Synthesis and characterization of cellulose ion exchangers. I. Polymerization of glycidyl methacrylate,dimethylaminoethyl methacrylate,and acrylic acid with cotton cellulose using thiocarbonate-H2O2 redox system

Polymerization of glycidyl methacrylate (GMA), dimethylaminoethyl methacrylate (DMAEMA) and acrylic acid (AA) with cotton fabric using a cellulose thiocarbonate-hydrogen peroxide redox system as an initiator was investigated under different conditions. This includes the nature and concentration of the initiator and monomer, polymerization time and temperature, and liquor ratio. The percent of polymer add-on is generally favored by increasing monomer and H₂O₂ concentration, as well as duration and temperature of the polymerization, but with the certainty that the percent of polymer add-on follows the following order: GMA > DMAEMA > AA. On the other hand, the percent of polymer add-on increases by decreasing the liquor ratio. Incorporation of Fe²⁺ or Cu²⁺ ion in the polymerization system enhances the percent of polymer add-on significantly. Replacing the H₂O₂ by other oxidants such as Cr⁶⁺ or Mn⁴⁺ is made, and the capability of such cations to expedite polymerization of the said monomers with cotton cellulose is studied. Also studied is the synthesis of cation exchanger via reaction of poly(GMA)-cellulose copolymer with hexamethylene tetramine. Furthermore, the ion exchange characteristics of the cellulosic copolymers obtained with this as well as with other monomers are reported. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1029–1037, 1997     

Behavior of chemically modified cellulose towards dyeing. IV. Dyeability of poly(methyl vinyl pyridine)-cellulose graft copolymers before and after treatment with epichlorohydrin

Grafting of 2-methyl-5-vinyl pyridine (MVP) onto partially carboxymethylated cotton having 6 meq COOH/100 g cellulose (PCMC) was effected by a Fe²⁺-H₂O₂ redox system. Different graft yields were obtained by varying MVP concentration from 10 to 100 wt % PCMC. In a subsequent step these graft copolymers were treated with epichlorohydrin. Dyeing of untreated cotton, PCMC, PCMC grafted with MVP, and epichlorohydrin-treated poly(MVP)-PCMC graft copolymers was carried out at room temperature (27°C) for varying lengths of time (2.5–60 min) in the absence of alkali catalyst or any other additives. Three reactive dyes, Procion Red M-GS, Procion Orange Brown H-2GS, and Remazole Brilliant Blue; a direct dye, Orangé Solophényle 2RL; and an acid dye, Erio Blue Marine 2GR were used at a concentration of 2% by weight of material. It was found that none of the three reactive dyes or the acid dye interacts with untreated cotton or PCMC. In contrast, the direct dye did. PCMC grafted with MVP, on the other hand, showed a substantial extent of dye exhaustion regardless of the dye used. After-treatment of poly(MVP)-PCMC graft copolymers with epichlorohydrin significantly enhanced the extent of dye exhaustion. The latter reacted almost 100% with all the dye examined, irrespective of the graft yield, which varied from 1.6% to 63%. Dyeings for reactive dyes withstood soaping for 1 hr at boil and extraction with 50% dimethylformamide, whereas dyeings for the direct dye and the acid dye failed to do so. It is believed that the presence of pyridine moieties in the graft act as an internal, built-in catalyst for expediting the reaction of reactive dyes with cellulose hydroxyls and behave as a weak base capable of salt-linkage formation in case of the acid and direct dyes.     

Behavior of cellulose grafted with poly(methyl methacrylate) and polyacrylonitrile toward some direct and reactive dyes

Viscose rayon fibers modified with polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) were dyed with some direct and reactive dyes. Exhaustion rate of the dye onto fibers was governed by the amount and nature of the polymer grafted. In general, the dye affinity for cellulose and dye exhaustion onto fibers decreased as the graft yield increased. Dye affinity for the PAN–cellulose graft copolymers was greater than that found with PMMA–cellulose graft copolymers. Except in a few cases, the tendency of cellulose graft copolymers of ca. 13% graft to accept direct dyes was more than that of the untreated cellulose, whereas the affinity of reactive dyes for cellulose graft copolymers of up to ca. 43% polymer was more than that of untreated cellulose. The dye fixation, based on the weight of cellulose component, increased as the graft yield increased. The dyeability of cellulose oxidized with ceric ammonium nitrate was also examined. Oxidation of cellulose prior to dyeing reduced the affinity of the dye for cellulose.     

