Preparation of hydrophilic polyethylene foam of open cell type by radiation grafting of acrylic acid

Hydrophilic polyethylene foam was synthesized by radiation grafting of acrylic acid onto polyethylene foam of open cell type using monomer solution containing Mohr's salt which inhibits homopolymerization of the monomer. The graft foam was easily dyed by cationic dyes and showed excellent moisture regain. The wicking properties were also excellent and were almost the same as those of commercially available PVA foam. The surface resistivity of 10¹⁶ ohm of the original foam decreased to 10⁶ ohm and half decay time of surface charge decreased from 8000 s to 1 s by the grafting, indicating that the grafted foam has excellent antistatic properties.     

Autoadhesion of high density polyethylene (HDPE) to HDPE by ultraviolet grafting of methacrylates and acrylates

A study has been made on the effect of the presence of grafted acrylic layers on the autoadhesion of polyethylene. Methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), and butyl methacrylate (BMA) were grafted onto high density polyethylene (HDPE). The grafting reaction was faster at higher temperature and methacrylates graft more easily than acrylates. For methacrylates and acrylates, the grafted amount increases with increasing length of the pendant alkyl chain. The grafting temperature is a crucial factor affecting the adhesion of grafted PE samples. For the samples grafted at lower temperature (in a room temperature water bath), the adhesion is very low (less than 50 N/m), even for very thick grafted layers. But for the samples grafted at higher temperature, much higher adhesion can be obtained. The presence of homopolymer was another factor affecting the adhesion of PE samples. When homopolymer is removed from the surface of the grafted sample, higher adhesion can be obtained. For some samples, the highest peel strength of more than 1000 N/m has been obtained. The low adhesion of the samples grafted at low temperature is attributed to the high branching of grafted chains.     

AUTOADHESION OF HIGH DENSITY POLYETHYLENE (HDPE) TO HDPE BY ULTRAVIOLET GRAFTING OF METHACRYLATES AND ACRYLATES

A study has been made on the effect of the presence of grafted acrylic layers on the autoadhesion of polyethylene. Methyl methacrylate (MMA), ethyl methacrylate (EMA), methyl acrylate (MA), ethyl acrylate (EA), and butyl methacrylate (BMA) were grafted onto high density polyethylene (HDPE). The grafting reaction was faster at higher temperature and methacrylates graft more easily than acrylates. For methacrylates and acrylates, the grafted amount increases with increasing length of the pendant alkyl chain. The grafting temperature is a crucial factor affecting the adhesion of grafted PE samples. For the samples grafted at lower temperature (in a room temperature water bath), the adhesion is very low (less than 50 N/m), even for very thick grafted layers. But for the samples grafted at higher temperature, much higher adhesion can be obtained. The presence of homopolymer was another factor affecting the adhesion of PE samples. When homopolymer is removed from the surface of the grafted sample, higher adhesion can be obtained. For some samples, the highest peel strength of more than 1000 N/m has been obtained. The low adhesion of the samples grafted at low temperature is attributed to the high branching of grafted chains.     

Graft copolymerization of polyethylene glycol methacrylate onto polyethylene film and its blood compatibility

In an attempt to produce surfaces that show low levels of adsorption of protein and adhesion of platelets, different molecular weights of polyethylene glycol methacrylate (PEG‐MA) were grafted onto polyethylene film by a preirradiation grafting process. The extent of grafting was found to be dependent on the storage condition of the irradiated polyethylene film, the preirradiated dose, reaction time and temperature, molecular weight of PEG‐MA, and the type of solvent. The grafting yield was found to decrease rapidly with storage time for irradiated polyethylene film stored at room temperature. On the other hand, the grafting yield in the irradiated polyethylene stored at −130°C remained nearly constant up to 20 days after irradiation. The grafting yield decreased with an increased PEG‐MA molecular weight. Human plasma protein was adsorbed onto control and PEG‐MA‐grafted polyethylene film surfaces, and the relative adsorbed amount of proteins on the surfaces was evaluated by electron spectroscopy for chemical analysis. The adsorbed protein and platelet adhesion on the polyethylene film surface decreased rapidly with the grafting yield. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 631–641, 1999     

Melting and glass transition of radiation-induced graft polyethylene

Melting and glass transition data are reported employing DSC for styrene-grafted high-density polyethylene obtained by γ radiation. Judging from the data of the melting point and the heat of fusion, the grafted polystyrene had no effect on the polyethylene crystallites, but the half-width of the thermogram was observed to increase slightly, showing an effect on the crystallite size distribution. As no effect was observed on the glass transition temperature by grafting, the amorphous region of the polyethylene apparently was not affected. It is suggested, therefore, that the free volume or segmental mobility will not be decreased by radiation-induced grafting. Very few but long grafted chains had negligible effect on the average polyethylene chain length available for segmental motion, and grafted polystyrene should be expected to differ little from the styrene homopolymer in thermal motions.     

