Synthesis and application of alkyl-substituted high chroma yellow dyes for unmodified polypropylene fiber

A series of new monoazo yellow dyes having different alkyl substituents was synthesized to dye unmodified polypropylene fiber. Color hue of the dyes exhibited light yellow with very high chroma enough to use as yellow primary color dyes. The affinity of the dyes onto unmodified polypropylene was increased with the increase of the length of alkyl substituents. Therefore, the hexyl-substituted dye having the longest alkyl group in this experiment showed very high color strength of dyeings with K/S value of over 26 at maximum absorption wavelength. The color fastnesses to washing, rubbing and light were also improved significantly for the longer alkyl substituted dyes, so that the hexyl-substituted dye exhibited a rating higher than 4∼5 for all kinds of fastnesses.     

Kinetic investigation of thermochromic transition,proton transfer reaction,and crystal-crystal phase transformation in 1,3-bis(hydroxyethylamino)-4,6-dinitrobenzene

This study investigated the main origin of the thermochromism of a novel compound, 1,3-bis(hydroxyethylamino)-4,6-dinitrobenzene (BDB). In order to unravel the relative dependence of reversible color change between yellow and orange on proton transfer reaction and crystal-crystal phase transformation, kinetic experiments were executed. The recovery rates of thermochromic transition, proton transfer reaction, and crystal-crystal phase transformation were calculated from the data measured through UV-vis spectrophotometry, IR spectrometry, and X-ray diffractometry with a lapse of time at fixedtemperatures (30, 40, and 50 °C) after cooling from heated temperature (150 °C). The kinetic experiments revealed that the recovery takes place more quickly at lower temperature. At each fixed-temperature, the recovery rate is in the order of the crystal-crystal phase transformation > the proton transfer reaction > the thermochromic transition. It is concluded that the proton transfer reaction is the main origin for thermochromism of BDB in solid state and the crystal-crystal phase transformation is a collateral one.     

Synthesis and application of alkyl-substituted disazo yellow dyes for unmodified polypropylene fiber

The several disazo dyes having different alkyl substituents were synthesized to dye unmodified polypropylene fiber. The affinity of the dyes onto unmodified polypropylene was increased with the increase of the length of alkyl substituents. Therefore, the heptyl-substituted dye having the longest alkyl group in this experiment showed very high color strength of dyeings with K/S value of over 24 at maximum absorption wavelength. The color fastnesses to washing, rubbing and light were also improved significantly for the longer alkyl substituted dyes, so that the heptyl-substituted dye exhibited a rating of 4∼5 for all kinds of fastnesses.     

Tensile behavior and structural evolution of poly(lactic acid) monofilaments in glass transition region

A series of amorphous poly(lactic acid) (PLA) monofilaments with various D-isomer contents of 1∼9 mol% have been prepared and then elongated uniaxially at 25∼65 °C in the glass transition region. Both initial modulus and maximum strength of PLA monofilaments are appreciably decreased with increasing the temperature, especially at ∼50 °C, and they were somewhat lower for the monofilament with higher D-isomer content. Structural evolution, chain orientation, and thermal properties of PLA monofilaments drawn uniaxially with various draw ratios at 65 °C were then investigated by using wide-angle X-ray diffraction, polarized Raman spectroscopy, and differential scanning calorimetry, respectively. X-ray diffraction patterns clearly exhibited the development of chain orientation and stain-induced crystallization of the monofilaments as a function of draw ratio (DR). The dichroic ratio, a measure of the chain orientation, was quantitatively evaluated from the polarized Raman spectra. It was revealed that the dichroic ratios increased up to DR=4 and decreased slightly at DR>4 owing to the strain-induced crystallization for PLA monofilaments with D-isomer contents of 1 and 4 mol%. The glass transition and cold-crystallization temperatures of PLA monofilaments increased and decreased, respectively, with the increment of DR. The strain-induced enthalpy relaxation endothermic peak appearing in glass transition region became intense with increasing the DR.     

