Synthesis of Flame-retardant Phosphaphenanthrene Derivatives with High Phosphorus Contents

2014 ◽  
Vol 67 (11) ◽  
pp. 1688 ◽  
Author(s):  
Jinyun Zheng ◽  
Yujian Yu ◽  
Lulu Zhang ◽  
Xiaomin Zhen ◽  
Yufen Zhao

Two novel types of phosphate derivatives of phosphaphenanthrene with a high phosphorus content were prepared by phosphorylation reaction between either 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-methanol (ODOPM) or 2-(6-oxido-6H-dibenz<c,e><1,2>oxaphosphorin-6-yl)-1,4-benzenediol (ODOPB) and dialkyl phosphoryl chloride. The structures of all compounds were characterised by 1H NMR, 13C NMR, 31P NMR, Fourier transform infrared spectroscopy, and high-resolution mass spectrometry. The thermal stability of representative compounds was determined by thermal gravimetric analysis and differential scanning calorimetry. The results showed that the compounds have excellent resistance to oxidation, high thermal stability with an onset decomposition temperature above 200°C, and a high char yield over 25 %, owing to the high P content. The representative compound was added to conventional electrolytes of lithium-ion batteries as flame retardant additive, and the self-extinguishing time and ionic conductivity were measured. The result showed that the compounds have effective flame retardant properties.


2013 ◽  
Vol 2013 ◽  
pp. 1-10 ◽  
Author(s):  
Ming-Yuan Shen ◽  
Chen-Feng Kuan ◽  
Hsu-Chiang Kuan ◽  
Chia-Hsun Chen ◽  
Jia-Hong Wang ◽  
...  

In this investigation, silane was grafted onto the surface of graphene nanosheets (GNSs) through free radical reactions, to form Si-O-Et functional groups that can undergo the sol-gel reaction. To improve the compatibility between the polymer matrix and the fillers, epoxy monomer was modified using a silane coupling agent; then, the functionalized GNSs were added to the modified epoxy to improve the thermal stability and strengthen the flame-retardant character of the composites. High-resolution X-ray photoelectron spectrometry reveals that when the double bonds in VTES are grafted to the surfaces of GNSs. Solid-state 29Si nuclear magnetic resonance presents that the distribution of the signal associated with the T3structure is wide and significant, indicating that the functionalization reaction of the silicone in the modified epoxy and VTES-GNSs increases the network-like character of the structures. Thermal gravimetric analysis, the integral procedure decomposition temperature, and limiting oxygen index demonstrate that the GNSs composites that contained silicon had a higher thermal stability and stronger flame-retardant character than pure epoxy. The dynamic storage modulus of all of the m-GNSs containing composites was significantly higher than that of the control epoxy, and the modulus of the composites increased with the concentration of m-GNSs.



Materials ◽  
2019 ◽  
Vol 12 (16) ◽  
pp. 2641 ◽  
Author(s):  
Tang ◽  
Wang ◽  
Wang ◽  
Cheng ◽  
Guo

The demand for eco-friendly renewable natural fibers has grown in recent years. In this study, a series of polypropylene-based composites reinforced with single bamboo fibers (SBFs), prepared by non-woven paving and a hot-pressing process, were investigated. The influence of the content of SBF on impact strength, flexural strength, and water resistance was analyzed. The properties of the composites were greatly affected by the SBF content. Impact strength increased as SBF content increased. The modulus of rupture and modulus of elasticity show an optimum value, with SBF contents of 40% and 50%, respectively. The surface morphology of the fractured surfaces of the composites was characterized by scanning electron microscopy. The composites showed poor interfacial compatibility. The water resistance indicates that the composites with higher SBF contents have higher values of water absorption and thickness swelling, due to the hydrophilicity of the bamboo fibers. The thermal properties of the composites were characterized by thermal gravimetric analysis and by differential scanning calorimetry. The thermal stability of the composites was gradually reduced, due to the poor thermal stability of SBFs. In the composites, the maximum decomposition temperature corresponding to SBF shows an increasing trend. However, the maximum decomposition temperature of polypropylene was not influenced by SBF content. The melting point of the polypropylene in the composites was lower relative to pure polypropylene, although it was not affected by increasing SBF content.



Polymers ◽  
2021 ◽  
Vol 13 (5) ◽  
pp. 707
Author(s):  
Ya-Ping Yang ◽  
An-Chi Huang ◽  
Yan Tang ◽  
Ye-Cheng Liu ◽  
Zhi-Hao Wu ◽  
...  

