Microencapsulated ammonium polyphosphate with urea–melamine–formaldehyde shell: preparation,characterization, and its flame retardance in polypropylene

Microencapsulated ammonium polyphosphate (MCU‐APP) with urea–melamine–formaldehyde (UMF) resin is prepared by in situ polymerization, and is characterized by FTIR and XPS. The microencapsulation of APP with the UMF resin leads to a decrease in the particle's water solubility. The flame retardant actions of MCU‐APP and APP in PP are studied using limiting oxygen index (LOI) and UL‐94 test, and their thermal stability is evaluated by thermogravimetric analysis. It is found that the LOI value of the PP/MCU‐APP composite is higher than the value of the PP/APP composite. In comparison with the PP/MCU‐APP composites, the LOI values of the PP/MCU‐APP/DPER ternary composites at the same additive loading increase, and UL‐94 ratings of most ternary composites are raised to V‐0. The water‐resistant properties of the PP composites containing APP and MCU‐APP are studied. Moreover, the combustion behavior of the PP composites is investigated by the cone calorimeter. Copyright © 2008 John Wiley & Sons, Ltd.     

金属氧化物对聚丙烯膨胀阻燃体系阻燃性能的影响

将Bi2O3、Sb2O3、SnO2添加到聚磷酸铵(APP)和双季戊四醇(DPER)膨胀型阻燃聚丙烯(PP)体系中,采用氧指数(OI)、热分析(TGA)、热红联用(TG-FTIR)和扫描电镜(SEM),考察它们对膨胀阻燃体系的催化协效作用,探讨其作用机理.结果表明,3种金属氧化物在适量的添加下都可以提高体系的氧指数.TG结果表明,Bi2O3的加入可以提高膨胀炭层在高温时的热稳定性,增加高温时残余物的量;TG-FTIR结果显示添加Bi2O3后,膨胀阻燃剂在热分解过程中,气体的释放过程发生了改变.膨胀炭层的SEM图表明,Bi2O3可以改善膨胀炭层的形貌,提高炭层的隔热隔质性能.0.1 wt%的Bi2O3和1 wt%的纳米黏土复配用于膨胀阻燃体系中,可以在阻燃剂添加20份下,样品氧指数达到28.3;在阻燃剂添加25时,样品(3.2 mm)通过UL-94 V-0级.0.1 wt%的Bi2O3和1 wt%纳黏粘土的添加,还可以提高体系的力学性能.     

Synergistic effects of cerium phosphate and intumescent flame retardant on EPDM/PP composites

An intumescent flame retardant system composed of ammonium polyphosphate (APP) and pentaerythritol (PER) was used for flame retarding ethylene–propylene–diene‐modified elastomer (EPDM)/polypropylene (PP) blends. Cerium phosphate (CeP) was synthesized and the effect on flame retardancy and thermal stability of EPDM/PP composites based on intumescent flame retardant (IFR) were studied by limiting oxygen index (LOI), UL‐94, and thermogravimetic analysis (TGA), respectively. Scanning electron microscopy (SEM) and Fourier transform infrared spectrometry (FTIR) were used to analyze the morphological structure and the component of the residue chars formed from the EPDM/PP composites, and the mechanical properties of the materials were also studied. The addition of CeP to the EPDM/PP/APP/PER composites gives better flame retardancy than that of EPDM/PP/APP/PER composites. TGA and RT‐FTIR studies indicated that an interaction occurs among APP, PER, and EPDM/PP. The incorporation of CeP improved the mechanical properties of the materials. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation of microencapsulated ammonium polyphosphate with montmorillonite‐melamine formaldehyde resin and its flame retardancy in EVM

