CMSs对新型聚丙烯膨胀阻燃体系性能的影响

为了进一步提高聚丙烯(PP)膨胀阻燃体系的阻燃性能,将碳微球(CMSs)添加至膨胀型阻燃聚丙烯(壳聚糖/聚磷酸铵/聚丙烯(CS/APP/PP))体系中,经熔融共混的方法制备出CMSs/CS/APP/PP复合材料。采用数显氧指数仪(LOI)、锥形量热仪(CONE)、电子万能试验机(EUT)等仪器对复合材料进行了测试,同时考察了CMSs对聚丙烯膨胀阻燃体系(CS/APP/PP)阻燃性能的影响。结果表明,CMSs的加入可提高材料的阻燃性;在CMSs添加量为3%时,复合材料的极限氧指数达到31.5%,较CS/APP/PP体系提高了18.9%;热释放速率峰值(PHRR)、平均热释放速率(MHRR)、平均有效燃烧热(MEHC)、总热释放量(THR)均明显降低,成炭率显著提高,炭层更加致密,火灾性能指数(FPI)达到最大,为0.089 3 m~2·s/kW,较CS/APP/PP体系提高了1倍多,材料的阻燃性大幅度提升。同时CMSs的加入显著提高了复合材料的抑烟性,使复合材料的总烟释放量(TSR)、CO和CO_2的排放均明显降低;且复合材料的火灾蔓延指数(FGI)显著减小,为1.16 kW/(m~2·s),较CS/APP/PP体系降低了29.9%,火灾危险性明显降低。     

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。     

用锥形量热法研究EVA/EG复合材料的阻燃性能

采用哈克转矩流变仪将阻燃剂可膨胀石墨(EG)、乙烯-乙酸乙烯酯共聚物(EVA)树脂和其它助剂进行熔融混和均匀,制备阻燃EVA/EG复合材料,并通过锥形量热仪研究其阻燃性能。研究结果表明:经膨胀石墨阻燃的EVA/EG复合材料的热释放速率峰值(PHRR)、总热释放速率(THR)、烟发生速率(SPR)、总释烟速率(TSR)逐渐降低,火灾性能指数(FPI)、点燃时间(TTI)及燃烧残渣逐渐增加,表现出明显的阻燃性和抑烟性特点。阻燃EVA/EG复合材料燃烧时,其EG片层受热膨胀形成保护层,有效延缓了热、氧传递,降低了材料的热分解和扩散速率,促进了成炭,是阻燃性提高的关键因素。     

新型有机硅阻燃成炭剂的热性能及成炭机理的研究

传统膨胀型阻燃剂(IFR)中的炭源为小分子醇类化合物,因此阻燃剂具有易吸湿、易迁移、与聚合物基体不相容等缺点。为了改进这些缺点,合成了一种新型的含有机硅的三嗪类大分子成炭剂(CA),将其与多聚磷酸铵(APP)复配成膨胀型阻燃剂用于聚丙烯(PP)阻燃。通过红外光谱、热失重分析、极限氧指数、垂直燃烧、锥形量热仪、扫描电子显微镜等手段研究了CA的热性能、燃烧性能、成炭机理以及APP与CA的配比对PP阻燃性能、热稳定性能的影响。结果表明,所合成的CA显示出较好的热稳定性和优异的成炭性,残炭率为25.6%(600℃)。另外,APP与CA在阻燃PP中具有协同阻燃作用;IFR的加入能大幅度降低PP阻燃体系的热释放速率和总释放热,有效地降低烟释放量及烟释放速率,提高PP的阻燃性能。     

PP复合材料的制备及其阻燃性能研究

将碳微球(CMSs)及聚磷酸铵(APP)添加至聚丙烯(PP)中,制备了PP复合材料。采用极限氧指数(LOI)、热重分析仪(TGA)、锥形量热仪(CONE)及电子万能试验机(EUT)等表征手段对PP复合材料的阻燃性能、热稳定性能以及力学性能进行了测试分析,考察了APP与CMSs的质量比以及添加量对PP阻燃体系性能的影响。结果表明:在APP与CMSs质量比为4:1,总添加量为30%时,PP/CMSs/APP复合材料的LOI为28.7%,较纯PP提高了59.4%;火灾性能指数(FPI)值较纯PP提高了约5倍;热释放速率峰值(PHRR)、总热释放量(THR)、平均热释放速率(MHRR)和平均有效燃烧热(MEHC)分别较纯PP降低了31.11%、14.2%、24.5%和32.1%;火灾蔓延指数(FGI)值较纯PP降低了55.3%,且复合材料的热稳定性有所提高,成炭能力显著提升,PP的阻燃性能得到明显改善。     

