Inorganic/organic phosphorus-based flame retardants synergistic flame retardant rigid polyurethane foam

The flame-retardant rigid polyurethane foam (RPUF) composites are fabricated by ammonium polyphosphate (APP) with pentaerythritol phosphate (PEPA), phenoxycycloposphazene (PCP), and aluminum diethylphosphinate (ADP), respectively, which are labeled as RPUF-1, RPUF-2, and RPUF-3. The influence of flame retardants on the apparent density and compressive strength of RPUF is studied. The results reveal that flame retardants not only improve the apparent density, but also improve the compressive strength of RPUF composites. The limiting oxygen index (LOI) results reveal that these inorganic/organic phosphorus-based flame retardants improve the LOI significantly, especially for RPUF-2 and RPUF-3 systems. The cone calorimeter test results suggest that the peak of heat release of RPUF-1, RPUF-2, and RPUF-3 systems decrease by 38%, 41%, and 52% likened to that of pure RPUF. And APP and ADP system performs best in declining the heat release. And APP and PEPA systems perform best in decreasing the smoke release. The flame retardancy mechanism of RPUF composites is analyzed in details.     

Preparation and smoke suppression mechanism of flame-retardant PBS composites with BNNS@DOPA

Currently, the flame-retardant modification of polybutylene succinate (PBS) is mainly focused on improving flame-retardant efficiency, ignoring the negative impact of the smoke produced by combustion on the human respiratory tract. To address this problem, PBS composites were prepared by melt blending method in this study. The effect of boron nitride-grafted DOPO flame retardant (BNNS@DOPA) on flame retardancy and smoke suppression of PBS composites was investigated. Incorporating 3% BNNS@DOPA into PBS composites results in a 90% improvement in thermal conductivity. This resulted in a reduction of the peak heat release rate, total heat release rate, and actual smoke rate to 453.7 kW m⁻², 86.3 MJ m⁻², and 1035.9 m², respectively, compared with pure PBS. The latter indicated a decrease of 34.0%, 37.6%, and 51.2%, respectively. Furthermore, the ignition time was extended by 45 s and the limiting oxygen index value increased by 12.5%. This functionalization approach presents a new way to study PBS flame retardancy improvement, consequently boosting its application in fire safety for polymer materials.     

Synergistic effect of carbon and phosphorus flame retardants in rigid polyurethane foams

Two kinds of carbon and phosphorus synergistic system used to improve the flame retardancy of rigid polyurethane foams (RPUF) were studied. One is the synergistic effect of expandable graphite and guanidinium phosphate; the other is red phosphorus and guanidinium phosphate. The flame retardant properties and mechanical properties of these composites were investigated by limiting oxygen index, cone calorimeter test, as well as tension and compression test. These 2 groups of mixed inorganic flame retardants can greatly improve the flame retardancy of RPUF composites, as the limiting oxygen index increases from 20.1% to about 33% and the HRR reduces from 395 kW/m² to below 200 kW/m². It provides a convenient and inexpensive way to obtain RPUF with demanding properties.     

Rigid polyurethane foams with halogen-free flame retardants: Thermal insulation,mechanical, and flame retardant properties

Rigid polyurethane foam (RPUF) composites with triphenyl phosphate (TPhP), aluminum trihydrate (ATH), and zinc borate (ZnB) alone, as well as their binary blends, were prepared via a one-shot process. The amount of flame retardant (FR) or FR blend was varied from 10 to 50% by polyol weight percentage, and the weight fraction of the blends was also fixed at 40%. The effects of additives on thermal insulation, mechanical, and flame retardancy properties of the composites were investigated. Thermal conductivity of the neat foam (RPUF) decreased from 22.53 to 21.04–21.58 mW m⁻¹ K⁻¹. The compressive strength of foams displayed an increase with increasing the amount of TPhP, ATH, and ZnB till 40% by weight. The limited oxygen index values of all foams increased and the flame spread rates of all foams significantly decreased. It was also observed that the flame was self-extinguished in some cases. The cone calorimeter test results indicated that the FR additives improved the flame retardancy of the RPUF. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47611.     

