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Butler, on as second half sub for John Mullin, fired Rotherham in front on 72 minutes, before Shaw wrapped up the three points five minutes later.
Rotherham started the brighter with Jonathon Forte, playing in his last game of a three-month loan spell from Sheffield United, forcing a good save from Steve Wilson.
Neat interplay created two chances for Stephen Quinn on the edge of the area but on both occasions he curled his effort wide.
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The visitors were nearly gifted a goal when Neil Cutler's deep punch fell to Steve Jennings but his effort was well wide of the target.
Rotherham were handed a glorious chance to open the scoring at the start of the second half when Michael Jackson blocked Forte's cross with his hands. However Lee Williamson saw his penalty saved by Wilson.
Millers' manager Alan Knill introduced Butler off the bench on 65 minutes and, seven minutes later, the substitute opened the scoring volleying home from 12 yards after Colin Murdock had headed Michael Keane's corner across the penalty box.
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Tranmere's best chances fell to Chris Greenacre but his efforts were blocked by Shaun Barker.
The game ended in ugly scenes as Keane and Jackson were sent off after a violent confrontation.