Free-Radical Polymerization of Dioxolane and Dioxane Derivatives: Effect of Fluorine Substituants on the Ring Opening Polymerization

Weihong Liu, František Mikeš, Yinzhong Guo, Yasuhiro Koike, Yoshi Okamoto

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

Partially fluorinated and perfluorinated dioxolane and dioxane derivatives have been prepared to investigate the effect of fluorine substituents on their free-radical polymerization products. The partially fluorinated monomer 2-difluoromethylene-1,3-dioxolane (I) was readily polymerized with free-radical initiators azobisisobutyronitrile or tri(n-butyl)borane-air and yielded a vinyl addition product. However, the hydrocarbon analogue, 2-methylene-1,3-dioxolane (II), produced as much as 50% ring opening product at 60°C by free-radical polymerization. 2-Difluoromethylene-4-methyl-1,3-dioxolane (III) was synthesized and its free-radical polymerization yielded ring opening products: 28% at 60°C, decreasing to 7 and 4% at 0°C and -78°C, respectively. All the fluorine-substituted, perfluoro-2-methylene-4-methyl-1,3-dioxolane (IV) produced only a vinyl addition product with perfluorobenzoylperoxide as an initiator. The six-membered ring monomer, 2-methylene-1,3-dioxane (V), caused more than 50% ring opening during free-radical polymerization. However, the partially fluorinated analogue, 2-difluoromethylene-1,3-dioxane (VI), produced only 22% ring opening product with free-radical polymerization and the perfluorinated compound, perfluoro-2-methylene-1,3-dioxane (VII), yielded only the vinyl addition polymer. The ring opening reaction and the vinyl addition steps during the free-radical polymerization of these monomers are competitive reactions. We discuss the reaction mechanism of the ring opening and vinyl addition polymerizations of these partially fluorinated and perfluorinated dioxolane and dioxane derivatives.

Original languageEnglish
Pages (from-to)5180-5188
Number of pages9
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume42
Issue number20
DOIs
Publication statusPublished - 2004 Oct 15

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Fluorine
Ring opening polymerization
Free radical polymerization
Derivatives
Monomers
Boranes
Hydrocarbons
Free radicals
Free Radicals
formal glycol
1,4-dioxane
Polymers
Polymerization
Air

Keywords

  • Fluorinated 2-methylene-1,3-dioxane
  • Fluorinated 2-methylene-1,3-dioxolane
  • Fluoropolymers
  • Radical polymerization
  • Ring opening polymerization

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

Free-Radical Polymerization of Dioxolane and Dioxane Derivatives : Effect of Fluorine Substituants on the Ring Opening Polymerization. / Liu, Weihong; Mikeš, František; Guo, Yinzhong; Koike, Yasuhiro; Okamoto, Yoshi.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 42, No. 20, 15.10.2004, p. 5180-5188.

Research output: Contribution to journalArticle

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abstract = "Partially fluorinated and perfluorinated dioxolane and dioxane derivatives have been prepared to investigate the effect of fluorine substituents on their free-radical polymerization products. The partially fluorinated monomer 2-difluoromethylene-1,3-dioxolane (I) was readily polymerized with free-radical initiators azobisisobutyronitrile or tri(n-butyl)borane-air and yielded a vinyl addition product. However, the hydrocarbon analogue, 2-methylene-1,3-dioxolane (II), produced as much as 50{\%} ring opening product at 60°C by free-radical polymerization. 2-Difluoromethylene-4-methyl-1,3-dioxolane (III) was synthesized and its free-radical polymerization yielded ring opening products: 28{\%} at 60°C, decreasing to 7 and 4{\%} at 0°C and -78°C, respectively. All the fluorine-substituted, perfluoro-2-methylene-4-methyl-1,3-dioxolane (IV) produced only a vinyl addition product with perfluorobenzoylperoxide as an initiator. The six-membered ring monomer, 2-methylene-1,3-dioxane (V), caused more than 50{\%} ring opening during free-radical polymerization. However, the partially fluorinated analogue, 2-difluoromethylene-1,3-dioxane (VI), produced only 22{\%} ring opening product with free-radical polymerization and the perfluorinated compound, perfluoro-2-methylene-1,3-dioxane (VII), yielded only the vinyl addition polymer. The ring opening reaction and the vinyl addition steps during the free-radical polymerization of these monomers are competitive reactions. We discuss the reaction mechanism of the ring opening and vinyl addition polymerizations of these partially fluorinated and perfluorinated dioxolane and dioxane derivatives.",
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AB - Partially fluorinated and perfluorinated dioxolane and dioxane derivatives have been prepared to investigate the effect of fluorine substituents on their free-radical polymerization products. The partially fluorinated monomer 2-difluoromethylene-1,3-dioxolane (I) was readily polymerized with free-radical initiators azobisisobutyronitrile or tri(n-butyl)borane-air and yielded a vinyl addition product. However, the hydrocarbon analogue, 2-methylene-1,3-dioxolane (II), produced as much as 50% ring opening product at 60°C by free-radical polymerization. 2-Difluoromethylene-4-methyl-1,3-dioxolane (III) was synthesized and its free-radical polymerization yielded ring opening products: 28% at 60°C, decreasing to 7 and 4% at 0°C and -78°C, respectively. All the fluorine-substituted, perfluoro-2-methylene-4-methyl-1,3-dioxolane (IV) produced only a vinyl addition product with perfluorobenzoylperoxide as an initiator. The six-membered ring monomer, 2-methylene-1,3-dioxane (V), caused more than 50% ring opening during free-radical polymerization. However, the partially fluorinated analogue, 2-difluoromethylene-1,3-dioxane (VI), produced only 22% ring opening product with free-radical polymerization and the perfluorinated compound, perfluoro-2-methylene-1,3-dioxane (VII), yielded only the vinyl addition polymer. The ring opening reaction and the vinyl addition steps during the free-radical polymerization of these monomers are competitive reactions. We discuss the reaction mechanism of the ring opening and vinyl addition polymerizations of these partially fluorinated and perfluorinated dioxolane and dioxane derivatives.

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KW - Radical polymerization

KW - Ring opening polymerization

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