Then you could use preg_match() to match the domains you don't want:
if ( preg_match ('/(hotmail\.com|\.ru)$/i', $domain) ) {
// bounce or show error message
} else {
// send the e-mail
}
This would work fine for blacklisting a few domains, but if you need to add a lot more you should do something more scalable. Perhaps a text file with one domain per line and a PHP function that loads the text file into an array and then checks the domain against each element. Or you could go all the way to a database-driven solution with an admin screen for updating your blacklist. It's all up to you...