Abstract
A kind of flame-retardant polyacrylonitrile fiber was prepared successfully by the modification with diethylenetriamine and zinc ions (Zn2+). The chemical, aggregation and morphological structures of the aminated fibers were studied by Fourier transform infrared (FTIR) spectra, X-ray diffraction and scanning electron microscope (SEM). Meanwhile, mechanical and adsorption properties were investigated by a tensile tester and atomic absorption spectrometry. The flame retardancy of the modified fibers was significantly improved after modification. And the thermal degradation behaviors and flame retardancy mechanisms were studied in detail. The microscale combustion calorimeter and TG-FTIR results showed that the modified fibers decomposed less combustible gases and more non-combustible gases comparing the original fibers. And thermogravimetric analysis and SEM tests revealed that Zn2+ would stabilize the main chains and promote formation of compact char layers. And differential scanning calorimetry tests indicated that Zn2+ would inhibit the cyclization exothermic process. Results showed that the combination of gas phase and condensed phase mechanisms optimized the flame retardancy performance.
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References
Zhang J, Hall ME. The flammability of polyacrylonitrile and its copolymers I. The flammability assessment using pressed powdered polymer samples. J Fire Sci. 1993;11:442–56.
Nametz RC. Flame-retarding textile fibers. Ind Eng Chem. 1970;62:41–53.
Ichibori K, Matsumoto T, Kanbara Y. Flame-retarded composite fiber. US Patent 5,208,105; 1993.
Tsai JS. The effect of flame-retardants on the properties of acrylic and modacrylic fibres. J Mater Sci. 1993;28:1161–7.
Wade BE. Modacrylic copolymer composition. US Patent 6,048,955; 2000.
Lu SY, Hamerton I. Recent developments in the chemistry of halogen-free flame retardant polymers. Prog Polym Sci. 2002;27:1661–712.
Bajaj P, Agrawal AK, Dhand A, Kasturia N, Hansraj. Flame retardation of acrylic fibers: an overview. J Macromol Sci-Polym Rev. 2000;40:309–37.
Hearle JW. High performance fibers. UK: Wood Head Publishing Ltd.; 2001.
Zhang S, Horrocks AR. A review of flame retardant polypropylene fibres. Prog Polym Sci. 2003;28:1517–38.
Chen XC, Ding YP, Tang T. Synergistic effect of nickel formate on the thermal and flame-retardant properties of polypropylene. Polym Int. 2005;54:904–8.
Zhang JJ, Ji Q, Wang FJ, Tan LW, Xia YZ. Effects of divalent metal ions on the flame retardancy and pyrolysis products of alginate fibres. Polym Degrad Stab. 2012;97:1034–40.
Xu JZ, Tian CM, Ma ZG, Gao M, Guo HZ, Yao ZH. Study on the thermal behaviour and flammability of the modified polyacrylonitrile fibers. J Therm Anal Calorim. 2000;63:501–6.
Bajaj P, Kumari S. Modification of acrylic fibers: an overview. J Macromol Sci Rev Macromol Chem. 1987;27:181–217.
Ieno M, Nishida R. Fiber and a fiber structure having a high flame-retarding property and high moisture-absorptive property. US Patent 7,696,283; 2010.
Zharkova MA, Kudryavtsev GI, Khudoshev IF, Romanova TA. Thermomechanical and chemical properties of cross-linked polyacrylonitrile fibres. Fibre Chem. 1969;1:191–4.
Liu RX, Zhang BW, Tang HX. Synthesis and characterization of poly (acrylaminophosphonic-carboxyl-hydrazide) chelating fibre. React Funct Polym. 1999;39:71–81.
Ko YG, Choi US, Kim TY, Ahn DJ, Chun YJ. FT-IR and isotherm study on anion adsorption onto novel chelating fibers. Macromol Rapid Commun. 2002;23:535–9.
Deng SB, Bai RB, Chen JP. Aminated polyacrylonitrile fibers for lead and copper removal. Langmuir. 2003;19:5058–64.
Zhang LH, Zhang XS, Li PP, Zhang WQ. Effective Cd2+ chelating fiber based on polyacrylonitrile. React Funct Polym. 2009;69:48–54.
Zeng XM, Hu J, Zhao JX, Zhang YW, Pan D. Investigating the jet stretch in the wet spinning of PAN fiber. J Appl Polym Sci. 2007;106:2267–73.
Sobhanipour P, Cheraghi R, Volinsky AA. Thermoporometry study of coagulation bath temperature effect on polyacrylonitrile fibers morphology. Thermochim Acta. 2011;518:101–6.
Dong XG, Wang CG, Juan C. Study on the coagulation process of polyacrylonitrile nascent fibers during wet-spinning. Polym Bull. 2007;58:1005–12.
Ko TH, Lin CH, Ting HY. Structural changes and molecular motion of polyacrylonitrile fibers during pyrolysis. J Appl Polym Sci. 1989;37:553–66.
Cai YB, Gao DW, Wei QF, Gu HL, Zhou S, Huang FL, Song L, Hu Y, Gao WD. Effects of ferric chloride on structure, surface morphology and combustion property of electrospun polyacrylonitrile composite nanofibers. Fiber Polym. 2011;12:145–50.
Doğan M, Erdoğan S, Bayramlı E. Mechanical, thermal, and fire retardant properties of poly (ethylene terephthalate) fiber containing zinc phosphinate and organo-modified clay. J Therm Anal Calorim. 2013;112:871–6.
Guin T, Krecker M, Milhorn A, Grunlan JC. Maintaining hand and improving fire resistance of cotton fabric through ultrasonication rinsing of multilayer nanocoating. Cellulose. 2014;21:3023–30.
Yang HY, Song L, Tai QL, Wang X, Yu B, Yuan Y, Hu Y, Yuen RKK. Comparative study on the flame retarded efficiency of melamine phosphate, melamine phosphite and melamine hypophosphite on poly (butylene succinate) composites. Polym Degrad Stab. 2014;105:248–56.
Wang JS, Liu Y, Zhao HB, Liu J, Wang DY, Song YP, Wang YZ. Metal compound-enhanced flame retardancy of intumescent epoxy resins containing ammonium polyphosphate. Polym Degrad Stab. 2009;94:625–31.
Zhang WX, Wang YZ, Sun CF. Characterization on oxidative stabilization of polyacrylonitrile nanofibers prepared by electrospinning. J Polym Res. 2007;14:467–74.
Shoushtari AM, Zargaran M, Abdouss M. Preparation and characterization of high efficiency ion-exchange crosslinked acrylic fibers. J Appl Polym Sci. 2006;101:2202–9.
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The device support for measurements and characterizations was mainly from State Key Laboratory of Polymer Materials and Engineering (Sichuan University) and Analysis and Testing Center (Sichuan University). Authors wish to thank all the testers for their help and suggestions. Authors would also like to thank College of Chemistry, Chemical Engineering and Materials Science of Soochow University for the TG-FTIR measurements.
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Yan, X., Zhou, W., Zhao, X. et al. Preparation, flame retardancy and thermal degradation behaviors of polyacrylonitrile fibers modified with diethylenetriamine and zinc ions. J Therm Anal Calorim 124, 719–728 (2016). https://doi.org/10.1007/s10973-015-5180-1
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DOI: https://doi.org/10.1007/s10973-015-5180-1