Enhancing the flame retardancy of polylactic acid nonwoven fabric through solvent-free transparent coating.

Polylactic acid (PLA) nonwovens, recognized as eco-friendly substitutes for petroleum-based synthetic fibers, face a significant challenge due to their inherent flammability. This work addresses this concern by synthesizing a hyperbranched polyphosphoramide flame retardant (TPDT) through a one-step polycondensation process without using solvent and catalyst. TPDT is subsequently applied to PLA nonwovens using a dip-pad finishing technique. Notably, with a mere 7 wt% weight gain of TPDT, the PLA nonwovens exhibit a substantial increase in the limited oxygen index (LOI) value, reaching 32.3 %. Furthermore, the damaged area in the vertical burning test is reduced by approximately 69.2 %. In the cone calorimeter test, 17 wt% weight gain of TPDT results in a 51.4 % decrease in peak heat release rate and a 56.0 % reduction in total heat release compared to the control PLA. Additionally, char residue increases from 1.5 wt% to 31.1 wt% after combustion. The strong affinity between TPDT and PLA molecules persists even after repeated abrasion, ensuring sustained flame retardancy. Importantly, the introduction of TPDT also imparts increased softness to the PLA nonwovens. This work addresses this concern by synthesizing a hyperbranched polyphosphoramide flame retardant (TPDT) through a solvent-free, catalyst-free, and one-step polycondensation process.

High-efficiency durable flame retardant with ammonium phosphate ester and phosphine oxide groups for cotton cellulose biomacromolecule.

Cotton fibers mainly consist of cellulose biological macromolecule, and its exceedingly flammable nature has severely restricted its application in the fields requiring flame retardancy. To endow cotton fabric with excellent flame retardancy and superior durability, a high-efficiency durable flame retardant (THPO-P) with ammonium phosphate ester and phosphine oxide groups was synthesized and chemically bonded to cotton fabric through padding-baking method. THPO-P showed high flame-retardant efficiency, and the add-on of 5.9% was sufficient to prepare cotton fabric with self-extinguished feature. With the add-on of 19.9%, treated fabric possessed excellent fire safety and durability. The total heat release and peak heat release rate values reduced by 77.1% and 91.8% in contrast to pristine fabric, respectively. Its LOI value still reached up to 33.4% even after 50 laundering cycles, which was far beyond the flame-retardant standard. THPO-P played flame-retardant role by restraining the release of flammable volatiles, liberating nonflammable gases and promoting the char formation during combustion. The flame-retardant treatment deteriorated the tensile strength, whiteness and softness of cotton fabric.

Synthesis of Novel Arginine-Based Flame Retardant and Its Application in Lyocell Fabric.

Lyocell fabrics are widely applied in textiles, however, its high flammability increases the risk of fire. Therefore, to resolve the issue, a novel biomass-based flame retardant with phosphorus and nitrogen elements was designed and synthesized by the reaction of arginine with phosphoric acid and urea. It was then grafted onto the lyocell fabric by a dip-dry-cure technique to prepare durable flame-retardant lyocell fabric (FR-lyocell). X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) analysis demonstrated that the flame retardant was successfully introduced into the lyocell sample. Thermogravimetric (TG) and Raman analyses confirmed that the modified lyocell fabric featured excellent thermal stability and significantly increased char residue. Vertical combustion results indicated that FR-lyocell before and after washing formed a complete and dense char layer. Thermogravimetric Fourier-transform infrared (TG-FTIR) analysis suggested that incombustible substances (such as H2O and CO2) were produced and played a significant fire retarding role in the gas phase. The cone calorimeter test corroborated that the peak of heat release rate (PHRR) and total heat release (THR) declined by 89.4% and 56.4%, respectively. These results indicated that the flame retardancy of the lyocell fabric was observably ameliorated.

Ecofriendly flame-retardant composite aerogel derived from polysaccharide: Preparation, flammability, thermal kinetics, and mechanism.

