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I haven't, but I would try a Linux box with two serial ports, connect both things to it so it's literally man in the middle. The PySerial module for Python, and it has an example bi-directional Serial to TCP/IP relay including a threaded serial listener, you might be able to hack that into a Serial <--> Serial relay with custom logging/interception fairly quickly.
Thanks for all the tips everyone. I wasn't aware it would be so easy to monitor RS232 at the physical level. I'm going to make a first attempt with software using a serial proxy program (https://github.com/rkubik/serial-proxy-c) that will allow you to define additional virtual serial ports that you can read/write to independently, while it retains control of the physical port. I believe I can then insert an RPi or similar system in between the serial devices, use that serial proxy to expose both sides in a way I can monitor, and finally attach the program "socat" to each virtual writable port to bind the two real systems together over my intercepted serial cable.