It's not so much mining techniques, or even new materials/minerals (although that helps), but manufacturing processes. Zero-G Manufacture would lead the pack.
AFAIK, no one has even attempted any kind of large-scale metal refining in space, but they haven't even scratched the surface of what materials may be out there. For the Primitive stuff, I would think some form of Carbon-60 Bucky Ball structure would be the name of the game, initially......