Personally I'd extract all the mail using exmerge and then disable the Exchange mailbox, set up the postfix one. Are the users using Outlook to connect? If so, give them their exmerged PST, etc. I wouldn't want to put their email back in to a server one at a time as Exchange uses one-to-many copies for email storage if multiple recipients are specified in the same domain to save space.
Just a thought.
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