Effect of tris(1-chloro-2-propyl)phosphate in combination with aluminum hypophosphite and melamine polyphosphate on flame retardancy and thermal decomposition of rigid polyurethane foams

2021 ◽  
pp. 0021955X2110019
Author(s):  
Daifang Xu ◽  
Kejing Yu ◽  
Kun Qian ◽  
Weiguo Zhao

RPUF with tris(1-chloro-2-propyl)phosphate (TCPP), melamine polyphosphate (MPP) and aluminum hypophosphite (AHP) alone, as well as their binary and ternary blends, were prepared via a one-step process. The effect of TCPP in combination with AHP and MPP on flame retardancy and thermal decomposition in the RPUF has been investigated. The results show that adding TCPP, MPP and AHP into RPUF simultaneously can significantly ensure the uniform cell structure, enhance the compressive strength, thermal stability and fire resistance of RPUF, decrease the thermal conductivity, the release of toxic HCN at high temperature. TGA results indicate that partial substitution of TCPP with MPP and AHP could improve the char residue. When the content of TCPP is 10 wt%, the optimal ratio of MPP and DPER was 1/2, the TCPP10/MPP3.3/AHP6.7/RPUF sample reached a V1 rating in vertical UL-94 test with a limiting oxygen index of 27.4%. The compressive strength and specific compressive strength (compressive strength/density) for TCPP10/MPP3.3/AHP6.7/RPUF sample increased about 82.6% and 44.3% compared to that of pure RPUF, respectively. The cone calorimeter test results showed that adding EG, MPP and AHP into RPUF simultaneously can significantly decrease the heat release rate (HRR), total heat release (THR) and smoke emission behavior of RPUF sample. Based on these facts, a potential flame-retardant mechanism was proposed.

Polymers ◽  
2019 ◽  
Vol 11 (7) ◽  
pp. 1129 ◽  
Author(s):  
Ningjing Wu ◽  
Jihang Yu ◽  
Wenchao Lang ◽  
Xiaobing Ma ◽  
Yue Yang

A novel flame-retardant and toughened bio-based poly(lactic acid) (PLA)/glycidyl methacrylate-grafted natural rubber (GNR) composite was fabricated by sequentially dynamical vulcanizing and reactive melt-blending. The surface modification of aluminum hypophosphite (AHP) enhanced the interfacial compatibility between the modified aluminum hypophosphite by silane (SiAHP) and PLA/GNR matrix and the charring ability of the PLA/GNR/SiAHP composites to a certain extent, and the toughness and flame retardancy of the PLA/GNR/SiAHP composites were slightly higher than those of PLA/GNR/AHP composites, respectively. The notched impact strength and elongation of the PLA composite with 20 wt. %GNR and 18 wt.% SiAHP were 13.1 kJ/m2 and 72%, approximately 385% and 17 fold higher than those of PLA, respectively, and its limiting oxygen index increased to 26.5% and a UL-94 V-0 rating was achieved. Notedly, the very serious melt-dripping characteristics of PLA during combustion was completely suppressed. The peak heat release rate and total heat release values of the PLA/GNR/SiAHP composites dramatically reduced, and the char yield obviously increased with an increasing SiAHP content in the cone calorimeter test. The good flame retardancy of the PLA/GNR/SiAHP composites was suggested to be the result of a synergistic effect involving gaseous and condensed phase flame-retardant mechanisms. The high-performance flame-retardant PLA/GNR/SiAHP composites have great potential application as replacements for petroleum-based polymers in the automotive interior and building fields.


2019 ◽  
Vol 2019 ◽  
pp. 1-8 ◽  
Author(s):  
Nhung Hac Thi ◽  
Duy Linh Pham ◽  
Nguyen Thi Hanh ◽  
Ho Thi Oanh ◽  
Thi Hai Yen Duong ◽  
...  

