Preparation and characterization of surface‐modified ammonium polyphosphate and its effect on the flame retardancy of rigid polyurethane foam

A functional surface‐modification agent was synthesized via a reaction between hexachlorocyclotriphosphazene and γ‐aminopropyl triethoxysilane. Ammonium polyphosphate (APP) was modified with this agent and then incorporated into a rigid polyurethane foam (RPUF). Fourier transform infrared spectroscopy, ¹H‐NMR, and X‐ray photoelectron spectroscopy were used to characterize the modified ammonium polyphosphate (M‐APP). The results show that the dispersibility was improved and the particle size decreased after the modification. The limiting oxygen index and cone calorimetry test results show that M‐APP enhanced the flame‐retardant properties of RPUF. The peak heat‐release rate of polyurethane (PU)/20% M‐APP decreased by 51.18% compared with that of PU–APP. The scanning electron microscopy results illustrate that M‐APP facilitated the formation of intumescent and compact char. The excellent flame‐retardant performance of M‐APP resulted from the flame‐inhibition and barrier effects, which were attributed to the phosphazene group and the intumescent char, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45369.     

Reactive flame retardant with core‐shell structure and its flame retardancy in rigid polyurethane foam

With a shell of poly (methyl methacrylate‐co‐hydroxyl ethyl acrylate) (PMMA‐HA), microencapsulated ammonium polyphosphate (MHAPP) is prepared by in situ polymerization. The core‐shell structure of the reactive flame retardant (FR) is characterized by Fourier transform infrared (FTIR) and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS). The results of water leaching rate and water contact angle measurements show that ammonium polyphosphate (APP) is well coated by a hydrophobic shell. Due to the presence of active groups (–OH) and hydrophobic groups (–CH₃) in shell, MHAPP exhibits better compatibility, flame retardancy, and water resistance compared with neat ammonium polyphosphate (APP) in rigid polyurethane foam (PU). Compression strength of PU/MHAPP with suitable loading is higher than that of PU/APP and PU, the reason is that the active groups in shell can improve the compatibility of MHAPP in PU composite. From thermal stability and residue analysis, it can be seen that the presence of reactive flame retardant shows positive effect on thermal stability of PU composite at high temperature, results also indicate that MHAPP can promote the carbonization formation efficiency of PU composite during combustion process compared with APP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42800.     

Flame retardancy of ceramic-based rigid polyurethane foam composites

In this work, ceramic fillers zirconia and alumina powder were incorporated in the rigid polyurethane foams derived from modified castor oil and their impact on the mechanical, thermal, and fire performances of composite foams have been analyzed. It was observed that the addition of ceramic filler showed improved mechanical and thermal properties and best properties were shown by 6% zirconia with compressive strength of 6.61 MPa and flexural strength of 5.72 MPa. Zirconia also demonstrated an increase in T_5% up to 260 °C. Cone calorimetry shows a decrease in peak of heat release from 118 to 84 kW m⁻² and 94 kW m⁻² by the incorporation of alumina and zirconia powder, respectively. Furthermore, total heat release (THR), smoke production rate (SPR), and total smoke release (TSR) were also found to decrease remarkably on the incorporation of ceramic fillers. So, these fillers have a great potential as an additive to incorporate good mechanical, thermal, and fire properties in bio-based rigid PU foams. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48250.     

Addition flame‐retardant effect of nonreactive phosphonate and expandable graphite in rigid polyurethane foams

A series of flame‐retardant rigid polyurethane foams (RPUFs) containing nonreactive phosphonate (5‐ethyl‐2‐methyl‐1,3,2‐dioxaphosphorinan‐5‐yl) methyl dimethyl phosphonate P‐oxide (EMD) and expandable graphite (EG) were prepared by water blown. The flame‐retardant properties and mechanism of EMD/EG on RPUFs were systematically investigated. The EMD/EG system effectively increased the limiting oxygen index (LOI) value and decreased the values of total heat release (THR), av‐effective heat of combustion (EHC), pk‐heat release rate (HRR), total smoke release (TSR) of RPUFs. The impact values of LOI, THR, and av‐EHC resulted by EMD/EG system are nearly equal to the sum of the impact values by EMD and EG individually in RPUFs, which implies the addition flame‐retardant effect from EMD and EG. EMD alone exerted excellent gas‐phase flame‐retardant effect by releasing PO fragments with quenching effect. The firm residue produced by EMD combined well with the loose and worm‐like expanded graphite from EG further to form compact and expanded char layer, which brought excellent barrier effect and filtration effect to matrix. That's why pk‐HRR and TSR values of RPUF reduced. Depending on the simultaneous actions of EMD/EG system in gas phase and condensed phase during combustion, the flame‐retardant effects from nonreactive phosphonate and EG on RPUFs were added together. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45960.     

