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.

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.

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.

Regulating the Localization of Intumescent Flame Retardant for Improving the Flame Retardancy of Ethylene-vinyl Acetate Copolymer Using Polyamide 6 as a Charring Agent

Polyamide 6 (PA6) was employed as a charring agent of intumescent flame retardant (IFR) to improve the flame retardancy of ethylene-vinyl acetate copolymer (EVA). Different processing procedures were used to regulate the localization of IFR in the EVA matrix. Localizations in which IFR was dispersed in the PA6phase or in the EVA phase were prepared. The effect of the localization of IFR on the flame retardancy of EVA was investigated. The limited oxygen index (LOI), vertical burning (UL 94) and cone calorimeter test (CCT)showed that the localization of IFR in the EVA matrix exhibited a remarkable influence on the flame retardancy.Compared with EVA/IFR, a weak improvement in the flame retardancy was observed in the EVA/PA6/IFR blend withthe localization of IFR in the PA6 phase. When IFR was regulated from the PA6 phase to the EVA matrix,a remarkable increase in the flame retardancy was exhibited. The LOI was increased from 27.8%to 32.7%, and the UL 94 vertical rating was increased from V-2 to V-0. Moreover, an approximately 41.36%decrease in the peak heat release rate was exhibited. A continuous and compact intumescent charring layer that formed in the blends with the localization of IFR in the EVA matrix should be responsible for its excellent flame retardancy.

A novel high-efficient P/N/Si-containing APP-based flame retardant with a silane coupling agent in its molecular structure for epoxy resin

A flame retardant containing multiple antiflaming elements usually exhibits high-efficient flame retardancy. Here, a novel P/N/Si-containing ammonium polyphosphate derivative(APTES-APP) is synthesized from ammonium polyphosphate(APP) and silane coupling agent(3-aminopropyl)triethoxysilane(APTES)via cation exchange, which is quite different in the chemical structure from APTES-modified APP for retaining silicon hydroxyls. APTES-APP is highly efficient for the epoxy resin. 8%(mass) APTES-APP imparts excellent flame retardancy to the epoxy resin, with a V-0 rating at the UL-94 test(1.6 mm)and an LOI value of 26%(vol). The peak heat release rate and total smoke production of the flameretardant epoxy resin are decreased by 68.1% and 31.3%, respectively. The synergy of P/N/Si contributes to the well-expanded char residue with a strong and dense surface layer, which is a very good barrier against heat and mass transfer. Besides, there is no significant deterioration in the mechanical properties of flame-retardant epoxy resin thanks to silicon hydroxyls forming hydrogen bonds with epoxy molecules. Meanwhile, other molecules can be grafted onto APTES-APP via these silicon hydroxyls, if needed.Briefly, this work has developed a new strategy for amino silane as flame retardants. In conjunction with a low-cost and simple preparation method, APTES-APP has a promising prospect in the high-performance flame-retardant epoxy.

Research on the effect of the common flame retardant in reducing the flammability of the bitumen

The bituminous defect that the binder is flammable will bring road safety risk.Once it catches fires,large quantities of heat,smoke and poisonous gas are produced,released and spread quickly,which seriously hinder escape and rescue and harms heavily traffic safety.The common flame retardant system is used to modify the asphalt.Cone Calorimeter is adopted to evaluate the burning property of asphalt.The performance of the flame retardant is evaluated by limiting oxygen index and orthogonal design method.The paper analyzes the synergism of the asphalt and flame-retardant,and analyzes the effect of the flame on preventing the smoke to spread and demonstrates that the use of common flame retardants which is added into binder is good at reducing the flammability of the binder.This way can increase the safety of asphalt pavement when fire occurs in the tunnel.The study suggests that flame retardancy of asphalt can be evaluated by Limit Oxygen Index (LOI) and the flame retardancy property of asphalt has marked change according to the content of flame retardant.SB has perfect flame retardancy property,and ATH is better than MH in the effect of flame retardant.

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.

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.

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.

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.

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.

