I've read recommendations that it's best when it's freshly expressed. But I can honestly say that that half of my frozen stash is from that time range and DS is just as happy with it
I think milk is only good in the fridge for up to 5 days so personally I would throw away 6 day old milk, if it was less than 5 days old I would assume it would be ok to freeze, but I'm not certain (p.s. I hate wasting expressed milk too, whoever said "dont cry over spoilt milk" has obviously never expressed!)
You could always taste it to see if it's still okay. Perhaps mark it for using in cooking later on, when LO's eating solids... or use it in food now for your older one
If it doesn't smell or taste sour, I'd keep it. I'm sure I froze milk that was 6 or 7 days old and DS never had any problems with it. When it's bad, you'll definitely be able to tell.
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