I thought I'd like working at home, as it turns out I didn't at all because once you're working at home, it's hard to draw the line.
I learned it well working for myself. After 5pm, no work unless it's a real emergency and those might happen 1-2x a year.
Having gone back into the workforce, people were always amazed I didn't carry the latest greatest phone (only got an iPhone once they added GPS, currently using a Lumia 1020). I don't need a computer in my pocket. I'm in front of a computer roughly 12-16 hours a day, that little time I'm not, I'm okay with being away from email, etc.
Even though I'm on my computer at night (like now). I never check work emails, they're also never sent to my phone. Only personal. If it's an emergency, call. It better fucking be an emergency (why I left my last job, owner didn't understand boundaries). I also don't work overtime. If you want 24/7 support, hire it.