Bio-based aerogel (polysaccharide cryogel) have led to a growing interest because of eco-friendliness, sustainability and excellent thermal insulation properties. Herein, we report an eco-friendly strategy to construct lightweight and porous sodium alginate/carboxymethyl cellulose/chitosan polysaccharide-based composite aerogels (SCC-B) by freeze-drying and post-cross-linking technology. The ester cross-linking of polysaccharide component achieved strong web-like entangled structure when using 1,2,3,4-butanetetracarboxylic acid and sodium hypophosphite as eco-friendly co-additives, meanwhile significantly improved flame retardancy of SCC-B due to phosphorylation. The thermal kinetic behavior of SCC-B was investigated by Flynn-Wall-Ozawa and Kissinger models. Results indicated that peak heat release rate and total heat release of SCC-B decreased from 30 W/g to 20 W/g and 15 kJ/g to 10 kJ/g, respectively. Furthermore, the second-degree burn time of SCC-B reached up to 87.1 s under heat exposure of 11.3 kW/m2. These characteristics combine to suggest hopeful prospects for use of SCC-B in the fields of fire-protection clothing as a renewable flame-retardant material.

An eco-friendly NP flame retardant for durable flame-retardant treatment of cotton fabric.

A halogen-free, formaldehyde-free, efficient, durable, NP flame retardant, the ammonium salt of meglumine phosphoric ester acid (ASMPEA), was prepared. The Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (1H NMR, 13C NMR, and 31P NMR) results indicated that ASMPEA was grafted onto cotton fibers by P-O-C covalent bonds. The LOI value of 30 wt% ASMPEA-treated cotton fabric was 40.2%, and after 50 laundering cycles (LCs), the LOI value decreased to 29.4%, indicating that the cotton fibers treated with ASMPEA were endowed with excellent durable flame retardancy. Thermogravimetry (TG), cone calorimetry, and vertical flammability test results showed that ASMPEA-treated cotton decomposed into phosphoric acid or polyphosphoric acid during combustion, which promoted the thermal degradation and charring of treated cotton fabrics and hindered the spread of flames. Scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy-dispersive spectrometry (EDS) verified that ASMPEA infiltrated the cotton fiber without obviously affecting its surface morphology or crystal structure; however, the mechanical properties of the treated cotton fabric decreased slightly. These results confirm that ASMPEA achieved excellent durable flame retardancy when used to coat cotton fabric.

Application of micro-nanostructured magnetite in separating tetrabromobisphenol A and hexabromocyclododecane from environmental water by magnetic solid phase extraction.

Two typical brominated flame retardants (BFRs), namely, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), were persistent organic pollutants widely detected in various environmental media. This study aimed to successfully synthesize micro-nano-structured magnetite particles (MNMPs) with surface modification by citric acid molecules. The synthesized composites served as an adsorbent for extracting TBBPA and HBCD from environmental water samples followed by gas chromatography-mass spectrometry analysis. The obtained MNMPs were characterized in terms of crystal structure, morphology, size distribution, hydrophobic and hydrophilic performance and magnetism. The results indicated that the MNMPs exhibited high surface area, good dispersibility, and strong magnetic responsiveness for separation. The parameters affecting the extraction efficiency were optimized, including sample pH, amount of sorbents, extraction time and desorption conditions. Under the optimum conditions, the recovery was 83.5 and 107.1%, limit of detection was 0.13 and 0.35µg/mL (S/N = 3), and limit of quantification was 0.37 and 0.59 µg/mL (S/N = 10) for TBBPA and HBCD respectively. The relative standard deviations obtained using the proposed method were less than 8.7%, indicating that the MNMP magnetic solid-phase extraction method had advantages of simplicity, good sensitivity and high efficiency for the extraction of the two BFRs from environmental water.

Renewable lignin-based surfactant modified layered double hydroxide and its application in polypropylene as flame retardant and smoke suppression.

