Sorry, but late on this, but you can get heat resistant expanding foam -
here.
Pack coarse steel wool (brillo pad is too fine really) into the hole and seal it up with foam, then trim it back when it sets. Or use grab adhesive - Gripfill, Pinkgrip, whatever - as well as steel wool. Coarse steel wool is fine as a mouse-deterrent, just remember they can get through a gap as small as the end of a pencil...
If your boiler is reasonably modern, it'll have a display that shows the "flow temperature"; they can get quite hot - mine's showing 70°right now with a room temp of less than 20°.
HTH, Pete