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Kakashi gained MS through the grief he suffered over an extended period of time. Its not confirmed when or exactly how he gained MS, but this is the assumed explanation. We know that Sasuke unlocked MS after being told the truth about Itachi, so its not the killing of your best friend that actually unlocks it but rather a period of extreme emotion. Based on this theory, its assumed that Kakashi unlocked it at some point over the timeskip where he was feeling an extreme amount of grief.