Characterization for graft polymerization of alkyl methacrylate onto polydimethylsiloxane membranes by electron beam and their permselectivity for volatile organic compounds

Polydimethylsiloxane (PDMS) membranes were improved by graft polymerization of fluoroalkyl methacrylates (FALMA) and alkyl methacrylates (AMA) by electron beam, and the effect of the solubility and diffusibility of a monomer on graft polymerization and the pervaporation through grafted membrane were investigated. The difference of the grafted amount was small for the monomers with various solubility parameters and log P_ow which is the logarithm of the octanol–water partition coefficient. Compared to each other in the same group of FALMA or AMA, the sorpted and grafted amount for a monomer that has low molecular volume was high, and the sorpted and grafted amount for a monomer that has high molecular volume was low. FALMA‐grafted PDMS membranes showed high separation performance compared to PDMS membranes. Among them, 2,2,3,3,3‐pentafluoropropyl methacrylate grafted PDMS membrane, which had a high grafted amount, and F/Si calculated by the grafted amount had high selectivity for trichloroethylene (TCE). The FALMA‐grafted PDMS membranes that had the high TCE concentrations in the sorbed solution exhibited high permselectivity for TCE. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 203–213, 2001     

Radiation‐induced GMA/DMAA graft copolymerization onto porous PE hollow‐fiber membrane

Radiation‐induced graft copolymerization is a powerful technique to prepare a grafted chain with the desired properties pending onto the trunk material. In this work, a polyethylene hollow‐fiber membrane was modified by this technique. The monomers glycidyl methacrylate (GMA) and N,N‐dimethylacrylamide (DMAA) were cografted onto macroporous polyethylene hollow fiber with a grafting degree in the order of 200%. DMAA/GMA cografted membranes were compared to GMA grafted ones for the introduction of an amino acid as a specific ligand. Grafted membranes with a copolymer composition between 0 and 2 DMAA/GMA were prepared by soaking them in solutions of different mixtures of monomers. Copolymers were characterized by FTIR and their composition was estimated by the analysis of the ratio of carbonyl signals. Copolymers with a higher proportion of DMAA showed improved hydrophilic properties and higher conversion rates of epoxy groups on phenyalanine ligands than those of the GMA grafted ones. However, copolymers with a DMAA/GMA ratio higher than 1 showed a detrimental effect on the pure water flux. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1646–1653, 2003     

Preirradiation‐induced emulsion graft polymerization of glycidyl methacrylate onto poly(vinylidene fluoride) powder

An epoxy‐group‐containing monomer, glycidyl methacrylate (GMA), was grafted onto poly(vinylidene fluoride) powder via preirradiation‐induced emulsion graft polymerization. The existence of graft chains was proven by chemical structure characterization with Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis. The degree of grafting was calculated by means of fluorine content analysis. A kinetic study indicated that, with the emulsion graft polymerization system, the GMA conversion rate was high, exceeding 80%. The variation in the molecular weight of the grafted polymer was measured by gel permeation chromatography, and its crystallinity was investigated with differential scanning calorimetry. The epoxy groups in graft chains were found to be suitable for further chemical modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Plasma-grafting of fluoroalkyl methacrylate onto PDMS membranes and their VOC separation properties for pervaporation

A polydimethylsiloxane (PDMS) membrane was improved by graft polymerization of 1H,1H,9H-hexadecafluorononyl methacrylate (HDFNMA) by plasma, which had the effect of increasing the selectivity for volatile organic compounds (VOCs). The use of an easy quantitative analysis for the pervaporation through plasma-grafted PDMS membranes was investigated. The degrees of grafting on the inside and reverse side of the grafted PDMS membranes were lower than on the surface. Only part of the HDFNMA sorbed into the PDMS membrane was grafted onto the PDMS membrane. The relationship between the feed concentration and the permeate concentration was observed to be linear. The pervaporation through the grafted PDMS membrane could be used for easy quantitative analysis. The solubility of VOCs for the grafted PDMS membrane was high when compared with the solubility for the PDMS membrane. The grafted PDMS membrane that had high VOC concentrations of the sorbed solution showed an excellent separation performance. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1835–1844, 1999     

Sorption and diffusion of volatile organic compounds in fluoroalkyl methacrylate‐grafted PDMS membrane

