Graft Copolymerization Of Glycidyl Methacrylate Research Articles

A NEW APPROACH FOR GRAFT COPOLYMERIZATION OF JUTE

The graft copolymerization of glycidyl methacrylate (GMA) on jute fibers at ambient conditions is the desired goal. Graft copolymerization of (GMA) on jute fibers was carried out using Ammonium Persulphate Acetone Sodium Bisulphite (APS/ASBS) initiating redox system. The grafting reaction was studied with respect to graft yield (GY), grafting efficiency (GE) and total conversion (TC). Factors such as pH value, liquor ratio (L: R), redox initiator concentration, addition sequence, reaction time, temperature and GMA concentration [M], were investigated. The results obtained showed that the optimal grafting yield is obtained at the following conditions: initiator concentration of 20/40 mmole/l for APS/ASBS respectively, liquor ratio(I:20), pH value 3, time 120 min., temperature 20°C, and monomer concentration [M] 150% based on weight of substrate (OWS). Grafted and scoured jute fibers were characterized via thermal gravimetric analysis (TGA) and infra red spectroscopic analysis (IR).

New Functionalities of PA6,6 Fabric Modified by Atmospheric Pressure Plasma and Grafted Glycidyl Methacrylate Derivatives

Oxidative atmospheric pressure plasma was utilized to activate surface of PA 6,6 fabrics followed by graft copolymerization of glycidyl methacrylate (GMA) and further reacted with triethylene tetramine (TETA), quaternary ammonium chitosan (HTCC) or β-cyclodextrin (β-CD). The inner CD cavity was complexed with some insecticidal perfumes. Modified PA6,6 fabrics were analyzed by differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. Antimicrobial activity and insect repelling assay were conducted and showed efficient antimicrobial and insect repelling properties.

Functionalization of industrial polypropylene films via the swift-heavy-ion-induced grafting of glycidyl methacrylate

Swift-silver-ion irradiation was explored as a means of forming chemically active sites on the surface of biaxially oriented polypropylene films. The active species, formed in air, was used to induce the graft copolymerization of glycidyl methacrylate in an aqueous solution. The surface structure, crystallinity, morphology, and hydrophilicity of the grafted samples were characterized with Fourier transform infrared, UV, wide-angle X-ray diffraction, scanning electron microscopy, and contact-angle measurements. Glycidyl methacrylate could be grafted onto biaxially oriented polypropylene after swift-heavy-ion irradiation without an additional initiator. The contact angle of the modified films decreased with the grafting percentage of glycidyl methacrylate on the polypropylene. The swift silver ions induced significant grafting only in small regions (i.e., the latent tracks) of the polymer. Furthermore, as the fluence of swift heavy ions increased beyond an optimum value, the overlapping of the latent tracks reduced the grafting yield. The observed findings could be very useful in developing an initiator-free grafting system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Atmospheric plasma‐aided biocidal finishes for nonwoven polypropylene fabrics. I. Synthesis and characterization

AbstractNovel biocidal fabrics were synthesized by the graft copolymerization of glycidyl methacrylate (GMA) onto plasma‐treated nonwoven polypropylene (PP) to produce PP/GMA grafts. Atmospheric oxygenated helium plasma was used to enhance the PP fabrics' initiation before GMA grafting. The grafted PP/GMA epoxide group was reacted with β‐cyclodextrin, monochlorotrizynyl‐β‐cyclodextrins, or a quaternary ammonium chitosan derivative [N‐(2 hydroxy propyl) 3‐trimethylammonium chitosan chloride]. Some interesting biocidal agents were complexed into the cyclodextrin (CD) cavity of PP/GMA/CD grafted fabrics. Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and optical and scanning electron microscopies were used to characterize the grafted complexed fabrics. These synthesized biocidal fabrics proved to be antistatic, antimicrobial, and insect‐repelling (see part II of this study). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1900–1910, 2007

Polystyrene microspheres having epoxy functional dangling chains linked by hydrolytically stable bonds via ATRP

