聚苯乙烯/次磷酸铝复合材料的制备及阻燃性能

采用熔融共混的方法制备了聚苯乙烯/次磷酸铝(PS/AHP)复合材料。采用热重分析测试研究了复合材料的热稳定性,通过极限氧指数、垂直燃烧和微型量热测试研究了复合材料的阻燃性能。研究表明:次磷酸铝(AHP)有效提高了PS/AHP复合材料的阻燃性能,当次磷酸铝添加量为20%时,复合材料可以达到UL-94 V-0级别,极限氧指数为24.0%;热重分析研究表明次磷酸铝的加入可以延缓聚苯乙烯分子链的降解,提高复合材料高温成炭率;微型量热(MCC)测试表明PS/AHP30与纯PS相比,其热释放速率峰值和总热释放分别下降40.5%和18.9%。     

阻燃聚氨酯弹性体复合材料的制备及性能研究

以次磷酸铝（AHP）和三聚氰胺氰脲酸盐（MCA）为阻燃剂,采用熔融共混法制备了一系列阻燃聚氨酯弹性体复合材料（FR-TPU）,采用热失重分析、极限氧指数、UL 94 垂直燃烧测试、锥形量热测试、力学性能测试、扫描电子显微镜研究了FR-TPU复合材料的热稳定性、阻燃性能、燃烧性能、力学性能和炭渣形貌。结果表明,AHP与MCA复配可明显提高FR-TPU复合材料的热稳定性、成炭率和阻燃性能;TPU/AHP-MCA20的极限氧指数为30.5 %,并达到UL 94 V-0级,热释放速率峰值(PHRR)和总热释放量(THR)分别下降至436 kW/m2和55.5 MJ/m2,拉伸强度和断裂伸长率分别为25.45 MPa和588.3 %;AHP与MCA复配可明显提高TPU/AHP-MCA20炭渣的致密性,从而有效抑制燃烧区域物质及能量交换,提高复合材料的火灾安全性。     

阻燃PLA复合材料的制备及其阻燃性能研究

采用熔融共混技术,将二乙基次膦酸铝（ADP）引入聚乳酸(PLA)中,制备了一系列阻燃聚乳酸复合材料(FR-PLA)。在此基础上,采用热重分析、极限氧指数、UL 94垂直燃烧、微型量热测试研究了二乙基次膦酸铝对阻燃聚乳酸复合材料热稳定性、阻燃性能以及燃烧性能的影响。结果表明,ADP可以有效提高复合材料的阻燃性能,30 %（质量分数,下同）的ADP使得PLA/ADP30通过UL 94 V-0级别,极限氧指数达到31.6 %（体积分数,下同）; ADP使得阻燃PLA复合材料的初始分解温度降低,但明显提高复合材料的成炭性; ADP使得复合材料的热释放速率峰值明显下降,PLA/ADP30热释放速率峰值为290 W/g,相对于PLA下降37.1 %,明显降低复合材料的火灾危险性。     

三位一体膨胀型烷基次膦酸盐对生物降解塑料PBS的阻燃与抗熔滴作用

采用熔融共混技术,将自制的三位一体膨胀型烷基次膦酸盐APTMP引入到聚丁二酸丁二醇酯(PBS)中,制备了不同添加量的系列PBS复合材料;采用极限氧指数(LOI)、微型量热(MCC)以及垂直燃烧(UL94)测试考查了复合材料的阻燃与抗熔滴效果;采用热重(TG)、热重红外联用(TG-FTIR)和扫描电镜(SEM)研究了复合材料的热性能和阻燃机理。结果表明,APTMP可以显着提高PBS的阻燃性和抗滴落性,并抑制燃烧过程中的放热;随着阻燃剂添加量的增加,复合材料在700℃时的残炭量明显增加,抗熔滴效果也得到增强;SEM观察形成了多孔的膨胀碳层,表现出凝聚相阻燃,当添加量为25%时,复合材料已具备良好的阻燃性能,LOI为28.4%,垂直燃烧通过UL94 V-0级。     

聚磷酸铵/次磷酸铝/聚氨酯密封胶阻燃体系的阻燃及热降解行为

以蓖麻油为基础多元醇,聚磷酸铵(APP)与次磷酸铝(AHP)复配协同聚氨酯阻燃体系,制备了阻燃聚氨酯密封胶(FRPUS)。研究了APP/AHP阻燃体系对FRPUS阻燃性能、热稳定性能的影响。结果表明,APP与AHP的质量比为5:1,添加量为50%时,FRPUS的极限氧指数(LOI)值达到35.1%,较纯PUS提高74.6%;TGA和热降解动力学表明APP/AHP提高了阻燃体系的热稳定性。     

