A37575 - Boeing DV windows are big enough for most pilots to exit through, although it is no mean feat and the ensuing drop to the ground if you get it wrong can kill.
Regarding 'SOPs', my training said that as a Captain (and F/O) my primary escape route was via the cabin where I would assist with the passenger evacuation ('primary duty' and all that) and only where this was not possible was the window to be used. Note we do not know this airline's procedures.