Synthesis and characterization of poly(fluorinated vinyl ether-alt-tert-butyl α-trifluoromethacrylate) copolymers

• Published in: Journal of polymer science. Part A, Polymer chemistry Vol. 47; no. 22; pp. 6116 - 6123
• Main Authors: Cracowski, Jean-Marc, Montembault, Véronique, Odobel, Fabrice, Améduri, Bruno, Fontaine, Laurent
• Format: Journal Article
• Language: English
• Published: Wiley Subscription Services, Inc., A Wiley Company 15.11.2009
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.23653

Radical copolymerizations of electron acceptor tert-butyl α-trifluoromethacrylate (MAF-TBE) and electron donor 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-heptadecafluoro-10-(vinyloxy)decane (FAV8) initiated by tert-butyl 2,2-dimethylperoxypropanoate were investigated. Although none of both monomers underwent radical homopolymerization under classical conditions, they readily copolymerized, producing a soluble copolymer containing 60-65 mol % of MAF-TBE. The reactivity ratios determined by the Kelen-Tüdos method were found to be rMAF₋TBE = 0.03 ± 0.01 and rFAV₈ = 0 at 74 °C, indicating the synthesis of alternated copolymers. The copolymer compositions were assessed from ¹⁹F-NMR spectroscopy and correlated with thermogravimetric analysis. Molecular weights and polydispersity indexes of poly(MAF-TBE-alt-FAV8) copolymers were both low and ranged from 5.5 to 6.9 x 10³ g mol⁻¹ and from 1.08 to 1.23, respectively. Copolymers were amorphous, and Tg were about 55 °C for all copolymers. TGA analyses showed the release of isobutene from MAF-TBE units in copolymers before a degradation of the resulting poly(α-trifluoromethacrylic acid-alt-FAV8) copolymers, occurring at 250-260 °C.