. The effects of the substrate nature, the discharge parameters, and the post-discharge wet treatment on the surface functional groups are discussed, and the effectiveness of functionalized surfaces on the yield of coupling reactions is shown.     

Study of oxidation after monoacrylate grafting on polyethylene

BACKGROUND: The surface properties of high‐density polyethylene and linear low‐density polyethylene were modified by grafting urethane monoacrylate monomer under UV irradiation. This graft polymerization was carried out on native substrates and on substrates pre‐treated by wet oxidation, for different oxidation times. RESULTS: As the urethane monacrylate layer is crosslinked, its grafting efficiency was checked by dissolving the polyethylene substrates in hot toluene. Grafting was evidenced by Fourier transform infrared spectroscopy of the obtained residues, which showed that both the characteristic urethane acrylate (3350 cm^?1) and polyethylene (2920, 730 and 720 cm^?1) bands were observable for any polyethylene oxidation time. For an oxidation time longer than 10 hours, acrylate grafting was homogeneous and the grafted surface was smooth with a roughness of less than 10 nm. In addition, X‐ray photoelectron spectroscopy analysis of the residues revealed that O/C had an average value of 0.19, which is lower than the value corresponding to pure acrylate (0.42), whereas N/C had an average value of 0.068, also lower than that of pure acrylate (0.09), thus confirming the grafting. CONCLUSION: A urethane monoacrylate layer was grafted on native and oxidized polyethylene films. For highly oxidized films, the grafted surfaces are smooth and homogeneous. Copyright © 2008 Society of Chemical Industry     

Silane grafting reactions of low-density polyethylene

Reactions of vinyl trimethoxysilane grafting onto low-density polyethylene (LDPE) were investigated using Fourier transform infrared spectroscopy, differential scanning calorimetry, and thermal gravimetric analysis. The silane grafting reactions were induced by a fixed amount of dicumyl peroxide at 0.2 part of reagent per hundred parts with respect to LDPE. Fourier transform infrared data demonstrated that the extent of the silane grafting reaction was increased as the amount of silane used, the reaction time, or the reaction temperature was increased. The apparent activation energy of the silane grafting reaction was 9.7 kJ mol⁻¹. Differential scanning calorimetry was used to follow the silane grafting reactions in situ at a heating rate of 20°C per minute. The silane grafting reaction was exothermic starting at about 150°C and ending at about 230°C, indicating a completion of the reaction in 4 min. The grafting reaction heat has linear relations to the amount of silane used. The grafting reaction heat of about 1 J/g of sample was generated during reaction per part of reagent per hundred parts of silane used. The reaction heat of silane grafting onto LDPE per mol of silane used was 14.5 kJ mol⁻¹ silane, and the reaction heat of peroxide that reacted with LDPE was −12 kJ mol⁻¹ peroxide. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 255–261, 1998     

Electron beam irradiation induced grafting of acrylonitrile to polyethylene powder

This study focuses on the influence of various parameters on the post-irradiation grafting of acrylonitrile monomer to a low density polyethylene powder having an average particle size of 20 μm diameter. The type of radiation used was 0.8 MeV electrons with a dose rate of either 0.1 Mrad/min or 4.0 Mrad/min. Irradiations were carried out in vacuum, air, and dry oxygen environments at room temperature to total doses ranging from 1 Mard to 15 Mrad. Several experimental techniques were used to investigate various interrelated aspects of both the graft copolymer product and the graft process, including infrared spectroscopy to measure percent graft, electron spin resonance to measure radical concentrations, scanning electron microscopy to investigate surface morphology, and differential scanning calorimetry to measure crystalline content. Comparisons of the percent graft determined from different probes were found to be consistent. The dose dependence of grafting exhibited a linear relationship below 8 Mrad. Initiation by both alkyl and peroxy radicals at 77°C was supported by results of decreased grafting with decreased temperature, increased dose rate or vacuum irradiation. Decreased grafting after oxygen irradiation suggested a unique change in grafting mechanism. Higher grafting yields were found for quenched relative to annealed samples. The amount of extractable homopolymer formed was found to be ～ 10% at a dose of 10 Mrad and a dose rate of 4 Mrad/min.     

