Synthesis and characterisation of microencapsulated 7‐alkyloxy‐4‐trifluoromethylcoumarin dyes

Five new 7‐alkyloxy‐4‐trifluoromethylcoumarin fluorescent dyes were synthesised using the Pechmann and Williamson etherification reactions. The structures of these coumarin dyes were characterised by Fourier Transform–infrared, proton and carbon nuclear magnetic resonance and mass spectra. One of the new coumarin compounds, 7‐isopropyloxy‐4‐trifluoromethylcoumarin, was microencapsulated with melamine–formaldehyde as the shell material by in situ polymerisation. The microcapsules were characterised in terms of Fourier Transform–infrared spectrum, particle size distribution and scanning electron microscopy morphology. The cotton fabric finished with the microencapsulated coumarin dye showed strong fluorescence under ultraviolet light.     

Energy transfer processes between primary and secondary dopants in polystyrene solutions dissolved in 1,4‐dioxane

High molecular weight polystyrene prepared by emulsion polymerization was characterized by gel permeation chromatography, differential scanning calorimetry, and solution viscosity. Prepared polystyrene was used to study the energy transfer processes using Exalite 416 and Coumarin 515 dyes as the primary and the secondary dopants. Absorption and emission spectra of the dyes in polystyrene (PS) solution of concentration 2.5 g/dL in 1,4‐dioxane have been measured. Absorption spectrum of the acceptor dye, Coumarin 515 (wavelength shifter), at 403 nm matches with the emission spectrum of the donor dye, Exalite 416. Continuous wave emission spectra of these wavelength shifters have been studied by changing the concentration of Coumarin 515 dye (accepter) while keeping the Exalite 416 (donor) concentration (10^?4 M) fixed in the PS solution. Energy transfer process has been discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 336–341, 2005     

Dyes based on the 6,7‐dichloro‐5,8‐quinolinedione skeleton as new type II photoinitiators for radical polymerisation

Several dyes based on the 6,7‐dichloro‐5,8‐quinolinedione skeleton have been synthesised and characterised by proton nuclear magnetic resonance spectroscopy and electron ionisation mass spectrometry. The spectroscopic and electrochemical properties of these dyes were investigated. Photoredox pairs consisting of the synthesised dyes and commercially available hydrogen donors (2‐mercaptobenzoxazole, 2‐mercaptobenzothiazole, 2‐mercaptobenzimidazole, and 2,5‐dimercapto‐1,3,4‐thiadiazole) were tested for use as effective initiator systems for radical polymerisation of trimethylolpropane triacrylate with visible light. The efficiencies of these initiator systems are discussed in terms of the free energy change for the electron transfer process from the dye to the hydrogen donor.     

Blue core–shell nanospheres prepared by dyeing poly(styrene‐co‐methacrylic acid) dispersions

Blue poly(styrene‐co‐methacrylic acid) nanospheres were prepared by dyeing polymer dispersions with CI Disperse Blue 56. The coloured nanospheres had a clear shell with a thickness of 32.5 nm. The average diameter of the nanospheres increased from 288 to 353 nm, and the glass transition temperature was raised from 109.6 to 117.9 °C after coloration. Ultraviolet‐visible absorption spectra, transmission electron microscopy, and differential scanning calorimetry show that the amino and/or hydroxyl groups of the disperse dyes formed hydrogen bonds with the carboxyl groups on the surfaces of the nanospheres during the coloration process, resulting in increased particle sizes and shell layers. The dye content increased almost linearly with increasing dye concentrations or dyeing temperatures within a certain range. By increasing the pH of the dyeing bath from 4 to 5, the dye content increased sharply from 0.68 to 1.49% because of the ionisation of the carboxyl groups of the macromolecules.     

Molecular modelling of inclusion compounds from hydrophobic dyes and γ‐cyclodextrin

This paper arises from studies aimed at developing new approaches to combining the fabric formation and coloration steps of fabric processing. A key aspect of these studies involved the evaluation of cyclodextrin (CD)‐based compounds as hosts for dye molecules that could be released onto a fabric surface following fabric formation. In this study, experimental data from wide‐angle X‐ray diffraction and differential scanning calorimetry experiments were used in tandem with molecular modelling studies to confirm the formation of γ‐CD–dye complex inclusion compounds and to demonstrate the utility of parameterised model number 3 (PM3) semi‐empirical molecular modelling methods for predicting the nature of the preferred γ‐CD–dye inclusion compounds. Calculations revealed that the inclusion compounds containing two dye molecules was preferred over the inclusion compound containing one dye molecule. Further, molecular modelling of the inclusion compound obtained using γ‐CD linked to an epichlorohydrin‐based oligomer and commercial disperse dyes showed inclusion compound formation to be an energetically favourable process.     

