Graft copolymerization of methyl methacrylate onto wool in presence of vanadyl sulfate–potassium bromate in aqueous medium

Graft copolymerization of methyl methacrylate onto wool was studied in the presence of vanadyl sulfate and potassium bromate. The experimental results suggested that the wool radicals produced in the reaction initated the graft copolymerization and that the graft polymer radicals terminated by mutual combination. An appropriate kinetic scheme was proposed and the rate and energy parameters were evaluated. Alkaline solubility, dye uptake, and tensile strength of the wool samples were determined before and after grafting.     

Grafting of wool with vinyl monomers by using trichloroacetic acid–bis(acetonylacetonato)-copper(II) cocatalyst

Graft copolymerization of wool with methyl methacrylate (MMA) and acrylonitrile (AN) was effected under the catalytic influence of trichloroacetic acid (TCA) together with bis(acetonylacetonato)copper(II). Investigation of the action of the cocatalyst on wool in the absence of monomer revealed that the treated wool is completely soluble in dilute alkali. The effect of storage on the catalyzed wool was also studied. Increasing the period of storage, before adding the monomer, causes a significant decrease in the graft yields, indicating vitiation of some of the free radicals on the wool backbone. Based on these studies, a mechanism for the grafting reaction was proposed. Moreover, grafting of wool modified through its disulfide bonds and amino and hydroxyl groups suggests that the thiol, hydroxyl, and amino groups participate in the grafting reaction as sites for graft attachment. Wool—graft copolymers show excellent antifelt properties, particularly at higher levels of grafting.     

Redox-initiated vinyl graft copolymerization onto wool with thiourea as the reductant. III. Di-tert.-butyl peroxide thiourea system

Graft copolymerization of wool with methyl methacrylate (MMA) induced by di-tert.-butyl peroxide (DTBP)/thiourea (TU) system in acid medium was studied. The rate of the copolymerization reaction depends on concentrations of DTBP, TU and MMA, temperature as well as kind of acid and solvent used. The graft yield increases by increasing the concentration of DTBP and MMA. Increasing the temperature enhances also the graft formation; 60°C produces higher grafting than 50°C. Carrying out the graft polymerization reaction in acid medium by using nitric acid has proved to be the best in comparison with sulphuric and formic acid. There is an optimal concentration of TU (0.4 M); lower grafting is achieved below and above this concentration. A mixture of isopropanol/water at a ratio of 10:90 constitutes the most favourable reaction medium since increasing the solvent content is accompanied by a reduction in the graft yield. The kind of solvent does affect the graft yield: for the solvent studied, the graft yield follows the order: isopropanol < acetone < dimethylsulphoxide. Incorporation of an acid dye in the polymerization system to affect concurrent dyeing and grafting was carried out and the properties of the products so obtained were examined. The changes in alkali solubility of wool by grafting was also investigated. In addition, a reaction mechanism based essentially on complexes formed between DTBP and wool and/or DTBP and TU and their subsequent dissociation to give wool macroradicals was suggested.     

Redox-initiated vinyl graft copolymerisation onto wool with thiourea as the reductant. II. Fe3+-thiourea co-catalyst induced graft copolymerisation of methyl methacrylate on wool and modified wool fibres.

The capability of Fe³⁺-thiourea redox system to induce graft polymerisation of methyl methacrylate onto wool fibres was investigated under various conditions. Variables studied include sequence of addition of reagents, acidity of the reaction medium, temperature, monomer concentration and nature of the substrate. In addition, alkali solubility of wool before and after grafting was examined. Allowing the ferric ion to be absorbed first on wool before addition of the thiourea and monomer leads not only to higher grafting but to greater grafting efficiency and total conversion than when all the reagents were present together. The graft yield increases significantly by increasing reaction time in the initial stages of the reaction but it does slow down on prolonging the duration of grafting. The effect of increasing monomer concentration is to bring about a significant enhancement in the graft yield. The same holds true for acidity of the reaction medium and temperature. The graft yields are considerably influenced by chemical modification prior to grafting. For instance, wool reduced via treatment with thioglycolic acid is more amenable to grafting than untreated wool. The opposite holds true for esterified and dinitrophenylated wools. The alkali solubility of wool decreases significantly by increasing the graft yield; a graft yield of ca. 95% makes wool practically unimpaired with aqueous sodium hydroxide.     

