Grafting of poly (methyl acrylate) onto sulfite pulp fibers and its effect on water absorbance

To prepare super water absorbent hydrogels of wood cellulose fibers, poly (methyl acrylate) (PMA) was copolymerized onto softwood sulfite pulp fibers using free radical initiator followed by alkaline hydrolysis. Ceric ammonium nitrate (CAN) was used as the free radical initiator. Effects of various parameters such as fiber concentration, monomer/pulp (M/pulp) ratio, CAN concentration, and reaction time on the grafting yield and on other grafting parameters were investigated. The graft conversion was the same from low to medium fiber concentration. The amount of initiator required was found to be independent of fiber concentration to achieve maximum grafting yield. Different fiber fractions (classified based on their length) have no effect on the grafting yield. The evidence of graft copolymerization was determined by using ATR‐IR spectroscopy. The X‐ray diffraction (XRD) analysis shows that grafting takes place both in amorphous and crystalline regions of cellulose fibers and the decrease in crystallinity of the grafted fibers with an increase in grafting yield was confirmed. The surface morphology of the PMA‐g‐cellulose was characterized by scanning electron microscopy (SEM). The water retention value of the hydrolyzed grafted pulp was determined based on a centrifugation technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Cellulose membranes grafted with vinyl monomers in homogeneous system

The homogeneous grafting of a hydrophilic monomer onto cellulose derivatives was carried out in an aqueous system at 30, 50, 70, and 90°C during reaction periods of 30–180 min. The graft polymer was isolated by ethanol from the reaction mixture, dried, and weighed. The grafted polymer was characterized by the IR method, as well as the microscopic sample morphology detected by scanning electron microscopy. The water absorption capacities and grafting values of the grafted cellulose derivatives were also determined. The maximum grafting yield was obtained at 30°C. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2629–2638, 2002     

Influence of grafting on structural and optical properties of nylon‐6 fibers

This study throws light on the change of the optical properties and some structural properties due to graft copolymerization of polydiallyldimethyl ammonium chloride (PDADMAC) and polyacrylamide (PAA) of nylon‐6 fibers. Multiple‐beam interferometric technique in transmission was used to study the change of the diameter, refractive indices, and birefringence of nylon‐6 fibers at different graft yields. The results were utilized to investigate the isotropic refractive index, the mean polarizabilities per unit volume, dielectric constant, dielectric susceptibility, and surface reflectivity for nylon‐6 and grafted nylon‐6 fiber. The effect of grafted PAA onto modified nylon‐6 fibers containing PDADMAC on the crystallinity was studied by X‐ray diffraction. These results reflect good effect of grafting on the optical and structural properties of nylon‐6 fibers. The opto‐thermal properties of grafted PAA with different graft yields have been studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Chemically induced graft copolymerization of vinyl monomers onto cotton fibers

We investigated the chemically induced graft copolymerizations of acrylic acid (AA), acrylamide, crotonic acid, and itaconic acid (IA) onto cotton fibers. Benzoyl peroxide was used as an initiator. The effects of grafting temperature, grafting time, and monomer and initiator concentrations on the grafting yields were studied, and optimum grafting conditions were determined for the sample material. The maximum grafting yield value obtained was 23.8% for AA. Swelling tests, Fourier transform infrared spectroscopy, and scanning electron microscopy analyses of grafted and ungrafted fibers were also performed to characterize fiber properties. IA‐grafted fibers were measured as the most swollen fibers, with a swelling value of 510%. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2343–2347, 2006     

微乳液法腈纶接枝聚苯胺及其性能研究

采用低温等离子体技术对腈纶纤维表面进行处理,使用苯胺微乳液在腈纶表面进行接枝聚合,对腈纶进行改性处理,通过增重率、导电率测试、接枝聚合的因素和接枝聚合对腈纶纤维结构、导电性能和强力进行分析评价;扫描电镜和红外测试显示聚苯胺成功接枝上腈纶表面;腈纶接枝聚苯胺后,导电性能增加,强力变化不大,但伸长率略有降低。     

Grafting of acrylic monomers onto cotton fabric using an activated cellulose thiocarbonate–azobisisobutyronitrile redox system

