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.     

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.     

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.     

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。     

Flammability and mechanical properties of wood flour‐filled polypropylene composites

Polypropylene (PP) composites filled with wood flour (WF) were prepared with a twin‐screw extruder and an injection‐molding machine. Three types of ecologically friendly flame retardants (FRs) based on ammonium polyphosphate were used to improve the FR properties of the composites. The flame retardancy of the PP/WF composites was characterized with thermogravimetric analysis (TGA), vertical burn testing (UL94‐V), and limiting oxygen index (LOI) measurements. The TGA data showed that all three types of FRs could enhance the thermal stability of the PP/WF/FR systems at high temperatures and effectively increase the char residue formation. The FRs could effectively reduce the flammability of the PP/WF/FR composites by achieving V‐0 UL94‐V classification. The increased LOI also showed that the flammability of the PP/WF/FR composites was reduced with the addition of FRs. The mechanical property study revealed that, with the incorporation of FRs, the tensile strength and flexural strength were decreased, but the tensile and flexural moduli were increased in all cases. The presence of maleic anhydride grafted polypropylene (MAPP) resulted in an improvement of the filler–matrix bonding between the WF/intumescent FR and PP, and this consequently enhanced the overall mechanical properties of the composites. Morphological studies carried out with scanning electron microscopy revealed clear evidence that the adhesion at the interfacial region was enhanced with the addition of MAPP to the PP/WF/FR composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synergistic effects of polyethylene glycol and ammonium polyphosphate on intumescent flame‐retardant polypropylene

A novel flame‐retardant system of isotactic polypropylene (iPP) is prepared using polyethylene glycol (PEG) and ammonium polyphosphate (APP). The flammability of iPP/PEG/APP composites containing 20 wt% APP improves with the increase of PEG concentration in the range of 3–15 wt%. The limit oxygen index (LOI) of iPP/PEG/APP composites reaches up to 30% with 15 wt% PEG concentration in the composites. At the same time, the mechanical properties of iPP/PEG/APP composites demonstrate that PEG can enhance toughness of iPP/APP composites. The results of cone calorimetry prove the synergistic effects of PEG and APP on intumescent flame‐retardant iPP, and those of the thermogravimetric analysis(TGA) reveal that iPP/PEG/APP samples decompose faster than iPP/APP composites. Investigated by scanning electronic microscopy (SEM), the morphology and structures of residues generated during LOI tests confirm the formation of effective char layer, and that the improvement of the flame retardancy and the impact strength of the composites are thanks to the presence of PEG. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

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。     

聚磷酸铵基复合膨胀型阻燃剂的制备及其对聚甲醛的阻燃作用

针对聚甲醛(POM)阻燃的难点,在传统简单共混膨胀阻燃体系聚磷酸铵(APP)/三聚氰胺(ME)/季戊四醇(PER)的基础上,采用高温热反应处理技术将APP(酸源)、ME(气源)和PER(炭源)集成在一个大分子膨胀阻燃体系(RMAPP)中,并将所得大分子一体化产物RMAPP阻燃POM,解决了简单共混膨胀体系中各组分混合不均匀、难分散以及与基体树脂相容性差的难题。研究结果表明:高温热反应产物RMAPP比传统的未经热处理简单共混阻燃体系具有较好的阻燃效果,当阻燃剂RMAPP的添加量为45%时,在垂直燃烧测试实验中,其3.2mm厚试样可达到UL94V—1级别。     

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.     