Acid Dye Diffusion in Solvent–assisted Dyeing

Rates of diffusion of Orange II into wool previously extracted with methanol and diethyl ether have been measured at 35°C and pH 7. 0 in the presence of a variety of organic solvents. In all cases studied, the presence of solvent decreases the rate of diffusion, which is found to be proportional to the total moles of solvent plus water in the fibre. The solvent can increase the uptake of this dye by wool if the wool is incompletely extracted.     

The effect of pH and temperature on the dye sorption of wool powders

The sorption behavior of wool powders for three acid dyes (C. I. Acid Red 88, C. I. Acid Red 13 and C. I. Acid Red 18) and a basic dye (methylene blue) was investigated as a function of pH and temperature. The sorption capacity of wool powders depends on the pH of dye solution. The maximum uptake of acid dyes and methylene blue by wool powders occurred at pH 2.5 and pH 7.5, respectively. The effect of pH on the sorption of the hydrophilic dyes (C. I. Acid Red 13 and C. I. Acid Red 18) was more significant than that of the uptake of the hydrophobic dye (C. I. Acid Red 88). Increasing temperature enhanced the dye sorption ability of coarse wool powders, but did not impact that of fine wool powders. The dye‐absorption models of wool powders agree with the Langmuir isotherm. Comparison to activated charcoal and other sorbents indicates that fine wool powders have excellent dye sorption capacity even at room temperature, and may be used as a potential sorbent. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Graft polymerization of methacrylate onto wool using dimethylaniline–benzyl chloride mixture as initiator

Graft polymerization of wool with methyl methacrylate (MMA) initiated by a dimethylaniline–benzyl chloride (DMA/BC) mixture was extensively studied. The grafting and homopolymerization reactions are influenced by the nature of the solvent used; ethanol proved to be the best. Using water as a cosolvent enhances significantly both graft formation and homopolymerization. A mixture of water/ethanol at a ratio of 90:10 constitutes the optimal medium for the grafting reaction. Addition of acetic acid or formic acid in low concentration (0.2 mole/l.) favors grafting. The opposite holds true for sulfuric and hydrochloric acid. Kinetic investigations showed that the rates of total conversion (R_p) and grafting (R_p′) are dependent of the concentrations of DMA, BC, acetic acid (Ac) and amount of wool (W), as well as temperature. They can be expressed by the following equations: The overall activation energies for the total conversion and grafting reactions amount to 8.5 and 9.0 kcal/mole, respectively; whereas the corresponding energies for initiations E_d are E_d′ 7.0 and 8.0 kcal/mole, respectively. The changes in the physical and/or chemical structure of wool via reduction, acetylation, and dinitrophenylation are reflected on the susceptibility of wool toward grafting. While reduced wool showed higher grafting, the graft yields obtained with acetylated and dinitrophenylated wools were quite poor. The alkali solubility of wool graft copolymer was determined and its tendency to felt was examined. Evidences for grafting were provided and a tentative mechanism for grafting initiation was suggested.     

UV-induced grafting of organic–inorganic antibacterial membrane on wool fiber

Wool fiber was modified by UV irradiation and then reacted with cross-linked chitosan-coated Ag-loading nano-SiO₂ (CCTS-SLS) composites to prepare antibacterial wool fiber. The results show the topography of wool surface was also modified along with the formation of active radicals during UV irradiation. These active groups were used to graft antibacterial materials CCTS-SLS. Compared with parent wool fiber, the antibacterial wool fiber was improved in dyeing property. The dyeing uptake increased by 98% in a dyeing time of 50 min. Also, the antifelting performance increased as a result of the decrease in directional frictional effect after UV irradiation modification.     