A novel and environmentally friendly lignin-based surfactant sodium lignosulfonate (SLS) modified layered double hydroxide (LDH) flame retardant (LDH-LS) was fabricated via co-precipitation method, and subsequently incorporated into polypropylene (PP) matrix to obtain the PP and LDH-LS composites (PP/LDH-LS) by melt blending method. The XRD, FT-IR and XPS results indicated that SLS had successfully modified LDH by adsorbing on the surface of the LDH nanosheet. The WCA and SEM results revealed that the hydrophobic property of LDH-LS had been evidently improved, and it displayed a more homogeneous dispersion than virgin LDH in the PP matrix. Furthermore, cone calorimetry tests (CCT) illustrated that the peak heat release rate (PHRR), total heat release (THR), and total smoke release (TSR) of PP/LDH-LS composites exhibited declines of 62.9%, 25.1%, and 43.3% compared with those of Neat PP, respectively. Besides, the PP/LDH-LS achieved a LOI value of 29.4% and a UL-94 V-0 rating, whereas the PP/LDH showed only a LOI value of 25.2% and a UL-94 V-2 rating at 20 wt% loading. These improvements of flame retardant properties can be attributed to that the well-dispersed LDH-LS and synergistic flame retardancy between LDH and SLS.

Eco-friendly flame retardant and dripping-resistant of polyester/cotton blend fabrics through layer-by-layer assembly fully bio-based chitosan/phytic acid coating.

Polyester/cotton blend fabrics are widely used in clothing and household textiles which combine the comfort of cotton and excellent mechanical strength of polyester. However, their high flammability due to the special "wick effect" resulting from the different thermal decomposition process of cotton and polyester causes greatly potential fire hazards. In this study, fully bio-based intumescent flame retardant (IFR) coating of chitosan/phytic acid (CS/PA) was layer-by-layer (LBL) assembly constructed on polyester/cotton blend fabrics. The LOI value of polyester/cotton blend fabric which was LBL assembly coated by 20 bilayers CS/PA reached 29.2%. And the dripping of coated fabric was eliminated. The results of cone calorimetry test confirmed CS/PA coating greatly improved the flame retardancy of polyester/cotton blend fabrics. Thermogravimetric analysis (TGA) results showed CS/PA coating changed the thermal decomposition process to promote the char formation of polyester/cotton blend fabrics. CS/PA coating on fabric could form the IFR system which acts through both condensed phase action by the catalysis dehydration reaction to forming stable char and gas phase action by the blowing effect. This research provides a new strategy to eco-friendly flame retardant and dripping-resistant for polyester/cotton blend fabrics by bio-based IFR system through facile LBL assembly method.

Brominated flame retardants (BFRs) in contaminated food contact articles: identification using DART-HRMS and GC-MS.

Any food contact material (FCM) must be approved by the US FDA as being compliant with Title 21 of the Code of Federal regulations Parts 170-199, and/or obtain a non-objection letter through the Food Contact Notification Process, before being placed into the United States market. In the past years, several scientific articles identified FCM or more specifically, food contact articles (FCAs), which were contaminated with brominated flame retardants (BFRs) in the European Union. Prior research has suggested the source of BFR contamination was likely poorly recycled plastics containing waste electrical and electronic equipment (WEEE). We conducted a retail survey to evaluate the presence of BFR-contaminated reusable FCA in the US market. Using a Direct Analysis in Real Time ionisation High-Resolution Mass Spectrometry (DART-HRMS) screening technique and extraction gas chromatography-mass spectrometry (GC-MS) confirmation we were able to identify BFRs present in retail FCAs. Among non-targeted retail samples, 4 of 49 reusable FCAs contained 1-4 BFRs each. The identified BFRs, found in greatest estimated concentrations, were 2,4,6-tribromophenol (TBP), 3,3',5,5'-tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), decabromodiphenylethane (DBDPE) and decabromodiphenylether (BDE-209). A second targeted FCA sampling (n = 28) confirmed these BFRs persisted in similar articles. Combined sample sets (n = 77) estimated DART false-positive/negative incidences of 5% & 4%, respectively, for BFR screening of FCAs. Because the presence of BFRs in some contaminated FCAs has been demonstrated and since these compounds are possible migrants into food, further studies are warranted. In order to estimate the potential exposure of the identified BFRs and conduct corresponding risk assessments, the next and logical step will be to study the mass transfer of BFRs from the contaminated FCM into food simulants and food.

