三嗪成炭剂对EVA阻燃性能的影响

三嗪成炭剂(CNCH-DA)与多聚磷酸铵(APP)复配成膨胀型阻燃剂(IFR)应用于EVA的阻燃改性,采用氧指数测定仪(LOI)、垂直燃烧测定仪(UL-94)分析了EVA/IFR复合材料的阻燃性能,采用微型量热仪(MCC)分析了其燃烧行为,并采用热重分析仪(TGA)和扫描电子显微镜(SEM)研究了其阻燃机理。结果表明,当APP与CNCH-DA的质量比为2∶1时,EVA/IFR复合材料的LOI值达到27. 7%,并且通过了UL-94 V-0级测试; MCC分析结果表明,添加了IFR后,EVA的燃烧性能下降; TGA分析结果表明,当添加IFR后,EVA/IFR复合材料的热降解推迟,残炭量增加;SEM分析表明,EVA/IFR在燃烧后能形成致密且蓬松的炭层,起到良好的阻燃效果,而EVA/CNCH-DA燃烧后,形成众多不致密的微球。     

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。     

有机-金属杂化化合物阻燃聚丙烯的研究

将有机-金属杂化三嗪化合物（SCTCFA-ZnO）与聚磷酸铵（APP）复配制备了膨胀型阻燃剂（IFR）,通过极限氧指数测试、垂直燃烧测试、锥形量热分析、热失重分析和扫描电子显微镜分析等表征方法研究了SCTCFA-ZnO/APP的协同作用对PP复合材料阻燃性能的影响。结果表明,APP与SCTCFA-ZnO复配可以有提高PP材料的阻燃性能,当IFR的添加量为25 %（质量分数,下同）,且APP/SCTCFA-ZnO的质量比为2/1时,复合材料的极限氧指数最高,达到31.1 %,达到UL 94 V-0级;IFR可提高复合体系的温热稳定性,阻燃复合材料燃烧后会形成一层致密、连续的炭层,从而起到良好的阻燃效果。     

新型膨胀阻燃剂在乙丙弹性体中的应用

以多聚磷酸铵(APP)与新型成炭剂(CNCA-DA)复配成膨胀型阻燃剂(IFR),应用于茂金属乙丙弹性体(MEP)的阻燃改性,并采用氧指数测定仪(LOI)、热重分析仪(TGA)和红外光谱仪(FTIR)研究了IFR对MEP的阻燃作用和协同作用机理。结果表明:APP与CNCA-DA复配成的膨胀型阻燃剂(IFR)对MEP具有良好的阻燃性能;当APP与CNCA-DA的质量比为2∶1时,阻燃效果最佳;当IFR的质量分数为30%时,MEP/IFR复合材料的氧指数值达到32.0%;TGA分析结果表明:APP与CNCA-DA复配后,能促使IFR形成更多的残炭,并使材料的热降解温度向高温方向移动。FTIR分析表明:APP与CNCA-DA复配后,残炭中形成了P-O-C、P-O-P的交联结构,并形成更多的聚芳烃结构。     

膨胀型阻燃剂/二乙基次磷酸铝阻燃改性不饱和树脂基复合材料

采用密胺包覆聚磷酸铵（APP）、季戊四醇（PER）和三聚氰胺（MEL）作为膨胀型阻燃剂（IFR）对不饱和树脂（UP）进行改性,研究了APP、PER和MEL不同复配比例及用量对不饱和树脂基复合材料阻燃性能和力学性能的影响。基于IFR最佳用量,以二乙基次磷酸铝（ADP）为协效剂,研究了ADP用量对IFR/UP阻燃复合材料阻燃性能、力学性能及热稳定性的影响。结果表明,当APP∶PER∶MEL复配比例为4∶1∶1,IFR添加量为15 %（质量分数,下同）时,复合材料综合性能最佳,其极限氧指数为27.4 %,UL 94垂直燃烧达到V?1等级,弯曲强度和冲击韧性分别为100.3 MPa和6.3 kJ/m²;ADP的引入能够进一步提高IFR/UP复合材料阻燃性能,且随着ADP质量分数的增加而增强;当ADP质量分数为2 %时,IFR?ADP/UP复合材料极限氧指数为28.5 %并达到V?0阻燃等级,弯曲强度和冲击韧性分别为110 MPa和7.8 kJ/m²,与IFR/UP复合材料相比,分别提高了9.7 %和23.8 %;ADP能够促进IFR/UP复合材料表面成炭,缓解基体的热降解。     

