Photoinitiated surface grafting of synthetic fibers,III. Photoinitiated surface grafting of poly(ethylene terephthalate) fibers

Photoinitiated surface grafting of acrylic acid (AA), acrylamide (AM) and 4-vinyl pyridine (VP) onto poly(ethylene terephthalate) (PET) fibers (a commercial textile yarn) has been studied using benzophenone (BP) as photoinitiator. A continuous process as previously described has been applied, which involves presoaking of the PET yarn in a solution of initiator and monomer in acetone and UV irradiation in nitrogen atmosphere. The resulting grafted polymer on the fiber surface has been analyzed by ESCA, titration of carboxy groups (grafted AA), and dye absorption. The relative ESCA intensities (RI) of O1s/C1s and N1s/C1s are used as measure for grafted AA, AM and VP, respectively, after recording the RI-values for ungrafted fibers. For grafting with AA, the RI-values increased from 32.8% (background) to 48.6% after 20 s irradiation time. The amount of carboxy groups measured by titration increased from 0.045 to 0.106 mmol/m². Assuming an even coverage of grafted AA polymer, this means a grafted layer of 4.8 nm thickness. After grafting, the adsorption of the dye Crystal Violet (CV) from aqueous solution increased by about 3 times. With AM as monomer, the RI-values increased from 2.6 (background) to 14.8% and the adsorption of a direct dye Sirius Lichtbordo B-LL increased by about 6 times. With VP as grafted monomer, the RI-values increased from about 2.6 (background) to 5.1% and the adsorption of the direct dye increased by about 4 times.     

Photoinitiated surface grafting of synthetic fibers,IV. Applications of textile dyes onto surface-photografted synthetic fibers

High-strength polyethylene (HSPE), polypropylene (PP), poly(ethylene terephthalate) (PET), and poly(vinyl alcohol) (PVA) textile yarns have been surface-photografted with various functional monomers, such as acrylic acid (AA), acrylamide (AM), glycidyl acrylate (GA) and 4-vinyl pyridine (VP), by means of the continuous presoaking process developed. The dyeing of these surface-modified yarns with various textile dyes has been investigated. In general, considerable improvements of dyeability have been observed. The dye adsorption of the surface-photografted fibers is influenced by many factors, such as type of fiber, amount and properties of the functional monomer grafted on the surface of the fibers, type of textile dye, etc. The fibers surface-grafted with a monomer containing basic groups, such as acrylamide and 4-vinyl pyridine, are efficiently dyed with an acid dye. Conversely, a fiber surface-grafted with acidic functional monomer is easily dyed to deep shades with basic dyes. The dye adsorption increases monotonically with increasing grafting measured in ESCA spectra as relative intensities of relevant lines. The ungrafted HSPE, PP and PET fibers can be dyed to some extent with certain dyes. In the present work, the dye adsorption increased by 3.4 times for HSPE fiber grafted with GA and dyed with the metal complex dye IO, by 7.9 times for PP fiber grafted with AA and dyed with the basic dye MB, by 6.1 times for PET with AM and with the direct dye SL, and by about 15.3 times for PVA with VP and with the acid dye TE.     