Facile synthesis of a high efficiency and durability L-citrulline flame retardant for cotton.

A novel flame retardant (FR), the ammonium salt of citrulline-penta (methylphosphonic acid) (ACPMPA) based on L-citrulline was synthesized, and its structure was characterized by 13C, 1H, and 31P nuclear magnetic resonance (NMR) spectroscopy. The ACPMPA flame retardant molecule contains five ammonium salts of phosphorus acid and one ammonium salt of carboxylic acid, which allowed the covalent attachment of ACPMPA onto cellulose via -P=O(-O-C) and -COOC bonds. The results showed that the treated cotton fabrics had very high flame retardance and excellent durability. The limiting oxygen index (LOI) of cotton fabric treated with 35%-ACPMPA reached 49.2% and only decreased to 34.2% after 50 laundry cycles. Vertical flame tests also demonstrated that the treated cotton fabric acquired good flame retardance. The thermogravimetry (TG) and TG-IR results showed that the treated cotton left more residues and released almost no flammable volatiles at high temperatures. The cone calorimetry results showed that the treated cotton released less heat than pure cotton. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results demonstrated that the structure of the treated cotton fabric was almost unchanged, and no free formaldehyde was detected, indicating that the treated cotton was safe. The treated cotton fabric also retained good tensile strength and whiteness.

A high molecular weight formaldehyde-free polymer flame retardant made from polyvinyl alcohol for cellulose.

Polyvinyl alcohol and phosphoric acid were used as primary raw materials to synthesize a polyvinyl alcohol/ammonium phosphate flame retardant (PVAAP) for cotton fabrics. The limiting oxygen index of the cotton fabric treated with 24% PVAAP was 42.1. After 50 standard laundry cycles, the limiting oxygen index remained relatively high (26.3), suggesting that the 24% PVAAP can be used as a durable flame retardant. The vertical flammability test of the cotton fabric treated with PVAAP exhibited no afterflame and afterglow. The cone calorimetry test indicated that the peak of the heat release rate and total heat release of the cotton fabric treated with 24% PVAAP were significantly lower than those of the control cotton. Thermogravimetric and thermogravimetric-infrared spectroscopy revealed that the initial decomposition temperature of the PVAAP-treated fabric was substantially lower than that of the control fabric, and more residual carbon was generated. The PVAAP altered the thermal decomposition pathway of the treated cotton. The X-ray diffraction patterns and scanning electron microscopy images suggested that the PVAAP treatment did not change the structure of the fibers.

Role of Copper Oxide on Epoxy Coatings with New Intumescent Polymer-Based Fire Retardant.

Epoxy resins (EP) have been used as a thermos-setting material in the field of coating, casting, bonding agent, and laminating. However, a major drawback associated with its use is the lack of good flaming properties, and it is responsible for heavy smoke along with hazardous gases considerably limiting its uses in various fields. In this study, N-ethanolamine triazine-piperizine, a melamine polymer (ETPMP), was established as a new charring-foaming agent and was successfully synthesized with ethanolamine, piperizine, cyanuric chloride, and melamine as precursor molecules via the nucleophilic substitution reaction method. Elemental analysis and Fourier transform infrared (FTIR) spectroscopy analysis were applied to approve the synthesis of ETPMP and confirmation of its structure and characterization. The epoxy coating of intumescent flame retardant (IFR) was equipped by introducing ETPMP, ammonium polyphosphate (APP), and copper oxide (CuO) in multiple composition ratios. CuO was loaded at various amounts into the IFR-coating system as a synergistic agent. The synergistic action of CuO on IFR coatings was scientifically examined by using different analytical tests such as vertical burning test (UL-94V), limited oxygen index (LOI), thermal gravimetric analysis (TGA), cone calorimeter, and scanning electron microscope (SEM). The results showed that small changes in the amount of CuO expressively amplified the LOI results and enhanced the V-0 ratings in the UL-94V test. The TGA data clearly demonstrate that the inclusion of CuO can transform the thermal deprivation behavior of coatings with a growing char slag proportion with elevated temperatures. Information from cone calorimeter data affirmed that CuO can decrease the burning factors by total heat release (THR) together with peak heat release rate (PHRR). The SEM images indicated that CuO can enrich the power and compression of the intumescent char that restricts the movement of heat and oxygen. Our results demonstrate a positive influence of CuO on the epoxy-headed intumescent flame retardant coatings.

