Synthesis of a novel flame retardant containing phosphorus-nitrogen and its comparison for cotton fabric

A new charring agent, a derivative of cyanuric chloride, mono-substituted, dimethyl (4,6-dichloro-1,3,5-triazin-2-yloxy)methylphosphonate (CN), was synthesized in good yield and characterized. Its flame retardant and thermogravimetric properties were compared to those of the di-substituted compound, tetramethyl (6-chloro-1,3,5-triazine-2,4-diyl)bis(oxy)bis (methylene)diphosphonate (CN-1), which was prepared in previous work. All untreated fabric showed limiting oxygen index (LOI) values of about 18 vol% oxygen in nitrogen. Fabrics treated with CN at 5?C21 wt% add-ons had high LOI values of 30?C40 vol%, while fabrics treated with CN-1 at 5?C19 wt% add-ons had low to high LOI value of 20?C36 vol%. In 45° angle flammability tests, all treated fabrics with CN and CN-1 were passed and some fabrics were not igniting at all. Thermal degradation revealed that onset of degradation and the char yield of CN compound is higher than that of CN-1. Treated fabric with CN, 21 wt% add-on, had an onset of degradation of 240 °C, while fabric treated with CN-1, 19 wt% add-on displayed an onset of degradation of 230 °C. Despite the differences in onset temperature, the two samples provided almost the same char yield at 600 °C, 35 and 36 %. With Fourier transform infrared (FTIR), samples of treated/unburned and treated/burned of CN and CN-1 showed the same functional groups and revealed the disappearance of triazine group and P-O-methyl after burning. Additionally, scanning electron microscopy (SEM) showed that both CN and CN-1 acted as flame retardants by the same mechanism and characterized the surface morphology of the flame retardant treated twill fabrics.     

Preparation and characterization of intumescent flame retardant biodegradable poly(lactic acid) nanocomposites based on sulfamic acid intercalated layered double hydroxides

A novel sulfamic acid intercalated MgAl-LDH (SA-LDH) was prepared by intercalating NH₃SO₃^? into MgAl-layered double hydroxides (LDH), and it was then introduced into poly(lactic acid) (PLA) resin in association with intumescent flame retardant (IFR) by melt blending to prepare a flame-retardant biodegradable PLA composite. The effects of SA-LDH on the flame retardancy of PLA composites were characterized by limiting oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter test (CONE). The results showed that the composite sample containing 19.0 wt% IFR and 1.0 wt% SA-LDH achieved the maximal LOI value of 48.7 %, passed the UL-94 V-0 rating, and significantly decreased the peak heat release rate from 306.3 kW/m² of neat PLA to 58.1 kW/m². Thermogravimetric analysis showed that both the thermal stability and the char formation were enhanced. The char morphology observation revealed that SA-LDH was beneficial to form dense and compact char layers. It was demonstrated that there existed a synergistic effect between IFR and SA-LDH in promoting the char formation and enhancing the fire resistance. The mechanical and crystallization properties were also tested and discussed.     

A novel DDPSi-FR flame retardant treatment and its effects on the properties of wool fabrics

A novel flame retardant monomer DDPSi-FR containing organophosphorus and silicon was prepared using 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-hydroxybenzaldehyde (HBA), and 3-glycidoxypropyltrimethoxysilane (GPTMS). The chemical structure of DDPSi-FR was characterized by Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). Subsequently, after treating the wool fabrics, the effects of the monomer on the flame retardancy, thermal stability, and mechanical properties were studied. The flame retardant and thermal properties were evaluated by conducting vertical flame tests, limiting oxygen index (LOI) determination, and thermogravimetric analysis (TGA). The results showed that improved flame retardancy and thermal stability were achieved. Notably, the flame retardancy was retained even after 15 washing cycles. The mechanical properties were evaluated using the bursting strength, and the results indicated that DDPSi-FR treatment improved the breaking strength.     

