It sounds like he's got a bit of petting aggression. My older cat used to have that tendency, too - he'd curl up beside me and be purring away and then just lunge.
I'm not sure if it's the best solution, but I ended up gripping him by the scruff of the neck, saying "No!" firmly and putting him on the floor every time he did it. After about a month or two, he stopped.
If it is an anxiety thing, maybe a Feliway dispenser would help?
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