Suitability and Modification of Different Renewable Materials as Feedstock for Sustainable Flame Retardants.

Due to their chemical structure, conventional flame retardants are often toxic, barely biodegradable and consequently neither healthy nor environmentally friendly. Their use is therefore increasingly limited by regulations. For this reason, research on innovative flame retardants based on sustainable materials is the main focus of this work. Wheat starch, wheat protein, xylan and tannin were modified with phosphate salts in molten urea. The functionalization leads to the incorporation of phosphates (up to 48 wt.%) and nitrogen (up to 22 wt.%). The derivatives were applied on wood fibers and tested as flame retardants. The results indicate that these modified biopolymers can provide the same flame-retardant performances as commercial compounds currently used in the wood fiber industry. Besides, the flame retardancy smoldering effects may also be reduced compared to unmodified wood fibers depending on the used biopolymer. These results show that different biopolymers modified in phosphate/urea systems are a serious alternative to conventional flame retardants.

Facile, one-pot, formaldehyde-free synthesis of reactive NP flame retardant for a biomolecule of cotton.

The NP flame retardant ammonium salt of hydroxyethyl hexahydrotristriazine-triphosphoric acid (AHTTPA) was prepared by a one-pot synthesis method under formaldehyde-free and solvent-free conditions. The AHTTPA was finished on the biomolecule of cotton by using the dip-roll-bake method. Nuclear magnetic resonance (NMR 1H, 13C, and 31P) demonstrated that AHTTPA was successfully synthesized. The flame retardancy of AHTTPA-treated cotton was studied by limiting oxygen index (LOI), vertical flaming test (VFT), scanning electron microscopy (SEM), and cone calorimetry (CC). The results from these tests indicate that AHTTPA-treated cotton exhibited favorable flame retardancy and durability (the LOI value of 40%-treated cotton after 50 laundering cycles (LCs) was 29.8%), the flame was immediately extinguished after removal from the treated cotton, no smoldering or continued burning, the burned part formed a complete carbon frame and generally maintained its original morphology, the peak heat release rate (PHRR) and total heat release (THR) of AHTTPA-treated cotton fabric were significantly lower than pure cotton. Thermogravimetric analysis (TGA) results showed that AHTTPA improved the thermal stability of cotton. The breaking strength and softness of AHTTPA-treated cotton was also retained.

Synthesis and Toxicity of Halogenated Bisphenol Monosubstituted-Ethers: Establishing a Library for Potential Environmental Transformation Products of Emerging Contaminant.