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。     

聚苯乙烯的无卤阻燃研究

采用正交设计法分析了聚磷酸胺(APP)、季戊四醇(PER)、三聚氰胺(MEL)作为一种混合体系对聚苯乙烯(PS)的阻燃作用。实验表明,酸源、炭源、气源组成的膨胀型阻燃剂有良好的阻燃效果,PER对PS阻燃性能的影响显著。各个因子对材料力学性能和加工性能的影响不同:PER用量是影响拉伸强度、弯曲强度和流动性的主要因素;APP用量是影响无缺口冲击强度的主要因素;MEL用量是影响缺口冲击强度的主要因素。当APP、PER、MEL 的用量分别为30,20,5摩尔份时,阻燃PS获得较好的综合性能。     

Effect of flame retardants on flame propagation and flammability properties of oil palm fibre reinforced polyester composite

Oil palm fibre reinforced polyester composite (OPFC) was modified with aluminium tri‐hydroxide (ATH), ammonium phosphate and gum arabic (APP‐GAP) intumescent compound, and their hybrid (ATH/APP‐GAP) flame retardants (FRs) at 0%, 12%, and 18% proportion using hand lay‐up compression moulding technique. The effect of the FR loadings on impact strength, flammability properties, and flame propagation were examined using an impact tester, cone calorimeter apparatus (CCA), and flame spread apparatus (FSA), respectively. The results shows that the FRs added to OPFC enhanced the impact strength of the composite showing greater absorbed energy for 0%OPFC and 12%APP‐GAP specimens. CCA results reveal that 18%ATH/APP‐GAP hybrid specimen enhanced the flammability properties better at 50 kW m^?2, while at 25 kW m^?2, the performance of the specimens varied in properties with content and type of FR loadings. FSA results reveal that with 18%ATH/APP‐GAP hybrid specimen, weakest flame energy for propagation and less flame travel distance could be achieved and suggests a better FR. This paper concludes that the hybrid FR specimen can be of great benefit to the building and transportation industries.     

Investigation of novel intumescent flame retardant low-density polyethylene based on SiO2@MAPP and double pentaerythritol

To improve the flame-retardant property of low-density polyethylene (LDPE) composites, a novel intumescent flame retardant (IFR) consisting of ammonium polyphosphate (APP) covered by silicon dioxide and 3-(Methylacryloxyl) propyltrimethoxy silane (KH-570) (SiO₂@MAPP) and double pentaerythritol (DPER) was synthesized. Various methods were applied to structural characterization and property investigations of different samples. The results indicated that the solubility of APP decreased after coating with silicon dioxide (SiO₂) and KH-570. The flame retardancy of LDPE composites was improved with addition of IFR containing SiO₂@MAPP/DPER. With 30 wt% addition of IFR containing SiO₂@MAPP /DPER, the limiting oxygen index reached 26.8% and the tensile strength was 3.30 MPa. The tensile strength was 7.14% higher than that of 30 wt% IFR without SiO₂@MAPP. The smoke density test showed that the flue gas emission was obviously improved. The addition of SiO₂@MAPP effectively increased the residual carbon content of composites and thermal stability of the composites.     

Synthesis of a novel intumescent flame retardant and its flame retardancy in polypropylene

Microencapsulated ammonium polyphosphate (GMFAPP) is prepared by in situ polymerization method with a shell of poly(ethylene glycol) modified melamine-formaldehyde resin. Due to the presence of shell, GMFAPP shows less size, higher water resistance and flame retardancy in polypropylene (PP) compared with ammonium polyphosphate (APP). The flame retardant action of GMFAPP and APP in PP are studied using LOI, UL-94 and cone calorimeter, and their thermal stability is evaluated by thermogravimetric apparatus. The limiting oxygen index (LOI) value of the PP/GMFAPP at the same loading is higher than the value of PP/APP. UL-94 ratings of PP/GMFAPP can reach V-0 at 30 wt% loading. The water resistant properties of the PP composites are studied, and the results of the composites containing with APP and GMFAPP are compared. The cone results put forward that GMFAPP is an effective flame retardant in PP compared with APP. Moreover, the thermal oxidative behavior of GMFAPP is evaluated by dynamic FTIR to study its flame retardant mechanism in PP.     