The feasibility of a cellulose thiocarbonate–azobisisobutyronitrile (AIBN) initiation system to induce graft copolymerization of methyl methacrylate (MMA) and other acrylic monomers onto cotton fabric was investigated. Other acrylic monomers were acrylic acid, acrylonitrile, and methyl acrylate. The initiation system under investigation was highly activated in the presence of a metal‐ion reductant or a metal‐ion oxidant in the polymerization medium. A number of variables in the grafting reaction were studied, including AIBN concentration, pH of the polymerization medium, nature of substrate, monomer concentration, duration and temperature of polymerization, and composition of the solvent/water polymerization medium. The solvents used were methanol, isopropanol, 1,4‐dioxane, cyclohexane, benzene, dimethyl formamide, and dimethyl sulfoxide. There were optimal concentrations of AIBN (5 mmol/L), MMA (8%), Fe²⁺ (0.1 mmol/L), Mn²⁺ (8 mmol/L), and Fe³⁺ (2 mmol/L). A polymerization medium of pH 2 and temperature of 70°C constituted the optimal conditions for grafting. The methanol/water mixture constituted the most favorable reaction medium for grafting MMA onto cotton fabric by using the Fe²⁺–cellulose thiocarbonate–AIBN redox system. MMA was superior to other monomers for grafting. The unmodified cotton cellulose showed very little tendency to be grafted with MMA compared with the chemically modified cellulosic substrate. A tentative mechanism for the grafting reaction was proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1261–1274, 2004     

Gentamicin‐loaded poly(acrylic acid)‐grafted cotton fibers,part 1: Synthesis,characterization, and preliminary drug release study

This study describes preparation of poly (acrylic acid)‐grafted cotton fibers and release of antibiotic drug gentamicin sulfate from them under physiological conditions. Poly(acrylic acid) has been grafted onto cellulose backbone of cotton fibers via Ce(IV)‐initiated polymerization in aqueous medium. The conditions obtained for optimum grafting were as follows: initiation time 30 min; initiation temperature 37°C; monomer concentration 27.8 mM; grafting temperature 30°C; nitric acid (catalyst) concentration 0.1M. The grafted fibers were characterized by FTIR, TGA, and SEM analysis. The antibiotic drug gentamicin sulfate (GS) was loaded into the grafted fibers by equilibration method and release was studied under physiological conditions. The kinetic release data was interpreted by first‐order kinetic model. Finally, drug‐loaded fibers showed fair antibacterial action against Escherichia coli. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel fishnet fibers with anti‐adhesion of seaweeds obtained by UV‐irradiation technique

A novel Nylon‐6 fishnet fiber with the antiadhesion of seaweeds was prepared by UV radiation‐initiated grafting of acrylic acid (AA) onto Nylon‐6 fibers, and its structure was characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The influences of grafting conditions, such as irradiation dose, temperature, concentration of monomer, inorganic acid, and inhibitor etc., on grafting rate were studied, and the antiadhesion of seaweeds was evaluated with Dunaliella. The results showed that the grafting amount of Nylon‐g‐AA was increased with the increase of irradiation time. With the increase of concentration of AA, temperature, reaction time, inorganic acid, and inhibitor, the grafting amount increased firstly and then decreased, respectively. Nylon‐6 fibers modified by Poly(acrylic acid) (PAA) had a strong effect on the adhesion of Dunaliella, and the antiadhesion was improved with the increase of the grafting amount. Results from the mechanical analysis revealed that the tensile strength of the UV‐irradiation fibers decreased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1252–1256, 2007     

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.     

Synthesis of a vinyl monomer containing β‐cyclodextrin and grafting onto cotton fiber

To chemically bond β‐cyclodextrin (β‐CD), which can form inclusion complexes, acrylamidomethyl CD (CD–NMA) obtained from the acid‐catalyzed reaction of N‐methylolacrylamide (NMA) and β‐CD was grafted onto cellulose fibers using CeIV as the initiator. The double‐bond content of CD–NMA increased with increase in the NMA/CD mol ratio, and a CD–NMA containing a maximum of three molecules of NMA bonded to a CD molecule could be obtained. Since the grafting condition is acidic, the hydrolytic stability of CD–NMA in aqueous nitric acid was studied. The temperature of hydrolysis proved to have a greater effect on the depletion of double bonds from CD–NMA compared with the concentration of the acid. Thus, CD–NMA was grafted onto cellulose fibers at a low temperature, and FTIR analysis of the CD–NMA‐grafted cotton fibers confirmed the chemical bonding of CD–NMA molecules to cellulose. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 438–446, 2001     

Synthesis and characterization of a poly(acrylic acid)‐graft‐methoxy poly(ethylene oxide) comblike copolymer

