Synthesis of conducting polyaniline‐montmorillonite nanocomposites via inverse emulsion polymerization in supercritical carbon dioxide

A new inverse emulsion polymerization and intercalation procedure in supercritical carbon dioxide (SCCO₂) was initially employed to synthesize polyaniline‐montmorillonite (PANI‐MMT) nanocomposites. The effect of chemical groups in MMT galleries on intercalation in SCCO₂ was investigated. The MMTs modified by different organic cationic surfactants were incorporated into the composite particles, and in unintercalated, partially delaminated or fully exfoliated state. The aminated MMT or fluorinated MMT were utilized to prepare conducting PANI‐MMT nanocomposites with highly concentrated (12–25 wt% loading to monomer), fully exfoliated MMT platelets in SCCO₂. The structure and morphology of PANI‐MMT nanocomposites were characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray powder diffraction pattern (XRD), and transmission electron microscope (TEM). Thermogravimetry analysis (TGA) was performed to demonstrate the enhancement of thermal stability of the composites. SCCO₂ was shown to be more effective for impregnation, disaggregation and exfoliation of MMTs than isooctane, which indicates that SCCO₂ is an alternative solvent for synthesis of some intercalated composite materials, not only based on the environmental friendly characteristic of SCCO₂, but also owing to that SCCO₂ can play an important role in intercalative polymerization. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

涤纶织物的丝胶改性和染色工艺研究

涤纶织物通过丝胶处理后,吸湿性、抗静电性和回潮率有了明显的提高,改善了涤纶织物的服用性能。用酸性染料对处理后的涤纶织物进行染色,染色均匀。经固色后,取得了较高的染色牢度。     

Modification of cellulose fiber with silk sericin

Cellulose fiber surface was modified with silk sericin (or simply, sericin). Sericin fixation on cellulose was confirmed by environmental scanning electron microscopy (ESEM) and Fourier transform infrared spectrophotometry–attenuated total reflectance (FTIR‐ATR). Sericin content in finished samples was estimated by dyeing treated fabrics with an acid dye, Supranol Bordeaux B, and determining K/S and L values of the dyed fabrics. The treated fabrics were tested for free formaldehyde content, crease recovery, tensile strength, electrical resistance, water retention, and biocidal activity. From ESEM and FTIR‐ATR results, it was found that sericin coated onto cotton surfaces as a film. Increasing sericin content in the finishing solution increased the amount of coated sericin, and a greater depth of color in dyed samples and reduced free formaldehyde content in treated samples were observed. The sericin content in samples was found to have a negligible influence on tensile strength and crease recovery angle. With increasing sericin content, electrical resistivity of the samples dramatically decreased and water retention increased, indicating that sericin‐treated fabrics may be comfortable to wear because of its maintenance of moisture balance with respect to human skin. Because cotton textile coated with sericin exhibited low formaldehyde content and no biocidal activity against Klebsiella pneumoniae and Staphylococcus aureus, the fabric may reduce skin irritation and disturbance of physiological skin flora arising from textile contact. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1421–1428, 2005     

A novel method of modifying poly(ethylene terephthalate) fabric using supercritical carbon dioxide

For the modification of poly(ethylene terephthalate) (PET) fabric, a type of epoxy compound, glycerol polyglycidyl ether (GPE), was impregnated as a cross‐linking agent into PET fabric by means of supercritical carbon dioxide (scCO₂), then, a series of immobilization processes were implemented, including the pad‐dry‐cure process and the solution process to finish the GPE‐PET fabric with natural functional agents (sericin, collagen, or chitosan). Chloroform was found to be an effective cosolvent, as evidenced by the mass transfer of GPE to PET during the treatment with scCO₂. Chemical analyses by X‐ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy showed that GPE can penetrate the surface of the PET fabric in scCO₂ pretreatment process, and natural functional agents (sericin, collagen, or chitosan) can also be immobilized on the surface of the GPE‐PET fabric especially for the method of pad‐dry‐cure. The nitrogen content in the modified PET fabrics was calculated accurately and confirmed by combustion analysis. The modified PET fabric displayed improvements in surface wettability, moisturization efficiency, and antibacterial characteristics against S. aureus, which demonstrated that the feasibility of this design for immobilizing natural functional agents (sericin, collagen, or chitosan) onto the surface of the PET fabric. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Alkaline dyeing of polyester and polyester/cotton blend fabrics using sodium edetate

