Preparation of Polyurea Elastomer with Flame Retardant, Insulation and Thermal Conductivity Properties

By using 6,6-((sulfonylbis(4,1-phenylene)bis(azanediyl))bis(thiophen-2-ylm-ethylene))bis6H-di-benzo[c,e][1,2]oxaphosphinine 6-oxide(DOPO-N)as phosphorus-nitrogen flame retardant,the polyurea(PUA)with flame retardant properties(PUA/DOPO-N)was prepared.In addition,organically modified montmorillonite(OMMT)and magnesium hydroxide(MH)were used as co-effectors respectively,and the flame retardant PUA(PUA/DOPO-N/OMMT and PUA/DOPO-N/MH)were also prepared.Thermal properties,flame retardant properties,flame retardant mechanism and mechanical properties of PUA/DOPO-N,PUA/DOPO-N/OMMT and PUA/DOPO-N/MH were investigated by thermogravimetric(TG)analysis,limiting oxygen index(LOI),UL 94,cone calorimeter test,scanning electron microscopy(SEM),and tensile test.The results show that the LOI value of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are 27.1%,27.7%,and 28.3%,respectively,and UL 94 V-0 rating is attained.Compared with PUA,the peak heat release rate(pk-HRR),total heat release(THR)and average effective heat combustion(av-EHC)of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH decrease significantly.SEM results indicate that the residual chars of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are completer and more compact.The complex of DOPO-N/OMMT and DOPO-N/MH have synergistic flame retardancy.The mechanical properties of PUA can be improved by the addition of DOPO-N,DOPO-N/OMMT and DOPO-N/MH,respectively.The insulation performance test shows that the volume resistivity of PUA/20%DOPO-N is 6.25×10^(16)Ω.cm.Furthermore,by using modified boron nitride(MBN)as heat dissipating material,the complex of PUA/MBN was prepared,and the thermal conductivity of PUA/MBN was investigated.The thermal conductivity of PUA/8%MBN complex coating at room temperature is 0.166 W/(M·K),which is a 163%improvement over pure PUA.

Synthesis of Organic-Inorganic Hybrid Aluminum Hypophosphite Microspheres Flame Retardant and Its Flame Retardant Research on Thermoplastic Polyurethane

Aluminum hypophosphite microspheres(AHP) were synthesized by hydrothermal method using NaH2PO2·H2O and AlCl3·6H2O as raw materials, and then the AHP microspheres were polymerized by surface polymerization of micro-nanospheres with cyclic cross-linked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)(PZS). A new organic-inorganic poly(phosphonitrile)-modified aluminum hypophosphite microspheres(PZS-AHP) were synthesized by encapsulation and applied to flame retardant thermoplastic polyurethane(TPU). The microstructure and chemical composition of the PZS-AHP microsphere were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray spectroscopy. The thermal stability of PZS-AHP microsphere was explored with thermogravimetric analysis. Thermogravimetric data indicate that the PZS-AHP microspheres have excellent thermal stability. The thermal and flame-retarding properties of the TPU composites were evaluated by thermogravimetric(TG), limited oxygen index tests(LOI), and cone calorimeter test(CCT). The TPU composite achieved vertical burning(UL-94) V-0 grade and LOI value reached 29.2% when 10 wt% PZS-AHP was incorporated. Compared with those of pure TPU, the peak heat release rate(pHRR) and total heat release(THR) of TPU/10%PZS-AHP decreased by 82.2% and 42.5%, respectively. The results of CCT indicated that PZS-AHP microsphere could improve the flame retardancy of TPU composites.

