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1.
The thermal and fire properties of PMMA modified with various loadings of melamine or zinc aluminum undecenoate LDH were evaluated using TGA, DTA and cone calorimetry. The additives were characterized by X-ray diffraction, TGA, FT-IR and elemental analysis. While the two additives are very effective with this polymer, a higher loading of melamine (30%) is required to reach a good reduction in PHRR (47%) relative to the pure polymer, while with the LDH, 10% loading is enough to obtain a similar reduction. The combinations of these additives in PMMA reveal that the time to PHRR and the amount of smoke produced are the key differences, with melamine increasing the first parameter and leading to less smoke production relative to LDH-rich PMMA systems at similar total additive loadings. Analysis of the residue shows that melamine is completely lost during combustion while the LDH forms ZnO and ZnAl2O4.  相似文献   

2.
A metal-doped organic and inorganic hybrid polyhedral oligomeric silsesquioxanes (POSS) with a titanium atom in the POSS cage and an ethanolamine substitute group in the corner, namely MEA-Ti-POSS, was synthesized through simple condensation reaction and substitute reaction. It was blended with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to form a kind of blending-type flame retardant system for the modification of epoxy resins. The thermal stability, flame retardancy and mechanical properties of cured epoxy resin composites were studied. Comparing with pure epoxy resin, the LOI value of EP/MEA-Ti-POSS/DOPO composites was raised from 25.2% to 32.7%, and the UL-94 grade reached V-0 level at a loading of the mixture of 5% MEA-Ti-POSS and 5% DOPO. In addition, the cone calorimetry results showed that the heat release rate, total heat release and total smoke production as well as smoke production rate were all reduced during the combustion of EP/MEA-Ti-POSS/DOPO composites. The residual char analysis revealed that carbon residues of EP/MEA-Ti-POSS/DOPO composite served as a physical protective layer to insulate the oxygen and combustible gases to reduce the ablation of the matrix. It was concluded that the mixture of MEA-Ti-POSS and DOPO not only effectively raised the thermal stability and flame retardancy of epoxy composited materials, but also improved their mechanical properties, which expanded a promising application of the metal-POSS derivatives as non-halogen additives in the flame retardant polymers.  相似文献   

3.
The flame‐retardant polylactic acid (PLA) has been prepared via mixing the flame retardant TGIC‐DOPO derived from phosphaphenanthrene and triazine groups into matrix. The flame retardancy of TGIC‐DOPO/PLA composites was characterized using the limiting oxygen index (LOI), vertical burning test (UL94), and cone calorimeter test. Results reveal that the 10%TGIC‐DOPO/PLA composite obtained 26.1% of LOI and passed UL94 V‐0 rating. The flame‐retardant mechanism of PLA composites was characterized via thermogravimetric analysis (TGA), pyrolysis gas chromatography/mass spectroscopy, and TGA‐Fourier transform infrared. It discloses that TGIC‐DOPO promoted PLA decomposing and dripping early, and it also released the fragments with quenching and dilution effects. These actions of TGIC‐DOPO contribute to reducing the burning intensity and extinguishing the fire on droplets, thus imposing better flame retardancy to PLA. When TGIC‐DOPO was partly replaced by melamine cyanuric with dilution effect and hexa‐phenoxy‐cyclotriphosphazene with quenching effect in composites respectively, the results confirm that TGIC‐DOPO utilize well‐combination in dilution effect and quenching effect to flame retard PLA. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

4.
本文研究了以聚磷酸铵(APP)为主阻燃剂,次磷酸铝(AHP)和三聚氰胺氰尿酸盐(MCA)为辅阻燃剂的协效阻燃体系对聚丙烯(PP)阻燃性能的影响。 采用垂直燃烧测试、极限氧指数(LOI)测试、热重分析、锥形量热仪测试、扫描电子显微镜分析等技术手段对所制备的阻燃样品进行了阻燃性能分析。 结果表明:单独添加任一质量分数30%阻燃剂,均不能使PP获得良好的阻燃性能;当阻燃剂总质量分数保持在30%,m(APP):m(AHP):m(MCA)=4:1:1时获得理想阻燃效果,此时阻燃PP的LOI为33%,垂直燃烧测试达到V-0级,热释放速率峰值(PHRR)从765.7 kW/m2降为122.7 kW/m2。  相似文献   

