Hostname: page-component-857557d7f7-8wkb5 Total loading time: 0 Render date: 2025-11-23T08:14:41.002Z Has data issue: false hasContentIssue false
  • English
  • Français

Mechanism and kinetics of stabilization reactions of poly(acrylonitrile-co-β-methylhydrogen itaconate)

Published online by Cambridge University Press:  16 July 2012

Anqi Ju ,
Hongyao Xu  and
Shanyi Guang
Anqi Ju
Affiliation:
College of Materials Science and Engineering & State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China
Hongyao Xu*
Affiliation:
College of Materials Science and Engineering & State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai 201620, China
Shanyi Guang
Affiliation:
Department of Basic Chemistry, College of Chemistry and Chemical Engineering & Bioengineering, Donghua University, Shanghai 201620, China
*
a)Address all correspondence to this author. e-mail: hongyaoxu@dhu.edu.cn
Get access

Abstract

To replace ternary polymer with binary polymer, a novel bifunctional comonomer β-methylhydrogen itaconate (MHI) was synthesized to prepare poly(acrylonitrile-co-β-methylhydrogen itaconate) [P(AN-co-MHI)] copolymer used for carbon fiber precursor. The structural evolution and stabilization mechanism of P(AN-co-MHI) and polyacrylonitrile (PAN) during stabilization were studied by Fourier transform infrared spectroscopy, x-ray diffraction, differential scanning calorimetry, thermogravimetry, and kinetic investigation. The activation energy (Ea) of the stabilization reactions were calculated by Kissinger method and Ozawa method. The results show that the P(AN-co-MHI) exhibits a lower stabilization temperature than terpolymers containing similar chemistry component and a significantly improved stabilization performance compared with PAN homopolymer, such as lower cyclization temperature, lower Ea (85.36 kJ/mol), and larger extent of stabilization under the same condition, which is mainly attributed to the initiation of MHI comonomer through an ionic cyclization mechanism. The dehydrogenation of P(AN-co-MHI) is also promoted by the incorporation of comonomer MHI into PAN chains. Simultaneously, the rheological analysis shows that P(AN-co-MHI) possesses better spinnability than PAN, which is beneficial for preparation of high performance carbon fiber.

Information

Type
Articles
Information
Journal of Materials Research , Volume 27 , Issue 20 , 28 October 2012 , pp. 2668 - 2676
Copyright
Copyright © Materials Research Society 2012

