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The Black Panther was the Crown Prince of Wakanda. His father the King was starting to open up to the outside world at the Sokovia Accords signing because the building that got blown up by the Avengers trying to deal with a suicide bomber Crossbones who survived his injuries from Captain America The Winter Soldier, was full of Wakandans on an outreach mission.
As the protector of Wakanda after the death of his father by Zemo's terrorist bombing he went after Bucky Barnes The Winter Soldier who was framed for the crime and intended to apply summery Wakandan, not Austrian or UN justice upon Bucky. The first anyone knew of any Black Panther or him as anything more than the Crown Prince, was during Bucky's escape from a German GSG9 special operations force when a helicopter gunner opened fire on him and Bucky and his Black Panther armor shrugged off the bullets.
When Iron Man and the loyal, for lack of a better term Avengers tried to arrest Bucky at the airport the Black Panther joined in since there where now to many enhanced heroes around Bucky for him to do a snatch arrest or killing alone. In the Civil War post credits we saw Bucky going back into a suspended animation in Wakanda pending the time they thought the Soviet wing of Hydra programming could be broken.
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