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childcare is a lucrative business already; there is probably nothing (short of administration work) stopping an existing childcare business taking on volunteers (talking about the most easy way to make this happen by slightly modifying the existing world). But I don't know of many (any) people willing to do that kind of thing.
Volunteers are a tricky business too. As is duty of care towards children, in more than just the assumed privacy, protection, but also in the direction of positive stimulating environment (which becomes more difficult to prove when relying on volunteers)