Answer: I believe you are using several lists or you are sending messages using previously saved documents. In both cases, unsubscribing recipients may not be enough.
You should seriously consider using the MaxBulk Mailer global blacklist. In fact, the Global Blacklist prevents you from sending messages to given addresses whichever the list you have selected. In other words, you just need to add the address once to the blacklist to get it automatically blocked everywhere else! Furthermore, you can even block a whole domain or a name independently from its domain!
As unsubscribed addresses, blacklisted recipients are automatically discarded by MaxBulk Mailer when sending messages. It is better explained here: How to unsubscribe emails in bulk using a blacklist.
And you can also watch this short video I made about this topic:
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