New route to functional polyolefins: sulfonation of poly[ethylene‐co‐(5,7‐dimethylocta‐1,6‐diene)] and evaluation of properties

An ethylene/5,7‐dimethylocta‐1,6‐diene copolymer was sulfonated using two different approaches, solution and surface modification, varying parameters such as reaction time, temperature and concentration of the sulfonation reagent. Techniques such as attenuated total reflectance Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and elemental analysis confirmed the successful sulfonation of the copolymer by both methods. Water uptake studies showed that the polarity of the initial copolymer was markedly changed upon functionalization and that the sulfonation by the in‐solution method produced more hydrophilic polymers compared to the surface procedure. Moreover, differential scanning calorimetry and thermogravimetric analysis pointed out additional changes to the thermal properties of the sulfonated polymers relative to the copolymer precursor. This study showed that the sulfonation process of the non‐polar ethylene–diene copolymer led to a new hydrophilic material with a potential wide range of applications. © 2017 Society of Chemical Industry     

6‐Pyridinium benzo[a]phenazine‐5‐oxide derivatives as visible photosensitisers for polymerisation

Several 6‐pyridinium benzo[a]phenazine‐5‐oxide derivatives have been synthesised and characterised by proton nuclear magnetic resonance spectroscopy and mass spectrometry. The spectroscopic and electrochemical properties of these dyes were examined. The dyes were used as reducible sensitisers for selected electron donors (phenylthioacetic acid, phenoxyacetic acid, N‐phenylglycine, and ethyl 4‐N,N‐dimethylaminobenzoate) and as oxidisable sensitisers for electron acceptors (onium and N‐alkoxypyridinium salts). These photoredox pairs were found to be effective visible‐wavelength photoinitiators for the free radical polymerisation of trimethylolpropane triacrylate under visible light. The cationic photopolymerisation of cyclohexene oxide by the studied dyes and the onium salt photoredox pairs was ineffective. The obtained results are discussed on the basis of both free energy change for electron transfer to or from the benzo[a]phenazine dyes and the photochemical properties of the dyes, particularly their photobleaching. The proposed mechanism of dye fading is supported by density functional theory calculations and spectroscopic characterisation of the radical cation of the dye.     

Synthesis,stability and printing properties of a novel 2‐sulphophenoxy‐4‐chloro‐s‐triazine reactive dye for ink‐jet printing of wool

We report here the synthesis and characterisation of a new medium‐reactivity reactive dye containing 2‐sulphophenoxy‐4‐chloro‐s‐triazine, having enhanced the activity of the chlorine atom for further substitution by the functional groups carried by wool fibre. In addition, a dichloro‐s‐triazine dye was also synthesised for the purpose of comparison. The progress of synthesis reactions and purity of the dyes were determined using capillary electrophoresis and thin layer chromatography. The molecular structure and the chemical compositions of the synthesised dyes were confirmed using Fourier Transform–infrared spectral data and elemental analyses. The inks containing the synthesised dyes were formulated and ink‐jet‐printed onto wool fabrics and then the printed fabrics were steamed at 102°C. Compared with the dichloro‐s‐triazine dye, superior performance in terms of ink stability, K/S and dye fixation was observed for the new 2‐sulphophenoxy‐4‐chloro‐s‐triazine dye. In addition, the light fastness of the fabric printed with the inks containing the new dye was 0.5‐grade greater than that of the fabric printed with the inks containing the dichloro‐s‐triazine dye, and no changes in shade and staining were observed following wash fastness tests of the fabrics printed with the inks containing the new dye.     