Pervaporation is known as an excellent method for the purification of contaminated water, the extraction of aroma compounds, etc., and has been widely studied. The prediction of permeation is important for treatment, extraction, and quantitative analysis. To predict permeation, a solution–diffusion mechanism is proposed. The octanol–water partition coefficient (Pow) has been generally used in expressing hydrophobicity. The hydrophobicity, Pow, is closely related to the solubility of organic compounds. Also, the molecular volume is closely related to the diffusion of organic compounds. In this study, we improved polydimethylsiloxane (PDMS) membranes by plasma grafting of fluoroalkyl methacrylates (FALMA) to enhance the affinity of PDMS to volatile organic compounds (VOCs). Furthermore, we investigated the pervaporation through the plasma‐grafted PDMS membrane and the PDMS membrane and the solution–diffusion mechanism of various VOCs. The permselectivity of tetrachloroethylene (PCE) and toluene determined by the sorption and the diffusion characteristics permeating in the membrane was high. Because the molecular volume of the VOCs is greated than that of water and the permeates quickly penetrate in rubbery membranes like PDMS, permselectivity was not affected by the diffussivity. Solubility significantly affected the permselectibity during pervaporation through a hydrophobic rubbery membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 773–783, 2000     

Radiation‐induced graft polymerization of glycidyl methacrylate onto PE/PP nonwoven fabric and its modification toward enhanced amidoximation

A nonwoven fabric made of polypropylene coated by polyethylene was used as the trunk polymer in the preparation of a highly efficient new adsorbent. Metal ion uptake capacity has been aimed to be increased by introducing double amidoxime groups per repeating unit of the chains grafted to trunk polymer. The base polymer was irradiated by electron beams with a dose of 200 kGy under N₂ atmosphere and glycidyl methacrylate (GMA) was grafted onto irradiated nonwoven fabric. Grafting conditions were optimized, and GMA‐grafted polymer was modified with 3,3′‐iminodipropionitrile in ethanol at 80°C. GMA grafting (150%) was determined to be the optimum degree given that higher extent of grafting rendered the materials brittle. Pendant nitrile groups were then amidoximated by using 6% hydroxylamine in methanol–water mixture (1 : 1). The all‐polymeric structures were characterized by using FTIR, SEM, and thermal analysis methods, confirming the grafting, modification, and amidoximation stages gravimetrically, spectroscopically, and visually. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

UV‐radiation–induced preirradiation grafting of methyl methacrylate onto lignocellulose fiber in an aqueous medium and characterization

The preirradiation method of grafting has been established by ultraviolet radiation. Methyl methacrylate (MMA) was grafted onto jute fiber in an aqueous medium. The variation of graft weight with UV‐radiation time, monomer concentration, and reaction time was investigated. The conversion of monomer into homopolymer and graft copolymer was evaluated. The graft weight passes through a maximum value (～ 122%) with UV‐radiation time. The optimum value of the monomer concentration was evaluated for maximum degree of grafting. Graft copolymerization of MMA onto lignocellulose fiber significantly increases the elongation at break (～ 65%) compared to that of the “as‐received” sample. However, a linear decrease on breaking load was observed with the increase of graft weight. The estimation of degree of grafting was achieved using an IR technique by correlating band intensities with the degree of grafting. Considering the water‐absorption property, the grafted sample showed a maximum up to 61% decrease in hydrophilicity compared to that of the as‐received sample. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1667–1675, 2004     

Bulk grafting of poly(styrene‐alt‐maleic anhydride) onto preirradiated polyolefin membranes in supercritical carbon dioxide

To take advantage of the property of supercritical carbon dioxide as both a solvent and swelling agent, the bulk grafting of poly(styrene‐alt‐maleic anhydride) [P(MAH‐alt‐St)] onto preirradiated polyolefin membranes was performed by a combination of γ‐ray‐preirradiation‐induced graft copolymerization and supercritical fluid‐swollen polymerization. The trapped radicals on the polyolefin backbones were uniformly distributed by γ‐ray irradiation under a nitrogen atmosphere. Subsequently, these polymeric trapped radicals initiated the alternating copolymerization of styrene (St) and maleic anhydride (MAH) infused into the swollen polymer matrix with the aid of supercritical CO₂. It was important that the graft copolymers were relatively pure without any contaminants, including homopolymers, monomers, and initiators. The experimental results show that the degree of grafting could be easily controlled. In addition, St/MAH could synergistically promote the bulk grafting process and strongly effect on the alternating trend; this was confirmed by element analysis and differential scanning calorimetry. Soxhlet extraction, X‐ray diffraction, and Fourier transform infrared spectroscopy indicated that the P(MAH‐alt‐St) was covalently bonded to the polymeric backbones. Scanning electron microscopy showed that the alternating graft chains were uniformly dispersed throughout the 5‐mm thickness of the polymer membranes on the nanometer scale. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Characterization and pervaporation of chlorinated hydrocarbon–water mixtures with fluoroalkyl methacrylate‐grafted PDMS membrane