Microencapsulated ammonium polyphosphate (MMT‐MF‐APP) with a montmorillonite‐melamine formaldehyde resin coating layer was successfully prepared by in situ polymerization. The product was characterized by Fourier‐transform infrared, X‐ray photoelectron spectroscopy, and scanning electron microscopy. Water absorption analysis showed that the microencapsulation of APP with the MMT‐MF resin leads to a decrease in the particle's water solubility. The microcapsules also exhibited better mechanical properties and higher flame retardancy in the ethylene–vinyl acetate copolymer with high vinyl acetate content (EVM) rubber compared with the common ammonium polyphosphate. Moreover, thermogravimetric analysis results showed that the EVM composites with MMT‐MF‐APP and dipentaerythritol (DPER) as flame retardants possess higher thermal stability than those with common APP and DPER as flame retardants. Copyright © 2011 John Wiley & Sons, Ltd.     

Microencapsulation of ammonium polyphosphate with PVA–melamine–formaldehyde resin and its flame retardance in polypropylene

With a shell of PVA–melamine–formaldehyde resin, microencapsulated ammonium polyphosphate (VMFAPP) is prepared by in situ polymerization and characterized by FTIR and XPS. Microencapsulation gives VMFAPP better water resistance and flame retardance compared with APP in PP. Thermal stability and fire resistance behavior have been analyzed and compared. The LOI value of the PP/VMFAPP composite is higher than that of the PP/APP composite. The UL 94 ratings of most of the PP/VMFAPP composites are V‐0, whereas PP/APP gives no rating at the 30% additive level. The water resistant properties of the PP composites are studied. Results of the cone calorimeter experiment show that VMFAPP is an effective flame retardant in PP compared with APP. The thermal degradation behaviors of APP and VMFAPP have been studied using TG and dynamic FTIR. Copyright © 2008 John Wiley & Sons, Ltd.     

Preparation and Characterization of Core/Shell-like Intumescent Flame Retardant and its Application in Polypropylene

With a shell of starch-melamine-formaldehyde (SMF) resin, core/shell-like ammonium polyphosphate (SMFAPP) is prepared by in situ polymerization, and is characterized by SEM, FTIR and XPS. The shell leads SMFAPP a high water resistance and flame retardance compared with APP in polypropylene (PP). The flame retardant action of SMFAPP and APP in PP are studied using LOI, UL 94 test and cone calorimeter, and their thermal stability is evaluated by TG. The flame retardancy and water resistance of the PP/SMFAPP composite at the same loading is better than that of the PP/APP composite. UL 94 ratings of PP/SMFAPP can reach V-0 at 30 wt% loading. The flame retardant mechanism of SMFAPP was studied by dynamic FTIR, TG and cone calorimeter, etc.     

Intumescent flame retardation and silane crosslinking of PP/EPDM elastomer

This study deals with the silane crosslinking and intumescent flame retardation of polypropylene/ethylene‐propylene‐diene copolymer (PP/EPDM) elastomers. The effect of silane crosslinking on the flame retardancy of the PP/EPDM composites containing melamine phosphate (MP) and dipentaerythritol (DPER) was studied by limiting oxygen index, UL 94 and cone calorimetry tests. The chemical composition of the silane crosslinked and flame retarded PP/EPDM composites treated at different temperatures was studied by X‐ray photoelectron spectroscopy and real time Fourier transform infrared (FTIR) spectrometry. Thermal decomposition and crystallization behavior of the PP/EPDM composites were investigated using thermogravimetric analysis and differential scanning calorimetry, respectively. Moreover, the mechanical properties of the composites were also studied. It is found that the flame retardancy, mechanical properties, and thermal decomposition behavior of the composites are influenced by silane grafting and crosslinking. Copyright © 2008 John Wiley & Sons, Ltd.     