5.
In order to improve the flame retardant of polylactide (PLA), the synergistic effect of graphitic carbon nitride (g‐C3N4) with commercial‐available flame retardants melamine pyrophosphate (MPP) and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) was investigated. The PLA composites containing 5 wt% g‐C3N4 and 10 wt% DOPO had a highest limited oxygen index (LOI) value of 29.5% and reached the V‐0 rating of UL‐94 test. The cone calorimeter tests exhibited that DOPO had a better synergistic effect with g‐C3N4 than MPP to improve flame retardancy of PLA. The peak heat release rate (pHRR) and total heat release (THR) of PLA composites containing 10 wt% DOPO could be reduced by 25.2% and 23.6%, respectively, as compared with those of pure PLA. The presence of rich phosphorus element and aromatic groups in DOPO contributed to obtain continuous compact char layer and increase the graphitization level of char residues, thereby, resulting in improving the flame retardancy of PLA together with g‐C3N4. In addition, the incorporation of DOPO can serve as a plasticizer to reduce the complex viscosity, improving the processability of PLA composites.  相似文献   

6.
In this work, a DOPO‐based imidazolone derivative named DHI was synthesized using DOPO, 5‐amino‐2‐benzimidazolinone and 4‐hydroxybenzaldehyde as raw materials. The chemical structure of DHI was characterized by 1H‐NMR, 31P‐NMR and Fourier transform infrared spectra (FTIR). Then, a series of different flame‐retardant epoxy resin (EP) thermosets were prepared by mixing flame retardant DHI. The thermal properties of the cured EPs was investigated by thermogravimetry analysis (TGA) and differential scanning calorimeter (DSC), and the results showed the thermal stability and glass transition temperature (Tg) of the cured EP modified with DHI declined slightly compared with that of neat EP. The limited oxygen index (LOI) and UL94 test results exhibited DHI imparted good flame retardancy to EP. The EP‐4 (phosphorus content of 1.25%) possessed a LOI value of 36.5% and achieved a V‐0 rating. Furthermore, the peak of heat release rate (PHRR) and total heat release rate (THR) of EP‐4 decreased by 38.7% and 24.5%, respectively. Excitedly, the total smoke production (TSP) of EP‐4 sample declined by 62.5%, which meant DHI also made EP obtain excellent smoke suppression property. Moreover, the flame‐retardant mechanism was studied by scanning electron microscopy (SEM) and pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS). It was reasonable inferred that DHI could not only promote EP to form dense char layer in condensed phase, but also restrain combustion in gaseous phase through catching the free radicals sourced from the degradation of EP.  相似文献   

7.
通过取代反应、 缩合反应和加成反应等合成了一种无机-有机杂化大分子阻燃剂 六-[4-(N-苯基氨基-DOPO-次甲基)苯氧基]环三磷腈(DOPO-PCP), 并利用傅里叶变换红外光谱、 1H和 31P核磁共振波谱对其进行结构表征. 将DOPO-PCP用于环氧树脂(DGEBA)阻燃, 得到环氧树脂阻燃固化物, 通过极限氧指数(LOI)、 垂直燃烧测试(UL-94)、 热重分析与锥形量热(Cone)测试等对阻燃环氧树脂固化物的热稳定性及燃烧性能进行分析; 利用扫描电子显微镜及Mapping观察并分析了燃烧碳层的形貌与元素分布. 研究结果表明, 产物的结构符合设计的DOPO-PCP分子结构; 当DOPO-PCP在DGEBA中添加量(质量分数)达12.2%时, 磷含量为1.3%, 制得的阻燃环氧树脂固化物垂直燃烧测试通过UL-94 V-0级, LOI值为36.2%; Cone测试结果表明, DOPO-PCP的添加有效降低了DGEBA燃烧时热量与烟气的释放, 且在高温下碳残余量显著增加. 研究表明DOPO-PCP兼具气相和凝固相阻燃机理, 对DGEBA有良好的阻燃性能.  相似文献   

8.
A novel phosphorus‐containing monomer, (6‐oxido‐6H‐dibenzo[c,e][1,2]oxaphosphinin‐6‐yl)methyl acrylate (DOPO‐AA), is first synthesized and characterized by Fourier transform infrared spectra (FTIR), 1H nuclear magnetic resonance (NMR) and 31P NMR. The monomer is then introduced into poly (methyl methacrylate) (PMMA) matrix via in situ copolymerization to produce a new PMMA based copolymer (PMMA/DOPO‐AA). From UV–vis spectra, microscale combustion calorimeter (MCC) and thermogravimetric analyses (TGA) results, the as‐fabricated PMMA/DOPO‐AA copolymers not only keep relatively high transparency, but also exhibit remarkable improvements in the flame retardancy and thermal stability, such as increased T0.5 by 60.2°C and limited oxygen index (LOI) by 4.1, and decreased peak heat released rate (PHRR) by 34.7%. Thermal degradation behaviors investigated by real time Fourier transform infrared spectra (RTIR), char structure analysis studied by scanning electron microscope (SEM) and pyrolysis gaseous products studied by TGA coupled with FTIR (TGA‐FTIR) demonstrate that the catalytic charring function of DOPO‐AA in condensed phase and DOPO flame retardant systems in the gas phase are two key factors for the property enhancements. This work not only provides a promising flame‐retardant monomer for polymers, but also will stimulate more efforts on the development of DOPO‐containing flame‐retardant monomers. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

