Combination of a hydroxy‐functional organophosphorus oligomer and a multifunctional carboxylic acid as a flame retardant finishing system for cotton: Part II. Formation of calcium salt during laundering

Multifunctional carboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid (BTCA), were used to bond a hydroxy‐functional organophosphorus oligomer (FR) to cotton fabric in the presence of a catalyst, such as sodium hypophosphite (NaH₂PO₂). Previously, it was found that the cotton fabric treated with FR and BTCA showed a high level of phosphorus retention after one home laundering cycle. However, the flame retardant properties quickly deteriorated as the number of home laundering cycles was increased. In this research, it was found that the free carboxylic acid groups bound to the cotton fabric form an insoluble calcium salt during home laundering, thus diminishing the flame retardant properties of the treated cotton fabric. It was also found that the free carboxylic acid groups on the treated cotton fabric were esterified by triethanolamine (TEA), and that the formation of calcium salt on the fabric was suppressed by the esterification of the free carboxylic acid groups by TEA. The cotton fabric treated with BTCA and the hydroxy‐functional organophosphorus oligomer significantly improved its flame retardance when a new catalyst system consisting of hypophosphorous acid (H₃PO₂) and TEA was used in the system. Copyright © 2003 John Wiley & Sons, Ltd.     

Flame retardant finishing of cotton fleece fabric: Part V. Phosphorus‐containing maleic acid oligomers

The high flammability of cotton fleece makes it necessary to apply a flame retardant system on cotton fleece so that it can meet the federal regulation ‘Standard for the Flammability of Clothing Textiles’ (16 CFR 1610). The objective of this research was to reduce the flammability of cotton fleece using the phosphorus‐containing maleic acid oligomers (PMAO) synthesized by aqueous free radical polymerization of maleic acid. We found that PMAO can be bound to cotton fleece by esterifying with cotton cellulose with sodium hypophosphite as the catalyst. Both the 45^° flammability and limiting oxygen index data indicated that the treatment of cotton using PMAO reduced the flammability of cotton fleece. The micro‐scale combustion calorimetric data revealed that PMAO reduced the peak heat release rate and heat release capacity of the treated cotton woven fabric. The cotton fleece treated with PMAO/NaH₂PO₂ passed the federal flammability test (16 CFR Part 1610) and achieved ‘Class 1’ flammability. The PMAO bound to cotton was durable to multiple home laundering cycles. The treated fleece also showed high strength retention with little change in fabric whiteness. The use of triethanolamine as an additive modestly enhanced the performance of PMAO with no significant changes in fabric physical properties. Copyright © 2009 John Wiley & Sons, Ltd.     

Polymeric multifunctional carboxylic acids as crosslinking agents for cotton cellulose: Poly(itaconic acid) and in situ polymerization of itaconic acid

Multifunctional carboxylic acids have been used as nonformaldehyde durable press finishing agents for cotton. In previous research we found that maleic acid (MA) and itaconic acid (IA) polymerize in situ on cotton fabric at elevated temperatures when both potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂) are present, thus imparting wrinkle resistance to the treated cotton fabric. We also found that MA and IA polymerize in aqueous solutions in the presence of K₂S₂O₈ and NaH₂PO₂. In this research, we compared the effectiveness of poly(itaconic acid) (PIA) applied to cotton fabric as a polymer and IA applied as a monomer and allowed to polymerize in situ for crosslinking cotton cellulose. We found that IA is more effective in esterifying cotton cellulose and imparting a high level of wrinkle resistance to the fabric as it polymerizes in situ than PIA applied as a polymer. We also found that tensile strength loss of the cotton fabric crosslinked by IA polymerizing in situ as a function of fabric wrinkle recovery angle is practically the same as that crosslinked by PIA applied as a polymer. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 319–326, 2001     

Thermogravimetric Analysis of a Cellulosic Fabric Incorporated by Synthetic Ammonium Magnesium Phosphate as a Flame-Retardant

We have investigated the effect of synthetic struvite (MgNH₄PO₄·6H₂o) on the flammability of a cellulosic fabric. It was synthesized by means of the multiple-bath method and deposited onto a cotton fabric. Its uniformity was ensured by means of squeeze rolls, obtaining the optimum effective add-on value of ammonium magnesium phosphate to impart flame retardancy to cotton fabric in the range of around 12 g anhydrous salt per 100 g fabric. A thermogravimetric analysis of pure cotton, treated cotton, and the salt was accomplished, and their thermograms were compared and commented upon. The results obtained fortified the chemical theory expressing the promotion of the formation of solid char rather than the formation of volatile pyrolysis products, during the fulfillment of thermal decomposition of the cellulosic substrate.     

