I'd hope with yours the PRV would operate before any real damage was done, but allowing the boiler to potentially freeze is not going to do you or it any favours.
No, it wouldn't. I remember, when I was a small boy, new tenants on the estate that we lived on was advised, on moving in during a very hard winter, to get a good fire going and get the new house warm. They did just that, and the boiler (behind the fireplace) blew up, blasting the entire fireplace and bricks, etc. at them. A child was killed by it. That's what was behind my concern. I shall put antifreeze inhibitor in the system, just to be sure.
A.W.