I guess it depends on how badly they enforce the ban on "internet for non-work-related" browsing. Could make it difficult, although it sounds like he is a programmer at a tech-ish company, so he should probably have access to most tech/programming oriented sites. Worst case, he could get a wifi hotspot and go to town.

At my last job, I kept a few programming books at my desk, and during slow periods would crack those open and do some self-learning. It was a consulting job though, so those moments were few and far between (as much as I hated having to fill out timecards, billable rates were a good approximation of employee productivity, if you weren't billable, you needed a really good excuse).