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Would this work for people who already maxed out their dropbox free account to the 19 gig limit (w/ .edu)?

Yes it would. I did this and I now have 25 GB of free Dropbox storage. That's about all I will ever need for what I use it for.

EDIT: and it's 5 GB total btw, not 4.5. 500 MB for just opting in.