Flame retardancy for cotton cellulose treated with H3PO3

The flame retardancy of cotton fabrics has been improved with treatment of phosphorous aqueous solution. In this study, cotton cellulose is treated with simple treatment and benign chemicals including an aqueous H₃PO₃ solution dipping and heat annealing. The flame retardancy of the H₃PO₃ treated cotton fabrics is enhanced to the degree that it is non‐flammable. Thermogravimetric analysis results show that the residue increased up to about 50% at 800 °C by the treatment. Scanning electron microscopy exhibit some disconnection of fibers and the fibers are fragile. X‐ray diffractometry reveal little damage to the crystalline structure of cellulose. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy show some portion of the added H₃PO₃ reacted with cellulose components to be phosphorylated and dehydrated. The resulting data and analysis demonstrate that these dehydrated and phosphorylated moieties formed by treatment of phosphorous solution help accelerate the formation of char components, resulting in improved flame retardancy of cellulose materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46497.     

Morphology,mechanical, and physical properties of wet-spun cellulose acetate fiber in different solvent-coagulant systems and in-situ crosslinked environment

Wet spinning is a popular fiber manufacturing process where the effects of solvent and coagulant on the wet-spun fiber are significant. In this study, we have explored the effect of solvent-coagulant interaction and in-situ crosslinking on the wet-spun cellulose acetate (CA) fiber. Investigation on 12 different solvent-coagulant systems revealed that variation in the systems resulted in significant variance in morphology and mechanical property of the fiber. Remarkable increase in mechanical property was observed after in-situ crosslinking with citric acid and polyethylene glycol (PEG). Inclusion of sodium hypophosphite (NaH₂PO₂) as catalyst further increased tensile modulus (~407%) and crystallinity index (~46%) compared to CA fiber crosslinked with only citric acid. It was established that fiber from CA-DMSO solution crosslinked with 10% citric acid and 10% PEG extruded in ethanol showed the highest tensile modulus (~30 MPa). This in-depth study found an appropriate combination of solvent-coagulant for forming stable CA fiber, with the addition of crosslinkers and catalyst further increasing the strength and usability of the fiber.     

Effect of chicken‐feather protein‐based flame retardant on flame retarding performance of cotton fabric

A new kind of eco‐friendly chicken‐feather protein‐based phosphorus–nitrogen‐containing flame retardant was synthesized successfully with chicken‐feather protein, melamine, sodium pyrophosphate, and glyoxal. And its structure was characterized by Fourier transform infrared spectroscopy, and the thermogravimetry of the agent was analyzed. Then the flame retarding performances of the chicken‐feather protein‐based flame retardant and in combination with the borax and boric acid in application to a woven cotton fabric were investigated by the vertical flammability test and limited oxygen index test. In addition, the surface morphologies of the treated and untreated fabrics were conducted by the scanning electron micrographs (SEM), and the thermogravimetric analyses of the treated and untreated cotton were explored, and the surface morphologies of char areas of the treated and untreated fabrics after burnt were tested by the SEM. The results showed that the flame retardancy of the cotton fabric treated by the chicken‐feather protein‐based flame retardant in combination with borax and boric acid was improved further, and the combination of the chicken‐feather protein‐based flame retardant and borax and boric acid could facilitate to form a homogenous and compact intumescing char layer, and the combination of them plays a good synergistic effect in the improvement of the flame retardancy of the treated cotton fabric. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40584.     

Synthesis of a novel organic–inorganic hybrid flame retardant based on Ca(H2PO4)2 and hexachlorocyclotriphosphazene and its performance in polyvinyl alcohol

To optimize the poor thermal stability and flammable of polyvinyl alcohol (PVA), a novel environmental-friendly organic–inorganic hybrid flame retardant Ca(H₂PO₄)₂@HCCP was successfully designed and synthesized via surface treatment technology and used to advance the flame retardancy of PVA. The thermogravimetric analysis implied that Ca(H₂PO₄)₂@HCCP can enhance significantly the thermal stability and char forming ability of PVA. Combustion results demonstrate that Ca(H₂PO₄)₂@HCCP could effectively suppress the melt dripping of PVA in the process of combustion. The presence of Ca(H₂PO₄)₂@HCCP can sharply reduce peak heat release rate and the total heat release up to 75% and 22.9%, respectively, in the microscale combustion calorimeter measurement. The results manifested that Ca(H₂PO₄)₂@HCCP could endow PVA with superior flame retardancy. Moreover, char residues analysis explained the flame retardant mechanism in condensed and gas phase, which is mainly attributed to the strong catalytic char formation, free radical trapping, and gas barrier effect. Therefore, the green flame retardant has great applications prospect in fire safety.     

