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

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 journal › Article › peer-review

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 language	English (US)
Pages (from-to)	228-241
Number of pages	14
Journal	ACS Symposium Series
Volume	834
State	Published - Dec 1 2002
Externally published	Yes

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)

Cite this

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

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.",

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T1 - An NMR study on the bulk cationic copolymerization of trioxane with 1,3-dioxepane

AU - Cui, Min Hui

AU - Zhang, Yuli

AU - Werner, Mark

AU - Yang, Nan Loh

AU - Fenelli, Steven P.

AU - Grates, John A.

PY - 2002/12/1

Y1 - 2002/12/1

N2 - 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.

AB - 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.

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

Abstract

ASJC Scopus subject areas

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