The rigid polyurethane foams (RPUFs) filled with organoclay cloisite 20A and expandable graphite (EG) were prepared by the one-step expanding foam method. Flame behavior, mechanical properties, and thermal conductivity of the composites were investigated. The vertical burning test (UL-94V) and limiting oxygen index (LOI) showed that the flame retardancy was increased proportionally with the content of EG in PU composite. However, the presence of EG filler impaired the thermal insulation and the compressive strength of the composite. In this report, we proved that organoclay could improve the compressive strength, thermal insulation, and flame retardancy of EG/polyurethane composites. This work can contribute to the development of environment-friendly flame-retardant products for green growth.


2020 ◽  
pp. 089270572092513
Author(s):  
Xincheng Guo ◽  
Nian Liu ◽  
Lingtong Li ◽  
Zhuyu Bai ◽  
Xiaolang Chen ◽  
...  

In this article, the flammable behaviors and synergistic effects of modified expanded graphite (MEG) with zinc borate (ZB) on flame-retardant high-density polyethylene/ethylene vinyl acetate (HDPE/EVA) composites containing magnesium hydroxide (MH) and aluminum hydroxide (ATH) are investigated by the Underwriters Laboratories-94 (UL-94) test, limiting oxygen index (LOI), cone calorimeter test (CCT), thermal gravimetric analysis (TGA), Fourier transform infrared (FTIR), differential scanning calorimetry, and tensile tests. The LOI, UL-94, and CCT results show that the synergistic effect of MEG and ZB can improve the flame retardancy of the composites. With the addition of ZB and MEG, the LOI value increases, and the UL-94 reaches the V-0 rating. The heat release rate and total heat release decrease, respectively. The data obtained from the TGA indicate that the synergistic effects of ZB with MEG increase the decomposition temperature when 2 phr ZB and 8 phr MEG are added into the composites. The data from FTIR show that HMEG8 and HMEG10 composites produce phosphate at high temperatures, which promotes the formation of stable and compact charred layer. All the results show that ZB and MEG have positive synergistic effects on HDPE/EVA composites containing MH and ATH. However, ZB and MEG play a negative role in the tensile properties of the HDPE/EVA composites.


2021 ◽  
Vol 41 (4) ◽  
pp. 281-288
Author(s):  
Hongmei Peng ◽  
Qi Yang

Abstract In this paper, cerium nitrate supported silica was prepared as a new type of catalytic synergist to improve the flame retardancy in polypropylene. When 1% of Ce(NO3)2 supported SiO2 was added, the vertical combustion performance of UL-94 of polypropylene composites was improved to V-0, the limiting oxygen index (LOI) was increased to 33.5. From the thermogravimetric analysis (TGA), the residual carbon of C and D was increased by about 6% at high temperature compared with B. When adding supported catalyst, the heat release rate (HRR) and total heat release (THR) were significantly reduced according to the microscale combustion calorimetry (MCC), the HRR of sample E with 2% synergist was the lowest. The combustion behaviors of intumescent flame retardant sample B and sample D were analyzed by cone calorimeter test (CCT), the HRR of sample D with supported synergist was significantly reduced, and the PHRR decreased from 323 kW/m2 to 264 kW/m2. The morphologies of the residue chars after vertical combustion of polypropylene composites observed by scanning electron microscopy (SEM) gave positive evidence that the supported synergist could catalyze the decomposition of intumescent flame retardants into carbon, which was the main reason for improving the flame retardancy of materials.


2021 ◽  
Vol 36 (5) ◽  
pp. 519-528
Author(s):  
J.-L. Li ◽  
C.-T. Gao ◽  
X. Sun ◽  
S.-G. Peng ◽  
Y.-W. Wang ◽  
...  

