If you're not going to use a third party like ItextSharp you simply must go straight for the documentation of the Pdf file format, learn it and implement it. Wiki may help getting a first overview.
There is a tutorial, the VB.Net tutorial project files is in downloads (previous link). You might find discussion about doing it in their forums, or searching the web, it is a well known library.
The effortless approch is of course just to print the rtf document to a Pdf printer, there are many free and not free Pdf printers available on the web.
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