Preparation and Properties of Bio-Based Flame Retardant Polyvinyl Alcohol

Polyvinyl alcohol (PVA) has been widely used in the fields of medical, food and packaging due to its excellentbiocompatibility, good fiber-forming and film-forming properties. However, the high flammability of PVA hasgreatly limited its wider applications. The flame-retardant PVA was prepared by melt blending of a bio-basedflame retardant (prepared from lignin, phosphoric acid and carbamide) with thermoplastic PVA (TPVA). Thechemical structure, morphology, thermal properties, mechanical properties, fire property and fluidity of thisflame retardant PVA were investigated by Fourier transform infrared spectrometer(FTIR), field emission scanning electron microscope(SEM), thermogravimetric analyzer(TGA), impact tester, universal testing machine,horizontal-vertical burning tester, limiting oxygen indexer(LOI) and melt flow rate meter(MFR). The resultsshowed that the prepared flame retardant had good compatibility with the PVA substrate;The impact strength,melt flow rate, fire property and char residue of this PVA material increased with the content of bio-based flameretardant. When the content of flame retardant was of 20%, the five indices including impact strength, meltflow rate, UL-94 level, LOI and char residual were 11.3 KJ/m^(2), 21.2 g/10 min, V-0 UL-94 level, 33.1%, and19.2%, respectively. This research can promote the high-value utilization of lignin and the application ofPVA in the fields of fire protection.

Tribological and flame retardant modification of polyamide-6 composite

A series of wear and flame resistant polyamide 6(PA6)composites were prepared using glass fiber(GF)and talc(T)as reinforcer,polytetrafluoroethylene(PTFE)and graphite(Gr)as solid lubricants,red phosphorus(RP)and zinc borate(ZB)as flame retardant.The tribological property,mechanical property,flame retardant property and the flame retardant mechanism were investigated.The tests show that the formula of the wear resistant PA6 composite(WRPA 6)is PA6/GF/T/PTFE/Gr in the ratio of 100/15/5/10/5 by mass.Because this composite exhibits the lowest friction coefficient(0.1429)and no wear mass loss,the introduction of RP and ZB can increase the flame resistance of WRPA6,and the synergistic effect of RP and ZB is obtained.Detailedly,the composite with 4 parts of ZB and 12 parts of RP shows the best flame retardant property,achieving the highest limiting oxygen index(LOI)(30.2 vol%)and a UL94 V-0 rating,and the flame retardant mechanisms may be gas phase along with condense phase mechanism.

Flame retardant synergy between interfacial and bulk carbonation in glass fiber reinforced polypropylene

Glass fiber reinforced polypropylene(GF-PP)composites have high flammability on account of wick effect which leads to accelerated flow of the polymer melt along the glass fibers(GF)surface to the flame zone.In this study,dipentaerythritol(DPER),a charring agent,was adsorbed on the GF surface through the hydrogen bond between silane coupling agent and DPER.DPER has a synergistic effect with the intumescent flame retardants(IFR)added in the composites,which can induce interfacial carbonization on the surface of GF,thus transforming the intrinsic smooth GF surface into roughness one.In this way,the negative effect of the wick effect in flame retardancy is weakened.Moreover,the char residues remained on the surface of GF can bring an improved adhesion between GF and char residues formed in the resin so that a more stable barrier char layer is formed.The PP composites with 20 wt%modified glass fiber(M-GF)and 30 wt%IFR can achieve the UL-94 V-0,and its limiting oxygen index(LOI)value increased from 16.5%to 29.5%.Simultaneously,the heat release rate(HRR),total heat release(THR)and total smoke release(TSR)decreased significantly,and the peak of heat release rate(PHRR)reduced60.6%compared with GF-PP.

Hyperbranched Polyurethane Acrylate Applied to UV Curable Flame Retardant Coatings

UV curable hyperbranched prepolymers based on amine-ester, ester-amide and ether-amide started with AB_2-type monomers have been prepared by the authors. A series of work on allyl ether maleate hyperbranched polyesters for UV curing coatings by Hult and his colleagues has been reported. However, the UV cured films from those materials are all flammable when attached to fire without addition of flame retardants.

