New Intermediates and Dyes for Synthetic–polymer Fibres

Condensation of benzo(k, l)thioxanthene–3, 4–dicarboxylic anhydride with o–phenylenediamines affords isomeric derivatives of the new heterocycles benzimiaazo(1, 2, b)–thioxantheno(2, 1, 9–d, e, f)iso–quinolin– 7–one and benzimidazo–(2, I–a)thioxantheno(2, 1, 9–d, e, f,) isoquinolin–8–one. They are excellent new dyes for polyester fibres, giving fluorescent orange to red dyeings of outstanding fastness to light and sublimation.     

Fluorescence from fluorescent dye based polyurethane ionomer(III)

A series of reactive fluorescent dyes were successfully synthesized and their structure was proven by IR spectra, NMR spectra, elemental analysis, and mass spectra. The fluorescence performance 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione and 2‐benzyl‐6‐hydroxy‐benzo[de]isoquinoline‐1,3‐dione appears at around 276 and 437.4 nm, respectively, and their quantum yields are 0.662 and 0.562, respectively. It is important to indicate that the fluorescence performance is better for 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione than for as a result of more electron donating groups linked to the 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione molecule. These fluorescent dyes further react with toluene diisocyanate and other additives to form fluorescent dye based polyurethane (PU) ionomer molecules, and their structures are demonstracted by IR spectra. In aqueous solution, the fluorescence performance appears to be better for 6‐amino‐2(‐3‐phenyl‐propyl)‐benzo[de]isoquinoline‐1,3‐dione based PU ionomer than for 6‐amino‐2‐phenyl‐ethyl‐benzo[de]isoquinoline‐1,3‐dione based PU ionomer. For the fluorescent dye based PU ionomer molecule system, the number‐average particle sizes of the fluorescent dye based PU ionomer molecules in water increase with increasing concentration of the fluorescent dye, as a result of the increased free volume of the ionomer molecule. This may be the result of increased intermolecular interactions between ionomer– molecules themselves. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 455–465, 2005     

Benzo[k,l], xanthene–3, 4–dicarboximides and benzimidazoxanthenoisoquinolinones – yellow and orange dyes for synthetic–polymer fibres

Condensation of 4–chloro–l, 8–naphthalic anhydride with 2–nitrophenol afforded 4–(2–nitrophenoxy)–l, 8–naphthalic anhydride, which on reduction followed by Pschorr intramolecular cyclisation gave benzo[k, l]xanthene–3, 4–dicarboxylic acid anhydride. The identity of the product was confirmed by its alternative synthesis from 5–amino–4–phenoxy–l, 8–naphthalic anhydride. Benzo[k, l]xanthene–3, 4–dicarbox–ylic acid anhydride condensed with alkylamines or arylamines and with o–phenylenediamines to yield the corresponding imides and imidazole derivatives, which coloured polyester in fluorescent greenish–yellow to orange hues, respectively, of good fastness to light and sublimation. The colour of the dyes is discussed with respect to analogous ring–closed sulphur– containing heterocycles.     

The Effect of Annelation on the Colour of 1, 4-Disubstituted Benzoanthraquinone Disperse Dyes

The visible spectra of a series of 1,4-disubstituted benzoanthraquinone dyes in benzene solution has been measured. The position of the absorption maxima of the dyes has been found to be well correlated with a mean ionization potential of the substituent groups. An annelation of anthraquinone dyes in the position of 2, 3 or 6, 7produced a small hypsochromic shift, while 5,6-annelation produced a large bathochromic shift. The additive properties on the absorption maximum of dibenzoanthraquinone dyes were also observed.     

Evaluation of Some Reactive Disperse Dyes for Sublimation Transfer Printing of Wool

The transfer printing of wool by the sublimation method using a number of low–molecular–weight dyes containing chloro– and bromo–acetyl, chloroacetamido, chloro– and bromo–propionamido, 2–bromoacryloyl, 2–chloroethylamino and epoxy groups has been examined. To achieve build–up of the dyes to heavy depths, it was necessary to pretreat the wool with a polymer or surfactant and to steam the prints after transfer of the designs. Several dyes exhibited good fastness properties on pure wool and on a wool–polyester blend fabric.     