An alkaline dyeing of polyester with an alkali‐stable disperse dye, Dianix® Scarlet AD‐RG, was developed using sodium edetate as an alkaline buffering agent. The results obtained indicate the suitability of using sodium edetate for alkaline dyeing of polyester when compared with the control alkaline dyeing using Dianix AD system. Selected mono and bifunctional reactive dyes were used in combination with the alkali‐stable disperse dye for dyeing of polyester/cotton blend. Different dyeing methods for cotton and polyester/cotton blend fabrics using sodium edetate were evaluated in comparison with their respective control alkaline dyeing methods. The results of using sodium edetate in one‐bath two‐stage and two‐bath dyeing of polyester/cotton blend were comparable with that of the control dyeing method. Particularly, no change in the leveling and fastness properties was evaluated for all samples irrespective of the dyeing method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, and time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 123–128, 2002     

Study of the Influence of Gemini Cationic Surfactants on the Dyeing and Fastness Properties of Polyester Fabrics Using Naphthalimide Dyes

In this paper, the dyeing and fastness properties of three monoazo naphthalimide dyes including different imide groups (dye 1: ethyl amine, dye 2: ethyl glycinate and dye 3: glycine) on a polyester fabric were investigated in the presence of two gemini cationic surfactants (symbolized as 12‐4‐12 or 14‐4‐14) and a conventional single chain surfactant, dodecyltrimethylammonium bromide (DTAB). The color strength (K/S) of naphthalimide dyes on polyester fabric was measured through the reflectance spectrophotometric method, and the values obtained in the presence of different cationic surfactants increased in the order of dye 3 < dye 2 < dye 1. Although the K/S values indicated that the gemini cationic surfactants had almost no effect on the dyeing behavior of dye 1, but they were effective in dyeing ability of dye 2 and dye 3. The data for dye 2 demonstrated that build up of polyester fabrics in the presence of gemini surfactants are more than the conventional cationic surfactant, and also K/S values of dye 3 on polyester fabrics were in the order: DTAB > 12‐4‐12 > 14‐4‐14. It was found that the washing and rubbing fastness properties improved with increasing the concentration of surfactants. In addition, the sublimation fastness of dye 3 was more than the other dyes owing to the presence of a polar group in its chemical structure, and the light fastness of naphthalimide dyes on polyester fabrics was generally moderate.     

Disperse dyeing of polyester fibers: Kinetic and equilibrium study

The effect of temperature on the dyeing rate constant k, diffusion coefficient D, time of half‐dyeing t_1/2 was evaluated for the dyeing of polyester fibers with two disperse dyes, an azo and an anthraquinone dye. Activation energies of diffusion E were calculated. The polyester dyeing equilibrium was also studied and the partition coefficient K and standard affinity Δμ° at various temperatures were determined for the anthraquinone dye. Standard enthalpy ΔH° and standard entropy ΔS° of dyeing were also obtained. The same equilibrium parameters were not obtained for the azo dye because of its dyeing behavior. A similar kinetic and equilibrium study was made for the pure azo and anthraquinone compounds free from the dispersing agents present in the commercial dyes and the results are discussed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2785–2790, 2002; DOI 10.1002/app.10254     

Study on the dyeing properties of hemicyanine dyes. II. Cationic dyeable polyester

The absorption spectra of two hemicyanine fluorescent dyes, namely, trans‐4‐[p‐(N,N‐di(2‐hydroxyethyl))‐amino‐styryl]‐N‐ethyl pyridinium bromide (DHEASPBr‐C₂) and trans‐4‐[p‐(N,N‐di(2‐hydroxyethyl))‐amino‐styryl]‐N‐octyl pyridinium bromide (DHEASPBr‐C₈), were studied at various levels of pH and high temperatures, and were then employed to dye cationic dyeable polyester. Their dyeing properties, fluorescent reflectance and colorimetric properties were explored. The novel fluorescent dyes existed in two forms of monocation and dication in solutions at low pH and high temperature. Overall, the influence of pH on colour depth and the maximum reflectance of dyed cationic dyeable polyester was extremely small. The adsorption mechanism of DHEASPBr‐C₂ and DHEASPBr‐C₈ on cationic dyeable polyester fibres was in good accord with the Langmuir type. Compared with DHEASPBr‐C₂, DHEASPBr‐C₈ exhibited comparatively faster adsorption rate, higher affinity and dye uptake, while its fluorescence shown by cationic dyeable polyester was slightly weak.     