Self-emulsification synthesis of epoxy phosphate ester and its flame-retardant mechanism in flexible poly(vinyl chloride)/magnesium hydroxide composites

A trade-off dilemma exists for simultaneously improving the mechanical properties and flame resistance of flexible polyvinyl chloride (fPVC)/magnesium hydroxide (MH) composites. In this study, epoxy phosphate ester (EPE), a hydrophobic surface modifier of MH, was synthesized using a self-emulsification method. After modification, EPE was bonded to the surface of MH (MHEPE) without altering its morphology. The results of limiting oxygen index and cone calorimetry tests indicated that fPVC/MHEPE exhibited better flame retardancy and smoke suppression effects than did fPVC/MH. The peak of the heat release rate, total heat release, peak of the smoke production rate, and total smoke production of the fPVC/MHEPE composite were 206.0 kJ m⁻², 45.90 MJ m⁻², 0.0729 m² s⁻¹, and 9.88 m², which were 8.64%, 14.00%, 27.61%, and 9.02% lower than those of the fPVC/MH composite, respectively. For the fPVC/MHEPE composite, a compact and continuous char residue formed, which could inhibit heat and flammable volatile migration between the matrix and burning zones. In the gas phase, the dilution effect of H₂O vapor reduced the concentrations of O₂ and flammable volatiles. The free-radical quenching effect of ·PO and ·PO₂ also played a vital role in extinguishing flame and terminating combustion. Further, the introduction of EPE improved the tensile and impact strengths of the fPVC/MH composites because of the excellent interfacial compatibility between MHEPE and the fPVC matrix. This study provides a simple and workable solution for the trade-off dilemma, and the remarkable flame retardancy and mechanical properties of the fPVC/MHEPE composite render it a promising cable material.     

聚氨酯／蒙脱土复合阻燃硬质泡沫材料的研究

采用原位聚合法制备了蒙脱土阻燃硬质聚氨酯泡沫材料,并用多种添加型阻燃剂制备了阻燃聚氨酯硬质泡沫,同时尝试有机改性蒙脱土与添加型阻燃剂并用对聚氨酯硬质泡沫进行阻燃。用锥形量热仪测试了阻燃聚氨酯泡沫材料的燃烧性能,结果发现,材料的热释放速率、质量损失速率与纯聚氨酯硬质泡沫相比均显著降低,峰值热释放速率最多降低到纯硬质泡沫的55％,表明制备的泡沫材料具有较好的阻燃性。用X-射线衍射和扫描电镜分析了蒙脱土及有机改性蒙脱土的微观结构。通过分析材料的燃烧性能和燃烧残余物,探讨了其可能的阻燃机理。     

Synergistic effect of expandable graphite and aluminum hypophosphite on flame‐retardant properties of rigid polyurethane foam

A series of flame retarding rigid polyurethane foam (RPUF) composites based on expandable graphite (EG) and aluminum hypophosphite (AHP) were prepared by the one‐pot method. The properties were characterized by limiting oxygen index (LOI) test, cone calorimeter test, thermogravimetric analysis (TGA), real‐time Fourier transform‐infrared spectra (RT‐FT‐IR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), etc. The results indicate that both EG and AHP could enhance the flame retardency of RPUF composites. Besides, the flame retardant effect of EG was better than that of AHP. The results also show that partial substitution of EG with AHP could improve the flame retardency of RPUF, and EG and AHP presented an excellent synergistic effect on flame retardancy. What is more, compared with RPUF/20EG and RPUF/20AHP, the heat release rate (HRR) and total heat release (THR) of RPUF/15EG/5AHP were lower.TGA results indicate that partial substitution of EG with AHP could improve the char residue which provided better flame retardancy for RPUF composites. The thermal degradation process of RPUF composites and the chemical component of the char residue were investigated by RT‐FT‐IR and XPS. And the results prove that RPUF/15EG/5AHP had higher heat resistance in the later stage. Compared with the RPUF composites filled with EG, a better cell structure and mechanical properties were observed with the substitution of AHP for part of EG. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42842.     

