You can pre check an email with their embedded ajax call:
https://flow.microsoft.com/providers/Internal.User/users/use...
If the JSON comes back with "consumerDomain":true, then it won't allow the signup.
They don't seem to be catching all free email services. At the moment, it appears you could sign up for a free Yandex email and get signed up for Flow:
https://flow.microsoft.com/providers/Internal.User/users/som...