聚乳酸/苯基次膦酸镧复合材料的制备及阻燃性能研究

采用简单方法制备了苯基次膦酸镧(LaP),并将其作为阻燃剂引入聚乳酸(PLA)中,制备了一系列PLA/LaP复合材料。采用热重分析(TG)、极限氧指数(LOI)、UL 94垂直燃烧、微型量热测试(MCC)等方法研究PLA/LaP复合材料的热稳定性、阻燃性能和燃烧性能。结果表明,LaP可以提高复合材料阻燃性能,30 %（质量分数,下同）的LaP使得复合材料的极限氧指数达到24.8 %,并通过UL 94 V-2级别;LaP可明显提高复合材料的热分解温度和成炭率;高添加量LaP可显著降低复合材料的热释放速率峰值（pHRR）和总热释放(THR),有效降低了复合材料的火灾危险性。     

焦磷酸哌嗪协同次磷酸铝阻燃聚丙烯复合材料性能

为提高聚丙烯(PP)的阻燃性能,以焦磷酸哌嗪(PAPP)和次磷酸铝(AHP)为原料,通过熔融挤出的方式制备了不同质量比的PP复合材料,采用极限氧指数(LOI)、UL94垂直燃烧、热重分析(TG-DTG)、锥形量热(CONE)和扫描电子显微镜(SEM)等测试手段对PP复合材料热稳定性及阻燃抑烟性能进行分析,研究PAPP和AHP不同配比对阻燃性能的影响。结果表明,PAPP和AHP膨胀阻燃剂的加入大幅提升了PP复合材料的阻燃抑烟性能,当PAPP和AHP质量比为4∶1,总添加量为25%时,PP复合材料LOI达到31.5%,通过UL94垂直燃烧V-0级,800℃残炭率为23.16%,说明PAPP和AHP两者发挥了较好的协同阻燃作用。此外,其热释放速率(HRR)、总热释放量(THR)、烟释放速率(SPR)和总烟释放量(TSP)都得到大幅降低,SEM结果表明阻燃成分在PP复合材料表面形成了连续、致密的膨胀炭层,提升了材料的阻燃和抑烟性能。     

聚乳酸/苯基次膦酸铝复合材料的制备及其阻燃性能研究

采用共沉淀法制备了苯基次膦酸铝(AlP)并对其进行表征。在此基础上,通过熔融共混法制备了一系列聚乳酸/苯基次膦酸铝（PLA/AlP）复合材料,采用热重分析（TG）、极限氧指数测试（LOI）、UL 94垂直燃烧测试、微型量热测试研究AlP对复合材料热稳定性、阻燃性能、燃烧性能的影响。结果表明,AlP可以有效提高PLA/AlP复合材料的阻燃性能, 当AlP含量为30 %（质量分数,下同）时,PLA/AlP30的极限氧指数达到25.6 %,并达到UL 94 为V-0级;AlP可以提高PLA/AlP复合材料初始分解温度和成炭性; PLA/AlP复合材料的热释放速率峰值和总热释放随着AlP添加量增大呈现先增高再下降的趋势。     

苯基次膦酸锌阻燃改性聚乳酸材料

采用共沉淀法合成了苯基次膦酸锌(ZnP)并对其进行表征,在此基础上通过熔融共混技术制备了一系列聚乳酸/苯基次膦酸锌(PLA/ZnP)复合材料,采用热重分析,极限氧指数测试（LOI）,UL 94垂直燃烧测试、微型量热(MCC)研究ZnP对复合材料热稳定性、阻燃性能以及燃烧性能的影响。研究表明,ZnP可以提高复合材料的热分解温度和成炭性,30 %（质量分数,下同）ZnP使得复合材料的分解温度相对于纯PLA上升8 ℃,750 ℃成炭率达到18.5 %;此外,ZnP可以提高复合材料阻燃性能,PLA/ZnP30的极限氧指数达到24.0 %,并通过UL 94 V-2级别,热释放速率峰值相对于PLA降低了24.9 %,有效提高了复合材料火灾安全性。     

