Moisture regain and dyeability of poly(acrylic acid)- and poly(styrene)-carbamoylethylated cotton graft copolymers induced by gamma radiation

Gamma radiation-induced graft copolymerization of either acrylic acid or styrene onto untreated cotton, alkali-treated cotton, and carbamoylethylated cottons having 0.392% N, 0.524% N, 0.725% N, 1.379% and 1.546% N was investigated under different conditions. Moisture regain and dyeability of these substrates before and after copolymerization were also examined. It was found that the graft yield increases by increasing monomer concentration and radiation dose irrespective of the monomer or substrate used. Using water-ethanol mixtures as polymerization media are advantageous for grafting of styrene. With both monomers, however, the graft yield for the modified cottons are substantially higher than untreated and alkali-treated cottons, indicating that the presence of carbamoylethyl in the molecular structure of cotton cellulose affords additional sites for graft copolymerization. Copolymers obtained using acrylic acid show much higher moisture regain that the ungrafted substrates, particularly when the carboxylic groups of the graft were in the sodium form. The opposite holds true for copolymers brought about by grafting with styrene. The color strength of all substrates dyed with a direct or a reactive dye decreases significantly after copolymerization with poly(acrylic acid) prior to dyeing. On the other hand, this copolymerization improves the affinity of the substrates for the basic dye and brings about perceptible shade. Copolymerization of the substrates in question with poly(styrene) improves the color strength of these substrates when dyed with direct, disperse, and basic dyes but decreases the color strength upon dyeing with a reactive dye.     

Modification of partially carboxymethylated cotton via crafting with acrylic acid and styrene using gamma radiation

Partially carboxymethylated cottons (PCMC) having 15.549, 27.409, and 46.834 meq ? COOH/100 g cellulose as well as untreated cotton and alkali-treated cotton, which was prepared in an analogous manner to PCMC but, in the absence of monochloroacetic acid, were graft-copolymerized with either acrylic acid or styrene using gamma radiation under different conditions. Moisture regain and dyeing properties of the copolymers so obtained were investigated. It was found that the graft yeld increases by increasing monomer concentration and radiation dose irrespective of the monomer or substrate used. Using water/methanol mixtures as polymerization media are advantageous for grafting of styrene onto the substrates in question. The graft yields of PCMCs are much lower than those of unmodified and alkali-treated cottons when they were grafted with acrylic acid. In case of styrene on the other hand, the graft yields for PCMCs are higher than the corresponding yields obtained with the unmodified and alkali-treated cottons. Poly(acrylic acid)–PCMC graft copolymers show much higher moisture regain than PCMCs particulary when the carboxylic groups of the graft were in the sodium form. The opposite holds true for polystyrene–PCMC graft copolymers which exhibit much lower moisture regain as compared with PCMCs. The color strength of PCMC dyed with direct or reactive dyes decreases significantly after being copolymerized with poly(acrylic acid) prior to dyeing. On the other hand, this copolymerization improves the affinity of PCMCs for the basic dye and brings about perceptible shade. Polystyrene–PCMC graft copolymers acquire higher color strength than the PCMC when dyed with direct, disperse, and basic dyes but lower color strength upon dyeing with the reactive dye. Also reported were the moisture regain and dyeability of unmodified and alkali-treated cotton before and after copolymerization with acrylic acid or styrene for comparison.     

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.     

Deep‐coloured polyester/cotton blends with low concentrations of polymethylol dyes by a one‐pass continuous dyeing process

An obvious limitation of the one‐pass continuous dyeing process for polyester/cotton blends is its inability to achieve deep colour depth, which is caused by the low dye fixation yields of commercial reactive dyes. In this study, the performances of polyester/cotton blends dyed with high‐fixation polymethylol dyes and disperse dyes were compared with those of polyester/cotton blends dyed with a mixture of reactive dyes and disperse dyes. Polymethylol dyes were observed to be suitable for dyeing polyester/cotton blends when used in low concentrations; the required concentrations of polymethylol dyes were only 23–58% of the concentrations of commercial reactive dyes required to reach a given colour level on polyester/cotton blends. The wash and crocking fastness of polyester/cotton blends dyed with polymethylol dyes were similar to those of polyester/cotton blends dyed with reactive dyes.     

Grafting onto polyformaldehyde fibers

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

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.     