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     

Radiation‐induced grafting of glycidyl methacrylate onto high‐density polyethylene (HDPE) and radiation lamination of HDPE

Radiation‐induced grafting of glycidyl meth‐acrylate (GMA) onto high‐density polyethylene (HDPE) and the radiation lamination of HDPE by bulk grafting of GMA were reported. The effects of irradiation dose, monomer concentration, and atmosphere on grafting were investigated. The extent of grafting initially increased with irradiation dose and then remained almost constant. The extent of grafting was higher in 2M GMA than in 1M GMA at the same irradiation dose. The extent of grafting in nitrogen was higher than that in air. The grafted samples were characterized with FTIR spectrometry and thermogravimetric (TG) analysis. A carbonyl group was found on grafted HDPE samples, and the carbonyl index increased with the extent of grafting. TG analyses proved the existence of grafted materials on HDPE and the grafted GMA thermally decomposes at a temperature lower than that of HDPE. Strong adhesion could be obtained with radiation lamination of HDPE by bulk grafting of GMA. Benzophenone facilitates the grafting in a proper concentration range. The adhesion mechanism of the laminated samples was the entanglement of the grafted chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 772–779, 2005     

Radiation-induced graft polymerization of vinyl benzyltrimethylammonium chloride onto polyethylene film

An attempt was made to introduce a strong base anion-exchange group by radiation-induced grafting of vinyl benzyltrimethylammonium chloride (VBTAC) onto polyethylene film. Both two-step grafting and comonomer grafting techniques were tried owing to the difficulty of direct graft polymerization of VBTAC onto polyethylene. 2-Hydroxyethyl methacrylate (HEMA) and ethyl methacrylate (EMA), having the same backbone structure except that the hydroxyl group of HEMA was grafted onto the polyethylene film and then VBTAC was grafted to examine the reactivity of VBTAC with each grafted polyethylene film. Co-grafting of the binary mixtures of VBTAC and HEMA, or EMA, onto polyethylene film was also carried out. © 1994 John Wiley & Sons, Inc.     

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     

Heat Shrinkable Polymer Blends Based on Grafted Low Density Polyethylene and Chlorosulfonated Polyethylene (Part-II)

Abstract

Heat shrinkability of the polymer which depends on elastic memory can be introduced into the system in the form of an elastomeric phase. The present study deals with the measurement of heat shrinkability of the blend of grafted polyethylene and CSM. Interchain crosslinking between grafted polyethylene and elastomer improved the shrinkability. Maleic anhydride and glycidyl acrylate is used as grafting materials. Glycin and 4 4prime; diamino diphenyl sulphone is used as coupling agents. Maximum amount of crosslinking is obtained when glycidyl acrylate is used as grafting agent Minimum amount of interchain crosslinking is observed when 4 4prime; diamino diphenyl sulphone is used as coupling agent. Probable interactions of rubber and plastic phase are confirmed by IR spectroscopy. Extraction of the elastomeric phase is restricted due to interchain crosslinking as confirmed by SEM study which is more prominent in the case of glycidyl acrylate grafted LDPE.     

Atomic force microscopy study of the photografting of glycidyl methacrylate onto HDPE and the microstructure of the grafted chains

This article presents an atomic force microscopy (AFM) study of the initial stage of the photografting of glycidyl methacrylate (GMA) onto high-density polyethylene (HDPE) surface and the microstructure of the grafted chains. The grafting was carried out in acetone, dichloromethane and tetrahydrofuran (THF), as well as without solvent. Granular structures were found on the surface of the samples grafted in the solvents. The height of the granules increased linearly with their diameter. Each granule was thought to be a single grafted chain with a highly branched (or superbranched) microstructure. The grafting density on HDPE was quite small when the grafting was carried out in the solvents. The grafted chains were more branched when grafting was carried out in THF than when the grafting was carried out in acetone and dichloromethane. The bulk (no solvent) grafting of GMA onto HDPE was much faster and more uniform than that carried out in the solvents. The thickness of the bulk grafted materials was a few nanometers after 30 s irradiation, and possibly, the grafting density was much higher and the grafted polymers were much less branched than those produced in solvent.     