Effects of metal oxides on intumescent flame‐retardant polypropylene

Variable amounts of transition metal oxides (MO), such as MnO₂, ZnO, Ni₂O₃, etc., were incorporated into blends of polypropylene (PP)/ammonium polyphosphate (APP)/dipentaerythritol (DPER) with the aim of studying and comparing their effects with main‐group MO on intumescent flame retardance (IFR). The PP/IFR/MO composites were prepared using a twin‐screw extruder, and the IFR behavior was evaluated through oxygen index and vertical burning tests. The progressive enhancement of flame retardancy has proved to be strongly associated with the interaction between APP and MO. With the aid of thermogravimetry (TG) analysis, Fourier transform infrared (FTIR) spectra and scanning electron microscopy, Ni₂O₃ has been shown to be the most effective among the aforementioned three MO. The flame‐retardant mechanism of the IFR system is also discussed in terms of catalytic charring, which relates to complex formation through the d‐orbitals of the transition metal elements. It is considered that the melt viscosity of a PP/APP/DPER blend containing Ni₂O₃ corresponds well to the gas release with increasing temperature. Copyright © 2009 John Wiley & Sons, Ltd.     

The investigation of intumescent flame-retarded polypropylene using poly(hexamethylene terephthalamide) as carbonization agent

A novel intumescent flame retardant, containing ammonium polyphosphate (APP), and poly(hexamethylene terephthalamide) (PA6T), was prepared for flame retarding polypropylene (PP). The flame retardation of the PP composites was characterized by limiting oxygen index (LOI). The thermal degradation of the composites was investigated by means of thermogravimetric analysis (TG) and TG coupled with Fourier transform infrared spectroscopy (TG-FTIR). The morphology of the char obtained after combustion of the composites was studied by scanning electron microscopy. It has been found the intumescent flame retardant showed good flame retardancy, with the LOI value of the PA6T/APP/PP (5/25/70) system increasing from 17.5 to 32. Meanwhile, the TG and TG-FTIR work indicated that PA6T could be effective as a carbonization agent and there was a synergistic reaction between PA6T and APP, which effectively promoted the char formation of the PP composites. Moreover, it was revealed that uniform and compact intumescent char layer was formed after combustion of the intumescent flame retarded PP composites.     

Water resistance,thermal stability,and flame retardation of polypropylene composites containing a novel ammonium polyphosphate microencapsulated by UV‐curable epoxy acrylate resin

In this work, ammonium polyphosphate (APP) was microencapsulated by UV‐curable epoxy acrylate (EA) resin. The resulting novel EA‐microencapsulated APP (EA‐APP) was characterized by Fourier transform infrared spectra, X‐ray photoelectron spectroscopy, X‐ray diffraction, scanning electron microscopy, granulometry, and thermogravimetric (TG) analysis. EA‐APP was used to flame retard polypropylene (PP). The water solubility of EA‐APP and the water resistance of PP/EA‐APP systems were investigated. The thermal stability and combustion behaviors of PP/EA‐APP composites were studied through TG and cone calorimeter (CC) tests, respectively. The water resistance test showed that the EA shell could significantly improve the water resistance of PP/APP. TG data illustrated that the char residue of EA‐APP greatly increased by 149% compared with uncoated APP, and the thermal stability of PP/EA‐APP composite was improved because of the microencapsulation of APP, with an increment of 248% for the char residue compared with PP/APP. CC test results indicated that the peak value of heat release rate, the total heat release, and the peak of smoke production rate of PP/EA‐APP decreased in comparison with PP/APP. The mechanism for the improvement of flame retardancy in CC test was discussed based on the experimental results. EA resin containing a large number of hydroxyl groups might promote the dehydration reaction in EA‐APP, which facilitated the formation of char residue and the stabilization of APP. Consequently, the flame‐retardant efficiency for APP was improved because of the presence of EA shell. Copyright © 2014 John Wiley & Sons, Ltd.     

