Skip to main content
SpringerLink
Log in

High molecular weight poly(acrylonitrile-co-3-aminocarbonyl-3-butenoic acid methyl ester) prepared by mixed solvent polymerization I. effect of monomer feed ratios on polymerization and stabilization

  • ORIGINAL PAPER
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

In order to improve the pre-oxidation performance and molecular weight of polyacrylonitrile (PAN). In this work, 3-aminocarbonyl-3-butenoic acid methyl ester) (ABM) was used as comonomers to formulate high molecular weight poly(acrylonitrile-co-3-amino-carbonyl-3-butenoic acid methyl ester) [P(AN-co-ABM)] copolymer by radical polymerization in the mixed solvent of dimethyl sulfoxide/deionized water =60/40 (wt/wt). The highest molecular weight of resultant P(AN-co-ABM) is 4.87 × 105 g/mol, 5 times larger than that prepared by solution polymerization under the same reaction conditions. The monomer reactivity ratios are calculated by Fineman-Ross and Kelen-Tüdõs methods based on the elemental analysis results. Thermal properties of P(AN-co-ABM) copolymer with different monomer feed ratios were studied by Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry in detail. The results show that the stabilization of P(AN-co-ABM) has been significantly improved by ABM, confirmed by the lower initiation temperature and broader exothermic peak in DSC curves, larger extent of stabilization from FTIR and XRD studies, and smaller Ea of cyclization, which is due to the initiation of ABM through ionic mechanism. This study clearly shows that high molecular weight P(AN-co-ABM) copolymer is a better material for carbon fiber precursor.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Scheme 1
Scheme 2
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12

Similar content being viewed by others

References

  1. Burkanudeen A, Krishnan GS (2013) Thermal behavior of carbon fiber precursor polymers with different stereoregularities. J Therm Anal Calorim 112:1261–1268

    Article  CAS  Google Scholar 

  2. Jiang HY, Yin QQ, Zhou MH, Pan D (2012) Effect of ultra high molecular weight Polyacrylonitrile (UHMW-PAN) on the rheological behavior of PAN/DMSO solution. Adv Mater Res 430-432:687–691

    Article  CAS  Google Scholar 

  3. Liu X, Zhu C, Dong H, Wang B, Liu R, Zhao N, Li S, Xu J (2015) Effect of microgel content on the shear and extensional rheology of polyacrylonitrile solution. Colloid Poly Sci 293:587–596

    Article  CAS  Google Scholar 

  4. Ouyang Q, Cheng L, Wang HJ, Li KX (2008) DSC study of stabilization reactions in poly(acrylonitrile-co-itaconic acid) with peak-resolving method. J Therm Anal Calorim 94:85–88

    Article  CAS  Google Scholar 

  5. Saxena A, Sadhana R, Rao VL, Kanakavel M, Ninan KN (2003) Synthesis and properties of Polyarylene ether nitrile copolymers. Polym Bull 50:219–226

    Article  CAS  Google Scholar 

  6. Zeng ZP, Shao ZC, Xiao R, Lu YG (2017) Structure EvolutionMechanism of poly(acrylonitrile/itaconic acid/acrylamide) during thermal oxidative stabilization process. Chin J Polym Sci 35:1020–1034

    Article  CAS  Google Scholar 

  7. Devasia R, Nair CPR, Sivadasan P, Katherine BK, Ninan KN (2010) Cyclization reaction in poly(acrylonitrile/itaconicacid) copolymer: an isothermal differential scanning calorimetry kinetic study. J Appl Polym Sci 88:915

    Article  Google Scholar 

  8. Cheraghi R, Bahrami SH, Arami M, Enayati M (2016) Effect of comonomer on the viscoelastic behavior of co-poly (acrylonitrile) solutions. J Polym Res 23:207

    Article  Google Scholar 

  9. Qin O, Lu C, Wang H, Li K (2008) Mechanism and kinetics of the stabilization reactions of itaconic acid-modified polyacrylonitrile. Polym Degrad Stabil 93:1415–1421

    Article  Google Scholar 

  10. Ju A, Guang S, Xu H (2014) A high performance carbon fiber precursor containning ultra-high molecular weight acrylonitrile copolymer: preparation and properties. J Polym Res 21:569

    Article  Google Scholar 

  11. Bajaj P, Sreekumar TV, Sen K (2001) Thermal behaviour of acrylonitrile copolymers having methacrylic and itaconic acid comonomers. Polymer 42:1707–1718

    Article  CAS  Google Scholar 

  12. Wu XP, Zhang XL, Lu CX, Ling LC (2010) Thermochemical reactions and structural evolution of acrylamide-modified poly acrylonitrile. Chin J Polym Sci 28:367–376

    Article  CAS  Google Scholar 

  13. Bahl OP, Manocha LM (1974) Characterization of oxidised pan fibres. Carbon 12:417–423

    Article  CAS  Google Scholar 

  14. Zhang W, Jie L, Gang W (2003) Evolution of structure and properties of PAN precursors during their conversion to carbon fibers. Carbon 41:2805–2812

    Article  CAS  Google Scholar 

  15. Ju A, Guang S, Xu H (2013) Molecular design and stabilization mechanism of acrylonitrile bipolymer. J Appl Polym Sci 129:3255–3264