Expandable graphite in polyurethane foams: The effect of expansion volume and intercalants on flame retardancy

Several expandable graphites (EGs), differing in expansion volume but with the same mean size, are compared as flame retardants in polyurethane (PUR) foams. Not only common sulfur‐intercalated graphites are investigated but also a new one intercalated with phosphorus. The main aim of this article is to understand which properties of EG are important for its flame retardancy effectiveness in PUR foams. Thermal stability, flammability, and fire behavior are analyzed through limiting oxygen index and cone calorimeter tests. Detailed characterization of the phosphorus‐intercalated graphite is also provided as well as physical–mechanical characterization. The results show that the well‐known sulfur‐intercalated graphites and the one with phosphorus both enhance the residue yield, induce a protective layer, and thus efficiently flame‐retard PUR foams. While the expansion volume of the EGs had a surprisingly limited influence on the performance of the foams, at least in the range tested, the most important feature controlling the effectiveness of EG in terms of flame retardant PUR foams was the type of intercalant. The presence of EG affected the physical–mechanical properties of the foams; however, no significant effect of the expansion volume or intercalant type has been revealed on the physical–mechanical properties of the foams. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45173.     

Preparation and characterization of microencapsulated ammonium polyphosphate and its synergistic flame‐retarded polyurethane rigid foams with expandable graphite

A facile and effective method for the preparation of microencapsulated ammonium polyphosphate (MAPP) by in situ surface polymerization was introduced. The ‘polyurethane‐like’ shell structure on the surface of MAPP was characterized by using Fourier transform infrared spectroscopy. The hydrophobicity and thermal behavior of MAPP were studied by using water contact angle tests and thermogravimetric analysis. The foam density and mechanical properties of polyurethane (PU) rigid foams were investigated. The flame retardancy of PU rigid foams formulated with MAPP was evaluated by using limiting oxygen index and cone calorimetry. The results show that MAPP can greatly increase the flame retardancy of PU materials. Also, there is a synergistic effect between MAPP and expandable graphite in flame retarding PU rigid foams. Moreover, the water resistance property of PU/MAPP composites is better than that of PU/ammonium polyphosphate. The morphology and chemical structure of PU/MAPP rigid foams after burning were systematically investigated. © 2013 Society of Chemical Industry     

Synergistic effects of hydroxides and dimethyl methylphosphonate on rigid halogen‐free and flame‐retarding polyurethane foams

Rigid halogen‐free and flame‐retarding polyurethane foams are prepared with aluminum hydroxide, brucite, and DMMP. The effects of the hydroxides and DMMP on the foaming process and flame retarding properties of the foams are investigated by thermo gravimetric analysis, limiting oxygen index, and X‐ray powder diffraction. The thermal stability of the rigid polyurethane foams is close to that of the hydroxide fillers, with aluminum hydroxide providing better flammability performance than brucite. The hydroxide fillers and DMMP play a synergistic role in the rigid polyurethane foams and the limiting oxygen indices are up to 28.4% and 32.4%, respectively. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Enhanced fire behavior of rigid polyurethane foam by intumescent flame retardants

Using expandable graphite (EG) and ammonium polyphosphate (APP) as flame retardants, we prepared two series of polyisocyanurate–polyurethane (PIR–PUR) foams (i.e., EG foams filled with different amounts of EG alone and APEG foams containing different amounts of expanded EG and APP) and evaluated the effect of the additives on the physical–mechanical property, fire behavior and thermal stability of the foams based on compressive strength test, limiting oxygen index (LOI), cone calorimeter test, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The addition of EG alone or both EG and APP into the foam greatly influences the physical–mechanical property. The compressive strength of APEG foams is closely related to the apparent density. The LOI value showed good improvement in both EG and APEG foams. The addition of APP in APEG foams gave better fire behavior than the EG foams with an obvious decrease in PHRR and increase in residue. In addition, the TGA curves illustrated that APP might be an effective charring agent to promote char formation. The SEM results showed that the incorporation of APP and EG allowed the formation of a cohesive and dense char layer, which inhibited the transfer of heat and combustible gas and increased the thermal stability of PIR‐PUR. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A novel polyurethane prepolymer as toughening agent: Preparation,characterization, and its influence on mechanical and flame retardant properties of phenolic foam