A P/N-containing flame retardant constructed by phosphaphenanthrene,phosphonate, and triazole and its flame retardant mechanism in reducing fire hazards of epoxy resin

A P/N-containing flame retardant (PPT) constructed by phosphaphenanthrene, phosphonate, and triazole groups was successfully synthesized and used as a reactive co-curing agent for epoxy resin (EP). The curing behavior, thermal property, combustion behavior, and flame retardant mechanism of EP thermosets were comprehensively investigated. According to the analysis of DSC and TGA, PPT accelerated the crosslinking reaction and enhanced the charring ability for EP thermosets at high temperature. The results of combustion test indicated that PPT endowed epoxy thermoset with outstanding flame retardancy. When the phosphorus content was 0.71 wt%, EP/DDS/PPT-2 achieved a LOI value of 33.2% and passed V-0 rating in UL-94 test, and its peak heat release rate and total heat release were decreased by 63.7 and 30.5%, respectively, relative to EP/DDS. Moreover, the FIGRA of EP/DDS/PPT-2 was reduced from 9.7 to 3.5 kW m⁻² s⁻¹, manifesting the significantly improved fire safety of EP thermoset. The flame retardant mechanism was summarized as two parts: (a) the barrier effect of continuous phosphorus-rich char layers in condensed phase, (b) the quenching effect of phosphorous radicals and diluting effect of nonflammable gases in gaseous phase.     

Preparation and properties of wear-resistant and flame-retardant polyphenylsulfoneurea/monomer casting nylon copolymers

A poly(phenylsulfone)-urea (PPSUU) macro-activator is synthesized by in situ anionic polymerization of 4,4′-diaminodiphenylsulfone and hexamethylene diisocyanate. The PPSUU segment is embedded into the nylon molecular chain through copolymerization to improve the wear resistance and flame retardancy of monomer cast nylon 6 (MC PA6) materials. The mechanical properties, thermal stability, friction and wear properties and combustion heat release rate of copolymers with different macro-activator contents are tested. Results indicate that a small amount of PPSUU can improve the wear resistance and impact properties of nylon materials. The wear loss of MC nylon is 54.8% less than pure MC nylon from 1.049 × 10⁻⁸ to 0.474 × 10⁻⁸ g/Nm with 6 wt% PPSUU. Moreover, better flame retardancy is verified. The peak of HRR reduced 36.8% from 654 to 413 kw/m² with 4 wt% PPSUU, accompanied by advanced ignition time and flame extinction time, thus reducing the risk of fire.     

Hierarchical Cellular Poly(m-phenylene isophthalamide) with High Flame Retardancy,Mechanical Robustness,and Heat Resistance at Extreme Situation

High-performance cellular foams with superior mechanical properties and heat resistance are urgently needed to fulfill the applications in extreme environments. However, they are difficult to be prepared because of low gas diffusion rate in high-performance polymers. In this work, a facile solution-foaming strategy to prepare multifunctional foams based on poly(m-phenylene isophthalamide) (PMIA) is reported. The achieved PMIA foams show a hierarchically cellular structure containing macropores and mesopores. Due to their high porosity, the PMIA foams exhibit low thermal conductivity (0.0447–0.0498 W m⁻¹ K⁻¹) and high sound absorption coefficient at different frequency. A bimodal distribution on acoustic absorption is observed. With a bulk density range of 0.089–0.122 g cm⁻³, PMIA foams possess compressive moduli of 3.2–14.2 MPa and bending strength of 1.1–2.1 MPa, respectively. Moreover, they exhibit a recoverable deformation of 55.4% after 10 cycling 10% strain compressions and maintain a dimensional stability under harsh environment (–196 to 250 °C). Despite generated byproducts like polyurea, they still show a limiting oxygen index (25.2–26.3%) and relatively low heat release rate (178.3 kW m⁻²). This work provides a facile strategy to efficiently prepare high-performance PMIA foams for broad application prospects.     

