Here's some information on this - if setting the secondary mail account as your default temporarily -- or there's a macro you can run but I have not tried it:
"In researching this, one of the answers I found is to change the default e-mail account to the one you've set up for the merge, for the duration of the merge. If that doesn't work, I also came across this website, but it involves creating a macro with VBA and I'm not a VBA developer so I'm not sure I can reliably say that this does what you want. I hope one of these helps!
http://word.mvps.org/FAQs/
http://en.allexperts.com/q
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by: chin2000Posted on 2009-08-03 at 11:56:25ID: 25007336
Set up the seccond email profile for the seccond email address.