Deactivation of α-bromoacrylamide dyes by wool

To achieve the highest wet fastness properties, reactive dyeings have to undergo an aftertreatment which removes unfixed dye from the fibre. The question of the origin of these unfixed dyes is discussed and new experimental results presented.     

Dynamic light-scattering studies of poly(γ-benzyl α, l-glutamate)–benzyl alcohol system

We report the concentration and temperature dependencies of the diffusion coefficients obtained from dynamic light-scattering studies for the poly(γ-benzyl α, l-glutamate)-benzyl alcohol (PBLG–BA) system. These studies were made at dilute and semidilute polymer concentrations, mainly in the isotropic phase. The measured translational and rotational diffusion coefficients in dilute solutions are consistent with predictions based on wormlike chain models. The mutual diffusion coefficient in semidilute solutions shows a marked deviation from scaling predictions, demonstrating the strong coupling between the translational and rotational motions. The measured time evolution of the scattered intensity after the PBLG–BA system is suddenly quenched into the gel phase demonstrates that aggregation is a significant mechanism in the formation of the gel phase.     

α-Methylierter Fencholen- und α-Campholenaldehyd – Synthese und Reaktionen

α-Methylated Fencholenic and α-Campholenic Aldehyde – Synthesis and Reactions The syntheses of α-methylated fencholenic ( 6a ) and α-campholenic aldehyde ( 6b ) via the corresponding azomethines ( 5 ) are reported. Aldol condensations of 6a, b with following reductions give the allylic alcohols ( 12–16 ) and hydrogenation the saturated alcohols ( 17–21 ) with strong woody odors, some of the allylic alcohols resembling that of sandal wood. Simple reduction or oxidation of 6a, b give the alcohols ( 24, 27 ), ethers ( 26 ), esters ( 23, 25, 28 ) and ketones ( 29 ) which have interesting woody odors with spicy, earthy and herbaceous notes.     

Reaction of α-cellulose with SbCl3–KOH–AsCl3

α-Cellulose dissolves in a mixture of SbCl₃, KOH, and AsCl₃. The resulting product as identified by PMR and infrared spectroscopy is α-D -glucose. This product is unexpected, and an explanation for its formation is suggested.     

Desorption of hydrolysed reactive dyes from wool

The desorption of the hydrolysed forms of nine reactive dyes from wool has been examined in soap solution (ISO 2 test) and in urea-surfactant solution. It was found that the desorption of the hydrolysed dyes was slower in soap solution than in the urea-surfactant solution. After the standard 45 min of the ISO 2 washing test equilibrium was not reached, while after 60 min in the urea-surfactant solution equilibrium desorption was reached with most of the hydrolysed dyes. These findings clearly explain the discrepencies which sometimes occur between the two methods when used to assess wash fastness in relation to fixation ratios. If the time of the ISO 2 test is extended until equilibrium desorption is achieved then the two methods give essentially the same results. It was also found that the desorption rate constants appear to be inversely related to the molecular weights of the hydrolysed dyes.     

Photochemistry of α,α′-Disubstituted Azoalkanes. I. Photosolvolytic Inversion and Substitution of α,α′-Dichloro- and α,α′-Dialkoyloxyazoalkanes

A series of α,α′-dichloro (α DClA), α,α′-dialkoyloxy- (αDAlA) and α,α′-dibenzoxy-azoalkanes (αDBeA) without α-aryl substituents was found to undergo meso ? dl photointerconversion upon direct irradiation through Pyrex in the presence of oxygen in a number of solvents. Furthermore, irradiation of α,α′-dipropionoxy-azoalkanes in benzene in the presence of excess acetic acid leads to substitution of the propionoxy groups by acetoxy groups in addition to meso ? dl photointerconversion. Similar irradiation in the presence of CH₃CO₂D does not lead to deuterium substitution of the β-hydrogens. The presence of benzenethiol radical scavenger does not affect the course of these photoreactions. Photosolvolysis schemes involving heterolysis (in the case of αDAlA and αDBeA) or an unstable intermediate (in the case of αDClA) are proposed.     