Abstract Synergistic flame-retardant effect of aluminum diethyl phosphinate (AlPi) in intumescent flame retardant polypropylene (PP/IFR) system and the flame-retardant mechanism were investigated. The flame retardancy of PP/IFR/AlPi (the mass ratio of IFR to AlPi is 2 : 1) was the best, which was proved by the results of the limiting oxygen index (LOI) test, UL-94 test, and cone calorimeter test ( CCT) test. Here, the LOI value of the sample was as high as 34% and passed the V–0 rating in UL–94 test. The peak heat release rate (PHRR) decreased by 92.57%, the total heat release (THR) reduced by 90.52%. Thermogravimetric (TGA) data showed that the introduction of AlPi improved thermal stability and changed the thermal degradation behavior of PP/IFR composites. Interestingly, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDXS) and laser Raman spectroscopy (LRS) proved that PP/IFR/AlPi had formed more residual carbon, but the flame retardancy was worse than PP/IFR/AlPi. This is because when the mass ratio of IFR to AlPi is 2 : 1, the synergy between IFR and AlPi was significant, gas-phase flame retardant and condensed-phase flame retardant reached a balance and obtained the best flame retardant effect.


2020 ◽  
Vol 17 (10) ◽  
pp. 760-771
Author(s):  
Qirui Gong ◽  
Niangui Wang ◽  
Kaibo Zhang ◽  
Shizhao Huang ◽  
Yuhan Wang

A phosphaphenanthrene groups containing soybean oil based polyol (DSBP) was synthesized by epoxidized soybean oil (ESO) and 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO). Soybean oil based polyol (HSBP) was synthesized by ESO and H2O. The chemical structure of DSBP and HSBP were characterized with FT-IR and 1H NMR. The corresponding rigid polyurethane foams (RPUFs) were prepared by mixing DSBP with HSBP. The results revealed apparent density and compression strength of RPUFs decreased with increasing the DSBP content. The cell structure of RPUFs was examined by scanning electron microscope (SEM) which displayed the cells as spherical or polyhedral. The thermal degradation and flame retardancy of RPUFs were investigated by thermogravimetric analysis, limiting oxygen index (LOI), and UL 94 vertical burning test. The degradation activation energy (Ea) of first degradation stage reduced from 80.05 kJ/mol to 37.84 kJ/mol with 80 wt% DSBP. The RUPF with 80 wt% DSBP achieved UL94 V-0 rating and LOI 28.3. The results showed that the flame retardant effect was mainly in both gas phase and condensed phase.


Polymers ◽  
2021 ◽  
Vol 13 (8) ◽  
pp. 1286
Author(s):  
Kyung-Who Choi ◽  
Jun-Woo Kim ◽  
Tae-Soon Kwon ◽  
Seok-Won Kang ◽  
Jung-Il Song ◽  
...  

The use of halogen-based materials has been regulated since toxic substances are released during combustion. In this study, polyurethane foam was coated with cationic starch (CS) and montmorillonite (MMT) nano-clay using a spray-assisted layer-by-layer (LbL) assembly to develop an eco-friendly, high-performance flame-retardant coating agent. The thickness of the CS/MMT coating layer was confirmed to have increased uniformly as the layers were stacked. Likewise, a cone calorimetry test confirmed that the heat release rate and total heat release of the coated foam decreased by about 1/2, and a flame test showed improved fire retardancy based on the analysis of combustion speed, flame size, and residues of the LbL-coated foam. More importantly, an additional cone calorimeter test was performed after conducting more than 1000 compressions to assess the durability of the flame-retardant coating layer when applied in real life, confirming the durability of the LbL coating by the lasting flame retardancy.


2018 ◽  
Vol 31 (2) ◽  
pp. 186-196 ◽  
Author(s):  
Shuang Yang ◽  
Yefa Hu ◽  
Qiaoxin Zhang