Ten-Minute Synthesis of a New Redox-Active Aqueous Binder for Flame-Retardant Li-S Batteries

As a critical role in battery systems,polymer binders have been shown to efficiently suppress the lithium polysulfide shuttling and accommodate volume changes in recent years.However,preparation processes and safety,as the key criterions for Li-S batteries'practical applications,still attract less attention.Herein,an aqueous multifunction binder(named PEI-TIC)is prepared via an easy and fast epoxy-amine ring-opening reaction(10 min),which can not only give the sulfur cathode a stable mechanical property,a strong chemical adsorption and catalytic conversion ability,but also a fire safety improvement.The Li-S batteries based on the PEI-TIC binder display a high discharge capacity(1297.8 mAh g^(-1)),superior rate performance(823.0 mAh g^(-1)at 2 C),and an ultralow capacity decay rate of 0.035%over more than 800 cycles.Even under 7.1 mg cm^(-2)S-loaded,the PEI-TIC electrode can also achieve a high areal capacity of 7.2 mA h g^(-1)and excellent cycling stability,confirming its application potential.Moreover,it is also noted that TG-FTIR test is performed for the first time to explore the flame-retardant mechanism of polymer binders.This work provides an economically and environmentally friendly binder for the practical application and inspires the exploration of the flame-retardant mechanism of all electrode components.

Biobased Furfurylated Poplar Wood for Flame-Retardant Modification with Boric Acid and Ammonium Dihydrogen Phosphate

Furfurylated wood exhibits excellent dimensional stability and corrosion resistance,making it a promising material for constructing buildings,but it is highly flammable.Herein,flame-retardant furfurylated poplar wood was produced via a two-step process utilizing boric acid(BA)and ammonium dihydrogen phosphate(ADP)as flame-retardant components,and biomass-derived furfuryl alcohol(FA)as a modifier.The acidity of BA and ADP allowed them to catalyze the polymerization of FA,which formed a cross-linked network that immobilized BA and ADP inside the wood.The addition of BA/ADP substantially delayed the time to ignition from 10 to 385 s and reduced the total heat release and total smoke release by 58.75%and 77.31%,respectively.Analysis of the pyrolysis process showed that the decomposition products of BA and ADP protected the underlying furfurylated wood and diluted combustible gases.This method significantly improved the fire retardancy and smokeless properties of furfurylated wood,providing promising prospects for its application as an engineering material.

Research Progress in Flame Retardant in Flame Retardant Coatings

Flame retardant coatings are functional materials that can serve as decorative and protec-tive substrates in the event of a fire.Flame retardant coatings generally consist of two parts:a base material and a flame retardant agent.A detailed introduction was given to the development of flame retardant coatings in recent years and the flame retardants used in flame retardant coatings.Flame retardants mainly include halogen flame retar-dants,phosphorus nitrogen flame retardants,expansion flame retardants,biomass flame retardants,and graphene flame retardants.The application of flame retardant coatings in the fields of epoxy resin,polyurethane,etc.was elaborated.In addition,the application of new biomass flame retardants and graphene flame retardants was introduced,and the future development of flame retardant coatings and flame retardants was described.

Study on the Flame-retardant Properties of High Flame-retardant Acrylic Fiber Knitted Fabrics

This paper involved five kinds of weft-knitted fabrics made from high flame-retardant acrylic/cotton(0/100,30/70,50/50,70/30,100/0).The article adopted the vertical burning method,limiting oxygen index method and Cone Calorimeter test method for testing fabric flame retardant property.By comparison with these five fabrics,the effects on the properties of high flame-retardant acrylic fiber knitted fabrics due to the content of high flame-retardant acrylic fiber were analyzed.

Research Progress on a Novel Brominated Flame Retardant :Tris(2,3- dibromopropyl) Isocyanurate(TBC)

This review summarizes the environmental levels,toxicity effects and analytical development of Tris(2,3-dibromopropyl)Isocyanurate(TBC).Further study is required on the environmental behavior of TBC,mechanism of toxicity and alternative development.

Superior and safer lithium sulfur batteries realized by robust polysulfides-retarding dam with high flame retardance