The influence of KH-550 on properties of ammonium polyphosphate and polypropylene flame retardant composites

Ammonium polyphosphate (APP)/polypropylene (PP) composites were prepared by melt blending and extrusion in a twin-screw extruder. APP was first modified by a silane coupling agent KH-550 then added to polypropylene. The surface modification of APP by the coupling agent decreased its water solubility and its interface compatibility with the PP matrix. Limiting oxygen index (LOI) and thermogravimetric analysis (TGA) were used to characterize the flame retardant property and the thermal stability of the composites. The addition of APP improved the flame retardancy of PP remarkably. The crystal structures of APP/PP composites were characterized by X-ray diffraction (XRD). The results indicated that β-crystal phase PP may be formed. The structures and morphologies of APP, KH-550/APP and APP/PP composites were characterized by field-emission scanning electron microscope (FESEM). The mechanical property tests showed good mechanical properties of composite materials. Compared with unmodified one, the impact strength, tensile strength and elongation of modified APP/PP were all improved.     

Synthesis of a novel ionic liquid containing phosphorus and its application in intumescent flame retardant polypropylene system

A novel ionic liquid containing phosphorus ([PCMIM]Cl) was synthesized and characterized by FTIR, ¹H NMR, ¹³C NMR and ³¹P NMR. Moreover, a new intumescent flame retardant (IFR) system, which was composed of [PCMIM]Cl and ammonium polyphosphate (APP), was used to impart flame retardancy and dripping resistance to polypropylene (PP). The flammability and thermal behaviors of intumescent flame‐retarded PP (PP/IFR) composites were evaluated by limiting oxygen index (LOI), UL‐94 test, thermogravimetric analysis (TGA) and cone calorimeter test. It was found that there was an obvious synergistic effect between [PCMIM]Cl and APP. When the weight ratio of [PCMIM]Cl and APP was 1:5 and the total amount of IFR was kept at 30 wt%, LOI value of PP/IFR composite reached 31.8, and V‐0 rating was obtained. Moreover, both the peak heat release rate and the peak mass loss rate of PP/IFR composites decreased significantly relative to PP and PP/APP composite from cone calorimeter analysis. The TGA curves suggested that [PCMIM]Cl had good ability of char formation, and when combined with APP, it could greatly promote the char formation of PP/IFR composites, hence improved the flame retardancy. Additionally, the rheological behaviors and mechanical properties of PP/IFR composites were also investigated, and it was found that [PCMIM]Cl could also serve as an efficient lubricant and compatibilizer between APP and PP, endowing the materials with satisfying processability and mechanical properties. Copyright © 2013 John Wiley & Sons, Ltd.     

Effects of zinc and nickel salts in intumescent flame-retardant polypropylene

Variable amounts of zinc and nickel salts, such as ZnSO₄·7H₂O and NiSO₄·6H₂O, have been incorporated into blends of polypropylene (PP)/ammonium polyphosphate (APP)/dipentaerythritol (DPER) with the aim of studying their effect on intumescent flame retardance (IFR). The PP/IFR/salt composites have been prepared using a twin-screw extruder, and their IFR behaviours have been evaluated through limiting oxygen index (LOI), vertical burning tests (UL-94), and cone calorimeter tests (CONE). The results show that, at an appropriate level, zinc and nickel salts can increase the LOI and decrease the heat release rate (HRR). The composites have been studied with the aid of thermogravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The flame-retardant mechanism of the PP/IFR/salts system is also discussed in terms of catalytic charring. ZnSO₄·7H₂O has been shown to be the most effective among the aforementioned metal salts, which has proved to be strongly associated with its low melting point and the interaction between DPER and SO₄²⁻.     

