MDF should never be used in an application where it is exposed to extreme weather conditions. Moisture resistant (MR MDF) is an available product to use although as its name states, it is moisture resistant not water resistant or waterproof. MR MDF is created to withstand moisture in areas which could susceptible to humidity (e.g laundries, kitchens)
However if you would like to waterproof MDF manually, you would need to apply a high quality wood sealant, varnish or stain.

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