The unparalleled energy density has granted lithium-sulfur batteries(LSBs)with attractive usages.Unfortunately,LSBs still face some unsurpassed challenges in industrialization,with polysulfides shuttling,dendrite growth and thermal hazard as the major problems triggering the cycling instability and low safety.With the merit of convenience,the method of designing functional separator has been adapted.Concretely,the carbon aerogel confined with CoS_(2)(CoS_(2)-NCA)is constructed and coated on Celgard separator surface,acquiring CoS_(2)-NCA modified separator(CoS_(2)-NCA@C),which holds the promoted electrolyte affinity and flame retardance.As revealed,CoS_(2)-NCA@C cell gives a high discharge capacity 1536.9 mAh/g at 1st cycle,much higher than that of Celgard cell(987.1 mAh/g).Moreover,the thermal runaway triggering time is dramatically prolonged by 777.4 min,corroborating the promoted thermal safety of cell.Noticeably,the higher coulombic efficiency stability and lower overpotential jointly confirm the efficacy of CoS_(2)-NCA@C in suppressing the lithium dendrite growth.Overall,this work can provide useful inspirations for designing functional separator,coping with the vexing issues of LSBs.

Synthesis and Structure of A Novel Caged Bicyclic Phosphate Flame Retardant

PI novel caged bicyclic phosphate flame retardant tri(1-oxo-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane-methyl) phosphate (Trimer) was synthesized from 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (PEPA) and phosphorus oxychloride in this paper. Its structure was characterized by elemental analysis. FTIR, H-1 NMR. P-31 NMR and X-ray diffraction analysis.

Levels and distribution of brominated flame retardants in the soil of Harbin in China

This study reports the presence of brominated flame retardants in the topsoil in and around Harbin, a city in northeastern China. Samples of soil were collected from 17 locations in 2006, and the levels of 9 polybrominated diphenylethers （PBDEs 17, 28, 47, 66, 99, 100, 153, 154, and 183） ranged from 2.45 to 55.9 pg/g dry weight （dw） with a mean of 26.3 pg/g dw. These levels are very low comparing with those for some cities in Europe and USA. BDE 209 and hexabromocyclododecane were the two dominant congeners, with mean concentrations of 520 pg/g dw and 1750 pg/g dw, respectively. The concentrations of the total nine PBDE congeners clearly decreased from urban areas to background, but the compositions of individual congeners differed. Proportions of heavier congeners decreased while those of lighter congeners increased, along urban-rural-background transect, providing evidence for an urban fractionation effect. Correlation analysis indicated similar sources for PBDEs, hexabromocyclododecane, and 1,2-bis（2,4,6-tribromophenoxy）-ethane from urban areas but pentabromoethylbenzene was probably present due to long-range atmospheric transport. Principal component analysis was used to determine the characteristics of the relationships among these brominated flame retardants in the field.

Microencapsulated ammonium polyphosphate by polyurethane with segment of dipentaerythritol and its application in flame retardant polypropylene

Dipentaerythritol(DPER),4,40-diphenylmethanediisocyanate(MDI)and melamine(MEL)are used as raw materials to microencapsulate ammonium polyphosphate(MAPP)in situ polymerization.The MAPP is characterized by Fourier transform infrared(FT-IR),scanning electron microscopy(SEM),transmission electron microscopy(TEM)and thermal gravimetric analysis(TGA).The results show that the coating operation can effectively improve water resistance of ammonium polyphosphate(APP),and MAPP has higher residual rate than that of APP after combustion.The flame retardant action of MAPP and APP in polypropylene(PP)is investigated by the limited oxygen index(LOI),vertical burning test(UL-94),TGA,SEM,and cone calorimeter test(CCT).The LOI value of the PP/MAPP composite at the same loading is higher than that of PP/APP composite.UL 94 ratings of PP/MAPP composites are raised to V-0 at 20 wt%loading.The results of CCT also show that MAPP is more efficient than APP.The morphological structures observed by digital photos and SEM demonstrated that MAPP could be promoted to form the continuous and compact intumescent char layer.The flame retardant mechanism of PP/MAPP is also discussed.

Synthesis and Application of Novel Triazine-Based Charring-Foaming Agents in Intumescent Flame Retardant Polypropylene

Three novel triazine-based charring-foaming agents (M2-CFA, M4-CFA, and M6-CFA) were synthesized successfully with only water as the solvent and were characterized by FT-IR and thermal gravimetric analysis (TGA). These three charring-foaming agents and the byproduct 944-by were employed to study the effectiveness of the novel intumescent flame retardant dopant on the fire retardancy of polypropylene(PP) investigated through UL-94 and limiting oxygen index (LOI) tests. TGA results showed that the M4-CFA presented good char formation ability (char residue: 26.8% at 700 °C). It was found that the sample with a 2/1 mass ratio of APP to M4-CFA exhibited the best flame retardancy among all the PP composites: 35.5% LOI and a V-0 rating of UL-94. Additionally, the microstructure and morphology of char residues were further studied by XRD, Raman spectroscopy and SEM. © 2017, Tianjin University and Springer-Verlag Berlin Heidelberg.