海泡石对膨胀阻燃聚丙烯燃烧和热分解的影响

将改性后的海泡石添加到聚磷酸铵(APP)和双季戊四醇(DPER)膨胀阻燃聚丙烯(PP/IFR)体系中,采用氧指数(LOI)、热重分析(TGA)、光电子能谱(XPS)、傅里叶变换红外(FTIR)光谱、锥形量热仪(CONE)和扫描电镜(SEM)考察其对膨胀阻燃体系的催化协效作用,探讨作用机理.LOI结果表明,改性的海泡石比纳米水滑石和有机改性的蒙脱土有更好的催化协效作用.CONE数据证实,海泡石可以降低膨胀阻燃聚丙烯体系的热释放速率和总的热释放量.通过观察SEM图片发现,海泡石可以改善膨胀炭层的形貌,提高炭层的隔热隔质性能.TGA结果表明,在氮气和空气气氛下,海泡石均可以提高膨胀炭层的热稳定性,增加高温时残余物的量,其主要作用对象为APP.FTIR和XPS测试发现加热过程中海泡石可以与APP发生化学反应,形成P—O—Si键,增加了APP高温时的稳定性.     

Preparation of microcapsulated ammonium polyphosphate,pentaerythritol with glycidyl methacrylate,butyl methacrylate and their synergistic flame‐ retardancy for ethylene vinyl acetate copolymer

A new series of microcapsules containing pentaerythritol (PER) and ammonium polyphosphate (APP) with glycidyl methacrylate and butyl methacrylate as shell materials were synthesized by in situ polymerization. The structure and performance of the microencapsulated APP and microencapsulated PER were characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and water contact angle. The flame retarded ethylene‐vinyl acetate copolymer (EVA) composites were studied by limiting oxygen index, UL‐94 test, and cone calorimeter. It was found that the microencapsulation of flame retardants (FRs) with the glycidyl methacrylate and butyl methacrylate lead to a decrease in the particle's water solubility and an improvement of the hydrophobicity. Results also demonstrated that the FR properties of EVA/microencapsulated APP/microencapsulated PER composites were better than those of the EVA/APP/PER composites at the same loading of FRs. The thermogravimetric analysis results reflected that the microencapsulated EVA composites had better thermal stability because of the forming of stable char during the combustion. Copyright © 2013 John Wiley & Sons, Ltd.     

Flammability and thermal degradation of flame retarded polypropylene composites containing melamine phosphate and pentaerythritol derivatives

The flammability of polypropylene (PP) composites containing intumescent flame retardant additives, i.e. melamine phosphate (MP) and pentaerythritol (PER), dipentaerythritol (DPER) or tripentaerythritol (TPER) was characterized by limiting oxygen index (LOI), UL 94 and the cone calorimeter, and the thermal degradation of the composites was studied using thermogravimetric analysis (TG) and real time Fourier transform infrared (RTFTIR). It has been found that the PP composite containing only MP does not show good flame retardancy even at 40% additive level. Compared with the PP/MP binary composite, the LOI values of the PP/MP/PER (PP/MP/DPER or PP/MP/TPER) ternary composites at the same additive loading are all increased, and UL 94 ratings of most ternary composites studied are raised to V-0 from no rating (PP/MP). The cone calorimeter results show that the heat release rate and smoke emission of some ternary composites decrease in comparison with the binary composite. It is noted from the TG data that initial decomposition temperatures of ternary composites are lower than that of the binary composite. The RTFTIR study indicates that the PP/IFR composites have higher thermal oxidative stability than the pure PP.     

Preparation of piperazine cyanurate by hydrogen‐bonding self‐assembly reaction and its application in intumescent flame‐retardant polypropylene composites

Piperazine cyanurate (PCA) is designed and synthesized via hydrogen‐bonding self‐assembly reactions between piperazine and cyanuric acid. Chemical structure and morphology of PCA are investigated by Fourier transform infrared spectroscopy and scanning electron microscopy, respectively. The prepared PCA is combined with ammonium polyphosphate (APP) to prepare flame‐retardant polypropylene (PP) composites. Thermostability, flammability, and combustion characteristics of PP composites are analyzed. The maximum thermal decomposition rate of flame‐retarded PP composites has an apparent reduction compared with that of pure PP, and obvious char is left for this intumescent flame retardant (IFR) system of APP and PCA. A high limiting oxygen index value and UL‐94 V‐0 rating are achieved with addition of APP and PCA. In cone calorimetry test, heat and smoke releases of PP are significantly decreased by this IFR system. Gaseous decomposition products during the thermal decomposition of flame‐retardant composites are studied. Chemical structure and morphology of char residues are analyzed. The results illustrate that APP and PCA have a superb synergistic action in the aspect of improvement in fire safety of PP. A possible flame‐retardant mechanism is concluded to reveal the synergism between APP and PCA.     