AbstractWe report application of copper‐mediated atom transfer radical polymerization in graft copolymerization of glycidyl methacrylate (GMA) from N‐bromosulfonamide groups on polystyrene‐divinyl benzene (PS‐DVB) microspheres (210–420 μm). The surface initiator groups were introduced by simple modification of crosslinked PS‐DVB (10% mol/mol) beads in three steps: (i) chlorosulfonation, (ii) sulfamidation with propylamine, and (iii) bromination. Initiation from surface‐bound N‐bromosulfonamide groups showed first‐order kinetics (k = 1.04 × 10−4 s−1 in toluene at 70 °C) and gave poly(GMA) graft chains linked to the surface by hydrolytically stable sulfonamide bonds. High graft yields were attained (up to 294.4% within 21 h) while retaining the epoxy groups. Epoxy content of the resulting product (5.41 mmol g−1) revealed an average 17 GMA repeating units in the graft per initiation site. Taking advantage of the hydrolytic stability of sulfonamide linkages and well‐known reactivity of the epoxy groups on dangling chains, “the hair‐like structure” of the polymer beads prepared can be considered when devising more efficient functional polymers as catalysts or reagent carriers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6708–6716, 2006

Immobilization of urease using glycidyl methacrylate grafted nylon-6-membranes

The graft copolymerization of glycidyl methacrylate (GMA) onto nylon-6-membrane using benzophenone (BP) as an initiator was carried out in an alcoholic aqueous solution. The acrylic double bond of GMA participated in the grafting onto the nylon-6-membrane backbone with the epoxy groups remaining unaffected. At the end of the grafting reaction, urease was immobilized onto the modified membrane. BP concentration, GMA concentration and organic solvent seperation were studied by determining the grafting percentage. The influence of urease concentration on the immobilization efficiency was also studied. With keeping other conditions constant, the optimum conditions were shown as following [BP]: 5 × 10 −2 mM; [GMA]: 10 M; [urease]: 10 mg/ml, organic solvent: methanol.

Graft copolymerization of glycidylmethacrylate onto modified nylon‐6 fibers

AbstractThe graft copolymerization of glycidylmethacrylate (GMA) onto modified nylon‐6 fibers containing polydiallyldimethylammonium chloride (PDADMAC) groups in the presence of (Cu 2+–K2S2O8) as a redox initiating system was carried out, with very high extent and almost without homopolymer formation. The mechanism of the graft polymerization induced by this system was suggested. The rate of grafting was determined by varying the monomer, K2S2O8, and cupric ion concentrations as well as the amount of PDADMAC. The kinetic investigation revealed that the rate of grafting (Rp) of GMA onto modified nylon‐6 fibers is proportional to [GMA]1.83, [CuSO4·5H2O]0.46, [PDADMAC]0.4, and [K2S2O8]1.43. The overall activation energy was 134.7 kJ/mol. The fine structure and thermal properties of the grafted nylon‐6 fibers were investigated. investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 613–618, 2006

Synthesis and Characterization of Poly(Acrylic Acid) and Poly(Glycidyl Methacrylate) Chitosan Graft Copolymers and Their Application to Cotton Fabric

: Graft polymerization of acrylic acid (AA) and glycidyl methacrylate (GMA) onto chitosan was independently effected in a homogeneous aqueous phase under different conditions by using potassium bromate/thiourea as a combined redox system. The grafting reaction was monitored for carboxyl and epoxy groups in the case of AA and GMA, respectively. Also monitored were percentages of graft yield (GY%), homopolymer (HP%), and total conversion (TC%). It was found that the extent of the grafting reaction, as measured by such analyses, are dependent upon monomer concentration, initiator concentration, reaction time, temperature, and material-to-liquor ratio. Based on the results obtained, the most appropriate conditions for graft copolymerization of AA onto chitosan were 4/4 mmole/L thiourea/potassium bromate and AA 30% based on weight of chitosan at 40°C for 1 hour. On the other hand, graft copolymerization of GMA occurs effectively when 6/6 mmole/L thiourea/potassium bromate and GMA 50% were used at 60°C for 1 hour. With both AA and GMA monomers, a material-to-liquor ratio of 1:25 was adequate. Chitosan-g-poly (AA) and chitosan-g-poly (GMA) were applied to cotton fabric to enhance the easy care properties. Crease recovery angle increased from 115° to 160° in the dry state and from 113° to 230° in the wet state; meanwhile, tensile strength increased from 54 Kg to 66 Kg. Dyeability, expressed as K/S, of cotton fabric treated with these copolymers also increased.