Novel Bio-based Flame Retardant Systems Derived from Tannic Acid

In this study,tannic acid(TA)was investigated as flame retardant agent for PLA.Different strategies to modify its thermal degradation pathway have been explored in order to improve its charring effect.The first one consists in combining TA with organomodified montmorillonite(oMMT),and enables limiting the thermo-oxidative degradation of TA and promoting the formation of an effective char layer.Flame-retardant(FR)behavior of PLA-based composition has been found to be positively impacted by this combination since a reduction of the peak of Heat Release Rate(PHRR),more important than the value recorded when oMMT and tannic acid are used separately,has been obtained.The second strategy,in which tannic acid was associated with a biosourced phosphorousbased compounds,i.e.metallic phytate salt,evidenced another alternative allowing enhancing TA flame retardant effect at 30 wt%loading content.The third and last strategy explored aims to chemically modify TA via a chemical grafting of phosphoric acid groups.This phosphorylated TA was shown to present the most effective flame-retardant(FR)effect.However,an important reduction of PLA molecular weight was observed.

A Vanillin-Derived,DOPO-Contained Bisphenol as a Reactive Flame Retardant for High-Performance Epoxy Thermosets

Quest for bio-based halogen-free green flame retardant has attracted many concerns in recent years.Herein a reactive functional flame retardant containing phosphorus VDP is synthesized from vanillin,9,10-dihydro-9-oxa-10-phosphophene-10-oxide(DOPO)and phenol via a facile way.VDP is characterized with^(1)H NMR,^(31)P NMR,FTIR and Time of Flight Mass Spectrometry,and used as a new reactive flame retardant for bisphenol epoxy thermosets.Thermogravimetry analysis shows that when the VDP loading is only 0.5P%(based on phosphorus content),the residue increases from 14.2%to 21.1%at 750℃ in N_(2)compare with neat DGEBA.Correspondingly,the limit oxygen index increased to 29.6%,and flame retardancy reaches UL-94 V0 grade.Micro combustion calorimetry(MCC)and cone calorimetry analyses demonstrate that VDP can significantly lower flammability of the epoxy thermoset.With only 0.5P%of VDP,the heat release rate,total heat release rate and smoke production are reduced markedly.At the same time,the mechanical properties of the modified epoxy thermosets are also improved.The impact strength increases by 34%and the flexural strength increased by 23%,with 1.5P%of VDP.In short,VDP not only improves the flame retardancy,but also improves the mechanical properties of the epoxy thermosets.

Preparation and Properties of Bio-Based Flame Retardant L-APP/Poly(L-lactic acid)Composites

Poly(L-lactic acid)(PLLA)is a thermoplastic material with complete degradability,high biocompatibility and excellent mechanical properties.It can replace petroleum-based polymers are currently being used in the fields of packaging,agriculture,textiles,medical and so on.However,PLLA’s extremely flammability greatly limits its wider application.An bio-based flame retardant L-APP/PLLA composites was prepared by melt blending of the L-APP and PLLA.The morphology,impact properties,thermal properties and flame retardant properties of composites were investigated by field emission scanning electron microscope(SEM),impact tester,differential scanning calorimeter(DSC),thermogravimetric analyzer(TGA),limiting oxygen indexer(LOI)and horizontalvertical burning tester.The results showed that the degree of crystallization(X_(c))and LOI of L-APP/PLLA composites increased as increasing of L-APP content.What’s more,the impact strength first increased and then decreased,the glass transition temperature(T_(g))and melting temperature(T_(m))do not changed significantly.The impact strength of composites was 9.1 kJ/m^(2) at a 5 wt%loading for L-APP,which was the highest level.When the content of L-APP was 20%,the LOI was 30.8%,the Xc was 42.3%and the UL-94 level was V-0.This research can promote the value-added utilization of lignin and the application of PLLA in the fields of flame retardant materials.