Improvement of the dyeing and fastness properties of a naphthalimide fluorescent dye using poly(amidoamine) dendrimer

In this study, 4‐amino‐9‐methoxypropylnaphthalimide fluorescent dye (dye 1 ) was reacted with poly(amidoamine) dendrimer G = ?0.5 to prepare a naphthalimide–dendrimer hybrid dye (dye 2 ). The chemical structures of the synthesised dyes were confirmed by elemental analysis, Fourier transform infrared spectroscopy, ¹H nuclear magnetic resonance spectroscopy, and ultraviolet‐visible spectroscopy. The solvatochromism of the dyes was evaluated in various solvents with respect to visible absorption properties, and positive solvatochromism was observed by solvent polarity change from chloroform to ethanol. The dyeing ability of the synthesised dyes was investigated by their application onto nylon fabric, and nylon substrates dyed with dye 2 exhibited marked enhancement both in terms of colour strength and general fastness properties. The results of this study clearly demonstrated the high potential and performance of dye 2 as a novel promising fluorescent dye as compared with dye 1 . Overall, it was inferred that the modification of the naphthalimide fluorescent dye with poly(amidoamine) denderimer could markedly improve the dyeing and fastness properties of the naphthalimide fluorescent dye on nylon fabrics.     

Preparation and drug‐release behavior of minocycline‐loaded poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] films

In this work, biocompatible hydrogel matrices for wound‐dressing materials and controlled drug‐release systems were prepared from poly[hydroxyethyl methacrylate‐co‐poly(ethylene glycol)–methacrylate] [p(HEMA‐co‐PEG–MA] films via UV‐initiated photopolymerization. The characterization of the hydrogels was conducted with swelling experiments, Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis (differential scanning calorimetry), and contact‐angle studies. The water absorbency of the hydrogel films significantly changed with the change of the medium pH from 4.0 to 7.4. The thermal stability of the copolymer was lowered by an increase in the ratio of poly(ethylene glycol) (PEG) to methacrylate (MA) in the film structure. Contact‐angle measurements on the surface of the p(HEMA‐co‐PEG–MA) films demonstrated that the copolymer gave rise to a significant hydrophilic surface in comparison with the homopolymer of 2‐hydroxyethyl methacrylate (HEMA). The blood protein adsorption was significantly reduced on the surface of the copolymer hydrogels in comparison with the control homopolymer of HEMA. Model antibiotic (i.e., minocycline) release experiments were performed in physiological buffer saline solutions with a continuous flow release system. The amount of minocycline release was shown to be dependent on the HEMA/PEG–MA ratio. The hydrogels have good antifouling properties and therefore are suitable candidates for wound dressing and other tissue engineering applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

New perylene dyes,derivatives of 1,6,7,12‐tetrachloroperylene‐3,4,9,10‐tetracarboxylic acid: synthesis and application

New dyes – aliphatic esters of 1,6,7,12‐tetrachloroperylene‐3,4,9,10‐tetracarboxylic acid – were prepared as potential fluorescent light‐stable colorants for high‐visibility safety wear. The structure of the 15 perylenes was confirmed by ¹H and ¹³C nuclear magnetic resonance spectroscopy and mass spectrometry, and their spectroscopic and physicochemical properties were determined. An attempt was made to apply the synthesised products as disperse dyes in the coloration of polyester as well as in the mass coloration of polystyrene and poly(methyl methacrylate). The light, wash, and rubbing fastness of the dyeings were determined, and chromaticity coordinates of selected samples were measured and discussed.     

Dye–fiber interactions in PET fibers: Hydrogen bonding studied by IR‐spectroscopy

Dye–fiber interactions are studied in poly (ethylene terephthalate) fibers by FT‐IR spectroscopy. It is shown for the first time that DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy) serves as an easy applicable and accurate technique for the study of fibrous structures. This article focuses on the possible hydrogen bond interactions in the dye–fiber system, where the PET fibers are dyed with anthraquinone‐based disperse dyes. The dyes and related anthraquinone structures are studied in both the dilute solution state, the solid state, and as present in the PET fibers. It is proven that 1‐amino anthraquinones show strong “chelate‐type” intramolecular hydrogen bonding in all three states. In the fibers an important supplementary intermolecular hydrogen bonding with the C?O groups in the PET fiber is observed. The extend of hydrogen bonding seems to be prone to dye concentration variations. Further analysis by modulated differential scanning calorimetry links the hydrogen bonding to an intrinsic plasticizing effect of the dyes affecting the dye diffusion process. This thus offers a tool for the fundamental understanding of the dyeing process and possible observed differences in dyeing behavior in dye–fiber systems. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Study of poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) hydrogels made using gamma radiation initiation

Poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) hydrogels were synthesized using gamma‐radiation‐initiated polymerization. The progress of copolymerization and crosslinking was observed by viscosity measurement on reaction mixtures subjected to varying radiation doses. The copolymer gels were characterized by differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, infrared spectroscopy, and elemental analysis. The swelling behavior and other properties of the gels were found to be very similar to those of poly(acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) hydrogels synthesized using conventional free‐radical initiation in the presence of crosslinkers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1322–1330, 2003     

Synthesis and application of KM‐type reactive dyes containing 2‐ethoxy‐4‐chloro‐s‐triazine

A new kind of hetero‐bifunctional reactive dye containing 2‐ethoxy‐4‐chloro‐s‐triazine, with better activity matching with β‐hydroxyethyl sulphone sulphate at a low fixation temperature, was successfully synthesised and characterised. An ethoxy group was designed to be introduced into triazine to increase the substantivity and the reactivity of the dyes. Thereby, the fixation of mono‐s‐chlorotriazine/hydroxyethyl sulphone sulphate (KM‐type) bifunctional reactive dyes on cotton was improved, and dyeing under mild conditions with high fixation was realised. Nineteen dyes with orange, red and blue colours were synthesised and characterised by UV‐Vis and infrared spectroscopy and mass spectrometry. Synthesised dyes were dyed at 60, 75 and 90°C, respectively. Exhaustion and reactivity for all of the ethoxy‐containing KM‐type dyes was over 90% at the optimal temperature, and fixation was over 87%, which was higher than the ethoxy‐free comparative dyes. The optimal fixation temperature of ethoxy‐containing dyes was initially reduced to 75°C, and then to 60°C. Compared with comparative dyes, the wash fastness and light fastness were basically unchanged, and the wet rub fastness of the H‐acid series was reduced by one grade.     

Spectral characterisation and computational studies of some novel phenylazoindol‐2‐one dyes

A series of novel phenylazo disperse dyes were prepared by coupling selected diazotised 3‐ or 4‐anilines with indol‐2‐one. The structures of the synthesised dyes were determined by spectroscopic and analytical methods. Solvent effects on the ultraviolet–visible absorption spectra of these novel dyes were studied. The colour of the dyes was evaluated with respect to the substituent therein. Acid and base effects on the visible absorption maxima of the dyes were also reported. The tautomerism of 3‐(phenyldiazenyl)indol‐2‐one was modelled by density functional theory at the B3LYP level. The ultraviolet–visible absorption spectra for the tautomers were reproduced with the time‐dependent density functional theory and semi‐empirical Zerner’s intermediate neglect of differential overlap/spectroscopic (ZINDO/S) method. The predominance of the keto–hydrazone tautomer was confirmed experimentally and theoretically.     

Synthesis of temporarily solubilised azo disperse dyes containing a β‐sulphatoethylsulphonyl group and dispersant‐free dyeing of polyethylene terephthalate fabric

Disperse dyes containing a β‐sulphatoethylsulphonyl group have temporary solubility and can be applied for dispersant‐free dyeing of hydrophobic fibre. Six novel temporarily solubilised azo disperse dyes having a β‐sulphatoethylsulphonyl group in their structures were synthesised, and their dyeing properties on polyester were investigated. As a dye intermediate, a diazo component having dibromo groups was prepared, and 4‐diethylamino‐4′‐(2‐sulphatoethylsulphonyl‐4,6‐dibromo)azobenzene dyes were prepared by a diazo‐coupling reaction. Then, the dyes containing dicyano groups were prepared by cyanation of corresponding dyes with dibromo groups. The absorption maxima of the dyes were affected by the substituents in the diazo and coupling component rings and varied from 434 to 616 nm in dimethylformamide. Polyethylene terephthalate woven fabric could be dyed with the synthesised temporarily solubilised dyes without using any dispersants. Dyebath pH affected the K/S value at maximum absorption as well as percentage exhaustion on polyethylene terephthalate fabric, and the optimum pH was 5. The dyes gave brownish orange, red, purple, and greenish blue hues on polyethylene terephthalate fabrics, and colour build‐up was good. Wash fastness was good to excellent, rubbing fastness was moderate to excellent, and light fastness was poor to moderate.     

