Synthesis of polyurethanes from fluorinated diisocyanates

A number of polyurethanes based on fluorinated aliphatic diisocyanates, perfluorinated aromatic diisocyanates, and chlorinated aromatic diisocyanates have been prepared. The polyurethane prepared from perfluorotrimethylene diisocyanate and hexafluoropentanediol was a rubbery solid which hydrolyzed readily in air to a liquid or sticky solid but was stable if protected from moisture. The products of hydrolysis were isolated and identified. Polyurethanes based on hexafluoropentamethylene diisocyanate were synthesized by reaction of hexafluoropentanediamine with hexafluoropentamethylene bischloroformate and with tetrafluoro‐p‐phenylene bischloroformate. Polyurethanes were synthesized by reaction of tetrafluoro‐p‐phenylene diisocyanate with hexafluoropentanediol and pentanediol. Other perfluoroaryl diisocyanate‐based polyurethanes were synthesized by reaction of tetrafluoro‐m‐phenylene diisocyanate with hexafluoropentanediol and with tetrafluoro‐p‐hydroquinone. Polyurethanes were also synthesized by reaction of tetrachloro‐p‐phenylene diisocyanate and 2,3,5,6‐tetrachloro‐p‐xylylene‐α,α′‐diisocyanate with hexafluoropentanediol.