Preparation of adsorbent for palladium ions by amination of acrylonitrile grafted polypropylene nonwoven fabrics

A new chelating fabrics are synthesized by radiation induced grafting of acrylonitrile (AN) onto polypropylene nonwoven fabrics (PP fabrics) and subsequent conversion of cyano to an imine by reaction with ethylene diimine (EDA). Influence of various parameters such as initial concentration, pH and adsorption time on the adsorption amount for palladium ions was investigated. It was found that adsorbent achieved excellent adsorption performance in palladium ion removal in the pH range of 1.88–5.70. The adsorption amount of ions increased with shaking time and initial concentration of palladium ions. The grafted and aminated fabrics were characterized by FT‐IR, TGA and SEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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

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

丙烯腈接枝羧甲基甲壳素水溶性衍生物的制备和表征

以羧甲基甲壳素和丙烯腈为原料,制备了丙烯腈接枝羧甲基甲壳素衍生物,讨论了反应温度、反应时间、溶剂用量、引发剂用量、单体用量对接枝反应的影响。结果表明,最佳反应条件为:羧甲基甲壳素0.4 g,溶剂水40.0 mL,过硫酸铵50.0 mg,丙烯腈2.5 g,反应温度60℃,反应时间2 h。所制共聚产物具有水溶性,分析了产物具有水溶性的原因。     

Reactivity ratios during radiation‐induced grafting of comonomer mixtures onto polyester fabrics

Radiation‐induced grafting of binary mixtures of acrylonitrile (AN)/styrene (S) and acrylamide (AAm)/styrene (S) onto polyester fabric (PET) has been investigated. Synergism during radiation grafting was investigated by determining the graft yield fraction for each monomer in the final graft copolymer. Moreover, by knowing the mole fraction of each monomer in the grafting solution, the reactivity ratio of the individual monomers in the comonomer mixture during graft copolymerization could be determined: in the case of AN/S comonomer mixture, the calculated reactivity ratios for AN and S are 0.04 and 0.05, respectively; the calculated reactivity ratios of AAm and S in their comonomer mixture are 1.82 and 0.41, respectively. © 2001 Society of Chemical Industry     

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     

Plasma induced graft polymerization of acrylic acid onto polypropylene monofilament

Plasma induced graft polymerization of acrylic acid onto polypropylene (PP) monofilament was carried to introduce carboxyl functionality on its surface. The monofilament was treated with oxygen plasma to create hydroperoxide groups and subsequent graft polymerization was initiated on this exposed monofilament. It was observed that in the absence of an added inhibitor, the grafting did not proceed because of the extensive homopolymerization which left behind hardly any monomer for the grafting reaction. The addition of ferrous sulfate to the grafting medium led to the homopolymer free grafting reaction. The addition of organics, such as methanol, butanone, and acetone led to complete inhibition of the homopolymerization at 60% content. However, the addition of butanone led to much lower degree of grafting than methanol and acetone. The contact angle of the monofilament showed drastic reduction by plasma treatment and by the subsequent grafting of acrylic acid. The grafting in ferrous sulfate medium showed higher contact angles as compared to the grafting in organic medium. The surface morphology was significantly influenced by the nature of the additive in the grafting medium. © 2007 Wiley Periodicals, Inc. JAppl Polym Sci, 2008     

UV‐radiation‐induced preirradiation graft copolymerization of methacrylic acid and acrylic acid onto jute fibre

UV‐radiation‐induced graft copolymerization of methacrylic acid and acrylic acid onto jute fibre was carried out using a preirradiation method with 1‐hydroxycyclohexyl‐phenylketone as a photoinitiator. 2‐methyl‐2‐propene 1‐sulfonic acid, sodium salt was incorporated into the grafting solution in suppressing the homopolymer/gel formation and facilitating graft copolymerization. In comparison, results showed that the type of monomer significantly influence on grafting. The results of the characterisation showed that the graft weight and the type of monomer have significant influence on the mechanical and water absorption properties in the case of grafted samples. Copyright © 2004 Society of Chemical Industry     

Adsorption of Pb2+ and Pd2+ on polyethylene membrane with amino group modified by radiation‐induced graft copolymerization

