EG与IFR复合阻燃ABS的动态燃烧性和协同效应

将可膨胀石墨(EG)与P-N型膨胀阻燃剂(IFR)复合阻燃丙烯腈-丁二烯-苯乙烯共聚物(ABS)树脂,阻燃剂添加量为20%(质量分数,下同),通过极限氧指数(LOI)仪、垂直燃烧测试(UL-94)仪、锥形量热(CONE)仪和扫描电镜(SEM)研究了EG与IFR复合阻燃ABS的协同效应。结果表明,EG/IFR质量比为1/1为最佳配比,阻燃ABS的LOI达到29%,UL-94为V-0级;EG与IFR复合阻燃ABS,表现出一定的协同作用;通过SEM观察ABS/EG/IFR试样燃烧后样品发现,EG与IFR起到协同阻燃作用。     

有机化坡缕石黏土-膨胀型阻燃聚丙烯复合材料的制备及性能

制备了优异阻燃性能(LOI36%)兼具良好力学性能的膨胀型阻燃聚丙烯复合材料OPGS/PA-APP/PP。将有机化坡缕石黏土引入到哌嗪-多聚磷酸铵(PA-APP)膨胀型阻燃(IFR)聚丙烯(PP)复合材料中,通过极限氧指数(LOI)、垂直燃烧(UL-94)、热重分析法(TGA)、扫描电子显微镜(SEM)、通用电子万能试验机研究了有机化坡缕石黏土添加量对PA-APP阻燃聚丙烯复合材料阻燃性能和力学性能的影响。结果表明,添加质量分数为2%的有机化坡缕石黏土提高了该复合材料的阻燃性能和力学性能。此外,所制备样品经垂直燃烧测试可达到阻燃V-0级别。实验证明,有机化坡缕石黏土在膨胀型阻燃聚丙烯复合材料中具有明显的协效阻燃作用。     

Flammable,thermal, and mechanical properties of intumescent flame retardant PP/LDH nanocomposites with different divalent cations

The flammable, thermal, and mechanical properties of intumescent flame retardant (IFR) polypropylene/layered double hydroxide (PP/IFR/LDH) nanocomposites with the LDHs of different divalent cations and IFR system of ammonium polyphosphate/pentaerythritol (APP/PER) have been studied by X-ray diffraction (XRD), cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), limiting oxygen index (LOI), UL-94 test, and mechanical measurements. The XRD results show that the exfoliated PP/IFR/LDH nanocomposites possess the nanoscaled dispersion characteristic. The data from the CCT tests show the synergistic effect of LDHs with IFR can decrease considerably the HRR, MLR, and EHC values of the PP/IFR/LDH nanocomposites, in which the pk-HRR, pk-MLR, and pk-EHC values of the PP/IFR/ZnAl-LDH sample decrease to 318 kW/m², 0.081 g/m² s, 61.8 MJ/kg from the corresponding values 506 kW/m², 0.115 g/m² s, 71.8 MJ/kg of the PP/IFR sample. The LOI and UL-94 data further support the evidence that the flame retardant synergistic effects of LDHs with IFR increase the LOI values and UL-94 rating, especially for the LDHs with the transition ions (Zn, Cu) the LOI values can reach 33% and the UL-94 pass the V-0 rating. The TGA results demonstrate the LDHs can greatly improve the thermal stabilities of PP/IFR/LDH nanocomposites by increasing the thermo-oxidation decomposition temperature and charred residues. The morphological structures observed by SEM have demonstrated the LDHs can promote formation of compact charred layers. The data from the mechanical tests show the tensile strength and elongation at break of the PP/IFR/LDH samples are basically unchanged compared with the PP/IFR sample. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

分子筛在无卤膨胀阻燃体系中的协效催化作用

考察了分子筛在自制膨胀型阻燃体系(IFR)中的协效催化作用。利用添加分子筛的IFR对聚丙烯(PP)进行阻燃。运用扫描电子显微镜、垂直燃烧仪等对膨胀阻燃PP体系的表面形态和性能进行了研究。结果表明,阻燃PP加入不同的分子筛后,燃烧级数达到V-0级,氧指数最高增加17.86%,有明显的成炭效果,可获得良好的阻燃性能。     