ATH和APP对聚乳酸/竹粉复合材料阻燃抑烟性能的影响

利用竹粉和聚乳酸为原料复合制备聚乳酸/竹粉复合材料,分别采用氢氧化铝(ATH)和聚磷酸铵(APP)阻燃剂对聚乳酸/竹粉复合材料进行阻燃抑烟处理并对阻燃处理后的复合材料进行性能测试。结果表明,两种阻燃剂的加入均使复合材料高温下的成炭率提高了约2倍,分别达到了24.7%和25.6%;ATH和APP的加入均有效提高了聚乳酸/竹粉复合材料的阻燃性能;其中,APP对复合材料燃烧过程中热量释放的抑制明显,其热释放速率在燃烧100s以后下降了近2倍,约为150kW/m2,但生烟量大;而ATH对复合材料的抑热效果不及APP,但抑烟效果显著,平均烟释放速率只有约0.02m2/s。     

聚磷酸铵阻燃体系对HIPS/OMMT阻燃研究

将钠基蒙脱土(Na~ -MMT)有机化改性,制成有机蒙脱土(OMMT),采用熔融插层法分别制备HIPS/OMMT复合材料和聚磷酸铵(APP)体系阻燃的HIPS/OMMT复合材料。结果表明,HIPS/OMMT复合材料具有一定的阻燃性能,但阻燃性能的提高比较有限;与仅添加OMMT时相比,APP体系阻燃的HIPS/OMMT复合材料的阻燃性和抑烟性均得到进一步提高,以APP、季戊四醇(PER)和硼酸锌(ZB)为膨胀型阻燃剂对HIPS/OMMT复合材料阻燃性和抑烟性的提高更为显著。力学性能测试结果表明,APP体系的加入对复合材料的拉伸强度和冲击强度都有负面影响。     

CaCO_3和EG与APP/PER/ZB体系协同阻燃交联EVAC基复合材料的研究

采用膨胀型阻燃剂[聚磷酸铵/季戊四醇/硼酸锌(APP/PER/ZB)体系]对交联乙烯–乙酸乙烯酯塑料(EVAC)进行阻燃改性,然后分别用CaCO3和可膨胀石墨(EG)进一步优化EVAC/APP/PER/ZB复合材料。采用极限氧指数(LOI)仪、锥形量热仪和扫描电子显微镜(SEM)研究了复合材料的阻燃性能及阻燃机理,并测试了复合材料的力学性能和介电性能。结果表明,随着APP/PER/ZB体系含量的增加,复合材料的LOI逐渐升高,热释放速率峰值、平均热释放速率、热释放总量逐渐降低;拉伸强度、断裂伸长率和介电常数逐渐下降,但介电损耗变化极小。CaCO3和EG优化的复合材料阻燃性能和拉伸性能均比未优化的有所提高,起到一定的协同阻燃效果,其中EG的优化效果最好;CaCO3对复合材料介电性能的影响与APP/PER/ZB体系大致相同,但高频下EG的影响较为显著,均明显降低了复合材料的介电常数和介电损耗峰值。     

阻燃处理对竹粉增强聚乳酸复合材料阻燃抑烟性能影响

分别采用氢氧化铝(ATH)、聚磷酸铵(APP)及ATH+ APP复合阻燃剂对竹粉增强聚乳酸复合材料进行阻燃抑烟处理,并对处理后的复合材料性能进行测试与表征.结果表明,两种阻燃剂均显著增加了复合材料的成炭率,ATH+ APP产生了协同作用,使复合材料成炭率提高了近4倍,达到了45.3％;复合材料经阻燃处理后其阻燃性能均得到了不同程度的提升.其中,APP对复合材料燃烧过程中热量释放的抑制作用最明显,ATH对复合材料表现出了较强的抑烟效果,而ATH +APP复合阻燃剂产生的协同作用使复合材料具有阻燃和抑烟的双重特性.     