Preparation and characterization of fire resistant PLA fibers with phosphorus flame retardant

The fire resistant poly(lactic acid) fibers with polysulfonyldiphenylene phenyl phosphonate flame retardant were prepared by melt spinning. The rheology property and spinnability of samples were measured by a capillary rheometer and recording the number of fiber breakage during a 30-min melt spinning. The thermal stability and combustion behaviors of fibers were investigated by Thermogravimetric Analysis, Limiting Oxygen Index and Vertical Burning tests, respectively. It was found that the flame retardation and anti-dripping performance of PLA were distinctly improved by OP. The pyrolysis behavior of fibers was tested by a Pyrolysis-Gas Chromatography-Mass Spectrometry, the structure and degree of graphitization of char residue were analyzed by Scanning Electronic Microscopy and Raman Spectroscopy. The results suggested that OP can promote the forming of char layer on the surface of PLA matrix during burning. The miscibility and spinnability of PLA was negatively affected by OP and the breaking strength of FR-PLA fibers dropped from 3.30 to 2.30 cN/dtex at the presence of 10 wt. % OP.     

Sound absorbent,flame retardant warp knitting spacer fabrics: Manufacturing techniques and characterization evaluations

This study proposes a combination for reciprocal reinforcement between warp knitting spacer fabrics and PU foams. PET/Kevlar nonwoven fabrics are made with an 80:20 ratio and an incorporation of various needle-punching speed of 100, 150, 200, 250, and 300 needles/min. Ascribing to having an optimal bursting strength, sound absorption coefficient, and limited oxygen index (LOI), the PET/Kevlar nonwoven fabric that is made by 200 needles/min are selected to be combined with a glass-fiber fabric by applying needle punch in order to form a surface layer. Next, warp knitting spacer fabrics and the nonwoven fabrics are laminated, followed by being combined with polyurethane (PU) foam that are featured with different densities of 200, 210, 220, 230, and 240 kg/m³ in order to form spacer fabric/PU foam composites with multiple functions. The composites are then tested with a drop-weight test, a compression test, a bursting strength test, a sound absorption test, and a horizontal burning test. The test results indicate that all spacer fabric/PU foam composites reach a horizontal burning level of HF1, and their sound absorption coefficients at 2500-4000 Hz also suggest a satisfactory sound absorption. In particular, the optimal residual stress and compressive strength are present when the composites contain 210 kg/m³ PU foam. Similarly, the optimal bursting strength of the composites occurs when they are composed of 230 kg/m³ PU foam. The spacer fabric/PU foam composites are proven to have high strengths, sound absorption, and fire retardant, and thus have promising potentials for use as construction materials and light weight composite planks.     

Synthesis of core-shell fluorinated acrylate copolymers and its application as finishing agent for textile

Core-shell fluorinated acrylate copolymers emulsion was thus synthesized via the core-shell emulsion polymerization with the fluorinated monomers and acrylic monomers as the main raw materials and its properties were studied. PFMA, the fluorinated acrylate monomers, was synthesized by the esterification of perfluorooctanoyl chloride (PFOC) and hydroxypropyl methacrylate (HPMA). Then the core-shell fluorinated acrylate copolymers emulsion with a poly(MMA/BA/St) core and a poly(PFMA/MMA/BA) shell was synthesized via a starved semi-continuous core-shell emulsion polymerization method by using KPS and sodium bicarbonate as the initiator/buffer system and SDS/Twain 80 as the commixture emulsifier. Lastly, the synthesized copolymers was applied as textile finishing agent for cotton textile. The results of FT-IR and NMR indicated that PFMA had been synthesized as expected and effectively combined in the emulsion copolymerization. The GPC, zeta potential, TEM and DSC showed that the particles had uniform spherical core-shell structure with a diameter of 65-150 nm, and the distribution and emulsion stability was satisfactory. As XPS, FESEM and AFM shown, a hydrophobic structure which was similar to the structure of the lotus leaf were formed and the surface hydrophobicity of the films can be improved. Based on the analysis of DSC, thermal stabilities of the films were enhanced with the increase of fluorine content. Besides, FESEM of textiles showed that the surface of treated textiles were smooth and the edges were clear and visible, indicating significant improvement of the performance on water and oil repellent.     

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.     

