Preparation and characterization of a novel nanofiltration membrane

In this study, poly[2-(N, N-dimethyl amino)ethyl methacrylate] (PDMAEMA) was prepared by bulk polymerization using AIBN as an initiator. Aqueous PDMAEMA solution was then purified by hollow fiber ultrafiltration membrane technology to remove oligomers. PDMAEMA/polysulfone (PSF) positively charged nanofiltration (NF) membrane was developed by interfacial polymerization by using PSF ultrafiltration membrane as the substrate, PDMAEMA aqueous solution as the coating solution and p-xylylene dichloride dissolved in n-heptane as the organic crosslinker. Effects of substrate material, concentration of monomer, pH value of PDMAEMA, coating time and crosslinking time were then carefully examined on the separation properties of the prepared NF membrane. Data suggested that the rejection rate of the composite NF membrane to 1 g/l of MgSO₄ was around 86.7 %, and the water flux was about 18.4 L·m⁻²·h⁻¹. Therefore, the developed NF membrane is suitable for rejection and desalination of alkaline dyes.     

Synthesis and properties of alkali-clearable azo disperse dyes containing a carboxylic ethyl ester group

Three alkali-clearable azo disperse dyes containing a carboxylic ethyl ester group (D1-D3) were readily synthesized using three different synthetic strategies. D1 was prepared from a carboxylic acid-containing dye by esterification with ethanol. D2 was prepared from a carboxylic ester-containing dye by transesterification with ethanol. D3 was prepared from a cyano group-containing dye by alcoholysis with ethanol and water. The molecular structures of the dyes were characterized by FTIR, mass spectrometry, ¹H NMR, ¹³C NMR, and elemental analysis. The synthesized dyes and the control dyes were used to dye poly(ethylene terephthalate) fabric, and their washing and rubbing fastness properties following different after-treatment methods (reduction clearing and alkali clearing) were examined and compared. The carboxylic ethyl ester-containing disperse dyes show good alkali clearing ability on poly(ethylene terephthalate) fabric and cause fewer environmental issues due to the absence of reductants, no production of aromatic amines with high toxicity and carcinogenicity, as well as the low toxicity of the dye hydrolysate ethanol.     

Removal of benzidine-based azo dye from aqueous solution using amide and amine-functionalized poly(ethylene terephthalate) fibers

In this study, amide and amine groups bound to poly(ethylene terephthalate) fibers are used to remove the colored toxic Congo red dye from aqueous solution. The effects of process variables like pH, contact time, graft yield, and initial dye concentration on the adsorption were investigated. The maximum adsorption of Congo red to amide and amine groups was observed at pH 3 and 5 respectively. Equilibrium was attained at approximately 60 min for the amine group. The adsorption capacity of amine group on the poly(ethylene terephthalate) fiber was 46.5 mg g⁻¹ at 25 °C, which was higher than that of the amide group on the poly(ethylene terephthalate) fiber. Desorption was done using 0.1 M NH₃, and recovery was measured at 58.2 %. The used adsorbent was regenerated and recycled six times. The results showed that the amine-functionalized fiber could be considered as potential adsorbents for removal of Congo red from aqueous solution.     

Theoretical analysis of the melt spinning process of poly(trimethylene terephthalate) fibers

Profiles development of the melt spinning process of poly(trimethylene terephthalate) (PTT) was simulated by a numerical method. The spinning speed of 3 km/min to 5 km/min was analyzed and the characteristic of PTT spinning process was compared with that of poly(ethylene terephthalate) (PET). Velocity development of PTT was slower than that of PET. Although PTT’s spinning temperature was lower than PET’s, the PTT solidified slower because of a smaller super-cooling and the large specific heat capacity. The diameter profile of PTT decreases gradually in comparison with that of PET. PTT’s strain rate has a broader distribution than PET’s and its maximum ranged from 541 to 570 s⁻¹ for PET and 136 to 149 s⁻¹ for PTT. PTT’s tensile stress was smaller than PET’s.     

High Light-Fastness Acid Dyes Synthesized from Corresponding Anthraquinone Chromophore Utilizing a Sulfonation Reaction. I. Dye Synthesis and Characterization

As the diameter of polyamide fibers decreased to finer denier, the dyeing fastness tends to be deteriorated due to the increase of their surface area, particularly both light fastness and wash fastness. In this study, three acid dyes were synthesized utilizing a sulfonation reaction starting from corresponding hydrophobic dye (for yellow and red dye) and dye intermediate containing a sulfonic acid group (for blue dye), those featured by high light fastness property. A Gaussian structural prediction model was used to determine the structure of the acid dyes prior to dye synthesis, and the optimal structures of three acid dyes were analyzed. Dye structures prepared were confirmed by ¹H-NMR, mass spectroscopy, and elemental analysis. By using a UV-vis spectrophotometer, the absorption maxima and molar extinction coefficient were also measured for three acid dyes comparing to that of the corresponding disperse dye or blue dye intermediate. Judging from spectroscopic data, the introduction of sulfonyl groups led to increase of molar extinction coefficient and a bathochromic shift.     

