Preparation and thermal properties of poly[acrylonitrile-co-(β-methylhydrogen itaconate)] used as carbon fiber precursor

Abstract

In order to replace terpolymer with bipolymer, a bifunctional comonomer β-methylhydrogen itaconate (MHI) containing carboxyl group and ester group was synthesized to prepare poly[acrylonitrile-co-(β-methylhydrogen itaconate)] [P(AN-co-MHI)] bipolymers used as carbon fiber precursor for improving the stabilization and spinnability at the same time. The P(AN-co-MHI) bipolymers with different monomer feed ratios were characterized by elemental analysis, Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). The results show that both the polymerization conversion and molecular mass of P(AN-co-MHI) reduce with the increasing MHI amounts in the feed due to the larger molecular volume of MHI than acrylonitrile (AN). The monomer reactivity ratios were calculated by Fineman–Ross and Kelen–Tudos methods, the results show good agreement and MHI possesses higher reactivity than AN. Two parameters \( E_{\text{s}} = A_{{1,629\,{\text{cm}}^{ - 1} }} /A_{{2,244\,{\text{cm}}^{ - 1} }} \) and \( SI = (I_{0} - I_{\text{S}} )/I_{0} \) were defined to evaluate the extent of stabilization, and the activation energy (Ea) of the cyclization was calculated by Kissinger method and Ozawa method. The FTIR, XRD, and DSC results show that P(AN-co-MHI) bipolymers exhibit significantly improved stabilization characteristics than PAN homopolymer, such as larger extent of stabilization, lower initiation temperature, and smaller Ea of cyclization, which is attributed to the ionic initiation by MHI comonomer and it is beneficial to preparing high-performance carbon fiber.