Yes, they do rent them, at about £10 per day.
https://www.avis.co.uk/drive-avis/car-hire-extras/child-safety-in-cars
There was a TESCO (similar to WalMart) in Slough the last time I went to Heathrow/Windsor, so they could be purchased there, but renting would be easiest. I know how sleep-deprived one can get on those flights, and I can't imagine doing the trip to a place as gigantic as Heathrow with 2+ kids, so the low-stress travel rules probably come into play. Rent them since you're only going for 4 days, and have that many fewer things to think about. I would not reccommend driving to a store to go buy car seats when jet lagged in the giant city they call Heathrow, while also driving on the other side of the road, other side of the car, and with 2+ kids after that long of a flight. If you're checking bags anyway, and need to save the money, maybe you can check your booster seats too, but I wouldn't reccommend going to deal with checked baggage for the booster seats alone. It's a huge place, the incoming international passport-checking line alone is enormous most every time, adding baggage to it when not necessary is no fun. Less is more. :)
Are you going to take them to Legoland in Windsor? A high school friend of mine married an Englishwoman there and took their 2 kids recently, they're adding a TON of stuff, they had a great time.
Happy travels !
-Alison