Catalytically synergistic effects of novel LaMnO3 composite metal oxide in intumescent flame‐retardant polypropylene system

The newly prepared LaMnO₃ was introduced as a novel perovskite composite metal oxide catalyst for the first time to improve the flame retardancy of flame‐retarded (FR) polypropylene with intumescent flame‐retardant (IFR) system consisting of ammonium polyphosphate (APP), pentaerythritol (PER), and melamine (MA). The synergistic effects of LaMnO₃ catalyst on the performance of IFR PP composites as well as the corresponding catalytically synergistic FR mechanism were investigated. The experimental results show that the incorporated LaMnO₃ catalyst plays an excellently catalytic and synergistic part in improvement of the flame retardancy of FR PP system. Compared with FR system without LaMnO₃, the incorporation of only 0.5 wt% LaMnO₃ into PP FR system could obviously improve the UL‐94 level from failure to V‐0 rating and decrease the micro‐scale calorimetry parameters peak heat release rate and heat release capacity. The remarkable improvement in flammability can be ascribed to the catalytic carbonization effect of LaMnO₃ on the intumescent flame retardant PP system. The incorporation of appropriate amount of LaMnO₃, on one hand, could improve the thermal stability of FR PP material, and on the other hand, could also act as nuclei to induce formation of the continuous, compact and smooth condensed phase intumescent charred layer with radialized spherulite‐like structure. As a result, the char yield and also the quality of the formed condensed phase charred layers are correspondingly enhanced remarkably, which is beneficial to improvement of the FR properties. POLYM. COMPOS., 35:2390–2400, 2014. © 2014 Society of Plastics Engineers     

Polystyrene-based composites and nanocomposites with reduced brominated-flame retardant

Polystyrene was melt blended with a halogen-based flame retardant (FR), hexabromocyclododecane, and a non-halogenated FR, triphenyl phosphate (TPP), in a twin-screw extruder. An organically modified montmorillonite (Cloisite 15A) was used to prepare FR polystyrene nanocomposites. The flammability properties and thermal stability of FR polystyrene composites and nanocomposites were investigated. X-ray diffraction analysis showed that the exfoliation structure of organically modified montmorillonite in polystyrene nanocomposites may be achieved by melt-compounding in a twin-screw extruder. Furthermore, a good dispersion of FRs and nanoparticles of organically modified montmorillonite was observed by energy dispersive X-ray analysis. Thermogravimetric analysis demonstrated that the thermal stability of FR nanocomposites enhanced in the presence of clay nanoparticles and antioxidant. The aim of this study was to reduce the FR level, especially in the brominated FRs. The good results obtained by the limiting oxygen index test showed high-performance flammability properties in the composites containing hexabromocyclododecane and TPP, resulted from the synergy effects between these two FRs. However, in spite of producing high thermal performance polystyrene nanocomposites and dispersing clay nanoparticles efficiently into the polystyrene matrix, the flame retardancy properties were deteriorated in the presence of clay nanoparticles. Therefore, the organically modified clay (Cloisite 15A) was not a good synergic compound to improve the flame retardancy of polystyrene nanocomposites.     

Microencapsulated ammonium polyphosphate by polyurethane with segment of dipentaerythritol and its application in flame retardant polypropylene

Dipentaerythritol (DPER), 4, 40-diphenylmethanediisocyanate (MDI) and melamine (MEL) are used as raw materials to microencapsulate ammonium polyphosphate (MAPP) in situ polymerization. The MAPP is characterized by Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and thermal gravimetric analysis (TGA). The results show that the coating operation can effectively improve water resistance of ammonium polyphosphate (APP), and MAPP has higher residual rate than that of APP after combustion. The flame retardant action of MAPP and APP in polypropylene (PP) is investigated by the limited oxygen index (LOI), vertical burning test (UL-94), TGA, SEM, and cone calorimeter test (CCT). The LOI value of the PP/MAPP composite at the same loading is higher than that of PP/APP composite. UL 94 ratings of PP/MAPP composites are raised to V-0 at 20 wt% loading. The results of CCT also show that MAPP is more efficient than APP. The morphological structures observed by digital photos and SEM demonstrated that MAPP could be promoted to form the continuous and compact intumescent char layer. The flame retardant mechanism of PP/MAPP is also discussed.     