Grafting onto polyformaldehyde fibers

Acrylic acid (AA), acrylonitrile (AN), and acrylamide (AM) were grafted onto polyformaldehyde (PF) fibers employing γ-ray irradiation as well as benzoyl peroxide initiation. The nature of the graft copolymer obtained from a given monomer was dependent on the type of method used for the grafting reactions. This was reflected in the various characteristics of the grafted PF fibers such as moisture regain and dyeability to disperse, direct, basic, and acid dyes. The extent of grafting was dependent on time, concentration of the initiator, concentration of monomer, and irradiation dose. The grafting reaction with all the three monomers and both methods of grafting studied followed first-order kinetics. The rate constant values for grafting with AA, AN, and AM were 0.493, 0.576, and 0.420 hr^?1, respectively for the irradiation method and 0.385, 0.385, and 0.346 hr^?1, respectively, for the benzoyl peroxide initiation technique. The increase in the moisture regain was directly proportional to the amount of graft in the fiber. Acrylic acid grafted PF fibers were rendered hydrophilic to the highest extent (7.9% M.R. for 42% graft), while AM-grafted fibers were rendered so to the lowest extent (7.23% M.R. for 76.5% graft). Considerable improvement in dyeability of PF fibers was observed as a result of grafting. In general, dyeability was proportional to the amount of graft introduced in the fibers. The AA-grafted PF fibers gave a six-to sevenfold increase in disperse dye content when the irradiation method was followed and a four-to fivefold improvement when the chemical method was used during the grafting reaction. The AA-grafted and AM-grafted PF fibers show considerable affinity toward direct cotton dyes. The two substrates could also be dyed with fiber-reactive dyes in deep fast shades, the AM-grafted PF fibers giving deeper shades as a result of higher reactivity imparted to the substrate by the NH₂ group of the graft copolymer. The AA- and AN-grafted PF fibers could be dyed in intense deep shades with cationic dyes. Similarly, AM-grafted substrates gave bright deep shades with acid dyes. Infrared studies, used to analyze the grafted PF fibers, indicated the presence of ? COOH, ? CN, and ? NH₂ groups introduced in the fiber structure as a result of grafting with AA, AN, and AM.     

Kinetic study of acrylic monomer grafting in the presence of a polyfunctional monomer onto radioperoxided poly(ethylene–tetrafluoroethylene) copolymer

Acrylic acid (AA), methacrylic acid (MA) and diethyleneglycol dimethacrylate (DEGDM) are grafted onto 100 μm radioperoxided poly(ethylene–tetrafluroethylene) copolymer (ETFE). The influences of the homopolymerization inhibitor, the solvent, the grafting temperature, and the monomer content on the grafting kinetics are studied. For the grafting of acrylic monomers, the limitation of the grafting yield is more important for AA grafting whatever the nature of the metallic salt; the difference between the two homopolymerization inhibitors is their respective concentration to obtain a given grafting yield. For the AA + DEGDM cografting, the grafting yield increases with the DEGDM content of the grafting solution. In both cases, the overall activation energy has been calculated, and its variation as a function of the composition of the grafting solution is discussed. © 1994 John Wiley & Sons, Inc.     

Melt grafting of a long-chain unsaturated carboxylic acid onto polypropylene

The melt grafting of a long-chain unsaturated carboxylic acid such as oleic acid (OA) and undecylenic acid (UA) onto polypropylene (PP) in a Haake Rheocord RC90 mixer was studied. The influence of initiator concentration, monomer concentration and reaction temperature on grafting was investigated. The experimental results show that a higher degree of grafting was obtained using mixed initiators (DCP/BPO=1:1). Increasing the monomer concentration leads to an initial rapid increase in the degree of grafting. The addition of styrene reduced the degradation of PP as well as the degree of grafting. The monomer chain length influenced grafting significantly, the degree of grafting decreasing with increasing chain length of the grafting monomer. The results of differential scanning calorimetry (DSC) indicated that the crystalline properties of PP grafted with OA and UA were different from those of PP grafted with acrylic acid (AA), which may be attributed to the nucleation effect of the grafted long chain of OA and UA.     

