A novel DOPO-containing flame retardant for epoxy resin

2016 ◽  
Vol 29 (8) ◽  
pp. 899-912 ◽  
Author(s):  
Liqiang Gu ◽  
Jianhui Qiu ◽  
Eiichi Sakai
Keyword(s):  
Flame Retardant ◽  
Nonisothermal Condition ◽  
Scanning Calorimetry ◽  
One Pot ◽  
Limiting Oxygen Index ◽  
Degradation Activation Energy ◽  
Index Value ◽  
Halogen Free ◽  
Modified Epoxy ◽  
Curing Procedure

A novel halogen-free flame retardant (6,6′-(((methylenebis(4,1-phenylene))bis(azanediyl))bis((4-hydroxy-3-methoxyphenyl)methylene))bis(6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide)(DP-DDM))) was synthesized via a one-pot procedure based on the Pudovik reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide and imine directly resulting from 3-methoxy-4-hydroxybenzaldehyde with 4,4′-methylenedianiline (DDM). The thermal curing behaviors of epoxy resins with different contents of DP-DDM were investigated by differential scanning calorimetry under a nonisothermal condition, aimed to suggest an optimized curing procedure in accordance with the property of DP-DDM. These DP-DDM-modified epoxy thermosets under optimized curing procedure showed high glass transition temperature and thermal degradation activation energy. Moreover, their high flame-retarding performance has been found: the epoxy thermosets with a relatively low addition amount of DP-DDM (on account of the phosphorus content of 0.75 wt%) can reach UL 94 V-0 (Instrumental analysis and measurements) rating with limiting oxygen index value of 34.5.

Synthesis and Characterization of Phosphorus-Containing Flame Retardant Polyamide 66

2020 ◽  
Vol 977 ◽  
pp. 102-107
Author(s):  
Yu Lei Zheng ◽  
Shuang Chen ◽  
Jia Hui Wang ◽  
Ru Xiao
Keyword(s):  
Flame Retardant ◽  
Oxygen Index ◽  
Mechanical And Thermal Properties ◽  
Index Test ◽  
Polyamide 66 ◽  
Scanning Calorimetry ◽  
One Pot ◽  
Limiting Oxygen Index ◽  
Step Process ◽  
Phosphorus Containing

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.

Synthesis of a 9,10-dihydro-9-oxo-10phosphaphenanthrene-10-oxide-based reactive flame-retardant curing agent

2020 ◽  
Vol 10 (9) ◽  
pp. 1470-1476
Author(s):  
Liang Yi ◽  
Zhixiong Huang ◽  
Cao Yu ◽  
Yongli Peng ◽  
Xinglong Liu
Keyword(s):  
Flame Retardant ◽  
Oxygen Index ◽  
Carbon Residue ◽  
Flexural Property ◽  
Curing Agent ◽  
Scanning Calorimetry ◽  
One Pot ◽  
Limiting Oxygen Index ◽  
H Nmr ◽  
Reactive Flame Retardant

This paper aims to prepare a new curing agent, reactive flame retardant (DTF), through one-pot synthesis of 9,10-Dihydro-9-oxo-10-phosphaphenanthrene-10-oxide (DOPO), formaldehyde and triacetonediamine for Epoxy resin (EP). This new DTF was successful prepared through Fourier-transform infrared, 1H NMR, and 31P NMR spectroscopy. The flame-retardant epoxy thermoset was prepared using the 4′4-diaminodiphenylmethane (DDM) as a co-curing agent. The analysis results using the differential scanning calorimetry (DSC) showed that DTF can cure EP and improve the carbon residue yield of epoxy thermoset after burning. It observed that if the content of phosphorus was 1.0 wt%, the limiting oxygen index (LOI) of EP/DDM/DPT-4 was 30.4%, and UL94 reached the V-0 rating. The highest tensile property of the epoxy thermoset reached 98.56 MPa (P content = 0.5%), whereas the highest flexural property reached 137.28 MPa (P content = 0.75%), and the highest impact property reached 24.1 KJ · m–2 (P content = 0.5%).