A methoxy poly(ethylene oxide) (MPEO) grafted poly(acrylic acid) (PAA) comblike copolymer was synthesized by the direct condensation of MPEO onto the PAA backbone in the presence of dicyclohexyl dimethylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP). Its chemical structure was characterized by Fourier transform infrared and ¹H‐NMR spectroscopies. The effects of different catalysts, solvents, reaction temperatures, and reaction times on the grafting degree of the PAA‐g‐MPEO comblike copolymer were investigated. Compared to p‐toluene sulfonic acid, DMAP/DCC as a catalyst markedly increased the grafting degree. The optimum reaction conditions were a tetrahydrofuran/water mixture solvent, a reaction temperature of 50°C, and a reaction time of 168 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthèse et caractérisation de copolymères cellulose–poly(méthacrylate de méthyle): Greffage par le système acide de Caro–ion Fe3+

Methyl methacrylate was grafted onto cellulose using Caro's acid-Fe³⁺ system as initiator. The effect of grafting time, ferric ion concentration, and cellulose/monomer ratio, on the per cent grafting, was investigated. From studies of the reaction mechanism with model compounds it was postulated that the grafting did not occur at the 1,2-glycol units or at the hemiacetal unit in the end of the cellulose molecule. Concurrent degradation of the cellulose during the graft copolymerization was examined. A linear relationship between the per cent grafting and the number of cellulosic broken chains by hydrolysis was found, from which it would seem that the structure of the graft copolymer was of block-type. The structure of the graft copolymers was also studied by determination of the molecular weights of the grafted PMMA branches, after hydrolysis of the cellulosic backbone. In all cases, independently of reaction conditions, the molecular weights of the grafted branches were very high and their number low. The number of graft branches per cellulose chain was calculated from the per cent grafting, the molecular weights of the PMMA branches and of the cellulosic backbone. This number was compared with the number of cellulosic bonds broken during grafting.     

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.     

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     

Biocompatibility and antibacterial activity of chitosan and hyaluronic acid immobilized polyester fibers

Poly(ethylene terephthalate) (PET) fibers were treated with ⁶⁰Co‐γ‐ray and grafted with acrylic acid. The resulting fibers were further grafted with chitosan (CS) via esterification. Afterward, hyaluronic acid (HA) was immobilized onto CS‐grafting fibers. The antibacterial activity of CS against S. aureus, E. coli, and P. aeruginosa was preserved after HA‐immobilization. After immobilizing HA, the L929 fibroblasts cell proliferation was improved forCS‐grafting PET fiber. The results indicate that by grafting with CS and immobilizing with HA, PET fibers not only exhibit antibacterial activity, but also improve the cell proliferation for fibroblast. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 220–225, 2007     

Lipases improve the grafting of poly(ethylene terephthalate) fabrics with acrylic acid

In this study, poly(ethylene terephthalate) (PET) fabrics were modified with two types of commercial lipases, namely, Lipex and Lipolase, and grafted with acrylic acid (AA) to improve their absorption properties. The effects of the enzyme concentration, reaction temperature, time, and pH on the grafting of AA onto PET were investigated. The pretreatment of PET with lipases increased the amount of AA that was introduced to the PET fibers, whereas AA grafting onto the untreated PET fabrics led to lower graft yields. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the AA‐grafted pretreated polyester fabrics. A new band appearing at 1546 cm^?1 in the Fourier transform infrared spectrum implied that AA was introduced onto the PET fabrics. The surfaces of the fabric fibers presented in scanning electron microscopy micrographs clearly indicated the formation of a layer of grafted poly (acrylic acid). The results show that the density of surface grafting was improved by the lipase pretreatment. The increase in grafting was higher for Lipex than for Lipolase. The highest graft yield was obtained with 1% Lipex and Lipolase for 30 min at pH values of 7 and 5, respectively. There were no significant changes in the tenacity or weight reduction of the fabrics. The moisture content of the samples increased linearly with increasing graft yield. This was higher for the pretreated fabrics grafted with Lipex. A higher color strength was obtained for grafted PET samples that were pretreated with Lipex when they were dyed in alkaline aqueous solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Adhesion of grafted polypropylene plates with enzymatically modified chitosan solutions and analysis of failed surfaces by X‐ray photoelectron spectroscopy

