Polymerization of glycidyl methacrylate,methacrylic acid,acrylamide and their mixtures with cotton fabric using fe2+-thioureadioxide-H2O2 redox system

Polymerization of glycidyl methacrylate (GMA), methacrylic acid (MAA), acrylamide (Aam) and their binary mixtures with cotton cellulose fabrics using Fe²⁺-thioureadioxide-H₂O₂ redox system was investigated under a variety of conditions. While temperatures of 50, 80, 65, and 95°C constituted the optimal polymerization temperature for GMA, MAA, Aam and GMA/MAA (8:2), respectively, maximum polymerization of GMA/MAA (2:8), Aam/MAA (8:2) and Aam/MAA (2:8) occurred at 75°C. The polymerization reaction proceeded initially very fast then levelled off irrespective of the monomer or monomer mixtures used. However, the magnitude of the polymer add-on at levelling off of polymerization followed the order GMA > GMA/MAA (2:8) ≥ GMA/MAA (8:2) > Aam/MAA (2:8) ≥ MAA ≥ Aam/MAA (8:2) > Aam. The polymer add-on enhanced by increasing the H₂O₂ concentration up to a certain limit and then decreased. The same situation was encountered with respect to thioureadioxide concentration. The involvement of the epoxy ring of GMA with MAA during polymerization of their mixture with cellulose occurred only at a higher ratio of GMA in the mixture. Also a significant contribution of Aam in the polymer add-on obtained with a Aam/MAA mixture could only be achieved at a higher ratio of Aam in this mixture.     

Fe2+–Thioureadioxide–H2O2-induced polymerization of glycidyl methacrylate and its mixtures with acrylamide,acrylonitrile, butylmethacrylate,or styrene with cotton fabric

Fe²⁺–thioureadioxide-H₂O₂-induced polymerization of glycidyl methacrylate (GMA) and its mixtures with acrylamide (Aam), acrylonitrile (AN), butylmethacrylate (BMA), or styrene was investigated at different temperatures (50–95°C), for different periods of time (5–130 min) using different concentrations of Fe²⁺-thioureadioxide and H₂O₂. The add-on increased by increasing the thioureadioxide concentration up to 0.05% then decreased. H₂O₂ concentration of 0.005% constituted the optimal for GMA and GMA/Aam mixtures, and 0.02% H₂O₂ for GMA/AN, GMA/BMA and GMA/styrene mixtures. Increasing the concentration of GMA either alone or in admixtures resulted in improved add-ons; the magnitude of this improvement relied on the nature of the monomer used along with GMA. The polymerization reaction was characterized by an initial fast rate followed by a slower one irrespective of monomer or monomer mixtures used. Presence of Aam along with GMA offset the fast termination observed with the latter at higher temperatures (above 60°C). GMA/Aam mixtures produced higher add-ons than Aam alone irrespective of their rations in the mixtures, indicating activation of Aam with GMA. On the other hand, Aam deactivated GMA. Similar situation was encountered when styrene or acrylonitrile was used instead of Aam except that the percent add-ons obtained with GMA/AN mixtures decreased upon raising the polymerization temperature above 80°C. Contribution of GMA in the add-ons obtained with the different mixtures was also examined. For instance, the add-on was composed mainly of poly(GMA) when GMA/Aam at a ratio of 8:2 was used. On the other hand, using GMA/Aam at a ratio of 2:8 brought about add-ons of poly(GMA/Aam) in which the concentration of GMA and Aam were roughly equal.     

Preparation of hydrophilic membranes by grafting acrylic acid onto pre-irradiated teflon-FEP films

Grafting of acrylic acid onto pre-irradiated poly(tetrafluoroethylene-hexafluoropropylene) (Teflon-FEP) films was investigated, and the reaction parameters dose, dose rate, monomer concentration and grafting temperature were examined. The results show that the degree of grafting depends on the dose (5-60 kGy), the weight of grafted specimen increased up to 37%. The degree of grafting was found to be independent of the dose rate. The overall activation energies were calculated to be 28.8 and 81.6 kJ mol^-1 for treatments at above and below 50°C, respectively. The swelling of grafted films was measured in water, aqueous potassium hydroxide and methanol. The degree of swelling was found to increase with the length of grafted chains.     