Effect of atmospheric pressure helium plasma on felting and low temperature dyeing of wool

Wool fabrics were treated with atmospheric pressure helium glow discharge plasma in an attempt to improve felting and dyeing behavior with cold brand reactive dyes using cold pad‐batch method at neutral pH. On glow plasma treatment, the hydrophilicity of wool surface and its resistance toward felting was greatly improved without any significant damage to the cuticle layer. The color strength of the plasma treated dyed wool on the surface (in terms of K/S) was found to be nearly double of the color strength of dyed untreated wool fabric. However, the corresponding total dye uptake of the treated wool increased by a much lower value of 40%–50%. The reason behind this altered dyeing behavior was investigated by studying the dye kinetics using infinite bath and surface characteristics using SEM and SIMS. It was found that the glow plasma treatment greatly transformed the chemical surface of the wool fibers. It resulted in uniform removal of hydrophobic cuticular layer, which resulted in better diffusion of the dye molecules into the fiber, and formation of hydrophilic ? NH₂ groups near the surface, which helped in anchoring the dye molecules close to the surface giving higher color strength than expected. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Silicon‐containing anionic water‐borne polyurethane with covalently bonded reactive dye

A silicon‐containing water‐borne polyurethane (PU) polymer with hydroxyl side groups was synthesized that was stable in basic conditions and also capable of reacting with a reactive dye to form a covalently bonded dye molecule. The silicon‐containing anionic water‐borne PU prepolymer was synthesized from H₁₂‐4,4′‐diphenylmethane diisocyanate (H₁₂‐MDI), polytetramethylene glycol, polydimethylsiloxane (PDMS), 2,2′‐bis(hydroxymethyl), propionic acid (anionic centers), and triethyleneamine using the prepolymer mixing method. Water was then added to emulsify and disperse the resin to form an anionic water‐borne PU prepolymer. N‐(2‐Hydroxyethyl ethylene diamine) (HEDA) was used to extend the prepolymer to form a water‐borne PU polymer with a side chain of hydroxyl groups, which can further react with the reactive dye to form a dyed PU. The reactive dye of chlorosulfuric acid esters of sulfatoethyl sulfones can react with the water‐borne PU polymer. Behaviors of alkali resistance and dyeing properties were observed. In consideration of thermal properties, the dye‐grafted PU polymers exhibited lower glass‐transition temperatures for soft segments and hard segments than those without dye. Concerning mechanical properties, it was found that the modulus and the strength of the dyed PU polymers decreased with grafting of the dye molecule, but elongation at break was increased. The alkali resistance increased with PDMS content. For dye‐uptake properties, the percentage of dye grafting was over 90%. Also, the dye‐grafted PU exhibited a lower percentage of dye migration than that of polymers with ethylene diamine instead of HEDA as a chain extender, and showed greater colorfastness to light. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2045–2052, 2003     

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.     

‘Masked’ Isocyanates as Reactive Groups for obtaining Dyes of High Fastness to Washing

Reactive dyes for wool which incorporate a water-stable bisulphite-isocyanate adduct as the ‘masked’ reactive group can be applied in the form of levelling acid dyes. High fastness to washing on wool can subsequently be attained by fixing the dye with alkali or steam treatments.     

REDOX INITIATED GRAFT COPOLYMERIZATION OF 4-VINYL PYRIDINE ONTO WOOL FIBER

The graft copolymerization of 4-Vinyl Pyridine (4VP) onto wool fiber in aqueous medium by peroxomonosulphate (PMS)—thioglycolic acid (TGA) redox pair in an inert atmosphere has been investigated. The effect of concentrations of 4VP, PMS, TGA on R_h, and graft parameters have been studied. In addition, the effect of time, temperature, and amount of wool fiber on R_h and graft parameters were also determined. Chemical grafting of 4VP onto wool fiber was confirmed by FTIR spectroscopy. The tensile strength of the grafts have been analyzed.     