Mechanical,thermal and combustion properties of intumescent flame retardant biodegradable poly (lactic acid) composites

ABSTRACT

Despite extraordinary mechanical properties and excellent biodegradability, poly (lactic acid) (PLA) still suffers from a highly inherent flammability, restricting its applications in the electric and automobile fields. Although a wide range of flame retardants have been developed to reduce the flammability, they normally compromise the mechanical strength of PLA. In this study, a series of composites based on PLA, have been prepared by melt-blending with intumescent flame retardants (IFRs). The morphology, thermal stability and burning behaviour of the composites were investigated using a scanning electron microscope–energy dispersive spectrometer (SEM–EDS), thermogravimetric analysis (TGA), the limiting oxygen index (LOI), vertical burning (UL-94) and the cone calorimeter test (CCT). The LOI value reached 38.5% and UL-94 could pass V-0 for the PLA/IFR composite containing only 12 wt-% IFR. The dispersion of IFR in PLA was observed using SEM–EDS. A significant improvement in fire retardant performance was observed for the PLA/IFR composite from the CCT (reducing the heat release rate and the total heat release). More importantly, compared to pure PLA, the addition of IFR did not seriously deteriorate the mechanical properties of the material.     

天然高分子对生物聚酯P(3,4)HB复合材料阻燃性能的影响

以三聚氰胺磷酸盐(MP)和季戊四醇磷酸酯(PEPA)复配的膨胀型阻燃体系阻燃聚(3-羟基丁酸酯-co-4-羟基丁酸酯)[P(3,4)HB], 分别用木质素、壳聚糖和海藻酸钠3种天然高分子作为成炭剂代替部分PEPA, 采用熔融共混法制备P(3,4)HB基阻燃复合材料。通过热重分析仪(TGA)、微型量热仪(MCC)、垂直燃烧仪(UL-94)、极限氧指数仪(LOI)及扫描电镜(SEM)等对其热稳定性、热燃烧性能、阻燃特性及炭渣形貌进行了表征与分析, 对比研究了3种天然高分子对P(3,4)HB基复合材料阻燃性能的影响。结果表明:含有木质素的复合材料体系燃烧后形成了致密而连续的炭层, 且能达到V-0级别, 而含壳聚糖或海藻酸钠的复合材料体系燃烧后形成的炭层结构多孔而疏松, 只能达到V-2级。     

不同芳基磷酸酯与膨胀型阻燃剂复配阻燃PP的研究

采用间苯二酚双(二苯基)磷酸酯(RDP)、双酚A双(二苯基)磷酸酯(BDP)、磷酸三甲苯酯(TCP)和异丙苯基磷酸酯(IPP)作为阻燃协效剂与膨胀型阻燃剂(IFR)复配阻燃聚丙烯(PP)。研究了芳基磷酸酯的种类对PP/IFR复合材料阻燃性能、热稳定性能和力学性能的影响,并通过热重分析(TGA)、扫描电镜(SEM)等对材料进行了表征。结果表明:芳基磷酸酯对PP/IFR复合材料具有一定的协同阻燃作用。当芳基磷酸酯用量为5.0%时,PP/IFR/TCP、PP/IFR/IPP、PP/IFR/RDP和PP/IFR/BDP复合材料的氧指数(OI)由PP/IFR的28.5%分别提高到29.5%、30.0%、30.5%和29.5%,垂直燃烧级别由UL 94V-1级提升至UL 94V-0级;同时,RDP和BDP可提高PP/IFR复合材料的热稳定性能,500℃时的残余率分别高达15.4%和12.9%。此外,RDP和BDP的加入有利于IFR粒子的分散,从而改善了材料的力学性能。     

改性赤泥协同膨胀型阻燃剂阻燃聚乙烯

以聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）复配的膨胀型阻燃体系（IFR）为主要阻燃剂,表面改性后的赤泥（Ti-MRM）作为协效剂阻燃聚乙烯（PE）,采用熔融共混法制备PE基阻燃复合材料（PE/IFR-Ti-MRM）。通过热重分析仪（TGA）、垂直燃烧仪（UL-94）、极限氧指数测定仪（LOI）及扫描电镜（SEM）等对其热氧稳定性、燃烧等级、阻燃性能和残炭形貌进行了表征与分析。结果表明：加入改性赤泥的PE/IFR-Ti-MRM复合材料形成的炭层更加致密和连续,当最优配比时,复合材料的极限氧指数达到32.2,燃烧等级达到V-0级;而PE/IFR阻燃复合材料的极限氧指数只能达到27.5,燃烧等级为V-2级。     

