If you do not pay the m/a premium nor are you the main member, can you claim out of pockets expense

Did you personally pay for these expenses and not claim them via the medical aid?

I paid for them myself, I did not submit them to the medical aid at all. I have a spreadsheet and copies of each of the invoices/receipts

Yes then you will be able to claim these expenses, however the Tax deductions for Out of Pocket expenses will be based on the new credit system as per the latest Medical Tax Credits guide issued by SARS.