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The pyrolysis and fire behavior of halogen-free flame-retarded DGEBA/DMC, RTM6 and their corresponding 60 vol.-% carbon fibers (CF) composites were investigated. A novel phosphorous compound (DOPI) was used. Its action is dependent on the epoxy matrix. DGEBA/DMC and DOPI decompose independently of each other. Only flame inhibition occurs in the gas phase. RTM6 shows flame inhibition and a condensed phase interaction increasing charring. Both mechanisms decrease with increasing irradiance, whereas in RTM6-CF charring is suppressed at low ones. RTM6+DOPI shows a higher LOI (34.2%) than DGEBA/DMC+DOPI and a V-0 classification in UL 94. Adding CF only enhances the LOI, DOPI+CF leads to a superposition in LOI for DGEBA/DMC-CF+DOPI (31.8%, V-0) and a synergism for RTM6-CF+DOPI (47.7%, V-0).
10-Ethyl-9-oxa-10-phosphaphenanthrene-10-oxide (1) can be nitrated using acetic anhydride and fuming nitric acid. The nitro group is reduced using palladium on charcoal and hydrogen. These reaction conditions are used for the synthesis of an analogous DOPO-based diaminic hardener (7). An evaluation of the curing behavior, mechanical properties and flammability of a neat resin made of DGEBA and 7 (DGEBA + 7) and of a carbon fiber-reinforced resin made of DGEBA, 4,4-diaminodiphenylsulfon (DDS) and 7 (DGEBA + DDS + 7) shows the potential of this hardener to lead to flame-retardant systems while keeping relevant properties on a high level; especially when compared to a similar system (DGEBA + DDS + 1).
Condensed-phase mechanisms play a major role in fire-retardant polymers. Generations of development have followed the concept of charring to improve fire properties. Whereas the principal reactions are believed to be known, the specific description for multicomponent systems is lacking, as is the picture across different systems. A two-step approach is proposed in general, and also presented in greater detail. The second step covers the specific reactions controlling charring, whereas the actual reactants are provided in the preceding step. This model consistently incorporates the variety of structureproperty relationships reported. A comprehensive case study is presented on seven phosphorus flame retardants in two epoxy resins to breathe life into the two-step approach.
Novel DOPO-based flame retardants in high-performance carbon fibre epoxy composites for aviation
(2011)
Two novel, halogen-free, phosphorus-based oligomeric flame retardants are investigated in the commercial epoxy resin RTM6 and ~70 wt.% carbon fibre RTM6 composites (RTM6-CF) with respect to pyrolysis and fire behaviour. The flame retardants are based on 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide (DOPO) units linked to the star-shaped aliphatic ground body tetra-[(acryloyloxy)ethyl] pentarythrit (DOPP), or heterocyclic tris-[(acryloyloxy)ethyl] isocyanurate (DOPI), respectively. The glass transition temperature is reduced by adding DOPP and DOPI, but the mechanical properties of the composites (e.g. interlaminar shear strength (ILSS) and Gc in mode I and II) remain unchanged. Decomposition models are proposed based on mass loss, evolved gas analysis (TGFTIR) and condensed product analysis (hot stage cell within FTIR). The fire behaviour is investigated comprehensively (UL 94, limiting oxygen index (LOI) and cone calorimeter). Both flame retardants act in the gas phase through flame inhibition and in the condensed phase through charring. The UL 94 of RTM6 is improved from HB to V-1 and V-0; the LOI from 25% to 3438%. Peak heat release rate (PHRR) and total heat evolved (THE) are lowered by 31-49% and 4044%, respectively. Adding CF increases the residue, reduces the THE, but suppresses the charring due to RTM6 and flame retardants. Thus the THE of RTM6-CF is reduced by about 25% when DOPI and DOPP are added. However, UL 94: V-0 and LOI of 45% and 48% are achieved with ~0.6 wt.% phosphorus.
Highly soluble 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-(DOPO)-based diamino hardener (2), bearing its amino groups directly on the DOPO framework, is investigated with respect to its use as a reactive flame retardant in thermosets. A mechanism for decomposition of the corresponding phosphorus-modified epoxy resin system based on a diglycidylether of bisphenol A DGEBA and 2 (DGEBA/2) is proposed and compared to the systems using DGEBA and 4,4'-diaminodiphenylsulfon (DGEBA/DDS) and to a similar system based on the structurally comparable non-reactive DOPO-based compound (DGEBA/DDS/1). Additive 1 changed the decomposition characteristics of the epoxy resin only slightly and phosphorus was released. Incorporating 2 induces two-step decomposition and most of the phosphorus remains in the residue. Furthermore, the fire behaviour of neat epoxy resin systems and a representative carbon fibre-reinforced composite based on DGEBA, DDS and 2 (DGEBA/DDS/2) were examined and compared to that of the analogous composite systems based on DGEBA/DDS and DGEBA/DDS/1. Based on different flame retardancy mechanisms both the reactive compound 2 and the additive compound 1 improve flammability (increase in LOI >13% and achieving V-1 behaviour) of the epoxy resin and composites. Under forced flaming only the flame inhibition of the additive compound 1 acts sufficiently. Lastly, the superior key mechanical properties of the epoxy resin and composite based on 2 are sketched.