Kinetics of non-isothermal decomposition and flame retardancy of goatskin fiber treated with melamine-based flame retardant

Fire-retardant fiber was prepared from goatskin fiber by treating with a melamine-based flame retardant. Kissinger and Flynn-Wall-Ozawa methods were used for analyzing the thermo-gravimetric data obtained from the goatskin fiber and the fire-retardant fiber at different heating rates. Kinetic parameters were calculated from the thermo-gravimetric data at different heating rates. Activation energies obtained using the Kissinger and Flynn-Wall-Ozawa methods were 154.57 kJ/mol and 158.45 kJ/mol, respectively, for the goatskin fiber and 210.15 kJ/mol and 212.52 kJ/mol, respectively, for the fireretardant fiber. The oxygen index of the fire-retardant fiber treated with 4 wt% melamine-based flame retardant increased significantly to a value of 31.7 %. The thermal stability and the flame retardant property of the fire-retardant fiber were improved significantly.     

Synthesis and characterization of novel self-colored PET (polyethylene terephthalate) by step-growth polymerization containing dye based on 1,8-naphthalimide group

A novel self-colored polyethylene terephthalate (PET) was synthesized using a synthesized dye, 4-amino-N-propanoic acid-1,8-naphthalimide. For this purpose, the prepared naphthalimide dye was added upon the polycondensation step and then a self-colored PET was prepared by step-growth polymerization. The characterization of synthesized self-colored PET and naphthalimide dye were carried out using TLC, FTIR, ¹HNMR, DSC, UV-visible and Fluorometery. Results indicated that, the novel fluorescent yellow-green PET with appropriate properties was obtained. The glass transition temperature of self-colored PET was 70 °C and it was measured by differential scanning calorimeter, which revealed that addition of dye to the chains of polymer did not affect the context of glass transition of polymer. UV-visible spectrum indicated that, 99 percent of dye was incorporated in polymer chains chemically. Furthermore, the intrinsic viscosity of self-colored PET was 0.556 dl/g and molecular weight of polymer was around 35000 (g/mol) and measured using the viscometer technique.     

Synthesis of urethane polycarboxylate as a novel adsorbent and its binary system dye removal ability from aqueous solution

In this paper, urethane polycarboxylate (UPC) as a novel adsorbent was synthesized and characterized. Dye removal ability of UPC from aqueous solution of single and binary systems was studied. Fourier transform infrared (FTIR) was used to characterize UPC. Basic Blue 41 (BB41), Basic Red 18 (BR18), and Basic Violet 16 (BV16) were used as cationic dyes. Dye removal isotherm and kinetic were evaluated. The effect of UPC dosage, initial dye concentration, and inorganic anions on dye removal was investigated. The capacity of UPC to remove BB41, BR18, and BV16 were 333 mg/g, 278 mg/g, and 222 mg/g, respectively. Dye removal kinetics and isotherm using UPC were fitted with the pseudo-second order and Langmuir model, respectively. The results showed the UPC might be used as a dye adsorbent to treat multicomponent systems containing cationic dyes.     

Synthesis and characterization of novel biocompatible four-arm star-shaped copolymers by using a new tetramethacrylate core

The objective of this study was to synthesize and characterize two novel four-arm star-shaped copolymers of N-isopropylacrylamide (NIPAAm), methacrylic acid (MAA), N,N-(dimethylamino) ethyl methacrylate (DMAEMA) and 1-vinyl-2-pyrrolidone (VP) that was initiated from a new tetramethacrylate monomer (TMAM) as the core by the free radical polymerization approach. Novel multiacrylic monomer was synthesized via three key consecutive reactions. All the intermediates and the final product have been fully characterized. The polymerization reaction was conducted by the core first method and the star-shaped copolymers were analyzed by FT-IR, ¹H NMR and Thermo-Gravimetric Analysis (TGA). MTT assay was used to evaluate in vitro cytotoxicity of the star copolymers on lung cancer cell lines. These star copolymers showed no in vitro cytotoxicity to A549 cells. The results showed that these copolymers can be promising drug carriers because they showed no in vitro cytotoxicity and they have various functional groups for association and interaction with drugs.     