Synthesis and application of alkyl-substituted red dyes for unmodified polypropylene fibers

Following the previous studies regarding blue and yellow dyes, a series of new red dyes having different length of alkyl substituents on the same chromophore were synthesized in order to dye unmodified polypropylene fiber. The affinity of the dyes onto unmodified polypropylene fiber was increased with the increase of the length of alkyl substituents. Therefore, the longest hexyl-substituted dye showed very deep shade of dyeing with K/S value of around 30 at maximum absorption wavelength. Within the range below 2 % o.w.f., the exhaustion (%) showed more than 80 %. The color fastnesses to washing, rubbing, and light of the dyeings were also improved greater for the dyes having longer alkyl substituents than the shorter ones. Since color hue of the dyes exhibited very strong red, they could be considered to be used as the primary red color dyes for unmodified polypropylene fibers.     

Properties of waterborne polyurethane (WBPU) coatings: Effect of alkyl chain length of tertiary amines of carboxylic acid salt groups

Waterborne polyurethane (WBPU) dispersions were prepared via a pre-polymer process using 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI), poly(tetramethyleneoxideglycol) (PTMG), 2,2-dimethylol propionic acid (DMPA), ethylene diamine (EDA), and tertiary amines (TAs) with varying amounts of DMPA and TAs. Three TAs with different alkyl chain lengths were used to neutralize the DMPA carboxylic group: N,N-dimethylbutylamine (DMBA, C4), N,N-dimethylhexylamine (DMHA, C6), and N,N-dimethyloctylamine (DMOA, C8). The structures of the synthesized WBPUs were determined via FT-IR and ¹H NMR spectroscopic techniques. The effects of DMPA and TA content and the TA alkyl chain length on stability of dispersions and properties such as water swelling (%), glass transition temperature (T _g ), tensile strength, binding energy and adhesive strength were investigated. The initial adhesive strength of the intact coatings increased with increasing DMPA and TA content and increasing alkyl chain length of TA. However, after immersion of the coatings in water, the adhesive strength decreased. The maximum adhesive strength under water was observed at a DMPA content of 20.20 mol% with 5.30 wt% DMOA, which has the longest alkyl chain.     

Coloration of ultra high molecular weight polyethylene fibers using alkyl-substituted monoazo yellow and red dyes

UHMWPE fibers were dyed with yellow and red dyes having different length of alkyl substituents on monoazo chromophores. The dyeability was investigated at various conditions and fastness of the dyeings was examined. As the length of alkyl substituents increased, the dyeability toward UHMWPE fibers tends to be improved gradually up to propyl or butyl groups and then decreased for the longer alkyl substituents. Color strength of the fabrics was increased with the increase of dyeing temperature from 100 to 130 °C. From the dyeing rate, equilibrium dyeing at 130 °C was achieved at 2～3 h. The color fastnesses to washing, rubbing, and light of the dyeings were good showing higher than 4 ratings except for light fastness of the red dye.     

Spinodal phase separation and isothermal crystallization behavior in blends of VDF/TrFE(75/25) copolymer and poly(1,4-butylene adipate) (I)

Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(1,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼34 °C above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (180 °C) to a two-phase region (205∼215 °C). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.     

Shelf life study of some Nigerian fruit juices inoculated with ascospores ofNeosartorya spp.

Mango, orange and pineapple juices containing various concentrations of sucrose were dispensed in 100 ml volumes into 100 ml conical flasks with stoppers. Each juice in a flask was inoculated with ascospores of one local isolate of eitherNeosartorya fischeri, N. fischeri var.spinosa orN. quadricincta to a final concentration of 120–140 ascospores/ml of juice, and then pasteurized at 80°C for 30 min. A set of 36 inoculated flasks with 12 controls was stored at 4–5°C and two sets, one protected with 100 mg/l sodium benzoate, were stored at room temperature (25–28°C). A shelf life study was carried out on all the juices for 64 days. Only fruit juices stored at 4–5°C and those containing sodium benzoate stored at room temperature were protected from spoilage by these fungi for 64 days. Addition of sucrose at levels of 9% to mango juice, 30% to pineapple juice and 31.5% to orange juice significantly (p=0.05) protected ascospores from inactivation during cold storage.     