Radiation-induced reactions with cellulose. III. Kinetics of styrene copolymerization in methanol

The kinetics of the radiation-induced grafting of styrene to cellulose in methanol have been studied in air at dose rates of 0.007, 0.014, and 0.078 Mrad/hr. in ⁶⁰Co and spent fuel element facilities. The variables affecting rate of grafting include monomer concentration, radiation dose rate, and total dose. Grafting reaches a maximum at 60–70% by volume methanol in styrene. The results have been interpreted in terms of possible grafting mechanisms, including charge-transfer intermediates; however, a complete mathematical treatment of the data is not possible at present because of the absence of appropriate swelling data for cellulose in mixtures of styrene and methanol. Poor grafting observed in solutions of up to 10% monomer is attributed to radical scavenging (predominantly from the solvent) by the monomer leading to the formation of scavenged products including homopolymer. Rate of grafting falls off for solutions above 80–90% monomer concentration and radical scavenging by monomer radicals is again postulated to account for the observed behavior.     

Grafting of vinyl monomers onto silk using redox systems. Yellowing of silk

The aim of this study is to investigate the influence of temperature, initiator concentration, and vinyl monomer on silk yellowing during grafting. A series of silk fabrics was treated at four different temperatures (70, 75, 80, and 88°C), with different concentrations of initiator in the range 1–4% owf, with and without methacrylamide (MAA) or 2-hydroxyethyl methacrylate (HEMA). By treating silk with ammonium persulphate (APS), in the absence of a monomer, the degree of silk yellowing increased linearly with increasing both initiator concentration and treatment temperature, indicating that the initiator plays a specific role in enhancing silk yellowing through macroradical formation. The graft copolymerization of MAA (with APS as the initiator) caused only slight changes in the intensity of silk yellowing compared to blank-treated fabrics. On the other hand, the use of HEMA resulted in a deeper yellowing of silk fabrics, especially in the 70–80°C temperature range, due to its higher reactivity and to the tendency to form a homopolymer, leaving unreacted macroradicals on silk fibroin backbone. Compared to APS, other initiators, such as 2,2′-azobis(isobutyronitrile) (AIBN) and 2–2′-azobis-(2-amidino propane) dihydrochloride (ADC), caused a significantly lower degree of silk yellowing when tested in the absebce of a monomer. The yellowness of silk fabrics tended to increase by grafting with HEMA, while decreased by grafting with MAA. The use of variable amounts of monomer (25–150% owf) did not influence the degree of yellowing with ADC as the initiator. The results reported in this study show that the extent of yellowing induced on silk fabrics by grafting MAA and HEMA with APS as the initiator can be limited by a suitable selection of the processing parameters (initiator concentration, temperature). Moreover, the use of both AIBN and ADC appears promising, owing to their negligible effect on silk yellowing. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 239–246, 1998     

Improving the colour fastness of dyed nylon‐6 fabric by graft copolymerisation and curing of acrylic acid

The influence of grafting and grafting–curing of acrylic acid on the colour fastness of nylon‐6 fabric dyed with an acid dye of low wash fastness was investigated. The variables involved in grafting were initially optimised for pristine nylon‐6 fabric prior to grafting the same monomer onto the dyed fabrics. The highest graft yield achieved for the pristine and dyed nylon‐6 fabrics was 44 and 14% respectively. Grey scale testing and colorimetric analysis revealed that the highest colour fastness and the smallest drop in colour strength belonged to the dyed–grafted–cured nylon‐6 fabric. The colour components were measured, and the total colour difference of each sample after five washing cycles was computed. The specific colour difference showed that the implementation of either grafting or grafting–curing processes will alter the reference colour of the dyed fabric. The tensile strength of the grafted and grafted–cured fabrics was respectively 2.7 and 6.3% lower than that of dyed nylon‐6.     

