Synthesis and characterization of perfluoro-3-methylene- 2,4-dioxabicyclo[3,3,0] octane

Homo- and copolymerization with fluorovinyl monomers

Frantisek Mikes, Hongxiang Teng, George Kostov, Bruno Ameduri, Yasuhiro Koike, Yoshiyuki Okamoto

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The synthesis of perfluoro-3-methylene-2,4-dioxabicyclo[3,3,0] octane (D), its radical homopolymerization, and copolymerization with fluoroolefins are presented. Fluorodioxolane (D) was synthesized through direct fluorination of the corresponding hydrocarbon precursor in a fluorinated solvent by F 2/N2 gas. It was polymerized in bulk using perfluorodibenzoyl peroxide as the initiator. The resulting homopolymer had a limited solubility in fluorinated solvents, and its glass transition temperature (Tg) was in the range of 180-190°C. The polymeric films prepared by casting from hot hexafluorobenzene (HFB) solution were transparent with low refractive index (1.329 at 633 nm). These films were thermally stable (T d > 350°C), and were hard and brittle. The copolymers of monomer (D) were prepared with fluorovinyl monomers such as chlorotrifluoroethylene (CTFE), perfluoropropyl vinyl ether, perfluoromethyl vinyl ether, and vinylidene fluoride. The kinetics of radical copolymerization of monomer (D) with CTFE led to the assessment of the reactivity ratios of both comonomers: rD = 3.635 and rCTFE = 0.737 at 74°C, respectively. The copolymers obtained were soluble in HFB and perfluoro-2-butyltetrahydrofuran, with Tg in the range of 84-145°C depending on the copolymer composition. The films of the copolymers were flexible and clear with a low refractive index (1.3350-1.3770 at 532 nm).

Original languageEnglish
Pages (from-to)6571-6578
Number of pages8
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Volume47
Issue number23
DOIs
Publication statusPublished - 2009 Dec 1

Fingerprint

Homopolymerization
Copolymerization
Copolymers
Monomers
Ethers
Refractive index
Fluorination
Peroxides
Hydrocarbons
Polymer films
Casting
Solubility
Gases
Kinetics
octane
Chemical analysis
vinyl ether
hexafluorobenzene
chlorotrifluoroethylene

Keywords

  • Amorphous
  • Fluorodioxolane
  • Reactivity ratios
  • Refractive index
  • Thermal Properties

ASJC Scopus subject areas

  • Materials Chemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Synthesis and characterization of perfluoro-3-methylene- 2,4-dioxabicyclo[3,3,0] octane : Homo- and copolymerization with fluorovinyl monomers. / Mikes, Frantisek; Teng, Hongxiang; Kostov, George; Ameduri, Bruno; Koike, Yasuhiro; Okamoto, Yoshiyuki.

In: Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 47, No. 23, 01.12.2009, p. 6571-6578.

Research output: Contribution to journalArticle

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abstract = "The synthesis of perfluoro-3-methylene-2,4-dioxabicyclo[3,3,0] octane (D), its radical homopolymerization, and copolymerization with fluoroolefins are presented. Fluorodioxolane (D) was synthesized through direct fluorination of the corresponding hydrocarbon precursor in a fluorinated solvent by F 2/N2 gas. It was polymerized in bulk using perfluorodibenzoyl peroxide as the initiator. The resulting homopolymer had a limited solubility in fluorinated solvents, and its glass transition temperature (Tg) was in the range of 180-190°C. The polymeric films prepared by casting from hot hexafluorobenzene (HFB) solution were transparent with low refractive index (1.329 at 633 nm). These films were thermally stable (T d > 350°C), and were hard and brittle. The copolymers of monomer (D) were prepared with fluorovinyl monomers such as chlorotrifluoroethylene (CTFE), perfluoropropyl vinyl ether, perfluoromethyl vinyl ether, and vinylidene fluoride. The kinetics of radical copolymerization of monomer (D) with CTFE led to the assessment of the reactivity ratios of both comonomers: rD = 3.635 and rCTFE = 0.737 at 74°C, respectively. The copolymers obtained were soluble in HFB and perfluoro-2-butyltetrahydrofuran, with Tg in the range of 84-145°C depending on the copolymer composition. The films of the copolymers were flexible and clear with a low refractive index (1.3350-1.3770 at 532 nm).",
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