Consecutive Graft Copolymerization of Glycidyl Methacrylate and Aniline on Poly(Tetrafluoroethylene) Films

Chemical modification of Ar plasma-pretreated poly(tetrafluoroethylene) (PTFE) film by UV-induced graft copolymerization with glycidyl methacrylate (GMA), followed by oxidative graft copolymerization of aniline and reactive immobilization of polyaniline (PANI) chains have been carried out to render the PTFE surface conductive. The surface compositions and microstructures of the graft-copolymerized PTFE films were studied by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), respectively. The PANI chains grafted onto PTFE film surface were similar to the PANI homopolymer. The surface resistance of the aniline graft-copolymerized PTFE film could be reduced to the order of about 104 Ω/sq, compared to the order of 1016 Ω/sq for the pristine PTFE film. Cohesive failure occurred inside the bulk of PTFE film when an epoxy adhesive was applied to peel off the grafted PANI layer from the GMA graft-copolymerized PTFE substrate. The strong adhesion arose from the fact that the PANI chains were...

Thermal graft copolymerization-induced adhesion improvement of a FR-4 ®/PETG ® laminate

The lamination of a glass fibre-reinforced and epoxy-based printed circuit board (PCB) substrate, FR-4 ®, to an amorphous thermoplastic copolyester of dimethyl terephthalate with ethylene glycol and 1,4-cyclohexanedimethanol, PETG ®, was studied. The lamination was achieved by the simultaneous surface graft copolymerization of glycidyl methacrylate (GMA) on the argon plasma-pretreated FR-4 ® substrate and PETG ® film at an elevated temperature. The plasma-treated surfaces and the delaminated surfaces were characterized by X-ray photoelectron spectroscopy (XPS). The adhesion strength between the FR-4 ® substrate and the PETG ® film was assessed by the T-peel test method. The adhesion strength was affected by the plasma pretreatment time of the substrates, the lamination time, and the lamination temperature. The FR-4 ®/GMA/PETG ® assembly from the simultaneous graft copolymerization with GMA and lamination exhibited a significantly more rapid lamination rate and a higher adhesion strength than those of the FR-4 ®/epoxy/PETG ® assembly from the epoxy adhesive-induced lamination of the plasma-pretreated FR-4 ® and PETG ® films. The phenomena are consistent with the presence of covalently bonded GMA graft chains on the surfaces of plasma-pretreated PETG ® and FR-4 ® films in the former assembly. The FR-4 ®/GMA/PETG ® assembly failed by a combined cohesive and adhesional mechanism.

Modification of poly(tetrafluoroethylene) and gold surfaces by thermal graft copolymerization for adhesion improvement

The adhesion between a poly(tetrafluoroethylene) (PTFE) film and a gold substrate was achieved by surface graft copolymerization of glycidyl methacrylate (GMA) on an argon plasma-pretreated PTFE film at elevated temperature with simultaneous lamination to a surface-modified gold substrate. The plasma pretreatment introduces peroxides which are thermally degraded into radicals to initiate the graft copolymerization of GMA on the PTFE surface. The gold surface, on the other hand, was first pretreated with 3-mercaptopropionic acid (MPA), 3-mercaptopropionic acid-2-ethylhexyl ester (MPAEE), or (3-mercaptopropyl)trimethoxysilane (MPTMS) to form self-assembled monolayers (SAMs) and then subjected to Ar plasma treatment. The simultaneous graft copolymerization and lamination of the PTFE film to the gold surface was carried out in the presence of GMA and an amine hardener at an elevated temperature under atmospheric conditions. The modified surfaces and interfaces were characterized by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The gold/GMA/PTFE assembly exhibited a T-peel adhesion strength above 10 N/cm and the joint delaminated by cohesive failure inside the bulk of the PTFE film. The strong adhesion of the Au/PTFE laminate is the result of concurrent graft copolymerization on both the Ar plasma-pretreated PTFE surface and the SAM of the Au surface to form a covalent network. The network is further strengthened by the crosslinking reaction promoted by the presence of the hardener.