含磷阻燃剂对碳纤维增强环氧树脂阻燃性能的影响

以DOPO为阻燃剂,短切碳纤维为增强体,环氧树脂为基体,制备了不同DOPO含量的DOPO/碳纤维/环氧树脂复合材料。采用极限氧指数测定法、锥形量热法和UL-94垂直水平燃烧测试法,分析了复合材料的燃烧特性以及DOPO添加量对复合材料阻燃性能的影响。研究结果表明:DOPO可以提高碳纤维环氧复合材料的阻燃性能;添加磷(P)含量为3%时,与未添加样品相比,极限氧指数提高了9%,达到21.8,热释放速率峰值降低了31.2%;当P含量大于2%时,样品的水平分级达到了FH-1级别;火焰增长指数计算表明,含有1%和3%P的复合材料火灾危险性较小,DOPO对复合材料的阻燃作用主要属于气相阻燃机理。     

Investigations of thermal degradation behavior and fire performance of halogen‐free flame retardant poly(1,4‐butylene terephthalate) composites

This work aims to develop halogen‐free poly(1,4‐butylene terephthalate) (PBT) composites with enhanced flame retardancy using ecofriendly flame retardants, aluminum hypophosphite (AHP) and melamine derivatives (melamine polyphosphate and melamine cyanurate). Microscale combustion calorimetry and thermal gravimetric analysis/infrared spectrometry (TG‐IR) technique were used to investigate the potential fire hazards of these PBT composites. For the PBT composites with the incorporation of AHP and melamine derivatives, the heat release capacity (HRC) which is an indicator of a material fire hazard was significantly reduced, and the intensities of a variety of combustible or toxic gases detected by TG‐IR technique were remarkably decreased. Moreover, a loading of 20 wt % flame retardant mixture fulfilled the PBT composites high limited oxygen index (LOI) and V‐0 classification in UL 94 testing. An intumescent flame retarded mechanism was speculated in this work, because numerous bubble‐like char residues were found on the surface of the samples containing flame retardant mixture after LOI testing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Preparation and study of intumescent flame retardant poly(butylene succinate) using MgAlZnFe‐CO3 layered double hydroxide as a synergistic agent

Intumescent flame retardant consisting of ammonium polyphosphate and melamine, and MgAlZnFe‐CO₃ layered double hydroxides (LDHs) prepared by the constant pH coprecipitation method, were added to poly(butylene succinate) (PBS) via melt blending to obtain novel intumescent flame retardant poly(butylene succinate) (IFR‐PBS) composites. A study on the effect of MgAlZnFe‐CO₃ LDHs on the mechanical, thermal, and flame retardancy properties of IFR‐PBS composites was investigated. It was revealed that IFR‐PBS composites exhibited both excellent flame retardancy and antidripping properties when the content of MgAlZnFe‐CO₃ LDHs was 1% (the total loading of flame retardant was 20%), for a goal of vertical flammability (UL‐94) V‐0 rate and a limiting oxygen index value of 35. The results showed that a suitable amount of MgAlZnFe‐CO₃ LDHs had a noticeable synergistic effect on IFR‐PBS composites. Importantly, tensile strength and flexural strength were improved by the presence of MgAlZnFe‐CO₃ LDHs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40736.     

一种双官能团膨胀型阻燃剂的合成与应用

以三氯氧磷与季戊四醇反应,制备了一种无卤的双官能团膨胀型阻燃剂——笼状季戊四醇磷酸酯(PEPA),并对其结构进行表征。将该阻燃剂与三聚氰胺氰脲酸酯(MC)协同作用于聚对苯二甲酸丁二醇酯(PBT),考察其对PBT阻燃性能的影响。结果表明:PEPA是良好的成炭剂,与基体有很好的相容性,与MC协同作用于PBT树脂具有出色的阻燃效果(达到UL94V-0级)。同时,由PEPA与MC协同作用的阻燃PBT树脂具有良好的力学性能和热性能。     

Synergistic effect between aluminum hypophosphite and a new intumescent flame retardant system in poly(lactic acid)

A hyperbranched charring agent (CT) was synthesized by triglycidyl isocyanurate and diethylenetriamine in water, and a new intumescent flame retardant (IFR) system was formed by ammonium polyphosphate (APP) and CT. The different formula and synergistic system between IFR and aluminum hypophosphite (AHP) have been studied through limit oxygen index (LOI), UL‐94, cone calorimetry test and TGA. It was found that the LOI for poly(lactic acid) (PLA) with 30 APP/CT (4:1) and 20 wt % IFR/AHP (3:1) were 41.2% and 43.5%, respectively, and the both could achieve UL‐94V‐0 rating with no melt dripping. The heat release rate (HRR), maximum HRR value and average mass loss rate of PLA could be dramatically decreased by combination of IFR and AHP while the thermal stability was greatly enhanced. The study of morphology and structure of char illustrated that more intumescent and compact char layer with good intensity was formed during the degradation of IFR/AHP, which resulting to better flame retardancy and anti‐dripping than IFR or AHP alone. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46359.     