Characterization of fluorinated polyethylene surfaces

Polyethylene foils, used as greenhouse foils stabilized with various types of sterically hindered amine light stabilizers (HALS), showed an extraordinary prolonged lifetime on exposure to natural or artificial weathering if a gas-phase fluorination under low-pressure conditions was applied. The fluorination was performed using F₂/N₂ mixtures and provided ca. 50 F/100 C (fluorination degree ≈25%). The lifetimes of fluorinated PE foils on exposure to artificial or natural weathering were increased at least by a factor of 2-4 as measured in terms of tensile strength and elongation at break.     

氯化聚乙烯溶胀悬浮法接枝HEA的研究

研究了氯化聚乙烯(CPE)溶胀悬浮法接枝丙烯酸-β-羟乙酯(HEA),考查了反应温度、反应时间,膨胀荆(EA)、分散介质水、单体HEA及过氧化苯甲酰(BP0)等的用量对HEA接枝率的影响.采用红外光谱对接枝物进行了定性表征.     

Photosensitized grafting of acrylamide and hydroxyethyl methacrylate onto cellulose

The photoinitiated copolymerization of acrylamide and hydroxyethyl methacrylate onto cellulose substrates, from acetone/water solutions, was studied using isopropyl thioxanthone as the photoinitiator. The graft copolymerization was carried out over a range of monomer and photoinitiator concentrations. Grafting is shown to be dependent on the nature of the monomer and the concentration of monomer and photoinitiator. In the case of acrylamide, it was found that there is an optimum concentration of the photoinitiator for grafting to occur effectively. The kinetics of graft copolymerization were studied in some detail and the results are considered.     

Application of hydrophilic starch-based coatings on polyethylene surfaces

Coatings were applied to polyethylene (PE) film surfaces by spraying formulations prepared from a jet cooked dispersion of waxy cornstarch, a water-born epoxy resin, a wax emulsion, and a fluorinated surfactant. The air-dried coatings were comprised of discontinuous areas of polymer that adhered tightly to the PE surface. Although the starch component separated rapidly from the coating when the film was placed in water at room temperature, heating the coated film for 24 h at 80°C increased the adhesion of starch and produced a surface coating that remained uniformly wet when the film was placed in water. Most of the starch, however, could be still be removed by gently rubbing the wet surface. If melamine-formaldehyde resin was added to the formulation as a crosslinking agent for starch, and the coated film was then heated for 24 h at 80°C, most of the starch remained bonded to the wet coating, even after the surface was gently rubbed. Identification of successful spray application techniques and formulations will allow the development of commercial production methods for starch-coated PE films and similar products. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Application of ultraviolet photografting technology to acrylamide/polyethylene to improve the interfacial adhesion of polyethylene/unsaturated polyester resin composites

This study was divided into two sections. In the first part, we used ultraviolet (UV) rays in the wavelength range 300–400 nm to remove the hydrogen atom from polyethylene (PE) and worked with a hydrophilic monomer to complete the grafting action. In the second part, we used the best conditions derived from the previous film grafting and applied them to fibers to achieve excellent adhesion for application in composite materials. For the handling process of the PE film, we initially used acrylamide (AM) as the monomer and then added acetone and benzophenone (BP) to form a reactive solution for the advanced photografting process. In general, the optimum concentrations of the monomer solutions obtained from the photografting of PE films were 2 mol/L of AM and 0.2 mol/L of BP. The UV irradiation time was fixed at 30 min. The optimum grafting conditions achieved in the first part of this research were applied in the photografting process for the PE fiber bundles in the second part. The unsaturated polyester (UP) resins were spread over the outer surfaces of the modified fibers. This was done to strengthen and increase the interface between the UP resins and the modified PE fiber. During the curing experiment of the grafted fiber bundles in the resin coatings, the best material quality was obtained under the following conditions: hardener content = 0.85% (relative to the UP resin weight), oven temperature = 80°C, and time frame = 5 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009