A novel bifunctional comonomer 2-methylenesuccinamic acid (MLA) was synthesized to prepare poly(acrylonitrile-co-2-methylenesuccinamic acid) [P(AN-co-MLA)] copolymers, which can improve the stabilization of polyacrylonitrile significantly as a carbon fiber precursor. The structure and stabilization of P(AN-co-MLA) copolymers with different monomer feed ratios of AN/MLA were characterized by elemental analysis (EA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Reactivity ratio studies shows that MLA possesses higher reactivity than AN, resulting in higher MLA content in P(AN-co-MLA) copolymers than in the feed. The molecular weight and conversion of copolymer decrease gradually with the increase of MLA content in the feed. Comparing with PAN homopolymer, P(AN-co-MLA) copolymer has two or even three exothermic peaks, and the initial temperature of P(AN-co-MLA) copolymer is ca. 70 C lower than that of PAN, which broadens the exothermic peak. The DH/DT reduces from 34.01 J g À1 C À1 to less than 17.67 J g À1 C À1, confirming that the incorporation of MLA can avoid centralized heat release effectively.In addition, the extent of stabilization increases as the MLA content in P(AN-co-MLA) copolymer increases under the same heat treatment conditions. The activation energy (E a ) calculation shows cyclization E a of P(AN-co-MLA) reduces from ca. 168 kJ mol À1 to ca. 110 kJ mol À1, it is concluded that synthesized comonomer MLA can significantly improve stabilization of PAN, which is conducive to the preparation of high performance carbon fiber.

Most of the hollow carbon submicro-fibers (HCSFs) reported today are made from polyacrylonitrile (PAN) homopolymer. The obtained HCSFs are fragile due to the poor stabilization and spinnability of PAN. In this study, a bifunctional comonomer, β-methylhydrogen itaconate (MHI), was synthesized to prepare poly(acrylonitrile-co-β-methylhydrogen itaconate) [P(AN-co-MHI)] copolymer, which was used as a precursor to produce HCSF by coaxial electrospinning. The stabilization of P(AN-co-MHI) was studied by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR); the structure of HCSFs was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and field emission scanning electron microscopy (FE-SEM). The stabilization of P(AN-co-MHI) has been improved significantly by MHI with lower cyclization temperature, broadened peak and lower activation energy, which is beneficial to producing high-performance HCSFs. HCSFs with fine and uniform structures were obtained after stabilization and carbonization; the diameter of the HCSFs shrinks due to the elimination of N and the extra H. The diameter and wall thickness of HCSFs can be controlled simply by the feeding ratio of P(AN-co-MHI) solution/styrene-co-acrylonitrile solution. The resultant HCSFs can be bent more than 280° without breaking, which has potential applications in lithium-ion rechargeable batteries, supercapacitors, fuel cells, and catalyst.

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