Six chelating hollow fiber membranes were prepared by radiation‐induced grafting of glycidyl methacrylate onto a polyethylene hollow fiber membrane and its subsequent amination. The adsorption characteristics of Pb²⁺ and Pd²⁺ for the chelating hollow fiber membranes were presented when the solution of Pb²⁺ and Pd²⁺ permeates across the chelating membrane, respectively. The degree of grafting for glycidyl methacrylate increases with increasing monomer concentration, reaction temperature, and preirradiation dose. The adsorption of Pd²⁺ by chelating hollow fiber membranes modified with five kinds of amines was in the following order: diethylene triamine > hexamethyl diamine > ethylene diamine > dimethyl amine > trimethyl amine. The chelating hollow fiber membrane modified with iminodiacetic acid adsorbed Pb²⁺ ions much more than Pd²⁺. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 643–650, 1999     

Preparation and characterization of pH‐sensitive hydrogels based on chitosan,itaconic acid and methacrylic acid

Novel pH‐sensitive hydrogels based on chitosan, itaconic acid and methacrylic acid were prepared in two steps. Chitosan was first ionically crosslinked with itaconic acid, after which a free radical polymerization and crosslinking of the chitosan/itaconic acid network was performed by adding methacrylic acid and a crosslinker in order to achieve better mechanical properties and tunable swelling. The samples were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, X‐ray diffraction, dynamic mechanical analysis and the swelling ratios of the hydrogels at various pH values (2.0–8.0). The hydrogel composition is found to have a great impact on the hydrogel structure, mechanical and thermal properties, morphology and swelling kinetics. The highly porous morphology of the gels is probably connected with the bulky chitosan/itaconic acid network which reduces the degree of crosslinking in the second step of the synthesis due to steric hindrances. The gels demonstrate substantial change in buffer absorbency with change of pH, low for acid buffers and the higher for pH values above 6 where the swelling is considerably slow, thus suggesting their strong candidature for use as oral drug‐delivery systems in the lower parts of the gastrointestinal tract and for drugs that require longer release times. Copyright © 2010 Society of Chemical Industry     

Preparation of antimicrobial sutures by preirradiation grafting of acrylonitrile onto polypropylene monofilament. III. Hydrolysis of the grafted suture

Polypropylene‐grafted‐polyacrylonitrile (PP‐g‐PAN) sutures were prepared by graft polymerization of acrylonitrile onto polypropylene (PP) monofilament using a preirradiation method. The grafted PP monofilaments were subsequently hydrolyzed to introduce carboxyl groups for antimicrobial drug immobilization. The maximum conversion of nitrile groups into carboxyl groups was limited to about 62% and produced sutures with carboxyl content ranging from 0.042 to 0.25 mmol/g. The physical characteristics of sutures were evaluated by FTIR, X‐ray diffraction, differential scanning calorimetry, and X‐ray photoelectron spectroscopy. In general, the hydrolysis did not cause any significant variation in crystalline structure. The mechanical strength was affected in all the grafted sutures. The tensile strength of sutures was investigated as a function of the degree of grafting. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2509–2516, 2004     

Ceric‐initiated free radical graft copolymerization of acrylonitrile onto kappa carrageenan

The polysaccharide, kappa carrageenan (kC), was modified using ceric‐initiated graft copolymerization of acrylonitrile (AN) under inert atmosphere in a homogeneous aqueous medium. Grafting was confirmed using FTIR spectroscopy, solubility test, elemental analysis, acid hydrolysis, and thermogravimetric analysis (TGA). kC‐graft‐poly(AN) products had a higher thermal stability than kC as revealed by TGA analysis. The polyacrylonitrile branches were isolated by acidic degradation of the carrageenan main chains and characterized by size exclusion chromatography (SEC). Residual monomers were not found by HPLC in graft copolymers stored even for longer periods. The effect of various factors affecting on grafting, i.e., concentration of the initiator, monomer, and polysaccharide as well as the reaction time and temperature were studied by conventional methods to achieve the optimum grafting parameters. The graft copolymerization reactions were kinetically investigated using semi‐empirical expressions and a suitable rate expression has been derived. According to the empirical rates of the polymerization and the graft copolymerization of AN onto kC backbone, the overall activation energy of the graft copolymerization reaction was estimated to be 20.96 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of novel graft copolymers by radiation‐induced grafting