Grafting onto wool

Summary In order to study the role of -SH group of wool in graft copolymerization, an attempt has been made to study grafting of acrylic acid (AAc) onto reduced wool in aqueous medium using ceric ammonium nitrate (CAN) as redox initiator. HNO₃ was found to catalyze the graft copolymerization. Reduction of wool was effected with thioglycolic acid (TGA) in aqueous medium. Percentage of grafting was determined as a function of concentration of (i) CAN, (ii) vinyl monomer (AAc), (iii) nitric acid, (iv) time and (v) temperature. Under optimum conditions, poly-(acrylic acid) was grafted to the reduced wool to the extent of 9.14%, the unreduced wool under optimum conditions afforded maximum grafting of poly(AAc) to the extent of 12.24%. Reduction of wool does not promote grafting of AAc in the presence of CAN.     

The Mode of Action of Levelling Agents in the Dyeing of Wool

When the rate of uptake of C. I. Acid Blue 138 on wool was held constant by continuously varying the temperature, either a non–ionic or a cationic ethylene oxide condensate effectively promoted level uptake of dye. Equilibrium sorption isotherms of the dye on wool in the presence of the cationic condensate showed a point of inflexion. Improved levelness in exhaustion dyeing was attained by delaying the addition of the cationic condensate until the concentration of dye had fallen to correspond to the point of inflexion in the isotherm.     

The Chemistry of Chrome Mordanting of Wool

The chemistry of chrome mordanting is discussed under the headings: reaction of wool with chromium(VI) anions; reaction of wool with chromium(III) cations; reduction of chromium(VI) to chromium(IlI); interaction between chromium(Vl) and dye; interaction between chromium(III) and dye; and interaction between chromium(III), dye and wool.     

Redox-initiated vinyl graft polymerization onto wool with thiourea as the reductant. I. Grafting of methyl methacrylate with the hydrogen peroxide–thiourea catalyst system

The interaction of methyl methacrylate with wool under the catalytic influence of the hydrogen peroxide–thiourea redox system was studied under a variety of conditions. The degree of grafting depends upon the method empolyed; it is advantageous to first immerse wool in thiourea solution, monomer and hydrogen peroxide being then subsequently applied. Increasing the hydrogen peroxide concentration from 4 to 8 mmole/1. causes a significant enhancement in the graft yield. The latter remains practically unchanged upon further increment in hydrogen peroxide concentration within the range studied, i.e., up to 12 mmole/1. This was also observed with respect to thiourea concentration. On the other hand, increasing monomer concentration is accompanied by a significant increase in the graft yield. The polymerization reaction is temperature dependent; at the three temperatures examined, the graft yields follow the order 80° > 60° > 40°C. The rate of grafting is also dependent on the pH of the reaction medium over the range of 2 to 8, being decreased as the pH increased. Furthermore, the presence of traces of cupric ions in the polymerization system accentuates the graft formation. The alkali solubility as well as the urea bisulfite solubility of wool grafted with poly(methyl methacrylate) are much lower than those of physical mixtures of wool and poly(methyl methacrylate). This demonstrates that grafting of poly(methyl methacrylate) into wool has occurred.     

