Synthesis of poly-p-oxyperfluorobenzylene and related polymers. A novel synthesis of the monomer 2,3,5,6-tetrafluoro-4-trifluoromethylphenol

Abstract

The sy nth esis and polymerization of 2,3,5,6-tetraAuoro-4-triA uoromethylphenol (he ptaAuoro-pcres ol) is desc ribed. Th e polymer , po ly-p-oxype rAu orobenzyle ne (polyperAuoro-p-benzy le ne oxide), is probab ly formed thro ugh the perAuoro -p-quinon e me th id e inte rm e di ate obtaine d by the intramol ec ular loss of e ithe r hydroge n Au oride or a me tal Au orid e. Th e polymer has a s tru c ture a nal ogo us to th at reported for the polymer d erive d from p-triAuoro me thy lphe no l und e r s imil ar co nditi ons.[n th e co urse of th e syn th es is of th e monom er, he ptafluoro-p-c reso l, a novel s yntheti c me thod was dis co vered. Th e sy nthes is cons ists in the prior preparation of I -t-but oxy-2,3,5,6-tetrafluoro -4-triAu orom e thylbenze ne and its s ubsequ e nt th ermal d eco mposition into th e isobutyl ene and the des ire d cresol. S imil arly, N-t-butyl-2,3,5,6-tet raAuoro-4-triAu orome th ylaniline und ergoes a s imil ar liquid phase pyrolys is into isobutyle ne and 2,3,5,6-tetraAuoro-4-triAu oromet hylaniline. However, during the course of thi s pyrolys is, prac ti ca ll y a ll of the ani line undergoes po lymerization with the concomitant los s of hydrogen Au orid e. T he polymer is form e d by th e same mec hani s m operative in the thermal po lymerization of p-heptafluorocresol exce pt th a t additional quantiti es of hydrogen Auoride ca n be elimin ated from th e -NHCF, -segme nts of the polymer c hain the re by introd uc ing -N = CF -units into the polymer bac kbone .Other t-b utyl derivatives were sy nthes ized and th e ir thermal deco mposition studied. Several poss ibl e mec hani s ms for the deco mpos ition of these t-butyl co mpo und s a re considered _ Key Words: I -t-Butoxy-2,3,5,6-te traAu oro-4-triAuorom e th ylbe nzen e , perAuoro-p-quinon e met hid e, po lyme rization, poly-p-oxyperAuorobenzy le ne, pyrolysis, 2,3,5,6-tetrafluoro-4-triAu orome thylph enol.