The Role of Anthraquinonoid Dyes in the Catalytic Fading'of Dye Mixtures– Substituent–dependent Triplet Yield of Diaminoanthraquinones

Taking various diaminoanthraquinones as model compounds for commercial anthraquinonoid dyes it was found that the ability of initiating catalytic fading via singlet oxygen mechanism is closely related to the quantum yield of triplet formation in these dyes. The quantum yields of triplet formation show a marked difference between the various diaminoanthraquinones. Whereas 1, 4– and 1, 2–diaminoanthraquinones have very small quantum yields, the 1, 5– and 1, 8–derivatives pass into the triplet state with a fairly high efficiency. From this it was concluded that catalytic fading occuring via singlet oxygen mechanism must be expected in dye mixtures consisting of 1, 5– or 1, 8–diamino substituted anthraquinonoid dyes and easily oxidizable azo–compounds.     

Substituent Effects on the Colour,Dyeing and Fastness Properties of Trisubstituted 4–N–β–Hydroxyethyl–N–β–Cyanoethylaminoazobenzenes

School of Chemistry and Chemical Technology University of Bradford Bradford West Yorkshire BD7 1DP The synthesis of a series of 2′, 4′, 6′-trisubstituted derivatives of 4–N–β–hydroxyethyl–4– N–β–cyanoeth ylaminoazobenzene is reported, and the effect of the nature of the substituents on the colour, dyeing and fastness properties of these dyes is described. The dyes coloured synthetic–polymer fibres well, with the exception of those containing a methylsulphonyl group, which gave weaker dyeings on polyester. Dyes substituted by 2′-nitro groups tended to have poor light fastness, and reasons for the variations in the light fastness of monoazo dyes of this type are discussed.     

Colour and Constitution of 1,4-Naphthoquinonoid Dyes - Modified PPP MO Calculations and Substituent Effects

Calculation of the n-electron excitation energies of naphthoquinonoid dyes has been carried out by means of the Pariser—Parr—Pople (PPP) method using the variable, β,γ-approximation. A good linear correlation between the observed and calculated values for the first π-π* excitation was found for a new series of naphthoquinonoid dyes. The effect of substituents on the colour of different dyes was studied on the basis of these calculated results, i.e. HOMO—LUMO energy levels and π-electron-density changes accompanying the excitation. The intramolecular charge-transfer character of the π-π* transition was shown to be the same as occurs in some anthraquinonoid dyes.     

Fading of Phenylazo–β–naphthol Dyes on Polypropylene*

The fading of a series of phenylazo–β–naphthol dyes on polypropylene by exposure to either long– or short–wavelength ultraviolet radiation and under nitrogen and oxygen atmospheres, respectively, is reported. The half–lives and relative rates of fading of the dyes were calculated at the wavelength of maximum absorption of the hydrazone band and the hydrazone–azo ratios of the dyes were determined on polypropylene and in ethanol. The relative rates of fading were plotted against the appropriate Hammett constants for the substituents. In general, a linear relation was observed. The graphs had positive slopes, but negative slopes were also obtained with the dyes bearing electropositive groups. Graphs of relative rates of fading against hydrazone?azo ratio were also drawn. The results were generally similar to those obtained with the plots of Hammett constants, but correlation was better. The results indicate that, on polypropylene, the most important fading mechanism for the hydrazone form of the dye is reductive, although there is evidence that oxidation may occur, especially in the presence of oxygen.     

Mass–spectra Studies of Disperse Dyes

The mass spectra of benzo(k, l)thioxanthene–3, 4–dicarboxylic anhydride and of several derived imides, dyes for synthetic–polymer fibres, are reported. Principal fragmentation trends are described and fragments which may be used in the characterisation of these dyes are described.     

Effect of “Ph–NH–CH2–” group on the luminescence properties of sol–gel silica xerogel

The effect of Ph–NH–CH₂– group (Ph: phenyl) on the luminescence properties of silica xerogel by sol–gel method has been investigated. The absorption spectra, excitation spectra and emission spectra of Ph–NH–CH₂– group embedded in the network of silica xerogel have a red shift with increasing the ratios of Ph–NH–CH₂– group in the samples. The relative photoluminescence (PL) intensity of the hybrid silica xerogel sample decreases with increasing the ratios of Ph–NH–CH₂– group. From the complex luminescent centers, the novel luminescence properties have been observed from the hybrid silica xerogel sample containing Ph–NH–CH₂– group.     