聚磷酸三聚氰胺对玻纤增强PA66的膨胀阻燃作用

采用自制的新型膨胀型阻燃剂——聚磷酸三聚氰胺(MPP)对玻纤增强PA66进行阻燃,以氧指数和垂直燃烧(UL94)评价了其阻燃作用;以热失重测定了材料的热分解性能;以扫描电镜观察了材料残炭的结构;并探讨了MPP阻燃玻纤增强PA66的阻燃机理。试验表明,单一MPP对玻纤增强PA66有良好的阻燃效果,当添加25％时,阻燃材料的氧指数为38,0％,达到UL94V-0级;MPP参与了玻纤增强PA66的降解过程,在材料表面形成了致密的隔热、隔氧的泡沫炭层。     

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。     

Synergistic flame retardancy of ZnO and piperazine pyrophosphate/melamine cyanurate in polypropylene

In order to improve the flame retardant efficiency and smoke-suppression of piperazine pyrophosphate/melamine cyanurate (PPAP/MCA) in PP, the synergism of ZnO and PPAP/MCA was investigated by limiting oxygen index (LOI) determination, UL-94 test, and cone calorimetry test (CCT). It is found that ZnO performs an exceptional synergism in flame retardant effect and inhibition on the flame propagation. Besides, ZnO can significantly inhibit the production of the smoke and CO. The TGA of the PP composites, the component and structure analysis of the heated composites and CCT residues reveal that ZnO performs the synergism primarily by the following modes: ZnO promotes obviously the charring of the composite, and improves the thermal stability as well as the strength of the intumescent layer, which brings about an improved flame retardant property and inhibiting ability on the flame propagation.     

类石墨氮化碳及其MCA杂化物的合成与阻燃

采用三聚氰胺作为原料,通过梯度加热制备了类石墨氮化碳(g-C3N4),再以三聚氰胺、氰尿酸和自制g-C3N4合成了三聚氰胺氰尿酸杂化物(CNMCA)。采用FTIR、XRP和TDA对g-C3N4和CNMCA的结构与热性能进行了表征。将CNMCA应用在聚酰胺6中制备了阻燃复合材料,同时,采用垂直燃烧和极限氧指数法分析了阻燃效果。结果表明,g-C3N4具有较高的热稳定性,其热失重5%(T-5%)的温度高达544.9℃。另外,g-C3N4的杂化不同程度地提高了MCA的热稳定性。当杂化比例为30%时,CNMCA的T-5%由345.5℃提升到352.3℃,在600℃下的残余质量由0.43%显著提升到23.45%。CNMCA的阻燃性能比MCA更佳,当添加到10%CNMCA30时,试样燃烧时的熔滴已无法使脱脂棉被引燃,因此,阻燃等级从UL94 V-2提升到UL94 V-0级,极限氧指数也从27.8%提升至31.3%。     

The effect of morphology on the flame‐retardant behaviors of melamine cyanurate in PA6 composites

Three types of melamine cyanurate (MCA) with micrometer‐size sphere‐like, micrometer‐scale rod‐like, and nanometer‐scale flake‐like morphologies were synthesized by changing the chemical circumstances of the reactions. The microcosmic morphologies of MCA were characterized via scanning electron microscopy and X‐ray diffraction. After the MCAs with different morphologies were incorporated into polyamide 6 (PA6), the flame‐retardant properties of the MCA/PA6 composites were investigated using the limited oxygen index (LOI), UL94, and cone calorimeter tests. The MCA/PA6 composites with nanometer‐scale flake‐like MCA obtained an LOI value of 29.5% and a UL94 V‐0 rating, which were higher than those with micrometer‐size sphere‐like and rod‐like MCAs. However, the different morphologies did not affect the heat release rate, total smoke release, average carbon monoxide yield, and average carbon dioxide yield based on the cone calorimeter. The flame‐retardant mechanism of MCAs with different morphologies was investigated via thermal gravimetric analysis (TGA) and TGA‐Fourier transform infrared spectra. The results show that the different morphologies of MCA resulted in different dispersed evenness of MCA. Further, the nanometer‐scale flake‐like morphology of MCA brought more interactions of hydrogen bond between MCA and PA6, which resulted in the delay of MCA decomposition and the enhancement of MCA flame‐retardant effect. The nanometer‐scale flake‐like MCA had a better performance compared with the other samples because of the delaying and even release of flame‐retardant effect by the decomposition of evenly dispersed MCA. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40558.