海泡石与APP对PVC/竹粉复合材料的阻燃抑烟机理

将海泡石(SEP)和聚磷酸铵(APP)同时加到聚氯乙烯(PVC)/竹粉复合材料中,考察SEP和APP对复合材料的协效阻燃抑烟作用及力学性能的影响。结果表明,在锥形量热实验中,热释放速率峰值相对减少42.8%,平均热释放速率和总热释放量相对减少29.5%和25.7%,总烟释放量相对降低了12.2%,一氧化碳平均产率相对降低了42.0%;扫描电子显微镜分析发现,APP具有催化成炭并形成膨胀泡沫炭层的作用,而SEP具有吸附聚集诱导成炭的作用;APP的阻燃机理主要属于气相阻燃机理,SEP的阻燃机理主要属于凝聚相阻燃机理;弯曲性能测试结果表明,SEP与APP对PVC/竹粉复合材料具有协同颗粒增强作用;拉伸性能测试结果表明,SEP对PVC/竹粉复合材料的塑性变形能力的损害比APP小。因此,SEP与APP联用能够对PVC/竹粉复合材料进行有效的阻燃抑烟,同时也能增强复合材料的力学性能。     

An efficient approach to improving fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene composites via incorporating organo‐modified sepiolite

In this work, an efficient approach to improving the fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene (PP) composites is developed via incorporating functionalized sepiolite (organo‐modified sepiolite [ONSep]). The PP composites with different amounts of intumescent flame retardants and ONSep were prepared by melt compounding. The morphology, thermal behavior, fire retardancy, smoke suppression, and mechanical property of flame‐retardant PP composites were studied. The results indicate an appropriate amount of ONSep in the flame‐retardant PP composites can increase thermal degradation temperature and char formation as well as a reduction of the peak heat release rate and total heat release; moreover, the addition of ONSep significantly decreases the CO production, total smoke production, smoke production rate, and smoke temperature. Simultaneously, the impact strength of intumescent flame‐retardant PP composite is also maintained by introducing an appropriate amount of ONSep as compared with that without ONSep.     

新型成炭剂对PE-LD阻燃性能的影响

以多聚磷酸铵（APP）与新型成炭剂（CNCH-DA）复配成新型膨胀型阻燃剂（IFR）,采用氧指数测定仪、垂直燃烧测定仪、微型量热仪、热重分析仪和扫描电子显微镜研究了CNCH-DA 对低密度聚乙烯（PE-LD）/IFR复合材料阻燃性能的影响。结果表明,当APP与CNCH-DA以质量比5:1复配时,PE-LD/IFR复合材料的极限氧指数达到27.5 %,且达到UL 94 V-0级;当APP与CNCH-DA复配后,PE-LD的燃烧性能下降;APP与CNCH-DA复配后,PE-LD/IFR复合材料的热降解有所推迟;PE-LD/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PE-LD/CNCH-DA则形成蓬松而不致密的微球,阻隔能力差。     

Thermal degradation and combustion behavior of intumescent flame‐retardant polypropylene with novel phosphorus‐based flame retardants

The objective of this study was to develop an environmentally friendly fire‐retardant polypropylene (PP) with significantly improved fire‐retardancy performance with a novel flame‐retardant (FR) system. The system was composed of ammonium polyphosphate (APP), melamine (MEL), and novel phosphorus‐based FRs. Because of the synergistic FR effects among the three FRs, the FR PP composites achieved a V‐0 classification, and the limiting oxygen index reached as high as 36.5%. In the cone calorimeter test, both the peak heat‐release rate (pHRR) and total heat release (THR) of the FR PP composites were remarkably reduced by the incorporation of the novel FR system. The FR mechanism of the MEL–APP–FR–PP composites was investigated through thermogravimetric analysis and char residue characterization, and the results reveal that the addition of MEL–APP–FRs promoted the formation of stable intumescent char layers. This led to the reduction of pHRR and THR and resulted in the improvement of the fire retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45962.     

Enhanced flame retardancy,smoke suppression,and acid resistance of polypropylene/magnesium hydroxide composite by expandable graphite and microencapsulated red phosphorus

Low flame retardant efficiency and poor acid resistance of filled polymer composites are two main drawbacks of magnesium hydroxide (MH) as a flame retardant (FR). To solve these problems, expandable graphite (EG) and microencapsulated red phosphorus (MRP) were introduced into polypropylene/magnesium hydroxide (PP/MH) composite by melt compounding. The obtained PP/MH/EG/MRP quadruple composite was studied regarding its fire behavior as well as acid resistance. Obvious flame retardant synergism among MH, EG, and MRP is found in PP, which diminishes the loading of FR from 63.0 to 37.5 wt% to obtain V-0 rating in UL-94 test and low smoke release. Compact intumescent char with high thermo-oxidative stability was generated on composite surface, which plays a vital role in flame retardancy. The removal of MH by acid erosion on PP/MH/EG/MRP composite surface does not affect production of intumescent char and fire behavior of this composite. The composite displays good fire retardancy, smoke inhibition, and acid resistivity concurrently. This article renders an easy and cheap route to overcome the main faults of MH.     

