Synthesis and Characterization of Perfluoro-3-methylene- 2,4-dioxabicyclo[3,3,0] octane: Homo- and Copolymerization with Fluorovinyl Monomers

Mikes Frantisek (1) , Teng Hongxiang (1) , Georges Kostov (2) , B. Ameduri (2) , Yasuhiro Koike (3) , Yoshi Okamoto (4)

1 Polytechnic Institute of New York University, Polymer Research Institute
2 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
3 Faculty of Science and Technology, Keio University
4 PINYU - Polytechnic Institute of New York University, Polymer Research Institute,

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 F2/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 (Td [ 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 ¼ 3.635 and rCTFE ¼ 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).

Mots clés: amorphous; fluorodioxolane; reactivity ratios; refractive index; thermal properties; fluorocopolymers

Domaines: Polymères

Mikes Frantisek, Teng Hongxiang, Georges Kostov, B. Ameduri, Yasuhiro Koike, et al.. Synthesis and Characterization of Perfluoro-3-methylene- 2,4-dioxabicyclo[3,3,0] octane: Homo- and Copolymerization with Fluorovinyl Monomers. Journal of Polymer Science Part A: Polymer Chemistry, 2009, 47, pp.6571-6578. ⟨10.1002/pola.23700⟩. ⟨hal-00447611⟩