Voltammetric behaviour of platinum in aqueous solutions containing sodium hypophosphite

The anodic and cathodic behaviour of polycrystalline Pt in sodium hypophosphite solutions has been investigated by cyclic voltammetry. In acid solutions the voltammograms show that, owing to the presence of the reducing agent, electrooxidation of species related to H₃PO₃ occurs in the potential range 0.6 to 1.4 V with respect to NHE. In alkaline solutins the presence of NaH₂PO₂ partially inhibits the HER and displaces the formation of the oxygen monolayer on platinum to higher potentials. The voltammetric peaks are attributed to the electrooxidation of the products resulting from the chemical decomposition of NaH₂PO₂ in contact with the Pt surface.     

Polymerization of maleic acid and itaconic acid studied by FT‐Raman spectroscopy

In this research, we used a new redox free radical initiation system consisting of potassium persulfate (K₂S₂O₈) and sodium hypophosphite (NaH₂PO₂). In the presence of NaH₂PO₂, the thermal decomposition of K₂S₂O₈ is accelerated, and the temperature required for the formation of free radical is reduced. We polymerized maleic acid (MA) using the K₂S₂O₈/NaH₂PO₂ initiation system in an aqueous solution, and monitored the polymerization process with FT‐Raman spectroscopy. The Raman spectroscopy data indicate the formation of a saturated carboxylic acid with the disappearance of the characteristic bands of MA as the thermal decomposition of K₂S₂O₈ progresses, thus indicating the formation of poly(maleic acid) (PMA). We also found that itaconic acid (IA) polymerizes in the presence of the new initiation system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 223–228, 2001     

Pretreatment of cotton fabrics with polyamino carboxylic acids for salt‐free dyeing of cotton with reactive dyes

In this study, polyamino carboxylic acids have been used to improve the dyeability of cotton in a salt‐free reactive dyeing process. These polyamino carboxylic acids were prepared by partial carboxylation of polyvinylamine. Cotton fabric was pretreated with polyamino carboxylic acids and dyed with reactive dyes. The colour strengths of the dyed fabrics were evaluated by measuring the K/S values. The fastness properties (washing, rubbing and light fastness) of the dyed cotton fabrics were also measured. The pretreatment of cotton with polyamino carboxylic acids creates positive charges on the fabric surface. In this way, salt‐free reactive dyeing of cotton or dyeing with only a small amount of electrolyte is possible.     

Combination of a hydroxy‐functional organophosphorus oligomer and a multifunctional carboxylic acid as a flame retardant finishing system for cotton: Part I. The chemical reactions

Multifunctional carboxylic acids, such as 1,2,3,4‐butanetetracarboxylic acid (BTCA), have been used as crosslinking agents for cotton cellulose to produce wrinkle‐resistant cotton fabrics and garments. Polycarboxylic acids were used to bond hydroxy‐functional organophosphorus oligomer to cotton, thus imparting durable flame retarding properties to the cotton fabric. This research investigated the chemical reactions between the hydroxy‐functional organophosphorus compound and BTCA on cotton. BTCA crosslinks cotton cellulose through the formation of a 5‐membered cyclic anhydride intermediate and esterification of the anhydride with cellulose. In the presence of the organophosphorus compound, BTCA reacts with both the organophosphorus compound and cellulose, thus functioning as a binder between cotton cellulose and the organophosphorus compound and making the flame retarding system durable to laundering. The cotton fabric treated by the combination of the organophosphorus compound and BTCA demonstrated lower wrinkle resistance and less tensile strength loss than that treated by BTCA alone. The phosphorus retention on the cotton fabric after one home laundering cycle was approximately 70%. Copyright © 2003 John Wiley & Sons, Ltd.     

