Salt-free dyeing of cotton cellulose with a model cationic reactive dye

A model cationic reactive dye based on an anthraquinone chromophore was prepared. The synthesis of this dye was achieved by the modification of the a free amino group of an anthraquinone-based dye, reacting first with cyanuric chloride and then with N -(2-aminoethyl)pyridinium chloride. TLC analysis was employed to follow the chemical reactions. The application of the prepared dye to cotton fabric was carried out using the exhaustion method without the addition of electrolytes. The results showed that, despite no electrolytes being present in the dye bath, a high percentage of dye exhaustion could be obtained. The high percentage of dye exhaustion was attributed to the attractive force between positive charges on the dye molecule and the negatively charged fibre surface. A high degree of dye fixation with excellent wash fastness was also achievable. Advantageously, it was found that this cationic reactive dye showed promising fastness to light when compared with that of analogous conventional basic dye on cotton. It is believed that the pyridinium cationic moiety, which attached separately to the chromophore via aliphatic spacer groups, was later eliminated during the washing-off process, hence causing an insignificant effect on the photofading of the dyed fabric.     

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.     

Co-application of hydroxyalkyl dyes and polyphosphonic acids to cotton to achieve dye—fibre covalent bonding

The dyeing of cotton to a high standard of wet-fastness with hydroxyalkyl dyes and a polyphosphonatecrosslinker system has been investigated. Dyes containing hydroxyalkyl groups were prepared, by the reaction of commercial reactive dyes with ethanolamine, and applied to cotton fabric in the presence of polyphosphonic acid crosslinking agents using cyanamide as a catalyst. The application was carried out using a pad-thermosol method. The effects of cyanamide concentration, the nature of the crosslinker and the type of hydroxyalkyl dye were studied in detail. It was concluded that multifunctional polyphosphonates are capable of producing dyeings on cellulosic fibres exhibiting a high degree of covalent bonding (fixation). The efficiency of dye fixation at ca. 2% pure dye (owf), obtained from this method, was greater than 90%.     

Spinning and characterizations of polypropylene/alkylphosphonic acid treated montmorillonite nanocomposite fiber

Fine and well‐dispersed clay was prepared via the in situ conversion of the dodecylamine intercalant inside the clay gallery to dodecylamino dimethylene diphosphonic acid (DDD), using a Mannich reaction, so as to create a repulsive force that delaminated the clay platelets. The clay structure and morphology were characterized by X‐ray diffraction (XRD), Scanning electron microscopy (SEM), and Transmission electron microscopy (TEM) analysis, which revealed changes in the multilayer stacks. XRD analysis showed that the interlayer spacing was largely expanded by the presence of DDD. SEM and TEM images revealed that DDD containing clay (PMMT), but not that without DDD, exhibited transparency, indicating the extremely fine and well‐dispersed clay. Polypropylene/PMMT nanocomposites containing 2, 4, 6, 8, and 10 wt % PMMT were prepared by melt extrusion. The obtained compounds were each spun into a monofilament fiber using a small scale spinning machine and then characterized by XRD, Differential scanning calorimetry (DSC), and Thermogravimetric analysis (TGA), plus the sonic modulus was evaluated. The XRD results revealed an increase in the β crystallinity peak in fibers loaded with 2–10 wt % PMMT, indicating that PMMT particles were capable of acting as a β‐form nucleating agent. However, only minimal changes in the thermal behavior (T_c) were observed due to the tested samples containing insufficient PMMT content. The mechanical properties, in terms of the tensile strength and sonic modulus value (E), of the polypropylene nanocomposite fibers were higher than those of virgin PP fibers, presumably due to the reinforcement effect of the filled PMMT nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improving the properties of polylactic acid by blending with low molecular weight polylactic acid‐g‐natural rubber

The low molecular weight (M_w) polylactic acid‐g‐natural rubber (PLA‐g‐NR) was synthesized by grafting the maleated natural rubber (MNR) with low molecular weight PLA at a weight ratio of 1:1 in toluene at 80°C. Two types of MNR (MNR10 and MNR20) having anhydride moieties of 10 and 20 wt%, respectively, were prepared. The reaction was followed by IR analysis. Next, the obtained PLA‐g‐NR was blended with pristine PLA using a twin‐screw extruder at PLA to PLA‐g‐NR weight ratios of 90:10, 80:20, 70:30, and 60:40 followed by compression to obtain specimens for testing. In case of 10 wt% PLA‐g‐NR having MNR10, it was found that blending of PLA with PLA‐g‐NR resulted in a 200% improvement in impact strength and twofold percent elongation at break (flexibility). Further SEM analysis confirmed that PLA‐g‐NR was compatible with PLA matrix. In contrast, NR was present as disperse particles which exhibited poor adhesion to PLA. From these findings, it was also found that PLA‐g‐NR was capable of improving the properties of PLA more than NR due to the fact that it exhibited higher compatibility. POLYM. ENG. SCI., 54:2770–2776, 2014. © 2013 Society of Plastics Engineers     