9.
A novel DOPO‐based pyrazine derivative 6‐((2‐hydroxyphenyl)(pyrazin‐2‐ylamino)methyl)dibenzo[c,e][1,2]oxaphosphinine 6‐oxide (DHBAP) was triumphantly synthesized by a two‐step addition reaction using 2‐aminopyrazine, 2‐hydroxybenzaldehyde and 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) as reactants, and characterized by Fourier‐transform infrared (FTIR), 31P nuclear magnetic resonance (NMR) and 1H NMR. Afterwards, the addition type flame retardant (DHBAP) was utilized to modify epoxy resin (EP) by blending method. When the content of DHBAP in neat EP was 8 wt%, it reached to the V‐0 rating and the limited oxygen index (LOI) value up to 34.0%. Furthermore, according to the cone calorimeter (CC) test results, the heat release rate (HRR), total heat release (THR), smoke produce rate (SPR) and total smoke production (TSP) of EP/8% DHBAP decreased by 26.3%, 21.3%, 37.0% and 60.9% when compared with neat EP, respectively, indicating that DHBAP had good inhibition on heat and smoke releases. Eventually, the flame‐retardant mechanism of DHBAP was further explored by X‐ray photoelectron spectroscopy (XPS), Raman spectroscopy, and pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS). The results showed that DHBAP had good flame‐retardant activity in the gasous‐condensed two phases.  相似文献   

10.
The 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) polymers, melamine polymers, and DOPO‐melamine copolymers have been successfully synthesized, and their flame retarding properties have also been investigated by blending with polypropylene (PP)/styrene‐ethylene‐butylene‐styrene (SEBS) alloys. Experimental results establish that all of them are good polymeric flame retardants. No blooming or color stains occur when they are incorporated into PP/SEBS alloys. Among lab‐made polymeric flame retardants, DOPO‐ melamine copolymers exhibit the best thermal stability and nonflammability. PP/SEBS alloys containing DOPO‐melamine copolymers display comparable thermal resistance and flame retarding behavior (Td = 290°C; char yield: 15.6%, LOI: 23, and flammability: UL‐94 V0) as the alloys containing common commercial flame retardants (i.e., DOPO, melamine, and ammonium polyphosphate). Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

11.
A novel inorganic and organic composite flame retardant (9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide [DOPO]–layered double hydroxide [LDH]) was synthesized via grafting DOPO with organic‐modified Mg/Al‐LDH, which was introduced into poly (methyl methacrylate) (PMMA) resin to prepare the flame‐retardant PMMA composites. Thermogravimetric analyzer (TGA) showed that the T‐50% of DOPO‐LDH/PMMA composites enhanced by about 20°C, and with the 20% flame retardant, the residual char content can be increased by 39.8% in the air atmosphere compared with LDH/PMMA composites. In the UL‐94 and the limiting oxygen index (LOI) tests, it can be found that compared with LDH/PMMA composites, the LOI value of DOPO‐LDH/PMMA composites were raised evidently with the increased flame retardants, and the droplet combustion was greatly improved. These results could be ascribed to the action of DOPO free‐radical, catalytic charring of polymer and the effect of LDH physical barrier. Moreover, the novel DOPO‐LDH not only given PMMA a good flame‐retardant property and thermal stability, but also have higher visible light transmittance, ultraviolet‐shielding effect, and low loss of mechanical properties, which could further facilitate the wide application of inorganic environment‐friendly flame retardants in general resins and engineering resins and broaden the application of polymers.  相似文献   