As an important branch of halogenated bisphenol compounds, the halogenated bisphenol monosubstituted-ether compounds have received a lot of attention in environmental health science because of their toxicity and variability. In this study, a synthetic method for bisphenol monosubstituted-ether byproduct libraries was developed. By using the versatile and efficient method, tetrachlorobisphenol A, tetrabromobisphenol A, and tetrabromobisphenol S monosubstituted alkyl-ether compounds were accessed in 39-82 % yield. Subsequently, the cytotoxicity of 27 compounds were screened using three different cell lines (HepG2, mouse primary astrocytes and Chang liver cells). Compound 2,6-dibromo-4-[3,5-dibromo-4-(2-hydroxyethoxy)benzene-1-sulfonyl]phenol was more toxic than other compounds in various cells, and the sensitivity of this compound to the normal hepatocytes and cancer cells was inconsistent. The compounds 2,6-dichloro-4-(2-{3,5-dichloro-4-[(prop-2-en-1-yl)oxy]phenyl}propan-2-yl)phenol and 2,6-dibromo-4-(2-{3,5-dibromo-4-[(prop-2-en-1-yl)oxy]phenyl}propan-2-yl)phenol were the most toxic to HepG2 cells, and most of the other compounds inhibited cell proliferation. Moreover, typical compounds were also reproductive and developmental toxic to zebrafish embryos at different concentrations. The synthetic byproduct libraries could be used as pure standard compounds and applied in research on environmental behavior and the transformation of halogenated flame retardants.

Biodegradable Flame Retardants for Biodegradable Polymer.

To improve sustainability of polymers and to reduce carbon footprint, polymers from renewable resources are given significant attention due to the developing concern over environmental protection. The renewable materials are progressively used in many technical applications instead of short-term-use products. However, among other applications, the flame retardancy of such polymers needs to be improved for technical applications due to potential fire risk and their involvement in our daily life. To overcome this potential risk, various flame retardants (FRs) compounds based on conventional and non-conventional approaches such as inorganic FRs, nitrogen-based FRs, halogenated FRs and nanofillers were synthesized. However, most of the conventional FRs are non-biodegradable and if disposed in the landfill, microorganisms in the soil or water cannot degrade them. Hence, they remain in the environment for long time and may find their way not only in the food chain but can also easily attach to any airborne particle and can travel distances and may end up in freshwater, food products, ecosystems, or even can be inhaled if they are present in the air. Furthermore, it is not a good choice to use non-biodegradable FRs in biodegradable polymers such as polylactic acid (PLA). Therefore, the goal of this review paper is to promote the use of biodegradable and bio-based compounds for flame retardants used in polymeric materials.

Synthesis of New Star-Shaped Liquid Crystalline Cyclotriphosphazene Derivatives with Fire Retardancy Bearing Amide-Azo and Azo-Azo Linking Units.

Two series of new hexasubstituted cyclotriphosphazene derivatives were successfully synthesized and characterized. These derivatives are differentiated by two types of linking units in the molecules such as amide-azo (6a-j) and azo-azo (8a-j). The homologues of the same series contain different terminal substituents such as heptyl, nonyl, decyl, dodecyl, tetradecyl, hydroxyl, carboxyl, chloro, nitro, and amino groups. All the intermediates and final compounds were characterized using Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (NMR), and Carbon, Hydrogen, and Nitrogen (CHN) elemental analysis. Liquid crystal properties for all compounds were determined using polarized optical microscope (POM). It was found that only intermediates 2a-e with nitro and alkoxyl terminal chains showed a smectic A phase. All the final compounds with alkoxyl substituents are mesogenic with either smectic A or C phases. However, other intermediates and compounds were found to be non-mesogenic. The study on the fire retardancy of final compounds was determined using limiting oxygen index (LOI) method. The LOI value of pure polyester resin (22.53%) was increased up to 24.71% after treating with 1 wt% of hexachlorocyclotriphosphazene (HCCP). Moreover, all the compounds gave positive results on the LOI values and compound 6i with the nitro terminal substituent showed the highest LOI value of 27.54%.

Flame Retardant-Functionalized Cotton Cellulose Using Phosphonate-Based Ionic Liquids.

