Intumescent Flame Retardation of EVA Using Microencapsulated Ammonium Polyphosphate and Pentaerythritols

With a melamine-formaldehyde (MF) resin coating layer, microencapsulated ammonium polyphosphate (MCAPP) is prepared by in situ polymerization and is characterized by XPS and water leaching test. The microencapsulation of APP with the MF resin leads to a decrease in the particle's water leaching rate. The flame-retardant action of MCAPP and APP in EVA are studied using LOI and UL 94 test, and their thermal stability is evaluated by thermogravimetric analysis (TGA). The LOI value of the EVA/MCAPP composite at the same loading is higher than the value of the EVA/APP composite. In comparison with the EVA/MCAPP composites, it is found that the LOI values of the EVA/MCAPP/PER and EVA/MCAPP/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 EVA composites are studied, and the results of the composites containing with APP and MCAPP are compared. Moreover, the peroxide cross-linking of the EVA composites is investigated, and the mechanical properties and thermal stability of the composites increase after the cross-linking.     

Microencapsulation of APP‐I and influence of microencapsulated APP‐I on microstructure and flame retardancy of PP/APP‐I/PER composites

In this article, the microencapsulated ammonium polyphosphate crystalline with form I (APP‐I) coated with melamine‐formaldehyde (MF) was prepared by in situ polymerization. Results of Fourier transform infrared spectra (FTIR), thermogravimetry (TG) energy dispersive spectroscopy (EDS), and scanning electron microscopy (SEM) demonstrate that APP‐I is successfully microencapsulated with MF. Compared with APP‐I, the microencapsulated APP‐I with MF (MFAPP‐I) is of much smaller spheroidal particle size and lower solubility in water. In this study, the polypropylene (PP)/APP‐I/penpaerythritol (PER) and PP/MFAPP‐I/PER composites are prepared, and flame retardancy, thermal stability, and microstructure of corresponding composites are carefully investigated by limiting oxygen index (LOI), UL‐94 testing, TG, EDS, and SEM. Experimental results show that PP/MFAPP‐I/PER composites have advantages over PP/APP‐I/PER composites in terms of flame retardant properties and water resistance. Results of TG, SEM, and EDS show that the microencapsulated APP‐I with MF resin is conducive to increase the amount of residual yield and improve thermal stability of PP/MFAPP‐I/PER composites and the compatibility and dispersion of MFAPP‐I. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study on flame retardance of co‐microencapsulated ammonium polyphosphate and dipentaerythritol in polypropylene

Co‐microencapsulated ammonium polyphosphate and dipentaerythritol [M(A&D)] was prepared using a melamine‐formaldehyde (MF) resin by in situ polymerization method, and characterized by XPS. The co‐microencapsulation of ammonium polyphosphate and dipentaerythritol (DPER) leads to a great improvement in water solubility of the additives. The flame retardant effect of M(A&D) in polypropylene (PP) is evaluated using limiting oxygen index (LOI) and UL 94 test, and the water resistance of the PP/M(A&D) composites is also studied. The flame retardant properties and water resistance of the PP/M(A&D) composites are much better than the ones of the PP/APP/DPER composites. Moreover, the thermal stability of the PP/M(A&D) composites is improved compared with the PP/APP/DPER composites. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Study on surface modification and flame retardants properties of ammonium polyphosphate for polypropylene

Microencapsulation ammonium polyphosphate used as flame‐retardant in polypropylene was prepared with hydroxyl silicone oil (HSO) and melamine‐formaldehyde (MF) resin in this article. Fourier transform infrared and energy dispersive spectrometer were used to identify the structure of HSO‐MFAPP. For the HSO‐MFAPP/polypropylene (PP) composites, the flame retardant effect was evaluated by the limiting oxygen index and UL‐94 testing, the compatibility was observed with scanning electron microscope, and the thermal stability was studied by thermogravimetric analysis. The results showed that the microencapsulation of ammonium polyphosphate (APP) with HSO‐MF was prepared by in situ polymerization, and the flame retardant properties and water resistance of the PP/HSO‐MFAPP/pentaerythritol (PER) composites were much better than the ones of the PP/APP/PER composites. Moreover, the compatibility of HSO‐MFAPP with PP was better than that of unmodified APP. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

