Monomer reactivity ratios for acrylonitrile-methyl acrylate free-radical copolymerization

K. B. Wiles, V. A. Bhanu, A. J. Pasquale, Timothy Edward Long, J. E. McGrath

Research output: Contribution to journalArticle

44 Citations (Scopus)

Abstract

Nonlinear monomer reactivity ratios for the homogeneous free-radical copolymerization of acrylonitrile and methyl acrylate were determined from 1H NMR and real-time Fourier transform infrared (FTIR) analyses. All 1H NMR data were obtained on polymers isolated at low conversions (<10%), whereas the FTIR data were collected in situ. The copolymerizations were conducted in N,N-dimethylformamide at 62°C and were initiated with azobisisobutyronitrile. The real-time FTIR technique allowed for many data points to be collected for each feed composition, which enabled the calculation of copolymer compositions (dM 1/dM 2) with better accuracy. Monomer reactivity ratios were estimated with the Mayo-Lewis method and then were refined via a nonlinear least-squares analysis first suggested by Mortimer and Tidwell. Thus, monomer reactivity ratios at the 95% confidence level were determined to be 1.29 ± 0.2 and 0.96 ± 0.2 for acrylonitrile and methyl acrylate, respectively, which were valid under the specific system conditions (i.e., solvent and temperature) studied. The results are useful for the development of acrylonitrile (<90%) and methyl acrylate, melt-processable copolymer fibers and films, including precursors for carbon fibers.

Original languageEnglish
Pages (from-to)2994-3001
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume42
Issue number12
DOIs
Publication statusPublished - 2004 Jun 15
Externally publishedYes

Fingerprint

Acrylonitrile
Free radicals
Copolymerization
Free Radicals
Fourier transforms
Monomers
Infrared radiation
Copolymers
Nuclear magnetic resonance
Dimethylformamide
Chemical analysis
Carbon fibers
Polymers
Fibers
methyl acrylate
Temperature

Keywords

  • Acrylonitrile
  • In situ FT-IR
  • Methyl acrylate
  • Nonlinear analysis
  • Reactivity ratios

ASJC Scopus subject areas

  • Polymers and Plastics
  • Organic Chemistry
  • Materials Chemistry

Cite this

Monomer reactivity ratios for acrylonitrile-methyl acrylate free-radical copolymerization. / Wiles, K. B.; Bhanu, V. A.; Pasquale, A. J.; Long, Timothy Edward; McGrath, J. E.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 42, No. 12, 15.06.2004, p. 2994-3001.

Research output: Contribution to journalArticle

Wiles, K. B. ; Bhanu, V. A. ; Pasquale, A. J. ; Long, Timothy Edward ; McGrath, J. E. / Monomer reactivity ratios for acrylonitrile-methyl acrylate free-radical copolymerization. In: Journal of Polymer Science, Part A: Polymer Chemistry. 2004 ; Vol. 42, No. 12. pp. 2994-3001.
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