Vinyl graft polymerization-induced modification of some properties of poly(ethylene terephthalate) fabric

Polymerization of glycidyl methacrylate (GMA), methyl methacrylate (MMA), and acrylic acid (AA)/styrene (St) mixtures with poly(ethylene terephthalate) (PET) fabric to different polymer add-ons was performed. Moisture regain, dyeability, and soiling properties of the modified PET were examined. It was found that introduction of poly(GMA) in PET structure brings about (a) improved moisture regain, (b) enhanced dyeing with disperse dyes, (c) affinity and possible dyeing with acid, direct, and reactive dyes, (d) improved aqueous and nonaqueous oily soil resistance, and (e) decreased ease of soil removal. The magnitude of moisture regain, dyeability, and soiling properties are dependent upon the percent of polymer add-on. Polymerization of MMA with PET improved the dyeability of the latter with the disperse dye as well as its resistance to nonaqueous oily soil while decreasing the resistance to aqueous soiling and ease of both aqueous and nonaqueous soil removal. In the case of PET polymerized with poly(AA/St), there was a considerable enhancement in moisture regain, dyeing with the disperse dye, and resistance to aqueous and non-aqueous oily soiling. On the other hand, both aqueous and nonaqueous soil characteristics of PET were imparted by polymerization of the latter with AA/St mixtures.     

Preparation of copolymer brush-type restricted access microspheres with adjustable adsorption selectivity to variety of dyes

Restricted access materials (RAMs) with adjustable selectivity was developed for the removal and detection of residual dyes for the solve problems of dye contamination. In this work, using homemade poly(4-vinylbenzyl chloride-co-divinylbenzene) (P_VBC/DVB) microspheres as substrate and successive two-step surface-initiated atom transfer radical polymerization (SI-ATRP) as synthesis method, the two types of monomers, sodium 4-vinylbenzene sulfonate (Nass) and styrene (St) were first grafted for constructing mixed interactions of adsorption sites, and then the hydrophilic glycidyl methacrylate (GMA) was polymerized, following by hydrolysis to construct diol groups on the external P_VBC/DVB as the restricted access sites. The developed P_VBC/DVB@poly(St-co-Nass)@poly(GMA) of adsorption properties was investigated by six dyes including methylene blue (MB), basic fuchsin (BF), acid fuchsin (AF), neutral red (NR), methyl orange (MO), and Congo red (CR), the adsorption capacities of those dyes and the removal rate for the binary mixed dye solution both rely on the ratio of St/Nass, confirming the adjustable adsorption selectivity. When P_VBC/DVB@poly(St-co-Nass)@poly(GMA) was packed as solid phase extraction adsorbent in couple with UV–vis spectrum, it was applied to the determination of MB and BF in the water, fish and shrimp, good linearity with satisfactory recoveries for MB and BF are obtained to show the favorable practicability.     

The Impact of Nitrogen Plasma Treatment upon the Physical-Chemical and Dyeing Properties of Wool Fabric

Pretreatment of wool fabric with low-temperature plasma (LTP) as an eco-friendly process was tested. The impact of plasma-treatment parameters on the surface morphology, physical-chemical, and dyeing properties of wool using anionic dyes were investigated. The LTP-treatment resulted in a dramatic improvement in fabric hydrophilicity and wettability, the removal of fiber surface material, and creation of new active sites along with improved initial dyeing rate. The nature of the plasma gas governed the final exhaustion percentage of the used acid dyes according to the following descending order: nitrogen plasma > nitrogen/oxygen (50/50) plasma > oxygen plasma > argon plasma ≥ control. Prolonging the exposure time up to 20 minutes resulted in a gradual improvement in the extent of exhaustion. Increasing the ageing period up to 100 hours resulted in a slight decrease in the extent of acid dye uptake. Increasing the salt concentration up to 5 g/L and the dyeing temperature up to 95°C resulted in an enhancement in the extent of exhaustion. The extent of improvement in dye bath exhaustion, using low temperature nitrogen plasma (LTNP)-treatment, was determined by the nature of the anionic dyes.     