Thermal and flammability studies of poly(vinyl alcohol) composites filled with sodium hydroxide

Poly(vinyl alcohol) (PVA) is a polymer of great value due to its wide spread applications. The present article describes the effect of sodium hydroxide on the flammability, thermal degradation, and tensile strength properties of PVA. The PVA/sodium hydroxide composite films at different loading levels of sodium hydroxide, i.e., 0.5, 1, 2, 3, and 4.5 wt % were prepared by solution casting technique. Dynamic thermogravimetry was used to study the thermal degradation behavior of samples at four different linear heating rates, i.e., 2.5, 5, 10, and 20 °C min^?1 under nitrogen atmosphere. The degradation activation energy values were calculated using reliable and preferred multiple‐heating rate methods. Limiting oxygen index (LOI) and UL 94 tests were carried out to check the flammability behavior of the samples. The presence of sodium hydroxide in PVA brought significant changes in the thermal and flammability performance. PVA/sodium hydroxide samples though showed lower initial decomposition temperature, but overall more thermal stability results as evidenced from the higher activation energy and char residue values. LOI and UL 94 tests indicate that sodium hydroxide greatly enhanced the flame retardancy of PVA/sodium hydroxide films. Based on the thermal and flammability level, the optimum concentration of sodium hydroxide is worked out. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of particle size on the flame retardancy of poly(butylene succinate)/Mg(OH)2 composites

Poly(butylene succinate)/magnesium hydroxide (PBS/Mg(OH)₂) composites were prepared by melt compounding to investigate the effect of particle size on the flame retardancy of PBS. Their flammability properties were investigated by limiting oxygen index, UL‐94, and cone calorimeter tests, which suggested that the medium‐sized Mg(OH)₂‐5 µm displayed the best flame retardancy. The residual char structure were analyzed and indicated that Mg(OH)₂‐5 µm could form a better protective layer than other sized particles, leading to the better flame retardancy to PBS. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.     

Improvement in the flame retardancy of cotton fabric by admicellar polymerization of 2‐acryloyloxyethyl diethyl phosphate using an anionic surfactant

The phosphorus‐containing acrylate monomer, 2‐acryloyloxyethyl diethyl phosphate (ADEP), was synthesized and applied to cotton fabric by using admicellar polymerization. Sodium dodecylbenzene sulfonate was used as the anionic surfactant. The film of polymerized monomer (PADEP) formed on the cotton surface was characterized by FTIR‐ATR spectroscopy and SEM. Thermal and flame retardant properties of PADEP‐coated cotton were investigated by TGA and flammability tests. Results showed that PADEP polymer film was successfully formed on the cotton fabric. The TGA and DTG analyses showed that the phosphorus‐containing PADEP lowered the decomposition temperature of the treated fabric resulting in a higher char yield than in the case of untreated cotton. The flammability tests showed that the treated cotton had much improved flame retardancy property after the treatment. The treated fabric also retained its good pliability and soft touch with good air permeability. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flame retardant finishing of cotton fleece fabric. II. Inorganic phosphorus‐containing compounds

Cotton fleece is not able to meet the federal flammability standard for general apparels (CFR 1610) without flame retardant treatment. Consequently, cotton fleece is not available in the market in spite of high demands. In our previous research, we studied the application of a hydroxyl‐functional organophosphorus oligomer as a flame retardant finishing agent for cotton fleece. In this research, we investigated the use of aluminum hydroxyphosphate (AHP) formed in situ on cotton by the reaction of aluminum sulfate and sodium phosphates to reduce the flammability of cotton fleece. We found that the AHP formed on cotton is effective in reducing the cotton fleece's flammability from “Class 3” to “Class 1.” Elemental analysis of aluminum and phosphorus in the AHP shows that the mole ratio of Al/P changes as the pH value of the sodium phosphates solution changes. The pH of the sodium phosphate solutions also affect the quantity of AHP formed on the cotton fleece. The treated cotton fleece retains “Class 1” flammability after one home laundering or the combination of dry‐cleaning and hand washing procedures. The treatment increases the whiteness of the cotton fleece whereas it reduces its bursting strength. The cotton fleece thus treated is also investigated using differential scanning calorimetry and scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Flame‐retardant finishing in cotton fabrics using zinc oxide co‐catalyst