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

Article purchase

Temporarily unavailable

References

REFERENCES

Shokuhfarl, A., Sedghi, A., and Farsani, R.E.: Effect of thermal characteristics of commercial and special polyacrylonitrile fibres on the fabrication of carbon fibres. Mater. Sci. Technol. 22(10), 1235 (2006).CrossRefGoogle Scholar
Ouyang, Q., Wang, H.J., Cheng, L., and Sun, Y.H.: Effect of boric acid on the stabilization of poly(acrylonitrile-co-itaconic acid). J. Polym. Res. 14, 497 (2007).CrossRefGoogle Scholar
Ji, M.X., Wang, C.G., Bai, Y.J., Yu, M.J., and Wang, Y.X.: Structural evolution of polyacrylonitrile precursor fibers during preoxidation and carbonization. Polym. Bull. 59, 527 (2007).CrossRefGoogle Scholar
Zhang, W.X., Liu, J., and Wu, G.: Evolution of structure and properties of PAN precursors during their conversion to carbon fibers. Carbon 41, 2805 (2003).Google Scholar
Gupta, A.K., Paliwal, D.K., and Bajaj, P.: Acrylic precursors for carbon fibers. Polym. Rev. 31(1), 1 (1991).CrossRefGoogle Scholar
Bahrami, S.H., Bajaj, P., and Sen, K.: Effect of coagulation conditions on properties of poly(acrylonitrile–carboxylic acid) fibers. J. Appl. Polym. Sci. 89(7), 1825 (2003).CrossRefGoogle Scholar
Bajaj, P., Sreekumar, T.V., and Sen, K.: Structure development during dry-jet-wet spinning of acrylonitrile/vinyl acids and acrylonitrile/methyl acrylate copolymers. J. Appl. Polym. Sci. 86(3), 773 (2002).CrossRefGoogle Scholar
Liu, J.J., Ge, H.Y., and Wang, C.G.: Modification of polyacrylonitrile precursors for carbon fiber via copolymerization of acrylonitrile with ammonium itaconate. J. Appl. Polym. Sci. 102, 2175 (2006).CrossRefGoogle Scholar
Devasia, R., Reghunadhan Nair, C.P., Sadhana, R., Babu, N.S., and Ninan, K.N.: Fourier transform infrared and wide-angle x-ray diffraction studies of the thermal cyclization reactions of high-molar-mass poly(acrylonitrile-co-itaconic acid). J. Appl. Polym. Sci. 100, 3055 (2006).CrossRefGoogle Scholar
Rahaman, M.S.A., Ismail, A.F., and Mustafa, A.: A review of heat treatment on polyacrylonitrile fiber. Polym. Degrad. Stab. 92, 1421 (2007).CrossRefGoogle Scholar
Bashir, Z.: A critical review of the stabilisation of polyacrylonitrile. Carbon 29, 1081 (1991).CrossRefGoogle Scholar
Fitzer, E. and Mϋller, D.J.: The influence of oxygen on the chemical reactions during stabilization of pan as carbon fiber precursor. Carbon 13, 63 (1975).CrossRefGoogle Scholar
Bajaj, P., Sreekumar, T.V., and Sen, K.: Thermal behaviour of acrylonitrile copolymers having methacrylic and itaconic acid comonomers. Polymer 42, 1707 (2001).CrossRefGoogle Scholar
Fitzer, E., Frohs, W., and Heine, M.: Optimization of stabilization and carbonization treatment of PAN fibers and structural characterization of the resulting carbon fibers. Carbon 24(4), 387 (1986).CrossRefGoogle Scholar
Watt, W.: Carbon work at the royal aircraft establishment. Carbon 10, 121 (1972).CrossRefGoogle Scholar
Bahl, O.P. and Manocha, L.M.: Characterization of oxidised pan fibres. Carbon 12, 417 (1974).CrossRefGoogle Scholar
Ferguson, J. and Debanath, N.R.: Pyrolysis of acrylonitrile copolymers. Fibre Sci. Technol. 13, 166 (1980).CrossRefGoogle Scholar
Kakida, H. and Tashiro, K.: Mechanism and kinetics of stabilization reaction of polyacrylonitrile and related copolymers. 2. Relationships between isothermal DSC thermograms and FT-IR spectral changes of polyacrylonitrile in comparison with the case of acrylonitrile methacrylic acid copolymer. Polym. J. 29, 353 (1997).CrossRefGoogle Scholar
Kakida, H. and Tashiro, K.: Mechanism and kinetics of stabilization reactions of polyacrylonitrile and related copolymers IV: Effects of atmosphere on isothermal DSC thermograms and FTIR spectral changes during stabilization reaction of acrylonitrile/methacrylic acid copolymer. Polym. J. 6, 463 (1998).CrossRefGoogle Scholar
Devasia, R., Reghunadhan, C.P., Sivadasan, N.P., Katherine, B.K., and Ninan, K.N.: Cyclizaiton reaction in poly(arylonitrile/itaconic acid) copolymer: An isothermal differential scanning calorimetry kinetic study. J. Appl. Polym. Sci. 88, 915 (2003).CrossRefGoogle Scholar
Wang, Y.X., Wang, C.G., Wu, J.W., and Jing, M.: High-temperature DSC study of polyacrylonitrile precursors during their conversion to carbon fibers. J. Appl. Polym. Sci. 106, 1787 (2007).CrossRefGoogle Scholar
Catta, P., Sakata, S., Garcia, G., Zimmermann, J.P., Galembeck, F., Galembeck, F., and Giovedi, G.: Thermal behavior of polyacrylonitrile polymers synthesized under different conditions and comonomer compositions. J. Therm. Anal. Calorim. 87(3), 657 (2007).CrossRefGoogle Scholar
Sen, K., Bajaj, P., and Sreekumar, T.V.: Thermal behavior of drawn arylic fibers. J. Polym. Sci., Part B: Polym. Phys. 41, 2949 (2003).CrossRefGoogle Scholar
