It is possible. I thought I saw a mod for it here but I cannot seem to find it atm. You could make a plugin to block certain extensions/domains.
This has not been tested, but something like:
Hook location: register_addmember_process
PHP Code:
PHP Code:
$emailcheck = @explode('@', $vbulletin->GPC['email']);
$emailcheck = $emailcheck[1];
if (strpos($emailcheck, 'domain.edu') === false)
{
$userdata->error('invalidemail');
}