It is desirable to enhance the selectivity of a polydimethylsiloxane (PDMS) membrane for chlorinated hydrocarbons. In this study, the PDMS membranes were improved by graft polymerization of 1H,1H,9H‐hexadecafluorononyl methacrylate (HDFNMA), which has the effect of increasing the selectivity for chlorinated hydrocarbons. The PDMS membrane and HDFNMA were irradiated simultaneously by a ⁶⁰Co source. The grafted membranes had a microphase‐separated structure, that is, a separated structure of PDMS and grafted HDFNMA. In the grafted PDMS membrane, a great separation performance for a TCE–water mixture was shown due to the introduction of the hydrophobic polymer, poly(HDFNMA). For the permeation of the grafted PDMS membrane, the permeability of molecules in the PDMS phase was significantly great, and that in the poly(HDFNMA) phase was too low to affect the whole permeation of the grafted PDMS membrane directly. However, the permeation of molecules at the interface of poly(HDFNMA) and PDMS played an important role because poly(HDFNMA) had a much stronger affinity for TCE than water. At a low feed concentration of the TCE solution, the diffusivity of TCE molecules must be much lower than that of water due to the larger molecular size of TCE. At a high concentration of TCE solution, TCE was sufficiently sorbed into the membrane so that the diffusion of water was prevented by TCE molecules; in turn, the permselectivity of TCE was increased significantly. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 273–287, 1999     

Temperature‐sensitive membranes prepared by the plasma‐induced graft polymerization of N‐Isopropylacrylamide into porous polyethylene membranes

A temperature‐responsive polymer, poly(N‐isopropylacrylamide) (PNIPAAm), was grafted onto porous polyethylene membranes by a plasma‐induced graft polymerization technique. A wide range of grafting was achieved through variations in the grafting conditions, including the postpolymerization temperature, time, monomer concentration, and graft‐reaction medium. The active species induced by plasma treatment was proven to be long‐living via a postpolymerization time of 95 h. Different solvent compositions, that is, water, methanol, benzene, and water/methanol, were used as reaction media, and water showed a much higher polymerization rate than the organic solvents. Based on the hydrophilicity of the active species, a mechanism explaining the solvent effect in plasma‐induced graft polymerization was examined. Characterizations by scanning electron microscopy, X‐ray photoelectron spectroscopy (XPS), and micro Fourier transform infrared showed that the grafted polymers were located on both the outer surface and inside pores of the membranes. The XPS analysis also confirmed that the polar amide groups tended to distribute more outward when grafted PNIPAAm was in its expanding state than when it was in its shrinking state. Water permeation experiments showed that the permeability of the grafted membranes varied dramatically with a slight temperature change in the vicinity of the lower critical solution temperature (LCST) of PNIPAAm. The effective pore radii of the grafted membranes above and below the LCST could be depicted by Hagen‐Poiseuille's law. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3180–3187, 2003     

Ce(IV)‐initiated graft polymerization of acrylic acid onto poly(ethylene terephthalate) fiber

Graft copolymerization of acrylic acid onto poly(ethylene terephthalate) (PET) fiber by a redox system using ceric (IV) initiator was studied with regard to various parameters of importance: acrylic acid concentration, ceric (IV) concentration, nitric acid concentration, reaction temperature, and reaction time. Based on the morphology of the PET fiber, it could be concluded that ceric (IV) in dilute nitric acid is a redox initiator for the surface graft copolymerization of the acrylic acid/PET system. The grafted PET fiber showed an increase in improved moisture regain to reach 900% at 39.5% graft yield. The dyeability with the basic dye and disperse dye significantly increased by 100 and 22%, respectively, as a result of the grafting onto PET fiber. Both tenacity and elongation gradually decreased by 51.2 and 28.9%, respectively, with increasing graft yield, which reduced the fiber service lifespan. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1952–1958, 2003     

Two‐stage grafting onto polyethylene fiber by radiation‐induced graft polymerization and atom transfer radical polymerization

Two‐stage graft polymerization onto polyethylene (PE) fiber was demonstrated. The graft side chain was formed by radiation‐induced graft polymerization. A PE fiber was irradiated with an electron beam and immersed in a vinyl monomer solution. The terminal of the formed graft chain was halogenated using N‐bromosuccinimide. The halogenated graft chain was then extended by atom transfer radical polymerization to obtain block‐copolymer grafted PE fibers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study on the phase behavior of ethylene–vinyl acetate copolymer and poly(methyl methacrylate) blends by in situ polymerization