Highly flame retardancy of cotton fabrics with a novel phosphorus/nitrogen/silicon flame-retardant treating system

A novel reactive flame retardant (FR) containing phosphorus, nitrogen, and silicon was synthesized successfully, and its chemical structure was fully characterized by Fourier transform infrared spectrometry and nuclear magnetic resonance spectrometry (¹H-NMR and ³¹P-NMR). Then it was used to impart flame resistance to cotton fabrics. Vertical flammability and limiting oxygen index test were used to evaluate the flame retardancy of the cotton fabrics treated with FR. When the cotton treated with 150 g/l FR and 50 g/l sodium hypophosphite, the finished cotton can pass the vertical flammability test. Thermogravimetry (TG) was used to evaluate thermal behavior of FR and cotton fabrics. TG results demonstrated that the FR has good thermostability and char-forming ability. After treatment with FR, the thermal stability of the cotton fabrics was clearly improved, indicating that the FR can protect cotton fabric from fire to a certain degree. Furthermore, attenuated total reflection Fourier transform infrared spectroscopy was utilized to characterize the chemical structure of FR treated cotton fabrics. Finally, the surface morphology in different regions of the treated cotton was observed using scanning electron microscopy.     

Synthesis and characterization of novel reactive dyes with simultaneous insect-repellent and anti-bacterial properties

N,N-Diethyl-m-toluamide (DEET) is widely used as an insect-repellent. Sulfonamides are an important class of anti-bacterial drugs. In order to combine the strength of anti-bacterial activities of sulfonamides and insect-repellent property of DEET, three azo reactive dyes were designed and synthesized. To do this, the diazoniom salts of sulfonamides viz. 4-amino-N-(4-methyl-2-pyrimidinyl) benzene sulfonamide, 4-amino-N-(4-dimethyl-2-pyrimidinyl) benzene sulfonamide and 4-amino-N-(4,6-dimethyl-2-pyrimidinyl) benzene sulfonamide were prepared using HCl and NaNO₂. The resulting diazoniom salts were then coupled to the coupling component containing N,N-diethyl-m-toluamide to produce the novel dyes. The synthesized dyes were filtered off and then purified. To investigate and analyze the dyes, analytical methods such as ¹H-NMR, FTIR, UV-visible spectroscopy, and elemental analysis were used. Consequently, the anti-bacterial activities of dyes were measured with E. coli and P. aeruginosa as a Gram-negative strain and S. aureus and S. mutans as a Gram-positive strain according to MIC method. The insect-repellent efficacy of the dyes was studied using standard methods for Anophle mosquito repellent. The results confirmed anti-bacterial and insect-repellent activity of the dyes.     

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 of a dodecylphenylsiloxane oligomer resin/silica nanocomposite and its application to cotton fabrics

A novel dodecylphenylsiloxane oligomer resin/nanocomposite (PHDESR-SiO₂) was prepared by graft copolymerization between dodecyl modified phenylsiloxane resin with pendent epoxy groups (PHDESR) and amino-functionalized silica nanoparticles (BTEPA-SiO₂). PHDESR-SiO₂ was then used to prepare a super hydrophobic surface on cotton fabric by a facile solution-immersion process method. Chemical structures, chemical compositions, wettability, surface morphology, and thermal properties were investigated by Fourier Transform Infrared Spectrum (FT-IR), ¹H-NMR spectrum, X-ray photoelectron spectroscopy (XPS), static contact angle analyzer, scanning electron microscopy (SEM), Particle size distribution (PSD) and thermo-gravimetric analysis (TGA). The results showed that the target product PHDESR-SiO₂ has an anticipative structure with many micro/nanostructure tubercles, a cross-linked network hydrophobic organosilicon resin film and many clusters of cylindrical dodecyl molecular brushes. This created super hydrophobic structure on the surface of the treated cotton fabrics. XPS analysis indicated that the long carbon chain groups had a slight tendency to enrich the film-air interface. In addition, PHDESR-SiO₂ can provide good hydrophobicity for the treated fabric. As the dose of PHDESR-SiO₂ increased, the hydrophobicity of the treated fabric enhanced and consequently the water static contact angle reached 152.5 °. This had little influence on the softness, color, and gas permeability of the fabrics. This makes it slightly stiff at high doses, and the super-hydrophobic cotton fabric also had good launderability.     

Synthesis, characterization and application of quinazolinone based reactive dyes for various fibers

Seven hot brand heterocyclic mono azo reactive dyes (7a–g) have been synthesized by coupling diazotized 2-phenyl-3{4′-[(4″-aminophenyl)sulphonyl]phenyl}-quinazoline-4(3H)-one-6-sulphonic acid (4) with various 2-chloro-4-nitro anilino cyanurated coupling components (6a–g) and their dyeing performance on silk, wool, and cotton has been assessed. The purity of dyes was checked by thin layer chromatography. These dyes were identified by recording IR and ¹H-NMR spectra. The λ _max, R _f value, %exhaustion, %fixation, light fastness, wash fastness, rubbing fastness, reflectance (%R) value, and K/S value have also been studied.     

