Did you check the above link?
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Originally Posted by calibre FAQ
Note: Microsoft/Google/Gmx can disable your account if you use it to send large amounts of email. So, when using these services to send mail calibre automatically restricts itself to sending one book every five minutes. If you don’t mind risking your account being blocked you can reduce this wait interval by going to Preferences->Tweaks in calibre.
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EDIT: Need to remember to refresh the page more often...