Poly(α,α,α′,α′-tetrafluoro-p-xylylene)

Poly(α,α,α′,α′-tetrafluoro-p-xylylene) was prepared by the pyrolysis of cyclo-di-(α,α,α′,α′-tetrafluoro-p-xylylene) and by the pyrolysis of α,α′-bis(alkylsulfonyl)-α,α,α′,α′-tetrafluoro-p-xylene. The pyrolysis of α,α′-dibromo-α,α,α′,α′-tetrafluoro-p-xylylene also gave the polymer, but the method is less satisfactory. Poly(α,α,α′,α′-tetrafluoro-p-xylylene) shows remarkable thermal and oxidative stability at elevated temperatures. Useful mechanical and electrical properties are retained after aging for 3000 hr at 250° in air. After initial change due to crystallization, tensile strength remains near 10,000 psi, elongation above 5%, and dielectric constants and dissipation factors at approximately 2.4 and .001, respectively.     

Oxygen‐Involved Oxidative Deacetylation of α‐Substituted β‐Acetyl Amides – Synthesis of α‐Keto Amides

α‐Substituted β‐acetyl amides could undergo C C bond cleavage to form α‐keto amides when treated with copper(II) chloride (CuCl₂) and boron trifluoride diethyl etherate (BF₃⋅OEt₂) under an oxygen atmosphere. The yield can be increased by the addition of tert‐butyl hydroperoxide which alone can also effect the reaction. The reaction provides a new protocol for the synthesis of α‐keto amides.

     

Neutral-fixing reactive dyes for cotton. Part 1 —synthesis and application of quaternised S-triazinyl reactive dyes

A number of different tertiary amines have been employed to prepare the corresponding quaternised triazines from a selected monochloro-s-triazine reactive dye. Preparation conditions have been established along with suitable analytical methods. The reactivity of the quaternised dyes with cellulose has been determined, special attention being paid to neutral fixation at high temperatures (100°C). Good neutral fixation was achieved with all the tertiary amine derivatives studied. In the case of the nicotinamide derivative an anomalous hydrolysis reaction involving ring opening was noted; this reaction led to the formation of aminotriazine rather than the expected hydroxytriazine.     

Kinetics and thermal analysis of copolymerization of m-isopropenyl–α,α′-dimethylbenzyl isocyanate with styrene

The copolymerizations of m-isopropenyl–α,α′-dimethylbenzyl isocyanate (m-TMI) with styrene (STY) was investigated. The weight conversion of the copolymerization reaction increased as the duration of copolymerization increased. The reaction temperature was maintained between 60 and 75°C. Molecular weights of the copolymers decreased with increasing molar fraction of m-TMI in the feed. This study obtained reactivity ratios, Alfrey–Price parameters, Mark–Houwink constant, characteristic ratio, thermal degradation activation energy, difference of reactive propagation activation energy, and intrinsic viscosity for the copolymers. The copolymers were characterized by using elemental analysis (EA), gel permeation chromatography, thermogravimetric analysis, and differential scanning calorimetry. The copolymer chains in solution were observed to have a high degree of stiffness and a lack of rotational freedom. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2763–2770, 1999     

Synthesis of α, α′, β-trideuterovinyl acetate

Reaction conditions for the synthesis of α, α′, β-trideuterovinyl acetate by the continuous vapour phase catalytic reaction of deuteroacetylene and acetic acid-d (CH₃COOD) are described.     

Sorption studies in a polyurethane–β-cyclodextrin blend

The sorption of toluene, butanol, methanol and n-hexane in polyurethane and a polyurethane–β-cyclodextrin blend has been studied. The time to reach equilibrium absorption was several times less in the blend in spite of nearly identical diffusion coefficients and % equilibrium absorptions of the diffusants in both materials. The study indicates that rapidity in polymeric membrane mediated separation can be attained by blending β-cyclodextrin.     

