TY - JOUR
T1 - Synthesis and characterization of perfluoro-3-methylene- 2,4-dioxabicyclo[3,3,0] octane
T2 - Homo- and copolymerization with fluorovinyl monomers
AU - Mikes, Frantisek
AU - Teng, Hongxiang
AU - Kostov, George
AU - Ameduri, Bruno
AU - Koike, Yasuhiro
AU - Okamoto, Yoshiyuki
PY - 2009/12/1
Y1 - 2009/12/1
N2 - 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).
AB - 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).
KW - Amorphous
KW - Fluorodioxolane
KW - Reactivity ratios
KW - Refractive index
KW - Thermal Properties
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U2 - 10.1002/pola.23700
DO - 10.1002/pola.23700
M3 - Article
AN - SCOPUS:72449165445
SN - 0887-624X
VL - 47
SP - 6571
EP - 6578
JO - Journal of Polymer Science, Part A: Polymer Chemistry
JF - Journal of Polymer Science, Part A: Polymer Chemistry
IS - 23
ER -