CFA/APP协同阻燃动态硫化热塑性弹性体的制备及其性能

将新型无羟基低聚三嗪衍生物(CFA)作为成炭剂与聚磷酸铵(APP)复配成膨胀型阻燃剂(IFR),并研究了不同含量和比例的IFR对动态硫化热塑性弹性体(TPV)阻燃性能、热稳定性能、流变性能和力学性能的影响。结果表明:IFR对TPV有良好的阻燃作用,当IFR(CFA与APP质量比1∶3)质量分数为40%时,TPV/IFR复合材料具有最佳的阻燃性能,极限氧指数为26.4%,且垂直燃烧测试等级为V-0级;TPV/IFR复合材料的热释放速率峰值与总热释放量均大幅降低;IFR能促使TPV/IFR复合材料形成更多的残炭,积分程序分解温度和表观活化能明显增加,材料的热稳定性显著提高;TPV/IFR复合材料虽然加工性能略有降低,但具有优异的力学性能,能满足加工使用要求。     

新型成炭剂对EVA/APP体系的阻燃性能影响研究

以新型成炭剂聚对苯二甲酰乙二胺(PETA)和聚磷酸铵(APP)复配制备了无卤阻燃乙烯-醋酸乙烯共聚物(EVA)/APP/PETA复合材料,通过极限氧指数法和垂直燃烧法表征了复合材料的阻燃性能,通过热失重分析仪(TGA)和扫描电镜(SEM)分析了复合材料的热稳定性能和残炭表面形貌。结果表明:APP与PETA复配(IFR)后可以极大地提高EVA的阻燃性能,EVA/APP/PETA(质量比70/25/5)体系极限氧指数(LOI)达到39%,较纯EVA提高了88.4%,UL 94测试为V-0级别;EVA/APP/PETA复合材料在600℃下的残炭率达到了42%,较纯EVA残炭率高37%。SEM表明:30%IFR(APP与PETA质量比5:1)的加入提高了样品残炭表面致密性。     

金属化合物对新型膨胀阻燃LDPE的协同作用

以新型的齐聚物式成碳剂(OCA)与多聚磷酸铵(APP)复配成新型膨胀型阻燃剂(IFR),采用氧指数测定仪(LOI)、垂直燃烧测定仪(UL)、热重分析仪(TGA)和红外光谱(FTIR)研究了碳酸镍(NC)、硼酸锌(ZB)和二氧化锰(MnO2)与LDPE/IFR体系的阻燃协同作用.结果表明:添加1％的金属化合物后,复合材料的氧指数值都有一定程度的提高,其中NC的效果最佳.TGA分析结果表明:金属化合物都能促使复合材料提前分解成碳,NC还能保留更多的残碳.FTIR分析表明:残碳中形成了聚芳烃和P-O-C、P-O-P的交联结构.     