Synthesis of a triazine-based macromolecular hybrid charring agent containing zinc borate and its flame retardancy and thermal properties in polypropylene

Abstract

A triazine-based macromolecular hybrid charring agent containing zinc borate (MCA-K-ZB) was synthesized and combined with ammonium polyphosphate (APP) to improve the flame retardancy of polypropylene (PP). The flame retardancy and thermal properties of PP composites were investigated using limited oxygen index, vertical burning test, and thermogravimetric analysis. The results showed APP/MCA-K-ZB can improve the flame retardancy of PP compared with APP/MCA-K/ZB. The morphology of the char residues was investigated by scanning electron microscopy (SEM). The SEM result shows that MCA-K-ZB can improve the compactness and continuity of char residue compared with MCA-K/ZB, therefore improving the flame retardancy of PP composites.     

Microencapsulation of ammonium polyphosphate with hydroxyl silicone oil and its flame retardance in thermoplastic polyurethane

Microencapsulated ammonium polyphosphate (MAPP) is prepared using hydroxyl silicone oil by in situ polymerization and characterized by XPS. Microencapsulation gives MAPP better water resistance and flame retardance compared with APP in thermoplastic polyurethane (TPU). Thermal stability and fire resistance behavior have been analyzed and compared. The LOI value of the TPU/MAPP composite is higher than that of the TPU/APP composite. The UL 94 rating of the TPU/MAPP composite is V-0 at the 20 wt% additive level, whereas TPU/APP gives V-2 rating at the same loading level. The water resistant properties of the TPU composites are studied. Results of the cone calorimeter and microscale combustion calorimeter experiment show that MAPP is an effective flame retardant in TPU compared with APP.     

Simultaneous improvement in the flame retardancy and water resistance of PP/APP through coating UV-curable pentaerythritol triacrylate onto APP

To improve the flame-retardant efficiency and water resistance of ammonium polyphosphate(APP), the UV-curable pentaerythritol triacrylate(PETA) was used to microencapsulate APP via the UV curing polymerization method. The prepared PETA-microencapsulated APP(PETA-APP) was characterized by Fourier transform infrared spectroscopy(FTIR), scanning electron microscopy(SEM), and thermogravimetric(TG) analysis. PETA-APP was used as intumescent flame retardant(IFR) alone to flame retard polypropylene(PP). The water resistance of PP/PETA-APP composites was investigated, and the effect of PETA on the combustion behaviors of PP/APP composites was studied through limiting oxygen index(LOI), vertical burning test(UL-94) and cone calorimeter(CC) test, respectively. With 40 wt% of PETA-APP, the PP/PETA-APP system could achieve a LOI value of 30.0% and UL-94 V-0 rating after treatment in hot water for 168 h, while the LOI value of the system containing 40 wt% uncoated APP was only 19.2%, and it failed to pass the UL-94 rating. CC test results showed that the heat release rate(HRR), mass loss rate(MLR) and smoke production rate(SPR) of PP/PETAAPP system decreased significantly compared with PP/APP system, especially the peak of HRR was decreased by 51.4%. The mechanism for the improvement of flame reatardancy for PP/PETA-APP composites was discussed based on FTIR and X-ray photoelectron spectroscopy(XPS) tests. All these results illustrated that simultaneous improvement of flame retardancy and water resistance for PP/APP was achieved through coating UV-curable PETA onto APP.