Evaluation of aminoquinoline‐imprinted polymers and the recognition mechanism

Three molecularly imprinted polymers P(2‐AQ), P(3‐AQ), and P(8‐AQ) based on methacrylic acid (MAA)–ethylene glycol dimethacrylate were prepared using isomers 2‐aminoquinoline (2‐AQ), 3‐aminoquinoline (3‐AQ), and 8‐aminoquinoline (8‐AQ) as template, respectively, by non‐covalent bulk polymerization technique. Neither P(3‐AQ) nor P(8‐AQ) exhibited imprinting effect for 3‐AQ or 8‐AQ, whereas P(2‐AQ) showed significant imprinting effect for 2‐AQ. This indicates that the position of amino group on the quinoline ring has crucial influence on imprinting effect. The recognition mechanism of P(2‐AQ) was investigated extensively by such methods as selective experiments, comparative study with 2‐aminopyridine‐imprinted polymer, and effect of different kinds of mobile phases. It is confirmed that there are complementary cavities in P(2‐AQ) both in size and in the arrangement of functional groups to 2‐AQ, and MAA binds 2‐AQ via cyclic hydrogen bond. Furthermore, the influence of synthetic conditions on 2‐AQ‐imprinted polymers was explored. We found 2‐AQ‐imprinted polymer synthesized in acetonitrile porogen showed higher imprinting effect for 2‐AQ than that prepared in chloroform. It is deduced that the morphology of the former might be more favorable to 2‐AQ binding, which is also supported indirectly by the fluorimetric experiments estimating the interaction of 2‐AQ with MAA in these two porogens. Additionally, 2‐AQ‐imprinted polymers prepared using two different amounts of acetonitrile exhibited very different imprinting effects, which suggested that porogen amount used in the imprinting process exerted significant influence. In addition to the in‐depth elucidation of the recognition mechanism of 2‐AQ‐imprinted polymer, this article provides the basis for the separation and enrichment of bioactive 2‐AQ. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterisation of benzothiazole‐based solid‐state fluorescent azo dyes

Novel solid‐state fluorescent azo dyes containing a 2‐[4‐(dimethylamino)phenyl]benzo[d]thiazol‐6‐amine as the electron donor group were synthesised. These dyes showed a molar extinction coefficient in the range of 20 000–30 000 l/mol/cm. These compounds were characterised by strong solid‐state fluorescence under long ultraviolet light (365 nm). Absorption and fluorescence spectra revealed that electron coupling originating from broad π‐electron delocalisation and the keto–enol form is responsible for the large Stokes shift. These dyes were readily soluble in common solvents such as dichloromethane, chloroform, dimethyl formamide , tetrahydrofuran and dimethyl sulphoxide and were characterised by means of elemental analysis, proton nuclear magnetic resonance and mass spectrometry. Thermogravimetric analysis of solid‐state fluorescent dyes show thermal stability up to 270 °C and can therefore be used for polymer application. The coloristic properties of these dyes were evaluated on polyester by the disperse dyeing method.     

Spiroannelation reactions of 3-trifluoroacetyl- and other 3-acyl-1-methyl-lactams

3-Trifluoroacetyl- and other 3-acyl-1-methyllactams ( 1–5 ) undergo the Robinson annelation with α,β-unsaturated ketones to produce spirocyclic cyclohexenones ( 6 ), their precursors hydroxycyclohexanones ( 7 ) or 3-acyl-3-oxobutyl-lactams ( 8 ) depending on the substitution.     

Dyes derived from 1,4‐naphthoquinone as initiators for radical and cationic photopolymerisation

Several 2‐phenylamino‐1,4‐naphthoquinone‐based dyes and two related benzo[2,3‐b]–phenazines were synthesised and characterised by proton nuclear magnetic resonance spectroscopy and electron ionisation mass spectrometry. The electrochemical and spectral properties of these compounds were investigated. The synthesised dyes were found to be capable photosensitisers for radical (reducible/oxidisable) and cationic polymerisations, respectively. In radical polymerization, better results in the oxidisable process were achieved.     

Photochemical Grafting of Acrylated Azo Dyes onto Polymeric Surfaces.

Kinetic studies of photochemical I y induced grafting [1] and graft polymerization [2] onto polypropylene fibres from N, N–dimethylformamide solutions of four acryloxy–substituted aromatic diazenes, chosen as model molecules of acrylated azo dyes, were carried ou t at 25°C by monochromatic irradiation at various wavelengths. The effect of dye concentration was systematically investigated, and quantum efficiencies at zero concentration of dyes, as well as lifetimes for processes (1) and (2), were evaluated using Stern– Volmer plots. The marked influence of wavelength and the constancy of the relatively long lifetimes at the various wavelengths support the hypothesis that quantum yields reflect efficiencies of conversion from the states populated by light absorption to reactive upper triplets.     

