Well, to tell you the truth, that might be a good solution to use the old PB as a conduit/chase out for your new PEX.... if it will fit. You'll have to check the ID of the PB and OD of the PEX. Depending on how tight a fit and how long the run, you might have a hard time pulling it though as the PEX may bind up inside the PB. If you have the time/patience it might be worth trying though.
Two things might help(already assuming it is physically possible):
1) Blow(with compressed air) a pull cord through the existing PB line so you can pull and push the PEX through. Just trying to push the PEX through is almost guaranteed to bind up at some point.
2) Get some cable pull "grease" and lube the PEX as it goes into the old PB "conduit". You can get this in the electrical section of your favorite big-box home improvement store, or an electrical supply.
This may all be academic though if:
1) It is somehow not code compliant(not sure why it would be, but...)
2) The PB has a lot of hard water deposits that make it no longer clear and round inside
You might also want to just double check with your local building department to make sure there isn't some odd code issue too. I can't imagine why it would an issue, but you never know.
I have an old galvanized 1-1.5 inch supply line coming from a 5/8 meter... who knows why.... but I've had the same possible idea if/when it starts leaking versus digging it up. It is about 80 years old, so it is probably due
Al