A novel phosphorus‐ and silicon‐containing polyurethane prepolymer (PSPUP) was synthesized by the chemical reaction of phenyl dichlorophosphate with hydroxy‐terminated polydimethylsiloxane (HTPDMS) and subsequently with toluene‐2,4‐diisocyanate. The structure of PSPUP was confirmed by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. Afterward, a series of phenolic foams (PF) with different loadings of PSPUP toughening agent were prepared. The apparent density and scanning electron microscopy results showed that the addition of PSPUP can increase the apparent density of phenolic foam. The compressive, impact and friability test results showed that the incorporation of PSPUP into PF dramatically improved the compressive strength, impact strength, and reduced the pulverization ratio, indicating the excellent toughening effect of PSPUP. The limiting oxygen index of PSPUP modified phenolic foams remained a high value and the UL‐94 results showed all samples can pass V0 rating, indicating the modified foams still had good flame retardance. The thermal properties of the foams were investigated by thermogravimetric analysis under air atmosphere. Moreover, the thermal degradation behaviors of the PF and PSPUP/PF were investigated by real‐time Fourier transform infrared spectra. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flame retardant polyurethane foam prepared from compatible blends of soybean oil‐based polyol and phosphorus containing polyol

A phosphorus containing polyether polyol (THPO‐PO) was synthesized by polymerization between tris(hydroxymethyl) phosphine oxide (THPO) and propylene oxide (PO). A soybean oil‐based polyol(SBP) was synthesized from epoxidized soybean oil by ring‐opening reaction with lactic acid. The corresponding polyurethane foams (PUFs) were prepared by mixing SBP with THPO‐PO. The density of these foams decreased as the content of THPO‐PO increased. The yield strength of PUFs was observed to be decreased firstly and then increased with the addition of THPO‐PO. Microphotographs of PUFs were examined by scanning electron microscope which displayed the cells as spherical or polyhedral. The thermal degradation and fire behavior of PUFs were investigated by thermogravimetric analysis, limiting oxygen index (LOI), and UL‐94 test. Although the thermal stability of PUFs were decreased with increasing THPO‐PO percentage, the flame retardancy of PUFs were improved. The LOI value increased to 27.5 with 40% THPO‐PO. THPO‐PO in sequence worked in inhibiting flame and forming phosphorus‐rich char layer, thus endowing PUFs with the increased flame‐retardant performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45779.     

Effects of expandable graphite and ammonium polyphosphate on the flame‐retardant and mechanical properties of rigid polyurethane foams

In this work, the effect of expandable graphite (EG) and ammonium polyphosphate (APP) on the flame retardancy and mechanical properties of the rigid polyurethane foam (RPUF) was studied. The results indicated that both EG and APP could effectively improve the flame retardancy of RPUF, while the retardancy of EG was better than APP. When the flame‐retardant loading was 15 wt %, the limited oxygen index (LOI) values of APP‐ and EG‐filled RPUF were 24.5 and 32 vol %, respectively. According to the LOI test, the optimal ratio of APP to EG in RPUF composites was 1 : 1 by weight, at which the LOI value of 15 wt % (APP + EG)/RPUF was 30.5 vol %. Thermal degradation test of RPUF composites by thermogravimetric analysis indicated that the addition of APP and EG to RPUF could lead to an increase in the amount of high‐temperature residue. Under the same conditions, the residue amount of EG/RPUF was less than that of APP/RPUF at the same temperature. Compression test and dynamic thermal mechanical analysis indicated that both the compressive strength and modulus decreased at a certain extent with the EG‐ or APP‐filled into RPUF, respectively, but with the mixture of EG and APP added into RPUF, the mechanical properties of these materials increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synergistic effect of expandable graphite and aluminum hypophosphite on flame‐retardant properties of rigid polyurethane foam