Surface Graft Copolymerization Enhanced Lamination of Poly(tetrafluoroethylene) Film to Copper and Epoxy-Based Print Circuit Board (PCB)

Lamination of poly(tetrafluoroethylene) (PTFE) film to a copper foil or to an epoxy-based print circuit board (PCB) Substrate (FR4®) was carried out. Lamination was achieved during surface graft copolymerization of glycidyl methacrylate (GMA) on an Ar plasma pretreated PTFE film at elevated temperature and in the presence of an epoxy resin adhesive. The plasma pretreatment introduces peroxides which are thermally degraded into free radicals to initiate the graft polymerization of GMA on the PTFE surface. The graft copolymerization with concurrent lamination is carried out in the complete absence of a polymerization initiator or system degassing. The modified surfaces and interfaces are characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The adhesion strength between the PTFE film and copper or the FR4® substrate was assessed by the T-peel strength test method. The adhesion strength was affected by plasma pretreatment time, as well as the grafting and curing temperature. The PTFE/GMA-epoxy resin/Cu and PTFE/GMA-epoxy resin/FR4 assemblies exhibit significant higher interfacial adhesion strengths compared to those assemblies in which only epoxy resin or GMA was used. They also exhibit better interfacial adhesion reliability. The PTFE/GMA-epoxy resin/Cu and PTFE/GMA-epoxy resin/FR4® joints delaminated by cohesive failure inside the bulk of PTFE film. The results suggest that the enhanced adhesion between the graft-modified PTFE film and copper or FR4® surfaces is attributable to the formation of covalent bonds between the tethered GMA graft chains on PTFE and the network of epoxy resin.

Adhesion improvement of polytetrafluoroethylene/metal interface by graft copolymerization

Copper-poly(tetrafluoroethylene) (PTFE) and gold-PTFE laminates were prepared by surface graft copolymerization of glycidyl methacrylate (GMA) on argon plasma-pretreated PTFE films at an elevated temperature with simultaneous lamination to copper foils or gold substrates. The plasma pretreatment introduces peroxides, which are thermally degraded into radicals to initiate the graft copolymerization of GMA on the PTFE surface. Before lamination, the gold surface was pretreated with alkanethiols to form self-assembled monolayers and then subjected to an Ar plasma treatment. The modified surfaces and interfaces were characterized by x-ray photoelectron spectroscopy and the adhesion strength was assessed by the T-peel test method. By this technique, the Cu-PTFE or Au-PTFE laminates exhibit significantly improved adhesion strengths and the joints are delaminated by cohesive failure inside the bulk of the PTFE film.

Thermal graft copolymerization with concurrent lamination of low density polyethylene and poly(tetrafluoroethylene) films

A simple technique of thermal graft copolymerization of glycidyl methacrylate (GMA) on argon plasma pretreated poly(tetrafluoroethylene) (PTFE) films or low density polyethylene (LDPE) films with simultaneous lamination of the two films was demonstrated. The effect of crosslinking agent on the adhesion strength of the PTFE/PTFE interface was also investigated. The simultaneous thermal grafting and lamination process was carried out under atmospheric conditions and in the complete absence of a polymerization initiator. The surface structure and composition of the graft copolymerized PTFE and LDPE films from either self-delamination in acetone or mechanical delamination were studied by X-ray photoelectron spectroscopy (XPS). The efficiency of surface graft copolymerization and lamination was found to be strongly dependent on the plasma pretreatment time of the substrate, graft concentration, thermal grafting/lamination temperature and time. T-peel adhesion strengths of about 0.9 and 1.7 N cm −1 were achieved for the PTFE/GMA/PTFE assemblies in the absence and presence, respectively, of the crosslinking agent, triallyl-1,3,5-benzenetricarboxylate (TBTC). The T-peel adhesion strength of the LDPE/GMA/LDPE assembly, on the other hand, can reach about 2.6 N cm −1 in the absence of TBTC. XPS analysis of the mechanically delaminated surfaces suggests that the failure mode of the PTFE/GMA/PTFE assembly and the PTFE/GMA + 2 vol% TBTC/PTFE assembly is adhesional in nature, and that of the LDPE/GMA/LDPE assembly is cohesive.

