Dispersant‐free dyeing of poly(lactic acid) fabric with temporarily solubilised disperse dyes from azopyridone derivatives

Poly(lactic acid) fibre is derived from annually renewable crops and known to be 100% compostable. In order to extend its environmental friendliness into the dyeing process, dispersant‐free dyeing of poly(lactic acid) fabric with three temporarily solubilised azo disperse dyes based on hydroxypyridone moiety containing a β‐sulphatoethylsulphonyl group was investigated. The dyes were successfully applied to poly(lactic acid) fabric without the use of dispersants. The colour yields of the dyes on poly(lactic acid) fabric were observed to be dependent on dyebath pH and dyeing temperature. The optimum results were obtained at pH 4–5 and 110 °C. One of the dyes showed a colour yield as good as that of a commercial disperse dye and good build‐up on poly(lactic acid) fabric. All of the dyes could be alkali cleared owing to ionisation of the dye under mild alkaline conditions. Wash fastness was good to very good, and light fastness was good. The chemical oxygen demand levels of the poly(lactic acid) dyeing effluent from the dyes were considerably lower than those from a commercial disperse dye.     

Pretreating poly(p‐phenylene benzobisoxazole) fibre with polyphosphoric acid and dyeing with disperse dyes

In recent years, many advanced composite materials based on poly(p‐phenylene‐2,6‐benzobisoxazole) fibres have become prominent in applications requiring high‐strength and flame‐retardance such as body armour, industrial reinforcement materials and military camouflage. However, the application of these fibres used as protective clothing is limited due to difficulties in dyeing and printing. In the present work, a process for pretreating poly(p‐phenylene benzobisoxazole) fibre with polyphosphoric acid was applied, and the pretreated fibre was then dyed with disperse dyes via dip dyeing. Effects of pretreatment temperature and time on structure and properties were investigated. Surface morphology, crystallinity, chemical structure and degree of orientation of fibres were characterised. The results indicated that the supramolecular structure of the fibre was relaxed or swelled by polyphosphoric acid in the pretreatment process, so that the dyeability of poly(p‐phenylene benzobisoxazole) fibre was improved, with satisfactory dye exhaustion, K/S values and dyeing fastness. Also, with the appropriate pretreatment process, the swelling effect of polyphosphoric acid on the structure of poly(p‐phenylene benzobisoxazole) fibre was limited, so as to control the decrease in tensile strength and limiting oxygen index of the dyed fibre.     

Microwave‐assisted dyeing of poly(butylene terephthalate) fabrics with disperse dyes

In this study, conventional heating and microwave dielectric heating in the exhaust dyeing of poly(butylene terephtalate) fabrics with disperse dyes were studied in order to determine whether microwave heating could be used to increase the dyeability of poly(butylene terephtalate) fibre in shorter processing times and enable dyeings of adequate wet fastness to be obtained. Accordingly, the samples of 100% poly(butylene terephtalate) single jersey knitted fabric were dyed with CI Disperse Yellow 160 and CI Disperse Yellow 42, CI Disperse Red 177 and CI Disperse Red 91, CI Disperse Blue 79:1 and CI Disperse Blue 54 at 98 °C with or without microwave dielectric heating. The colouristic properties, colour fastnesses and the tensile properties of the dyed fabrics were investigated and compared with each other. Microwave dielectric heating is regarded as a tool for ‘green chemistry’ and provides many advantages over conventional heating without any deterioration in the properties of the dyed materials. Microwave heat dyeing enhances the exhaustion and the fixation of dye, and good colour fastnesses and repeatability in dyeings are achieved in short heating times of the dyebath.     

The dyeing of poly(lactic acid) fibres with disperse dyes using ultrasound: Part 2 - Fastness

The use of ultrasound imparted greater colour strength to 1% omf dyeings of five of six disperse dyes studied, both before and after reduction clearing and had no effect on either the colour or λ_max of the dyeings. The lower fastness obtained to both wet and dry rubbing as well as to the first two/three of the five repeated wash cycles was attributed to the greater colour strength of the dyeings imparted by the use of ultrasound during dyeing.     

Synthesis and spectral properties of azohydroxypyridone disperse dyes containing a fluorosulphonyl group

A series of azohydroxypyridone disperse dyes containing fluorosulphonyl groups have been synthesised and their spectral properties were investigated. Azohydroxypyridone dyes, containing a nitro group instead of a fluorosulphonyl group para to the azo group in the diazo component, were also synthesised in order to compare spectral properties. The fluorosulphonyl substituted derivatives absorb maximally at shorter wavelengths and are tinctorially weaker than the nitroarylazopyridone dyes, although the former dyes have higher molar extinction coefficients. Also, the synthesised dyes exhibit positive solvatochromism so that the absorption bands of the dyes move toward longer wavelengths as the polarity of the solvent increases. Molecular computational methods provided reasonable predictions in the direction of solvatochromism for the dyes prepared.     

