After clicking "I want to participate in the event." and then "Challenge the Valentines Boss!" Angelique says "I'm sorry, you cannot enter the boss map just again, please try again later. I was in the event once, when the double boss spawn was around, but now when I try to participate, I'm unable to enter with everybody else. I made sure to install the latest setup files, reboot pc, etc EDIT: cooldown on entry after exchanging romantic present.
There is a cooldown on entry after you exchange your romantic present. Try to remember to exchange the present right after each time you do the boss and you shouldn't have issues.