Kinetics study of radiation‐grafting of acrylic acid,acrylonitrile, and their mixture onto wool fabric

The effect of monomer concentration, exposure time, irradiation temperature, and weaving direction on the kinetics of grafting acrylic acid (AA), acrylonitrile (AN), and their mixture onto wool fabric has been studied at the dose rate of 1.38 Gy/s. The degree of grafting is found to depend on the methanol‐to‐water solvent ratio and fabric‐to‐liquor ratio. The grafting rate and rate constant are dependent on irradiation temperature, type of grafted monomer, and weaving direction. The grafting rates increase with the increase in irradiation temperature (276–308 K). The calculated activation energy is nearly the same (16.4–17.2 kJ mol^?1) and the preexponential rate constant is dependent on the type of grafted monomer. The grafting of AA, AN, and their mixture are confirmed from the dyeing affinity of grafted fabrics towards Sandocryl Blue (SB), a basic dye. The formation of wool grafts and structural changes resulting from grafting were verified by using FTIR spectrometry and X‐ray diffraction analysis. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4328–4340, 2006     

Tailoring bulk and surface grafting of poly(acrylic acid) in electron-irradiated PVDF

Endowing conventional hydrophobic poly(vinylidene fluoride) (PVDF) films with hydrophilic properties was conducted using electron beam irradiation. Grafting of acrylic acid (AA) in/onto pre-irradiated PVDF films was investigated. Reaction parameters, monomer concentration and inhibitor concentration were examined. Radiation grafted films (PVDF-g-PAA) were synthesized with various grafting yields ranging from 12 to 130 wt % in presence of Mohr's salt (25 wt %). Below 80 wt % of monomer concentration, the degree of swelling was found to increase with the grafting yield. The PAA was arranged randomly in all PVDF matrix (grafting through). Above 80 wt % of monomer concentration, the PAA was grafted only onto the surface of PVDF films leading to a highly dense layer of PAA. Grafting through or surface grafting processes were achieved by varying the water fraction in the initial monomer solution. Water molecule acts not only as a carrier for the monomer but also as a plasticizer expanding the film in the three dimensions. Evidences of grafting through and surface grafting were produced using FTIR in ATR mode, SEM coupled to X-ray detection and XPS. An accurate quantification of AA units was possible up to the micromole via a Cu²⁺–EDTA complex analyzed by UV–vis spectroscopy.     

Thermal behavior and the determination of the polymer-polymer interaction parameter of polycarbonate and a thermotropic liquid crystalline polymer blends

Summary The surface modification of low-density polyethylene(PE) by liquid phase photograft polymerization with acrylic acid(AA), acrylamide(AM) and glycidyl methacrylate(GMA) was described. The grafting of AA and AM was proved and characterized by electron spectroscopy for chemical analysis(ESCA). It was found that fully hydrophilic surface can be obtained in very short irradiation time. With ESCA and attenuated total reflection infrared spectroscopy(ATR-IR), it can be confirmed that bifunctional monomer GMA was grafted onto the PE film surface. Through further reaction with GMA grafted film, heparin and protamine were immobilized onto the grafted film surface.     

Controllable surface modifications of polyamide by photo‐induced graft polymerization using immobilized photo‐initiators

A novel two‐step UV initiated grafting method has been developed and applied on surface modification of polyamide. Anthraquinone‐2‐sulfonate sodium, an acid dye, was chosen as the photo‐initiator. In the first step, photo‐initiators were ionically bonded onto polyamide through a normal acid dye dyeing process. Vinyl monomers such as acrylic acid were then grafted onto polyamide surface in the following step. During UVA irradiation, not only monomers were grafted onto polymer surface, photo‐initiator itself was also covalently bonded onto polymer. The grafted polymers were characterized by Fourier transform infrared spectrometer (FTIR), X‐ray photoelectron spectroscopy (XPS) and scanning electron microscope (SEM).The degree of photo‐grafting can be controlled by adjusting concentrations of photo‐initiator and monomer, as well as UVA exposure time. This process demonstrated the feasibility of efficiently modifying polymer surface under low UV intensity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Radiation grafting of acrylic and methacrylic acid to cellulose fibers to impart high water sorbency

