One thing to remember is the T_a of 85C is completely irrelevant, what matters is the T_die spec of 105C. If you're running the micro full blast, then the temp rise of die is ~10C, but by reducing clock, peripherals used, VCC, and other such stuff, that delta reduces drastically.
I don't see why you can't use this micro for a PFC from a temp rating perspective, if the ambient conditions are too much for it, then they are also way too much for the electrolytic caps, switching devices, etc etc.