一种磷-氮阻燃剂的合成及其在聚丙烯中的应用

采用高温高压溶液聚合法合成了一种新型磷-氮阻燃剂N-对苯二甲酸-N'-(N-亚磷酸-乙二胺)-乙二胺(IFR)。将制得的阻燃剂与聚磷酸铵(APP)进行复配,并与聚丙烯(PP)进行共混,制备了阻燃PP复合物。通过极限氧指数(LOI)测定、垂直燃烧实验(UL94)、热重分析(TG)测试对复合材料的阻燃性能和热稳定性进行了表征,并借助扫描电子显微镜(SEM)表征了残炭表面形态。结果表明,当添加9%IFR和21%APP时,PP/IFR/APP体系的极限氧指数达到最大,为28.8%,并通过了UL94 V-0级。在该比例下燃烧所形成的炭层呈现出膨胀的连续结构,可以很好覆盖于材料表面形成阻隔效果。这表明该阻燃剂与APP复配对PP具有良好的阻燃作用。     

磷酸硼协效膨胀型阻燃剂对聚丙烯阻燃性能的研究

在膨胀型阻燃剂（IFR）中添加不同比例的协效剂磷酸硼（BP）制备复合阻燃剂,将复合阻燃剂加入聚丙烯（PP）中,制备阻燃PP复合材料。通过垂直燃烧、极限氧指数测试、锥形量热测试、热重分析和力学性能测试对PP复合材料进行表征。结果表明：BP对IFR具有显著的协同阻燃效果。当添加2%BP和13%IFR时,PP/IFR/BP复合材料（样品4#）阻燃性能最佳,燃烧等级达到V-0,极限氧指数达到30.8%。样品4#的热释放速率峰值、平均热释放速率、总产烟量和总释放热与加入15%IFR的阻燃PP相比,分别降低19.51%、4.40%、34.00%和6.87%,700℃时样品4#的质量保留率增加50%。燃烧过程中,PP/IFR/BP复合材料的硼元素在凝聚相中催化IFR交联成炭,较未添加BP的复合材料,PP/IFR/BP炭层膨胀程度更高且更致密。BP协效剂的添加降低了阻燃剂的添加量,明显提升复合材料的力学性能。     

Flame retardation and thermal degradation of intumescent flame‐retarded polypropylene composites containing spirophosphoryldicyandiamide and ammonium polyphosphate

A novel halogen‐free intumescent flame retardant, spirophosphoryldicyandiamide (SPDC), was synthesized and combined with ammonium polyphosphate (APP) to produce a compound intumescent flame retardant (IFR). This material was used in polypropylene (PP) to obtain IFR‐PP systems whose flammability and thermal behavior were studied by the limiting oxygen index (LOI) test, UL‐94, thermogravimetric analysis, and cone calorimetry. In addition, the mechanical properties of the systems were investigated. The results indicated that the compound intumescent flame retardant showed both excellent flame retardancy and antidripping ability for PP when the two main components of the IFR coexisted in appropriate proportions. The optimum flame retardant formulation was SPDC:APP = 3:1, which gave an LOI value of 38.5 and a UL‐94 V‐0 rating. Moreover, the heat release rate, production of CO, smoke production rate, and mass loss rate of the IFR‐PP with the optimum formulation decreased significantly relative to those of pure PP, according to the cone calorimeter analysis. The char residues from the cone calorimetry experiments were observed by scanning electron microscopy, which showed that a homogeneous and compact intumescent char layer was formed. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

无卤膨胀阻燃剂在低密度聚乙烯中的应用研究

以干法合成的P-N无卤膨胀阻燃剂(IFR)为基础,配合聚磷酸胺(APP)并且将金属氧化物(ZnO)作为协效剂阻燃改性低密度聚乙烯(PE-LD)。采用扫描电子显微镜对该体系燃烧后的炭层结构进行了分析。通过红外光谱和X射线光电子能谱研究了该体系在不同温度热处理后的残炭组成,并分析了该膨胀型阻燃体系对PE-LD的阻燃机理。结果表明,PE-LD/IFR/APP/ZnO体系的极限氧指数可以达到27.9%,垂直燃烧性能达到UL 94V-0级。     

