Mechanism and kinetics of stabilization reactions of poly(acrylonitrile-co-3-aminocarbonyl-3-butenoic acid methyl ester)

• Published in: Journal of thermal analysis and calorimetry 2014-07, Vol.117 (1), p.205-215
• Main Authors: Ju, Anqi, Luo, Miao, Zhang, Kun, Ge, Mingqiao
• Format: Article
• Language: English
• Subjects: Acrylonitrile; Analytical Chemistry; Calorimetry; Chemistry; Chemistry and Materials Science; Copolymers; Diffraction; Esters; Infrared spectroscopy; Inorganic Chemistry; Lubrication; Measurement Science and Instrumentation; Physical Chemistry; Polymer Sciences; Precursors; Stabilization; Terpolymers; X-rays
• ISSN: 1388-6150; 1588-2926; 1572-8943
• DOI: 10.1007/s10973-014-3687-5

A bifunctional comonomer 3-aminocarbonyl-3-butenoic acid methyl ester (ABM) was designed and synthesized to prepare poly(acrylonitrile- co -3-aminocarbonyl-3-butenoic acid methyl ester) [P(AN- co -ABM)] copolymer which can be used as carbon fiber precursor instead of poly(acrylonitrile–acrylamide–methyl acrylate) [P(AN–AM–MA)] terpolymer. The stabilization mechanism and structural evolution of P(AN- co -ABM) and P(AN–AM–MA) during stabilization were studied by Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, and thermogravimetry. The activation energy ( E a ) of the cyclization reactions was calculated by Kissinger method and Ozawa method. The results show that the stabilization of P(AN- co -ABM) has been remarkably improved by ABM compared with P(AN–AM–MA) terpolymer, such as lower initiation temperature, broadened exothermic peak, larger extent of stabilization, and smaller E a of cyclization, which is attributed to the initiation of ABM through ionic mechanism. Moreover, the spinnability of P(AN- co -ABM) is also improved by ABM due to the lubrication of ester groups in ABM. This study clearly shows that P(AN- co -ABM) copolymer is a better material used as carbon fiber precursor than P(AN–AM–MA) terpolymer.