12.
Poly (diallyldimethylammonium chloride) (PDDA) and ammonium polyphosphate (APP) deionized chloride ions and ammonium ions by ionizing in aqueous solution respectively, then combined to form poly (diallyldimethylammonium) and polyphosphate (PAPP) polyelectrolyte complexes as an all‐in‐one flame retardant for polypropylene and its composites were characterized by Fourier transform infrared (FTIR) spectroscopy and X‐ray photoelectron spectroscopy. One flame retardant system composed of PAPP and PP, the other flame retardant system composed of PAPP, Polyamide‐6 (PA6) and PP were tested by limiting oxygen index (LOI), UL‐94, cone calorimeter tests and thermogravimetric analysis (TGA) and compared with pure PP. The results showed that the LOI value of PP/PAPP composite can reach 27.5%, and UL‐94 V‐2 rating can be reached at 25 wt% PAPP loading. Meanwhile the cone calorimetry results displayed that the peak heat release rate (PHRR) and total heat release (THR) were reduced up to 69.3% and 22.5%, respectively, compared with those of pure PP. After adding 5 wt% PA6, the carbon source missing due to the early PAPP decomposition can be made up, and PHRR and THR can be further reduced slightly. The flame retardant mechanism of PAPP was studied by FTIR spectroscopy and X‐ray photoelectron spectroscopy. Six‐membered ring of C─N containing conjugate double bonds, cross‐linked phosphate structure formed stable, intumescent, compact char layer which greatly improved the flame retardancy of PP.  相似文献   

13.
Water blown rigid polyurethane foam (PUF) was prepared with melamine polyphosphate (MPP) and melamine cyanurate (MC) as fire retardant (FR) additives. The effect of these additives on the properties of rigid PUF such as physico-mechanical, morphological, thermo-oxidative stability, flame retardancy and smoke density properties were studied. The mechanical and thermo-oxidative stability of PUF filled with MC was found to be better than those of MPP filled PUF. The insulation property of both MPP and MC filled PUF was improved with respect to the neat PUF. The FR properties of these filled PUF were evaluated by cone calorimeter, limiting oxygen index (LOI), smoke density, rate of burning and char residue estimation. The FR property of MPP filled PUF was better than that of the MC filled PUF.  相似文献   

14.
高振昊  任向征  苗志伟 《化学通报》2021,84(11):1191-1199,1190
磷系阻燃剂具有阻燃效率高、低烟、低毒、与基质材料相容性好等优点,在阻燃高分子材料领域得到广泛应用。本文介绍了磷系阻燃剂的分类及阻燃机理,综述了近年来磷酸酯阻燃剂、膦酸酯阻燃剂、DOPO磷杂菲类阻燃剂、磷腈类阻燃剂和无机磷阻燃剂在阻燃聚碳酸酯领域的研究进展,为新型磷系阻燃剂的研发提供参考。  相似文献   

15.
In this work, based on castor oil (CO), flame retardant polyurethane sealants (FRPUS) with ammonium polyphosphate (APP) and aluminum hypophosphite (AHP) were prepared. The synergistic flame retardant effects between APP and AHP on flame retardancy, thermal stability, and flame retardant mechanisms of FRPUS were investigated. It was found that when the mass ratio of APP and AHP was 5:1, the limiting oxygen index (LOI) value of FRPUS increased to 35.1%, In addition, at this ratio, the parameters from cone calorimeter testing (CCT) were reduced; these parameters include peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR) and total smoke production (TSP). The thermal decomposition behavior of the FRPUS was investigated by thermogravimetric analysis (TGA). The results showed that AHP improved the thermal stability of the PUS/APP system and increased char residue at high temperatures. Moreover, the residual carbon was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscope (SEM), gas phase pyrolysis products were investigated by thermogravimetric analysis/infrared spectrometry (TG-IR) and thermogravimetric analysis/mass spectrometry (TG-MS). It was observed that the flame retardant mechanisms of the APP/AHP system was the combination of gas and condensed phase flame retardant mechanisms.  相似文献   

16.
《先进技术聚合物》2018,29(1):497-506
A novel phosphorus‐containing, nitrogen‐containing, and sulfur‐containing reactive flame retardant (BPD) was successfully synthesized by 1‐pot reaction. The intrinsic flame‐retardant epoxy resins were prepared by blending different content of BPD with diglycidyl ether of bisphenol‐A (DGEBA). Thermal stability, flame‐retardant properties, and combustion behaviors of EP/BPD thermosets were investigated by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The flame‐retardant mechanism of BPD was studied by TGA/infrared spectrometry (TGA‐FTIR), pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), morphology, and chemical component analysis of the char residues. The results demonstrated that EP/BPD thermosets not only exhibited outstanding flame retardancy but also kept high glass transition temperature. EP/BPD‐1.0 thermoset achieved LOI value of 39.1% and UL94 V‐0 rating. In comparison to pure epoxy thermoset, the average of heat release rate (av‐HRR), total heat release (THR), and total smoke release (TSR) of EP/BPD‐1.0 thermoset were decreased by 35.8%, 36.5% and 16.5%, respectively. Although the phosphorus content of EP/BPD‐0.75 thermoset was lower than that of EP/DOPO thermoset, EP/BPD‐0.75 thermoset exhibited better flame retardancy than EP/DOPO thermoset. The significant improvement of flame retardancy of EP/BPD thermosets was ascribed to the blocking effect of phosphorus‐rich intumescent char in condensed phase, and the quenching and diluting effects of abundant phosphorus‐containing free radicals and nitrogen/sulfur‐containing inert gases in gaseous phase. There was flame‐retardant synergism between phosphorus, nitrogen, and sulfur of BPD.  相似文献   