Effect of a nanoclay/triphenyl phosphate hybrid system on the fire retardancy of polycarbonate/acrylonitrile–butadiene–styrene blend

The effect of a hybrid system of nanoclay and triphenyl phosphate (TPP) on the fire retardancy of a polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) blend was examined in this study. The nanoclay in the polymers decreased the peak heat release rates (PHRRs) with no significant effect on the ease of ignition and times to extinguishment. Improvements in the flame retardancy were observed only when nanoparticles were used with conventional flame‐retardant (FR) additives. Thermogravimetric analysis (TGA), cone calorimetry, and limited oxygen index (LOI)/UL 94 (Underwriters Laboratory) testing were used to investigate the thermal degradation, fire behavior, and flammability of the materials. The results show that when we used a combination of TPP and nanoclay as an FR system, degradation of the polymer blends was reduced as the TGA curves shifted to higher temperatures. PHRR in cone calorimetry testing decreased from 1032 kW/m² for the PC/ABS blend to 300 kW/m² for the PC/ABS/(12% TPP–2% nanoclay) sample, and the LOI increased from 23 to 35%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of different reactor types on Nannochloropsis oculata microalgae culture for lipids and fatty acid production

Greenhouse gases emitted into the atmosphere by burning of fossil fuels cause global warming. One option is obtaining biodiesel. Nannochloropsis oculata was cultured under different light intensities and reactors at 25°C for 21 days with f/2 medium to assess their effects on cell density, lipid, and fatty acids (FAs). N. oculata improved cell density on fed-batch glass tubular reactor (7 L) at 200 μmol E m⁻² s⁻¹, yielding 3.5 × 10⁸ cells ml⁻¹, followed by fed-batch Erlenmeyer flask (1 L) at 650 μmol E m⁻² s⁻¹ with 1.7 × 10⁸ cells ml⁻¹. The highest total lipid contents (% g lipid × g dry biomass⁻¹) were 44.4 ± 0.8% for the reactor (1 L) at 650 μmol E m⁻² s⁻¹ and 35.2 ± 0.2% for the tubular reactor (7 L) at 200 μmol E m⁻² s⁻¹, until twice as high compared with the control culture (Erlenmeyer flask 1 L, 80 μmol E m⁻² s⁻¹) with 21.2 ± 1%. Comparing the total lipid content at 200 μmol E m⁻² s⁻¹, tubular reactor (7 L) and reactor 1 L achieved 35.2 ± 0.2% and 28.3 ± 1%, respectively, indicating the effect of shape reactor. The FAs were affected by high light intensity, decreasing SFAs to 2.5%, and increased monounsaturated fatty acids + polyunsaturated fatty acids to 2.5%. PUFAs (20:5n-3) and (20:4n-3) were affected by reactor shape, decreasing by half in the tubular reactor. In the best culture, fed-batch tubular reactor (7 L) at 200 μmol E m⁻² s⁻¹ contains major FAs (16:0; 38.06 ± 0.16%), (16:1n-7; 30.74 ± 0.58%), and (18:1n-9; 17.15 ± 0.91%).     

可膨胀石墨与含磷阻燃剂在聚氨酯硬泡材料中的应用

通过氧指数仪与锥形量热仪研究了可膨胀石墨（EG）与低聚磷酸酯多元醇（OP550）、二乙基N,N二(2羟乙基)胺基甲基膦酸酯（WSFR 6）2种反应型含磷阻燃剂对聚氨酯硬泡材料（RPUF）阻燃性能的影响。结果表明,在OP550与WSFR 6的存在下,RPUF具有较好的成炭性,且炭层较为致密;添加EG后,体系的阻燃性能进一步提高,当其含量为14 %（质量分数,下同）时,RPUF体系的极限氧指数达到33.6 %,热释放速率峰值降低到106.93 kW/m2。     