Compatibilization of polypropylene/ poly(3‐hydroxybutyrate) blends

Blending polypropylene (PP) with biodegradable poly(3‐hydroxybutyrate) (PHB) can be a nice alternative to minimize the disposal problem of PP and the intrinsic brittleness that restricts PHB applications. However, to achieve acceptable engineering properties, the blend needs to be compatibilized because of the immiscibility between PP and PHB. In this work, PP/PHB blends were prepared with different types of copolymers as possible compatibilizers: poly(propylene‐g‐maleic anhydride) (PP–MAH), poly (ethylene‐co‐methyl acrylate) [P(E–MA)], poly(ethylene‐co‐glycidyl methacrylate) [P(E–GMA)], and poly(ethylene‐co‐methyl acrylate‐co‐glycidyl methacrylate) [P(E–MA–GMA)]. The effect of each copolymer on the morphology and mechanical properties of the blends was investigated. The results show that the compatibilizers efficiency decreased in this order: P(E–MA–GMA) > P(E–MA) > P(E–GMA) > PP–MAH; we explained this by taking into consideration the affinity degree of the compatibilizers with the PP matrix, the compatibilizers properties, and their ability to provide physical and/or reactive compatibilization with PHB. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of reactive group types on the properties of core-shell modifiers toughened PA6

Summary  Reactive monomers such as acrylic acid (AA), maleic anhydride (MA) and glycidyl methacrylate (GMA) were grafted onto acrylonitrile-butadiene-styrene core-shell copolymer (ABS) by emulsion polymerization method. These functionalized ABS were used to toughen PA6. FTIR and Molau tests showed that these monomers were introduced onto ABS copolymers and compatibilization reactions took place between PA6 and the AA, MA and GMA grafted ABS. TEM result showed that the modified ABS copolymer dispersed in PA6 matrix uniformly and no obvious difference could be found between the different PA6 blends. However, mechanical test showed that GMA and MA modified ABS achieved much better toughening effect than the AA grafted ABS copolymer due to the stronger interfacial reactions. Fracture characterization indicated that PA6 toughened with GMA and MA modified ABS showed higher G_ivalues according to the Vu-Khanh approach and much obvious shear yielding in the deformed zone could be found.     

Grafting of Methacrylic Acid and Other Vinyl Monomers Onto Cotton Fabric Using Ce (IV) Ion–Cellulose Thiocarbonate Redox System

Graft copolymerization of methacrylic acid (MAA) onto cotton fabric using tetravalent ceric ion (Ce^IV)–cellulose thiocarbonate redox system was investigated under different conditions including pH of the polymerization medium (1–4), ceric sulphate (CS) concentration (4–20 m mole/l), MAA concentration (1%–6%), polymerization time (1/4–2 h) and polymerization temperature (0–70°C). Results obtained indicated that the optimal conditions for MAA grafting onto cotton fabric using the said redox system consisted of: [CS], 20 m mole/l; [MAA], 4%; pH of the medium, 2; time, 2 h; temperature, 60 °C keeping a material-to-liquor ratio at 1:0. Applying optimized conditions to different monomers, namely, acrylic acid (AA), methacrylic acid (MAA), acrylamide (Aam), acrylonitrile (AN), butyl acrylate (BuA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and glycidyl methacrylate (GMA) onto the same substrate, the rates of grafting followed the order:

Synthesis and characterization of magnetic beads containing aminated fibrous surfaces for removal of Reactive Green 19 dye: kinetics and thermodynamic parameters

BACKGROUND: Poly(HEMA‐co‐MMA) beads were prepared from 2‐hydroxyethyl‐methacrylate (HEMA) and methylmethacrylate (MMA) in the presence of FeCl₃. Thermal co‐precipitation of Fe(III) ions containing beads with Fe(II) ions was carried out under alkaline conditions. The magnetic beads were grafted with poly(glycidylmethacrylate; p(GMA)), and the epoxy groups of the grafted p(GMA) brushes were converted into amino groups by reaction with ammonia. RESULTS: The magnetic beads were characterized by surface area measurement, electron spin resonance (ESR), Mössbauer spectroscopy and scanning electron microscopy (SEM). The maximum adsorption of Reactive Green‐19 (RG‐19) dye on the p(GMA) grafted and amine modified magnetic beads was around pH 3.0. The adsorption capacity of magnetic beads was 84.6 mg dye g^?1. The effects of adsorbent dosage, ionic strength and temperature have also been reported. Batch kinetic sorption experiments showed that a pseudo‐second‐order rate kinetic model was applicable. CONCLUSION: The p(GMA) grafted and amine modified magnetic beads (adsorbent) were expected to have the advantage of mobility of the grafted chains in the removal of acidic dyes from aqueous solutions. The magnetic beads have potential as an adsorbent for removal of pollutants under various experimental conditions without significant reduction in their initial adsorption capacity. Copyright © 2011 Society of Chemical Industry     

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.     

