If I call someone on the phone and he picks up and says that he doesn't have time to talk right now, can I say: Okay. We'll just catch up later. -- to mean that I'll just talk to him at some other time (maybe later that day) when he's not busy?
Yes.
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catch up means talk to a friend you haven't talked to for a long time.
Don't say it if the call is business-related.
Clive