scholarly journals Synthesis of Novel Polymeric Acrylate-Based Flame Retardants Containing Two Phosphorus Groups in Different Chemical Environments and Their Influence on the Flammability of Poly (Lactic Acid)

Polymers ◽  
2020 ◽  
Vol 12 (4) ◽  
pp. 778 ◽  
Author(s):  
Jacob Sag ◽  
Philipp Kukla ◽  
Daniela Goedderz ◽  
Hendrik Roch ◽  
Stephan Kabasci ◽  
...  

Novel polymeric acrylate-based flame retardants (FR 1–4) containing two phosphorus groups in different chemical environments were synthesized in three steps and characterized via nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mass spectrometry (MS). Polylactic acid (PLA) formulations with the synthesized compounds were investigated to evaluate the efficiency of these flame retardants and their mode of action by using TGA, UL94, and cone calorimetry. In order to compare the results a flame retardant polyester containing only one phosphorus group (ItaP) was also investigated in PLA regarding its flame inhibiting effect. Since the fire behavior depends not only on the mode of action of the flame retardants but also strongly on physical phenomena like melt dripping, the flame retardants were also incorporated into PLA with higher viscosity. In the UL94 vertical burning test setup, 10% of the novel flame retardants (FR 1–4) is sufficient to reach a V-0 rating in both PLA types, while a loading of 15% of ItaP is not enough to reach the same classification. Despite their different structure, TGA and cone calorimetry results confirmed a gas phase mechanism mainly responsible for the highly efficient flame retardancy for all compounds. Finally, cone calorimetry tests of the flame retardant PLA with two heat fluxes showed different flame inhibiting efficiencies for different fire scenarios.

Polymers ◽  
2018 ◽  
Vol 11 (1) ◽  
pp. 30 ◽  
Author(s):  
Vera Realinho ◽  
David Arencón ◽  
Marcelo Antunes ◽  
José Velasco

The present work deals with the study of phosphorus flame retardant microcellular acrylonitrile–butadiene–styrene (ABS) parts and the effects of weight reduction on the fire and mechanical performance. Phosphorus-based flame retardant additives (PFR), aluminum diethylphosphinate and ammonium polyphosphate, were used as a more environmentally friendly alternative to halogenated flame retardants. A 25 wt % of such PFR system was added to the polymer using a co-rotating twin-screw extruder. Subsequently, microcellular parts with 10, 15, and 20% of nominal weight reduction were prepared using a MuCell® injection-molding process. The results indicate that the presence of PFR particles increased the storage modulus and decreased the impact energy determined by means of dynamic-mechanical-thermal analysis and falling weight impact tests respectively. Nevertheless, the reduction of impact energy was found to be lower in ABS/PFR samples than in neat ABS with increasing weight reduction. This effect was attributed to the lower cell sizes and higher cell densities of the microcellular core of ABS/PFR parts. All ABS/PFR foams showed a self-extinguishing behavior under UL-94 burning vertical tests, independently of the weight reduction. Gradual decreases of the second peak of heat release rate and time of combustion with similar intumescent effect were observed with increasing weight reduction under cone calorimeter tests.


Molecules ◽  
2019 ◽  
Vol 24 (22) ◽  
pp. 4123 ◽  
Author(s):  
Kata Decsov ◽  
Katalin Bocz ◽  
Beáta Szolnoki ◽  
Serge Bourbigot ◽  
Gaëlle Fontaine ◽  
...  

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.


Polymers ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 180 ◽  
Author(s):  
Neeraj Mandlekar ◽  
Aurélie Cayla ◽  
François Rault ◽  
Stéphane Giraud ◽  
Fabien Salaün ◽  
...  

In this study, two different types of industrial lignin (i.e., lignosulphonate lignin (LL) and kraft lignin (DL)) were exploited as charring agents with phosphorus-based flame retardants for polyamide 11 (PA11). The effect of lignins on the thermal stability and fire behavior of PA11 combined with phosphinate additives (namely, aluminum phosphinate (AlP) and zinc phosphinate (ZnP)) has been studied by thermogravimetric analysis (TGA), UL 94 vertical flame spread, and cone calorimetry tests. Various blends of flame retarded PA11 were prepared by melt process using a twin-screw extruder. Thermogravimetric analyses showed that the LL containing ternary blends are able to provide higher thermal stability, as well as a developed char residue. The decomposition of the phosphinates led to the formation of phosphate compounds in the condensed phase, which promotes the formation of a stable char. Flammability tests showed that LL/ZnP ternary blends were able to achieve self-extinction and V-1 classification; the other formulations showed a strong melt dripping and higher burning. In addition to this, cone calorimetry results showed that the most enhanced behavior was found when 10 wt % of LL and AlP were combined, which strongly reduced PHRR (−74%) and THR (−22%), due to the interaction between LL and AlP, which not only promotes char formation but also confers the stability to char in the condensed phase.