Acrylic and methacrylic acids have been directly grafted to rayon and cotton using the preirradiation technique with ⁶⁰ Co γ rays. The rate of grafting increased with increasing temperature and monomer concentration, as did the final degree of grafting. The amount and rate of grafting also increased with the total irradiation dose but tended to level off at higher doses, in agreement with the leveling off of the radical content reported previously. Methacrylic acid grafted more and faster than acrylic acid to both rayon and cotton. Methacrylic acid grafted more with rayon than cotton, but acrylic acid gave somewhat similar yields with both fibers. The water absorbency of the grafted fibers depended strongly on their posttreatment. Decrystallizing with 70% zinc chloride or with hot sodium hydroxide developed supersorbency. The two treatments in succession, respectively, gave the highest values. Methacrylic acid brought about less sorbency than the corresponding acrylic acid grafts. Useful levels of grafting and supersorbency could be readily and practically achieved by the methods described.     

Photoinitiated cationic polymerization of epoxides

Difunctional epoxy monomers have been polymerized cationically by UV irradiation in the presence of a triarylsulfonium photoinitiator. The curing process was followed quantitatively by monitoring the disappearance of the epoxy group by infrared spectroscopy and the insolubilization and hardening of the resin upon UV exposure. The addition of epoxidized soyabean oil (ESO) to an aromatic diepoxide was shown to accelerate the crosslinking reaction with formation of a tight polymer network. The photoinitiated copolymerization of ESO with a cycloaliphatic diepoxide proceeds extensively and leads within seconds to a fully cured insoluble material showing increased hardness, flexibility and scratch resistance. Interpenetrating polymer networks have been generated by a short UV‐irradiation of blends of acrylate and epoxy monomers. © 2001 Society of Chemical Industry     

Modification of polyolefin surfaces by plasma-induced grafting

Polar monomers have been grafted onto polyolefin surfaces with the aid of inert gas plasma. In the first stage, an inert gas plasma (argon plasma) was used to generate free radicals on the polyolefin surface. In the second stage, the plasma generator was turned off and a vinyl monomer introduced as a vapor. Monomer was surface grafted by free radical polymerization. After cleaning and drying, the samples were analyzed by XPS, IR, and contact angle. LD–PE was successfully grafted with acrylic acid, glycidyl methacrylate, methyl acrylate, and 2-hydroxy ethylacrylate. The grafting of acrylic acid was studied in more detail, and the rate of grafting was observed to increase with increasing monomer pressure and to decrease with time. The increasing of grafting temperature was found to reduce the degree of grafting. This last factor can be explained by the reduced concentration of monomer at the polymer surface or by a deactivation of surface radicals. © 1996 John Wiley & Sons, Inc.     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. I. Relationship between adhesive bond strength and surface composition

A number of vinyl monomers have been surface grafted onto a polyethylene sheet by the mutual irradiation in monomer vapor and by a trapped-radical technique. The surface composition of the grafted sheets has been determined by means of ATR infrared spectrophotometry and compared with the peel strength of the joints bonded with conventional structural adhesives. In the methyl acrylate grafts followed by a saponification treatment, only the surfaces having graft compositions of more than 80 mole-% methyl acrylate give a high peel strength. A similar relationship between peel strength and surface composition is found in the surface grafts of vinyl acetate, acrylic acid, acrylamide, and methylolacrylamide. It is concluded that the formation of a surface with such a high monomer content is a necessary condition for the strong adhesive bonding of grafted polyethylenes at bonding temperatures below the softening point. Moreover, the adhesive bondability of the highly modified surfaces with epoxy adhesives is significantly enhanced by the introduction of carboxy and carbamyl radicals.     

