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 language | English |
|---|---|
| Pages (from-to) | 5180-5188 |
| Number of pages | 9 |
| Journal | Journal of Polymer Science, Part A: Polymer Chemistry |
| Volume | 42 |
| Issue number | 20 |
| DOIs | |
| Publication status | Published - 2004 Oct 15 |
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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 journal › Article
}
TY - JOUR
T1 - Free-Radical Polymerization of Dioxolane and Dioxane Derivatives
T2 - Effect of Fluorine Substituants on the Ring Opening Polymerization
AU - Liu, Weihong
AU - Mikeš, František
AU - Guo, Yinzhong
AU - Koike, Yasuhiro
AU - Okamoto, Yoshi
PY - 2004/10/15
Y1 - 2004/10/15
N2 - 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.
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.
KW - Fluorinated 2-methylene-1,3-dioxane
KW - Fluorinated 2-methylene-1,3-dioxolane
KW - Fluoropolymers
KW - Radical polymerization
KW - Ring opening polymerization
UR - http://www.scopus.com/inward/record.url?scp=6944244854&partnerID=8YFLogxK
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U2 - 10.1002/pola.20309
DO - 10.1002/pola.20309
M3 - Article
AN - SCOPUS:6944244854
VL - 42
SP - 5180
EP - 5188
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
SN - 0887-624X
IS - 20
ER -