Plasticization of amorphous perfluoropolymers

Poly(perfluoro‐4‐vinyloxy‐1‐butene), which is also known as Cytop, and poly4,5‐difluoro‐2,2‐bis(trifluoromethyl)‐1,3‐dioxole]‐co‐poly(tetrafluoroethylene) copolymers with dioxole monomer contents of 65% or 87% (known as Teflon AF1600 and Teflon AF2400, respectively) were plasticized with four fluorous compounds. While plasticization of all polymers with perfluoroperhydrophenanthrene, perfluoro(1‐methyldecalin), a perfluorotetraether with three trifluoromethyl side groups and one hydrogen atom, and a linear perfluorooligoether with an average of 14.3 ether groups per molecule was successful, these four plasticizers affected the 12 blends very differently. A threshold of plasticization beyond which further increases in the plasticizer volume fraction did not further affect the glass transition temperature, T_g, was observed for some blends. Also, the limit of miscibility ranged from as low as 20% plasticizer content to complete miscibility at all volume fractions. The blends of Teflon AF2400 or Teflon AF1600 with high contents of the oligoether provided T_g values as low as ?114 °C, lower than for any other fully miscible blend. The occurrence of two glass transitions in an intermediate range of plasticizer volume ratios for these two types of blends can be explained by distinct local environments rather than macroscopic phase separation, as anticipated by the Lodge‐McLeish model. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 516–525, 2008