Preparation and Characterization of Soybean Oil-based Flame Retardant Rigid Polyurethane Foams Containing Phosphaphenanthrene Groups

2020 ◽  
Vol 17 (10) ◽  
pp. 760-771
Author(s):  
Qirui Gong ◽  
Niangui Wang ◽  
Kaibo Zhang ◽  
Shizhao Huang ◽  
Yuhan Wang
Keyword(s):  
Soybean Oil ◽  
Flame Retardant ◽  
Chemical Structure ◽  
Cell Structure ◽  
Polyurethane Foams ◽  
Limiting Oxygen Index ◽  
Rigid Polyurethane Foams ◽  
Degradation Activation Energy ◽  
Ft Ir

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.

Synthesis, characterization and thermal degradation kinetics of azomethine-based halogen-free flame-retardant polyphosphonates

2018 ◽  
Vol 31 (1) ◽  
pp. 86-96 ◽  
Author(s):  
R Vini ◽  
S Thenmozhi ◽  
SC Murugavel
Keyword(s):  
Tensile Strength ◽  
Thermal Degradation ◽  
Flame Retardant ◽  
Degradation Kinetics ◽  
Thermal Degradation Kinetics ◽  
Spectroscopic Techniques ◽  
Scanning Calorimetry ◽  
Limiting Oxygen Index ◽  
Weight Percentage ◽  
Ul 94

In this study, azomethine polyphosphonates were synthesized by solution polycondensation of phenylphosphonic dichloride with various azomethine diols such as [4-(4-hydroxy phenyl) iminomethyl] phenol, [(4-(4-hydroxy-3-methoxy phenyl) iminomethyl)] phenol and [4-(4-hydroxy-3-ethoxy phenyl) iminomethyl] phenol using triethylamine catalyst at ambient temperature. The structure of the synthesized polymers was confirmed by Fourier transform infrared and 1H-, 13C- and 31P- nuclear magnetic resonance spectroscopic techniques. Thermal properties of the polymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry under nitrogen atmosphere. The TGA data showed that the synthesized polyphosphonates produce high char yield at 600°C due to the presence of phosphorous atom in the polymer chain and hence have good flame-retardant properties. One of the synthesized polyphosphonate was blended with commercial diglycidyl ether of bisphenol-A (DGEBA) resin in various weight percentage and cured with commercial curing agent triethylene tetramine (TETA). The polyphosphonates-blended epoxy thermosets have tensile strength in the range of 5–41 MPa and the percentage of elongation at breaks was 4–18. It was found that the incorporation of polyphosphonates into epoxy thermoset decreased the tensile strength from 41 MPa to 5 MPa, whereas the elongation at break value increased with increase in the weight percentage of polyphosphonate. The influence of polyphosphonates on the flame retardancy of blended thermosets was examined by limiting oxygen index (LOI) and vertical burning (UL-94) tests and found that the polymer samples achieved an increased UL-94 rating and the LOI values were in the range of 24–26. Broido and Horowitz–Metzger methods have been used to study the thermal degradation kinetic parameters.

A Facile Preparation of Environmentally-Benign and Flame-Retardant Coating on Wood by Comprising Polysilicate and Boric Acid

2021 ◽  
Author(s):  
Kaihao Wang ◽  
Shuheng Wang ◽  
Dan Meng ◽  
Dong Chen ◽  
Chenzhong Mu ◽  
...  
Keyword(s):  
Boric Acid ◽  
Flame Retardant ◽  
Wood Sample ◽  
Low Cost ◽  
Treated Wood ◽  
Environmentally Benign ◽  
Wood Combustion ◽  
Flame Resistance ◽  
Limiting Oxygen Index ◽  
Index Value

Abstract For the sake of direct using on the built wooden buildings, a green flame resistance coating comprising sodium polysilicate (SPS) and boric acid was prepared. With weight gain of only 10 wt.%, the treated wood sample (SPS/B-wood) performed improved limiting oxygen index value of 40.3% and passed the V-0 rating in UL-94 test. Additionally, the total heat release, total smoke production and peak carbon monoxide production of SPS/B-wood sample were decreased by 24.5%, 36.0% and 59.4% respectively, compared with that of control wood sample. The residue of SPS/B-wood sample was increased to 54.0% from 18.4% of control wood sample at 800oC in the thermogravimetry analysis. The flame retardant mechanism was suggested that SPS and boric acid formed Si-O-B and Si-O-Si contained structures, isolating the heat and smoke transfer during wood combustion. Notably, NaOH, introduced by the SPS/B coating, catalyzed the lignin to form compact and high-quality char. To conclude, this low-cost and easily-operated coating has a promising future utilizing in the villages with dense wood buildings.