Synthesis and thermal stability of a novel phosphorus-nitrogen containing intumescent flame retardant

A novel phosphorus-nitrogen containing intumescent flame retardant （P-N IFR） was prepared via the reaction of dichlor-opentate with N-methylaniline. The structure of the product was confirmed by ^1H NMR, ^31p NMR, MS and IR. TGA analysis showed it has effective thermal stability.

Preparation and characterization of tung oil-based flame retardant polyols

Three kinds of tung oil-based structural flame retardants polyols(TOFPs) were prepared by new methods in this paper. First, tung oil was used to produce monoglyceride and diglyceride by transesterification with glycerol by sodium methoxide. The products after transesterification were epoxidized by peracetic acid which was in-situ generated from acetic acid and hydrogen peroxide in the presence of sulfuric acid catalyst. And then, TOFPs were prepared from epoxidized alcoholysis tung oil(EGTO) with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO), diethyl phosphate(DEP) and diethanolamine(DEA) by ring-opening reactions, respectively. GPC was used to evaluate the conversion rate, at optimum reaction conditions, selectivity for monoglyceride in transesterification. The influence of different parameters such as temperature, mole ratio or mass ratio on the conversion rate of transesterification and epoxidation were investigated. The molecular structures of TOFPs were characterized by FTIR and ~1HNMR. Finally, tung oil-based polyurethane foams(TOPUFs) were prepared by a one-shot process using TOFPs with polyisocyanate. The LOI values of TOPUFs whose content of DOPO-EGTO,DEP-EGTO and DEA-EGTO were 100 wt% can reach to 26.2%, 25.1%, and 24.4%, respectively.

STUDIES ON FLAME-RETARDANT PC/ABS MULTIPLE-ELEMENT ALLOY

The preparation technology of flame-retardant PC/ABS alloys was studied in this paper. Using a high-efficiency flame retardant system and by means of multiple-ingredient compatibilizing, PC/ABS alloys with excellent impact strength and flame retardant property were prepared. The experimental results showed that by using PS-g-MAH and SMA as synergistic compatibilizers, the notched Izod impact strength and flammability of PC/ABS alloy obtained in the present work can be up to 175 J/m and UL-94 VO, respectively.

A NEW SYNERGIST FOR INTUMESCENT FLAME RETARDANT POLYPROPYLENE

The synergistic effects of silicotungstic acid (SiW12) as a catalyst in the phosphorus-nitrogen compounds AM-based intumescent flame-retardant (IFR) polypropylene (PP) were studied using the limiting oxygen index (LOI), the UL-94 test, thermogravimetric analysis (TGA), real time Fourier transform infrared (FTIR), laser Raman spectroscopy (LRS). The LOI data show that SiW12 added to PP/IFR systems has a synergistic FR effect with an IFR additive named AM. The TGA data show that SiW12 apparently increases the thermal stability of the PP/IFR systems at high temperature (T > 500degreesC). The FTIR results provide the positive evidence that IFR can improve the thermal stability of PP and SiW12 can induce a higher rate of formation of phosphoric acid and its derivatives. The LRS measurements provide useful information on the carbonaceous microstructures. In short, a suitable amount of SiW12 (1.5 wt%) exerts synergistic effects with the IFR by increasing the LOI value and the thermal stability at high temperature and promoting the formation of charred structures on the burning PP surface.