Canola oil extracted by supercritical carbon dioxide and a commercial organic solvent

Samples of crushed and cooked canola seeds (Okapy Double Zero) were extracted using supercritical carbon dioxide (SCCO₂) (34.0 MPa and 40.0 °C) and a commercial organic solvent (AW406). Oil solubility was obtained through several stepwise extractions under the conditions of this study, and then three additional extractions were performed to measure fatty acid compositions, iodine values, chlorophyll concentrations and unsaponifiable matter. The yield of SCCO₂ extraction was lower than that after extraction with AW406 solvent, due to the incomplete SCCO₂ extraction process. Fatty acid composition analysis showed that the SCCO₂‐extracted oil was slightly higher in polyunsaturated fatty acids and lower in erucic and behenic acids. However, iodine values and unsaponifiable matter did not indicate significant differences (p >0.05) in the two extracted oils. The chlorophyll concentration of SCCO₂‐extracted oil was lower than that in the AW406 solvent, and as a result, the color of SCCO₂‐extracted oil was lighter.     

Effect of supercritical CO2 on three‐dimensional colloid arrays of PS‐MA–EGDMA

Using emulsifier‐free emulsion polymerization method, monodispersed crosslinked poly(styrene‐co‐methacrylic acid‐co‐ethylene glycol dimethacrylate) colloid microspheres were synthesized. The microspheres were treated in supercritical carbon dioxide (SCCO₂) after they have self‐assembled into ordered three‐dimensional (3D) colloid arrays. The CO₂ absorbed into the polymer microspheres enhances chain segments mobility and reduces the glass transition temperature (T_g) of polymer, which induce the microspheres coalesce at the relatively low temperature. The coalescence degree of microspheres was studied by varying the experimental temperature, pressure, and exposure time in SCCO₂. The results were shown by scanning electron microscopy (SEM). Further, the lattice spacing of the assembled 3D colloid microspheres was calculated from the SEM images. It was illustrated that the coalescence degree enhanced with the increase of CO₂ pressure; however, this tendency became weak when CO₂ pressure reached a certain value. Extending exposure time in SCCO₂ or elevating temperature can also increase coalescence degree, and the effect of temperature is more significant. It is believed that these results will make sense when the polymer microspheres are considered to be used as templates in SCCO₂; meanwhile, it raises a new method about tuning the final morphology of the stabilized colloidal crystals and porous materials via controlling the coalescence degree with the assistance of SCCO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of silk sericin peptides–L‐asparaginase bioconjugates and their characterization

The natural silk sericin, recovered from Bombyx mori silk waste by degumming and degrading, is a water‐soluble peptide with different molecular masses, ranging from 20 to 60 kDa. It is composed of 15 sorts of amino acids, among which the polar amino acids with hydroxyl, carboxyl and amino groups such as aspartic acid, serine and lysine account for 72%. The covalent attachment of the silk sericin peptides to L ‐asparaginase (ASNase) produces silk sericin peptides–L ‐asparaginase (SS–ASNase) bioconjugates that are active, stable, have a lower immune response, and have extended half‐lives in vitro in human serum. The modified enzyme coupled with sericin protein retains 55.8% of the original activity of the native enzyme. The optimal pH of SS–ASNase derivatives shifts considerably, to 5.0 in comparison with pH 6.0–8.0 of the native form. The thermostability and resistance to trypsin digestion of the modified enzyme are greatly enhanced as compared with ASNase alone. The Michaelis constant (K_m) of SS–ASNase is 65 times lower than that of the enzyme alone. This suggests that the affinity of the enzyme to its substrate L ‐asparagine greatly increases when bioconjugated with silk sericin. The in vivo experiments also show that the silk sericin peptides have no immunogenicity, and the antigenicity of the enzyme is obviously decreased when coupled covalently with the silk sericin peptides. Copyright © 2005 Society of Chemical Industry     