One‐bath union dyeing of wool/polytrimethylene terephthalate blends†

The one‐bath dyeing of blends of polytrimethylene terephthalate (PTT) staple and wool has been investigated. The exhaustion of selected Terasil disperse dyes on PTT fibre and Lanasol reactive dyes on wool was measured as a function of temperature, together with the cross‐staining of the Terasil dyes on the wool component and the Lanasol dyes on PTT component. Most Terasil disperse dyes achieved satisfactory dye uptake on PTT at 110 °C, whereas on conventional polyester (polyethylene terephthalate) temperatures of up to 130 °C are required. An optimised union‐dyeing technique for wool/PTT blends was developed which minimised the staining of Terasil disperse dyes on wool and produced dyed goods with high levels of wet colour fastness. Carriers were not required to enhance the dyeability of PTT at low temperatures. The wool component appeared to be protected against damage at 110 °C by the reactive dyes. The results indicate the potential for blending PTT fibre and wool to produce fabrics that are easier to dye at lower temperatures than conventional wool/polyester blends.     

Alkali reduction and reactive dye dyeing of T/N nonwoven fabrics dipped into silicon‐containing,water‐borne polyurethane

Two series of anionic water‐borne polyurethanes with alkali resistance and covalent bonds of a reactive dye were synthesized with different molar ratios of poly(tetramethylene glycol) (PTMG). They were classified with respect to PTMG 1000 and PTMG 2000. The fiber blends of polyester/nylon nonwoven fabrics were dipped into silicon‐containing, water‐borne polyurethane and squeezed to an 80% pickup ratio. Finally, the manmade leather was treated with alkali reduction and dyed with a reactive dye. The alkali reduction and the thermal, mechanical, and dyeing properties of the manmade leather were studied. For alkali reduction, different ratios of NaOH and Na₂CO₃ concentrations were used. Na₂CO₃ was used because of its better spreading and buffering properties. The softness and breaking load were measured and related to the weight reduction. For the dyeing properties, a reactive dye with vinyl sulfone groups was found to bond with the OH group of water‐borne polyurethane by covalent bonding. On the basis of alkali reduction, a mixture of NaOH and Na₂CO₃ with a concentration ratio of 0.1N/0.2N could lead to better softness and alkali reduction of leather. For the mechanical properties, leather of the PTMG 1000 series showed a higher breaking load than leather of the PTMG 2000 series. However, less elongation in the PTMG 1000 series resulted. Differential scanning calorimetry showed an endothermic peak at 50–100°C. This indicated that the glass‐transition temperature of the hard segment decreased with an increasing amount of the soft segment in leather; meanwhile, both the glass‐transition temperature of the soft segment and the melting temperature of the hard segment also decreased as the content of the soft segment increased. For the dyeing properties, the reactive blue dye could reach up to 96.1% dye uptake in the polyurethane part of the leather. Moreover, the washing fastness could be graded as high as 4–5, and the light resistance was also graded to 4–5, in the dyed leather. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2324–2335, 2005     

Dyeing of natural and synthetic textiles in supercritical carbon dioxide with disperse reactive dyes

Polyester, nylon, silk and wool were dyed with disperse reactive dyes in supercritical carbon dioxide (scCO₂). The dyes were substituted with either vinylsulphone or dichlorotriazine reactive groups. Since earlier research showed that water, distributed over the scCO₂ and the textile, increased the colouration, experiments were done with the vinylsulphone dye with varying amounts of water in the dyeing vessel, to investigate if there is an optimum water concentration. The amounts were such, that no liquid water was present. The maximum colouration was obtained when both the scCO₂ and the textiles were saturated with water. At the saturation point, deep colours were obtained with the vinylsulphone dye for polyester, nylon, silk and wool, with fixation percentages between 70 and 92% when the dyeing time was 2 h. The positive effect of water was due to its ability to swell fibres or due to an effect of water on the reactivity of the dye–fibre system. Also the dichlorotriazine dye showed more colouration when the scCO₂ was moist. With this dye, experiments were conducted in water-saturated scCO₂, varying the pressure from 225 to 278 bar and the temperature from 100 to 116 °C. The colouration of polyester increased with pressure, the results for silk and wool were not sensitive to pressure. Increasing the temperature had no influence on the dyeing of polyester, silk and wool. The fixations on polyester, silk and wool, being between 71 and 97%, were also independent of pressure and temperature.