Firstly, Prime 95 is designed to test the OC capability of a CPU, and thus runs it with all the boost at 100%, so those temperatures are likely.
Secondly, that VCore on OC is very high, it should never get above 1.3V no matter what you do. 1.25 is the maximum recommended with 4.5GHz OC.
Thirdly, anything above the 72C is really hot for the CPU, and shouldn't be sustained. Since you have a Liquid cooler, I'd expect better results. 90C is nowhere near to those better results!
Your temp while running Prime 95 is pretty high, but still ok. When you OC, manually set your VCore to 1.25V. It should not go beyond 72-75C with a good cooler like the one you got.
I'd say check if its mounted properly. Also, what's your idle temp, temp while browsing/ streaming and temp while gaming at high-ultra?