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You certainly can do this, and it is a good idea. I do not see too many 2x6 rafters, but if I had to insulate them I would do exactly what you are proposing. Rigid insulation costs a little more than batt, but you will get R-5 per inch and air cannot pass thru it, like it can with batt insulation. If you can afford it, you can even lose the batt insulation alltogether and just use thicker rigid. If you seal all the edges of the rigid insulation with spray foam or caulk, you can reduce air movement which will add to the R-value as well. Definitely keep the air gap at the top for venting the eaves to the ridge; this will save your roof.
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Best of Luck, Brian
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