Lithium-ion batteries with conventional LiPF6 carbonate electrolytes are prone to failure at high temperature. In this work, the thermal stability of a dual-salt electrolyte of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium difluoro(oxalato)borate (LiODFB) in carbonate solvents was analyzed by accelerated rate calorimetry (ARC) and differential scanning calorimetry (DSC). LiTFSI-LiODFB dual-salt carbonate electrolyte decomposed when the temperature exceeded 138.5 °C in the DSC test and decomposed at 271.0 °C in the ARC test. The former is the onset decomposition temperature of the solvents in the electrolyte, and the latter is the LiTFSI-LiODFB dual salts. Flynn-Wall-Ozawa, Starink, and autocatalytic models were applied to determine pyrolysis kinetic parameters. The average apparent activation energy of the dual-salt electrolyte was 53.25 kJ/mol. According to the various model fitting, the thermal decomposition process of the dual-salt electrolyte followed the autocatalytic model. The results showed that the LiTFSI-LiODFB dual-salt electrolyte is significantly better than the LiPF6 electrolyte in terms of thermal stability.



2021 ◽  
Author(s):  
Yajun Chen ◽  
Jingxiu He ◽  
Zhe Sun ◽  
Bo Xu ◽  
Juan Li ◽  
...  

Abstract Cellulose nanocrystals (CNCs) have been used as bio-based carbon source in intumescent system. However, CNCs have the disadvantages of low onset decomposition temperature and decompose and carbonize during processing. We, herein, demonstrated the design of phosphazene-containing CNCs (P/N-CNCs) with great thermal stability and outstanding charring ability. The TGA results showed that the initial decomposition temperature of P/N-CNCs was increased from 202.4 ℃ to 272.2 ℃ (increased by 34.5%), and the residual char at 700 ℃ was increased from 24.9 wt% to 55.8 wt% compared with CNCs. Then, flame retardant PLA composites were prepared by blending PLA, P/N-CNCs with ammonium polyphosphate (APP), melamine (MPP), aluminum hypophosphite (AHP) and piperazine pyrophosphate (PPAP), respectively. The thermal stability, flame retardant properties and mechanical properties of PLA composites were investigated. The results showed that the flame retardant system constructed by 7 wt% APP and 3 wt% P/N-CNCs had the best effect in PLA. PLA/7APP/3P/N-CNCs had the highest limit oxygen index value (28.1%), the lowest peak heat release rate (266 kW/m2) and reached UL 94 V-0 rating. Moreover, the tensile strength, impact strength and elongation at break of PLA/7APP/3P/N-CNCs were increased by 7.3%, 18.6% and 29.4%, respectively, compared with these properties of PLA/7APP/ 3CNCs. This work provides a new idea for the design of CNCs with great thermal stability and outstanding charring ability, and offers a new method for the preparation of high-performance flame-retardant PLA composites.



Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1562
Author(s):  
Yunxian Yang ◽  
De-Yi Wang ◽  
Laia Haurie ◽  
Zhiqi Liu ◽  
Lu Zhang

Some crop by-products are considered to be promising materials for the development of novel biobased products for industrial applications. The flammability of these alternatives to conventional materials is a constraint to expanded applications. Polylactide (PLA) composites containing a combination of oxidized corn pith fiber (OCC) and a biobased flame retardant (PA-THAM) have been prepared via an in situ modification method. SEM/EDS, FTIR and TGA were performed to establish that PA-THAM was coated onto the surface of OCC. The mechanical properties, thermal stability and fire behavior of PLA-based biocomposites were investigated. The incorporation of 5 phr PA-THAM imparted biocomposite good interfacial adhesion and increased decomposition temperature at 10% mass loss by 50 °C. The flame retardant properties were also improved, as reflected by an increased LOI value, a UL-94 V-2 rating, reduction of PHRR, and increased formation of char residue. Therefore, the introduction of 5 phr PA-THAM can maintain a good balance between flame retardancy and mechanical properties of this PLA/OCC system.



2013 ◽  
Vol 785-786 ◽  
pp. 714-717 ◽  
Author(s):  
Yi Zhou ◽  
Yong Zhu Cui ◽  
Guo Jun Liu ◽  
Li Hua Lv

An intumescent flame retardant (IFR) containing phosphorus and APP was applied to polyester fabric. The finishing process was optimized and the properties of treated fabric were characterized. The optimum process was as follows: the total dosage of IFR system was 40%, the mass ratio of phosphorus-containing flame retardants and APP was 7:3, and curing temperature was 180°C. The treated PET fabrics imparted good resistance to melt drop. Characterization of the thermo-gravimetric analysis, differential scanning calorimetry (DSC) indicated that much more residual char with intumescent structure, the incombustible gas and water were formed during combustion of flame retardant polyester fabric, whose decomposition temperature was lower compared to that of the untreated sample.



