scholarly journals Study on Thermal and Flame Retardant Properties of Phosphorus-containing Polyimides

2020 ◽  
Vol 72 (4) ◽  
pp. 13-21
Author(s):  
Diana Serbezeanu ◽  
Tachita Vlad-Bubulac ◽  
Elena Hamciuc ◽  
Corneliu Hamciuc ◽  
Gabriela Lisa ◽  
...  

The present study aimed to design macromolecular architectures having imide core in the main chain and bearing two 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide heterocycles in the side chain of each structural units as a synergetic two components key factor to induce attractive flame retardant properties in the resulted materials. The synthesis pathway consisted in the classical polycondensation reaction strategy using a phosphorus-containing diamine synthesized in the laboratory and three commercial dianhydrides co-monomers. The chemical structure confirmation of the phosphorus-containing polyimides has been performed by means of FTIR and NMR spectroscopy. The thermal stability of the products was introspected through TGA analysis. The char yields measured at 900oC ranged between 35% and 54%. Using these parameters limiting oxygen index values were theoretically calculated. Also, the microscale combustion calorimetry measurements have been conducted, in order to investigate the combustion mechanism of the synthesized phosphorus-containing polyimides.

Polymers ◽  
2018 ◽  
Vol 10 (8) ◽  
pp. 871 ◽  
Author(s):  
Rong-Kun Jian ◽  
Long Xia ◽  
Yuan-Fang Ai ◽  
De-Yi Wang

The aim of this work is to prepare flame-retardant biobased poly(lactic acid) materials through incorporating a novel flame retardant dihydroxy-containing ammonium phosphate (DAP) derived from 2-chloro-5,5-dimethyl-1,3,2-dioxaphosphinane-2-oxide (DOP) and 2-amino-2-methyl-1,3-propanediol (AMPD). Interestingly, PLA modified with only 0.5% DAP passed UL-94 V-0 rating, and possessed a limiting oxygen index (LOI) value of 24.6%, which would further increase with the increasing loading of DAP. PLA/DAP did not exhibit obviously improved results in terms of heat release rate (HRR), as the loading of DAP was relatively low. It was found that DAP showed little effect on the thermal stability of PLA and the onset decomposition temperatures of PLA and PLA/DAP blends were very close. Besides, the degree of crystallization increased because of the plasticized effect of DAP. Based on the analyses of flame-retardant mechanism of DAP, it disclosed that DAP decomposed to generate incombustible compounds, such as water and ammonia, to dilute the concentration of oxygen and fuels, and then release some phosphorus-containing fragments that could produce phosphorus-containing free radicals to interrupt free-radical reactions, and finally noncombustible melt dripping was produced so as to bring away large amount of heat and stop the feedback of heat to the matrix.


Polymers ◽  
2018 ◽  
Vol 11 (1) ◽  
pp. 48 ◽  
Author(s):  
Muhammad Maqsood ◽  
Gunnar Seide

Starch, being a polyhydric compound with its natural charring ability, is an ideal candidate to serve as a carbonization agent in an intumescent system. This charring ability of starch, if accompanied by an acidic source, can generate an effective intumescent flame retardant (IFR) system, but the performance of starch-based composites in an IFR system has not been tested in detail. Here, we describe a PLA-based IFR system consisting of ammonium polyphosphate (APP) as acidic source and cornstarch as carbon source. We prepared different formulations by melt compounding followed by molding into sheets by hot pressing. The thermal behavior and surface morphology of the composites was investigated by thermogravimetric analysis and scanning electron microscopy respectively. We also conducted limiting oxygen index (LOI), UL-94, and cone calorimetry tests to characterize the flame-retardant properties. Cone calorimetry revealed a 66% reduction in the peak heat release rate of the IFR composites compared to pure PLA and indicated the development of an intumescent structure by leaving a residual mass of 43% relative to the initial mass of the sample. A mechanism of char formation has also been discussed in detail.