Flame retardancy of ceramic-based rigid polyurethane foam composites

In this work, ceramic fillers zirconia and alumina powder were incorporated in the rigid polyurethane foams derived from modified castor oil and their impact on the mechanical, thermal, and fire performances of composite foams have been analyzed. It was observed that the addition of ceramic filler showed improved mechanical and thermal properties and best properties were shown by 6% zirconia with compressive strength of 6.61 MPa and flexural strength of 5.72 MPa. Zirconia also demonstrated an increase in T_5% up to 260 °C. Cone calorimetry shows a decrease in peak of heat release from 118 to 84 kW m⁻² and 94 kW m⁻² by the incorporation of alumina and zirconia powder, respectively. Furthermore, total heat release (THR), smoke production rate (SPR), and total smoke release (TSR) were also found to decrease remarkably on the incorporation of ceramic fillers. So, these fillers have a great potential as an additive to incorporate good mechanical, thermal, and fire properties in bio-based rigid PU foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48250.     

Enhanced flame-retardant performance of rigid polyurethane foam by using APTES-MMT and ATH mixed intumescent coatings

The design of environment-friendly fireproof rigid polyurethane foams (RPUFs) that completely prevent ignition or the spread of fires is important for energy conservation and emission reductions. In this paper, an intumescent flame-retardant coating was prepared and coated onto the surface of a RPUF to improve its flame retardancy. Vertical combustion experiments (UL-94) showed that, compared with the pure RPUF, a RPUF coated with the expansion coating successfully self-extinguished without a droplet formed after ignitor removal. Thermogravimetric analyses showed that the expanded coating effectively increased the rate of carbon residue formation. Cone calorimetry showed that when the pigment-to-binder ratio was 3.5:1, with 5% modified montmorillonite, 6% aluminum hydroxide, and 4% titanium dioxide, the intumescent coating effectively reduced the heat release rate and total heat release of the RPUF. Remarkably, the smoke release rate and total exhaust gas volume showed that the expanded coating provided obviously enhanced smoke suppression. Therefore, the flame retardancy and toxic smoke suppression provided by the RPUF thermal insulation material is essential and very useful for healthy development of human society and the environment.     

Thermal energy storage performance of hierarchical porous kaolinite geopolymer based shape-stabilized composite phase change materials

Phase change materials (PCMs) are prospective energy materials that are widely applied in building energy conservation, waste heat recovery, infrared stealth technology and solar dynamic power system. The enhancement of heat transfer and leak-proof performance are critical to PCMs. Although geopolymers have been applied in thermal energy storage, meanwhile, hierarchically porous geopolymers have already shown superb performance in various functional applications, to the authors’ knowledge, no report concerning the application of hierarchical porous ones have been issued. This paper concerns the preparation of a shape-stabilized composite PCMs, consisting of hierarchically porous kaolinite-based geopolymer (PKG) embedding polyethylene glycol 4000 (PEG4000), which shows promising prospects in thermal energy storage. Optimized porous geopolymer matrices feature high porosity (>83%), combined with high specific surface area (4.7 m²/g) and thermal conductivity (TC, 1.324 W·m⁻¹·K⁻¹). Furthermore, the shape-stabilized composite PCMs show excellent thermal energy storage properties: loading rate of 80.93 wt%, latent heat of 168.80 J g⁻¹ and TC of ∼0.36 W·m⁻¹·K⁻¹ at 20–30 °C, which is 1.64 times of the TC of pure PEG4000. Finally, the photothermal conversion performances of the shape-stabilized composite PCMs were also simulated.     

