The company I work for organises all international flights it can through United. There's also some deal that allows us to get priority upgraded if possible which occurs quite frequently.
Every time I've flown to the US, I've gone Business and returned Economy. One time when travelling with a colleague, returning from Boston, I checked in first and was given Economy to LA and Economy to Sydney. He checked in 10 minutes after me and got First Class to LA and Business to Sydney. His tickets were booked before mine. Order of when we checked in made no difference.
If you're just purchasing a ticket from a travel agent and turning up early, I'd say the chances of you being upgraded are exceptionally slim - there will be priority customers earmarked for those seats regardless of the time you turn up to check in.
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