Materials ◽  
2019 ◽  
Vol 13 (1) ◽  
pp. 127 ◽  
Author(s):  
Yu Sun ◽  
Yazhen Wang ◽  
Li Liu ◽  
Tianyuan Xiao

A 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO) acrylate, (6-oxidodibenzo [c,e][1,2] oxaphosphinin-6-yl) methyl acrylate (DOPOAA), has been prepared. Copolymers of styrene (St) and DOPOAA were prepared by emulsion polymerization. The chemical structures of copolymers containing levels of DOPOAA were verified using Fourier transform infrared (FT-IR) spectroscopy and 1H nuclear magnetic resonance (1H-NMR) spectroscopy. The thermal properties and flame-retardant behaviors of DOPO-containing monomers and copolymers were observed using thermogravimetric analysis and micro calorimetry tests. From thermogravimetric analysis (TGA), it was found out that the T5% for decomposition of the copolymer was lower than that of polystyrene (PS), but the residue at 700 °C was higher than that of PS. The results from micro calorimetry (MCC) tests indicated that the rate for the heat release of the copolymer combustion was lower than that for PS. The limiting oxygen index (LOI) for combustion of the copolymer rose with increasing levels of DOPOAA. These data indicate that copolymerization of the phosphorus-containing flame-retardant monomer, DOPOAA, into a PS segment can effectively improve the thermal stability and flame retardancy of the copolymer.


2012 ◽  
Vol 125 (2) ◽  
pp. 1219-1225 ◽  
Author(s):  
Yuan-Qin Xiong ◽  
Xu-Yong Zhang ◽  
Jia Liu ◽  
Ming-Ming Li ◽  
Fei Guo ◽  
...  

2015 ◽  
Vol 2015 ◽  
pp. 1-7 ◽  
Author(s):  
Shibin Nie ◽  
Chi Zhang ◽  
Chao Peng ◽  
De-yi Wang ◽  
Daowei Ding ◽  
...  

A char forming agent (CFA) and silica-gel microencapsulated ammonium polyphosphate (Si-MCAPP) were selected to form novel intumescent flame retardant system to prepare flame retardant polypropylene (PP) composites, and then the influences of nanoporous nickel phosphates (NiP) on the thermal and flame retardant properties of flame retardant PP composites were studied by the real time FTIR (RTFTIR) spectra, limited oxygen index (LOI) test, and the scanning electron microscopy. RTFTIR shows the addition of NiP can improve the thermal stability of flame retardant PP composites. LOI test shows LOI value is increased with the increase of the content of NiP, and the optimized concentration of NiP is 1.0%. Furthermore, smoke toxicity of the novel flame retardant PP composites was studied by mice experiment. The upper limit of the no death smoke concentration of the composite is 12.37 mg/L.


Polymers ◽  
2019 ◽  
Vol 11 (2) ◽  
pp. 380 ◽  
Author(s):  
Wei Zhao ◽  
Yongxiang Li ◽  
Qiushi Li ◽  
Yiliang Wang ◽  
Gong Wang

The flame retardant modification of epoxy (EP) is of great signification for aerospace, automotive, marine, and energy industries. In this study, a series of EP composites containing different variations of phosphorus-containing polysulfone (with a phosphorus content of approximately 1.25 wt %) were obtained. The obtained EP/polysulfone composites had a high glass transition temperature (Tg) and high flame retardancy. The influence of phosphorus-containing compounds (ArPN2, ArPO2, ArOPN2 and ArOPO2) on the thermal properties and flame retardancy of EP/polysulfone composites was investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), a UL-94 vertical burning test, and cone calorimeter tests. The phosphorus-containing polysulfone enhanced the thermal stability of EP. The more stable porous char layer, less flammable gases, and a lower apparent activation energy at a high degree of conversion demonstrated the high gas inhibition effect of phosphorus-containing compounds. Moreover, the gas inhibition effect of polysulfone with a P–C bond was more efficient than the polysulfone with a P–O–C bond. The potential for optimizing flame retardancy while maintaining a high Tg is highlighted in this study. The flame-retardant EP/polysulfone composites with high thermal stability broaden the application field of epoxy.