A series of flame retarding rigid polyurethane foam (RPUF) composites based on expandable graphite (EG) and aluminum hypophosphite (AHP) were prepared by the one‐pot method. The properties were characterized by limiting oxygen index (LOI) test, cone calorimeter test, thermogravimetric analysis (TGA), real‐time Fourier transform‐infrared spectra (RT‐FT‐IR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), etc. The results indicate that both EG and AHP could enhance the flame retardency of RPUF composites. Besides, the flame retardant effect of EG was better than that of AHP. The results also show that partial substitution of EG with AHP could improve the flame retardency of RPUF, and EG and AHP presented an excellent synergistic effect on flame retardancy. What is more, compared with RPUF/20EG and RPUF/20AHP, the heat release rate (HRR) and total heat release (THR) of RPUF/15EG/5AHP were lower.TGA results indicate that partial substitution of EG with AHP could improve the char residue which provided better flame retardancy for RPUF composites. The thermal degradation process of RPUF composites and the chemical component of the char residue were investigated by RT‐FT‐IR and XPS. And the results prove that RPUF/15EG/5AHP had higher heat resistance in the later stage. Compared with the RPUF composites filled with EG, a better cell structure and mechanical properties were observed with the substitution of AHP for part of EG. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42842.     

Flame retardation and thermal stability of novel phosphoramide/expandable graphite in rigid polyurethane foam

A novel flame retardant named diethylene N,N',N''‐tri (diethoxy)phosphoramide (DTP) was synthesized using diethyl phosphate and diethylenetriamine via Atherton–Todd reaction. Then, series of flame‐retardant water‐blown rigid polyurethane foams (RPUFs) with expandable graphite (EG) and DTP were prepared through box‐foaming. The results of thermogravimetric analysis showed that DTP/EG changed thermal degradation process of RPUF and promoted enhancing char residues. The complex flame‐retardant system (EG/DTP) endowed RPUF higher limiting oxygen index (LOI) values (29.1%–30.2%) and lower heat release rate peak (PHRR) values according to LOI and microscale combustion calorimeter tests. More importantly, the synergistic flame‐retardant effect between EG and DTP in RPUF was proved by the analysis of synergistic effectivity values. Based on the analysis of cone calorimetric tests, EG/DTP revealed remarkable effects to inhibit the fire intensity and smoke release of RPUF with decreased PHRR and total smoke production due to good char‐forming action. To further investigate the char‐residues of the foams after combustion, scanning electron microscope and energy dispersive X‐ray spectroscopy analyses were conducted. The results suggested that EG/DTP flame‐retardant system promoted RPUF forming a compact, continuous and phosphorus‐rich char layer as a good fire barrier in combustion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46434.     

Synthesis of a phosphorus‐ and nitrogen‐containing flame retardant and evaluation of its application in waterborne polyurethane

A phosphorus‐ and nitrogen‐containing intumescent flame retardant, pentaerythritol di‐N‐hydroxyethyl phosphamide (PDNP), was synthesized with phosphorus oxychloride, pentaerythritol, and ethanolamine as raw materials. Using the prepared PDNP as a chain extender, a series of flame‐retardant waterborne polyurethanes (WPU) were prepared, and their structures were characterized using NMR and Fourier transform infrared spectroscopy (FTIR). Additionally, the thermal properties and flame retardancy of WPU films were investigated by thermogravimetric analysis, limiting oxygen index (LOI) tests, cone calorimeter tests, and thermogravimetry‐FTIR. These results indicated that PDNP materials exhibit good char‐forming ability at high temperature and that PDNP‐modified waterborne polyurethane obtained an LOI value of 26.0% for a PDNP content of 9 wt %. Finally, the morphology and the element distributions of char residues of WPU were analyzed by scanning electron microscopy and energy dispersive spectrometry after combustion. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46093.     

Synergistic effect of aluminum hydroxide and expandable graphite on the flame retardancy of polyisocyanurate–polyurethane foams

For the first time, expandable graphite (EG) and aluminum hydroxide (ATH) was combined to improve the flame retardancy of polyisocyanurate–polyurethane (PIR–PUR) foam. The limited oxygen index increased from 26.5 for the PIR–PUR matrix to an incredible value of 92.8 when 24 phr (parts per 100 of matrix) EG and 60 phr ATH were incorporated into the matrix. Based on morphology observation and thermogravimetric analysis, it was speculated that two factors contributed to the improvement of flame retardancy primarily. First, ATH could effectively induce “villi” like particles, which was useful to form a dense char. The compact char layer could effectively impede the transport of bubbles and heat. Second, ATH and EG accelerated the initial degradation and fluffy char was quickly generated on the surface of the composites. Thus, the degradation of the composite was slowed down and the diffusion of volatile combustible fragments to flame zone was delayed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39936.     