This study examines the phase behavior of ethylene–vinyl acetate copolymer (EVA) and poly(methyl methacrylate) (PMMA) blends during MMA polymerization. The ternary PMMA/MMA/EVA mixtures are considered to create a triangular phase diagram, which responds the phase changes during polymerization. The phase changes during MMA polymerization are also examined by optical microscope and photometer. Since the PMMA and EVA are well‐known immiscibles, the polymer solution undergoes phase separation at the initial stage of the MMA polymerization. Additionally, the phase inversion occurs as the conversion of MMA between 13.8 and 20.8%. On the other hand, the EVA‐graft‐PMMA, which can reduce the dispersed EVA particle size, is induced efficiently by taking tert‐butyl peroctoate (t‐BO) as initiator during MMA polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1001–1008, 2003     

N,N‐diethyl dithiocarbamato group induced photografting of methyl methacrylate onto polyurethane

The N,N‐diethyl dithiocarbamato group present in a variety of compounds acts as an initiator in the photopolymerization processes. The photolability of this group is due to the cleavage of the C S bond by UV irradiation. N,N‐Diethyl dithiocarbamato‐(1,2)‐propane diol with a pendent N,N‐diethyl dithiocarbamato group was prepared from 3‐chloro‐(1,2)‐propane diol and sodium diethyl dithiocarbamate. A polyurethane macrophotoinitiator was then synthesized by a two‐step process, where N,N‐diethyl dithiocarbamato‐(1,2)‐propane diol was used as the chain extender. Other components used included 4,4′‐diphenylmethane diisocyanate and poly(propylene glycol) (molecular weight = 1000). The polyurethane thus synthesized had pendent N,N‐diethyl dithiocarbamato groups. This polyurethane macrophotoinitiator was then used to polymerize methyl methacrylate in a photochemical reactor (Compact‐LP‐MP 88) at 254 nm. The resulting graft copolymer, polyurethane‐g‐poly(methyl methacrylate), was freed from the homopolymer by a standard procedure. The graft copolymer was characterized by Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, solution viscometry, and scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Free‐radical graft copolymerization of phosphonated methacrylates onto low‐density polyethylene

Dimethyl 2‐methacryloxyethylphosphonate, its monosodium salt, and methyl 2‐methacryloyloxyethylphosphonic acid were synthesized, characterized, and grafted onto low‐density polyethylene (LDPE) powder under melt‐processing conditions in a Rheocord batch mixer (Karlsruhe, Germany). We studied the graft copolymerization onto LDPE in the presence of free‐radical initiators, benzoyl peroxide, and dicumyl peroxide, and we performed grafting onto ozone‐pretreated LDPE without any free‐radical initiator. Effects of reaction time, initiator concentration, and reaction temperature were studied. The possibility of modifying LDPE in the molten state with phosphonated methacrylates was clearly demonstrated. Graft copolymers were characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, scanning electron microscopy, and water contact angles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2011–2020, 2002     

Synthesis of cassava starch‐g‐poly(methyl methacrylate) copolymers with benzoyl peroxide as an initiator

Graft copolymers of cassava starch and methyl methacrylate (MMA) were synthesized by free‐radical polymerization with benzoyl peroxide (BPO) as an initiator in an aqueous medium at 80°C. The formation of graft copolymers was confirmed by analysis of the obtained products with Fourier transform infrared spectroscopy and scanning electron microscopy. The effects of the amount of cassava starch, the amount of MMA monomer, the amount of BPO, and the reaction time on the grafting characteristics were studied. The optimum condition for grafting were obtained when 5 g of cassava starch, 5 g of MMA, 0.1 g of BPO, and a reaction time of 3 h were used. These condition provided a graft copolymer with 25.00% add‐on, 81.40% monomer conversion, 54.30% homopoly(methyl methacrylate) formed, 45.70% grafting efficiency, 37.20% grafting ratio, and 95.54% yield. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4083–4089, 2006     

Irradiation grafting of methyl methacrylate monomer onto ultra‐high‐molecular‐weight polyethylene: An experimental design approach for improving adhesion to bone cement