    Article  CAS  Google Scholar 

  16. Fineman M (1950) Calculation of the heats of formation of alkali halide solid solutions from Hildebrand's equation. J Chem Phys 18:771–772

    Article  CAS  Google Scholar 

  17. Kennedy JP, Kelen T, Tüdös F (1975) Analysis of the linear methods for determining copolymerization reactivity ratios. II. A critical reexamination of cationic monomer reactivity ratios. J Polymer Sci Polymer Chem Ed 13:2277–2289

    Article  CAS  Google Scholar 

  18. Zhao Y, Wang C, Wang Y, Zhu B (2010) Aqueous deposited copolymerization of acrylonitrile and itaconic acid. J Appl Polym Sci 111:3163–3169

    Article  Google Scholar 

  19. Zhang H, Quan L, Xu L (2015) The effects of carbon nanotubes with acid-groups on the structural evolution and cyclization kinetics of poly(acrylonitrile-co-itaconic acid) composite microspheres. Fiber Polym 16:263–270

    Article  CAS  Google Scholar 

  20. Chouhan S, Bajpai AK, Bajpai J, Katare R, Dhoble SJ (2017) Mechanical and UV absorption behavior of zinc oxide nanoparticles: reinforced poly(vinyl alcohol- g -acrylonitrile) nanocomposite films. Polym Bull 1–23

  21. Rahaman MSA, Ismail AF, Mustafa A (2007) A review of heat treatment on polyacrylonitrile fiber. Polym Degrad Stabil 92:1421–1432

    Article  CAS  Google Scholar 

  22. Baskan H, Unsal C, Karakas H, Sarac AS (2017) Poly(acrylonitrile-co-itaconic-acid)–poly(3,4-ethylenedioxythiophene) and poly(3-methoxythiophene) nanoparticles and nanofibres. Bull Mater Sci 40:1–13

    Article  Google Scholar 

  23. Yu MJ, Bai YJ, Wang CG, Xu Y, Guo PZ (2007) A new method for the evaluation of stabilization index of polyacrylonitrile fibers. Mater Lett 61:2292–2294

    Article  CAS  Google Scholar 

  24. Fu Z, Yu G, Cao C, Liu B, Zhou C, Zhang H (2014) Structure evolution and mechanism of polyacrylonitrile and related copolymers during the stabilization. J Mater Sci 49:2864–2874

    Article  CAS  Google Scholar 

  25. Devasia R, Nair CR, Ninan KN (2005) Effect of oxalic acid on the rheological properties of dope solution of poly[acrylonitrile- co -(methyl acrylate)- co -(itaconic acid)]. Polym Int 54:381–385

    Article  CAS  Google Scholar 

  26. Gupta AK, Paliwaal DK, Bajj P (2015) Effect of the nature and mole fraction of acidic comonomer on the stabilization of polyacrylonitrile. J Appl Polym Sci 59:1819–1826

    Article  Google Scholar 

  27. Fu Z, Liu B, Zhang H (2017) Study on thermal oxidative stabilization reactions of poly(acrylonitrile- co -itaconic acid) copolymers synthesized at different polymerization stages. J Appl Polym Sci 134:45245

    Article  Google Scholar 

  28. Ju A, Guang S, Xu H (2013) Effect of comonomer structure on the stabilization and spinnability of polyacrylonitrile copolymers. Carbon 54:323–335

    Article  CAS  Google Scholar 

Download references

Acknowledgements

Financial support of this work from National Natural Science Foundation of China (No. 51503086), China Postdoctoral Science Foundation (No. 1893), State Key Laboratory for Modification of Chemical Fibers and Polymer (18 M1060120), The Open Project Program of Key Laboratory of Advanced Textile Materials and Manufacturing Technology (Zhejiang Sci-Tech University), Ministry of Education (No. 2016001) and the Fundamental Research Funds for the Central Universities (NO. 17D110620) was gratefully acknowledged.

Author information

Authors and Affiliations

  1. College of Materials Science and Engineering & State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Donghua University, Shanghai, 201620, China

    Chenglin Liu, Xuepeng Ni, Huifang Chen & Anqi Ju

  2. Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Houyong Yu & Anqi Ju

Authors
  1. Chenglin Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Xuepeng Ni
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Huifang Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Houyong Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Anqi Ju
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Anqi Ju, Huifang Chen and Houyong Yu designed the research strategy; Chenglin Liu and Xuepeng Ni performed the experiments; Anqi Ju, Huifang Chen and Shengfei Hou analyzed data and wrote the paper. All the authors took part in fruitful discussions during paper preparation.

Corresponding author

Correspondence to Anqi Ju.

Ethics declarations

Conflicts of interest

The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, C., Ni, X., Chen, H. et al. High molecular weight poly(acrylonitrile-co-3-aminocarbonyl-3-butenoic acid methyl ester) prepared by mixed solvent polymerization I. effect of monomer feed ratios on polymerization and stabilization. J Polym Res 26, 276 (2019). https://doi.org/10.1007/s10965-019-1927-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-019-1927-x

Keywords

Search

Navigation