Dyeing natural fibres in supercritical carbon dioxide using a nonionic surfactant reverse micellar system

A reverse micellar system in supercritical carbon dioxide has been developed as a dyeing medium. Water-soluble dyes such as reactive dyes and acid dyes could be sufficiently solubilised in the interior of a specially constituted reverse micelle. Protein fabrics, silk and wool, were satisfactorily dyed even in deep shades with conventional acid dyes without any special pretreatment. Cotton cellulose fabric was also dyed with conventional reactive dyes when the electrostatic force of repulsion between dye and cotton was eliminated. Compared to previously proposed supercritical dyeing methods, dyeing of fabrics with this system could be performed at low temperatures and pressures in a short time.     

Synthesis of cotton-bearing DEAE,carbamoyethyl, carboxyethyl,and poly(acrylamide) graft for utilization in dye removal

Cotton cellulose in the fabric form was subjected to etherification and grafting reactions with the purpose of obtaining cotton with ionic properties. Thus, cottons bearing DEAE, carbamoylethyl, and carboxyethyl groups, along with partially hydrolyzed poly(Aam) graft, were synthesized. The ability of these cotton substrates to function as ion exchangers, particularly for removal of direct, basic, acid, and reactive dyes from aqueous solution was examined. The obtained results reveal that such modifications increase the ability of cotton to remove these dyes to about 150 times. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1007–1014, 1999     

Effect of reactive dyes upon the uptake and antibacterial action of poly(hexamethylene biguanide) on cotton. Part 1: Effect of bis(monochlorotriazinyl) dyes

Poly(hexamethylene biguanide) (PHMB) is of interest as a bactericide for fabrics. It has affinity for cotton by reaction with the cellulosic carboxylate groups. In this study, the capacity of undyed cotton to absorb PHMB has been determined and compared with cotton dyed with anionic bis(monochlorotriazinyl) reactive dyes. When cotton is dyed with these dyes the absorption of PHMB increases, the dye providing sulphonic acid sites with which the PHMB can react. The reacted PHMB and the percentage fixation of reactive dye were determined and from this the concentration of sulphonic acid on the dyed fibre. In the case of cotton dyed with Procion Yellow H-E4R, the dye increased the absorption of PHMB to approximately 1.45 mequiv. of biguanide per sulphonic acid group. For Procion Red H-E3B and Navy H-ER the figures were 1.18 and 1.00, respectively.     

Application of polycarboxylic acid sodium salt in the dyeing of cotton fabric with reactive dyes

In this study, the effects of polycarboxylic acid sodium salt on the dyeing of cotton with reactive dyes were evaluated by measuring and comparing the K/S values and dyeing fastnesses of the dyed cotton fabric samples. Results showed that the K/S value and dyeing fastness of cotton fabrics dyed with polycarboxylic acid sodium salt, substituting inorganic salts as exhausting agent were close to that of with sodium chloride when dip‐dyeing process was used. While, in pad‐dry dyeing, the K/S value of cotton fabric samples dyed with polyacid salts as exhausting agent was higher than that of with sodium sulfate, and the dyeing fastnesses of these samples were nearly the same. The dyeing mechanism of cotton fabric with reactive dye, using polycarboxylic acid sodium salt as exhausting agent was analyzed. The dyeing exhausting mechanism of reactive dye seems different when the inorganic salt and polycarboxylic acid sodium salt were used as exhausting agent in the dyeing of cotton fabric with reactive dye. The polycarboxylic acid sodium salt, as weak electrolyte, increased the dye‐uptake of reactive dye on cotton fabric not only by screening negative charges on cotton surface, but also by the effect of salting‐out or hydrophobic combination. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Electrostatic self‐assembly dyeing of cotton fabrics

A new approach to the dyeing of cotton fabrics using an electrostatic self‐assembly method was evaluated. Cotton fabrics were pretreated with 2,3‐epoxypropyltrimethylammonuium chloride and cationic charges were produced on the fabric surfaces. For the dyeing of cotton fabric, reactive and acid dyes were used. Oppositely charged anionic reactive/acid dyes and cationic poly(diallyldimethylammonium chloride) were alternately deposited on the surface of cationised cotton fabrics. Ten multilayer films of dye/poly(diallyldimethylammonium chloride) were deposited on the cotton fabric surfaces using a padder. The build‐up of the multilayer films and the level of colour strength (K/S) achieved are discussed. Samples of cotton fabrics were also dyed with the same dyes, but using the exhaust method, and both types of dyed samples were compared. The washing, rubbing and light fastness properties were evaluated for the dyed fabrics.     