H2O2-induced graft polymerization of acrylic acid/styrene mixtures on poly(ethylene terephthalate) fibers

Graft polymerization of acrylic acid/styrene mixtures on poly(ethylene terephthalate) fibers using H₂O₂ as initiator was investigated under different conditions including acrylic acid/styrene ratio, monomer mixtures concentration, initiator concentration, polymerization temperature, pH of polymerization medium, addition of metallic salts, and use of solvent/water mixture instead of aqueous medium. It was found that the rate and extent of grafting for acrylic acid/styrene mixtures were much higher than those of single monomers, indicating a synergestic effect. Maximum percent grafting occurred when acrylic acid/styrene mixture at a ratio of 30:70 was used. Increasing the monomer mixture concentration from 2% to 40% was accompanied by a significant enhancement in percent grafting. The latter increased also significantly as the H₂O₂ concentration increased from 10 to 150 meq/L; a further increase in H₂O₂ concentration decreased grafting. No grafting took place at 65°C even after 4 h. Raising the polymerization temperature to 75°C expedited grafting; the magnitude of the latter increased by increasing the temperature up to 95°C. Addition of copper sulphate and ferrous ammonium sulphate to the polymerization system offset grafting, the opposite holds true for lithium chloride provided that its concentration does not exceed 15 mmole/L. Methyl alchol/water mixture (20:80) constituted the optimal medium for polymerization. Grafting of acrylic acid/styrene mixtures to poly(ethylene terephtalate) fibers resulted in considerable improvement in moisture regain of the latter.     

Gamma ray induced graft copolymerization of N-vinylpyrrolidone,acrylamide and their mixtures onto polypropylene films

The radiation initiated grafting of N-vinylpyrrolidone (NVP) acryl-amide (AAm) and their mixtures onto polypropylene (PP) films using a direct radiation technique has been investigated. Different solvents were used for diluting the monomers and it was found that dioxane was suitable for this grafting system. The influence of other grafting parameters such as inhibitor, monomer concentration and dose rate on the rate of grafting and grafting yield was studied. The values of the coefficients relating the grafting rate to monomer concentration and dose rate were found to be 1·4 and 1·5 for (NVP), and 1·6 and 1·47 for (AAm), respectively. Also, the coefficients relating grafting rate to co-monomer concentration for 20/80 and 50/50 AAm/NVP mixtures were found to be 1·6 and 1·7. Some physicochemical properties such as swelling, thermal behaviour, mechanical and electrical conductivity were also investigated, and the possibility of some practical uses, e.g. the removal of heavy metals from solution, for the grafted membranes is discussed. © 1998 SCI.     

Radiation-induced grafting of methacrylic acid onto polyurethane in the presence of solvents

The radiation-induced grafting of methacrylic acid onto polyurethane has been carried out in the presence of solvents. The swelling of polyurethane was highest when the solubility parameter of the monomer solution was 11.0. The molecular weight of polyurethane did not change with the irradiation dose up to 30 Mrad in the absence of solvent. The irradiation in the presence of solvent, on the other hand, decreased the molecular weight. The grafting yield in CCl₄, benzene, and n-hexane decreased monotonously with the decrease in monomer concentration. The large decrease of the grafting yield in CCl₄ was proved to be due to the high possibility of chain transfer to CCl₄. When such solvents as water, methanol, and DMF were used, on the other hand, a maximum grafting yield was obtained when the monomer concentration was ca. 75%. The hydrogen bonding among polyurethane, methacrylic acid, and solvent was found to affect both the swelling and the grafting yield.     

Graft copolymerization of acrylonitrile onto bagasse and wood pulps

Graft copolymerization of acrylonitrile onto bagasse and wood pulps has been studied using ceric ammonium nitrate as initiator. The effect of order of reactants addition on grafting was examined: three methods were studied. Addition of the pulp to a mixture of initiator and monomer (method A) resulted in more efficient grafting than the other two methods. The reaction produced more grafting at 50°C than at 30°C or at 40°C. The results showed that the monomer and initiator concentrations are the major factors influencing the grafting rate of acrylonitrile. Increasing the acrylonitrile or initiator concentration was accompanied by a substantial increase in graft yields. Increasing the initiator concentration is more effective on polymerization rate than the increase in monomer concentration. The extent of grafting of this monomer can best be controlled by reaction time. Water swelling of pulps significantly affected the grafting rate of acrylonitrile as well as the ceric consumption during grafting. The reactivity of bagasse pulp towards grafting of acrylonitrile is higher than that of wood pulp due to a more open structure of cellulose in bagasse pulp as well as the presence of some lignin which accelerates grafting. Ceric consumption during grafting depends on the nature of the pulp as well as the monomer and initiator concentrations, time, temperature, and the method of grafting. More Ce(IV) is consumed during grafting than during oxidation of the pulps under identical reaction conditions, due to homopolymer formation which accompanied grafting. The ceric consumption by bagasse during grafting or oxidation is somewhat greater than that consumed by wood pulp under similar reaction conditions.     