三聚氰胺-甲醛树脂微胶囊包覆聚磷酸铵阻燃PP的性能

通过原位聚合法制备三聚氰胺-甲醛树脂(MF)微胶囊包覆聚磷酸铵(APP)粒子,研究了APP粒径对微胶囊化APP(MCAPP)结构与性能的影响。将两种MCAPP(APP平均粒径分别为5,15μm)添加至聚丙烯(PP)基体中,研究了PP/MCAPP阻燃材料的性能。结果表明:不同粒径的APP均能成功被MF包覆,且包覆后的APP粒子的水溶性均大幅下降。PP/MCAPP阻燃材料的耐渗析性和极限氧指数均得到一定程度的提高。粒径小的APP有利于MF的包覆,包覆结构层更完整。MF和APP有很好的协同作用,在APP包覆不完全的情况下,能更有效地发挥两者的相互作用,提高PP复合材料的阻燃性。     

Effect of charring agent THEIC on flame retardant properties of polypropylene

Tris(2‐hydroxyethyl) isocyanurate (THEIC) was used as charring agent and combined with ammonium polyphosphate (APP) to form an intumescent flame retardant (IFR) for polypropylene (PP). The flame retardancy and combustion performance of PP/IFR composite was tested by limiting oxygen index (LOI), UL‐94 vertical burning test and cone calorimeter. The results showed that PP/IFR composite had highest LOI of 34.8 and obtained V‐0 rating when 30 wt % IFR was loaded and mass ratio APP/THEIC was 2 : 1. The peak heat release (PHRR) and total heat release (THR) values of PP composite containing FRs were remarkably reduced compared with that of pure PP. However, water resistant test demonstrated the PP/IFR composite had poor flame retardant durability, both the LOI value and UL‐94 V‐rating decreased when PP/IFR composite was soaked in water at 70°C after 36 h. The degradation process and the char morphology of IFR and PP/IFR composite were investigated by TGA and SEM images. The possible reaction path between APP and THEIC in the swollen process was proposed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41214.     

Effect of microencapsulated ammonium polyphosphate on flame retardancy and mechanical properties of wood flour/polypropylene composites

Microencapsulated ammonium polyphosphate (MCAPP) was prepared by using melamine–formaldehyde (MF) resin via polymerization in situ. The product was characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, energy dispersive spectroscopy, water solubility tests, water contact angle, and thermogravimetric analysis. The tests indicate that ammonium phosphate (APP) was successfully coated by the MF resin, and MCAPP with lower water solubility and higher water resistance outperformed APP. After modification by MCAPP, the flammability of wood–plastic composites (WPCs) was investigated by limiting oxygen index (LOI) and cone calorimetry. The results showed that MCAPP/WPC had higher LOI value, lower heat release rate, and more char residual at the end of cone calorimetry than APP/WPC, indicating that the WPC used MCAPP as flame retardant performed better flame retardancy than the WPC mixed with unmodified APP. Moreover, all measured mechanical properties of MCAPP/WPC were distinctly better than APP/WPC. POLYM. COMPOS., 37:666–673, 2016. © 2014 Society of Plastics Engineers     

Synthesis of amino trimethylene phosphonic acid melamine salt and its application in flame‐retarded polypropylene

Amino trimethylene phosphonic acid melamine salt (MATMP) was synthesized and used as acid source and blowing agent in intumescent flame‐retarded polypropylene (PP); its compositions were characterized by Fourier transform infrared spectroscopy and X‐ray powder diffraction. An intumescent flame retardant (IFR) system composed of MATMP, pentaerythritol (PER), and PP was tested by limiting oxygen index (LOI), UL‐94, cone calorimeter tests, and thermogravimetric analysis and compared with an ammonium polyphosphate (APP)/PER system. The results showed that MATMP had better water resistance than APP, the LOI value of PP/MATMP/PER composite can reach 30.3%, and a UL‐94 V‐0 rating can be reached at 25 wt % IFR loading. The amount of residual char of IFR MATMP/PER was 20.3 and 9.5 wt % at 400 and 600 °C, respectively. A thermooxidative degradation route and a possible flame‐retardant mechanism of IFR were proposed according to the analysis of evolved gases and residual chars. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46274.     