scholarly journals Bio-Based Polyamide 1010 with a Halogen-Free Flame Retardant Based on Melamine–Gallic Acid Complex

Polymers ◽  
2020 ◽  
Vol 12 (7) ◽  
pp. 1482
Author(s):  
Nicoleta Levinta ◽  
Mihai Cosmin Corobea ◽  
Zina Vuluga ◽  
Cristian-Andi Nicolae ◽  
Augusta Raluca Gabor ◽  
...  
Keyword(s):  
Flame Retardant ◽  
Gallic Acid ◽  
Fire Behavior ◽  
Dynamic Mechanical Properties ◽  
Melt Mixing ◽  
Acid Complex ◽  
Limiting Oxygen Index ◽  
Molar Ratios ◽  
Halogen Free ◽  
Polyamide 1010

This work aims at developing polyamide 1010 (PA1010) composites with improved fire behavior using a halogen-free flame-retardant system based on melamine (Me) and gallic acid (GA) complexes (MA). The MA complexes were formed by hydrogen bonding, starting from 1:2, 1:1, 2:1 Me:GA molar ratios. PA1010 composites were obtained by melt mixing, followed by compression molding. MA provided a plasticizing effect on the PA1010 matrix by decreasing the glass transition temperature. The influence of MA on PA1010 chain packaging was highlighted in the X-ray diffraction patterns, mainly in the amorphous phase, but affected also the α and γ planes. This was reflected in the dynamic mechanical properties by the reduction of the storage modulus. H-bonds occurrence in MA complexes, improved the efficiency in the gaseous form during fire exposure, facilitating the gas formation and finally reflected in thermal stability, thermo-oxidative stability, LOI results, and vertical burning behavior results. PA1010 containing a higher amount of GA in the complex (MA12) displayed a limiting oxygen index (LOI) value of 33.6%, much higher when compared to neat PA1010 (25.8%). Vertical burning tests showed that all the composites can achieve the V-0 rating in contrast with neat PA1010 that has V-2 classification.

scholarly journals Synthesis of a DOPO-triazine additive and its flame-retardant effect in rigid polyurethane foam

e-Polymers ◽  
2019 ◽  
Vol 19 (1) ◽  
pp. 235-243 ◽  
Author(s):  
Lin Liu ◽  
Rui Lv
Keyword(s):  
Flame Retardant ◽  
Polyurethane Foam ◽  
Cell Structure ◽  
Rigid Polyurethane Foam ◽  
Flame Resistance ◽  
Limiting Oxygen Index ◽  
Flame Retarded ◽  
Flame Retardant Properties ◽  
Mechanical Performances ◽  
Halogen Free

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.

Flame-retardant activity of modified boron nitride nanosheets to cotton

2019 ◽  
Vol 90 (5-6) ◽  
pp. 512-522 ◽  
Author(s):  
Hong Liu ◽  
Yang Du ◽  
Shaohua Lei ◽  
Zhuoqun Liu
Keyword(s):  
Boron Nitride ◽  
Flame Retardant ◽  
Hexagonal Boron Nitride ◽  
Cotton Fabrics ◽  
High Yield ◽  
Limiting Oxygen Index ◽  
Boron Nitride Nanosheets ◽  
Boron Nitride Powder ◽  
Coated Fabrics ◽  
Index Value

Boron nitride nanosheets (BNN) were prepared by molten hydroxide-assisted liquid exfoliation from hexagonal boron nitride powder with an effectively high yield, and then modified with hexachlorocyclotriphosphazene (HCCP) to obtain HCCP-BNN. The series of samples were applied to prepare flame-retardant cotton fabrics with the impregnation-drying method, and successful treatment was confirmed by scanning electron microscopy. The combustion performance of the as-prepared cotton fabrics was tested and evaluated. After coating with HCCP-BNN, the combustion rate of the fabric is reduced in vertical and horizontal combustion conditions and the limiting oxygen-index value of cotton fabric increases to 24.1, becoming less flammable than the blank cotton. The fibrous structure of the BNN and HCCP-BNN coated fabrics is relatively complete after combustion, which indicates that BNN have a certain protective effect on the fabric. The results demonstrate HCCP-BNN as an effective flame-retardant for cotton fabrics.