Flame‐retardant and mechanical properties of high‐density rigid polyurethane foams filled with decabrominated dipheny ethane and expandable graphite

The article reported the flame‐retardant and the mechanical properties of expandable graphite (EG), an intumescent type, and decabrominated dipheny ethane (DBDPE), a gas‐phase type of flame‐retardant‐containing high‐density rigid polyurethane foams (RPUF) with a constant density of 0.5g/cm³. The results indicated that both EG and DBDPE could effectively interdict the burning of RPUF, besides, the EG exhibited more effective flame retardancy than the DBDPE. When the flame‐retardant loadings were 20 wt %, the LOI value of DBDPE‐filled RPUF increased to 33 vol %, while, surprisingly, the EG‐filled RPUF reached 41 vol %. Unfortunately, when they were both simultaneously added into RPUF, there was not any flame‐retardant synergistic effect. Although EG had outstanding flame retardancy, the compressive strength and modulus of 20 wt % EG‐filled RPUF dropped to only 9.1MPa and 229.7MPa respectively, which were lower than those of DBDPE (12.4 MPa and 246.8 MPa). The phenomena were ascribed to the different flame‐retardant mechanisms of EG and DBDPE, which were verified by scanning electronic microscope (SEM) observation of the burned surfaces. Besides, the dynamical mechanical analysis (DMA) demonstrated that the additions of EG and DBDPE made the glass transition temperature shift to the high temperatures, and the EG‐filled RPUF had the higher storage modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物（GTO）,GTO经环氧化得到环氧化桐油醇解产物（EGTO）,EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）发生开环反应生成新型含磷阻燃型桐油基多元醇（PTOP）。PTOP部分取代聚醚多元醇（PPG4110）与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡（RPUF）。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明：随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数（LOI）由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。     

Properties of a novel inherently flame-retardant rigid polyurethane foam composite bearing imide and oxazolidinone

A novel inherently flame-retardant rigid polyurethane (PU) foam with imide and oxazolidinone was prepared by using 3,3′,4,4′-biphenyltetracarboxylic dianhydride (PTDA) and 9,10-dihydro-9-oxa-(10-glycidoxypropylene)-10-phosphap-henanthrene-10-oxide (e-DOPO) as reactive flame retardants. The physical and mechanical properties of the prepared PU foams were investigated. The compressive strength was improved to 0.22 MPa, the thermal conductivity decreased, and the density hardly changed. Thermogravimetric (TG) analysis and TG analysis coupled with Fourier transform infrared spectroscopy indicated that the PTDA and e-DOPO showed a small improvement in thermal properties. The fire behaviors were evaluated based on the limited oxygen index (LOI), cone-calorimetry experiment, and smoke-density test. The LOI of the PU foam with PTDA and e-DOPO reached 22.4%. The peak of heat release rate and total heat release decreased to 227.50 kW m⁻² and 11.27 MJ m⁻² from 281.28 kW m⁻² and 14.05 MJ m⁻², respectively. The morphologies of the PU foam and residues after the cone-calorimetry test were characterized by scanning electron microscopy. X-ray photoelectron spectroscopy analysis indicated that PTDA and e-DOPO lead to an increase in graphite in the residue and the formation of a better barrier to prevent burning by the condensed-phase mechanism. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47943.     

Designing of an rGO-based heterostructure for highly efficient microwave absorption performance and flame retardancy

To meet the increasingly serious challenges of electromagnetic pollution and fire hazards, highly efficient electromagnetic absorbing materials with good flame retardancy have been accurately developed. A complex high-performance electromagnetic absorber was designed by doping graphene oxide heterostructures (including zero-dimensional nanoparticles and two-dimensional graphene) containing cobalt, nickel and iron oxyhydroxide through the coordination effect. When 20 wt% CNFO@rGO was incorporated into paraffin, the minimum reflection loss (RL) reached -51.6 dB at a thickness of 3.5 mm, showing a high electromagnetic absorption efficiency. It was concluded that the excellent impedance matching, the best dielectric loss and the higher magnetic loss caused by the heterostructure combined with the electromagnetic parameters, Cole-Cole semicircle, impedance matching (Z) and attenuation coefficient resulted in excellent electromagnetic wave absorption performance. Moreover, the peak heat release (PHRR) and heat release rate (HRC) decreased by 55.5% and 55.1%, respectively, when 10 wt% CNFO@rGO was incorporated into the epoxy resin (EP), indicating enormous potential for the enhancement of flame-retarding electromagnetic absorbing materials.