Synergistic effect between silicone‐containing macromolecular charring agent and ammonium polyphosphate in flame retardant polypropylene

A novel silicone‐containing macromolecular charring agent (Si‐MCA) was synthesized via polycondensation, and it was combined with ammonium polyphosphate (APP) to flame retard polypropylene (PP). The results showed that Si‐MCA exhibited a good synergistic effect with APP in flame retardant PP. When the content of APP was 18.7 wt % and Si‐MCA was 6.3 wt %, the limiting oxygen index value of the PP/APP/Si‐MCA composite was 33.5%, and the vertical burning (UL 94) test classed a V‐0 rating. The peak heat release rate, total heat release, average mass loss rate, and total smoke production of the composite were also decreased significantly. Moreover, the PP/APP/Si‐MCA composite showed an outstanding water resistance. After soaking in 70°C water for 168 h, the PP/APP/Si‐MCA composite could still reach a UL 94 V‐0 rating at 20.0 wt % IFR loading, whereas the PP/APP/PER composite failed to pass the UL 94 test even at 25.0 wt % IFR loading. Thermogravimetric analysis, thermogravimetry‐Fourier transform infrared spectrometry, and scanning electron microscopy‐energy dispersive X‐ray spectrometry results revealed that a compact and thermostable intumescent char was formed by APP/Si‐MCA during burning, thus effectively improved the flame retardancy of PP. The possible synergistic mechanism between APP and Si‐MCA was also discussed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41580.     

Component ratio effects of hyperbranched triazine compound and ammonium polyphosphate in flame‐retardant polypropylene composites

A hyperbranched derivative of triazine group (EA) was synthesized by elimination reaction between ethylenediamine and cyanuric chloride. The different‐mass‐ratio EA and ammonium polyphosphate (APP) were mixed and blended with polypropylene (PP) in a constant amount (25%) to prepare a series of EA/APP/PP composites. The component ratio effect of EA/APP on the flame‐retardant property of the EA/APP/PP composites was investigated using the limiting oxygen index (LOI), vertical burning (UL‐94), and cone calorimetry tests. Results indicated that the EA/APP/PP (7.50/17.50/75.00) composite with the appropriate EA/APP mass ratio had the highest LOI, UL94 V‐0 rating, lowest heat release rate, and highest residue yield. These results implied that the appropriate EA/APP mass ratio formed a better intumescent flame‐retardant system and adequately exerted their synergistic effects. Furthermore, average effective combustion heat values revealed that EA/APP flame retardant possessed the gaseous‐phase flame‐retardant effect on PP. Residues of the EA/APP/PP composites were also investigated by scanning electron microscopy, Fourier‐transform infrared, and X‐ray photoelectron spectroscopy. Results demonstrated that the appropriate EA/APP mass ratio can fully interact and lock more chemical constituents containing carbon and nitrogen in the residue, thereby resulting in the formation of a dense, compact, and intumescent char layer. This char layer exerted a condensed‐phase flame‐retardant effect on EA/APP/PP composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41006.     

Enhanced mechanical and flame-resistant properties of polypropylene nanocomposites with reduced graphene oxide-functionalized ammonium polyphosphate and pentaerythritol

A novel functionalized graphene oxide grafted by ammonium polyphosphate (GO-APP) was synthesized through acylating chlorination method to improve the flame retardancy and mechanical properties of polypropylene (PP) nanocomposites in combination with pentaerythritol (PER). During the mixing process, GO-APP nanosheets were thermally reduced and PP/rGO-APP/PER composites were finally obtained. In comparison, PP/rGO-APP/PER composites exhibit better mechanical, thermal, and flame-retardant performances than those of PP/APP/PER composites when containing the same loading of total additives. PP/APP/PER 30 wt % composite only passes V-1 rating in vertical burning tests (UL-94), whereas PP/rGO-APP/PER 25 wt % composite ranks V-0 rating. Furthermore, PP/rGO-APP/PER 30 wt % composite reaches the highest limiting oxygen index (LOI) value of 31.2%, and its impact strength is almost three times higher than pure PP. The improvement in the fire safety is mainly due to the enhanced char yield, and the “tortuous path” effect caused by intercalate-exfoliated structures formed in PP/rGO-APP/PER composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48036.     