The radiation‐induced graft copolymerization of N‐vinyl‐2‐pyrrolidone (NVP), 4‐vinyl pyridine (4VP), and 2‐vinyl pyridine (2VP) monomers onto poly (ethylene‐alt‐tetrafluoroethylene) (ETFE) was investigated. The influence of synthesis conditions particularly the solvent was studied. Various solvents, such as n‐propanol, isoproponol, benzyl alcohol, methanol, ethanol, cyclohexanone, tetrahydrofuran (THF), nitromethane, 1,4‐dioxane, and n‐heptane were examined for this purpose. Graft copolymers were characterized by Fourier transform infrared (FTIR) spectroscopy, dynamic mechanical analysis (DMA), and scanning electron microscopy‐energy dispersive spectroscopy (SEM‐EDAX). It was found that the nature of the solvent had profound influence over the grafting reaction. Cyclohexanone, n‐propanol, and isoproponol for 4VP/ETFE grafting, THF and 1,4‐dioxane for NVP/ETFE grafting, and benzyl alcohol and methanol for 2VP/ETFE grafting were found to be the suitable solvents yielding highest graft levels. Isoproponol and n‐propanol are promising in terms of both graft level and mechanical properties for 4VP/ETFE. Grafting of NVP, 4VP, and 2VP onto ETFE were verified through FTIR spectroscopy. Storage modulus and glass transition temperature of the copolymers were found to increase as graft level increased. Surface profile of representative films was also investigated by viewing the distribution of elemental nitrogen using SEM‐EDAX. Results indicated that copolymers of 4VP, NVP, and 2VP are considerably different from each other. 4VP‐based copolymers exhibited relatively more homogenous grafting over the surface compared with NVP‐ and 2VP‐based copolymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polymerization of maleic acid and itaconic acid studied by FT‐Raman spectroscopy

In this research, we used a new redox free radical initiation system consisting of potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂). In the presence of NaH₂PO₂, the thermal decomposition of K₂S₂O₈ is accelerated, and the temperature required for the formation of free radical is reduced. We polymerized maleic acid (MA) using the K₂S₂O₈/NaH₂PO₂ initiation system in an aqueous solution, and monitored the polymerization process with FT‐Raman spectroscopy. The Raman spectroscopy data indicate the formation of a saturated carboxylic acid with the disappearance of the characteristic bands of MA as the thermal decomposition of K₂S₂O₈ progresses, thus indicating the formation of poly(maleic acid) (PMA). We also found that itaconic acid (IA) polymerizes in the presence of the new initiation system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 223–228, 2001     

Plasma‐induced graft polymerization of acrylic acid onto poly(ethylene terephthalate) films

The graft polymerization of acrylic acid was carried out onto poly(ethylene terephthalate) films that had been pretreated with argon plasma and subsequently exposed to oxygen to create peroxides. The influence of synthesis conditions, such as plasma treatment time, plasma power, monomer concentration, temperature, and the presence of Mohr's salt, on the degree of grafting was investigated. The observed initial increase in grafting with monomer concentration accelerated at about 20% monomer. The grafting reached a maximum at 40% monomer and subsequently decreased with further increases in monomer concentration. The reaction temperature had a pronounced effect on the degree of grafting. The initial rate of grafting increased with increasing temperature, but the degree of grafting showed a maximum at 50°C. The activation energy of the grafting obtained from an Arrhenius plot was 29.1 kJ/mol. The addition of Mohr's salt to the reaction medium not only led to a homopolymer‐free grafting reaction but also diminished the degree of grafting. The degree of grafting increased with increasing plasma power and plasma treatment time. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2993–3001, 2001     

Preparation of pH‐sensitive hydrogels by graft polymerization of itaconic acid on tragacanth gum

Graft polymerization of itaconic acid on tragacanth gum (TG) was carried out using potassium persulfate as initiator to develop smart hydrogels for drug delivery systems. The effect of the grafting parameters on the degree of grafting was investigated. The grafting was significantly influenced by the reaction medium, the reaction temperature and the monomer concentration. The monomer dependency of the system was found to be 1.52. The hydrogels were characterized using Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X‐ray diffraction. The grafted TG had an amorphous nature and exhibited excellent swelling in water and strong dependence on the pH of the medium. The grafted TG showed pH‐dependent release of ciprofloxacin which offers the possibility of using these materials in colon‐specific drug targeting for human healthcare systems. © 2018 Society of Chemical Industry     