Physicochemical, Rheological and Structural Characteristics of Starch in Maize Tortillas

Fresh and stored maize (white and blue) tortillas were evaluated for physicochemical, rheological and structural characteristics assessed by calorimetry, x-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, dynamic viscoelastic tests, and high-performance size-exclusion chromatography. Two endotherms were found in studies of fresh and stored tortillas. The low temperature endotherm (50–56 °C) was due to reorganized (retrograded) amylopectin, while the high temperature endotherm (105–123 °C) was attributed to retrograded amylose. The enthalpy value for the lower temperature transition was minor than that of the high temperature transition. Fresh tortillas showed an amorphous starch arrangement by x-ray diffraction study. Stored samples showed the presence of peaks at 2θ = 17o and 23o, indicating re-crystallization of starch components. FTIR results confirmed the development of higher levels of starch crystals during storage. Differences in the viscoelastic parameters were also observed between fresh and stored samples. At the longest storage times, white tortillas were more rigid than blue tortillas. Molar mass values for starch increased for both white and blue tortillas as storage time progressed, though relatively higher values were obtained for white tortillas. More starch reorganization occurred in white tortillas, in accordance to calorimetric, x-ray diffraction, FTIR and rheological results. These results corroborate that changes occurring in tortillas during storage are related to reorganization of starch components, and the maize variety more than the color plays an important role.     

Synthesis of hydrophobic anthraquinoid magenta dyes having linear alkyl substituents

A new series of magenta dyes having different length of alkyl substituents was synthesized to dye unmodified polypropylene (PP) and ultra-high molecular weight polyethylene (UHMWPE) fiber. It could be concluded that the affinity of the dyes onto unmodified PP and UHMWPE fibers was increased with the increase of the length of alkyl substituents. The optimum length of alkyl group was determined as the longest dodecyl-substituted dye in this study. Their absorption spectra appeared almost the same at visible range, which meant that the length of alkyl substituents did not affect the color appearance of the dyes. The color fastness properties of the dyeings to washing, rubbing and light were good enough for commercialization.     

Synthesis and application of novel high light fastness red dyes for ultra high molecular weight polyethylene fibers

A new series of anthraquinoid red dyes were synthesized with 1-amino-2-bromo-4-hydroxyanthraquinone and nalkylphenols to dye UHMWPE fibers with high light fastness. Their dyeability was examined depending on the length of alkyl chains. As the length of alkyl substituents increases, the dyeability toward UHMWPE fibers improves rapidly from methyl to ethyl substituents and maintains almost same level of color strength, and then decreases from heptyl to octyl groups. The color strength of dyeings increased dramatically with the increase of dyeing temperature from 100 °C to 130 °C. The maximum build-up was shown at around 5 % owf dye amount. From the dyeing rate, equilibrium dyeing was achieved at around 5 h at 130 °C. All kinds of fastnesses were good enough showing higher than ratings 4-5 to washing and rubbing for the longer alkyl substituents. Especially, much improvement was achieved in light fastness showing ratings 4, which was higher than ratings 2 of the previous study.     

Coloration of ultra high molecular weight polyethylene fibers using alkyl-substituted anthraquinoid blue dyes

UHMWPE fibers were dyed with a series of anthrquinoid blue dyes having different length of alkyl substituents at general dyeing condition. The dyeability was investigated at various conditions and fastness of the dyeings was examined. As the length of alkyl substituents increased, the dyeability toward UHMWPE fibers tends to be improved gradually. Color strength of the fabrics was increased with the increase of dyeing temperature from 100 to 130 °C. From the dyeing rate, equilibrium dyeing at 130°C was achieved at 2–3 h. The tensile strength of UHMWPE fibers after dyeing at 130 °C for 1 h was maintained at a level of 95 % of untreated fiber. However, at prolonged dyeing time at 130 °C, the tensile strength was significantly decreased to a practically unacceptable level. The color fastnesses to washing, rubbing and light of the dyeings were very good showing higher than 4 ratings.     

