Synthesis and Flame Retardant Applications of DOPO Derivatives: an Overview
ZHOU Ying1, ZHANG Daohai1,2, QIN Shuhao1,2
1 National Engineering Research Center for Compounding and Modification of Polymer Materials, Guiyang 550014; 2 College of Materials Science and Metallurgy Engineering, Guizhou University, Guiyang 550025
Abstract: As halogen-containing flame retardants suffers from toxicity and environmental concerns, phosphorus-containing flame retardants have received increasing attention as alternatives for their environmental friendliness. Since the emergence of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) as a kind of phosphorus-containing flame retardant, numerous efforts have been successively put in optimizing the synthetic approaches and chemical structure of the DOPO derivatives, and recently fruitful achievements have been made. DOPO-derivatives are considered as favorable alternatives for extensive applications in flame retardant polymer materials because of their high thermal stability, excellent water resistance, and versatile flame extinguishing behavior in the gas phase and condensed phase. DOPO derivatives can be used as reactive or additive flame retardants for epoxy resin, polyester and engineering plastics, according to their diverse functional groups. Various DOPO derivatives with P-C, P-N and P-O functional groups have been developed, among which a majority of P-C contained DOPO derivatives act as flame retardants in epoxy resins, while P-N and P-O contained DOPO derivatives are mostly applied in polyurethane foams, engineering plastics and epoxy resins. The phosphinate derivatives of DOPO are prepared by replacing P-H bond with P-C bond through chemical processes, which mainly include two approaches, namely nucleophilic addition/substitution and molecular rearrangement. In addition, there are primarily two types of P-heteroatoms contained DOPO derivatives, representing by P-O contained phosphonate DOPO-derivatives and P-N contained phosphonamidate DOPO derivatives. In both cases, P-H bond activation of DOPO is crucial step to achieve P-N or P-O bond transformation. According to the literature, Atherton-Todd reaction and using DOP-Cl as starting material constitute the two major reaction pathways for synthesizing DOPO derivatives. The addition of phosphorus flame retardants is able to endow polymer with satisfactory flame retardant performance. Nevertheless, the introduction of the phosphoric weak bonds of P-O and P-C may exert negative effects on the mechanics of flame retardant polymer. The negative effects of phosphorous groups will be weakened in DOPO derivatives with low loading amount of phosphorus. Therefore, the flame retardant macromole-cular materials with DOPO derivatives are superior in mechanical properties compared with other phosphorus flame retardants. Understanding the principle of reaction is the key to developing novel DOPO based derivatives. This review offers a retrospection of the research efforts with respect to the synthesis principle and approaches of DOPO derivatives, and flame retardant applications, aiming at provide a refe-rence for the synthesis and application of novel flame retardant of DOPO derivatives. It has been proposed that the impact of DOPO derivatives on the mechanical properties of polymers will be the focus of research in the future.
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2019, Vol. 33 
