The solvent keeping the caulk sticky isn’t water. It’s able to move throughout the caulk, and then evaporate from the surface. The outside sets a skin pretty quickly, to keep the caulk in position, and then the solvent slowly leaks out through the skin.
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Most silicone calks are moisture cure. There is moisture in the air. You can also mist it with water to speed up the curing. Read the ~~tune~~ tube.
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