Kinetics on the copolymerization of acrylonitrile with itaconic acid or methyl acrylate in dimethylsulfoxide by NMR spectroscopy

Wang, Jing; Zhang, Mingyao; Fu, Zongwen; Zhou, Tingting; Xu, Xiaohui; Liu, Baijun

doi:10.1007/s12221-015-5573-6

Cited by 10 publications

(3 citation statements)

References 35 publications

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“…1,2 MA is the most studied among the acrylate monomers used for the production of PAN-based precursors. [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Copolymers of AN and MA are usually synthesized in bulk, [21][22][23] solution [33][34][35] or by precipitation polymerization in water. 36 The solvent environment is known to affect the reactivity of this monomer pair.…”

Section: Introductionmentioning

confidence: 99%

“…36 The solvent environment is known to affect the reactivity of this monomer pair. AN is a more reactive monomer in solution polymerization with MA (r AN = 1.22-1.29, r MA = 0.61-0.96 in N,N-dimethylformamide (DMF); 33,34 r AN = 1.02-1.33, r MA = 0.46-0.76 in dimethylsulfoxide (DMSO); 34,35,37 r AN = 1.20, r MA = 0.62 in dimethylacetamide 34 ) and their reactivity is close in bulk copolymerization (r AN = 0.56, r MA = 0.51 23 ); in contrast, MA is more reactive in precipitation copolymerization with AN (r AN = 0.83, r MA = 1.17 36 ).…”

Section: Introductionmentioning

confidence: 99%

“…MA is the most studied among the acrylate monomers used for the production of PAN‐based precursors 21–36 . Copolymers of AN and MA are usually synthesized in bulk, 21–23 solution 33–35 or by precipitation polymerization in water 36 . The solvent environment is known to affect the reactivity of this monomer pair.…”

Section: Introductionmentioning

confidence: 99%

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Reversible addition–fragmentation chain transferbased copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

Томс

Balashov

Gervald

et al. 2021

Polymer International

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Copolymers of acrylonitrile and alkyl acrylates with various alkyl substituents (methyl, ethyl, butyl, 2‐ethylhexyl and lauryl) were synthesized via reversible addition–fragmentation chain transfer polymerization in dimethylsulfoxide. It is demonstrated that reactivity of alkyl acrylate in copolymerization decreases with increase of the length of the alkyl substituent. The molar fractions of homodiads and homotriads of acrylonitrile and the number‐average sequence length of acrylonitrile units decreases with a decrease in the acrylate content in the copolymer or with an increase in the length of the alkyl substituent in the acrylate. The copolymer composition was held constant throughout copolymerization in all the studied systems resulting in the formation of copolymers with high compositional homogeneity. Additionally the reversible addition–fragmentation chain transfer mechanism provides low dispersity of the copolymers. Both factors enable the effect of the alkyl substituent in alkyl acrylate on the thermal behavior of acrylonitrile copolymers to be carefully revealed. Being inert in the cyclization reaction, alkyl acrylates have no effect on the activation energy of the reaction. However, increase of the length of the alkyl substituent is followed by a slower evolution of the ladder structure. In contrast, in conditions of oxidative stabilization, the stabilization index increases in the order of increase of the number‐average sequence length of the acrylonitrile units in the copolymers. Thus, the use of alkyl acrylates with longer alkyl substituents provides an increase of chain flexibility and the formation of an enhanced ladder structure during oxidative stabilization which is profitable for carbon fiber production. © 2021 Society of Industrial Chemistry.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Reversible addition–fragmentation chain transferbased copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

Томс

Balashov

Gervald

et al. 2021

Polymer International

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The suitable itaconic acid content in polyacrylonitrile copolymers used for PAN‐based carbon fibers

Liu

Deng

et al. 2016

J of Applied Polymer Sci

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This article was to provide some new insights into the influences of itaconic acid (IA) content in polyacrylonitrile (PAN) copolymers on polymerization, structural evolution, thermal behaviors and carbon yield relatively comprehensively. High IA containing poly(acrylonitrile-co-itaconic acid) (PAI) oligomers were successfully extracted from PAI copolymers with 2.0 and 3.0 mol % IA. PAI copolymers with 0.5 mol % and 1.0 mol % IA possessed more cyclized structures, conjugated carbonyl group, conjugated nitrile group, and less b-amino nitrile group as well as faster structural evolution rate than those of the other three PAI copolymers. Kinetic parameters indicated that excessive IA content in PAI copolymer did not have advantages in promoting cyclization reaction. The PAI copolymers with 0.5 wt % to 1.0 mol % IA possessed better crystalline parameters as well as higher carbon yield than those of the other two PAI copolymers after carbonization at 1350 C. In summary, PAI copolymers with 0.5 mol % to 1.0 mol % IA will be more suitable for fabricating of high performance PAN-based carbon fibers.

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Monte Carlo simulation of sequential structure control of AN-MA-IA aqueous copolymerization by different operation modes

Tong

Zhao

et al. 2022

Chinese Journal of Chemical Engineering

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Kinetics on the copolymerization of acrylonitrile with itaconic acid or methyl acrylate in dimethylsulfoxide by NMR spectroscopy

Cited by 10 publications

References 35 publications

Reversible addition–fragmentation chain transferbased copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

Reversible addition–fragmentation chain transferbased copolymers of acrylonitrile and alkyl acrylates as possible precursors for carbon fibers: synthesis and thermal behavior during stabilization

The suitable itaconic acid content in polyacrylonitrile copolymers used for PAN‐based carbon fibers

Monte Carlo simulation of sequential structure control of AN-MA-IA aqueous copolymerization by different operation modes

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