Low‐temperature carrier dyeing of poly(vinyl chloride) fibers with disperse dyes

The effects of various carriers on the color yield of poly(vinyl chloride) (PVC) filaments in a disperse dyeing system were investigated. The dyeability of disperse dyes on PVC fiber was improved using appropriate carriers. The enhancement of dye uptake imparted by carriers coincided with the reduction in glass‐transition temperature, which in turn coincided approximately with the similarity of the inorganic/organic ratio values between PVC fibers and carriers. The results clearly demonstrate that hydrophobic carriers function as diluents of PVC fiber, facilitating dye diffusion by increasing segmental mobility of the fiber. The dyed PVC filaments with disperse dyes showed reasonable levels of build‐up and color fastness properties in the carrier‐assisted dyeing. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3896–3904, 2003     

The dyeing of poly(lactic acid) fibres with disperse dyes using ultrasound: Part 1 - Initial studies

Six disperse dyes were applied at 0.5%, 1% and 2% omf depths of shade to poly(lactic acid) fabric at 30-80 °C for 20, 50 and 90 min in both the presence and absence of ultrasound. Whilst ultrasound enhanced the colour strength obtained for three of the six disperse dyes used at temperatures upto 70 °C, ultrasound did not always result in enhanced colour strength being achieved in the case of the three other dyes. The observed intensification of colour strength was attributed to dye disaggregation. Dyeing at 80 °C in the presence of ultrasound resulted in pale, dull dyeings of reduced colour strength, which was attributed to breakdown of the dye dispersions at this particular temperature.     

Synthesis,characterization, and properties of degradable poly(l‐lactic acid)/poly(butylene terephthalate) copolyesters containing 1,4‐cyclohexanedimethanol

High‐molecular‐weight copolyesters based on poly(butylene terephthalate) as rigid aromatic segments and poly(l‐lactic acid) (PLLA) as degradable aliphatic segments were synthesized via the polycondensation of terephthalic acid, 1,4‐butanediol (BDO), 1,4‐cyclohexanedimethanol (CHDM), and PLLA oligomer. By tailoring the molar ratio of diols (BDO and CHDM), we investigated in detail the effects of the CHDM rigid hexacyclic ring on the synthesis, mechanical properties, thermal stabilities, and degradation behaviors of the copolyesters. With increasing CHDM content, the initial decomposition temperature increased from 282.5 to 322.2°C, and the tensile strength improved by nearly four times, from 5.4 to 19 MPa. When the molar ratio of BDO/CHDM was 95/5, the weight‐average molecular weight of the copolyester was 89,400 g/mol with a polydispersity of 1.96. In addition, hydrolytic degradation results in phosphate buffer solution indicate that the degradation rate of the copolyesters displayed a strong dependency on the temperature and CHDM composition. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal migration of selected disperse dyes on poly(ethylene terephthalate) and poly(lactic acid) (Ingeo†) fibres

A study has been carried out to correlate the wet fastness properties of dyed knitted fabrics, derived from both poly(ethylene terephthalate) and poly(lactic acid) (Ingeo) fibres, with the thermal migration properties of the disperse dyes during heat treatment. The results indicate a greater amount of disperse dye at the surface of the Ingeo fibre fabric than the poly(ethylene terephthalate) fabric, after post heat‐setting using the conditions needed for fabric stabilisation, correlating well with its slightly lower wash fastness properties.     

Dyeing of poly(lactic acid) fibres with synthesised novel heterocyclic disazo disperse dyes

Poly(lactic acid) (PLA) is the first melt‐processable, renewable, sustainable and biodegradable natural‐based synthetic fibre. It has a broad range of uses and combines ecological advantages with outstanding performance in textiles. PLA fibre, as an aliphatic polyester, can be dyed with disperse dyes. Apart from the limited number of commercial disperse dyes, disperse dye exhaustion on PLA is generally lower than that on  poly(ethylene terephthalate) (PET). In this study, new heterocyclic disazo disperse dyes, substituted with methyl, nitro and chloro groups at their ortho‐, meta‐ and para‐ positions, synthesised in our previous study, were applied to PLA and PET fibres to examine their dyeing performance, and colour fastness and dye exhaustion properties. Different shades of yellow, orange, reddish brown and brown were obtained. Most of the synthesised novel heterocyclic disazo disperse dyes exhibited good build‐up properties with high K/S levels on both fibres. Para‐ bonding substituent provided higher K/S values than meta‐ and ortho‐ positions for –NO₂ and –Cl substituents for both fibres. Overall, the most synthesised novel heterocyclic disazo disperse dyes in this study exhibited good build‐up properties with high K/S, exhaustion and wet fastness levels on both PLA and PET fibres.      