Miscibility of flame retardant epoxy resin with poly(ethylene terephthalate) and the characterizations of the blends

Epoxy resin containing bromine compound was melt blended with PET to obtain flame retardant polymer. The blend product was characterized by DSC, SEM, intrinsic viscosity and melt index measurements. The reaction between the epoxy group of DGEBBA (diglycidyl ether of brominated bisphenol A) and the carboxyl (or hydroxyl) end group of PET led to cross-linking of PET chains, and the intrinsic viscosity and melt index (MI) were increased in the range of equivalent amount of epoxy resin (within 1 %). DSC data revealed that the epoxy resin was not located in the crystalline region but was appeared in the amorphous region of PET matrix. Good miscibility of epoxy resin resulted in the decrease of crystallization temperature and glass transition temperature of PET. The blend was spun into fiber without any problems such as swelling or draw resonance, however, the mechanical properties were decreased as the amount of the DGEBBA was increased.     

Relationship between curing temperature and low stress mechanical properties of titanium dioxide catalyzed flame retardant finished cotton fabric

N-methylol dimethylphosphonopropionamide is a flame-retardant agent commonly combined with melamine resin and phosphoric acid catalyst to impart flame-retardant property to cotton fabrics. A co-catalyst titanium dioxide (TiO₂) is added into the formulation in order to improve the flame-retardant performance by enhancing the crosslinking reaction and physically attaching on to cotton fabrics. The fabrics cured at temperature of 150 °C and 170 °C have a better flame-retardant ability and can withstand multiple times of home laundering compared with those cured at temperature of 110 °C and 130 °C. The flame-retardant ability is further enhanced by treating the fabrics in the presence of TiO₂. In addition, the low stress mechanical properties measured by Kawabata Evaluation System for Fabric (KES-F) are altered after flame-retardant treatment. These changes are contributed by the formation of crosslinks after treatment, acid-catalyzed depolymerization in a strong acidic medium and the presence of co-catalyst TiO₂. In addition, the properties of cotton fabrics depend greatly on the choice of curing temperature. High curing temperature usually caused poor hand properties of the fabrics due to the extensive crosslinks formation. Lastly, the existence of TiO₂ in the treatment not only improves the reaction efficiency but also has positive enhancement with respect to compressional recovery ability and tensile properties.     

Encapsulation of phase change materials by complex coacervation to improve thermal performances and flame retardant properties of the cotton fabrics

This paper reports a study on the thermal stability and flame-retardant properties of microencapsulated phase change materials (PCMs) with clay nano-particles (Clay-NPs) doped gelatin/sodium alginate shell. The novel microcapsules were fabricated by the technique of complex coacervation using gelatin and sodium alginate as the shell and PCM n-eicosane as the core. Their flame retardant property as well as their practicable thermal performances when incorporated into woven cotton fabrics by pad-dry-cure were investigated. Thermal storage/release properties of the prepared microcapsules were analyzed using DSC instrument. Thermal gravimetry (TG) analysis was performed to measure the thermal stability and surface morphology of the microcapsules was observed by means of optical microscopy and SEM. The DSC results indicated that the latent heat storage capacity of prepared microcapsules changed in range of 97-114 J/g. The microcapsules had spherical shape with particle sizes between 1.37 μm and 1.6 μm. The PCM microcapsules (PCMMs) and nano-composite PCM microcapsules (NCPCMMs) with clay-NPs doped gelatin/sodium alginate shell were found to have good potential for developing thermal comfort in textiles. Comparing with conventional PCMMs, NCPCMMs have significantly better thermal stability. Nano-composite structure of the NCPCMMs, in which clay-NPs doped in the polymeric shell structure, attributed to increase the shell thermal stability. Improved flame retardant properties of the cotton fabrics treated with NCPCMs were declared as a result of flame retardant tests. Thermo-regulating properties of the fabrics were proved by thermal history (THistory) measurement results from releasing heat from microcapsules.