Blocking a host by it's IP address is not always a good idea, because IPs can be changed by the user, so it's very easy to get access to services blocked by IP-base... Maybe you could try blocking by the host's MAC address... iptables is the utility you need, but I am not sure if OpenWrt images have the necessary modules compiled in them to allow filtering by MAC-address (they should have... but I'm unsure)
Unfortunately, I don't have the time (and maybe the knowledge) to help you, but I could tell you the basic steps, you need to take:
1, Block the access to the host, using a firewall rule (iptables) in the /etc/firewall.user file
2, Set up a record in the crontab file, which enables access to that host at 1pm - use iptables here, too
3, Set another record, which should run at 4pm every day, use the same command as you used in the firewall.user file
That's all, I think.
Bye!