Effects of comonomer with carboxylic group on stabilization of high molecular weight polyacrylonitrile nanofibrous copolymers

Lei, Danyun; Devarayan, Kesavan; Li, Xiang‐Dan; Choi, Woong-Ki; Seo, Min‐Kang; Kim, Byoung‐Suhk

doi:10.5714/cl.2014.15.4.290

Cited by 15 publications

(2 citation statements)

References 17 publications

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“…In order to solve this problem, several acidic comonomers, such as itaconic acid (IA) [15], acrylic acid (AA) [16], crotonic acid (CA) [17], 2-ethyl hexyl acrylate (EHA) [18], 2-methylenesuccinamic acid (MLA) [19], and vinyl acetate (VA) [20], have ever been incorporated into PAN macromolecular chains to improve the TOS using an ionic cyclization mechanism. Among these comonomers, IA with two carboxylic acid groups is the most efficient comonomer to initiate the cyclization of the nitrile group during the TOS process [21,22].…”

Section: Introductionmentioning

confidence: 99%

Preparation, Stabilization and Carbonization of a Novel Polyacrylonitrile-Based Carbon Fiber Precursor

et al. 2019

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The quality of polyacrylonitrile (PAN) precursor has a great influence on the properties of the resultant carbon fibers. In this paper, a novel comonomer containing the sulfonic group, 2-acrtlamido-2-methylpropane acid (AMPS), was introduced to prepare P(AN-co-AMPS) copolymers using itaconic acid (IA) as the control. The nanofibers of PAN, P(AN-co-IA), and P(AN-co-AMPS) were prepared using the electrospinning method. The effect of AMPS comonomer on the carbon nanofibers was studied using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Raman spectrum. The structural evolutions of PAN-based nanofibers were quantitatively tracked by FTIR and XRD during the thermal oxidative stabilization (TOS) process. The results suggested that P(AN-co-AMPS) nanofibers had the lower heat release rate (ΔH/ΔT = 26.9 J g−1 °C−1), the less activation energy of cyclization (Ea1 = 26.6 kcal/mol and Ea2 = 27.5 kcal/mol), and the higher extent of stabilization (Es and SI) during TOS process, which demonstrated that the AMPS comonomer improved the efficiency of the TOS process. The P(AN-co-AMPS) nanofibers had the better thermal stable structures. Moreover, the carbon nanofibers derived from P(AN-co-AMPS) precursor nanofibers had the better graphite-like structures (XG = 46.889). Therefore, the AMPS is a promising candidate comonomer to produce high performance carbon fibers.

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Section: Introductionmentioning

confidence: 99%

Preparation, Stabilization and Carbonization of a Novel Polyacrylonitrile-Based Carbon Fiber Precursor

et al. 2019

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“…In order to modify the properties of the acrylonitrile (AN) homopolymer, various comonomers, such as acrylic acid (AA), methacrylic acid (MAA), itaconic acid (IA), methyl acrylate (MA) and methyl methacrylate (MMA), were reported to copolymerize with AN. [12][13][14][15][16][17][18][19][20][21] The PAN/acid system cannot be produced by the melt-spinning process because the acid group becomes an active catalyst of cross-linking during melt spinning. 1,19 MA is a commonly used comonomer industrially to improve the melt-spinning properties of PAN-based copolymers, 20,21 such as reducing interactions between nitrile groups, lowering activation energy, reducing the formation of a core-shell structure and improving solubility.…”

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confidence: 99%

Thermal analysis and melt spinnability of poly(acrylonitrile-co-methyl acrylate) and poly(acrylonitrile-co-dimethyl itaconate) copolymers

Rwei

Way

Chiang

et al. 2017

Textile Research Journal

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This work investigated the cyclization possibility and melt spinnability of carbon fiber precursors, poly(acrylonitrile-co-methyl acrylate) (AN/MA) and poly(acrylonitrile-co-dimethyl itaconate) (AN/DMI). The onset temperature of cyclization of the AN/DMI copolymer is lower than that of the AN/MA copolymer and also the polyacrylonitrile (PAN) homopolymer. The enthalpy (ΔH) of the AN/DMI copolymer is about 3–4 times that of the PAN homopolymer and about 1.8 times that of the AN/MA copolymer, indicating that the degree of cyclization of the AN/DMI copolymer is relatively higher. The melt dwell time of the AN/DMI copolymer is increased to about 3–5 times that of the AN/MA copolymer, especially when synthesized with a feed molar ratio of AN/DMI = 85/15. The AN/DMI copolymer (AN/DMI = 85/15) has the longest melt dwell time, 24.8 min, at the lowest melting temperature, 190oC, among all the PAN-related copolymers synthesized herein. Furthermore, the AN/DMI copolymer (AN/DMI = 85/15) can be rapidly cyclized at the cyclization temperature of 260℃, which is 25℃ lower than that of the AN/MA copolymer (AN/MA = 85/15). In short, this work demonstrates that the carbon fiber precursor made by the AN/DMI copolymer (AN/DMI = 85/15) will be superior to that of the AN/MA copolymer (AN/MA = 85/15) with respect to the melt spinnability and cyclization at low temperature.

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Polymers of vinylphosphonic acid, acrylonitrile, and methyl acrylate and their nanofibers

Yılmaz

Akar

Köken

et al. 2020

J of Applied Polymer Sci

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In this study, a small amount of vinylphosphonic acid was used to produce fire‐retardant copolymers and terpolymers from acrylonitrile and methyl acrylate. The structures of copolymer and terpolymers were elucidated by 1H‐NMR and phosphorous analysis. Thermal decomposition of vinylphosphonic acid‐containing copolymers and terpolymers started at lower temperatures than of poly(acrylonitrile‐co‐methyl acrylate). Methyl acrylate contributes to the thermal resistance of the terpolymers. Poly(acrylonitrile‐co‐methyl acrylate‐co‐vinylphosphonic acid) with a phosphorous content about 0.25% burned at a slower rate and emitted less smoke compared to poly(acrylonitrile‐co‐methyl acrylate). The burning tests showed that both copolymer and terpolymers containing vinylphosphonic acid behaved as a fire‐retardant polymer. The phosphonate and phosphonic acid groups in the copolymer and terpolymers accelerate the cyclization of nitrile groups and inhibit the fire in the gas phase. Nanofibers were successfully produced by the electrospinning method from the copolymers and terpolymers containing vinylphosphonic acid moiety.

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Effects of comonomer with carboxylic group on stabilization of high molecular weight polyacrylonitrile nanofibrous copolymers

Cited by 15 publications

References 17 publications

Preparation, Stabilization and Carbonization of a Novel Polyacrylonitrile-Based Carbon Fiber Precursor

Preparation, Stabilization and Carbonization of a Novel Polyacrylonitrile-Based Carbon Fiber Precursor

Thermal analysis and melt spinnability of poly(acrylonitrile-co-methyl acrylate) and poly(acrylonitrile-co-dimethyl itaconate) copolymers

Polymers of vinylphosphonic acid, acrylonitrile, and methyl acrylate and their nanofibers

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