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Yes, should be fine on neoprene. A quick check says it has the same melt point as nylon but I'd be safe a check the iron temp on a small bit first,
With the stretch and battering overshoes get, and depending how big the hole is, it might be worth placing one on the interior too to help stabilise the area and increase durability.
Chopsicle
Rik_Van_Looy
Quick question on repair patches - would they work OK on neoprene or should I be looking at a wetsuit repair patch for a pair of overshoes?