Kinetic study of radical polymerization. VII. Investigation into the solution copolymerization of acrylonitrile and itaconic acid by real‐time 1H NMR spectroscopy

Free radical solution copolymerization of acrylonitrile (AN) and itaconic acid (IA) was performed with DMSO‐d₆ as the solvent and 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. Weight ratio of the monomers to solvent and molar ratio of initiator to monomers were constant in all experiments. The initial comonomer composition was the only variable in this study. On‐line ¹H NMR spectroscopy was applied to follow individual monomer conversion. Mole fraction of AN and IA in the reaction mixture (f) and in the copolymer chain (F) were measured with progress of the copolymerization reaction. Overall monomer conversion versus time and also compositions of monomer mixture and copolymer as a function of overall monomer conversion were calculated from the data of individual monomer conversion versus time. Total rate constant for the copolymerization reaction was calculated by using the overall monomer conversion versus time data and then k_p/k_t^0.5 was estimated. The dependency of k_p/k_t^0.5 on IA concentration was studied and it was found that this ratio decreases by increasing the mole fraction of IA in the initial feed. The variation of comonomer and copolymer compositions as a function of overall monomer conversion was calculated theoretically by the terminal model equations and compared with the experimental data. Instantaneous copolymer composition curve showed the formation of alternating copolymer chain during copolymerization reaction. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3253–3260, 2007     

Electron‐beam‐radiation‐induced grafting of acrylonitrile onto polypropylene fibers: Influence of the synthesis conditions

Electron‐beam‐radiation‐induced grafting of acrylonitrile onto polypropylene fibers was investigated with a pre‐irradiation method. Grafting conditions such as the solvents, additives, monomer concentration, radiation dose, and temperature were varied, and the effects on the degree of grafting were studied. The nature of the reaction medium and additives had a considerable influence on the degree of grafting. The dilution of acrylonitrile with N,N‐dimethylformamide significantly enhanced the degree of grafting in comparison with other solvents. The addition of sulfuric acid to the reaction mixture led to an increase in the degree of grafting and an acceleration of the rate of grafting. The order of dependence of the rate of grafting on the pre‐irradiation dose and monomer concentration was found to be 1.31 and 1.21, respectively, in the presence of sulfuric acid. The activation energy for grafting was calculated to be 21.9 kJ/mol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚丙烯无纺布预辐射接枝改性及胺化研究

采用丙烯酸(AA)、二乙烯三胺(DETA)依次对聚丙烯(PP)无纺布进行预辐射接枝改性及胺化处理,研究了接枝反应及胺化反应的影响因素,并用红外光谱对产物进行表征。结果表明:随着AA用量的增加,接枝率呈先增长后下降趋势;随着反应温度的升高,反应时间的延长,接枝率增加;随着接枝率的增大,胺化反应温度的升高及反应时间的增加,胺化率增加。接枝反应温度为95℃,25 mL AA与无纺布反应2 h,接枝率可达到276%;接枝率为250%的无纺布与50 mL DETA反应7 h,胺化温度205℃,胺化率可达到73%。红外光谱分析表明,经辐射接枝及胺化处理后的PP无纺布有胺基基团。     

Studies on grafting of acrylic acid onto polypropylene melt‐blown nonwovens induced by electron‐beam preirradiation

We report the graft copolymerization of acrylic acid onto the polypropylene (PP) melt‐blown nonwovens induced by electron beam (EB) preirradiation in this article. The occurrence of the graft copolymerization was confirmed by means of XPS, FTIR, and SEM. The effects of preirradiation dose, monomer concentration, bath ratio, reaction time, and temperature on the graft ratio were investigated. The water conservation, water absorption rate, and K⁺ exchange capacity were also determined on the grafted PP melt‐blown nonwovens, which showed that EB preirradiation‐induced grafting was an effective way to improve the hydrophicility of PP melt‐blown nonwovens. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4971–4977, 2006