Flammability,thermal stability,and mechanical properties of ethylene-propylene-diene monomer/polypropylene composites filled with intumescent flame retardant and inorganic synergists

Three kinds of inorganic particles, zinc borate (ZB), organic montmorillonite (OMMT), and expanded graphite (EG) as synergistic flame retardants, are incorporated into ethylene-propylene-diene monomer/polypropylene (EPDM/PP) composites filled with intumescent flame retardants (IFR). The effect of three synergistic flame retardants on the combustion, thermal stability, and mechanical properties of the EPDM/PP/IFR composites are investigated by limiting oxygen index (LOI), UL-94 test, cone calorimeter test (CCT), thermogravimetric analysis (TGA), scanning electron microscopy, mechanical property testing, and dynamic mechanical analysis (DMA). The results from LOI, UL-94, and CCT show that the synergistic effect of IFR with ZB and EG is better than IFR with OMMT in the flame retardant EPDM/PP/IFR composites. The TGA results indicate that the thermal stability and char residues of the composites is improved with the addition of inorganic particles, which is attributed to the formation of dense char layers to isolate heat flow. DMA results including storage modulus (G'), loss modulus (G"), and loss factor (tan δ) suggest that the composites with inorganic particles exhibit more rubber-filler interaction, which limits the movement of the rubber chains.     

Synergistic Effects of Nanoporous Nickel Phosphates VSB-1 on an Intumescent Flame-Retardant Low-Density Polyethylene (LDPE) System

Nanoporous nickel phosphates VSB-1 was synthesized by hydrothermal method, and its structure was characterized by X-ray diffraction (XRD), thermogravimetric analyses (TGA) and high resolution transmission electron microscopy (HRTEM). The flame retardancy and thermal behaviour of intumescent flame retardants (IFR) with and without VSB-1 for low-density polyethylene (LDPE) were evaluated by LOI, UL-94 burning test, TGA and cone calorimeter test. With the addition of 2 wt% VSB-1 to LDPE/IFR systems, the LOI value increases from 28.7 to 31, and UL-94 rating raises from V-1 rating to V-0 rating. The results of cone calorimeter show that heat release rate (HRR) peak decrease substantially from 511 KW/m² to 407 KW/m² with 2 wt% VSB-1 in LDPE/IFR systems. The scanning electron microscopy (SEM) indicates the quality of char forming of LDPE/IFR/ VSB-1 is superior to that of LDPE/IFR.     

硅酮粉协同膨胀阻燃剂阻燃HIPS研究

通过熔融共混制备硅酮粉(GM)协同膨胀阻燃剂(IFR)阻燃的高抗冲聚苯乙烯(HIPS)复合材料,并通过红外光谱、扫描电子显微镜、热重分析、X射线衍射以及电子拉力机等对材料和残炭进行表征。结果表明:与只加入IFR相比,GM的加入能明显提升阻燃材料的力学性能,改善IFR与HIPS的相容性,有效提高HIPS的阻燃性能。当加入2%GM和33%IFR时,阻燃HIPS的极限氧指数达到31%、UL-94测试达到V-0级。     

Synthesis of a bio-based triazine derivative and its effects on flame retardancy of polypropylene composites

A triazine derivative CC–Cy was synthesized using cytosine (Cy) and cyanuric chloride (CC). The CC–Cy was used as a charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame-retardant (IFR) system. The IFR system was applied to improve the flame retardancy of polypropylene (PP). Moreover, bisphenol-A bis(diphenyl phosphate) (BDP) was introduced in the IFR system to regulate the suitability between the IFR and PP. The results showed the PP containing 20 wt % APP and 5 wt % CC–Cy achieves the UL-94 V-2 rating. While the PP with 18 wt % APP/CC-Cy (4:1) and 3 wt % BDP obtains the UL-94 V-0 rating indicating the improved flame-retardant efficiency. Thermal degradation behaviors and char morphology both showed that the reactions between APP and CC–Cy promote the formation of char residues, and BDP works in gas phase to enhance the flame retardancy of PP composites. Thus, a synergistic IFR system based on APP, CC–Cy, and BDP is formed, which can protect PP from fire effectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47367.     