Adhesion improvement of a poly(tetrafluoroethylene)- copper laminate by thermal graft copolymerization

Poly(tetrafluoroethylene) (PTFE)-copper laminates were achieved by surface graft copolymerization of glycidyl methacrylate (GMA) on an argon plasma-pretreated PTFE film at elevated temperature with simultaneous lamination of a copper foil in the presence of an epoxy resin adhesive. The plasma pretreatment introduces peroxides which are thermally degraded into radicals to initiate the graft copolymerization of GMA on the PTFE surface. The graft copolymerization with concurrent lamination of copper was carried out in the complete absence of a polymerization initiator or system degassing. The modified surfaces and interfaces were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The adhesion strength between the PTFE film and copper was assessed by the T-peel test method. The adhesion strength was affected by the plasma pretreatment time, as well as by the grafting and curing temperatures. The PTFE/GMA-epoxy resin/Cu assembly exhibits a significantly higher measured adhesion strength, compared with those of the PTFE/epoxy resin/Cu and PTFE/GMA/Cu assemblies. The PTFE/GMA-epoxy resin/Cu joint delaminated by cohesive failure inside the bulk of the PTFE film. This suggests that the enhanced adhesion between the graft-modified PTFE film and the copper surface is attributable to the formation of covalent bonds between the tethered GMA graft chains on PTFE and the epoxy resin network.

Graft Copolymerization of Glycidylmethacrylate onto Fibrin Prepared from Slaughter-House Waste

Fibrin collected from the slaughter house in crude form was purified. The purified fibrin was graft copolymerised with poly-glycidylmethacrylate (PGMA) and characterised for the percentage of grafting. The infrared spectroscopy and thermogravimetric anlysis, of the composite were studied. This biomaterial could be used as a drug delivery system after coupling the suitable antibiotic through the epoxy functional groups introduced by PGMA.

Graft Copolymerization of Glycidyl Methacrylate onto Ethylene-propylene Copolymer via Melt Extruding

Graft Copolymerization of Glycidyl Methacrylate onto Ethylene-propylene Copolymer via Melt Extruding

Graft Copolymerization of Glycidyl Methacrylate onto Ethylene-propylene Copolymer via Melt Extruding

Graft Copolymerization of Glycidyl Methacrylate onto Ethylene-propylene Copolymer via Melt Extruding

Studies on graft copolymerization of glycidyl methacrylate onto poly(vinyl chloride) and curing behavior of its grafted copolymer

AbstractPoly(vinyl chloride) was dehydrochlorinated in an alkali solution and then grafted with glycidyl methacrylate (GMA) using benzol peroxide as the free‐radical initator under a nitrogen atmosphere. The efficiency of grafting GMA under the influence of an alkali, GMA concentration, and duration of the grafting reaction, the viscosity properties, and the curing behavior with diamine were investigated. Maximum grafting to the extent of 46.4% was obtained. The optimum curing reaction condition were investigated. © 1995 John Wiley & Sons, Inc.

Photoinitiated graft copolymerization of glycidyl methacrylate and 2‐hydroxyethyl methacrylate onto polyacrylonitrile and application of the synthesized graft copolymers in penicillin–amidase immobilization

AbstractThe photoinitiated graft copolymerization of hydroxyethyl methacrylate and/or glycidyl methacrylate onto polyacrylonitrile (PAN) and the applicability of the matrices synthesized in this way for penicillin–amidase immobilization are discussed. The copolymers are prepared by putting irradiated PAN fibers with preliminary adsorbed benzophenone on them into the polymerization feed that includes hydroxyethyl methacrylate and/or glycidyl methacrylate dissolved in a water–methyl ethyl ketone mixture. The degree of grafting varies between 11.7 and 46.0%, and its efficiency, between 27.8 and 78.9%. The concentration of epoxy groups in the synthesized copolymers is in the range between 210 and 2220 μmol/g. The reactivity ratios of the two comonomers are determined to be rGM = 0.70 ± 0.15 and rHEMA = 2.73 ± 0.14. The grafted copolymers containing HEMA units provide milder conditions for penicillin–amidase covalent binding. The optimum pH and temperature values of penicillin–amidase immobilized on these matrices are 7.5 and 45°C, respectively. © 1994 John Wiley & Sons, Inc.