Synthesis,structure, and thermal property of poly(trimethylene terephthalate-<Emphasis Type="Italic">co</Emphasis>-trimethylene 2,6-naphthalate) copolymers

Poly(trimethylene terephthalate-co-trimethylene 2,6-naphthalate)s (P(TT-co-TN)s) with various copolymer composition were synthesized, and their chain structure, thermal property and crystalline structure were investigated by using¹H-NMR spectroscopy, differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD), respectively. It was found from sequence analysis that all the P(TT-co-TN) copolymers synthesized have a statistical random distribution of TT and TN units. It was also observed from DSC thermograms that the glass transition temperature increases linearly with increasing the TN comonomer content, whereas the melting temperature of copolymer decreases with increasing the corresponding comonomer content in respective PTT- and PTN-based copolymer, showing pseudo-eutectic melting behavior. All the samples melt-crystallized isothermally except for P(TT-co-66 mol % TN) exhibit multiple melting endotherms and clear X-ray diffraction patterns. The multiple melting behavior originates from the dual lamellar population and/or the melting-recrystallization-remelting. The X-ray diffraction patterns are largely divided into two classes depending on the copolymer composition, i.e., PTT and PTNβ-form diffraction patterns, without exhibiting cocrystallization.     

Conductive polymer-coated threads as electrical interconnects in e-textiles

An organic polymer electrical interconnect is demonstrated. The ionomer mixture poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS; 1:2.5, w:w) was cast onto silk fibers from a 50:50 (v:v) ethylene glycol solution by a dip-coating process. Dynamic mechanical analysis (DMA) results show that Young’s modulus and mechanical strength are maintained during the coating process from acidic solution (pH ∼1). DMA dynamic temperature scans reveal two new thermal transitions once PEDOT:PSS is applied to the silk fiber, and they are assigned to the glass transition temperature (59 °C) and melting point (146 °C) of the ionomer pair. Electrical conductivities of 8.5 S/cm were achieved with four cycles of the dip-coating process, only 10x less than Ag-coated thread control samples. SEM imaging of the PEDOT:PSS-coated fibers show slight texturing to the fibers due to the coating, as well as significant charging in the uncoated samples when compared to PEDOT:PSS-coated samples. The conductive fibers fabricated by this process were successfully applied as electrical interconnects in flexible, fully functional 555 timer circuits stitched into fabric substrates.     

Effects of Alkyl Chain Length of Aliphatic Dicarboxylic Ester on Degradation Properties of Aliphatic-Aromatic Water-Soluble Copolyesters for Warp Sizing

In order to study the effects of alkyl chain length of aliphatic dicarboxylic ester (ADE) monomers on enzymatic and hydrolytic degradation properties of aliphatic-aromatic water-soluble copolyesters for warp sizing, dimethyl terephthalate, dimethyl isophthalate-5-sulfonic sodium, and ADE monomers with various alkyl chain lengths were copolymerized through a two-step method, i.e. transesterification and polycondensation. The enzymatic and hydrolytic degradation properties of the copolyesters were studied in terms of reduction rates of molecular weight, glass transition temperatures, and surface morphology after being cultivated for 24-96 h. It was found that, enzymatic degradation of the copolyesters strongly depended on alkyl chain length of ADE monomers. After being enzymatically degraded for 96 h, reduction rate of molecular weight of the copolyester using dimethyl malonate as ADE monomers could reach 22.2 %. Meanwhile, the hydrolytic degradation of the copolyesters was not directly related to the alkyl chain length.     

Dyeing characteristics of Nylon,cotton and N/C mixture fabrics with reactive-disperse dyes containing a sulphatoethylsulphone group