Chen, G.L., Ju, A.Q., Xu, H.Y., and Pan, D.: Solution polymerization and thermal properties of acrylonitrile and monomethyl itaconate for carbon fiber precursor. Polym. Mater. Sci. Eng. 26(2), 146 (2010).Google Scholar
Ouyang, Q., Cheng, L., Wang, H.J., and Li, K.X.: Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile. Polym. Degrad. Stab. 93, 1415 (2008).CrossRefGoogle Scholar
Cui, C.S., Yu, L.N., and Wang, C.G.: The degradation and prestabilization of acrylonitrile copolymers. J. Appl. Polym. Sci. 117, 1596 (2010).CrossRefGoogle Scholar
Bajaj, P., Sreekumar, T.V., and Sen, K.: Effect of reaction medium on radical copolymerization of acrylonitrile with vinyl acids. FT-IR study of the stabilization reactions of polyacrylonitrile in the production of carbon fibers. J. Appl. Polym. Sci. 79, 1640 (2001).3.0.CO;2-7>CrossRefGoogle Scholar
Shimada, I. and Takahagi, T.: FT-IR study of the stabilization reactions of polyacrylonitrile in the production of carbon fibers. J. Polym. Sci., Part A: Polym. Chem. 24, 1989 (1986).CrossRefGoogle Scholar
Zhu, Y. and Wilding, M.A.: Estimation, using infrared spectroscopy, of the cyclization of poly(acrylonitrile) during the stabilization stage of carbon fibre production. J. Mater. Sci. 31, 3831 (1996).CrossRefGoogle Scholar
Ouyang, Q., Cheng, L., Wang, H.J., and Li, K.X.: FTIR study of the retardation effect of boric acid on the cyclization reaction of polyacrylonitrile. e-Polymers 15, 1 (2009).Google Scholar
Jing, M., Wang, C.G., Wang, Q., Bai, Y.J., and Zhu, B.: Chemical structure evolution and mechanism during pre-carbonization of PAN-based stabilized fiber in the temperature range of 350-600°C. Polym. Degrad. Stab. 92, 1737 (2007).CrossRefGoogle Scholar
Zhao, Y.Q., Wang, C.G., Bai, Y.J., Chen, G.W., Jing, M., and Zhu, B.: Property changes of powdery polyacrylonitrile synthesized by aqueous suspension polymerization during heat-treatment process under air atmosphere. J. Colloid Interface Sci. 329, 48 (2009).CrossRefGoogle ScholarPubMed
Yu, M.J., Wang, C.G., Bai, Y.J., Wang, Y.X., Wang, Q.F., and Liu, H.Z.: Combined effect of processing parameters on thermal stabilization of PAN fibers. Polym. Bull. 57, 525 (2006).CrossRefGoogle Scholar
Jing, M., Wang, C.G., Bai, Y.J., Zhu, B., and Wang, Y.X.: Effect of temperatures in the rearmost stabilization zone on structure and properties of PAN-based oxidized fibers. Polym. Bull. 58, 541 (2007).CrossRefGoogle Scholar
Dalton, S., Heatley, F., and Budd, P.M.: Thermal stabilization of polyacrylonitrile fibres. Polymer 40, 5531 (1999).CrossRefGoogle Scholar
Xue, T.J., Mckinney, M.A., and Wilkie, C.A.: The thermal degradation of polyacrylonitrile. Polym. Degrad. Stab. 58, 193 (1997).CrossRefGoogle Scholar
Yu, M.J., Bai, Y.J., Wang, C.G., Xu, Y., and Guo, P.Z.: A new method for the evaluation of stabilization index of polyacrylonitrile fibers. Mater. Lett. 61, 2292–2294 (2007).CrossRefGoogle Scholar
Bell, J.P. and Dumbleton, J.H.: Changes in the structure of wet-spun acrylic fibers during processing. Text. Res. J. 41, 196 (1971).CrossRefGoogle Scholar
Devasia, R., Reghunadhan Nair, C.P., Sivadasan, P., and Ninan, K.N.: High char-yielding poly[acrylonitrile-co-(itaconic acid)-co-(methyl acrylate)]: Synthesis and properties. Polym. Int. 54, 1110 (2005).CrossRefGoogle Scholar
Kissinger, H.E.: Reaction kinetics in differential thermal analysis. Anal. Chem. 29, 1702 (1957).CrossRefGoogle Scholar
Ozawa, T.: New method of analyzing thermogravimetric data. Bull. Chem. Soc. Jpn. 38, 1881 (1965).CrossRefGoogle Scholar
Tiptipakorn, S., Damrongsakkul, S., Ando, S., Hemvichian, K., and Rimdusit, S.: Thermal degradation behaviors of polybenzoxazine and silicon-containing polyimide blends. Polym. Degrad. Stab. 92, 1265 (2007).CrossRefGoogle Scholar
Reghunadhan, N.C.P., Krishnan, K., and Ninan, K.N.: Differential scanning calorimetric study on the Claisen rearrangement and thermal polymerization of diallyl ether of bisphenols. Thermochim. Acta 359, 61 (2000).CrossRefGoogle Scholar
Jain, M.K. and Abhiraman, A.S.: Conversion of acrylonitrile-based precursors to carbon fibers. Part 2. Precursor morphology and thermooxidative stabilization. J. Mater. Sci. 22, 278 (1987).CrossRefGoogle Scholar
Chiu, H. and Wang, J.: Influence of thermal history on the formation of liquid crystalline phase of hydroxyethyl cellulose acetate. J. Appl. Polym. Sci. 70, 1009 (1998).3.0.CO;2-1>CrossRefGoogle Scholar
Wang, Y. and Wu, D.C.: Extrusion, fiber formation, and characterization of thermotropic liquid crystalline copolyesters. J. Appl. Polym. Sci. 66, 1389 (1997).3.0.CO;2-Y>CrossRefGoogle Scholar
Zhou, Z., Wu, X., and Wang, M.: Rheological properties of thermotropic liquid crystalline aromatic copolyesters. Polym. Eng. Sci. 28, 136 (1988).CrossRefGoogle Scholar