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In this study, we have investigated the structure–flame-retardant (FR) efficacy relationships of phosphoramidates (PRs) on flexible polyurethane foam (FPUF). FPUFs that contain model monosubstituted secondary PRs, monosubstituted tertiary PRs, and trisubstituted secondary PRs were prepared and evaluated for FR efficacy and thermal decomposition characteristics. The fire test results indicate that methyl ester PRs exhibit better FR behavior, compared to analogous phenyl ester derivatives at equal weight percentage in polyurethane (PU) foams. Within the same class of PRs, the monoallyl derivatives exhibited the highest level of flame retardancy. The multiallyl PR derivatives did not offer any advantage, in terms of improved flame retardancy. Evolved gas analysis from the thermal degradation of PU foams indicates that the PRs are volatilized in the first stage of thermal decomposition and are primarily active in the gas phase with the exception of the triallyl-PR derivative, which is primarily active in the condensed phase.

The fundamental processes of protonation and ethylation, occurring in a methane chemical ionization source, have been investigated for a variety of aromatic amines. The positions of protonation and ethylation on the substrate amines were determined by generating isomeric ions either by protonation of neutral ethyl substituted amines or by ethylation of the amines themselves. The product ions were investigated for structural differences via collision induced dissociation and subsequent analysis via mass analysed ion kinetic energy spectrometry. Similarities and differences between mass analysed ion kinetic energy/collision induced dissociation spectra of these isomeric ions were used to determine protonation and ethylation sites for imidazole, benzimidazole, indazole, pyrrole, pyridine and aniline.

The role of various additives (emulsifier, anti-dripping agent) and formulation procedures (pre-dispersion of solid additives in polyol via milling) which influence the flame retardancy of 6,6′-[ethan-1,2-diylbis(azandiyl)]bis(6H-dibenzo[c,e][1,2]oxaphosphin-6-oxid) (EDA-DOPO) containing flexible polyurethane foams has been investigated in this work. For comparison, the flame retardancy of two additional structurally-analogous bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based compounds, i.e., ethanolamine-DOPO (ETA-DOPO) and ethylene glycol-DOPO (EG-DOPO) were also evaluated together with EDA-DOPO in flexible PU foams of various formulations. The flame retardancy of these three bridged-DOPO compounds depends on the type of PU formulation. For certain PU formulations containing EDA-DOPO, lower fire performance was observed. Addition of emulsifier and polytetrafluoroethylene (PTFE) to these PU formulations influenced positively the flame retardancy of EDA-DOPO/PU foams. In addition, dispersion of EDA-DOPO and PTFE via milling in polyol improved the flame retardancy of the PU foams. Mechanistic studies performed using a microscale combustion calorimeter (MCC) and its coupling to FTIR showed no difference in the combustion efficiency of the bridged-DOPO compounds in PU foams. From MCC experiments it can be concluded that these bridged-DOPO compounds and their decomposition products may work primarily in the gas phase as flame inhibitors. The physiochemical behavior of additives in PU formulation responsible for the improvement in the flame retardancy of PU foams was further investigated by studying the dripping behavior of the PU foams in the UL 94 HB test. A high-speed camera was used to study the dripping behavior in the UL 94 HB test and results indicate a considerable reduction of the total number of melt drips and flaming drips for the flame retardant formulations. This reduction in melt drips and flaming drips during the UL 94 HB tests help PU foams achieve higher fire classification.