Cellulose from cotton fibers was functionalized through a dissolution-regeneration process with phosphonate-based ionic liquids (ILs): 1,3-dimethylimidazolium methylphosphonate [DIMIM][(MeO)(H)PO2] and 1-ethyl-3-methylimidazolium methylphoshonate [EMIM][(MeO)(H)PO2]. The chemical modification of cellulose occurred through a transesterification reaction between the methyl phosphonate function of ILs and the primary alcohol functions of cellulose. The resulting cellulose structure and the amount of grafted phosphorus were then investigated by X-ray diffraction, ICP-AES, and ¹³C and ³¹P NMR spectroscopy. Depending on the IL type and initial cotton / IL ratio in the solution, regenerated cellulose contained up to 4.5% of phosphorus. The rheological behavior of cotton cellulose/ILs solutions and the microscale fire performances of modified cellulose were studied in order to ultimately prepare flame retardant cellulosic materials. Significant improvement in the flame retardancy of regenerated cellulose was obtained with a reduction of THR values down to about 5-6 kJ/g and an increase of char up to about 35 wt%.

Natural antioxidant functionalization for fabricating ambient-stable black phosphorus nanosheets toward enhancing flame retardancy and toxic gases suppression of polyurethane.

Herein, as a natural antioxidant, tannin (TA) is firstly used to functionalize black phosphorous (BP) nanosheets to improve the ambient stability and toxic suppression, thus decreasing the fire hazards of polymer materials. Compared to pure BP nanosheets, higher temperature for thermal oxidation decomposition is achieved for TA-BP nanosheets, directly confirming the ambient stability of TA-BP nanosheets. Meanwhile, from high resolution TEM and XPS results, TA-BP nanosheets after being exposed at air for 10 days present well-organized crystal structure and low POx bonds content. Cone calorimeter results illustrate that the incorporation of 2.0 wt% TA-BP nanosheets significantly decreases the peak value of heat release rate (-56.5 %), total heat release (-43.0 %), CO2 concentration (-57.3 %) of TPU composite. Meanwhile, with addition of low to 1.5 wt%, the release of highly-toxic CO gas is significantly suppressed, confirmed by lower peak value (0.52 mg/m3) and decreased total release amount (-55.1 %). The obviously enlarged tensile strength (36.7 MPa) and desirable elongation at break (622 %) are also observed. This strategy not only firstly adopts bio-based antioxidant to impart excellent environmental stability for BP nanosheets, but also promotes the promising potentials of BP nanosheets in the fire safety application of polymer composites.

Facile synthesis of bromo- and mixed bromo/chloro dibenzo-p-dioxins and [14C]-labeled 1,3,7,8-tetrabromodibenzo-p-dioxin.

Polybrominated dibenzo-p-dioxins (PBDDs) and mixed bromo/chloro dibenzo-p-dioxins (PXDDs) are persistent organic pollutants that can possess the same toxicity as their fully chlorinated analogs (PCDDs) and have been identified in the same matrices. Herein a general synthetic methodology is described to produce multiple congeners of PBDDs and PXDDs with varying degrees of halogenation and substitution patterns for use as analytical and/or internal standards, and for absorption, disposition, metabolism, and excretion (ADME) studies. The syntheses of PBDDs and PXDDs were accomplished by condensing a common precursor, 4,5-dibromo catechol, with variable precursors, i.e., polychlorinated 1-chloro-2-nitrobenzenes or polybrominated 1-fluoro-2-nitrobenzenes, to introduce a desired number of halogens and specific substitution patterns. Initial attempts to synthesize PBDDs and PXDDs were performed in potassium carbonate with DMSO at 145-150 °C. PXDDs syntheses resulted in formation of the desired products at >90% purity but attempts at higher brominated PBDDs syntheses resulted in dehalogenated by-products. To preclude by-product formation, additional syntheses for some PBDDs were conducted by refluxing the precursors in acetonitrile, which resulted in pure products at higher yield. Six PXDDs ranging from four to six halogens were synthesized (20-84% yield), of which three contained the halogen substitution pattern of 2,3,7,8. Five PBDDs ranging from four to six bromines were produced in 23-83% yield, three of which were toxic. Using the initial DMSO method, [14C]-1,3,7,8-tetrabromodibenzo-p-dioxin (0.26 µCi/µmol; 11% overall yield) was synthesized from commercially available [14C]-phenol to allow an ADME study to be conducted.