The plastic as you call it is actually cellophane. Cellophane is a form of paper (well, that is to say it is made from cellular pulp such as hemp and wood). It is 100% biodegradable, and being cellular pulp is as recyclable as paper.
So the answer is, no, you don't have to remove plastic windows from envelopes unless you are convinced it really is plastic, not cellophane.
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