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.

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.

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.

Intumescent Flame-retardant Modification of Polypropylene/Carbon Fiber Composites

To improve the flame resistance of polypropylene(PP)/carbon fiber(CF)composite materials,triazine char-forming agent(TCA)was compounded with ammonium polyphosphate(APP)or modified APP(CS-APP)in a 2:1 ratio to prepare intumescent flame retardant(IFR)and the modified intumescent flame retardant(CS-IFR)in this paper.Flame retardancy and thermal degradation behaviors of the composites modified by IFR and CS-IFR were characterized by Fourier Transform Infrared(FTIR),contact angle measurement,oxygen index(OI),vertical burning tests(UL-94),thermogravimetric analyer(TGA),and thermogravimetric analyzer coupled with Fourier transform infrared(TG-FTIR).It was found that 25.0 phr of IFR and 24.0 phr of CS-IFR could improve the LOI value of PP/CF composites to 28.3%and 28.9%,respectively.At the same time,a UL-94 V-0 rating was achieved.The experimental results show that the IFR and CS-IFR prepared could effectively improve the flame retardancy and thermostability of PP/CF composites,and they would greatly expand the application range of PP/CF composite materials.

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.

Effect of MMT on Flame Retardancy of PLA/IFR/LDH Composites

Nano filler synergistic intumescent flame retardant(IFR)system is an effective way to improve the flame retardant properties of polymer.In this study,the effects of montmorillonite(MMT)on the flame retardant properties of polylactic acid/layered double hydroxides(PLA/LDH)and PLA/IFR/LDH were investigated.The results show that both LDH and LDH/IFR can reduce the peak heat release rate(HRR)of PLA and prolong the combustion time of PLA;When a proportionate MMT is introduced into PLA/LDH and PLA/IFR/LDH systems,respectively,MMT will not only affect the degradation process of PLA composites during combustion,but also the PLA composites can form a more stable carbon layer during combustion,which could decrease the peak HRR and prolong combustion time of PLA composite.Furthermore,when 0.5 wt%MMT is incorporated,the peak HRR of LDH/IFR/LDH composite is reduced by 16.17%and the combustion time is prolonged by about 70 s.This study can provide an opportunity to further optimize the properties of intumescent flame retardant polymer.

AN S-AND P-CONTAINING FLAME RETARDANT FOR POLYPROPYLENE

A novel charring agent,bis(1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane) phenylphosphine sulfide (BCPPS),has been synthesized,and it is combined with ammonium polyphosphate (APP) and melamine phosphate (MP) to impart flame retardance and dripping resistance for polypropylene (PP).The fire performance of the treated PP is investigated by limiting oxygen index (LOI),vertical burning test (UL-94) and cone calorimeter,and the thermal stability and thermal oxidative stability of the composite...

Synergistic effects of zeolitic imidazolate frameworks(ZIFs)with different transition metals on intumescent flame-retarded polypropylene composites:A comparative study

The use of intumescent flame retardants(IFRs)is considered an environmentally friendly and cost-effective strategy to suppress potential fire hazards from synthetic polymers.However,some conventional IFRs are neither efficient in developing a thermally stable char layer nor reducing the release of toxic byproducts during polymer combustion.In this work,we aim to discuss the effects of zeolitic imidazolate frameworks(ZIFs)on synergistically improving the flame retardancy behaviors in polypropylene(PP)composites,including thermal degradation(evolved gas analysis),free radical reactions in the gaseous phase(in-situ chemiluminescent image analysis),and carbonaceous structure in the condensed phase(micro-morphology and composition analysis).It is found that the transition metals in ZIFs can catalytically accelerate the crosslinking reaction at a lower initial temperature and decrease the amount of hydrocarbon volatiles in the gaseous phase.Once ignited,the embedded ZIFs can firstly bridge adjacent phosphorus chains in the polymer matrix to expand crosslinking degrees and then they are anchored in the developed N-doped phospho-carbonaceous networks after pyrolysis.As a result,more compact char residue structures are observed in the condensed phase for ZIF-reinforced composites.For example,by replacing 2 wt%of IFR with ZIF-67,the peak heat release rate,peak smoke production rate,and peak CO production rate are reduced by 69%,80%,and 72%,respectively,when compared to the conventional composite.These results indicate an excellent solution to resolve inherent fire hazards associated with IFRs in polymers and achieve necessary efficiency for industrial applications.It also provides a new strategy for determining flammability characteristics and combustion mechanisms of polymer composites using in-situ chemiluminescence analysis.