Halogen Free flame retardant rigid polyurethane foam with a novel phosphorus−nitrogen intumescent flame retardant

A novel phosphorous‐nitrogen containing intumescent flame retardant, toluidine spirocyclic pentaerythritol bisphosphonate (TSPB), was synthesized and characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR). Flame retardant rigid polyurethane foams (TSPB‐RPUF) were prepared by using TSPB. The flame retardancy of TSPB on rigid polyurethane foams (RPUF) was investigated by the limiting oxygen index (LOI), vertical burning test, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and FTIR. The results showed TSPB exhibited better compatibility with RPUF and lesser negative influence on the mechanical properties of TSPB‐RPUF. When the content of TSPB was 30 pph, the LOI of TSPB‐RPUF could reach 26.5%, and a UL‐94 V‐0 rating was achieved. Furthermore, the TSPB‐RPUF exhibited an outstanding water resistance that it could still obtain a V‐0 rating after water soaking. TGA showed the charring ability of RPUF was relatively poor, However, the residual weight of TSPB‐RPUF was improved greatly. SEM and FTIR indicated the intumescent chars formed from TSPB‐RPUF were compact and smooth, which was a critical factor for protecting the substrate material from burning. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39581.     

Synergistic effect of expandable graphite and α‐type zirconium phosphate on flame retardancy of polyurethane elastomer

Organically modified zirconium phosphate (OZrP) was prepared by cation exchange of natural counterions with hexadecyltri‐n‐butylphosphonium bromide. Subsequently, OZrP and expandable graphite (EG) were incorporated into polyurethane elastomer (PUE), and the thermal stability and flame retardancy of PUE composites were investigated. The thermogravimetric analysis indicated that partial substitution of EG with OZrP could improve both the thermal stability and char yield of PUE composites. The cone calorimetry and limiting oxygen index test showed that partial substitution of EG with OZrP could further enhance the flame retardancy of PUE composites and presented an excellent synergistic effect. Moreover, the char residue of PUE composites was analyzed by X‐ray photoelectron spectroscopy and laser Raman spectroscopy. Their results indicated that the synergistic effect of the physical barrier to prevent transmission of heat and mass between condensed and gas phases. Therefore, the further combustion of the nether material could be inhibited, which created better flame retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45188.     

Mechanical property improvement and fire hazard reduction of ammonium polyphosphate microencapsulated in rigid polyurethane foam

Ammonium polyphosphate (APP) is an effective phosphorus-containing flame retardant. But APP also has excellent hygroscopic capacity and decreases the mechanical property of composite. The aim of the study was to microencapsulate APP with polymethyl methacrylate (PMMA) to prepare microencapsulated ammonium polyphosphate (PMAPP) in order to eliminate the harmful effects caused by the mechanical property of composite. The microcapsules are characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and hydroscopicity test and observed by scanning electron microscopy (SEM). Fire hazard of rigid polyurethane foam (RPUF) is evaluated using a cone calorimeter and limited oxygen index test. The mechanical property of RPUF is studied by compressive strength test. The results show that APP has been microencapsulated by PMMA successfully and the shell does not decrease the beneficial effect of APP on fire hazard of RPUF. Furthermore, the shell also reduces the damage of APP on the mechanical property of composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48307.     

Preparation and properties of a novel flame retardant polyurethane quasi‐prepolymer for toughening phenolic foam

A novel phosphorus‐ and nitrogen‐containing polyurethane quasi‐prepolymer (PNPUQP) was synthesized and incorporated into phenolic foam (PF) in different ratios in order to improve the toughness. The structure of PNPUQP was confirmed by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR). The effects of PNPUQP on the flame retardant properties, thermal stability and mechanical properties of modified PF were investigated. The results suggested that the addition of 3 wt % PNPUQP increased the toughness of PF and improved the flame retardancy. The investigation on the morphology of PF and modified PF by scanning electron microscope (SEM) certified the good toughness of the PNPUQP on PF. Additionally, the thermal properties of the foams were investigated by thermogravimetric analysis (TGA) under N₂ atmosphere. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42424.