In this article, N‐Methylol dimethylphosphonopropionamide (FR) in combination with a melamine resin (CL), phosphoric acid (PA) catalyst and zinc oxide (ZnO) or nano‐ZnO co‐catalyst were used (FR‐CL‐PA‐ZnO or nano‐ZnO system) to impart flame‐retardant property on cotton fabrics. FR‐CL or FR‐CL‐PA‐treated cotton specimen showed roughened and wrinkled fabric surface morphology, which was caused by the attack of the FR with slightly acidity. In addition, FTIR analysis showed some new characteristic peaks, carbonyl, CH₂ rocking and CH₃ asymmetric and CH₂ symmetric stretching bands, in the chemical structure of treated cotton specimens. Apart from these, the flame ignited on the flame‐retardant‐treated fabrics (without subjected to any post‐wet treatment) extinguished right after the removal of ignition source. However, FR‐CL treated specimens were no longer flame‐resistant when the specimens subjected to neutralization and/or home laundering, while FR‐CL‐PA treated specimens showed opposite results. By using 0.2% and 0.4% of ZnO or nano‐ZnO as co‐catalyst, the flame spread rate of neutralized and/or laundered test specimens decreased, even the specimens were undergone 10 home laundering cycles. Moreover, flame‐retardant‐treated cotton specimens had low breaking load and tearing strength resulting from side effects of the crosslinking agent used, while addition of ZnO or nano‐ZnO co‐catalyst could compensates for the reduction. Furthermore, the free formaldehyde content was dropped when ZnO and nano‐ZnO co‐catalyst was added in the treatment. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Some theoretical aspects of bromine-containing triazine flame retardants

We studied flame retardancy of cotton fabric treated with five diaminotriazines containing bromine—three compounds with the bromine on aliphatic groups and two with the bromine on phenyl groups. Flame retardancy, as measured by oxygen index and FF3-71 flammability standards, was better on the fabrics containing aliphatic bromine than on the fabrics containing aromatic bromine. Thermogravimetric analyses (TGA) and differential thermogravimetric analyses (DTG) were obtained on the fabrics, results of which supported the theory that HBr liberated during burning lowers the ignition temperature and decomposition point of the cellulose causing a reduction in flammable gases and an increase in residual char. Since C? H and C? Br bond strengths are stronger on aromatic groups than on aliphatic groups, our results agree with the theory that flame retardancy increases as the C? Br bond strength decreases. In other words, since bromine inhibits oxidation reactions in the gas phases, the heat evolved is expected to become less as the C? Br bond strength decreases.     

Flame retardant finishing of the polyester/cotton blend fabric using a cross‐linkable hydroxy‐functional organophosphorus oligomer

Blend fabrics of cotton and polyester are widely used in apparel, but high flammability becomes a major obstacle for applications of those fabrics in fire protective clothing. The objective of this research was to investigate the flame retardant finishing of a 50/50 polyester/cotton blend fabric. It was discovered previously that N,N′‐dimethyloldihydroxyethyleneurea (DMDHEU) was able to bond a hydroxy‐functional organophosphorus oligomer (HFPO) onto 50/50 nylon/cotton blend fabrics. In this research, the HFPO/DMDHEU system was applied to a 50/50 polyester/cotton twill fabric. The polyester/cotton fabric treated with 36% HFPO and 10% DMDHEU achieved char length of 165 mm after 20 laundering cycles. The laundering durability of the treated fabric was attributed to the formation of polymeric cross‐linked networks. The HFPO/DMDHEU system significantly reduced peak heat release rate (PHRR) of cotton on the treated polyester/cotton blend fabric, but its effects on polyester were marginal. HFPO/DMDHEU reduced PHRR of both nylon and cotton on the treated nylon/cotton fabric. It was also discovered that the nitrogen of DMDHEU was synergistic to enhance the flame retardant performance of HFPO on the polyester/cotton fabric.     

Flame retardant cotton

The water‐soluble organophosphorus compound, namely, hexahydroxymethylamidocyclotriphosphatriazatriene (HHMAPT) was synthesized by reacting phosphonitrile chloride with liquid ammonia followed by reaction with formaldehyde. It is rich in phosphorus and nitrogen and as a polyfunctional compound it can undergo several reactions with itself forming an in situ polymer or with cotton cellulose similar to conventional N‐methylol finishing agents. It was successfully used as a flame retarding agent in the absence and presence of etherified methylolated melamine (EMM). Investigations into the different factors that affect these reactions and the effect of these on the properties of the finished fabrics give rise to the following points; (1) P%, N% and crease recovery increase by increasing the curing time and temperature; (2) the most effective catalyst is NH₄Cl; P% and N% increase by increasing the concentration of NH₄Cl from 5 to 12.5 g/l (3) an increase in EMM and HHMAPT concentrations is accompanied by enhancement in P%, N% and crease recovery; (4) the fabric samples exhibit durable flame retardancy at temperatures higher than 120°C in the absence of EMM while in the presence of EMM, all samples exhibit durable flame retardancy properties, regardless of the temperature of curing; (5) the durable flame retardancy is achieved at concentrations higher than 60 g/l HHMAPT and 7.5 g/NH₄Cl. All samples exhibit loss in tensile properties but within an acceptable range (20%), crease recovery is improved in all samples. Copyright © 1999 John Wiley & Sons, Ltd.