A bit of a bump because I have to put this somewhere.
Way back in 2010 or so when this first started coming up, I messaged Rudy Deanin, an extremely knowledgable PhD polymer chemist at UMass in search of an explanation for the photodegradation and the mechanism by which H202 and sunlight worked.
I don't know how I got his name, but I am somewhat abashed in retrospect that I approached him with something so trivial, the man was a Plastics Hall Of Famer with some extreme credentials! 36 patents, 13 books, 313 technical papers. But he was very friendly and helpful. I really enjoyed our little correspondence.
Only just today, however, I learned that this had been just about my LAST chance to have such a correspondence...Dr. Deanin passed away in 2011, at the age of 90.
Here is part of what he told me at the time.
QUOTE(Dr. Rudy Deanin) In answer to your December 8 inquiry, the 3 monomer units of ABS all contain somewhat unstable atoms or groups which are activated by UV + atmospheric oxygen (photooxidation). They all contain double or triple bonds, which absorb UV. When one C=C bond absorbs light, it is only in the far UV, so we don't see it. It activates an adjacent group and forms another (conjugated) C=C group. This C=C-C=C (allylic) group is more active, so it forms a third, and so on. As this conjugated (-C=C-) chain grows longer, it absorbs longer and longer wavelengths. When it is about 6 C=C groups in a row, it reaches the wavelength of visible light, and we see the degradation. As it grows till longer, it absorbs mores and more visible light, and the color grows darker and darker. The reason peroxide and sunlight cause bleaching is that they destroy a C=C bond and break the conjugated chain.
Embrittlement is caused by crosslinking. When UV and/or oxygen attack an unstable -C:H bond, they split it into -C. and .H radicals. When 2 adjacent polymer molecules have -C. radicals, they pair and form a -C:C- crosslink.
That's my simple-minded explanation. If you read very far into the literature, they get much more complicated, sometimes even contradictory.
Rudy Deanin
In short, the yellowing is caused by the formation of chained double-bonds. In another message he explained that the H202 did not restore the original form of the polymer chain, but converted one of the double bonds to an epoxide (C-O-C triangle) interrupting the chain and making the visible color go away. This is why oxidation via peroxide can seemingly reverse a process which is also oxidation (photo-oxidation)....it is not really reversing it, but oxidizing it further. It was a really great discussion....the real geniuses of the scientific field always seem so easy to talk to!