It depends on the environment: if this is web based (and that's the only time that IP addresses are relevant) there are two problems:
1) Internet IP addresses are not specific to a single machine: they are specific to the router which connects the PC's to the internet. So if you have a hundred PC's in the same company they will all have the same IP address. Your system will prevent 99 of those from registering, which may not be optimal...
2) Most domestic IP addresses are not static: they change every time the router connects to the internet and the ISP assigns an address from it's "free pool". See here:
Using IP based Geolocation - and why it's pretty much useless.[
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If this is a LAN based IP address, you also can't rely upon it, as most DHCP servers allocate these on a "first come, first served" basis - meaning the IP address is likely to reflect the order in which the PC's were last turned on for the day.
Basically? I'd drop the idea - it's easy to do, but it's going to cause you more grief than it will help!