Effect of Flame Retardant Containing Phosphorus and Silicone on Thermal Performance of PC/ABS

A flame retardant （DPA-SiN） containing phosphorus, nitrogen and silicon elements was synthesized. The halogen free flame retardant was incorporated into PC/ABS to improve its flame retardancy. The flame-retardant properties of the PC/ABS/DPA-SiN blends were estimated by limiting oxygen index （LOI） values and CONE Calorimeter, while thermal stabilities were investi- gated through thermo gvavimetric analysis （TGA）. The PC/ABS/DPA-SiN blends were thermally degraded at 400℃ for different amounts of time and studied by Fourier transform infrared spectroscopy （FTIR） to better understand the degradation behavior of PC/ABS/DPA-SiN.

Synergistic effect of MXene on the flame retardancy and thermal degradation of intumescent flame retardant biodegradable poly(lactic acid)composites

The effect of Ti3C2 MXene nanosheets on the intumescent flame retardant(IFR)poly(lactic acid)(PLA)composites was investigated among a series of PLA/IFR/MXene,which were prepared by melt blending 0-2.0 wt%MXene,10.0 wt%-12.0 wt%IFR and PLA together.The results of limiting oxygen index(LOI)and vertical burning(UL-94)discover that the combination of 0.5 wt%MXene and 11.5 wt%IFR synergistically improves the fire safety of PLA to reach UL-94 V-0 rating with LOI value of 33.0%.The PLA/IFR/MXene composites perform an obvious reduction in peak of heat release rate(HRR)in cone calorimeter tests(CCTs).Furthermore,the carbon residues after CCTs were characterized by scanning electron microscope(SEM),laser Raman spectroscopy(LRS),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).It is demonstrated that both the titanium composition of the MXene structure and the characteristics of the two-dimensional material enhance the PLA/IFR/MXene composite materials’ability to produce a dense barrier layer to resist burnout during thermal degradation.

Flame-retardant concentrated electrolyte enabling a Li F-rich solid electrolyte interface to improve cycle performance of wide-temperature lithium–sulfur batteries

Lithium–sulfur batteries have been regarded as the most promising high-energy electrochemical energy storage device owing to the high energy density, low cost and environmental friendliness. However, traditional lithium–sulfur batteries using ether-based electrolytes often suffer from severe safety risks(i.e. combustion). Herein, we demonstrated a novel kind of flame-retardant concentrated electrolyte(6.5 M lithium bis(trifluoromethylsulphonyl)imide/fluoroethylene carbonate) for highly-safe and widetemperature lithium–sulfur batteries. It was found that such concentrated electrolyte showed superior flame retardancy, high lithium-ion transference number(0.69) and steady lithium plating/stripping behavior(2.5 m Ah cm^(-2) over 3000 h). Moreover, lithium–sulfur batteries using this flame-retardant concentrated electrolyte delivered outstanding cycle performance in a wide range of temperatures(-10 °C, 25 °C and 90 °C). This superior battery performance is mainly attributed to the LiF-rich solid electrolyte interphase formed on lithium metal anode, which can effectively suppress the continuous growth of lithium dendrites. Above-mentioned fascinating characteristics would endow this flame-retardant concentrated electrolyte a very promising candidate for highly-safe and wide-temperature lithium–sulfur batteries.

Synergistic Flame Retardant Effect of Ammonium Polyphosphate and Aluminum Hydroxide on Polyurethane

The flame-retardant properties of polyurethane(PU)containing ammonium polyphosphate(APP)and aluminum hydroxide(ATH)were investigated.Moreover,the flame retardant performance was investigated through thermogravimetric analysis,limiting oxygen index(LOI),vertical combustion(UL 94),and cone calorimeter.When 15 wt%APP and 5 wt%ATH were added together,the PU/15%APP/5%ATH sample shows better thermal stability and flame-retardant properties.When 15 wt%APP and 5 wt%ATH were added together,the LOI value of the PU/15%APP/5%ATH sample was 30.5%,and UL 94 V-0 rating was attained.Compared with PU,the peak heat release rate(PHRR),total heat release(THR),and average effective heat combustion(av-EHC)of the PU/15%APP/5%ATH sample decreased by 43.1%,21.0%,and 29.4%,respectively.In addition,the flame-retardant mechanism was investigated through cone calorimeter.The APP/ATH addition simultaneously exerted condensed phase and gas phase flame retardant effects.APP and ATH have synergistic flame retardant properties.