Abstract
MMA has been copolymerised with pentavalent phosphorus-containing monomers and the flame retardance of the resulting copolymers has been assessed by limiting oxygen indicies (LOI) and cone calorimetry experiments. The thermal stability of the copolymers has also been assessed by conventional thermogravimetric analysis (TGA). Poly(methyl methacrylate) (PMMA) modified with phosphorus-containing additives have also been synthesised and the flame retardance assessed. All of the modified PMMA samples contain 3.5 wt.\%, allowing a comparison of the relative merits of an additive and a reactive approach to flame retardance. The chemical environment of the phosphorus in terms of flame retardance achieved is also considered in this paper. The incorporation of 3.5 wt.\% phosphorus in both reactive and additive approaches increases the limiting oxygen index of PMMA from 17.8 to over 21. However, cone calorimetry shows that the phosphorus-containing copolymers are inherently more flame retardant than PMMA and the PMMA modified with phosphorus-containing additives. The methyl methacrylate (MMA) copolymers have significantly reduced peak rates of heat release and leave substantial char residue during combustion, as compared to PMMA. Cone calorimetry has also shown that the phosphates are more effective flame-retardants for PMMA than are the phosphonates in both additive and reactive approaches. TGA of the polymers indicates that the copolymers are more thermally stable than PMMA whilst PMMA containing the additives are less thermally stable. A condensed phase mechanism in which diethyl(methacryloyloxymethyl)phosphonate reduces the flammability of PMMA has been identified.