Improving flame retardancy of in-situ silica-epoxy nanocomposites cured with aliphatic hardener: Combined effect of DOPO-based flame-retardant and melamine

Silica-epoxy nanocomposites were prepared via an “in-situ ”sol-gel synthesis process and a phosphorus (P) flame-retardant i.e. 6H-dibenz[c,e][1,2]oxaphosphorin,6-[(1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]oct- 4-yl)methoxy]-, 6-oxide (DP) and melamine (Mel) were further added to the matrix to improve its fire perfor- mance. The main components of epoxy resin were bisphenol A diglycidyl ether (DGEBA) and isophorone diamine (IPDA) hardener. The addition of DP as well as silica alone into the epoxy system stopped the melt dripping phe- nomena in the vertical fire test (UL 94), however, the addition of melamine was crucial for achieving the highest fire classification (UL 94-V0 rating). The presence of DP and Mel in the silica-epoxy nanocomposite promoted a large reduction (ranging from 53% up to 80%) in the heat release rate (HRR) and a delay (up to 31%) in the igni- tion time in the cone calorimetry experiments. Improved fire performance of the epoxy system was attributed to i) a condensed phase activity of silica, DP and melamine to form a protective thermal barrier during combustion and ii) a minor gas phase flame inhibition activity of DOPO component of DP. The mechanical characterization of the epoxy nanocomposites through tensile tests showed that the addition of DP increases the stiffness of the epoxy resin, resulting in a strong increase of Young modulus (up to 32%) and in a slight decrease of fracture strength, elongation at break and toughness. An increased glass transition temperature (up to 8%) of the epoxy system possibly due to hydrogen bonds and polar interactions of DP with the matrix was also observed

Fire and mechanical properties of DGEBA-based epoxy resin cured with a cycloaliphatic hardener: combined action of silica, melamine and DOPO-derivative

The effect of the addition of additives such as melamine (Mel), silica nanoparticles and a phosphorus-based compound, i.e. 3-(6-oxidodibenzo[c,e][1,2]oxaphosphinin-6-yl)propenamide (DA), on the fire and mechanical performance of a bisphenol A diglycidyl ether (DGEBA)-based epoxy resin cured with isophoronediamine has been investigated. A UL 94-V0 classification was achieved for epoxy resin containing DA at 2 wt% of phosphorus loading. However, addition of silica nano particleswas necessary to avoid melt dripping. The incorporation of DA and Mel to the epoxy resin promoted a remarkable reduction (48% to 70%) in the heat release rate (HRR) values, a significant delay (up to 47%) in the ignition time in cone calorimetry experiments, and thus an increase (~75%) in the time to flashover. Evolved gas, thermal and fire analysiswas used to propose the combined mode of action of DA, Mel and silica in the fire performance improvement of the epoxy system. Tensile and three-point bending flexural tests showed that the addition of DA increases the rigidity of the resin, resulting in a strong increase in the Young's modulus (up to 34%) and in a slight reduction in fracture strength, elongation break and toughness which is typical for non-reactive additives

Multiparameter toxicity assessment of novel DOPO-derived organophosphorus flame retardants

Halogen-free organophosphorus flame retardants are considered as replacements for the phased-out class of polybrominated diphenyl ethers (PBDEs). However, toxicological information on new flame retardants is still limited. Based on their excellent flame retardation potential, we have selected three novel 9,10- dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives and assessed their toxicological profile using a battery of in vitro test systems in order to provide toxicological information before their large-scale production and use. PBDE-99, applied as a reference compound, exhibited distinct neuroselective cytotoxicity at concentrations ≥10 μM. 6-(2-((6-Oxidodibenzo[1,2]oxaphosphinin-6-yl)amino)ethoxydibenzo[1,2]oxaphosphinine-6-oxide) (ETA-DOPO) and 6,6′-(ethane-1,2-diylbis(oxy))bis(dibenzo[1,2]oxaphosphinine-6-oxide) (EG-DOPO) displayed adverse effects at concentrations >10 μM in test systems reflecting the properties of human central and peripheral nervous system neurons, as well as in a set of non-neuronal cell types. DOPO and its derivative 6,6′-(ethane-1,2-diylbis(azanediyl))bis(6H-dibenzo[1,2]oxaphosphine-6-oxide) (EDA-DOPO) were neither neurotoxic, nor did they exhibit an influence on neural crest cell migration, or on the integrity of human skin equivalents.The two compounds furthermore displayed no inflammatory activation potential, nor did they affect algae growth or daphnia viability at concentrations ≤400 μM. Based on the superior flame retardation properties,biophysical features suited for use in polyurethane foams, and low cytotoxicity of EDA-DOPO, our results suggest that it is a candidate for the replacement of currently applied flame retardants