Effect of silane monomer on the improvement of mechanical and degradable properties of photografted jute yarn with acrylamide

UV radiation was used to graft acrylamide (AA) to jute yarn in order to improve the mechanical properties. The physicomechanical properties of the grafted jute yarn were investigated. A series of solutions of different AA concentrations in methanol along with photoinitiator (Irgacure‐907, 2%) were prepared. The jute yarns were soaked in the solution for 30 min before radiation. The effect of irradiation time, concentration of monomer on polymer loading, and tensile properties of the jute yarn were studied. The highest polymer loading (22%) and tensile strength (95%) of the yarn were observed when the yarn was treated in 30% AA in methanol with 60 min of UV radiation. The surfaces of both treated and untreated jute were characterized by X‐ray photospectrometry, infrared spectroscopy, and environmental scanning electron microscopy, and it was observed that the AA reacted or deposited on the jute surface. A minute amount (1%) of silane monomer [3‐(trimethoxysilyl)‐propyl methacrylate] was used as an additive in the AA solution to further improve the mechanical properties of jute yarn. Better improvement was achieved by using 1% silane monomer. Water uptake, simulating weathering, and soil degradation tests of untreated and treated yarns were also performed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3530–3538, 2003     

Physical properties of silk fibers grafted with vinyltrimethoxysilane

Silk fibers from Bombyx mori silkworms were grafted using a novel grafting monomer, vinyltrimethoxysilane (VTMSi), with various grafting initiators. The effects of these grafting initiators were evaluated. It was possible to successfully copolymerize VTMSi within the silk fiber matrix without disturbing the fine structure of the fiber matrix, which was shown by FTIR analysis and refractive index measurements. The physical properties of VTMSi grafted silk were analyzed and compared to fibers grafted with conventional monomers such as methyl methacrylate, methacrylamide, and 2‐hydroxyethyl methacrylate. No trend in the tensile strength and elongation at break was observed when grafting silk fibers with VTMSi. Crease recovery in the wet state improved significantly, suggesting that this new grafting technique is important for the production of washable silk fabrics. The thermal stability of VTMSi grafted silk fibers was improved as shown by the shift of the endothermic peak for the thermal decomposition toward higher temperatures. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1764–1770, 2001     

The study on radiation grafting of acrylic acid onto fluorine-containing polymers. IV. Properties of membrane obtained by preirradiation grafting onto poly(tetrafluoroethylene–hexafluoropropylene)

Some properties of the membranes obtained by preirradiation grafting of acrylic acid onto poly(tetrafluoroethylene–hexafluoropropylene) (FEP) film have been investigated. Swelling behavior, dimensional change by grafting, electric conductivity, and mechanical properties of the grafted films were found to depend largely on the degree of grafting and to increase as the grafting proceeds. These properties were also found to be independent of the preparation conditions such as irradiation dose, grafting temperature, film thickness, and monomer concentration lower than 60 wt %. The electric conductivity of the membranes prepared at lower monomer concentration (lower than 60 wt %) is higher than that prepared at 80 wt % acrylic acid concentration. X-ray microscopy of the grafted film revealed that the grafting proceeds from both surfaces of the film to the direction of center to give finally homogeneous grafting through the whole bulk of film. At lower monomer concentration the homogeneous grafting was achieved at a degree of grafting around 18%, while at 80 wt % acrylic acid it was achieved at a degree of grafting higher than 70%. The homogeneously grafted membranes show good electrochemical and mechanical properties which make them acceptable for practical uses as cation-exchange membranes.     

Photo-initiated vapor-phase grafting of acrylic monomers onto fibrous substrates in the presence of biacetyl