Influence of ammonium polyphosphate on the flame retardancy and mechanical properties of ramie fiber‐reinforced poly(lactic acid) biocomposites

Fully degradable natural fiber/degradable polymer composites have received much research attention and have various applications such as in automotive components. But flammability limits their application; it is important to improve the flame retardancy of fully degradable composites with environmentally friendly flame retardants. Flame‐retarded ramie fiber‐reinforced poly(lactic acid) (PLA) composites were prepared using three processes: (1) PLA was blended with ammonium polyphosphate (APP), and then the resulting flame‐retarded PLA was combined with ramie fibers; (2) ramie fibers underwent flame‐retardant treatment with APP, which were then compounded with PLA; and (3) PLA and ramie, both of which had been flame‐retarded using APP, were blended together. The APP in the composites is shown to be very effective in improving flame retardancy according UL94 test and limiting oxygen index measurements. Thermogravimetric analysis shows that the improved flame retardancy is due to increased char residue at high temperature. The loading of APP disturbs the compatibility between PLA and fibers, which can be directly observed using scanning electron microscopy. Furthermore it has an influence on the dynamic mechanical properties and mechanical properties according dynamic mechanical analysis and mechanical measurements. The results show that composites produced using the third process not only have the best flame retardancy but also comparatively better mechanical properties. Copyright © 2009 Society of Chemical Industry     

Synergistic effects of ammonium polyphosphate/melamine intumescent system with macromolecular char former in flame-retarding polyoxymethylene

The improvement of the flame retardancy of polyoxymethylene (POM) is a world-wide difficult problem due to its zippered decomposition property. This paper reported the preparation of the flame-retarding (FR) POM with the synergistic combination of ammonium polyphosphate (APP)/melamine (ME) intumescent flame retardant system and macromolecular char former (MC). The UL94 testing, mechanical properties testing, thermogravimetric analysis (TGA), cone calorimetry and scanning electron microscopy (SEM) were used to investigate the corresponding structure, performance and synergistic flame retardant mechanism. The experimental results showed that, in the used macromolecular char formers (novolac, PA6 and TPU), the combination of novolac with APP/ME intumescent system has the best synergism in flame-retarding POM, greatly enhancing the quality of the formed condensed charred layer and hence the corresponding flame retardancy. The obtained FR POM composite could achieve flame retardancy of UL94 3.2 mm V-0 level and remarkably decreased heat release rate relative to pure POM. The synergistic effect of novolac was shown to be the char formed cross-linking reaction of it with APP. Due to the thermodynamic compatibility of novolac and POM, the prepared FR POM composite also has fairly good mechanical performance, having tensile strength of 49.1 MPa and Izod notched impact strength of 2.60 kJ/m².     

Preparation of thermally stable and flame-retardant sugarcane bagasse-ammonium dihydrogen phosphate/epoxy composites and their performance

Epoxy resin was often applied in fiber-reinforced composite materials, adhesives, and encapsulation materials. However, epoxy was easily flammable and limited its usage in certain applications. The study recycled and reused agricultural waste sugarcane bagasse to prepare a halogen-free bio-based intumescent flame retardant and then mixed with epoxy resin to prepare a composite containing polymer with improved thermal properties and flame retardancy of the materials. The work followed the concept of circular economy and sustainability. Bagasse-ammonium dihydrogen phosphate (ADP) flame retardant was added to an epoxy resin to prepare epoxy/bagasse-ADP composites, an effective flame-retarding composite material through hydrothermal method. Adding bagasse-ADP increased the thermal stability and flame retardancy of the composite materials compared with that of pure epoxy. For the material with 30 wt% added bagasse-ADP, the char yield was 32.3 wt%, which was 18.2 wt% higher than that of pure epoxy (14.1 wt%) through thermogravimetric analysis. In addition, the limiting oxygen index increased from 21% to 30%, and the UL-94 classification improved from “Fail” to “V-0.” This performance was attributed to the nitrogen, phosphorus, and silicon content of the flame retardant.