Radiation-induced copolymerization of α,β,β-trifluoroacrylonitrile with α-olefin

Homopolymerization and copolymerization of α,β,β-trifluoroacrylonitrile (FAN) with γ-olefins were carried out in bulk by γ-ray irradiation at 25°C. FAN gives very small quantities of brown and greasy low molecular weight polymer. Cyano groups in FAN polymer were found to be readily hydrolyzed to acid amide groups in the atmosphere. FAN was found to copolymerize with ethylene, propylene, and isobutylene via a radical mechanism to form equimolar copolymers in a wide range of monomer compositions. The polymerization rate increases linearly with FAN fraction in the monomer mixture. These copolymers are also hydrolyzed in the atmosphere, and the hydrolysis proceeds with more difficulty for the copolymer with higher α-olefin. The reactivity ratios r₁ (FAN) and r₂ (α-olefin) were determined to be 0.01 and 0.12 for the FAN/ethylene copolymerization and 0.01 and 0.07 for the FAN/propylene copolymerization. These results confirm that an alternating copolymerization takes place in the FAN/α-olefin system.     

Reactive dyeing systems for wool fibres based on hetero-bifunctional reactive dyes. Part 1: Application of commercial reactive dyes

The wool dyeing properties, such as exhaustion and fixation parameters, of selected hetero-bifunctional Sumifix Supra dyes and some other commercial reactive dyes were quantified under various dyebath pH conditions. Studies of the dyeing of wool serge fabric indicated that Sumifix Supra dyes could produce reasonably high fixation values. However, remarkably improved fixation values were obtained when these dyes were pre-activated to the vinylsulphone form and dyed in this form, especially at low pH values (pH 4 or lower).     

Polymerization of α, α-disubstituted-β-propiolactones and lactams. 9. ABA block copolymers of α-methyl-α-butyl-β-propiolactone and pivalolactone

ABA block copolymers were prepared by the anionic polymerization of α-methyl-α-butyl-β-propiolactone, MBPL (B block), and pivalolactone, PL (A blocks). The MBPL block had a very low decree of crystallinity and a glass temperature of ? 13°C, so phase separation with extensive crystallization of the PL blocks gave thermoplastic elastomers when the MBPL block constituted the principal and continuous phase. The observed crystallinity and melting point of 40–45°C in the MBPL homopolymer have not been previously reported. Measurements were obtained by electron microscopy of the initial size distribution of the PL domains as a function of copolymer composition and degree of polymerization, and on the effect of annealing on this parameter. Tensile strengths and elongations at break were both less than those previously observed for equivalent ABA block copolymers of PL and α-methyl-α-propyl-β-propiolactone.     

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.     

Synthesis of α‐Arylphosphonates using Copper‐Catalyzed α‐Arylation and Deacylative α‐Arylation of β‐Ketophosphonates

Efficient methods for the direct arylation and deacylative arylation of β‐ketophosphonates with iodoarenes in presence of a copper(I) or a copper(II) salt as the catalysts have been developed. The corresponding α‐arylphosphonates were obtained in high yields. A tentative mechanism for the deacylative arylation reaction was proposed on the basis of the experimental data.     

Influence of isomer ratio and ring substituents in decomposition activation energies of α,α,α′,α′‐tetrasubstituted dibenzyls

Diethyl‐2,3‐dicyano‐2,3‐di‐(X‐substituted phenyl) succinates (X = p‐OCH₃, p‐CH₃, p‐Cl, H, p‐NO₂) can initiate the free‐radical polymerization of styrene. The decomposition rate constant and activation energy were measured by means of a dilatometer, and the results showed that they were strongly dependent on the ratio of meso‐ and dl‐isomers in the polysubstituted dibenzyl compounds and the properties of the ring substituents. On the other hand, it was found that the polystyrenes, which were obtained by initiation with hydrogen, had a much larger average molecular weight than that with p‐OCH₃ and p‐CH₃. The experimental phenomena were correlated with the structure of the radical resulting from hydrogen. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2964–2971, 2001