2020 ◽  
Vol 977 ◽  
pp. 102-107
Author(s):  
Yu Lei Zheng ◽  
Shuang Chen ◽  
Jia Hui Wang ◽  
Ru Xiao

Polyamide 66 (PA66) benefits from excellent mechanical properties and good chemical resistance, which enabled wide application of this material in various industrial fields; however, it suffers from high flammability. Generally, preparation of a flame retardant PA from a reactive flame retardant involves a two-step process. In this study, the flame retardant PA66s (FRPA66s) are synthesized via a one-pot melt copolycondensation route by using a reactive phosphorus-containing flame retardant (FR-B). Then, molecular weight, some mechanical and thermal properties along with flame retardant properties of FRPA66s were investigated by gel permeation chromatography (GPC), instron material testing, differential scanning calorimetry (DSC), thermogravimetry (TG) analysis, vertical burning test (UL 94), and limiting oxygen index test (LOI) techniques. The experimental results confirmed that FRPA66s synthesized by the one-pot method have very similar properties compared to those obtained via the two-step process. Moreover, the prepared materials showed good non-flammability behavior with limiting oxygen index value of over 30% and a vertical burning test result of V-0 rating.


2015 ◽  
Vol 30 (6) ◽  
pp. 816-826 ◽  
Author(s):  
Yiren Huang ◽  
Jianwei Yang ◽  
Zhengzhou Wang

Flame-retardant properties of ammonium polyphosphate (APP) and its two microcapsules, APP with a shell of melamine–formaldehyde (MF) resin (MFAPP) and APP with a shell of epoxy resin (EPAPP), were studied in styrene–butadiene–styrene (SBS). The results indicate that APP after the microencapsulation leads to an increase in limiting oxygen index in SBS compared with APP. When dipentaerythritol is incorporated into the SBS composites containing the APP microcapsules, a further improvement in flame retardancy of the composites is observed. The microencapsulation does not result in much improvement of mechanical properties. Moreover, the effect of a compatibilizer (SBS grafted with maleic anhydride) on flame-retardant and mechanical properties of SBS/APP composites was investigated.


2014 ◽  
Vol 1033-1034 ◽  
pp. 931-936
Author(s):  
Cong Yan Chen ◽  
Rui Lan Fan ◽  
Guan Qun Yun

A novel intumescent flame retardant (IFR) containing ferrocene and caged bicyclic phosphate groups, 1-oxo-4-[4'-(ferrocene carboxylic acid phenyl ester)] amide-2, 6, 7-trioxa-1-phosphabicyclo- [2.2.2] octane (PFAM), was successfully synthesized. The synthesized PFAM were added to flammable polyurethane (PU) as flame retardants and smoke suppressants. The structure of PFAM was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H NMR) and elemental analysis. Thermal stability of PFAM was tested by themogravimetric analysis (TGA). The results revealed that PFAM had good thermal stability and high char weight, the char weight up to 54% at 600 °C. Flammability properties of PU/PFAM composites were investigated by limiting oxygen index (LOI) test and UL-94 test, respectively. The results of LOI tests showed that the addition of PFAM enhanced flame retardancy of PU. When the content of PFAM reaches to 3%, the LOI value is 22.2. The morphologies of the char for PU and PU/3% PFAM composite can be obtained after LOI testing were examined by SEM. The results demonstrated that PFAM could promote to form the compact and dense intumescent char layer. Experiments showed that, the PFAM application of polyurethane showed positive effect.


e-Polymers ◽  
2019 ◽  
Vol 19 (1) ◽  
pp. 235-243 ◽  
Author(s):  
Lin Liu ◽  
Rui Lv

AbstractA DOPO (9,10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide)-based halogen-free flame retardant (ODOPM-CYC) was synthesized and incorporated in rigid polyurethane foam (RPUF). The structure of ODOPM-CYC was characterized by Fourier transform infrared spectra (FTIR), 1H NMR and 31P NMR. The effects of ODOPM-CYC on the flame resistance, mechanical performances, thermal properties and cell structure of RPUF were also investigated. The results showed that the incorporation of ODOPM-CYC strikingly enhanced flame retardant properties of RPUF. The flame retarded RPUF acquired a limiting oxygen index (LOI) value of 26% and achieved UL-94 V-0 rating with the phosphorus content of 3 wt%. The smoke production rate (SPR) also showed an obvious decrease and total smoke release (TSR) was 39.8% lower than that of neat RPUF. Besides, the results demonstrated that the incorporation of ODOPM-CYC provided RPUF better thermal stability but did not show any obvious influence on its thermal conductivity.


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