A method for dyeing cotton fabric with anthocyanin dyes extracted from mulberry (Morus rubra) fruits

For the first time, the natural anthocyanin dyes (mainly consisting of cyanidine 3‐glycoside) extracted from mulberry (Morus rubra) fruits has been successfully used to dye cotton fabric, with a dyeing property performance good enough for potential commercial applications. In this study, succinic acid was firstly incorporated into cotton fabrics by esterification to the hydroxyl groups of cellulose, forming an anionic site for the dyes. The performance of the modified material was characterised by Fourier transform infrared spectroscopy and tensile strength. Results showed that the tensile strength of cotton fabrics was mostly retained after modification. The anthocyanin extracts from mulberry fruits were used to study the dyeability of the control and modified cotton fabrics. Red and deep purple (aubergine) are two main shades of cotton fabrics dyed with mulberry fruit extracts. Most importantly, aubergine shade is rare in cotton fabrics dyed with natural dyes. Modification with succinic acid clearly increased the colour strength of the dyed cotton fabric. The colour strength of dyed cotton fabric was improved from 2.7 to 5.3 in the case of dyeing without mordants, and from 3.2 to 6.9 in the case of dyeing with tin mordanting. Meanwhile, the colour fastness was improved by 0.5–2 grades with increasing succinic acid concentration in the finish solution. The colour fastness to perspiration, crocking, light, and washing of fabric dyed with simultaneous tin mordanting and modified with 30 g l^?1 of succinic acid was found to be acceptable, with a grey scale grade of at least 3. As for home laundering, neutral soapy solution was more acceptable than alkaline soapy solution.     

Dyeing of chemically modified cellulose. IV. Dyeing of oxidized celluloses with some reactive and direct dyes

Oxidation of cotton cellulose with potassium periodate, potassium dichromate-sulfuric acid, and potassium dichromate-oxalic acid results in creation of variable amounts of acidic and reducing groups along the cellulose molecule, being dependent upon the type of oxidizing agent used. Such groups were found to have a profound effect on the acceptability of cellulose for reactive and direct dyes. The rate and extent of dye uptake for the oxidized celluloses were significantly lower than those of the unoxidized cellulose. While presence of the acidic groups in cellulose molecules induces a negative environment thereby making approach of the dye anions to the cellulose difficult, presence of the reducing groups lowers the magnitude of cellulose reactivity as well as decreasing its adsorptive power. Further modification of the oxidized celluloses via either borohydride or chlorous acid treatment brought about modified celluloses the dyeability of which confirms the inhibiting effect of the acidic and reducing groups of those oxidized celluloses on the rate and extent of dyeing with reactive and direct dyes.     

Chemical modification of cotton to improve fibre dyeability

A new fibre-reactive quaternary compound containing an acrylamide residue was synthesised and used as a cotton modification reagent. The agent was applied to cotton fabrics using a pad-bake process. It was found that the treated fibre could be dyed with reactive dyes without the addition of salt or alkali. The reactive dyes were almost completely exhausted and showed a high degree of covalent bonding with the pretreated cellulose. The effect of varying the pretreatment conditions was investigated and the optimum conditions for pretreating and dyeing were established.     

Levelling properties of some reactive dyes on cellulose

The levelling properties of nine reactive dyes containing one or two sulphatoethylsulphone reactive groups or one sulphatoethylsulphone and one monochlorotriazine reactive groups have been investigated. A novel test method specifically applicable to reactive dyes has been used in order to evaluate levelling. Undyed and dyed cotton samples were simultaneously dyed in the same bath and the fractions of the additional dye fixed on each of the cotton samples were determined afterwards. A dye distribution index has been proposed that predicts reactive dye levelling according to whether the index exceeds 50% or not. The index was found to depend not only on the nature of the dyes, but also on the concentration of the dye fixed on cotton, the dyeing temperature and the salt concentration in the dye liquor. In redyeing tests the degrees of primary and secondary exhaustion and of dye fixation were measured as a function of concentration of the dye fixed on cotton. Finally a satisfactory correlation was found between the index and the classical inorganicity/organicity value of the dyes. The results also suggest that the levelling properties depend on the degree of dye aggregation.     