Modified 2,4‐difluoro‐5‐chloro‐pyrimidine dyes and their application in ink‐jet printing on wool fabrics

This paper describes the modification of three commercially available 2,4‐difluoro‐5‐chloropyrimidine dyes (Drimarene Brilliant Red K‐4BL, Drimarene Brilliant Blue K‐BL and Drimarene Golden Yellow K‐2R) by the reaction of the parent dye with 4‐hydroxybenzensulphonic acid sodium salt. Capillary electrophoresis was used to monitor both the course of the above reaction and to ascertain the dye stability of the dyes in an ink formulation. Inks prepared from the modified dyes showed much higher storage stability compared with the parent dye‐containing inks; this was confirmed by capillary electrophoresis analysis. Inks containing the modified dyes were printed on wool fabrics and diffusion/fixation achieved by ‘batching’ the prints at 25 °C; high fixation values were obtained for all three modified dyes. These prints exhibited excellent colour fastness to washing, rubbing and light, the former test confirming a high degree of dye–fibre covalent bonding.     

Adsorption of VO2+ by poly[(tetrafluoroethylene)‐co‐(perfluorovinyl ether)] copolymer grafted with acrylic acid using γ‐irradiation

Grafted films were prepared by the reaction of acrylic acid (AAc) onto poly[(tetrafluoroethylene)‐co‐(perfluorovinyl ether)] copolymer (PFA) using γ‐irradiation by the mutual technique. The grafted copolymer was complexed with the vanadyl group, VO²⁺, in aqueous solution. The grafted copolymer–metal complexes were examined by infrared and ultraviolet spectrometry, energy‐dispersive spectroscopy (EDS) and X‐ray diffraction (XRD). The amount of vanadium in the grafted films was estimated using EDS. The thermal stability of the films was investigated through thermogravimetric and differential scanning calorimetry measurements. The degree of crystallinity of the grafted and complexed films decreased by treatment with VO²⁺ ions and also by heating at 300 °C. When heated at a temperature above 300 °C, the grafted chains degraded till they disappeared and the original polymer was almost completely separated. XRD investigation revealed that the metal oxide may be formed as a separate phase with subsequent decrease in the crystallinity of the copolymer. Furthermore, scanning electron microscope (SEM) investigation of the grafted and modified films, both unheated and heated (300 °C), showed changes in the structure and morphology. The tendency of the graft copolymer to adsorb and/or bind to VO²⁺ from aqueous solution is of promising use in the field of waste treatment of rare metals in the environment. Copyright © 2004 Society of Chemical Industry     

Green synthesis of reactive dye for ink‐jet printing

Chloropyrimidine‐based reactive dyes are reported as well suited to textile printing; however, nucleophilic aromatic substitution of chloropyrimidines with amino‐containing chromophores is slow and often suffers from poor yields. In this study, a novel and simple method was developed for the synthesis of chloropyrimidine‐based reactive dye under microwave irradiation. In addition, the dye was also synthesised by conventional heating for comparison, which took both the reaction time and yield into account. The progress of the synthesis reactions concerned were monitored using capillary electrophoresis and the purity of the dye obtained was assessed by thin‐layer chromatography. The structure of the synthesised trichloropyrimidine dye was confirmed by Fourier Transform–infrared spectroscopy and elemental analysis. It was found that the reaction rate of the nucleophilic aromatic substitution carried out under microwave irradiation was 4‐fold faster than that carried out under conventional heating, although the enhancement in product yield was modest. These results suggest that microwave irradiation is an effective technique for the synthesis of chloropyrimidine‐based reactive dyes. The synthesised chloropyrimidine dye was formulated into an ink and applied onto a wool fabric by ink‐jet printing. The printed fabrics were steamed at 102°C for 5‐25 minutes at 5‐minute intervals. Good K/S and rate of dye fixation were obtained, both of which improved with increasing steaming time. The prints obtained exhibited reasonably good light and wash fastness properties.     

Synthesis of methine dyes derived from indol‐2‐ones and their dyeability on polyester fibres

Three series of methine dyes were synthesised by the condensation of indol‐2‐ones with aryl acroleins. The structures of these dyes were confirmed by ¹H nuclear magnetic resonance spectroscopy, infrared spectrometry and elemental analysis. The ultraviolet‐visible absorption spectra of the dyes were examined in different solvents. The maximum absorption wavelength ranged from 386 to 495 nm. The dyes were applied to polyester fibres, and the colour gamut and dyeing properties were investigated. Results showed that the dye uptake (percentage exhaustion) was 86.9–92.0%, with the hue changing from yellow to red. The rubbing fastness, wash fastness, and sublimation fastness were between 4 and 5.