Umm, not to state the obvious, but can you just say stop or your fired? Flex your IT muscle. :-) Is this a small buisness?
Sounds like basically they are using a proxy redirect. A IP block won't stop it, and neither will a domain. Might be able to put certian local restrictions that will stop them from signing into the site, but stopping them from viewing it is pretty hard. You could set set a static DNS dyndns.com but you need a pro account. Its only 15$ a year, so not that bad. Then you would have better control and be able to insert wildcards in your domain blocks. Like block anything that had the word facebook in it. But then they could use Tor...and then the arms race would start.
Basicaly, get your HR to write up a fair use internet agreement. Have them sign it. 3 strikes your out.