Synergistic Effect of Montmorillonite and Intumescent Flame Retardant on Flame Retardance Enhancement of ABS

The synergistic effects of organic montmorillonite (OMMT) and intumescent flame retardant (IFR) based on the ammonium polyphosphate (APP) and pentaerythritol (PER) on flame retardant enhancement of acrylonitrile-butadiene-styrene copolymer (ABS) were investigated by using the limiting oxygen index (LOI), the UL-94 (vertical flame) test, thermogravimetric analysis (TGA), x-ray diffractometry (XRD) and scanning electron microscopy (SEM). The LOI data and vertical flame tests show that OMMT has a synergistic flame retardant effect with IFR and the LOI value of ABS/OMMT/IFR (96/4/20) reaches 28.7%. The TGA data demonstrate that the incorporation of OMMT and IFR is very effective in enhancing the thermal stability of ABS/OMMT/IFR system at high temperature (T > 500°C). The results of XRD show that the composite of ABS/OMMT is a kind of intercalated nanocomposite and the gallery height of ABS/OMMT nanocomposite is 3.5 nm. The microstructures observed by SEM demonstrate that a suitable amount of OMMT with IFR can promote formation of compact intumescent charred layers in ABS blends.     

Synergistic flame retardant effect of piperazine salt and ammonium polyphosphate as intumescent flame retardant system for polypropylene

Amino trimethylene phosphonic acid piperazine (ATPIP) salt, as a novel charring agent, is prepared via a simple ionic reaction in distilled water using amino trimethylene phosphate (ATMP) and piperazine as raw materials. The synergistic flame retardant effect of ATPIP and ammonium polyphosphate (APP) as an intumescent flame retardant (IFR) is investigated by various characterization and testing methods. The results show that the polypropylene (PP)/modified APP with piperazine (MAPP)/ATPIP ternary blend passes UL-94 V-0 rating and achieve a limiting oxygen index (LOI) of 30% at a loading level of 25 wt% IFR (MAPP:ATPIP = 3:1). Meanwhile, the total smoke production (TSP) value of IFR-PP samples is 3.3 m², which decreases by 93.2% compared with that of pure PP, exhibiting excellent smoke suppression performance. Besides, the analysis of gaseous pyrolysis products and char residue indicates that the IFR-PP samples show a synergistic flame-retardant mechanism including the gas phase and the condensed phase.     

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.     

Enhanced dispersibility and uniform distribution of iron phosphonate to intensify its synergistic effect on polypropylene-based intumescent flame-retardant system

Good dispersion and distributed nanoscaled synergists are expected to greatly enhance the performance of flame retardants. Here, a new type of iron organic-phosphonate (FeP) nanoparticles was synthesized and utilized as the synergist for polypropylene-based intumescent flame-retardant system (IFR/PP). To improve the dispersion of the FeP in the IFR/PP system, a master-batch method was used to achieve separation between the FeP particles, which included hydrogen bonding with ammonium polyphosphate (APP). To improve its compatibility with PP, the hybrid synergist FeP@APP@CS was produced by electrostatic interaction with chitosan (CS). The results showed that the FeP@APP@CS nanoparticles were homogeneously dispersed in the PP matrix and selectively located on the IFR particles, achieving compatibility between the PP and IFR. The FeP@APP@CS/IFR/PP system exhibited an enhanced limiting oxygen index (LOI) of up to 28.5%, and achieved an improved vertical burning rating of V-0 (UL-94), compared to the IFR/PP system. The improved flame-retardant properties, even at low levels of IFR loading, were attributed to the homogeneous dispersion of the FeP@APP@CS throughout the IFR system and the fine synergistic effect between the FeP@APP@CS and IFR.     

