Melt-Spinning of an Intrinsically Flame-Retardant Polyacrylonitrile Copolymer

Poly(acrylonitrile) (PAN) fibers have two essential drawbacks: they are usually processed by solution-spinning, which is inferior to melt spinning in terms of productivity and costs, and they are flammable in air. Here, we report on the synthesis and melt-spinning of an intrinsically flame-retardant PAN-copolymer with phosphorus-containing dimethylphosphonomethyl acrylate (DPA) as primary comonomer. Furthermore, the copolymerization parameters of the aqueous suspension polymerization of acrylonitrile (AN) and DPA were determined applying both the Fineman and Ross and Kelen and Tudos methods. For flame retardancy and melt-spinning tests, multiple PAN copolymers with different amounts of DPA and, in some cases, methyl acrylate (MA) have been synthesized. One of the synthesized PAN-copolymers has been melt-spun with propylene carbonate (PC) as plasticizer; the resulting PAN-fibers had a tenacity of 195 +/- 40 MPa and a Young's modulus of 5.2 +/- 0.7 GPa. The flame-retardant properties have been determined by Limiting Oxygen Index (LOI) flame tests. The LOI value of the melt-spinnable PAN was 25.1; it therefore meets the flame retardancy criteria for many applications. In short, the reported method shows that the disadvantage of high comonomer content necessary for flame retardation can be turned into an advantage by enabling melt spinning.