超支化芳胺三嗪聚合物的合成及其对聚丙烯阻燃性能影响的研究

以三聚氯氰和对苯二胺为原料,以丙酮为溶剂,采用一步法合成了一种具有超支化结构的新型芳胺三嗪聚合物,用红外光谱证实了其结构,将该产物与聚磷酸铵(APP)复配成膨胀型阻燃剂(IFR),研究了其对聚丙烯(PP)阻燃性能的影响。结果表明,在氮气氛围下,合成的新型芳胺三嗪聚合物在600 ℃的残炭量为44.8 %,具有较好的成炭阻燃性能;添加该类新型IFR后,PP的极限氧指数从17.5 %提高到27.0 %,热释放时间延后625 s,热释放速率峰值降低85.7 %。     

新型磷-氮膨胀阻燃剂在改性聚丙烯中的应用研究

采用自制干法合成的磷-氮膨胀型阻燃剂(磷酸酯三聚氰胺盐,IFR)复配聚磷酸胺(APP)和聚四氟乙烯(PT-FE)阻燃改性聚丙烯(PP),利用极限氧指数法、垂直燃烧法分析了阻燃PP的燃烧性能,通过热重分析仪、傅里叶变换红外光谱仪、扫描电子显微镜和X射线光电子能谱对阻燃PP的热降解过程、燃烧性能、残炭结构进行了分析,并研究了燃烧过程中复配阻燃体系对PP的阻燃机理。结果发现,IFR、APP和PTFE之间具有明显的阻燃协效作用;当阻燃剂总添加量为24%(APP为6%、IFR为17.5%、PTFE为0.5%)(质量分数)时,阻燃PP的极限氧指数达到30.1%,垂直燃烧测试达UL 94V-0级;加入阻燃剂还能提高PP的热稳定性。     

无卤阻燃SBR的阻燃性能及热失重行为

利用锥形量热仪(CONE)和热失重分析(TG)研究了化学膨胀阻燃剂(IFR)、氢氧化铝/红磷(Al(OH)3/P)及二者复合阻燃SBR的阻燃性能及热失重行为。结果表明,阻燃剂用量为40份,聚磷酸铵(APP)与季戊四醇(PER)质量比为3∶1时,SBR/APP/PER的热释放速率及生烟速率均大幅度下降,阻燃效果较好;Al(OH)3与P质量比为26∶14时,可有效降低SBR/Al(OH)3/P的热释放速率,但生烟速率较大;将APP/PER∶Al(OH)3/P=1∶1复配,SBR/IFR/Al(OH)3/P的热释放速率和生烟速率没有进一步改善,协同效应不明显。热失重研究表明,空气气氛下,试样SBR/IFR/Al(OH)3/P在300~500℃时,Al(OH)3/P反应使得SBR分解速度下降;在500~800℃时,APP与PER形成炭层,有效地起到隔热隔氧的作用,从而抑制炭黑的分解;两者复合使用,使阻燃SBR分解速度降低,热稳定性提高。     

Flame Retardancy and Thermal Performance of Polypropylene Treated With the Intumescent Flame Retardant,Piperazine Spirocyclic Phosphoramidate

Piperazine spirocyclic phosphoramidate (PSP), a novel halogen‐free intumescent flame retardant, was synthesized and used to improve the flame retardancy and dripping resistance of polypropylene (PP) combined with ammonium polyphosphate (APP) and a triazine polymer charring‐foaming agent (CFA). The optimum flame‐retardant formulation was PSP:APP:CFA = 3:6:2 (weight ratio). The flammability and thermal behavior of the (intumescent flame‐retardant)‐PP (IFR‐PP) were investigated via limiting oxygen index (LOI), vertical burning tests (UL‐94), thermogravimetric analysis, and cone calorimetry (CONE). The results indicated that the IFR‐PP had both excellent flame retardancy and anti‐dripping ability. The optimum flame‐retardant formulation gave an LOI value of 39.8 and a UL‐94 V‐0 rating to PP. Moreover, both the heat release rate and the total heat release of the IFR‐PP with the optimum formulation decreased significantly relative to those of pure PP, according to the cone calorimeter analyses. The residues of IFR‐PP obtained after CONE tests were observed by scanning electron microscopy, and it was found that the char yield was directly related to the flame retardancy and anti‐dripping behavior of the treated PP. J. VINYL ADDIT. TECHNOL., 20:10–15, 2014. © 2014 Society of Plastics Engineers     

