Abstract A practical and direct electrophilic polymerization of hexafluoroacetone hydrate with diphenyl ether toward the preparation of semi‐fluorinated polyaryl ethers (PAE) is reported. Electrophilic aromatic substitution (EAS) polymerization under interfacial conditions with phase transfer catalyst (Aliquat 336) proceeds in trifluoromethanesulfonic anhydride by generation of trifluoromethanesulfonic acid and the protonated hexafluoroacetone (HFA) in situ affording 1,1,1,3,3,3‐hexafluoroisopropylidene (6F) PAE with high regioselectivity (4,4’‐DPE) and high molecular weight (≈60 kDa). Although first reported in a 1966 US Patent by DuPont using harsh conditions, improved synthetic methods or modern characterization has not been disclosed until now. Despite the presence of the 6F group, known to impart disordered morphology, this simple semi‐fluorinated PAE exhibits anomalous crystallinity with polymorphic melting points (Tm) ranging from 230–309 °C, high solubility in common organic solvents, a glass transition (Tg) of 163 °C, and thermo‐oxidative stability above 500 °C. Tough optically clear films prepared from solution give transmittance higher than 90% throughout the visible region. Synthesis, mechanistic aspects, and characterization including surface and dielectric properties are discussed.
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Improved Characterization of Polyoxazolidinones by Incorporating Solubilizing Side Chains
Carbon dioxide-based polyoxazolidinones (POxa) are an emerging subclass of non-isocyanate polyurethanes for high temperature applications. Current POxa with rigid linkers suffer from limited solubility that hinders synthesis and characterization. Herein, we report the addition of alkyl and alkoxy solubilizing groups to rigid spirocyclic POxa and their poly(hydroxyoxazolidinone) (PHO) precursors. The modified polymers were soluble in up to six organic solvents, enabling characterization of key properties (e.g., molar mass and polymer structure) using solution-state methods. Dehydration of PHO to POxa changed solubility from highly polar to less polar solvents and improved thermal stability by 76–102 °C. The POxa had relatively high glass transition (85–119 °C) and melting (190–238 °C) temperatures tuned by solubilizing group structure. The improved understanding of factors affecting solubility, structure–property relationships, and degradation pathways gained in this study broadens the scope of soluble POxa and enables more rational design of this promising class of materials.
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- Award ID(s):
- 1901635
- PAR ID:
- 10385928
- Date Published:
- Journal Name:
- Macromolecules
- ISSN:
- 0024-9297
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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