Immobilization horseradish peroxidase on amine-functionalized glycidyl methacrylate-<Emphasis Type="Italic">g</Emphasis>-poly(ethylene terephthalate) fibers for use in azo dye decolorization

Activated fibers were used as a new support material for the immobilization of horseradish peroxidase (HRP). Poly(ethylene terephthalate) (PET) fibers were grafted with glycidyl methacrylate (GMA) using benzoyl peroxide (Bz₂O₂) as initiator. 1,6-diaminohexane (HMDA) was then covalently attached to this GMA grafted PET fibers. HMDA-GMA-g-PET fibers were activated with glutaraldehyde and HRP was successfully immobilized. Both on the free HRP and the immobilized HRP activities, pH, temperature, thermal stability, and reusability were investigated. Both free enzyme and immobilized enzyme were used in a batch process for the degradation of azo dye. About 98% of azo dye removal was observed with immobilized HRP, while 79% of azo dye removal was found with the free HRP. 45 min of the contact time is sufficient for the maximum azo dye removal. The HRP immobilized on modified PET fibers were very effective for removal of azo dye from aqueous solutions.     

Mechanical properties of poly(vinyl chloride) blends and corresponding graft copolymers

The mechanical properties of the poly (vinyl chloride) (PVC) and poly (glycidyl methacrylate) [poly (GMA)] blend system and the PVC and poly (hydroxyethyl methacrylate) [poly (HEMA)] blend system and their crosslinked films were investigated. At the same time, the mechanical properties for the corresponding graft copolymers such as PVC-g-GMA, PVC-g-HEMA, and their crosslinked films were also investigated in this study. The results showed that the tensile strengths for PVC–poly (GMA) blend systems were higher than those for PVC-g-GMA graft copolymer, and the tensile strengths for PVC-g-HEMA were higher than those for PVC-poly (HEMA) blend systems. However, the mechanical properties for the PVC–poly (GMA) blend system were not affected by the crosslinking of the blend system, but those for PVC-poly (HEMA) and their graft copolymers decreased with an increase of the equivalent ratio ([NCO]/[OH]) of the crosslinker. Finally, the surface hydrophilicity of the PVC-g-HEMA graft copolymer and PVC-poly (HEMA) blends were also assessed through measuring the contact angle. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 307–319, 1998     

Supercritical fluid dyeing of PMMA films with azo-dyes

In situ ultraviolet–visible spectroscopy has been used to study diffusion of two azo-dyes in a CO₂-swollen matrix of poly(methyl methacrylate) (PMMA). The diffusivity of both dyes can be tuned simply be changing the system pressure. Higher pressure of CO₂ enhances diffusion of a dye in PMMA. The diffusion of dyes in CO₂-swollen PMMA can also be influenced by specific interactions. The partitioning of the dyes between the polymer phase and the fluid phase was measured, and the partition coefficients are large (10⁴–10⁵). Thus, supercritical fluid dyeing is possible, although the solubility of the dyes in the fluid phase is low. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 911–919, 1998     

Preparation and application of glycidyl methacrylate and methacrylic acid monomer mixture‐grafted poly(ethylene terephthalate) fibers for removal of methylene blue from aqueous solution

A novel fibrous adsorbent that grafts glycidyl methacrylate (GMA) and methacrylic acid (MAA) monomer mixture onto poly(ethylene terephthalate) (PET) fibers was used for removal of methylene blue (MB) in aqueous solutions by a batch equilibration technique. The operation parameters investigated included, pH of solution, removal time, graft yield, dye concentration, and reaction temperature. The adsorption rate of MB is much higher on the MAA/GMA‐grafted PET fibers than on the ungrafted PET fibers. MB was removed 99% the initial dye concentration at 10 mg L⁻¹ and 93% at 200 mg L⁻¹ by monomers mixture‐grafted PET fibers. Pseudofirst order and pseudosecond order kinetic equations were used to examine the experimental data of different graft yield. It was found that the pseudosecond order kinetic equation described the data of dye adsorption on fibrous adsorbent very well. The experimental isotherms data were analyzed using Langmuir and Freundlich isotherm models. The data was that Freundlich isotherm model fits the data very well for the dyes on the fibers adsorbent. The dye adsorbed was easily desorbed by treating with acetic acid/methanol mixture (50% V/V) at room temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymerization of glycidyl methacrylate with poly(ethylene terephthalate) fibers using Fe+2–H2O2 redox system

Fe⁺²–H₂O₂ redox system initiated polymerization reactions of glycidyl methacrylate (GMA) from aqueous solution with poly(ethylene terephthalate) fibers (PET) were investigated. The polymer add-on is greatly influenced by H₂O₂ concentration, GMA concentration, as well as reaction time and temperature. Polymer add-on was directly related to H₂O₂ concentration up to 30 meq/L and GMA concentration up to 4%. Further increase in concentrations of H₂O₂ and GMA resulted in lower polymer add-on. Raising the reaction temperature from 65°C to 95°C caused a significant enhancement in the rate of polymerization, the latter follows the order 95 > 85 > 75 > 65°C. However, at 65°C, the polymerization reaction showed an induction period of about 120 min, in contrast with reactions at 75°C, 85°C, and 95°C, where no induction period was observed though the polymer add-on was quite low at 75°C during the initial stages of the reaction. Using dimethylformamide (DMF) alone or mixed with water as polymerization medium offset the polymerization reaction. Incorporation of thioureadioxide in the polymerization system decreased the polymer add-on significantly.     