The effect of red phosphorus on the fire properties of intumescent pine wood flour – LDPE composites

Red phosphorus (RP) was used to improve the fire performance of wood flour – low density polyethylene (LDPE) composites containing ammonium polyphosphate (APP). The fire performance of LDPE‐based composites was investigated by using limiting oxygen index (LOI), UL‐94 standard, thermogravimetric analysis, and cone calorimeter. The addition of 30 wt% APP increased the LOI value from 17.5 to 24.2 and still burned to clamp (BC) in UL‐94 test. The RP showed beneficial effect when combinedly used with APP. The maximum beneficial effect was seen at ratio of 5:1 (APP : RP) with the highest LOI value of 27.2 and UL‐94 rating of V0. RP showed its beneficial effect via increasing the gas phase action of the flame retardant system. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Preparation and characterization of double shell microencapsulated ammonium polyphosphate and its flame retardance in polypropylene

Microencapsulated ammonium polyphosphate (MUFAPP) with a double shell is prepared by in situ polymerization, and is characterized by FTIR, XPS and SEM, etc. The microencapsulation of APP can increase its flame retardance and water resistance in PP. The flame retardant action of MUFAPP and APP in PP are studied using LOI and UL 94 test, and their thermal stability is evaluated by TG. The LOI value of the PP/MUFAPP composite at the same loading is higher than that of PP/APP composite. The LOI values of the PP/MUFAPP/ dipentaerythritol are higher than that of the PP/MUFAPP, and UL 94 ratings of most ternary composites are raised to V-0 at 30 wt.% loading. The results of the cone calorimeter also indicate that MUFAPP is an effective flame retardant in PP. The thermal degradation behaviors of APP and MUFAPP are studied using TG and dynamic FTIR.     

Vinyl polysiloxane microencapsulated ammonium polyphosphate and its application in flame retardant polypropylene

Vinyl polysiloxane microencapsulated ammonium polyphosphate (MAPP) was prepared by a sol-gel method using vinyltrimethoxysilane as a precursor to improve its thermal stability and hydrophobicity. The MAPP was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and thermogravimetric analyzer (TGA). The results showed that ammonium polyphosphate (APP) was successfully coated with vinyl polysiloxane. MAPP and pentaerythritol (PER) were used together to improve the flame retardancy of polypropylene (PP). The flame retardant properties of PP composites were investigated by limiting oxygen index (LOI), UL-94 test, TGA and SEM. When the MAPP was added as a flame retardant, with PER as a char forming agent, the LOI of PP/MAPP/PER composites was 33.1%, and it reached the UL-94 V-0 level. The results also demonstrated that the flame retardant properties of PP/MAPP/PER composites were better than those of PP/APP/PER composites at the same loading. Moreover, the addition of flame retardant and carbon forming agent could promote the crystallization behavior of PP.     

Polyamide‐enhanced flame retardancy of ammonium polyphosphate on epoxy resin

An attractive intumescent flame retardant epoxy system was prepared from epoxy resin (diglycidyl ether of bisphenol A), low molecular weight polyamide (cure agent, LWPA), and ammonium polyphosphate (APP). The cured epoxy resin was served as carbonization agent as well as blowing agent itself in the intumescent flame retardant formulation. Flammability and thermal stability of the cured epoxy resins with different contents of APP and LWPA were investigated by limited oxygen index (LOI), UL‐94 test, and thermogravimetric analysis (TGA). The results of LOI and UL‐94 indicate that APP can improve the flame retardancy of LWPA‐cured epoxy resins. Only 5 wt % of APP can increase the LOI value of epoxy resins from 19.6 to 27.1, and improve the UL‐94 ratings, reaching V‐0 rating from no rating when the mass ratio of epoxy resin to LWPA is 100/40. It is much interesting that LOI values of flame retardant cured epoxy resins (FR‐CEP) increase with decreasing LWPA. The results of TGA, FTIR, and X‐ray photoelectron spectroscopy (XPS) indicate that the process of thermal degradation of FR‐CEP consists of two main stages: the first stage is that a phosphorus rich char is formed on the surface of the material under 500°C, and then a compact char yields over 500°C; the second stage is that the char residue layer can give more effective protection for the materials than the char formed at the first stage do. The flame retardant mechanism also has been discussed according to the results of TGA, FTIR, and XPS for FR‐CEP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