Dyeing properties of 4-amino-4′-fluorosulfonylazobenzene disperse dyes on poly(ethylene terephthalate)

Dyeing properties of a series of 4-amino-4′-fluorosulfonylazobenzene disperse dyes on poly(ethylene terephthalate) (PET) were investigated. Build-up properties and color properties on PET were examined. In particular, the 4-aminoazobenzene dyes containing a nitro group instead of a fluorosulfonyl group at 4′-position were also synthesized in order to compare their dyeing properties on PET with that of 4′-fluorosulfonyl analogues.     

Synthesis and spectral properties of phthalimide based alkali-clearable azo disperse dyes

The synthesis of a series of phthalimide based azo disperse dyes and their spectral properties were investigated. The azo dyes containing phthalimide and N-methyl phthalimide structure in diazo component were synthesized in order to compare their spectral properties. The synthesized dyes developed the color of yellow to violet and the N-substitution of the phthalimide gave a bathochromic effect on the color change. Most of the synthesized dyes exhibit negative solvatochromism so that the absorption band of dyes moves toward shorter wavelengths as the polarity of the solvent increases. In the case of halochromic effect, the bathochromic shift decreased steadily with the general electron donating capacity of the substituents in the coupling component, and became negative especially when more powerful electron donating groups are present in the coupling components ring.     

Coloration of poly(lactic acid) with disperse dyes. 1. Comparison to poly(ethylene terephthalate) of dyeability, shade and fastness

The dyeability of poly(lactic acid) [PLA] with a range of commercial disperse dye was examined and compared to that of poly(ethylene terephthalate) [PET] in addition to the colour and fastness of the resultant dyeings. A screening exercise in which twenty dyes of differing energy types and chemical classes were applied to PLA revealed a substantial variation between the dyes in terms of dye uptake (12–88 % at 4 %o.w.f.). Nine dyes exhausted above 70 % and were selected for further study, which involved comparison of shade and fastness of PLA dyeings with those of the corresponding PET dyeings. Differences in shade depended on hue while wet fastness of each of the PLA dyeings was either the same or 0.5–1.0 point lower than its PET counterpart. In all but one case, dye photostability in PLA was found to be very similar to that in PET. Dye build-up profiles on PLA were also investigated and from these results mixtures of compatible dyes identified.     

Functinalization of poly(ethylene terephthalate) fibers by grafting of maleic acid/methacrylamide monomer mixture

Functionalized poly(ethylene terephthalate) (PET) fibers were synthesized by grafting of maleic acidmethacrylamide (MAA-MAAm) monomer mixtures by using benzoylperoxide as initiator onto PET fibers in an aqueous medium. The functionalized fibers were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, differential scanning calorimeter, and scanning electron microscopy. The effects of reaction conditions, such as monomer mixture ratio, monomer mixture and initiator concentration, polymerization time, and temperature on grafting were investigated. In alone grafting of MAA, grafting was not observed. However, the use of MAAm as a comonomer increased the amount of MAA inserted to the PET fiber up to 40.7 %. An increase in the temperature between 75 and 95 °C and also, increase in monomer mixture concentration between 0.50 and 1.00 M increased the grafting rate and saturation graft yield. The graft yield has shown an increase up to an initiator concentration of 1.0×10⁻² M and decreased afterwards. The grafting increased the dyeability with disperse, acidic and basic dyes, and water absorption capacity but decreased the thermal stability of the fibers.     

Improvement of mechanical and electrical properties of poly(ethylene glycol) and cyanoresin based polymer electrolytes

Ionic conductivity and mechanical properties of a mixed polymer matrix consisting of poly(ethylene glycol) (PEG) and cyanoresin type M (CRM) with various lithium salts and plasticizer were examined. The CRM used was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) with a molar ratio of 1:1, mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) at a volume ratio of 1:1. The conductive behavior of polymer electrolytes in the temperature range of 298∼338 K was investigated. The PEG/LiClO₄ complexes exhibited the highest ionic conductivity of ∼10⁻⁵ S/cm at 25°C with the salt concentration of 1.5 M. In addition, the plasticized PEG/LiClO₄ complexes exhibited improvement of ionic conductivity. However, their complexes showed decreased mechanical properties. The improvement of ionic conductivity and mechanical properties could be obtained from the polymer electrolytes by using CRM. The highest ionic conductivity of PEG/CRM/LiClO₄/(EC-PC) was 5.33×10⁻⁴ S/cm at 25°C.     

