I'm not sure if this type of information is available to PHP, meaning the only way to find out would be to execute the relative system command that displays information about the network adapter(s) installed, using PHP to parse that information for IP addresses.
EDIT: Hmm.. if your DNS server knows all of your IP's, it might be possible. What if you do something like this:
$hosts = gethostbynamel($_SERVER['SERVER_NAME']);
print_r($host);