I'm no medical type. But it does sound like a blood pressure thing. It might be something you can easily fix, so I'm with the others in saying to see your GP.
Could be compression of the blood vessels supplying the arm caused by tightness in the 'thoracic outlet' - the area between the neck and the collarbone. It is a very small space where a lot of nerve and blood vessels pass as well as a whole lot of muscles and other tissues. When people have tightness in this area (- often caused by forward head posture) it squeezes the vessels, both nerve and blood (a bit like what happens in carpel tunnel if you are familiar with that). It is exacerbated when you raise your arm over your head as that squeezes the area more and when you brush your hair it can compress the area more again due to the fact that you are using the muscles in the area.
A physio, osteo, chiro or a good massage therapist (think Myotherapist or Remedial Massage therapist) should be able to work out what is going on, and if there is another underlying thing, they should be able to recognise that also.
I find I get that when I haven't been sleeping well - ie I'm jammed into the bed with a child on either side so I've slept on the one shoulder all night.
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