白泥填料在膨胀阻燃环氧树脂中的协效阻燃和抑烟作用

为实现氨碱白泥的资源化利用,以氨碱白泥为原料,通过烘干、粉碎和表面改性制备白泥填料,并将其作为阻燃协效剂应用于膨胀阻燃环氧树脂,系统研究了白泥填料对膨胀阻燃环氧树脂的阻燃性能、抑烟性能和成炭能力的影响。结果表明,添加白泥填料能够显著降低膨胀阻燃环氧树脂的热释放和生烟量,表现出优异的协效阻燃和抑烟作用。当添加5%烷基化白泥填料时,阻燃和抑烟效率最高,峰值热释放速率和峰值生烟速率降低至234.6 kW/m^(2)和0.048 m^(2)/s,极限氧指数提高到30.5%。此外,白泥填料具有优异的协效成炭作用,添加5%烷基化白泥填料可以促进膨胀阻燃环氧树脂生成更多的芳香结构和含磷的交联结构,增强炭层的致密性和隔热隔质性,提高炭层质量,在700℃下残炭量达到24.5%。

阻燃丙烯酸树脂涂料的制备及其性能

为解决丙烯酸树脂在使用过程中存在阻燃性能低的问题,通过超声和机械搅拌相结合的方法在丙烯酸树脂乳液中加入由聚磷酸铵(APP)、季戊四醇(PER)和三聚氰胺(MEL)以不同配比复合而成的膨胀型阻燃剂(IFR),制得阻燃丙烯酸树脂涂料(PA-IFR)。利用红外光谱仪、X射线衍射仪、铅笔硬度计和极限氧指数仪对PA-IFR的化学结构、透光率、硬度以及阻燃性能进行测试。结果表明:当膨胀型阻燃剂的质量分数为30%,APP/PER/MEL的配方比为2∶1∶1时,PA-IFR的硬度达到5H,极限氧指数LOI值达32.6%,属于难燃材料。

聚苯胺-碳化硅复合材料在膨胀型防火涂料中的应用

膨胀型防火涂料在阻隔基材迅速升温方面具有明显效果。试验合成了聚苯胺-碳化硅(PANI-SiC)复合材料,通过SEM、FTIR、XRD等手段分析了复合材料的形貌、组成和结构,考察了单组分膨胀型防火涂料乳液的种类及复合材料含量对涂层防火耐火性能的影响。结果表明:醋酸乙烯-乙烯(VAE)乳液相比于苯丙乳液和丙烯酸乳液可以更好地提升涂层的膨胀倍率和耐火性能。随着PANI-SiC含量的增加,涂层的膨胀倍率增加,背面温度降低,10%含量复合材料的防火涂层表现出优异的耐火性能。