In this article, a phosphorus–nitrogen-containing flame retardant (DOPO-T) was successfully synthesized by nucleophilic substitution reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and cyanuric chloride. The chemical structure of DOPO-T was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance (NMR) and phosphorous-31 NMR, and elemental analysis. DOPO-T was then blended with diglycidyl ether of bisphenol-A to prepare flame-retardant epoxy resins. Thermal properties, flame retardancy, and combustion behavior of the cured epoxy resins were evaluated by differential scanning calorimetry, thermogravimetric analysis, limited oxygen index (LOI) measurement, UL94 vertical burning test, and cone calorimeter test. The results indicated that the glass transition temperature ( Tg) and temperature at 5% weight loss of epoxy resin (EP)/DOPO-T thermosets were gradually decreased with the increasing content of DOPO-T. DOPO-T catalyzed the decomposition of EP matrix in advance. The flame-retardant performance of EP thermosets was significantly enhanced with the addition of DOPO-T. EP/DOPO-T-0.9 sample had an LOI value of 36.2% and achieved UL94 V-1 rating. In addition, the average of heat release rate, peak of heat release rate, average of effective heat of combustion, and total heat release (THR) of EP/DOPO-T-0.9 sample were decreased by 32%, 48%, 23%, and 31%, respectively, compared with the neat EP sample. Impressively, EP/DOPO-T thermosets acquired excellent flame retardancy under low loading of flame retardant.


Polymers ◽  
2020 ◽  
Vol 12 (1) ◽  
pp. 90
Author(s):  
Xiao Wu ◽  
Ganglan Jiang ◽  
Yan Zhang ◽  
Lin Wu ◽  
Yanjiang Jia ◽  
...  

Enhancement of flame retardancy of a colorless and transparent semi-alicyclic polyimide (PI) film was carried out by the incorporation of phosphazene (PPZ) flame retardant (FR). For this purpose, PI-1 matrix was first synthesized from hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA) and 4,4′-oxydianiline (ODA). The soluble PI-1 resin was dissolved in N,N-dimethylacetamide (DMAc) to afford the PI-1 solution, which was then physically blended with PPZ FR with the loading amounts in the range of 0–25 wt.%. The PPZ FR exhibited good miscibility with the PI-1 matrix when its proportion was lower than 10 wt.% in the composite films. PI-3 composite film with the PPZ loading of 10 wt.% showed an optical transmittance of 75% at the wavelength of 450 nm with a thickness of 50 μm. More importantly, PI-3 exhibited a flame retardancy class of UL 94 VTM-0 and reduced total heat release (THR), heat release rate (HRR), smoke production rate (SPR), and rate of smoke release (RSR) values during combustion compared with the original PI-1 film. In addition, PI-3 film had a limiting oxygen index (LOI) of 30.9%, which is much higher than that of PI-1 matrix (LOI: 20.1%). Finally, incorporation of PPZ FR decreased the thermal stability of the PI films. The 10% weight loss temperature (T10%) and the glass transition temperature (Tg) of the PI-3 film were 411.6 °C and 227.4 °C, respectively, which were lower than those of the PI-1 matrix (T10%: 487.3 °C; Tg: 260.6 °C)


Polymers ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 168 ◽  
Author(s):  
Pablo Acuña ◽  
Zhi Li ◽  
Mercedes Santiago-Calvo ◽  
Fernando Villafañe ◽  
Miguel Rodríguez-Perez ◽  
...  

Three types of expandable graphite (EG) differing in particle size and expansion volume, are compared as flame retardant additives to rigid polyurethane foams (RPUFs). In this paper we discuss microstructure, thermal stability, fire behavior, and compression performance. We find that ell size distributions were less homogeneous and cell size was reduced. Furthermore, thermal conductivity increased along with EG loading. Thermogravimetric analysis (TGA) showed that EG only increased residue yield differently. The results indicate that a higher expansion of EG increased the limiting oxygen index (LOI) value, whereas a bigger particle size EG improved the rating of the vertical burning test (UL94). Results from the cone calorimeter test showed that a bigger particle size EG effectively reduced peak of heat release rate (pHRR). Furthermore, a higher expansion, led to a decrease in smoke production (TSP). The combination of both characteristics gives extraordinary results. The physical–mechanical characterization of the EG/RPUF foams revealed that their compression performance decreased slightly, mostly due to the effect of a bigger size EG.


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