This is a tough one, because both of these are interesting drives. I've never been in upstate NY other than Buffalo, and it would be interesting to explore. You're also running parallel to the Blue Ridge Parkway for a while through Virginia, which is likely pretty.
My initial reaction was to go with I-81, but that's also a fair amount of driving over the course of a week. PR-2 is a lot shorter, so I can stay someone for a couple of days, move on, and explore somewhere else. I've never been to Puerto Rico, so I decided to go with PR-2. There's not a weak choice here, though.
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