Effect of charring agent THEIC on flame retardant properties of polypropylene

Tris(2‐hydroxyethyl) isocyanurate (THEIC) was used as charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The flame retardancy and combustion performance of PP/IFR composite was tested by limiting oxygen index (LOI), UL‐94 vertical burning test and cone calorimeter. The results showed that PP/IFR composite had highest LOI of 34.8 and obtained V‐0 rating when 30 wt % IFR was loaded and mass ratio APP/THEIC was 2 : 1. The peak heat release (PHRR) and total heat release (THR) values of PP composite containing FRs were remarkably reduced compared with that of pure PP. However, water resistant test demonstrated the PP/IFR composite had poor flame retardant durability, both the LOI value and UL‐94 V‐rating decreased when PP/IFR composite was soaked in water at 70°C after 36 h. The degradation process and the char morphology of IFR and PP/IFR composite were investigated by TGA and SEM images. The possible reaction path between APP and THEIC in the swollen process was proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41214.     

Synthesis of a novel char-forming agent (PEIC): Improvement in flame retardancy,thermal stability,and smoke suppression for intumescent flame-retardant polypropylene composites

A novel char-forming agent named PEIC was designed and synthesized combining pentaerythritol octahydrogen tetraphosphate (PEPA) and tris(2-hydroxyethyl) isocyanurate. PEIC was combined with the silica-gel-microencapsulated ammonium polyphosphate (OS-MCAPP), preparing intumescent flame-retardant polypropylene (PP) composites. The results of the limiting oxygen index (LOI) show that the composite containing 30 wt % IFR with OS-MCAPP:PEIC = 2:1 presents the optimal LOI of 32.7%. Meanwhile, the cone calorimeter tests show that its peak heat release rate is 432 kW m⁻², which decreases by 62.1% compared with that of pure PP, showing a high-efficient flame retardancy. The exhibited UL-94 V-0 rating for all the composites indicates that the IFR composed of PEIC and OS-MCAPP has high-efficient flame retardancy in PP. The analysis of residue char reveals that PEIC could improve the quality of char in compactness, intumescentia, and the degree of graphitization. Further, the effect of IFR on the mechanical properties of PP composites was also evaluated and discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48296.     

Synergistic effects of aluminium hypophosphite on the flame retardancy and thermal degradation behaviours of a novel intumescent flame retardant thermoplastic vulcanisate composite

ABSTRACT

The synergistic effects of aluminum hypophosphite (AHP) on the flame retardancy, thermal degradation behaviors of a novel intumescent flame retardant thermoplastic vulcanizate (TPV/IFR) composite were investigated. The results showed that the combination of AHP with IFR showed evident synergistic effects on the increase in the LOI value and reduction of the combustion parameters for the TPV/IFR/AHP composites at the optimum weight ratio of IFR/AHP (6/1) as evidenced by LOI, UL-94 and CCT. The TGA data revealed that AHP could change the degradation behavior of TPV/IFR composites and enhance the thermal stability of the TPV/IFR composites at high temperature. The results of FTIR, EDXS, LRS and SEM demonstrated that TPV/IFR/AHP composites could form more continuous, dense and stable char layer on the materials surface, and consequently improving the flame retardancy. Based on these results, the possible condensed flame retardant mechanism of TPV/IFR/AHP composites was concluded in detail.     

Enhancement of wollastonite on flame retardancy and mechanical properties of PP/IFR composite

Wollastonite, a natural calcium metasilicate possessing acicular crystal habit structure, was used together with intumescent flame retardant (IFR) to flame retard polypropylene (PP). The synergistic effects between wollastonite and IFR were investigated using limiting oxygen index (LOI) test, cone calorimeter test, thermogravimetric analysis, scanning electron microscope‐energy dispersive spectrometer (SEM‐EDS), etc. The results revealed that wollastonite could effectively improve mechanical properties and flame retardancy of the PP/IFR composite. When 2.0 wt% wollastonite substituted for the same amount of IFR in the composite, the impact strength was enhanced from 4.6 kJ/m² to 6.8 kJ/m², which was increased by 47.1%. Meanwhile, the LOI was increased from 33.0% to 35.5%, a UL‐94V‐0 rating was achieved and the peak heat release rate decreased substantially from 314.4 kW/m² to 262.8 kW/m². Furthermore, the SEM‐EDS results provided positive evidence that the quality of char layer of the PP/IFR/wollastonite was superior to that of the PP/IFR composite due to synergism between wollastonite and IFR. POLYM. COMPOS., 35:158–166, 2014. © 2013 Society of Plastics Engineers