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It synchronizes passwords after you have set it up to do so.https://www.avast.com/faq.php?article=AVKB254
No, it will not ask you.As I said, you need to set it up.Please read the FAQ.
Ofcourse you need to install avast passwords before you can use it.https://www.avast.com/en-eu/faq.php?article=AVKB96