Synergistic effects of molybdenum disulfide on a novel intumescent flame retardant polyformaldehyde system

A novel intumescent flame retardant (IFR) composed of ammonium polyphosphate (APP), benzoxazine containing trialkoxysilane (BA-a-Si) and melamine (ME), is compounded with different specifications of MoS₂ as synergist to flame retard polyformaldehyde (POM). The flame retardancy and mechanism of the composites are analyzed by limiting oxygen index (LOI), vertical combustion (UL-94) and cone calorimeter. At the same time, the mechanical properties and lubricating properties are tested by electromechanical testing machine and wear testing machine. The experimental results show that MoS₂ has a good synergistic effect with IFR, and the smaller the average particle size of MoS₂ is, it seems to be more beneficial to improve the flame retardancy of POM composites. Only a small amount of MoS₂ (0.8 wt%) is needed to synergize with IFR, the flame retardant POM composite (FR-POM) can achieve UL-94 (3.2 mm) V-0 rating, LOI of 62.5%, and heat release rate reduction of 25.3%, total smoke release decreased by 29.5%. In addition, from the mechanical properties analysis, it is found that the microscale MoS₂(M2) can better improve the bending and tensile properties of the FR-POM composites, while the nanoscale MoS₂(N80) is more helpful to improve the lubricating properties.     

壳聚糖/聚磷酸铵膨胀阻燃PP的阻燃及抑烟性能

为了提高聚丙烯(PP)的阻燃和抑烟性能,将壳聚糖(CS)作为膨胀型阻燃剂的碳源、聚磷酸铵(APP)作为膨胀型阻燃剂的酸源和气源,在此基础上通过熔融共混的方法制备了PP/CS/APP复合材料。采用极限氧指数仪、锥形量热仪等仪器研究了PP/CS/APP复合材料的的抑烟性及阻燃性。研究结果表明:CS/APP添加量为30%时,复合材料的极限氧指数值最大可达28.1%;且复合材料在烟气释放总量、CO和CO_2排放上明显降低,抑烟性得到了提升;热释放速率峰值、平均热释放速率值、平均有效燃烧热值、总热释放量值降低,成炭率升高,PP/CS/APP复合材料更难点燃;火灾性能指数明显提高,阻燃性能得到了大幅度提升,火灾蔓延指数显著减小,同时火灾危险性也相应降低。     

A novel lanthanum-based phosphorus-containing flame retardant agent and its application in polylactic acid

Currently, intumescent flame retardants (IFR) are often used in the flame retardant modification of polylactic acid (PLA). Due to the high loading, it will weaken the mechanical properties of PLA. In this study, lamellar lanthanum-based DOPO derivative (La@DDP) is prepared by solution method, and it acts as a flame retardant agent was added into PLA with IFR. The results show that PLA composite passes the UL94 V-0 rating with a limiting oxygen index (LOI) of 32.0, in the addition of 4.5 wt% IFR and 1.5 wt% La@DDP. Moreover, the peak heat release rate (PHRR) and total heat release (THR) of the PLA composite reduces by 31.0% and 23.2% compared to pure PLA, respectively. IFR/La@DDP agents assign the PLA composite with excellent thermal stability and carbon-forming ability. Through the analysis of residual char, the synergistic flame retardant mechanism between IFR and La@DDP in PLA composite is discussed. Notably, the tensile strength and elongation at break of the PLA composites are only reduced by 4.03% and 9.51% compared to pure PLA. This work provides a novel lanthanum-based flame retardant agent for designing PLA composites with good fire safety and mechanical properties, and it will broaden the application range of PLA.