Glycidyl methacrylate–grafted linear low‐density polyethylene fabrication and application for polyester/polyethylene bonding

The grafting of glycidyl methacrylate (GMA) onto linear low‐density polyethylene (LLDPE) was investigated. The grafting was performed by free‐radical grafting in the melt state in a twin‐screw extruder using an organic peroxide as initiator. The effect of initial GMA and peroxide concentration, styrene comonomer addition, as well as initial resin viscosity, on the final content in grafted moieties, unbound homopolymer, and unreacted monomer was assessed. The effect of process parameters such as flow rate, screw rotation speed, and barrel temperature was also investigated. Chemical composition was shown to be the main parameter for controlling grafting level and grafting efficiency. Grafting levels up to 1.8% and efficiency of 90% were reported even though in most conditions, the graft efficiency was severely decreased by the homopolymerization of GMA into polyGMA chains not bound to LLDPE. Finally, the effect of grafting level and the presence of unbound GMA‐based species on the efficiency GMA‐grafted LLDPE as adhesive between polyethylene and polyester were discussed. Good adhesion to poly(ethylene terephthalate) copolymer was found for low viscosity grafted polyethylene resins. A significant improvement in adhesive strength on polyester was observed when the molecular weight of the grafted LLDPE was increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3180–3191, 2004     

Distribution of grafted poly(acrylic acid) in polyethylene film

The morphology of acrylic acid-grafted high-density polyethylene film and the distribution of poly(acrylic acid) in grafted film are examined. The grafting was carried out in the acrylic acid aqueous solution with or without Mohr's salt (an inhibitor of homopolymerization) by preirradiation method. It has become clear that without Mohr's salt the grafted poly(acrylic acid) layer is formed on the surface of the film, while in the presence of Mohr's salt the grafting layer consisting both of poly(acrylic acid) and polyethylene is formed on the inside of the surface.     

Radiation-grafting of acrylic acid onto ultrahigh molecular,high-strength polyethylene fibers

Radiation-induced grafting of acrylic acid onto ultrahigh molecular weight (UHMW) high-strength polyethylene fibers to impart heat resistance and dyeability was undertaken. A preirradiation method was employed for grafting in an aqueous solution of acrylic acid containing a small amount of Mohr's salt as inhibitor. The grafting rate for UHMW high-strength polyethylene fibers is one-tenth of that for high-density polyethylene fibers currently in use, and one-hundredth, for high-density polyethylene film. It has become clear that the preirradiation dose should be as low as 1 Mrad to keep the high strength of the starting fibers. The starting UHMW high-strength polyethylene fiber begins to shrink remarkably at around 145°C, showing a maximum shrinkage of 90%, and then breaks at 154°C. When a 24% acrylic acid graft is converted to calcium salt, the grafted fiber retains the fiber form even at 300°C and gives only a maximum shrinkage of 11%. The less than 1% acrylic acid graft UHMW high-strength polyethylene fibers and their calcium salt can be dyed to a deep shade with cationic dyes, whereas the starting fibers cannot be dyed with usual dyes including the cationic dye. © 1993 John Wiley & Sons, Inc.     

Hydrophilic and adhesive properties of methacrylic acid-grafted polyethylene plates

Methacrylic acid (MAA) was grafted onto polyethylene (PE) surfaces by simultaneous irradiation with UV rays in the liquid phase to estimate hydrophilic and mechanical properties for MAA-grafted PE plates. The amount of grafted MAA increased sigmoidally with UV irradiation time, and the higher grafted amount was obtained at higher monomer concentrations. With an increase in grafting of MAA, the wettabilities from the contact angles of water were enhanced and the refractive indices from the ellipsometry decreased. Though the contact angles remained constant above the grafted amount of 0.02 mmol/cm², the refractive indices approached the value of PMAA around 0.009 mmol/cm², indicating that the PE surfaces were fully covered with grafted PMAA chains. Then, at a fixed grafted amount, the grafted layer can absorb more water and the grafted PE plates possessed higher tensile shear adhesive strength, in case grafting was carried out at lower monomer concentrations. Surface properties depended on the density of carboxyl group at the surfaces of grafted layers, whereas adhesive properties depended on the structural properties of grafted chains as well as on the density of carboxyl group of the whole grafted layers.     

Photoinitiated surface grafting of synthetic fibers,I. Photoinitiated surface grafting of ultra high strength polyethylene fibers

