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Vinyl doesn't cause rust.
The vinyl top itself doesn't cause rust. If moisture is getting trapped in there (speeding up the rust process) something was wrong to start with(i.e. it's old).
I personally don't like vinyl tops, but if i wanted to stay original, I would without fear of rust from caused by a vinyl top. A hardtop car can rust just as easily if it's not properly maintained. As for your DIY good luck & don't make a mess. I make a good living off of a lot of well intentioned car guys who thought they could do it themselves. As for the window trim question, only an experienced professional could pull something like that off and end up with a presentable final project. If you don't know what "material" to fill that in with, I would suggest you leave it up to someone else. You would need to extend the metal in toward the windshield edges to allow a much tighter fit, then when you re-install the glass they make a gasket that slips onto the edge of the glass & has a small flange that extends onto the surround painted edge(much like what comes on some late model trucks & a few cars). Just use your better judgement, don't bite off more than you can chew just because you don't want to spend the money to do it right. Listen to the professionals around you! Good luck.
P.S. That "material" is steel.
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