Studies on the ternary blends of liquid crystalline polymer and polyesters

Thermotropic liquid crystalline polymer made up of poly(p-hydroxybenzoate) (PHB)-poly(ethylene terephthalate) (PET) 8/2 copolyester, poly(ethylene 2,6-naphthalate) (PEN) and PET were mechanically blended to pursue the liquid crystalline phase of ternary blends. Complex viscosities of blends decreased with increasing temperature and PHB content. DSC thermal analysis indicated that glass transition temperature (Tg) and melting temperature (Tm) of blends increased with increasing PHB content. Both tensile strength and initial modulus increased with raising PHB content and take-up speed of monofilaments. In the WAXS diagram, only PEN crystal reflection at 2Θ=15.5^o appeared but PET crystal reflection was not shown in all compositions. The degree of transesterification and randomness of blends increased with blending time but sequential length of both PEN and PET segment decreased.     

Processing and characterization of liquid crystalline copoly-(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate)/polycarbonate blends

Liquid crystalline (LC) poly(ethylene terephthalate-co-2(3)-chloro-1,4-phenylene terephthalate) (50/50, mole/mole) [PECPT] was synthesized and blended with polycarbonate (PC). LC properties of PECPT and thermal, morphological, and rheological behaviors of the PECPT/PC blend were studied. PECPT showed the nematic LC phase and much longer relaxation time than poly(ethylene terephthalate) (PET). The apparent melt viscosity of PECPT was one third of that of PET. An abrupt torque change was observed during the blending process due to the orientation of LC domains. For the blends containing 10∼30 wt% of PECPT, the complex viscosities were higher than that of PC. As PECPT content increases above 40 wt%, shear thinning was observed. The lowest complex viscosity was obtained at 40∼50 wt%. Transesterification of PECPT and PC was confirmed by the selective chemical degradation of carbonate groups in PC.     

Relation between chemical structure of yellow disperse dyes and their lightfastness

Five yellow disperse dyes were synthesized and their dyeing, fastness and photodegradation behaviors were investigated. It was found that dyes derived from phenylindole and N-alkylaminobenzene showed dye uptake directly proportional to the dye concentration, but the build-up of dyes derived from carbazole and pyridone were not good. The wavelength at maximum absorption, molar extinction coefficient, and the tendency to the photodegradation were strongly dependent on the electron donating ability of the coupling component. The dye, whose coupling component was phenylindole, possessed the excellent dyeing properties and the high degree of lightfastness. UVA had an effect on the inhibition of the photodegradation especially for the easily photodegradable dyes.     

Poly(vinylidene fluoride)/poly(ethylene-co-vinyl acetate) (20/80) blend. I. Miscibility and crystallization behavior

The miscibility and crystallization behavior of the blends of poly(vinylidene fluoride) (PVDF) and ethylene/vinyl acetate(20/80) copolymer (EVAc80) have been studied using a differential scanning calorimeter and a polarizing microscope equipped with a heating stage. From the melting point depression, the values of interaction energy densityB were calculated to be −1.3004 (cal/cm³) and the Flory-Huggins interaction parameterχ ₁₂ was found to be −0.0818 at 445.6 K. With increasing concentration of EVAc80, the radial growth rate of spherulite was reduced drastically. The FT-IR analysis of samples quenched from the melt to various temperatures showed increasing content ofβ-phase with increasing amount of blended EVA80 along with lower quenching temperature.     

Characterization of conductive poly(acrylonitrile-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate) composites: Matrix polymerization of pyrrole derivatives

In this study, poly(acrylonitrile-co-vinyl acetate) (P(AN-co-VAc)) composite films were prepared by chemical polymerization of pyrrole(Py), N-methyl pyrrole (NMPy) and N-phenyl pyrrole (NPhPy) with cerium(IV) [Ce(IV)] on P(AN-co-VAc) matrix. An increase was observed in the absorbances of CN ring stretching vibration (1451 cm⁻¹) by introducing pyrrole (Py) derivatives on P(AN-co-VAc) matrix. The nitrile (CN) and carbonyl (C=O) groups played a significant role on the interactions with cationic sites of Py derivatives. Conductivity was increased in the presence of carbonyl (C=O) groups due to their additional negative charges on P(AN-co-VAc) matrix compared to PAN. Poly(N-Phenyl Pyrrole) (PNPhPy) exhibited higher dielectric constant and AC conductivity in the frequency range between the 10⁻²–10⁷ Hz. The TGA results exhibited shifts of peak to higher temperatures by the presence of Py derivatives by increasing the weight loss %.     

