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Molecular design and pre-oxidation mechanism of acrylonitrile copolymer used as carbon fiber precursor

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Abstract

In order to improve the pre-oxidation and spinnability of polyacrylonitrile (PAN) at the same time, a bifunctional comonomer 3-ammoniumcarboxylate-butenoic acid-methyl ester (ACBM) was designed and synthesized to prepare poly(acrylonitrile-co-3-ammoniumcarboxylate-butenoic acid-methyl ester) [P(AN-co-ACBM)] copolymers used as carbon fiber precursor instead of acrylonitrile terpolymers. The P(AN-co-ACBM) copolymers with different compositions were characterized by elemental analysis, Fourier transform infrared spectroscopy, X-ray diffraction and differential scanning calorimetry. Both the conversion of polymerization and molecular weight decease with the increasing of ACBM content in P(AN-co-ACBM) due to the larger molecular volume of ACBM than AN, and the monomer reactivity ratios study shows that ACBM possesses higher reactivity than AN. Two parameters \( {E}_s={A}_{1619c{m}^{-1}}/{A}_{2244c{m}^{-1}} \) and SI = (I 0 − I S )/I 0 were defined to evaluate the extent of pre-oxidation, and the activation energy (E a) of the cyclization was calculated by Kissinger and Ozawa methods. The results show that P(AN-co-ACBM) copolymers exhibit significantly improved pre-oxidation characteristics than PAN homopolymer, such as lower initiation temperature, larger extent of pre-oxidation and smaller E a of cyclization, which is attributed to the initiation of ACBM through ionic mechanism. In addition, the rheological analysis shows that the spinnability of P(AN-co-ACBM) copolymer is better that that of PAN, which is beneficial to preparing high performance carbon fiber.

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Acknowledgments

Financial support of this work from National Science Foundation of China (No 51073031), Important National Research Program “863” (No 2012AA030313-1) and the Fundamental Research Funds for the Central Universities (No JUSRP21003) was gratefully acknowledged.

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Authors and Affiliations

  1. College of Textile & Clothing, Jiangnan University, Wuxi, China

    Anqi Ju & Mingqiao Ge

  2. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, China

    Zixiao Liu & Hongyao Xu

  3. School of Pharmacy, Eest China University of science and technology, Shanghai, China

    Miao Luo

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  1. Anqi Ju
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  2. Zixiao Liu
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  3. Miao Luo
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  4. Hongyao Xu
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Correspondence to Anqi Ju.

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Ju, A., Liu, Z., Luo, M. et al. Molecular design and pre-oxidation mechanism of acrylonitrile copolymer used as carbon fiber precursor. J Polym Res 20, 318 (2013). https://doi.org/10.1007/s10965-013-0318-y

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