Grafting and phosphonic acid functionalization of hyperbranched polyamidoamine polymer onto ultrafine silica

In this study, grafting of hyperbranched polyamidoamine (PAMAM) polymer onto ultrafine silica followed by functionalization via the introduction of phosphonic acid groups into the branch ends was performed. First, an initiating site was incorporated into the silica surface by reacting the silica silanol group with 3‐aminopropyltriethoxysilane, producing amino‐functionalized silica. The free amine group content was altered by varying the ratio of methanol to water in the hydrolysis step of the silanization reaction. Grafting of PAMAM was attained by three rounds of sequential Michael addition of silica amino groups to methyl acrylate and amidation of the resulting terminal methyl ester groups with ethylenediamine. Completion of the grafting reaction in each step was clearly confirmed using FTIR analysis. Excessive ethylenediamine and unattached hyperbranched PAMAM present in the reaction product were removed by dialysis with a molecular weight cutoff of 6000–7000 Daltons. However, the amino group content determined in each step was found to be significantly lower than theoretically expected, perhaps indicative of side reactions and, in later stages, steric hindrance. The resultant hyperbranched PAMAM‐grafted onto silica was functionalized by phosphorylation of the terminal amino groups by a Mannich type reaction, producing the phosphorylated hyperbranched PAMAM‐grafted silica. Then its application on cotton fabric to produce fire‐retardant cellulose was tentatively investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Triazinylamino-alkylphosphonate reactive dyes for cellulosic fibres

A bifunctional reactive bis-phosphonoalkylaminotriazine dye was synthesised by condensing 2 mol of aminoethylphosphonic acid with the commercially available bis-monochloro- s -triazinyl dye, CI Reactive Red 120. A similar but much lower molecular weight dye was prepared by condensing the commercially available dichloro- s -triazine dye, Procion Red MX 8B, with aminomethylphosphonate. A model aryl-phosphonate dye was also prepared by diazotising m -aminobenzene-phosphonic acid and coupling the diazonium salt to R-salt. These dyes were isolated as their free acids and then converted to their ammonium salts. Pad liquors containing dye, cyanamide and ammonium dihydrogen phosphate were applied to cotton fabric. In the case of the bis-phosphonoethylamino- s -triazine dye, very high dye–fibre fixation values (>90%) were achieved using a pad–batch–bake procedure; for the Procion T model dye, the comparative maximum fixation was only modest. In the absence of cyanamide, no fixation could be obtained for the arylphosphonate dye but both bis-phosphonoalkylaminotriazine dyes gave significant fixation.     

Preparation and properties of bacterial cellulose/graphene oxide composite films using dyeing method

In this study, bacterial cellulose (BC) hydrogels were cultured from a kombucha SCOBY starter. The scanning electron microscopy (SEM) results indicated that the dried BC exhibited an interpenetrating fibrous mat. The BC films harvested for 5, 10, and 15 days were 15–19, 14.4–24, and 30–31 μm thick, respectively. Then, BC/graphene oxide (GO) composite films were prepared via the exhaust dyeing method. GO sheets penetrated the BC matrix, resulting in the formation of a BC/GO composite, as revealed by the SEM analysis results. The mechanical properties of the composite films were investigated. Compared with virgin BC, the tensile strength of the composite films was higher, while the %E at break was lower, resulting in a significant increase in the Young's modulus. The X-ray diffraction results indicated that an increase in the dyeing time (0.5–2 h) gradually induced cellulose crystalline conformation, which in turn affected the swelling ability, mechanical properties, and electrical properties of the BC/GO composite films. After the reduction of GO to reduced GO (rGO), flexible conductive BC/rGO films were obtained, as confirmed by their resistivity values. Thus, flexible conductive composite films with excellent mechanical properties were successfully fabricated.