A novel vapor-phase process has been developed for grafting relatively volatile acrylic monomers onto various polymeric substrates, using photo-initiation by near ultraviolet irradiation in the presence of biacetyl vapors. With it, very even graft polymerizations on the substrates, with minimum amounts of homopolymerization, were found. Furthermore, there were essentially no changes in the tensile or aesthetic properties of the treated surfaces. The degree of photografting is dependent upon the chemical composition and porosity of the substrate, the volatility and reactivity of the monomers, prewetting of the substrate with a suitable wetting agent, and the conditions of irradiation used. The effects of various reaction parameters on the photo-induced grafting of methyl acrylate, methyl methacrylate, and acrylonitrile on wool keratin are studied in detail. Increasing biacetyl and monomer flow rates and flow times, irradiation times, and moisture content of the wool all caused progressive increases in the amount of polymer grafted to the wool, up to limiting values dependent on the reaction parameters involved and monomer used. In all instances, the amount of homopolymer found on the fiber was limited and remained essentially constant over the range of conditions studied. A series of acrylic monomers of different volatilities and reactivities including methyl acrylate, methyl methacrylate, butyl acrylate, acrylic acid, acrylamide, acrylonitrile, N,N-dimethylaminoethyl methacrylate, and 2,2,2-trifluoroethyl methacrylate was successfully grafted onto several hydrophilic and hydrophobic textile fibers (wool, cotton, rayon, nylon, acrylics, polyester, and polypropylene) and other polymeric surfaces such as filter paper, cellophane, and acetate film by this process. The wetting agents used included water, methyl and n-propyl alcohol, N,N-dimethylformamide, dimethylsulfoxide, benzene, and chlorinated hydrocarbon solvents.     

pH Sensitive polypropylene porous membrane prepared by grafting acrylic acid in supercritical carbon dioxide

pH sensitive membrane was prepared by grafting acrylic acid (AA) on the porous polypropylene (PP) membrane using supercritical (SC) CO₂ as a solvent. The monomer (AA) and the initiator (benzyl peroxide, BPO) were impregnated into the PP substrate with the aid of SC CO₂, and were grafted onto the microporous PP substrate. The grafted membranes were characterized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), and the water permeability of the virgin and grafted membranes were determined at different pH values. It was demonstrated that the grafting degree (Dg) could be easily controlled by varying operating conditions, such as the monomer concentration, pressure, and temperature during the soaking process. The water permeation of the virgin membrane is nearly independent of pH. However, the water permeation of grafted membranes decreases dramatically with pH as the pH varies from 3 to 6 because the conformation of the PAA changes significantly with the pH of the contacting solution.     

Study on the surface grafting of polypropylene fibers

In this article, the surfaces of polypropylene (PP) fibers were grafted by three different grafting systems, of which the initiators belonged to three different types, namely, the water‐soluble initiator, the redox initiator, and the oil‐soluble initiator, respectively. The grafted products were characterized by FTIR, and the grafting degrees were determined by acid–base titration. In comparison, it was found that the oil‐soluble initiator might be more suitable for the surface grafting modification of PP fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 734–737, 2006     

Characterization of nylon 6 fibers grafted by acrylic monomers

Samples of nylon 6 fibers grafted with the acrylic monomers methyl methacrylate (MMA), ethyl methacrylate (EMA), and n-butyl methacrylate (n-BMA) with various graft levels were investigated by infrared, X-ray and scanning electron microscopic studies and the changes due to grafting with respect to the parent nylon 6 fibers were studied. The IR spectra of grafted nylon 6 samples show that there is a little change in the peak heights by grafting of nylon 6 with various monomers. The characteristic peaks of parent nylon are, more or less, maintained in the case of grafted samples. A peak at 1730 cm^?1 of the ester group was noted which confirms that the polymer has been grafted with the monomer. X-ray diffraction data on the grafted samples show some remarkable variations with the degree of grafting, depending upon the nature of the graft monomer. The percentage of crystallinity varies with the degree of grafting. In the initial stages of grafting it shows a decrease in the case of PMMA graft and an increase in the case of PEMA and Pn-BMA graft. At higher degrees of grafting (above 50% graft add-on) the percentage of crystallinity decreases in all the three cases. Orientation index has been found to increase in the initial stages of grafting in the case of EMA and n-BMA grafted nylon 6 and it decreases later on, whereas in the case of MMA graft it decreases continuously even at low graft level. The studies of surface characteristics for the parent and grafted samples show that spectacular changes on the surface of the various samples have taken place. With the increase in the graft level the diameter of the fiber increases and also the voids and cracks appear on the surface.