Here's a report of a chemical that was used in a most unusual way. Look at the starting material was a modified form of a dye called rylene: (The brackets in the picture even suggests that this monomer is a polymer itself, although they are in fact used to indicate that the number of naphthalene groups can vary a small amount.)
The rylene was modified by the addition of phenyl triflurovinyl ether groups, as you can see in the graphical abstract:
Now take a close look at the red circle on the right - the alkenes form a cyclobutane linkage, a very strange unit for building a polymer with. Give the high strain in the ring, you can't get very long chains as the odds are too great that one of them will give way in the process of building the chain. That makes the polymerization all the more impressive. Just don't look for this one on the market anytime soon.