How? All orders with your employee discount needs to be done in the Apple Store behind their firewall which has access to that page. So the answer is likely no.
If you have an EPP, it's done through a specific site specifically for your company/employer. If that's the case then it's like ordering from the online Apple Store. The layout is the exact same but just with discounted prices (but you wouldn't know since the discount isn't big to begin with, we only had 10% which was nothing).
If it's possible, it would depend. For us, we had Apple ID's created for our job which we needed to use. I don't know if they become inactive or removed once you leave. I'm pretty sure it would apply to all businesses with an EPP. Best to check with your employer.