scholarly journals Development of Bioepoxy Resin Microencapsulated Ammonium-Polyphosphate for Flame Retardancy of Polylactic Acid

Molecules ◽  
2019 ◽  
Vol 24 (22) ◽  
pp. 4123 ◽  
Author(s):  
Kata Decsov ◽  
Katalin Bocz ◽  
Beáta Szolnoki ◽  
Serge Bourbigot ◽  
Gaëlle Fontaine ◽  
...  
Keyword(s):  
Ftir Spectroscopy ◽  
Flame Retardant ◽  
Polylactic Acid ◽  
Ammonium Polyphosphate ◽  
Cone Calorimetry ◽  
Scanning Calorimetry ◽  
Electron Microscopic ◽  
Sem Images ◽  
Limiting Oxygen Index ◽  
Microencapsulated Ammonium Polyphosphate

Ammonium-polyphosphate (APP) was modified by microencapsulation with a bio-based sorbitol polyglycidyl ether (SPE)-type epoxy resin and used as a flame retardant additive in polylactic acid (PLA) matrix. The bioresin-encapsulated APP (MCAPP) particles were characterized using Fourier transform infrared (FTIR) spectroscopy and Raman mapping, particle size distribution was determined by processing of scanning electron microscopic (SEM) images. Interaction between the APP core and the bioresin shell was revealed by combined thermogravimetric analysis (TGA)‑FTIR spectroscopy. The APP to SPE mass ratio of 10 to 2 was found to be optimal in terms of thermal, flammability, and mechanical properties of 15 wt% additive containing biocomposites. The bioresin shell effectively promotes the charring of the APP-loaded PLA composites, as found using TGA and cone calorimetry, and eliminates the flammable dripping of the specimens during the UL-94 vertical burning tests. Thus, the V-0 rating, the increased limiting oxygen index, and the 20% reduced peak of the heat release rate was reached compared to the effects of neat APP. Furthermore, better interfacial interaction of the MCAPP with PLA was indicated by differential scanning calorimetry and SEM observation. The stiff interphase resulted in increased modulus of these composites. Besides, microencapsulation provided improved water resistance to the flame retardant biopolymer system.

scholarly journals Flame-Retardant Mechanism of Layered Double Hydroxides in Asphalt Binder

Materials ◽  
2019 ◽  
Vol 12 (5) ◽  
pp. 801 ◽  
Author(s):  
Kai Zhu ◽  
Yunhe Wang ◽  
Daquan Tang ◽  
Qiang Wang ◽  
Haihang Li ◽  
...  
Keyword(s):  
Flame Retardant ◽  
Layered Double Hydroxides ◽  
Photoelectron Spectroscopy ◽  
Cone Calorimeter ◽  
Asphalt Binder ◽  
Bound Water ◽  
Asphalt Binders ◽  
Scanning Calorimetry ◽  
Limiting Oxygen Index ◽  
Double Hydroxides

The flame retardancy of asphalt binders with layered double hydroxides (LDHs) was investigated using limiting oxygen index (LOI) and cone calorimeter tests. The flame-retardant mechanism of the LDHs was also studied with thermogravimetry and differential scanning calorimetry (TG–DSC), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). The cone calorimeter testing results indicated that 2 wt.% of the LDHs can decease the peak heat and smoke release rate of asphalt binders. Because a low dose of LDHs can be well dispersed in asphalt binder and favor the formation of polyaromatic structures during combustion, the thermal oxidation resistance and compactness of the char layer can be improved. The LOI of asphalt binder can be increased and the heat and smoke release during combustion can be decreased with 25 wt.% LDHs. The decomposition of LDHs can absorb the heat release of the initial two stages of asphalt combustion and reduce the burning rate of asphalt. Due to the loss of loosely bound water in the LDHs during the blending process and the decrease of dispersibility at a high LDH dose, the improvement of thermal stability is limited.

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