I think it's used as an inhibitor to the setting process more than a solvent, but I agree with you on the niff. The small screw-cap versions are easier to use, less niffy and they stay useable after opening longer than the big tubes used in caulking guns even though they work out three to four times as expensive.
Must've been exciting to be developing caulk. And those break'n'shake glowsticks - they use acetic acid as a moderator to prevent catastrophic exothermic excursion.
Real science should occasionally explode violently, as I explained to my chemistry teacher.