The grafting of methyl methacrylate (MMA) onto ultra‐high‐molecular‐weight polyethylene (UHMWPE) and chromic acid etched UHMWPE was conducted with a preirradiation method in air in the presence of a Mohr salt and sulfuric acid. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, a gravimetric method, differential scanning calorimetry, scanning electron microscopy (SEM), and interfacial bonding strength measurements. The FTIR results showed the presence of ether and carbonyl groups in the MMA‐grafted UHMWPE (MMA‐g‐UHMWPE) samples. The Taguchi experimental design method was used to find the best degree of grafting (DG) and bonding strength. The efficient levels for different variables were calculated with an analysis of variance of the results. SEM micrographs of MMA‐g‐UHMWPE samples showed that with increasing DG and chromic acid etching, the MMA‐g‐UHMWPE rich phase increased on the surface; this confirmed the high interfacial bonding strength of the grafted samples with bone cement. The grafting of the MMA units onto UHMWPE resulted in a lower crystallinity, and the crystallization process proceeded at a higher rate for the MMA‐g‐UHMWPE samples compared to the initial UHMWPE; this suggested that the MMA grafted units acted as nucleating agents for the crystallization of UHMWPE. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and characterization of poly(L‐lactide) membranes prepared by γ‐radiation‐induced grafting of N‐vinyl pyrrolidone

A copolymer, poly(L ‐lactide)‐g‐poly(N‐vinyl pyrrolidone) (PLLA‐g‐PVP) was prepared with poly(L ‐lactide) (PLLA) and N‐vinyl pyrrolidone in the presence of methanol as a solvent by γ‐ray irradiation. The structure of PLLA‐g‐PVP was characterized by ¹H‐NMR and Fourier transform infrared spectroscopy. The PLLA‐g‐PVP graft ratio calculated by the percentage increase in weight increased with the increase of absorbed dose, and the percentage crystallinity of PLLA‐g‐PVP decreased with increasing graft ratio. The introduction of the poly(N‐vinyl pyrrolidone) chain into PLLA resulted in a decrease in the contact angle of PLLA‐g‐PVP with increasing graft ratio. In vitro degradation testing showed that PLLA‐g‐PVP had a higher degradation rate both in the weight‐loss test and molecular weight measurement because of a lower crystalline percentage and higher hydrophilicity compared to PLLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Swelling behaviors of a three‐component copolymer (starch graft sodium acrylate and 2‐acrylamido‐2‐methyl‐propanosulfonic acid) synthesized by microwave polymerization

A superabsorbent of starch, 2‐acrylamido‐2‐methyl‐propanosulfonic acid (AMPS), and sodium acrylate was synthesized by microwave irradiation, and the effect of AMPS on the performance of the polymer was investigated. The best mass fraction of the three components was determined (starch/acrylic acid/AMPS = 2 : 5 : 3). The structure of the polymer was characterized by Fourier transform infrared, ¹³C cross‐polarization/magic‐angle spinning NMR, and scanning electron microscopy, and the morphology of the surface of the sample was studied. The results showed that the morphology of the polymer was changed to some extent under microwave irradiation, and the swelling rate of the polymer synthesized by microwave polymerization was faster than the swelling rate of a polymer synthesized by a traditional method. The best absorbent capacities of the product in distilled water and a 0.9% sodium chloride solution were 450 and 53 g/g, respectively. Meanwhile, the introduction of AMPS to a superabsorbent resin was an effective method for improving the performance of the polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1050–1054, 2005     

PEEKWC ultrafiltration hollow‐fiber membranes: Preparation,morphology, and transport properties

A series of hollow‐fiber membranes was produced by the dry–wet spinning method from PEEKWC, a modified poly(ether ether ketone) with good mechanical, thermal, and chemical resistance. The fibers were prepared under different spinning conditions, varying the following spinning parameters: polymer concentration in the spinning solution, height of the air gap, and bore fluid composition. The effect of these parameters on the water permeability, the rejection of macromolecules (using dextrane with an average molecular weight of 68,800 g/mol), and the morphology of the membranes was studied. The results were also correlated to the viscosity of the spinning solution and to the ternary polymer/solvent/nonsolvent phase diagram. The morphology of the cross section and internal and external surfaces of the hollow fibers were analyzed using scanning electron microscopy (SEM). All membranes were shown to have a fingerlike void structure and a skin layer, depending on the spinning conditions, varying from (apparently) dense to porous. Pore size measurements by the bubble‐point method showed maximum pore sizes ranging from 0.3 to 2 μm. Permeability varied from 300 to 1000 L/(h^?1 m^?2 bar) and rejection to the dextrane from 10 to 78%. The viscosity of polymer solutions was in the range of 0.2 to 3.5 Pa s. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 841–853, 2004