Photoinitiated surface grafting of acrylic monomers has been carried out onto high strength polyethylene (HSPE) yarn by means of a continuous process. The grafting reaction is initiated by UV irradiation of the yarn after presoaking in an acetone solution of initiator and monomer. Four initiators, benzophenone (BP), 4-chlorobenzophenone (4-CBP), 2-hydroxy-2-cyclohexylacetophenone (HHA), and 2,2-dimethoxy-2-phenylacetophenone (DMPA), and two monomers, acrylic acid (AA) and acrylamide (AM), have been used. After short irradiation time (10 to 20 s) successful grafting is obtained, as shown by ESCA and IR-ATR spectra, dye adsorpotion from aqueous solution, and measurements of adhesion of single filaments to epoxy resin. Grafting efficiency of 74% has been reached for AA as monomer (26% is homopolymer). The tensile strength and modulus of the HSPE yarn are retained in the grafting process. The degree of surface grafting is mainly a function of structure and concentration of monomer and photoinitiator in the presoaking solution and of the irradiation conditions used. Increasing irradiation time gives increasing amounts of grafted polymer up to a certain limiting value. The reactivities of the four initiators have been compared showing the highest grafting yields of AA with BP and of AM with 4-CBP as photoinitiator. AA grafted HSPE yarn can be dyed to rather deep color by dipping in an aqueous solution of Crystal Violet. Increased dye absorption by a factor of up to seven has been measured for yarn grafted with AA to the maximum level obtained. The filaments of the grafted yarn show increased adhesion to epoxy resin by a factor of up to five compared with the ungrafted filaments.     

Influence of the solvent viscosity on surface graft-polymerization reactions

Solvent viscosity was found to be a predominant parameter to control free-radical surface graft polymerization. Poly(ethylene-alt-tetrafluoroethylene) foils were lithographically exposed to 92 eV photons in order to create patterns of radicals at their surface, which react with the oxygen of the ambient air to produce peroxides. Glycidyl methacrylate was then radically polymerized from these peroxide initiators. We discovered that increasing the viscosity of the grafting solution by addition of polyethylene glycol boosts the grafting reaction, leading to an order of magnitude increase in the height of the grafted layer. Further increasing the viscosity leads to thinner layers of grafted material. The increase of the grafted layer thickness in the low viscosity range is interpreted to be due to a diminution of the termination rate while for higher viscosity, the reduction of the initiation rate causes the observed decrease of the grafted thickness. This interpretation is in agreement with observed morphological and structural differences of nanostructures grafted at different viscosities. We conclude that viscosity is an essential and very easily controllable parameter for surface graft-reactions.     

Basic functionalization of polyethylene in the melt

The production of a polymer containing basic functional groups via the reactive processing of polyethylene was investigated. Grafting of dimethylamino ethyl methacrylate, DMAEMA, to linear low-density polyethylene in the melt was carried out, and the effects of initiator type, feed composition, and reaction time and temperature were studied. The extent of grafting was determined by Fourier transform infrared and ¹H nuclear magnetic resonance spectroscopy, and the degree of cross-linking was observed by measuring the products' melt indices. Thermal stability of the product was investigated using differential scanning calorimetry. Materials containing up to 3 wt% of grafted DMAEMA were prepared. The choice of appropriate feed compositions and reaction conditions allows the production of a material containing the maximum amount of grafted DMAEMA, while minimizing cross-linking. The grafted polyethylene produced under these conditions is more stable than the starting material, suggesting an antioxidant effect of the grafted moieties. The functional polymer produced should be of interest for the preparation of polymer blends with acidic polymers by virtue of the miscibility enhancement that could occur as compared with the hydrocarbon precursor.     

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     

Search for nonoxidative,hydrogen-abstracting initiators useful for melt grafting processes

Using organic peroxide initiators in the melt grafting of monomers containing amino groups onto polyethylenes is known to cause serious discoloration of the resulting polymers. To eliminate the discoloration while preserving the controlled degree of grafting, a nonoxidative and hydrogen-abstracting initiator with appropriate thermal stability is needed. In this study, the hydrogen-abstracting capability of three azo initiators with suitable decomposition rates in the melt grafting temperature ranges was evaluated using polyethylene cross-linking and polypropylene degradation experiments (called “hydrogen-abstracting experiments”). Among the three azo initiators tested, only a phenylazo initiator, 2 - phenylazo - 2,4 - dimethyl - 4 - methoxyl - valeronitrile (V-19), demonstrated strong hydrogen-abstracting capability from polymer backbones. These three azo initiators were used in the melt grafting of 2 - (N, N - dimethylamino) ethyl methacrylate (DMAEMA) and 2-(N-t -butylamino) ethyl methacrylate (tBAEMA) onto a linear low-density polyethylene (LLDPE). In agreement with the results obtained from the hydrogen-abstraction experiments, only V-19 led to a considerable amount of grafting of both DMAEMA and tBAEMA onto LLDPE. As expected, polymers grafted with V-19 showed significantly reduced discoloration compared with those grafted with peroxide initiators. Further examination of the grafting results indicated that the initiator efficieny, defined as the number of grafted monomer units per radical generated from initiator decomposition, was higher with the phenylazo initiator than with peroxide initiators. The hydrogen-abstracting capability of the phenyl free radical generated from the decomposition of V-19 was estimated to be higher than peroxide and methyl free radicals produced in the decomposition of peroxide initiatros. © 1993 John Wiley & Sons, Inc.