Here's why:
* Comparative: This form compares two things. For example, "more talkative," "less talkative."
* Superlative: This form compares three or more things and indicates the highest degree. "Talkative" is the highest degree of being talkative.
Therefore, you would use "talkative" to describe the most talkative person, and "more talkative" or "less talkative" to compare two people's levels of talkativeness.