open_ssl_random_pseudo_bytes is a cryptographically secure pseudo random number generator (CSPRNG).
In layman's terms, this means that it can generate an unpredictable, uniformly distributed sequence, that is suitable for key generation. The unpredictable property is important, because even if the full state of the random number generator is known, an attacker cannot recreate previously generated sequences, and it is unfeasible for an external observer to guess the state in order to predict future sequences.
This is in contrast to say a random number generator that takes its seed from the number of seconds past midnight and then generates predictable sequences based on this seed. In this case an attacker can simply set their own system to generate numbers using the same seed and can effectively guess token values in order to use them for their own nefarious purposes.
64 bytes will give you 512 bits of entropy. Since MD5 outputs hashes of 128 bits, there is no advantage of having the entropy generated being greater than 128. If the code is ran one billion times then there is a statistically probable chance of it always being unique because you have an output keyspace of 2128 (3.4 * 1038). The collision rate of MD5 is about 264 which is about 18 billion billion.