Synthesis and properties of crystalline dicarboxylated poly(L‐lactic acid) prepolymers

Crystalline dicarboxylated poly(L ‐lactic acid)s (dcPLLAs) with number‐average molecular weights (M_n's) of 10³ to 10⁴ g/mol were synthesized via the melt polycondensation of L ‐lactic acid (LLA) in the presence of succinic anhydride (SAD), with tin(II) chloride and toluene‐4‐sulfonic acid as binary catalysts. They were characterized by end‐group titration, ¹H‐NMR, differential scanning calorimetry, and wide‐angle X‐ray diffraction. The terminal COOH percentage reached over 98%, and the molecular weight could be controlled by the molar ratio of LLA to SAD. The thermal behaviors depended on the molecular weight. The poly(L ‐lactic acid)s (PLLAs) crystallized slowly for M_n ≤ 2000 but quickly for M_n ≥ 4000. The crystallinity increased from 27 to 40% when M_n grew from 4000 to 10,000. With comparison to ordinary PLLA, the dcPLLA had the same crystallization structure but a slightly lower crystallizability. The glass‐transition temperature was clearly higher than that of amorphous dcPLLAs. With a controllable molecular weight, high COOH percentage, and crystallinity, the dcPLLA with M_n ≥ 4000 appeared to be a suitable prepolymer for the preparation of high‐molecular‐weight crystalline PLLA via chain extension. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of acid dyes containing polyetheramine moieties and their low‐temperature dyeing properties on wool fiber

To realize the low‐temperature dyeing of wool fibers, the use of auxiliaries and wool modification are common methods. Low‐temperature auxiliaries may cause water‐pollution problems, and wool modification is a costly and uncontrollable process. In this study, new acid dyes, named D1–D3, containing polyetheramine groups were synthesized and applied to wool fiber by conventional and low‐temperature exhaust dyeing procedures. The results indicate that the new acid dyes could interact with wool‐fiber‐like auxiliaries and render a high exhaustion rate to the wool fiber at a dyeing temperature of 80 °C. In comparison with Acid Blue 25, the D1–D3 dyes showed an increased dyeing rate, especially under a dyeing temperature of 80 °C. Despite the bigger relative molecular masses of D1–D3, the exhaustion rates of D1–D3 were still higher, and the times of half‐dyeing were shorter than that of Acid Blue 25. The color differences between the wool fabrics dyed with the four dyes at 80 and 98 °C, respectively, were compared. We found that the color differences of D1–D3 between 80 and 98 °C were smaller than that of Acid Blue 25. The interactions between the dyes and wool fiber were analyzed and manifested by the measurement of the ζ potential of the dyes and wool fiber. The leveling and transfer properties of the D1–D3 dyes were also investigated, and the color differences of the wool fabrics dyed with Acid Blue 25, D1, and D2 were very low at all measured pH values and temperatures. The fastnesses of D1–D3 on wool fabric were almost the same as that of Acid Blue 25. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45793.     

Synthesis,physical properties,and crystallization of optically active poly(L‐phenyllactic acid) and poly(L‐phenyllactic acid‐co‐L‐lactic acid)

Optically active poly(L ‐phenyllactic acid) (Ph‐PLLA), poly(L ‐lactic acid) (PLLA), and poly(L ‐phenyllactic acid‐co‐L ‐lactic acid) with weight‐average molecular weight exceeding 6 × 10³ g mol^?1 were successfully synthesized by acid catalyzed direct polycondensation of L ‐phenyllactic acid and/or L ‐lactic acid in the presence of 2.5–10 wt % of p‐toluenesulfonic acid. Their physical properties and crystallization behavior were investigated by differential scanning calorimetry, thermogravimetry, and polarimetry. The absolute value of specific optical rotation ([α]) for Ph‐PLLA (?38 deg dm^?1 g^?1 cm³) was much lower than that of [α] for PLLA (?150 deg dm^?1 g^?1 cm³), suggesting that the helical nature was reduced by incorporation of bulky phenyl group. PLLA was crystallizable during solvent evaporation, heating from room temperature, and cooling from the melt. Incorporation of a very low content of bulky phenyllactyl units even at 4 mol % suppressed the crystallization of L ‐lactyl unit sequences during heating and cooling, though the copolymers were crystallizable for L ‐phenylactyl units up to 6 mol % during solvent evaporation. The activation energy of thermal degradation (ΔE_td) for Ph‐PLLA (200 kJ mol^?1) was higher than that for PLLA (158 kJ mol^?1). The ΔE_td for the copolymers increased with an increase in L ‐phenyllactyl unit content. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of poly(lactic acid)‐based polyurethanes