17.
In this work, an organic inorganic hybrid intumescent flame retardant (functionalized expandable graphite, FEG) was synthesized and characterized by Fourier transform infrared spectrometry (FTIR). The flame retardant effects of FEG in silicone rubber (SR) composites were investigated by cone calorimeter test (CCT), and the thermal stability of SR composites was studied using TGA. The CCT results showed that FEG can effectively reduce the flammable properties including peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), total smoke release (TSR), and smoke factor (SF). An improvement of thermal stability of SR/FEG was also observed. Compared with EG, FEG can further reduce THR, SPR, and TSR of SR/FEG composites in combustion process. Moreover, there is a more obvious intumescent char layer formed from the sample with FEG than the sample with EG at the same loading in SR composites. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

18.
Polystyrene based nanocomposites (PNCs) with and without flame retardant additives were successfully prepared through a single-screw extrusion technique. The combination effect of nanoparticles and flame retardants was investigated with nanosilica and attapulgite clay as nanofillers, and with a NASA formulated SINK flame retardant. A comprehensive study was done by Cone Calorimetry, UL94 and TGA.The addition of nanoparticles to polystyrene generally improved the OI of polystyrene. The horizontal burning tests suggested that nanofiller types have different impacts on the flammability of nanocomposites. According to the vertical burning tests and oxygen indices, it was found that polystyrene/silica and polystyrene/attapulgite clay PNCs alone are not flame retardant. In fact, the materials burned faster. However, the combination of nanocomposites with the SINK flame retardant significantly altered the thermal stability, and flammability of the materials. A remarkable reduction in heat release rates of polystyrene was achieved for both silica and attapulgite with flame retardant nanocomposites. For instance, the introduction of 20% SINK into PS reduced the PHRR of PS from 1212 to 838 (−31%); 10% silica reduced it from 1212 to 1060 (−13%), while the combination of silica and SINK reduced it to 530 (−56%), which clearly shows interaction between nanosilica and SINK.  相似文献   

19.
Phosphorus tailings and fly ash both are solid wastes and do harm to the environment. Here, they were added into thermoplastic polyurethane (TPU) matrices together with intumescent flame retardants (IFR), and the synergistic effects between IFR and phosphorus tailings or fly ash for improving the flame retardancy of TPU were investigated. The cone calorimeter test (CCT) results indicated that adding phosphorus tailings or fly ash substitute for part of IFR could obtain a better flame retardant effect. The peak heart release rate (PHRR) of TPU/25 wt% IFR composites exhibited a reduction of 77% than that of neat TPU, and the total smoke production presented a reduction of 16%. However, the PHRR value and total smoke production of the sample TPU/20 wt% IFR/5 wt% phosphorus tailings were reduced by 91% and 57%, respectively, compared to that of neat TPU. The dense char promoted by the presence of IFR and phosphorus tailings or fly ash delayed the diffusion of volatile pyrolysis products and transmission of heat and oxygen to the underlying material. Therefore, a certain amount of phosphorus tailings or fly ash can be used as synergistic agents with IFR to enhance the fire safety of TPU materials. From another aspect, it also provides a promising way for recycling use of phosphorus tailings and fly ash.  相似文献   

20.
In this paper, an efficient flame retardant, 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO) was covalently grafted onto the surface of expandable graphite (EG). The resultant DOPO‐grafted expandable graphite (EG‐g‐DOPO) was characterized by Fourier transform infrared spectroscopy, energy dispersive spectroscopy, and X‐ray photoelectron spectroscopy (XPS), respectively. The thermal stability of EG‐g‐DOPO was also evaluated by thermogravimetric analysis (TGA). Moreover, a series of flame‐retardant ultra‐high‐molecular‐weight polyethylene (UHMWPE) composites with various concentrations of EG‐g‐DOPO were prepared and evaluated. The results show that the UHMWPE composite with 20 wt% EG‐g‐DOPO possesses a satisfactory UL‐94 flame‐retardant grade (V‐0) and a high limiting oxygen index (30.6%). The residual char of the UHMWPE composite with higher EG‐g‐DOPO concentration shows more compact and integrated, providing an efficient barrier for heat release.  相似文献   

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