Process of dyeability modification and bleaching of cotton in a single bath

Graft polymerisation of the cationic monomer, methacryloylaminopropyltrimethylammonium chloride (MAPTAC), onto scoured cellulose was carried out in the bleaching process, aiming at modifying the fibre using a single bath. The extent of MAPTAC fixation on cellulose was measured. The bleaching performance of hydrogen peroxide in the presence of the modifying agent was found to be slightly reduced. The modified bleached cotton fabric was then dyed with a commercial reactive dye in the absence of salt. The dye uptake and colour strength of the modified fabric was markedly increased with an increase in the concentration of MAPTAC. This was attributed to the presence of the cationic groups of the MAPTAC which played a crucial role in attracting the anionic dyes from the dyebath. The results suggest that the dyeing properties of the modified fabric are closely dependent on the efficiency of MAPTAC fixation on cellulose during concurrent modifying and bleaching of cotton.     

Behaviour of Bifunctional and Polyfunctional Reactive Dyes Applied to Cotton Cellulose

Analytical techniques, viz. electron microscopy, surface area determination, and swelling in cadoxen solvent, have been used to obtain results which provide positive evidence for the formation of crosslinks between adjacent cellulose chains in cotton dyed with different classes of bi- and poly-functional reactive dyes. Reactive dyes selected include those where either the reactive groups are present in the same nucleus (dichlorotriazinyl, monomethoxymonochlorotriazinyl, dichloroquinoxaline, trichloropyrimidinyl and difluoromonochloropyrimidinyl) or where the two reactive groups are present at different positions in the dye molecule (Procion HE (ICI) and Procion Supra (ICI)). The extent of changes observed in the morphology of cotton fibre as a result of dyeing with bi- and poly-functional reactive dyes has been found to depend on the amount of dye present in the fibre and the conditions of application.     

Graft copolymerization of hydrophilic monomers onto irradiated polypropylene fibers

A method of graft copolymerization of hydrophilic monomers, such as 1-vinyl-2-pyrrolidone, acrylonitrile, acrylic acid, and acrylamide, onto irradiated polypropylene fibers has been studied. γ ray as well as electron beam were employed for the irradiation processes. Graft-copolymerization kinetics and the properties of grafted fibers have been investigated. Moisture regain, dyes absorption, and melting point of the grafted fibers were found to increase with the increasing of the degree of grafting. Polypropylene for 1-vinyl-2-pyrrolidone grafted fibers showed excellent dye absorption for almost all kinds of dyes such as direct, basic, acid, reactive, disper, and naphthol dyes. However, for polypropylene acrylic acid grafted fibers, the colorfastness to washing was found to be unsatisfactory. The colorfastness to washing for polypropylene 1-vinyl-2-pyrrolidone grafted fibers was found to be fairly good for certain types of dyes such as vat and naphthol dyes.     

Design,synthesis, and application of amphoteric macromolecular dyes with controllable solubility

A series of amphoteric macromolecular dyes were designed and synthesized from poly(acrylamide‐co‐vinylamine) oligomer and reactive dyes. The structure of the synthesized dyes was characterized by fourier transform infrared spectra, mass spectra, and ultraviolet–visible spectroscopy analysis. The solubility of the dyes was also investigated. The results showed that the solubility of the dyes can be controlled by tuning the ratio of amino to sulfonate groups in amphoteric macromolecular dyes. Based on the results of controllable solubility conducted by visible light transmittance measurements, amphoteric macromolecular dyes were used to dye cotton fiber; the fixation of the dye on cotton was more than 95% when crosslinking agent was added. The dyed samples exhibited good fastness to washing and rubbing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41120.     

Improving the environmental and economic aspects of cotton dyeing using a cationised cotton†

One approach to improve the affinity of anionic dyes for cotton is to add cationic dye sites to the fibre. The dyeing behaviour of cotton that had been rendered cationic by reaction with 2,3‐epoxypropyltrimethylammonium chloride was examined. Dye yields and fastness properties are reported for a number of direct, reactive and acid dyes with the modified fibre. Excellent dye yields and colour fastness properties were obtained without the use of electrolytes, multiple rinsings or fixation agents which are normally employed in cotton dyeing.