苯基聚硅氧烷微胶囊化聚磷酸铵的制备及其在PP中阻燃性能研究

采用苯基三甲氧基硅烷为前驱体,通过溶胶凝胶法制备出苯基聚硅氧烷微胶囊化聚磷酸铵（MAPP）。将MAPP作为阻燃剂,季戊四醇（PER）作为成炭剂,制备阻燃聚丙烯（PP）。用傅里叶红外光谱、扫描电子显微镜、能谱仪及热重分析仪对MAPP进行表征。结果表明,聚磷酸铵（APP）被苯基聚硅氧烷成功包覆;较之APP,MAPP的热稳定性和疏水性显著提高;MAPP的阻燃性能优于APP,PP/MAPP/PER复合材料达到V-0级别;阻燃剂及成炭剂的加入对PP的结晶行为有促进作用。     

Synergistic effect of metal oxides on the flame retardancy and thermal degradation of novel intumescent flame‐retardant thermoplastic polyurethanes

The synergistic effects of some metal oxides on novel intumescent flame retardant (IFR)–thermoplastic polyurethane (TPU) composites were evaluated by limiting oxygen index (LOI), vertical burning test (UL‐94), thermogravimetric analysis (TGA), cone calorimetry, and scanning electron microscopy. The experimental data indicated that the metal oxides enhanced the LOI value and restricted the dropping of the composites. The IFR–TPU composites passed the UL‐94 V‐0 rating test (1.6 mm) in the presence of magnesium oxide (MgO) and ferric oxide (Fe₂O₃) at 35 wt % IFR loading, whereas only the MgO‐containing IFR–TPU composite reached a UL‐94 V‐0 rating at 30 wt % IFR loading. The TGA results show that the metal oxides had different effects on the process of thermal degradation of the IFR–TPU compositions. MgO easily reacted with polyphosphoric acid generated by the decomposition of ammonium polyphosphate (APP) to produce magnesium phosphate. MgO and Fe₂O₃ showed low flammability and smoke emission due to peak heat release rate, peak smoke production rate, total heat release, and total smoke production (TSP). However, zinc oxide brought an increase in the smoke production rate and TSP values. Among the metal oxides, MgO provided an impressive promotion on the LOI value. The alkaline metal oxide MgO more easily reacted with APP in IFRs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

Fire performance and thermal stability of polypropylene nanocomposites containing organic phosphinate and ammonium polyphosphate additives

In order to develop polymer‐clay nanocomposites with reduced flammability by incorporation of char‐forming conventional nitrogen and phosphorus based flame retardants at low loading levels, the polypropylene‐clay nanocomposites were prepared by melt blending method with Cloisite 15A (15A), organic phosphinate (OP) and ammonium polyphosphate (AP) additives. Thermal analysis shows that addition of 5% 15A along with 15% (w/w) OP in polypropylene (PP)/PPgMA increases the thermal stability of PP/PPgMA/OP/15A composite by 82 °C showing synergistic effect, and the PP/PPgMA/AP/15A sample with same loading becomes thermally stable by 70 °C. Cone calorimeter analysis of the PP/PPgMA/OP/15A and PP/PPgMA/AP/15A composites measures the reduction in peak heat release rate values by 66% and 58%, respectively. Addition of 20% OP to PP/PPgMA enhances the limiting oxygen index (LOI) value and gives V‐2 rating of UL‐94 test. Further, on replacing 5% OP with 5% 15A for PP/PPgMA/OP/15A sample without changing the total 20% loading, the LOI value increases further slightly but give no UL‐94 rating. Also, PP/PPgMA/AP/15A sample with same loading similar to that of PP/PPgMA/OP/15A sample shows an enhancement in LOI value and gives no rating in UL‐94 test. No relation was observed between LOI values and UL‐94 test rating in the present study. Copyright © 2012 John Wiley & Sons, Ltd.