Radiation-induced grafting of N,N′-dimethylaminoethylmethacrylate onto chitosan films

Chitosan films were grafted with N,N ′-dimethylaminoethylmethacrylate using the ⁶⁰Co gamma irradiation method. The effect of solvent composition, monomer concentration, dose rate, and total dose on grafting was studied. The solvent composition has a marked effect on the degree of grafting. Maximum yield was obtained in the water-methanol (1 : 1) system. The percent grafting increased with monomer concentration and was found to be higher at a lower dose rate for a constant total dose of 0.216 Mrad. The tensile strength, crystallinity, and degree of swelling of grafted films decreased on increasing graft level. However, the graft copolymers showed improved thermal stability. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 869–877, 1997     

聚丙烯无纺布预辐射固相接枝丙烯酸的研究

以聚丙烯(PP)无纺布为基材,以丙烯酸为单体,进行预辐射固相接枝聚合,考察了外部环境、辐射剂量、温度、反应时间、单体用量、介质、阻聚剂、交联剂对接枝率的影响。结果表明,通过预辐射固相接枝聚合方法,可将丙烯酸单体接枝在PP无纺布上,辐射剂量增大可提高接枝率;反应时间对接枝率的影响在低、高温阶段有所不同。最佳反应条件为:氮气环境,辐射剂量大于50 kGy,反应温度65℃,反应时间3 h,单体浓度30%,反应介质为水,阻聚剂0.8 g,交联剂用量为5 mL。     

Chemically induced graft copolymerization of acrylic acid onto polyester fabrics. I. Kinetic investigation of grafting

The kinetics of grafting of acrylic acid onto poly(ethylene terephthalate) fabrics initiated by benzoyl peroxide has been studied. Extent of grafting depended upon time, concentration of the initiator and the monomer, as well as the presence of the activator used. From the temperature dependence of the initial rate of grafting the overall activation energy for grafting was found to be 90 kJ/mol. The results of the monomer and temperature dependence found in this study are consistent with the rate expression derived from a normal kinetic scheme for grafting.     

Graft polymerization of acrylic acid onto polyethylene film by preirradiation method. I. Effects of preirradiation dose,monomer concentration,reaction temperature,and film thickness

Low-and high-density polyethylenes were irradiated by electron beams with dose of 2–50 Mrad and then immersed in aqueous solution of acrylic acid (monomer concentration from 30 to 100 wt %) for 10 min?5 h at a temperature of 25–40°C. The degree of grafting increases with time and levels off. High density polyethylene shows lower grafting rate and higher final % grafting in compared with low-density polyethylene. Both grafting rate and final % grafting increase with total dose of preirradiation, but show some saturation at high doses. The highest grafting rate was observed at 60 wt % of monomer concentration where the grafted polyethylene swells to the largest extent in the monomer mixture. Apparent activation energies for the grafting are 19.6 and 27.3 kcal/mol for low- and high-density polyethylenes, respectively, reflecting the proces of monomer diffusion in the film. Grafting rate decreases with increasing film thickness. Graft polymerization starts on the surface of the film and proceeds to the inner part with monomer diffusion through the grafted layer.     