Poly(trimethylene terephthalate) fiber melt-spinning: Material parameters and computer simulation

In this work, the method, in principle of the box complex algorithm was adopted to obtain stress-induced crystallization coefficient C and the strain-optical coefficientA _op with the value of 295 and 1.5×10⁻⁹, respectively, and some parametersA ₁=0.27,A ₂=5.06,a=3.5,b=1.8 relative to the elongational viscosity of poly(trimethylene terephthalate)(PTT) fiber. The vitrification distance as a function of the take-up velocity and mass throughput was also gotten. The effects of spinning conditions on filament temperature, velocity gradient, spinning tension, birefringence and crystallinity, and effect of viscoelasticity on take-up velocity had been discussed.     

The preparation and characterization of conductive poly(ethylene terephthalate)/polyaniline composite fibers using benzoyl peroxide

Conductive polyaniline (PAn)/poly(ethylene terephthalate) (PET) composite fibers were prepared by chemical polymerization of aniline in the presence of PET fibers using benzoyl peroxide (Bz₂O₂) in organic solvent/aqueous hydrochloric acid mixtures. The effects of polymerization conditions such as organic solvent/water ratio, oxidant, aniline and hydrochloric acid concentrations and temperature were investigated on the amount of PAn deposited on PET fiber and the electrical surface resistance of composite fibers. The maximum PAn content and the lowest electrical surface resistance of composite fibers were observed at HCl concentrations of 0.5 mol L⁻¹. The properties of PAn/PET composite fibers such as density, diameter, tensile strength and breaking elongation were also investigated in comparison with those of pure PET. Characterization of conductive composite fibers was carried out by FTIR, TGA, SEM techniques, surface resistance measurements, and cross section images taken by optical microscope.     

Synthesis and thermo-responsive properties of chitosan-g-poly (N-isopropylacrylamide) and HTCC-g-poly(N-isopropylacrylamide) copolymers

Carboxyl group-terminated poly(N-isopropylacrylamide) (PNIA-COOH) was synthesized via radical polymerization of N-isopropylacrylamide (NIA) using mercaptoacetic acid (MAA) as a chain transfer agent. The molecular weight of the PNIA-COOH was controlled by changing the molar ratio of MAA to NIA. A water-soluble chitosan derivative, N-(2-hydroxy)propyl-3-trimethylammonium chitosan chloride (HTCC), was also synthesized by reacting chitosan with glycidyltrimethylammonium chloride. Then, chitosan-g-PNIA and HTCC-g-PNIA copolymers were synthesized using the “graft-onto” method by reacting PNIA-COOH with chitosan and HTCC, respectively. The formation of the grafted copolymers was confirmed by Fourier transform infrared spectroscopy, solubility test in water, and scanning electron microscopy — energy dispersive spectroscopy. The thermo-responsive behaviors of the grafted copolymers and the change in lower critical solution temperature (LCST) were also studied. Chitosan-g-PNIA was insoluble in water and behaved like a thermo-responsive hydrogel due to the crosslinking-point action of the chitosan backbone. The swelling ratio of chitosan-g-PNIA increased with increasing PNIA content. HTCC-g-PNIA behaved as a water-soluble thermo-responsive polymer. Compared to the homo PNIA, the LCST of HTCC-g-PNIA was slightly increased.     

A Comparative study of redox parameters and electrochemical impedance spectroscopy of polycarbazole derivatives on carbon fiber microelectrode

In this study, N-Carbazole and its derivatives (N-Vinylcarbazole, N-Ethylcarbazole, N-Vinylbenzylcarbazole, and N-Benzylcarbazole) were electrochemically polymerized on carbon fiber microelectrodes (diameter ∼7 μm) by cyclic voltammetry within a potential range from 0.0 to 1.4 V. Redox parameters, Scanning electron microscopic (SEM) images were determined and also capacitance behaviors of polymers were examined via electrochemical impedance spectroscopy (EIS). EIS measurements of polycarbazole derivatives were given comparatively. The existence of a capacitance behavior is shown by Nyquist, Bode magnitude, Bode-phase, Admittance plots relationship. Although the highest low frequency capacitance (C_LF=12901 μA cm⁻²) and maximum phase angle of 81.9 ° at a frequency of 1 Hz were obtained for N-Vinylbenzylcarbazole, the lowest anodic and cathodic potential difference (ΔE=0.04 V) and double layer capacitance (C _dl =0.11 μA cm⁻²) were indicated in 0.1 M LiClO₄/PC.