Poly(lactic acid) (PLA) is a biodegradable aliphatic polyester, but its brittleness makes it unsuitable for many packaging and appliance applications. The goal of the work reported was to create novel poly(ester urethane)s that incorporate biodegradable poly(lactic acid) diols (PLA‐OHs) and good mechanical properties of increased molecular weight via crosslinked network formation for engineering plastics applications. Three kinds of polyols (PLA‐OHs, PLA‐OHs/poly(tetramethylene ether) glycol or PLA‐OHs/poly(butylene adipate) glycol (PBA)) and two kinds of diisocyanates (4,4‐diphenylmethane diisocyanate (MDI) or toluene 2,4‐diisocyanate (TDI)) were chosen for the soft and hard segments to compare their mechanical properties. In addition, 1,4‐butanediol and trimethylolpropane were each used as chain extender agents. Results showed the PLA/PBA‐polyurethanes (PLA/PBA‐PUs) of the MDI series and the PLA/PBA‐PUs of the TDI series had improved thermal stability and enhanced mechanical properties. Degradation behavior showed the PLA‐based polyurethanes could be degraded in phosphate‐buffered saline solution and enzyme solution. © 2012 Society of Chemical Industry     

Synthesis and spectroscopic properties of novel phthalimide‐derived monoazo disperse dyes containing ester groups

The synthesis and spectroscopic properties of monoazo dye series, whose members consist of N‐alkylphthalimide diazo components combined with a coupling component containing two ester groups, are reported. Such colourants are potentially alkali‐clearable as a consequence not only of the presence of diester functionality on the coupler, but also through use of the base‐sensitive phthalimide system. Shortening the N‐alkyl group by removing one or two methylene units from a butyl chain made little difference to absorption properties, as would be expected given the relatively minor differences in inductive character produced. Shifts in the absorption maximum of the dyes associated with dibromination of the phthalimidylazo motif and its subsequent cyanodehalogenation were in agreement with theory and literature data for related series. Diester substitution on the coupling component brought about hypsochromism and hypochromism.     

Synthesis,spectral properties and dyeing on polyester of monoazo dyes from indol‐2‐one derivatives

Three series of phenylazo disperse dyes were prepared by coupling diazotised 4‐aniline dyes with 5‐indol‐2‐one dyes. The structures of these dyes were determined by proton nuclear magnetic resonance, Fourier Transform–infrared and elemental analysis. The effects of solvent on the ultraviolet–visible absorption spectra of these dyes were studied. The dyes displayed a λ_max shift of between 399 and 438 nm. The dyes were finally applied in the dyeing of polyester fibres in order to investigate their colour range and dyeing properties. Most of the dyes displayed high rubbing fastness and good washing and sublimation fastnesses on polyester fibres.     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and dyeing properties of novel disperse dyes. Part 2: Pyrazole disperse dye derivatives

Several new disperse dyes derived from thiosemicarbazides and acetoacetanilide have been synthesised. The dye structures were ascertained by chemical analysis and infrared measurements. Prepared dyes were used for dyeing nylon fabric by the exhaustion method. The colour strengths and dye fixation on the fabric were also determined. The results suggest a practical significance.     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal and mechanical properties of plasticized poly(L‐lactic acid)

Acetyl tri‐n‐butyl citrate (ATBC) and poly(ethyleneglycol)s (PEGs) with different molecular weights (from 400 to 10000) were used in this study to plasticize poly(L‐lactic acid) (PLA). The thermal and mechanical properties of the plasticized polymer are reported. Both ATBC and PEG are effective in lowering the glass transition (T_g) of PLA up to a given concentration, where the plasticizer reaches its solubility limit in the polymer (50 wt % in the case of ATBC; 15–30 wt %, depending on molecular weight, in the case of PEG). The range of applicability of PEGs as PLA plasticizers is given in terms of PEG molecular weight and concentration. The mechanical properties of plasticized PLA change with increasing plasticizer concentration. In all PLA/plasticizer systems investigated, when the blend T_g approaches room temperature, a stepwise change in the mechanical properties of the system is observed. The elongation at break drastically increases, whereas tensile strength and modulus decrease. This behavior occurs at a plasticizer concentration that depends on the T_g‐depressing efficiency of the plasticizer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1731–1738, 2003