I've got 3 unique weapons, thus far (but I'm only 11 hours into the game at the moment).
Chopper, Big Boomer and That Gun.
The Chopper is basically just lying around at a certain farmhouse location, only picked it up when I noticed it's valuation. Big Boomer I collected after inadvertantly shooting the owner. It's a shotgun worth around 2500 caps. I loved the Terrible Shotgun on F3, so this should be right up my street. However, I'm actually contemplating restarting from prior to that as the owner in question has a few quests I'd like to do, first. That Gun is for sale in Novac, and again is a great weapon, although the reload time on it is poor. My usual weapon of choice is either the Mercenary Grenade Launcher (as part of my bonus pack), or one of the shotguns, but I've been using That Gun a fair bit since I bought it.