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Caulk will go bad even in unopened tubes fairly quickly. The only thing that even works kind of temporarily is the long nail/screw in the spout covered with 2 layers of plastic wrap and a rubber band.
Silicone containing caulks cure by moisture from the air. Even the body of the tube is permeable to water vapor over time. Water vapor also leaks in around the piston inside the tube. Almost every plastic or organic compound is permeable to water. Solvent based caulks also dry out because of the leakage around the piston.
Buy only enuf caulk to do the job and return any excess to the store immediately.