2014 ◽  
Vol 881-883 ◽  
pp. 863-866
Author(s):  
Chao Peng ◽  
Shi Bin Nie ◽  
Lei Liu ◽  
Qi Lin He ◽  
Yuan Hu ◽  
...  

Nanoporous nickel phosphates (VSB-1) was synthesized by hydrothermal method. Then VSB-1 was added to the ammonium polyphosphate and pentaerythritol system in polypropylene (PP) matrix.The synergistic effect of VSB-1 with intumescent flame retardants (IFR) was studied by cone calorimetry test. The results of cone calorimetry show that heat release rate peak (pHRR) and total heat release (THR) of intumescent flame retardant PP with 2wt% VSB-1 decrease remarkably compared with that of without VSB-1. The pHRR and THR decrease respectively from 1140 to 286.0 kW/m2, and from 96.0 to 63.2 MJ/m2.


BioResources ◽  
2020 ◽  
Vol 16 (1) ◽  
pp. 1311-1324
Author(s):  
Yating Hua ◽  
Chungui Du ◽  
Huilong Yu ◽  
Ailian Hu ◽  
Rui Peng ◽  
...  

Flame-retardant silicate-intercalated calcium aluminum hydrotalcites (CaAl-SiO3-LDHs) were synthesized to treat bamboo for retardancy, to overcome the bamboo’s flammability and reduce the production of toxic smoke during combustion. The microstructure, elemental composition, flame retardancy, and smoke suppression characteristics of the bamboo before and after the fire-retardant treatment with different pressure impregnation were studied using a scanning electron microscope (SEM), elemental analysis (EDX), and cone calorimetry. It was found that CaAl-SiO3-LDHs flame retardants can effectively fill and cover the cell wall surface and the cell cavity of bamboo without damaging the microstructure. As compared to the non-flame-retardant bamboo, the heat release rate (HRR) of the CaAl-SiO3-LDHs flame-retardant bamboo was significantly reduced, the total heat release (THR) decreased by 31.3%, the residue mass increased by 51.4%, the time to ignition (TTI) delay rate reached 77.8%, the mass loss rate (MLR) decreased, and the carbon formation improved. Additionally, as compared to the non-flame-retardant bamboo, the total smoke release (TSR) of the CaAl-SiO3-LDHs flame-retardant bamboo decreased by 38.9%, and the carbon monoxide yield (YCO) approached zero. Thus, the CaAl-SiO3-LDHs flame-retardant bamboo has excellent flame-retardancy and smoke suppression characteristics.


Materials ◽  
2019 ◽  
Vol 12 (14) ◽  
pp. 2217 ◽  
Author(s):  
Tianxiang Liang ◽  
Jianan Cai ◽  
Shumei Liu ◽  
Hualin Lai ◽  
Jianqing Zhao

A way to suppress the deterioration in mechanical properties of polyamide 6 (PA6) is required, especially with high loading of flame retardants in the matrix. In this study, a novel aromatic Schiff base diepoxide (DES) was synthesized. It exhibited an efficient chain extension effect on PA6 and a synergistic flame-retardant effect with aluminum diethylphosphinate (AlPi) for PA6. The PA6 composite with 16 wt.% AlPi only passed UL-94 V-0 rating at 1.6 mm thickness, while the combination of 1.5 wt.% DES with 13 wt.% AlPi induced PA6 to achieve a UL-94 V-0 rating at 0.8 mm thickness. The tensile, flexural, and Izod notched impact strengths were increased by 16.2%, 16.5%, and 24.9%, respectively, compared with those of V-0 flame-retarded PA6 composites with 16 wt.% AlPi. The flame-retarded mechanism of PA6/AlPi/DES was investigated by cone calorimetry and infrared characterization of the char residues and pyrolysis products. These results showed that DES had a synergistic effect with AlPi in condensed-phase flame retardation by promoting the production of aluminum phosphorus oxides and polyphosphates in the char residues.


Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4305 ◽  
Author(s):  
Valeriia Karaseva ◽  
Anne Bergeret ◽  
Clément Lacoste ◽  
Hélène Fulcrand ◽  
Laurent Ferry

The aim of this work was an investigation of the ability of gallic (GA) and ellagic (EA) acids, which are phenolic compounds encountered in various plants, to act as flame retardants (FRs) for epoxy resins. In order to improve their fireproofing properties, GA and EA were treated with boric acid (to obtain gallic acid derivatives (GAD) and ellagic acid derivatives (EAD)) to introduce borate ester moieties. Thermogravimetric analysis (TGA) highlighted the good charring ability of GA and EA, which was enhanced by boration. The grafting of borate groups was also shown to increase the thermal stability of GA and EA that goes up respectively from 269 to 528 °C and from 496 to 628 °C. The phenolic-based components were then incorporated into an epoxy resin formulated from diglycidyl ether of bisphenol A (DGEBA) and isophorone diamine (IPDA) (72, 18, and 10 wt.% of DGEBA, IPDA, and GA or EA, respectively). According to differential scanning calorimetry (DSC), the glass transition temperature (Tg) of the thermosets was decreased. Its values ranged from 137 up to 108 °C after adding the phenolic-based components. A cone calorimeter was used to evaluate the burning behavior of the formulated thermosets. A significant reduction of the peak of heat release rate (pHRR) for combustion was detected. Indeed, with 10 wt.% of GA and EA, pHRR was reduced by 12 and 44%, respectively, compared to that for neat epoxy resin. GAD and EAD also induced the decrease of pHRR values by 65 and 33%, respectively. In addition, a barrier effect was observed for the resin containing GAD. These results show the important influence of the biobased phenolic compounds and their boron derivatives on the fire behavior of a partially biobased epoxy resin.


Polymers ◽  
2020 ◽  
Vol 12 (8) ◽  
pp. 1701 ◽  
Author(s):  
Farzad Seidi ◽  
Elnaz Movahedifar ◽  
Ghasem Naderi ◽  
Vahideh Akbari ◽  
Franck Ducos ◽  
...  

Polypropylene (PP) is a commodity plastic known for high rigidity and crystallinity, which is suitable for a wide range of applications. However, high flammability of PP has always been noticed by users as a constraint; therefore, a variety of additives has been examined to make PP flame-retardant. In this work, research papers on the flame retardancy of PP have been comprehensively reviewed, classified in terms of flame retardancy, and evaluated based on the universal dimensionless criterion of Flame Retardancy Index (FRI). The classification of additives of well-known families, i.e., phosphorus-based, nitrogen-based, mineral, carbon-based, bio-based, and hybrid flame retardants composed of two or more additives, was reflected in FRI mirror calculated from cone calorimetry data, whatever heat flux and sample thickness in a given series of samples. PP composites were categorized in terms of flame retardancy performance as Poor, Good, or Excellent cases. It also attempted to correlate other criteria like UL-94 and limiting oxygen index (LOI) with FRI values, giving a broad view of flame retardancy performance of PP composites. The collected data and the conclusions presented in this survey should help researchers working in the field to select the best additives among possibilities for making the PP sufficiently flame-retardant for advanced applications.


1995 ◽  
Vol 13 (2) ◽  
pp. 104-126 ◽  
Author(s):  
Edward D. Weil ◽  
Veena Choudhary

Melamine has shown broad utility as a flame retardant in plastics although its commercial use to date as a flame retardant additive has been principally in coatings and flexible urethane foams. Its mode of action appears to involve endothermic sublimation and vapor-phase dissociation, but it also undergoes conversion to non-volatile products and ammonia. Combinations of melamine with other flame retardants of all types have been reported as hav ing advantageous performance. The present review covers the patent and non- patent literature with 130 references.**


2021 ◽  
Vol 11 (13) ◽  
pp. 5952
Author(s):  
Julio Marti ◽  
Jimena de la Vega ◽  
De-Yi Wang ◽  
Eugenio Oñate

Many polymer-made objects show a trend of melting and dripping in fire, a behavior that may be modified by adding flame retardants (FRs). These affect materials properties, e.g., heat absorption and viscosity. In this paper, the effect of a flame retardant on the fire behavior of polymers in the UL 94 scenario is studied. This goal is achieved essentially by applying a new computational strategy that combines the particle finite element method for the polymer with an Eulerian formulation for air. The sample selected is a polypropylene (PP) with magnesium hydroxide at 30 wt.%. For modelling, values of density, conductivity, specific heat, viscosity, and Arrhenius coefficients are obtained from different literature sources, and experimental characterization is performed. However, to alleviate the missing viscosity at a high temperature, three viscosity curves are introduced on the basis of the viscosity curve provided by NIST and the images of the test. In the experiment, we burn the specimen under the UL 94 condition, recording the process and measuring the temperature evolution by means of three thermocouples. The UL 94 test is solved, validating the methodology and quantifying the effect of FR on the dripping behavior. The numerical results prove that well-adjusted viscosity is crucial to achieving good agreement between the experimental and numerical results in terms of the shape of the polymer and the temperature evolution inside the polymer.


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