Preparation of biphenyl perfluorocyclobutyl (BP-PFCB) polyethylene glycol (PEG) copolymers by the formation of fluorinated arylene vinylene ether (FAVE)

• Published in: Polymer bulletin (Berlin, Germany) Vol. 72; no. 6; pp. 1393 - 1405
• Main Authors: Brown, Dakarai K., Cracowski, Jean-Marc, Iacono, Scott T., Christensen, Ken, Smith, Dennis W.
• Format: Journal Article
• Language: English
• Published: Berlin/Heidelberg Springer Berlin Heidelberg 01.06.2015; Springer Nature B.V
• Subjects: Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Chromatography; Complex Fluids and Microfluidics; Copolymers; Fluorination; Fourier transforms; Fractions; Gel chromatography; Glass transition temperature; Nitrogen; NMR; Nuclear magnetic resonance; Oligomers; Organic Chemistry; Original Paper; Physical Chemistry; Polyethylene glycol; Polymer Sciences; Polymers; Soft and Granular Matter; Spectrum analysis; Thermal analysis; Thermogravimetric analysis; Trifluorovinyl ether; Fluorinated arylene vinylene ether (FAVE) polymer; Fluoropolymer; Polyethylene glycol (PEG); Perfluorocyclobutyl (PFCB); Fox equation
• ISSN: 0170-0839; 1436-2449
• DOI: 10.1007/s00289-015-1344-1

A series of biphenyl per fluorocyclobutyl (BP-PFCB) polyethylene glycol (PEG) copolymers were prepared by nucleophilic addition the hydroxyl end groups of PEG to trifluorovinyl ether (TFVE) end groups of biphenyl perfluorocyclobutyl (BP-PFCB) oligomers. Upon addition, copolymers are linked through a new fluorinated arylene vinylene ether (FAVE) bond. Resulting copolymers were characterized by ATR-FTIR, 1 H, and 19 F NMR analysis. Gel permeation chromatography (GPC) showed a number-average molecular weights ( M n s) of polymers from 9000 to 16,000. A moderated increase in M n s was observed compared to corresponding oligomers. Differential scanning calorimetry (DSC) thermograms revealed glass transition temperatures ( T g s) from −25 to 127 °C. All copolymers showed one copolymer-specific T g . All T g s were compared to the theoretical values calculated from the Fox equation. Comparisons showed T g s became more agreeable at the lowest and highest PEG weight fractions. Thermal gravimetric analysis (TGA) studies showed a two-stage degradation in nitrogen and air that corresponded to copolymer weight percent. The onsets of degradations were from 343 to 360 °C for copolymers in air and from 333 to 343 °C for copolymers in nitrogen.