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse dyes

Carrier‐free dyeing of radiation‐grafted polyester fabrics with disperse red dye was studied in the temperature range 283–363 K. 1‐vinyl 2‐pyrrolidone (NVP), acrylic acid (AA) or their mixture was used to graft poly(ethylene terephthalate) (PET) fabric. The effects of pH of the dye solution, graft yield (GY), dyeing time (t), dye concentration (C), and dyeing temperature (T) on the colour difference (CD) of PET fabric were studied. The best dyeing condition was achieved at pH 5.5. CD increases linearly with the increase in GY, with slopes depending on the type of grafted copolymer. CD increased rapidly as the dyeing time increased; this was followed by a relatively slow dyeing rate within a few minutes. The initial dyeing rate (R) was found to increase with an increase in C and T. The dyeing rates for all grafted samples followed 0.35‐order kinetics and are temperature‐independent. Average activation energy 9.26 kJ mol^?1 is calculated for the dyeing process and is independent of the fabric treatment. Pre‐exponential rate constants 1976, 1839, and 1579 (CD/GY) s^?1 were calculated for dyeing PET samples grafted with AA/NVP mixture, NVP and AA, respectively, while 1074 CD s^?1 was evaluated for carrier dyeing of ungrafted fabric. Analysis of the kinetic parameters and the dyeing mechanism revealed that dyeing PET fabric was diffusion‐controlled. Grafting PET fabric improved significantly the dyeing affinity of the DR dye over ungrafted samples dyed in solutions containing a carrier. Copyright © 2005 Society of Chemical Industry     

Dyeing properties of silk produced by silkworms reared on artificial and mulberry leaf diets

The dyeing properties were investigated for silk proteins produced by silkworms reared entirely on an artificial diet (A) and a mulberry leaf diet (M). The dyeing experiments were carried out with CI acid orange 7 at pH 3.9 and 60°C. The sericin contents of the A and the M raw silk samples were determined to be 26.0% and 23.7%, respectively. The equilibrium dye uptake and the dyeing rate of the A silk fibroin were almost the same as those of the M silk fibroin. The equilibrium dye uptake on each silk sericin was 3–4 times higher than that of the silk fibroin. On the other hand, the equilibrium dye uptake of the A silk sericin was higher than that of the M silk sericin, but the dyeing rate of the former was slower than that of the latter.     

Optimising by response surface methodology the dyeing of polyester with a liposome‐encapsulated disperse dye

Optimisation of conditions for dyeing polyester with liposome‐encapsulated CI Disperse Red 50 was performed using response surface methodology. The effects of temperature, time, and lecithin:dye ratio on the colour strength of dyed fabrics were investigated by a central composite design. The coefficient of determination, the probability value in analysis of variance, and the normality plot of residuals demonstrated sufficient significance of the proposed fitness function. It was found that the temperature and time of the dyeing cycle were effective factors in the dyeing of polyester fabrics with encapsulated dye. It was also established that the colour yield of dyed fabrics was above 25 in the case of a dyeing time of >80 min, a lecithin:dye ratio of ≤2, and a temperature of ca. 128 °C. Comparison of colour strengths produced by liposome‐encapsulated dye and commercial dye revealed that there was approximately the same build‐up on polyester. Dyeings from encapsulated CI Disperse Red 50 exhibited very similar fastness to dyeings from conventional CI Disperse Red 50.     

Dyeing of natural and synthetic textiles in supercritical carbon dioxide with disperse reactive dyes

Polyester, nylon, silk and wool were dyed with disperse reactive dyes in supercritical carbon dioxide (scCO₂). The dyes were substituted with either vinylsulphone or dichlorotriazine reactive groups. Since earlier research showed that water, distributed over the scCO₂ and the textile, increased the colouration, experiments were done with the vinylsulphone dye with varying amounts of water in the dyeing vessel, to investigate if there is an optimum water concentration. The amounts were such, that no liquid water was present. The maximum colouration was obtained when both the scCO₂ and the textiles were saturated with water. At the saturation point, deep colours were obtained with the vinylsulphone dye for polyester, nylon, silk and wool, with fixation percentages between 70 and 92% when the dyeing time was 2 h. The positive effect of water was due to its ability to swell fibres or due to an effect of water on the reactivity of the dye–fibre system. Also the dichlorotriazine dye showed more colouration when the scCO₂ was moist. With this dye, experiments were conducted in water-saturated scCO₂, varying the pressure from 225 to 278 bar and the temperature from 100 to 116 °C. The colouration of polyester increased with pressure, the results for silk and wool were not sensitive to pressure. Increasing the temperature had no influence on the dyeing of polyester, silk and wool. The fixations on polyester, silk and wool, being between 71 and 97%, were also independent of pressure and temperature.     