Radiation grafting of acrylic and methacrylic acids onto poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) TFB films

A study has been made for the preparation of membranes by the direct radiation grafting of acrylic and methacrylic acids onto poly(tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride) TFB films. The appropriate reaction conditions were selected under which the graft polymerization was carried out successfully. In this grafting system, ammonium ferrous sulfate (Mohr's salt), ferric chloride, and cuppric chloride were used as inhibitors to minimize the homopolymerization of acrylic acid and methacrylic acid. Also, the effect of monomer concentration on the rate of grafting was investigated. The dependence of the grafting rate on monomer concentration was found to be of the order of 1.1 and 1.0 for acrylic acid and methacrylic acid, respectively. This grafting system was proceeded by a front mechanism. Some selected properties of the grafted films such as swelling behavior, dimensional change, and mechanical and electrical properties were investigated. It was found that the grafted membranes possess good hydrophilic properties that may make them promising in some practical applications. © 1993 John Wiley & Sons, Inc.     

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     

Modification of polypropylene fiber by radiation-induced graft copolymerization of acrylonitrile monomer

Modification of polypropylene fiber was carried out by graft copolymerization of acrylonitrile monomer using the preirradiation method. The influence of synthesis conditions (preirradiation dose, monomer concentration, temperature, draw ratio, and storage) on the degree of grafting was investigated. For all preirradiation doses, the degree of grafting was found to increase with the reaction time. The higher the preirradiation dose, the higher the degree of grafting was. The dilution of monomer with DMF showed peak maxima for the degree of grafting at 80% monomer concentration. Both the initial rate of grafting and the final degree of grafting were found to increase with an increase in the reaction temperature. An activation energy of 31.2 kJ/mol was found for the grafting reaction. The degree of grafting in the drawn fiber showed different behavior as compared to the undrawn fiber. The storage of the irradiated fiber at −4°C prior to the grafting showed a decrease in the degree of grafting initially for a period of 8 days, beyond which the degree of grafting remained constant. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1343–1348, 1998     

Radiation grafting of acrylic acid on to polypropylene filaments. I: Effect of reaction conditions

Graft copolymerization of acrylic acid on to polypropylene filaments was investigated by a simultaneous irradiation technique. The effect of various solvents and solvent combinations on swelling behaviour and on percentage grafting was studied. At a constant dose, the percentage grafting was found to be higher at low dose rates and it increased linearly up to 0.25 Mrad and then saturated. It was also observed that grafting increases with increasing monomer concentration up to 2 mole/litre. Graft copolymers were characterized by infrared spectroscopy and colour formation with methylene blue.     

Modification of natural rubber tubes for biomaterials. II. Radiation-induced grafting of N,N-dimethylaminoethylacrylate (DMAEA) onto natural rubber (NR) tubes

Radiation-induced simultaneous grafting of N,N-dimethylaminoethylacrylate (DMAEA) onto NR tubes has been studied to improve blood compatibility of NR tubes. In the grafting of DMAEA onto NR tubes, effect of grafting parameters such as solvent, monomer concentration, temperature, dose, and dose rate on the grafting yield was investigated. As the results, it was found that the grafting proceeds effectively in the presence of carbontetrachloride (CCI₄) as a solvent. The initial rate of grafting was found to be proportional to 0.70 power of dose rate and to 0.95 power of monomer concentration. The activation energy for this grafting system was calculated to be 6.78 kcal/mol. The evaluation of blood compatibility of NR-g-DMAEA was carried out by ex vivo test. Blood compatibility of those samples was found to be dependent on only grafting yield. When the degree of grafting is higher than 30 wt %, blood compatibility of NR tube could be improved by DMAEA grafting. This is the same tendency which that of previous grafting system of NR-g-DMAA.     

Development of membranes by radiation grafting of acrylamide into polyethylene films: Influence of synthesis conditions

SYNOPSIS: The graft copolymerization of acrylamide monomer into polyethylene films was carried out by the preirradiation method. The influence of synthesis conditions, such as monomer concentration, preirradiation dose, reaction temperature, Mohr's salt, and pregrafting storage was investigated. The order of dependence of the rate of grafting on preirradiation dose and monomer concentration was found to be 0.87 and 1.86, respectively. An activation energy of 22.9 kJ/mol for the grafting reaction was obtained. The storage of preirradiated polyethylene film at −4°C prior to the reaction showed a decrease in the degree of grafting up to 10 days, beyond which the degree of grafting remained constant. The addition of FeSO₄ in the grafting medium not only inhibits the homopolymerization of the monomer but also decreases the degree of grafting. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1331–1337, 2000