Crystals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 376
Author(s):  
Su-Mei Huang ◽  
Jiunn-Jer Hwang ◽  
Hsin-Jiant Liu ◽  
An-Miao Zheng

In this study, the montmorillonite (MMT) clay was modified with NH4Cl, and then the structures were exfoliated or intercalated in a polylactic acid (PLA) matrix by a torque rheometer in the ratio of 0.5, 3.0, 5.0 and 8.0 wt%. X-ray diffraction (XRD) revealed that the organic modified-MMT(OMMT) was distributed successfully in the PLA matrix. After thermal pressing, the thermal stability of the mixed composites was measured by a TGA. The mixed composites were also blended with OMMT by a co-rotating twin screw extruder palletizing system, and then injected for the ASTM-D638 standard specimen by an injection machine for measuring the material strength by MTS. The experimental results showed that the mixture of organophilic clay and PLA would enhance the thermal stability. In the PLA mixed with 3 wt% OMMT nanocomposite, the TGA maximum decomposition temperature (Tmax) rose from 336.84 °C to 339.08 °C. In the PLA mixed with 5 wt% OMMT nanocomposite, the loss of temperature rose from 325.14 °C to 326.48 °C. In addition, the elongation rate increased from 4.46% to 10.19% with the maximum loading of 58 MPa. After the vibrating hydrolysis process, the PLA/OMMT nanocomposite was degraded through the measurement of differential scanning calorimetry (DSC) and its Tg, Tc, and Tm1 declined.



Molecules ◽  
2020 ◽  
Vol 25 (9) ◽  
pp. 2158
Author(s):  
Nanci Vanesa Ehman ◽  
Diana Ita-Nagy ◽  
Fernando Esteban Felissia ◽  
María Evangelina Vallejos ◽  
Isabel Quispe ◽  
...  

Bio-polyethylene (BioPE, derived from sugarcane), sugarcane bagasse pulp, and two compatibilizers (fossil and bio-based), were used to manufacture biocomposite filaments for 3D printing. Biocomposite filaments were manufactured and characterized in detail, including measurement of water absorption, mechanical properties, thermal stability and decomposition temperature (thermo-gravimetric analysis (TGA)). Differential scanning calorimetry (DSC) was performed to measure the glass transition temperature (Tg). Scanning electron microscopy (SEM) was applied to assess the fracture area of the filaments after mechanical testing. Increases of up to 10% in water absorption were measured for the samples with 40 wt% fibers and the fossil compatibilizer. The mechanical properties were improved by increasing the fraction of bagasse fibers from 0% to 20% and 40%. The suitability of the biocomposite filaments was tested for 3D printing, and some shapes were printed as demonstrators. Importantly, in a cradle-to-gate life cycle analysis of the biocomposites, we demonstrated that replacing fossil compatibilizer with a bio-based compatibilizer contributes to a reduction in CO2-eq emissions, and an increase in CO2 capture, achieving a CO2-eq storage of 2.12 kg CO2 eq/kg for the biocomposite containing 40% bagasse fibers and 6% bio-based compatibilizer.



2021 ◽  
Author(s):  
Pundalik Mali ◽  
Narendra Sonawane ◽  
Nilesh Pawar ◽  
Vikas Patil

Abstract A novel melamine-phosphate trifunctional acrylate MPTO) was successfully synthesized via simple cyclization of hexamethylolmelamine (HMM) with phosphorous oxychloride (POCl3) followed by addition reaction of hydroxyethylmethacrylate (HEMA). The molecular structure of MPTO was identified by FTIR and 1H-NMR, 13C-NMR, and GC-MS spectra. The synthesized MPTO oligomer was impregnated with polyurethane acrylate to make the various formulation of UV-cured coatings. The polyurethanes-MPTO oligomers were coated on wood and galvanized steel panels. The properties of UV-cured PU-MPTO were studied by differential scanning calorimeter (DSC), while their crystallinity by X-ray diffraction analysis (XRD). The thermo-gravimetric analysis (TGA) exhibited a high char yield of 18.4% at 800 °C. Moreover, coating films show prominent flame retardancy with UL-94 V-0 rating and maximum limiting index value (LOI) values of 34.8%, which are much higher than the common polyurethane coatings. The polyurethane coatings cured with MPTO exhibited excellent mechanical properties were estimated various tests such as adhesion, pencil hardness, solvent resistance, flexibility, and corrosion test. The coating performance revealed that MPTO improves the mechanical, thermal, and flame retardant properties because their unique structure contains melamine-phosphate moiety and long aliphatic chains of an acrylate ester. These high-performance melamine-based UV-curable coatings are promising for extensive applications.



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