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The flame retardancy and mechanical properties of polyamide‐6 (PA6)/aluminum diethylphosphinate (AlPi) composite are greatly improved by the addition of novelly synthesized phosphorus flame retardant‐based diepoxide (DEP) during extrusion. The PA6/AlPi/DEP composite passes V‐0 rating of UL94 test with limiting oxygen index (LOI) of 32.6% at 13 wt% AlPi and 1 wt% DEP, as revealed by the results of flammability. The synergistic flame retardation mechanism offered by the two additives (AlPi and DEP) is studied in terms of in‐depth characterization of the charred residue and evolved gas. The deteriorated mechanical strength of PA6 due to existence of AlPi is compensated by the simultaneous chain extension effect of DEP. Accordingly, the flexural and impact strengths of PA6/AlPi/DEP composite are even superior to those of neat PA6.

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Addition of DOPO-based chain extender (DEP) simultaneously enhanced the flame retardancy and mechanical properties of PA6/MCA through chain extension and coaction in flame-retarding.

A 9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide (DOPO)‐triazine based anhydride (2,4,6‐tris‐(DOPO‐methylformatephthalic anhydride‐phenoxy)‐1,3,5‐triazine (TDA)) is synthesized and used as a halogen‐free flame retardant co‐curing agent for diglycidyl ether of bisphenol A/methylhexahydrophthalic anhydride (DGEBA/MHHPA) system. The conjugation of anhydride group is increased by the utilization of TDA, leading to the reduction in the curing activation energy. The cured epoxy resin passes V‐0 rating of UL 94 test with the limiting oxygen index of 32.7 vol% when the phosphorus content is only 1.5 wt%. The flame‐retarding action of triazine ring and DOPO moiety is investigated by the residue analysis and the characterization of pyrolysis gas. Due to the presence of bulky aromatic subunits in the molecular structure of TDA, the flame‐retarded epoxy resins maintain the high glass transition temperature of DGEBA/MHHPA. Besides, the moisture absorption is diminished following the usage of TDA.