直接染料对棉和大豆纤维的染色性能比较

测定了三种不同类型的直接染料在不同盐浓度和温度条件下对棉和大豆纤维的上染曲线，并对它们在这两种纤维上的染色性能进行了分析和比较。对于匀染型和温度效应型直接染料在大豆纤维上的上色率高于棉纤维；在不加盐的条件下，盐效应型染料上染率低于棉纤维，加盐后两者接近；提高温度，对匀染型染料影响不大，对温度效应型染料随温度的提高，上染率提高。     

One‐bath dyeing of polyester/cotton blends with disperse and bis‐3‐carboxypyridinium‐s‐triazine reactive dyes. Part 2: Application of substantive reactive dyes to cotton at 130 °C and neutral pH†

An earlier paper reported that the reactive dyes (not the disperse dyes) were responsible for the inability to achieve heavy depths of shade, when dyeing polyester/cotton blends by a one‐bath process at 130 °C and neutral pH using reactive dyes containing a 3‐carboxypyridinium‐s‐triazinyl group. It was shown that the poor colour yield of the bis‐3‐carboxypyridinium‐s‐triazine reactive dyes was because of their low exhaustion level at 130 °C and pH of 7.0–7.5. We now report the synthesis and evaluation of some bis‐3‐carboxypyridinium‐s‐triazine reactive dye structures, possessing highly substantive chromophores, as a means of obtaining high colour yield, on 100% unmercerised cotton, under the specified dyeing conditions. The technical performance of these dyes under such conditions was compared with that of selected Novacron (Cibacron) LS and Procion H‐E dyes, applied under their recommended (atmospheric) dyeing conditions.     

Removal of Cationic Dyes from Aqueous Solution by Hydrophobically Modified Poly(acrylic Acid) Hydrogels

Hydrophobically modified poly(acrylic acid) hydrogels were synthesized using acrylic acid (AA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and butyl methacrylate (BMA) as copolymer monomers. These hydrogels were carried out for removal cationic dyes from aqueous solution. It was found that the adsorption of cationic dye depended on the length of the side chain, hydrophobic monomer (MMA, EMA and BMA) content and pH of the solution. Increasing the hydrophobic monomer content led to an increase in the adsorption of cationic dyes on the hydrogels. The adsorption kinetics and isotherms of hydrogels were in good agreement with pseudo–second-order equation and the Langmuir equation, respectively. The cationic dyes adsorption of hydrogels involved a mechanism that combined swelling and electrostatic and hydrophobic interaction.     

Photoinitiated polymerization of glycidyl methacrylate with cotton cellulose

Unsensitized, photoinitiated polymerization reactions of glycidyl methacrylate from solutions of water and water–methanol with cotton cellulose fabrics were investigated. When several layers of cotton fabrics were immersed in solutions of glycidyl methacrylate and only the surface layer was exposed to light, polymerization reactions were initiated in this layer and also initiated in inner layers of fabrics, probably by chain transfer reactions. Photoinitiated (350 nm, 24 W, 34 min) polymerizations of glycidyl methacrylate (7.5 vol-%) from water (43 vol-%)–methanol (57 vol-%) with cotton fabrics in one-, three-, and six-layered configurations were: one-layered, 32% polymer; three-layered, 30%, 27%, and 25% polymer; and six-layered, 29%, 25%, 22%, 20%, 14%, and 11% polymer. Electron-microscopic examination of the distribution of poly(glycidyl methacrylate) within the cotton fibrous structure showed that polymer was distributed throughout the cross section of the fiber. At the surface of the fibers, the polymer tended to be more concentrated than within the cross section of the fibers and to encapsulate them. Photoinitiated polymerization reactivities of several vinyl monomers from solution with cotton cellulose fabrics were compared with those of glycidyl methacrylate as follows: methyl methacrylate > glycidyl methacrylate > diacetone acrylamide > 1,3-butylene dimethacrylate > methacrylic acid > acrylonitrile > divinylbenzene.