Synthesis and thermal behavior of acrylonitrile/guanidine crotonate copolymer for carbon fiber precursor

Abstract

The thermal oxidation stabilization of polyacrylonitrile (PAN) copolymer is a highly exothermic process. It significantly impacts the quality of the finished PAN‐based carbon fiber, which is often addressed by adding appropriate comonomers. This paper synthesized guanidine crotonate (GCA) as a comonomer and copolymerized with acrylonitrile (AN) to prepare P(AN‐GCA). DSC analysis revealed that when compared to PAN and P(AN‐CA) copolymers, the initial exothermic temperature, maximum exothermic heat flux, and heat flux of P(AN‐GCA) copolymer were greatly reduced. FT‐IR spectroscopy showed that the degree of pre‐oxidation increased with the increasing comonomer GCA content, indicating that the addition of comonomer GCA could promote PAN pre‐oxidation cyclization and improve the copolymer's degree of pre‐oxidation. The activation energies of PAN and P(AN‐GCA) were 160 and 126 KJ/mol, respectively. It was shown that the addition of GCA could effectively reduce the activation energy of the cyclization reaction of the polymer while simultaneously promoting it. TGA analysis shows that the introduction of GCA improves the copolymer's thermal stability, and the yield at 800°C is more than 54%, which is at least 19% higher than PAN homopolymer. P(AN‐GCA) has the potential to be carbon fiber precursor.