壳聚糖基膨胀阻燃涤纶/棉混纺织物的制备及其性能

为得到阻燃且满足实际应用需求的涤纶/棉混纺织物(T/C),选用亚磷酸化壳聚糖(PCS)和γ-哌嗪基丙基甲基二甲氧基硅烷(GP-108)制备阻燃整理剂(PCS/GP),通过一步浸渍法对涤纶/棉混纺织物进行整理,并研究其微观表面形貌、热稳定性能、阻燃性能、拉伸性能以及白度等。结果表明:PCS/GP成功在涤纶/棉混纺织物表面沉积成膜,包裹住涤纶/棉纤维;T/C-PCS/GP呈现典型的涤纶/棉混纺织物二步热降解过程,在700℃时保留有28.5%的残炭量,说明PCS/GP提高了阻燃涤纶/棉混纺织物在高温区的热稳定性能;T/C-PCS/GP的LOI值提升至26.5%,实现了垂直燃烧测试中的离火自熄,残炭扫描电镜照片表明,PCS/GP的沉积改善了涤纶/棉混纺织物燃烧时存在的“支架”效应;T/C-PCS/GP的热释放速率峰值和火灾蔓延指数较T/C分别降低了20%和40%,表明其火灾危险性大幅度降低;锥形量热测试后的残炭电镜照片表明,T/C-PCS/GP能够保留完整的织物编织结构,残炭表面存在明显的膨胀炭层,与垂直燃烧测试结果相符;热重红外测试结果表明,T/C-PCS/GP分解提前,主要影响棉组分热降解并促进其成炭,而高温区的红外谱图表明,在致密炭层的保护下,T/C-PCS/GP的热降解得到抑制。T/C-PCS/GP与T/C-PCS相比,断裂强力提升17%,其断裂强力与T/C的断裂强力相差不大;同时,GP-108的使用改善了T/C-PCS的黄变问题,提升了T/C-PCS/GP的白度。然而,阻燃样品耐久性较差,需要后续改进。

蒙脱土改性酚醛树脂微球制备及其协效阻燃聚丙烯

为了提升聚丙烯(PP)的阻燃性,以苯酚、甲醛、蒙脱土(MMT)、4-羟基苯磺酸为主要原料,采用悬浮缩聚法制备MMT改性酚醛树脂微球(MPF)。通过傅里叶红外光谱、热重分析、扫描电子显微镜、激光粒度仪等对MPF进行表征,研究MMT对酚醛树脂微球的微观形貌以及热稳定性的影响。测试结果表明,成功制备了MPF,其粒径均匀分布在1~20μm,相比于酚醛树脂微球,拥有良好的热稳定性,最大失重率温度为542℃,800℃下残炭率为59.3%。将MPF引入PP,采用熔融共混法制备了PP/膨胀阻燃剂/MPF复合材料,利用垂直燃烧(UL94)、极限氧指数(LOI)、力学性能测试探究MPF的用量对复合材料性能的影响。研究发现,MPF由于良好的成炭性和基体相容性,使PP复合材料的阻燃性能和力学性能同时提高。当MPF添加量为2%时,复合材料的LOI值为29.3%,并且通过UL94 V-0测试,拉伸强度为23.6 MPa,断裂伸长率为25.2%。MPF燃烧时生成碳微球,调控了膨胀炭层,形成了连续且致密的炭层,可隔绝氧气与热量,从而提升了复合材料的阻燃性。

基于ReaxFF反应力场的膨胀阻燃体系热解反应机制研究

采用ReaxFF反应分子动力学模拟添加不同膨胀阻燃体系的聚丙烯(PP)的热解过程,从分子水平探究嵌段共聚物(PAPO⁃MP)与共混(PAPP/MPP)2种状态下阻燃体系的热解反应机制。结果表明,模拟热重曲线与实验结果误差低于2.1%;加入膨胀阻燃体系后,反应活化能从200.16 kJ/mol分别降至154.64 kJ/mol(PAPO⁃MP)和159.14 kJ/mol(PAPP/MPP),说明阻燃剂优先反应从而保护基材;气体小分子数量分别减少10%(PAPO⁃MP)和17.5%(PAPP/MPP),P—O—P结构可以促进大分子团聚物生成,从而降低有毒有害气体生成及提高残炭质量;添加PAPO⁃MP比添加PAPP/MPP的体系势能平均降低11.6×10^(3)kcal/mol,因此添加嵌段共聚物材料稳定性更优。

