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I usually throw it out within 28 hours or so. I throw it in the fridge just before going to bed at night and it's slushy by morning. Another option you have is to pump into the Playtex drop-ins using the Playtex One Step System and freezing the exact amount that baby eats right in those... then no bottle prep is needed and they can go straight to daycare from the freezer.
I believe the rule is 24 hours from when it finishes defrosting, but I bet you could push it a little as long as it was kept well refrigerated. For daycare I would try to store in amounts he takes for a bottle.