Fluoropolyethers end‐capped by polar functional groups. I. Kinetic approach to the reaction of hydroxy‐terminated fluoropolyethers with cycloalyphatic and aromatic diisocyanates

Urethane reactions of cycloaliphatic and aromatic diisocyanates with hydroxy‐terminated fluoropolyethers (FPEs) of various molecular weights and structure, at NCO : OH = 2, have been studied by monitoring, by IR analysis, the rate of decrease in NCO absorbance at 2264–2268 cm⁻¹. Different diisocyanates have been tested, among them the following: 4,4′‐dicyclohexylmethane diisocyanate (H₁₂MDI); 5‐isocyanato‐1,3,3‐trimethylcyclohexylmethyl isocyanate or isophorone diisocyanate (IPDI); 2,4‐toluene diisocyanate (TDI). Ethyl acetate (EA), methyl isobutyl ketone (MIBK), and hexafluoroxylene (HFX) have been used as solvents in presence of dibutyltin dilaurate (DBTDL) or 1,4‐diazabicyclo2.2.2]octane (DABCO) as catalysts. These reactions gave rise to NCO‐end‐capped FPE–oligourethanes. Preliminary solubility tests for HO‐terminated FPEs in various solvents made it possible to select proper candidates for carrying out reaction in homogeneous conditions at high concentrations of reagents (30–50% w/w). The second‐order kinetic mechanism was shown to be valid. Positive deviations from linearity for the second‐order kinetics around 40–80% conversion, found for most of the FPE diols, were attributed to the autocatalysis of the isocyanate–hydroxyl reaction by the arising urethane groups. Uncatalyzed reactions with cycloaliphatic diisocyanates are very slow at 40°C. The tertiary amine DABCO is a much less effective catalyst than DBTDL. FPEs having terminal OH groups separated from the perfluorinated main molecular chain by  (OCH₂CH₂)_n segments (n = 1–2) are generally more reactive than FPEs with end  CH₂OH groups. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 557–570, 1999