Were you able to sort this problem as I have exactly the same issue? - i.e. the merchant website requires an email address to be entered, which an additional user does not have. We have been able to process payments if the particular user is already logged into Paypal.com (using their UserID and password) within a different tab on the same web browser but this is not at all ideal. Surely all it would need is for additional users on a business account to have their email addresses entered as part of the setup?!
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