One-Pot Synthesis of P(O)-N Containing Compounds Using N-Chlorosuccinimide and Their Influence in Thermal Decomposition of PU Foams

Synthesis of intermediate containing P(O)-Cl bonds is the key to converting P(O)-H bonds to P(O)-N. In this work we have performed chlorination reactions of different H-phosphinates and H-phosphonates using N-chlorosuccinimide as an environmentally-benign chlorinating agent. The chlorination reaction showed high yield and high selectivity for transformation of P(O)-H bonds into P(O)-Cl analogues, resulting in an easily separable succinimide as the by-product. Using a one-pot synthesis methodology, we have synthesized a series of P(O)-N containing derivatives whose synthesis was found to be dependent on the reaction solvents and the starting materials. The synthesized P(O)-N compounds were incorporated in flexible polyurethane foam (FPUF) and screened for their influence in thermal decomposition of FPUFs using thermogravimetric analysis (TGA) and a microscale combustion calorimeter (MCC). All solid P(O)-N compounds influenced the first-stage decomposition of FPUFs, which resulted in an accelerated decomposition or temporary stabilization of this stage. However, the liquid P(O)-N derivatives volatilize at an earlier stage and could be active in the gas phase. In addition, they also work in condensed phase via acid catalyzed decomposition for FPUFs

Insight into the Synthesis and Characterization of Organophosphorus-Based Bridged Triazine Compounds

In this article, we report the synthesis of 2,4,6-substituted s-triazine-based organophosphorus compounds via a two-step process, which enables their production in high yields, and with a high purity as solids. In the first step, a Michaelis–Arbuzov rearrangement of cyanuric chloride with triethyl phosphite afforded 2,4,6-trisdiethoxyphosphinyl-1,3,5-triazine (HEPT). Subsequently, the nucleophilic substitution reaction on the triazine carbon was achieved, owing to the electron-withdrawing ability of the phosphonate groups. This characteristic of HEPT facilitated its derivatization with bi-functional amines, producing novel P–C containing bridged triazine organophosphorus compounds. The molecular structures of all of the compounds were confirmed by NMR spectroscopy, CHN elemental analysis, and single crystal X-ray analysis. In the thermogravimetric analysis in an N2 environment, >33% char formation was observed for the bridged compounds. The chemical composition analysis of the char obtained under the oxidative thermal decomposition of the bridged compounds confirmed the presence of phosphorus- and nitrogen-enriched species, which indicate their function in the condensed phase. Comparatively, the detection of HPO and H–C≡P in the gas phase during the pyrolysis of the bridged compounds can act as a source for PO•, which is known for its gas phase flame inhibition reactions. The synergy of significant char formation and the generation of intermediates leading to PO• during pyrolysis makes these molecules promising flame-retardant additives

Flammability of Cellulose-Based Fibers and the Effect of Structure of Phosphorus Compounds on Their Flame Retardancy

Cellulose fibers are promoted for use in various textile applications due their sustainable nature. Cellulose-based fibers vary considerably in their mechanical and flammability properties depending on their chemical composition. The chemical composition of a cellulose-based fiber is further dependent on their source (i.e., seed, leaf, cane, fruit, wood, bast, and grass). Being organic in nature, cellulose fibers, and their products thereof, pose considerable fire risk. In this work we have compared the flammability properties of cellulose fibers obtained from two different sources (i.e., cotton and peat). Compared to cotton cellulose textiles, peat-based cellulose textiles burn longer with a prominent afterglow which can be attributed to the presence of lignin in its structure. A series of phosphoramidates were synthesized and applied on both cellulose textiles. From thermogravimetric and pyrolysis combustion flow analysis of the treated cellulose, we were able to relate the flame retardant efficacy of the synthesized phosphorus compounds to their chemical structure. The phosphoramidates with methyl phosphoester groups exhibited higher condensed phase flame retardant effects on both types of cellulose textiles investigated in this study. In addition, the bis-phosphoramidates exhibited higher flame retardant efficacy compared to the mono-phosphoramidates