Synergistic effects of hydroxy silicone oil on intumescent flame retardant polypropylene system

The effects of hydroxy silicone oil as a synergistic agent on the flame retardancy of intumescent flame retardant polypropylene composites (IFR-PP) were studied, and the IFR system mainly consisted of the ammonium polyphosphate (APP), melamine (MEL) and pentaerythritol (PER). The UL 94 rating, thermogravimetric analysis (TGA), cone calorimeter (CONE) and digital photograph were used to evaluate the synergistic effects of hydroxy silicone oil (HSO). It has been found that the PP composite containing only APP, MEL and PER does not show good flame retardancy at 30% additive level. The cone calorimeter results show that the heat release rate, mass loss rate, mass, total heat release, carbon monoxide and carbon dioxide of PP/APP/MEL/PER/HSO composites decrease in comparison with the PP/APP/MEL/PER composite. The digital photographs demonstrated that HSO could promote to form the homogenous and compact intumescent char layer. Thus, a suitable amount of HSO plays a synergistic effect in the flame retardancy.     

Effect of Phosphorus-Based Flame Retardants and PA6 on the Flame Retardancy and Thermal Degradation of Polypropylene

The investigation mainly focuses on the effect of polyamide 6 (PA6) and phosphorus based flame retardants (FRs) on improving the flame retardancy of polypropylene (PP). The flame retardant properties have been studied by limiting oxygen index, vertical burning test tests and cone calorimeter testing. The results demonstrate that PA6 and FRs can greatly improve the flame-retardant and thermal properties of PP. It’s found that the addition of PA6/APP/FRs can promote the formation of stable intumescent char layers. Those indicate that the flame retardancy of PA6/APP/FRs/PP composites is improved by the condensed-phase action of PA6/APP/FRs.     

Influence of the pentaerythritol phosphate melamine salt content on the combustion and thermal decomposition process of intumescent flame‐retardant ethylene–vinyl acetate copolymer composites

Pentaerythritol phosphate melamine salt (PPMS) as a single‐molecule intumescent fire retardant was synthesized and characterized. The influence of the PPMS content on the combustion and thermal decomposition processes of intumescent‐flame‐retardant (IFR) ethylene–vinyl acetate copolymer (EVA) composites was studied by limiting oxygen index (LOI) measurement, UL 94 rating testing, cone calorimetry, thermogravimetric analysis, and scanning electron microscopy. The LOI and UL 94 rating results illustrate that PPMS used in EVA improved the flame retardancy of the EVA composites. The cone calorimetry test results show that the addition of PPMS significantly decreased the heat‐release rate, total heat release, and smoke‐production rate and enhanced the residual char fire performance of the EVA composites. The IFR–EVA3 composite showed the lowest heat‐release and smoke‐production rates and the highest char residue; this means that the IFR–EVA3 composite had the best flame retardancy. The thermogravimetry results show that the IFR–EVA composites had more residual char than pure EVA; the char residue yield increased with increasing PPMS content. The analysis results for the char residue structures also illustrated that the addition of PPMS into the EVA resin helped to enhance the fire properties of the char layer and improve the flame retardancy of the EVA composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42148.     

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     

四溴双酚-A阻燃体系在HIPS／OMMT复合材料中的阻燃性研究

采用熔融插层法分别制备高抗冲苯乙烯／有机蒙脱土（HIPS／OMMT）复合材料和四溴双酚-A／三氧化二锑（TBBPA—Sb2O3）体系阻燃的HIPS／OMMT复合材料,透射电镜研究表明,有机蒙脱土均匀地分散于HIPS基体当中,形成了插层复合结构,锥形量热仪和氧指数仪研究表明：与纯的HIPS相比,HIPS／OMMT复合材料的阻燃性和抑烟性有所提高,但阻燃性的提高幅度较有限：与仅添加OMMT时的HIPS／OMMT复合材料相比,添加相同量OMMT时TBBPA—Sb2O3体系阻燃的HIPS／OMMT复合材料的热释放速率（HRR）和热释放速率峰值（PHRR）均有所降低,氧指数有所增加,且随TBBPA—Sb2O3阻燃剂添加量的增加阻燃性能的提高越明显,但TBBPA—Sb2O3的加入会导致聚合物燃烧过程生烟速率和生烟量的显著增加．因此此类阻燃剂的加入量不宜过高。     

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。