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.     

Independent investigation on the influences of the processing conditions on the reclamation of crosslinked isoprene rubber after the impregnation of a reclaiming reagent

In this study, the reclamation of sulfur (S)‐cured isoprene rubber (IR) was investigated independently after the impregnation process of the reclaiming reagent diphenyl disulfide (DD) into the crosslinked IR matrix with supercritical carbon dioxide (scCO₂) as the transmission medium. According to the mass uptake of DD into IR and scanning electron microscopy–energy‐dispersive X‐ray spectrometry measurements, DD was highly impregnated and homogeneously dispersed in the network under 12 MPa at 80°C for 11 h in scCO₂. During the impregnation process, almost no reclaiming reaction occurred. Then, through three different reclaiming methods, a mechanochemical method, a chemical method with oxygen, and a chemical method without oxygen, the influences of the shear force, reclaiming atmosphere, reaction time, and amounts of reclaiming reagent on the reclamation with crosslinked IR with pre‐impregnated DD were independently investigated and compared with those of the reaction without pre‐impregnated DD. The sol fraction of the reclaimed rubber and molecular weight of the sol were measured. The results show that the reclaiming speed greatly depended on the amount of reclaiming reagent and that the reclaiming reaction was dramatically accelerated when the reclaiming reagents were pre‐impregnated into the crosslinked IR under the same processing conditions. This indicated that the impregnation time of the reclaiming reagent into the crosslinked network constituted a large proportion of the reclaiming time. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40298.     

Improving properties of superabsorbent composite induced by using alkaline protease hydrolyzed‐sericin (APh‐sericin)

A series of superabsorbent polymer composites based on sericin hydrolyzed with alkaline protease (AP) were prepared by grafting with acrylic acid (AA) and acrylamide (AM). The properties of the superabsorbent polymers (SAP) by using hydrolyzed sericin with different amount of alkaline protease (nAPh‐sericin) were compared. It was found that the polymer prepared from 5APh‐sericin (the mass ratio of AP to sericin was 5.0 mg g⁻¹) showed the highest graft percentage and water absorbency, this phenomenon may be attributed to the change of molecular weight of resulting sericin molecules. The molecular structure of the grafted polymers was proved by thermal gravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) measurements. Comparing with PAA‐AM (poly AA‐co‐AM) and 0APh‐sericin/PAA‐AM polymer, 5APh‐sericin/PAA‐AM polymer had the most excellent water retention capacity and enzyme degradability. The morphological features of the polymers with different drying methods were evidenced by SEM images. The water absorbencies of 5APh‐sericin/PAA‐AM polymer prepared with freeze‐drying were 896 g g⁻¹ in deionized water, 424 g g⁻¹ in tap water, and 83 g g⁻¹ in 0.9 wt% aqueous NaCl solution. POLYM. COMPOS., 35:509–515, 2014. © 2013 Society of Plastics Engineers     

A significant approach to dye cotton in supercritical carbon dioxide with fluorotriazine reactive dyes

A series of fluorotriazine reactive dyes have been synthesized and applied to dye cotton in supercritical carbon dioxide (scCO₂) with good dyeing results. The pieces of cotton to be dyed were previously presoaked in a protic solvent and cosolvents were applied during dyeing. The colour strength of the dyeings was evaluated by K/S measurements. The K/S values achieved on cotton dyed were up to 35.8 ± 4.2. Even after the cotton was subjected to a Shoxlet extraction at 358 K for 1 h, a maximum K/S value of 20.2 ± 1.8 was measured. The percentage of dye molecules chemically fixed to the cotton was on average 85%. The excellent reactivity of fluorotriazines allowed a reduction of 3 h on the dyeing time. It is noticeable that a dye concentration of 10% on weight of the fibre (owf) can be applied to dye cotton with fluorotriazines, since no damage of the cotton fibres occurred, as observed for the chlorotriazines at this high dye concentration.Dyes with fluorotriazine as reactive group were found to be the most preferable dyes for dyeing cotton in scCO₂, as they were able to exceed the limitation of the reaction with the cotton.