Of course, there are better sources now than TV Land ever was. METV, Cozi, Antenna TV, Laff, and others. And a lot of the really obscure stuff is on YouTube.
I assume that they do, since about half have already turned up. There's no way only a single 16mm print of each episode would have been struck, so copies must be out there. I am surprised that Julie Newmar doesn't have copies herself.
That is not true about "My Living Doll". Other episodes exist, albeit on 16mm, in private collections. It is true that the 35mm negatives were destroyed.