Synthesis, spectral characterisation and anti-bacterial activity of various 1,3,4-oxadiazine cyanine dyes

A number of new styryl, aza-styryl, acyclic mero, cyclic mero and mixed cyanine dyes with a benzo[2,3- e ; 2',3'- e ']bis-1,3,4-oxadiazine nucleus were synthesised. The absorption spectra in the visible region of all the synthesised cyanine dyes in 95% ethanol solution were examined and studied in detail. Anti-bacterial activity for a number of selected dyes was evaluated against various bacterial strains. The structural determination was carried out using elemental and spectroscopic analysis.     

Dyeing of Wool–Polyester Blends with Reactive Disperse Dyes: Variation of Dye Distribution and Reactivity for Wool

The dyeing behaviour of structural analogs of some commercial reactive disperse dyes on a simulated 70:30 wool–polyester blend has been studied. By varying the hydrophi/ic– hydrophobic balance of the dye molecule major changes in the distribution of dye between wool and polyester were observed. The reactivity of the γ–halo–β–hydroxypropyl group was found to be dependent on the halogen atom, while the reactivity of the N–bromoalkylsulphonamide group was found to be dependent on the position of the bromine atom.     

Synthesis and photoluminescence of the Eu3+ composite with dibenzoylmethane and oligoacrylic acid

An Eu³⁺–dibenzoylmethide (DBM) –oligoacrylic acid (OAA) composite was prepared in water, ethanol, and a glycerin mixed solvent. Influence of pH value on the synthesis was also given. A composite with pH of 10.0 was most suitable for the synthesis. It was confirmed by UV–VIS, Fourier transform infrared (FTIR), excitation spectra, and conductivity measurement that DBM, the second ligand, which had low molecular weight, coordinated with Eu³⁺ in the ionomer chain, instead of dispersing in the OAA matrix. When the molar ratio of DBM–Eu³⁺ was 2:1, which was found to be the best ratio to obtain the maximum intensity of fluorescence (due to the ⁵D₀→⁷F₂ transition), the fluorescence intensity of the Eu³⁺– DBM–OAA (emitted at 616 nm) increased logarithmically with the increase of the molar ratio of Eu³⁺–OAA in the range of 0 to 6 : 1. Energy transfer in the composite was also discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2588–2593, 1999     

Synthesis and properties of some fluorescent 1,8‐naphthalimide derivatives and their copolymers with methyl methacrylate

Six new fluorescent derivatives of 1,8‐naphthalimide were synthesized. Three were dyes, and three were fluorescent whitening agents (FWAs) containing a tetramethylpiperidine (TMP) stabilizer fragment. The FWAs were obtained under phase‐transfer catalysis conditions. Five of the compounds were copolymerized with methyl methacrylate, so copolymers with an intense color and/or fluorescence stable against solvents were obtained. The chemical bonding of the synthesized monomers in the polymers was confirmed spectrophotometrically. The participation of the monomer compounds did not significantly affect the process of copolymerization or the molecular masses of the obtained copolymers. The quantity of chemically bonded naphthalimide monomer in the copolymers was determined to be over 60%. The spectral properties of the compounds and their photostability in solution and in the copolymers were studied. The influence of the compounds on the photostability of the copolymers was determined. The compounds, especially those containing a stabilizer (TMP) fragment in their molecules, showed a positive stabilizing effect on the photodegradation of poly(methyl methacrylate). Polyamide fabrics with 2‐allyl‐6‐hydrazino‐benzo[de]isoquinoline‐1,3‐dione, 2‐allyl‐6‐(2‐amino‐ethylamino)‐benzo[de]isoquinoline‐1,3‐dione, and 2‐chloro‐N′‐(2‐methyl)‐1,3‐dioxo‐2,3‐dihydro‐1H‐benzo[de] isoquinoline‐6‐yl) acetohydrazide were dyed, and materials with an intense yellow color and fluorescence were obtained. Cotton fabrics were whitened with 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐methoxy‐benzo[de]isoquinoline‐1,3‐dione, 2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐6‐allyloxybenzo[de]isoquinoline‐1, 3‐dione, and 2‐[2‐(2,2,6,6‐tetramethyl‐piperidin‐4‐yl)‐1,3‐dioxo‐2,3‐dihidro‐1H benzo [de]isoquinoline‐6‐oxy]ethyl‐2‐methacrylate, and materials with bright whiteness and intense bluish fluorescence were obtained. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009