An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane

Min-Hui Cui, Yuli Zhang, Mark Werner, Nan Loh Yang, Steven P. Fenelli, John A. Grates

Research output: Contribution to journalArticle

Abstract

The mechanism of cationic copolymerization of trioxane with 1,3-dioxepane was investigated using in situ 13C NMR based on microsequence data established via PFG-HMQC and PFG-HMBC two-dimensional NMR. Kinetic profiles of pentad sequences and butylene oxide (CH2CH2CH2CH2O) counit placement were obtained. The incorporation of 1,3-dioxepane into the copolymer sequences was found to involve its initial homopolymerization followed by redistribution of counits through chain transfers, e.g. transacetalization. Unlike the copolymerization of trioxane with dioxolane, the insertion of formaldehyde into 1,3-dioxepane to form a larger acetal ring prior to substantial copolymerization does not play a significant role. For the first time, nonad sequences were observed directly by NMR analysis of the copolymer.

Original languageEnglish (US)
Pages (from-to)228-241
Number of pages14
JournalACS Symposium Series
Volume834
StatePublished - 2002
Externally publishedYes

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Copolymerization
Nuclear magnetic resonance
Copolymers
Acetals
Homopolymerization
Formaldehyde
Oxides
Kinetics
vitamin B 12 factor III
formal glycol
butylene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Cui, M-H., Zhang, Y., Werner, M., Yang, N. L., Fenelli, S. P., & Grates, J. A. (2002). An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane. ACS Symposium Series, 834, 228-241.

An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane. / Cui, Min-Hui; Zhang, Yuli; Werner, Mark; Yang, Nan Loh; Fenelli, Steven P.; Grates, John A.

In: ACS Symposium Series, Vol. 834, 2002, p. 228-241.

Research output: Contribution to journalArticle

Cui, M-H, Zhang, Y, Werner, M, Yang, NL, Fenelli, SP & Grates, JA 2002, 'An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane', ACS Symposium Series, vol. 834, pp. 228-241.
Cui M-H, Zhang Y, Werner M, Yang NL, Fenelli SP, Grates JA. An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane. ACS Symposium Series. 2002;834:228-241.
Cui, Min-Hui ; Zhang, Yuli ; Werner, Mark ; Yang, Nan Loh ; Fenelli, Steven P. ; Grates, John A. / An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane. In: ACS Symposium Series. 2002 ; Vol. 834. pp. 228-241.
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