The dyeing and color fastness properties of three reactive-disperse dyes containing a sulphatoethylsulphone group on Nylon, cotton and N/C mixture fabrics were examined. Reduction-clearing was more effective in removing the unfixed dyes than soaping since the reactive-disperse dye became hydrophobic during dyeing process. Nylon was dyed well with three reactive-disperse dyes at pH 5∼8 and difference in chemical structure between dyes did not affect the final color strength of the dyed Nylon fiber, but their build-up properties on Nylon were not so good. The color strength of the dyed cotton was not as high as that of Nylon. The color strength of cotton increased by lowering dyeing temperature when the reactive-disperse dyes having hydroxy group were used. Nylon absorbed more dye molecules than cotton in simultaneous dyeing, the color difference between Nylon and cotton could be reduced as the dyeing temperature decreased. N/C mixture fabric was dyed well at 60 °C with the reactive-disperse dyes having hydroxyl group when applied at pH 7 and 60 °C, and their build-up properties were good. It was also found that washing fastness and rubbing fastness of dyed Nylon, cotton and N/C fabrics with the reactive-disperse dyes were excellent, while light fastness was moderate.     

Crystal structure and thermal properties of poly(vinylidene fluoride)-carbon fiber composite films with various drawing temperatures and speeds

PVDF-CF composite films were prepared using a melt pressing method. The PVDF-CF composite films were cut into rectangular shapes with a gauge length and width of 10 and 5 mm, respectively. The films were drawn using a universal testing machine equipped with a hot chamber. The drawing temperatures and speeds were 50∼150 °C and 100∼000 %/min, respectively. The crystal structure and physical properties of the resulting PVDF-CF films were investigated by wide angle X-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis and scanning electron microscopy. The crystal form of the initial films was the 〈alpha〉 phase (non polarity, lamellar structure) of PVDF. The maximum draw ratio was 4.2. The drawn PVDF-CF films prepared at 100 °C were mainly the 〈beta〉 phase (polarity, fibrillar structure) of PVDF. With increasing drawing speeds, the 〈alpha〉 phase became the dominant phase of PVDF in the PVDF-CF films. The thermal properties of the PVDF-CF films improved with increasing drawing temperature, and the dynamic mechanical properties improved with increasing drawing speed.     

Preparation and properties of polypropylene nanocomposites reinforced with exfoliated graphene

We have prepared a series of polypropylene/exfoliated graphene (PP/EG) nanocomposite films via efficient meltcompounding and compression, and investigated their morphology, structures, thermal transition behavior, thermal stability, electrical and mechanical properties as a function of EG content. For the purpose, EG, which is composed of disordered graphene platelets as reinforcing nanoscale fillers, is prepared by the oxidation/exfoliation process of natural graphite flakes. SEM images and X-ray diffraction data confirm that the graphene platelets of EG are well dispersed in PP matrix for the nanocomposites with EG contents less than 1.0 wt%. It is found that thermo-oxidative degradation of PP/EG nanocomposites is noticeably retarded with the increasing of EG content. Electrical resistivity of the nanocomposite films was dramatically changed from ∼10¹⁶ to ∼10⁶ Ω·cm by forming electrical percolation threshold at an certain EG content between 1 and 3 wt%. Tensile drawing experiments demonstrate that yielding strength and initial modulus of PP/EG nanocomposite films are highly improved with the increment of EG content.     

Structure development and dynamic properties in high-speed spinning of high molecular weight PEN/PET copolyester fibers

The structure development and dynamic properties of fibers produced by high-speed spinning of P(EN-ET) random copolymers were investigated. The as-spun fibers were found to remain amorphous up to the spinning speed of 1500 m/min, and subsequent increases in speed resulted in the crystalline domains containing primarilyα crystalline modification of PEN. Theβ modification was not found up to spinning speeds of 4500 m/min. On the other hand, annealing of constrained fibers spun at the 2100 m/min at 180, 200, and 240°C exhibitedβ-form crystalline structure, while the annealed fibers spun in 600–1500 m/min range exhibited dominantlyα-form. Howeverβ-form crystals disappeared above the spinning speed of 3000 m/min. With increasing spinning speeds from 600 to 4500 m/min, the storage modulus of as-spun fibers increased continuously and reached a value of about 10.4 Gpa at room temperature. The tanδ curves showed theα-relaxation peak at about 155–165°C, which is considered to correspond to the glass transition. Theα-relaxation peaks became smaller and broader, and shift to higher temperatures as the spinning speed increases, meaning that molecular mobility in the amorphous region is restricted by increased crystalline domain.