阻燃剂对水性钢结构防火涂料性能的影响

[目的]为实现碳达峰、碳中和目标,水性涂料的需求日益增加。应用于石化领域的防火涂料更有耐特种火的性能要求。[方法]研制了一种基于乙酸乙烯酯乳液的水性膨胀型钢结构防火涂料,通过热重分析,以及阻燃性、烟密度和耐特种火性能测试,考察了分别以二苯基磷酸乙酯、苯基磷酰氨酸二苯基酯和(4-乙酰基苯基)-磷酸二乙酯作为阻燃剂对其性能的影响。[结果]综合残炭量、热分解温度、氧指数、UL94标准水平/垂直测试结果、烟密度、钢结构升温曲线等指标,采用苯基磷酰氨酸二苯基酯的水性钢结构防火涂料具有最长的点燃时间、最低的燃烧速率、最小的烟密度和最低的最终升温,综合性能最佳。[结论]该涂料满足GB 14907-2018《钢结构防火涂料》标准对室内防火涂料的全部性能要求,配套水性聚氨酯面漆后也可通过全部室外防火涂料测试,可望用于石化领域。

一种生物基应急隔热材料的制备及其性能研究

近年来储罐朝着大型化方向发展,自身火灾危险性日趋升高,一旦发生火灾事故则后果严重。传统的罐区火灾防护仍然存在薄弱之处,难以完全满足应急需求。在此背景下,本文研究制备出一种生物基应急隔热材料以进一步完善储罐区火灾防护体系。以水性聚合的聚丙烯酸钾PP为基体材料,向其中加入制备的阻燃协效剂制成隔热材料PPSL。向PPSL中加入以茶多酚、浒苔和聚磷酸铵复合而成的膨胀阻燃剂TE,最终制成一种生物基隔热材料PPSL-TE。对材料的隔热性能和热稳定性能研究,结果发现,协效剂和阻燃剂的加入使材料受热后形成的炭层膨胀高度增加,PPSL-TE3(质量分数1.4%TE)炭层高度上升至7.5 cm,且结构更为完整致密;残炭率由质量分数19.3%提升至31.5%。此外,PPSL-TE材料在耐火测试中表现出良好的隔热能力。

硼酸锌对腐植酸基膨胀型防火涂层阻燃性能的影响

用生物质腐植酸(HA)、聚磷酸铵(APP)、三聚氰胺(MEL)及硼酸锌(ZB),通过复配混合的方法制备了一系列膨胀涂层,并将其应用于钢结构防火处理。经热重分析(TGA)确定了各防火涂层的热稳定性,经锥形量热测试对其阻燃防火性能进行了分析表征。结果表明,将2%的ZB替代APP-MEL-HA膨胀组分的涂层(C4)表现出最佳的防火性能,其峰值热释放速率(PHRR)和总热释放(THR)分别为53.2 kW/m^(2)和22.7 MJ/m^(2),与对照环氧涂层(C1)相比,分别降低了86%和61%,残炭量达到30.3%。通过对锥形量热残炭、SEM图像及拉曼结果分析揭示了其作用机制。APP、MEL、HA和ZB的组合促进了钢板表面形成连续且致密的墨化膨胀炭层,有效阻止了热量的传递,从而提高了膨胀型涂层的阻燃性能。

利用OVMT和CMS提高IFR/H-PP复合材料的阻燃和力学性能

以打包盒PP废塑料(H-PP)为原料、膨胀型阻燃剂(IFR)为阻燃剂、有机蛭石(OVMT)和碳微球(CMS)为阻燃协效剂,制备阻燃H-PP复合材料,对复合材料的极限氧指数(LOI)、UL 94阻燃等级和力学性能进行测试,并且,采用TG、锥形量热仪和SEM进行分析。结果表明,OVMT和IFR在H-PP中具有协同阻燃效果,当H-PP中OVMT含量为4%、IFR含量为24%时,复合材料的LOI值为29.8%,阻燃级别达到UL 94 V-0级,OVMT提高了IFR/H-PP的力学性能;CMS和IFR在H-PP中具有协同阻燃效果,CMS能提高IFR/H-PP的力学性能;在IFR/H-PP中同时加入OVMT和CMS,复合材料的阻燃和力学性能均得到提高,2-OVMT/2-CMS/24-IFR/H-PP的LOI为32.4%,阻燃级别达到UL 942.0 mm V-0级,其拉伸强度、弯曲模量、弯曲强度和缺口冲击强度分别为22.5、1132.1、26.2 MPa和3.8 kJ/m^(2),与28-IFR/H-PP相比,分别提高了11.9%、0.3%、8.3%和31.0%。