In this study, hydrophilic monomers were photografted onto the PP plates at different monomer concentrations and temperatures, and grafted PP plates were bonded with enzymatically modified chitosan solutions. Their adhesive strength properties were discussed in relation to the grafting conditions and hydrophilic properties such as wettability and water‐absorptivity. In addition, the location of failure was investigated by X‐ray photoelectron spectroscopy analysis of failed surfaces. Wettability of the grafted PP plates except for the PP grafted with acrylic acid (PP‐g‐PAA) plates remained constant above the grafted amounts at which the PP surfaces were fully covered with grafted polymer chains. On the other hand, wettability of the PP‐g‐PAA plates passed through the maximum value and then gradually decreased with the grafted amount probably because of the aggregation of grafted PAA chains. Water‐absorptivity of the grafted layers formed at lower monomer concentrations or temperatures sharply increased at lower grafted amounts. The adhesive strength increased with an increase in the grafted amount and substrate breaking was observed for PP‐g‐PAA plates because enzymatically modified chitosan solutions were successfully penetrated in the grafted layers and quinone derivatives reacted with carboxy groups of grafted PAA chains. Failure occurred in the layers composed of grafted PAA chains and components containing in enzymatically modified chitosan solutions and the location was shifted to the inside of grafted layer, as the grafted amount increased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1369‐1376, 2013     

Peroxydiphosphate–metal ion–cellulose thiocarbonate redox system‐induced graft copolymerization of vinyl monomers onto cotton fabric

The grafting of methacrylic acid (MAA) and other vinyl monomers onto cotton cellulose in fabric form was investigated in an aqueous medium with a potassium peroxydiphosphate–metal ion–cellulose thiocarbonate redox initiation system. The graft copolymerization reaction was influenced by peroxydiphosphate (PP) concentration, the pH of the reaction medium, monomer concentration, the duration and temperature of polymerization, the nature of vinyl monomers, and the nature and concentration of metallic ions (activators). On the basis of a detailed investigation of these factors, the optimal conditions for the grafting of MAA onto cotton fabric with the said redox system were as follows: [Fe²⁺] = 0.1 mmol/L, [PP] = 2 mmol/L, [MAA] = 4%, pH‐2, grafting time = 2 h, grafting temperature = 70°C, and material/liquor ratio = 1 : 50. Under these optimal conditions, the graft yields of different monomers were in the following sequence: MAA ? acrylonitrile > acrylic acid > methyl acrylate > methyl methacrylate. The unmodified cellulosic fabric (the control) had no ability to be grafted with MAA with the PP–Fe²⁺ redox system. The percentage of grafting onto the thiocarbonated cellulosic fabric was more greatly enhanced in the presence of iron salts than in their absence. This held true when the lowest concentrations of these salts were used separately. A suitable mechanism for the grafting processes is suggested, in accordance with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1879–1889, 2003     

Modification of cellulosic fabrics to impart flame retardancy properties

Graft copolymerization of dimethylaminoethyl methacrylate (DMAEMA) onto cotton‐cellulose in the fabric form was carried out using a cellulose‐thiocarbonate‐ammonium persulphate redox initiation system. Effects of the concentration of the monomer, effect of liquor ratio, grafting time, and temperature were studied. The results point out the following important aspects of flame retardation of cellulose fabrics. (1) The graft polymerization of DMAEMA can improve the flame retardant properties of cellulose fabrics. (2) Tertiary amine grafted to cellulosic fabrics is suitable for nitrogen compounds that can effectively operate as synergists. The flame retardant properties of the poly‐DMAEMA‐ grafted‐phosphorylated cellulosic materials were found to be excellent even after 25 dry clean washings. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Improvement in adhesive‐free adhesion by the use of electrostatic interactions between polymer chains grafted onto polyethylene plates

The tensile shear adhesive‐free adhesion properties induced by electrostatic interactions between poly(acrylic acid) (PAA) and poly[2‐(dimethylamino)ethyl methacrylate] (PDMAEMA) chains grafted onto polyethylene (PE) with low‐density (LDPE) or high‐density (HDPE) plates were studied. PAA‐ or PDMAEMA‐grafted PE plates were immersed in a HCl or NaOH solution or water for 24 h, and their electrostatic properties were changed before they were overlapped with each other and heat‐pressed. The breaking of the substrate between the two plates with water‐swollen grafted layers was observed in the low range of grafted amounts in comparison with immersion in the acidic and basic solutions. The ability of the two plates with grafted polymer chains swollen in water to strongly bond with each other was a result of electrostatic interactions formed by positively charged PDMAEMA and negatively charged PAA chains. The breaking of the substrate in the case of adhesive‐free adhesion between quaternized PDMAEMA‐grafted and PAA‐grafted PE plates immersed in the basic solution occurred with lower grafted amounts of PAA. This came from the strong attractive force between dissociated anionic PAA chains and quaternized cationic PDMAEMA chains in the basic solution. In addition, the adhesive‐free adhesion strength of HDPE plates with the same grafted polymer chains encountered the breaking of the substrate with lower grafted amounts than that of LDPE plates. It was concluded that the grafting of polymer chains onto HDPE plates with high crystallinity was considerably restricted to the outer surface regions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2632–2638, 2006