I didn't see the episode, but reading online it looks like Mythbusters agreed that insufficient skin ventilation could cause dangerous spikes in temperature or BP. Plus there's the risk of toxic or allergic reactions. But none of those have to do with asphyxiation.
It was deemed plausible, not confirmed. In either event, this film was made in 1964 and featured:
A man who's thrown hat can decapitate you
A laser that can chop your balls off (in 1964)
A radioactive bomb that will irradiate gold, supposedly cornering the market
A aerosol chemical that knocks you out, then disperses safely
Bond successfully seduces a lesbian
A gadget-laced car, many features of which Mythbusters "Busted"