HCHO + H<SUB>2</SUB>O qe H<SUB>2</SUB>C(OH)<SUB>2</SUB>
Formaldehyde peroxidation
H<SUB>2</SUB>O<SUB>2</SUB> +
H<SUB>2</SUB>C(OH)<SUB>2</SUB> qe HOCH<SUB>2</SUB>OOH +
H<SUB>2</SUB>O
HOCH<SUB>2</SUB>OOH +
H<SUB>2</SUB>C(OH)<SUB>2</SUB> qe HOCH<SUB>2</SUB>OOCH&l
t;SUB>2</SUB>OH + H<SUB>2</SUB>O
One approach was to use another difunctional peroxide that those already in use (hydrogen and adipoyl peroxides were already patented). I looked at
some texts and noted one could make an aldol peroxide from formaldehyde and hydrogen peroxide. I put together some concentration variations of
butadiene, isopropanol, formaldehyde, and hydrogen peroxide, to make the initiator in- situ. We set them up in the standard sealed polymerization
bottles at 75 degrees Centigrade. Nothing happened for about two hours, and I looked in one them hourly. Just after the 2nd hour inspection, I went
back to my desk for coffee, and one of the technicians raced up saying "Did you hear the explosion?". I hadn't, but went with him to the
polymerization lab external door just in time to hear another one "cook off".
The lab was cleared of all personnel already, and one just barely missed being inundated by the 75 degree water as the first explosion went off. I put
on face mask and rubber apron and crawled into the lab to turn off the steam and fill the bath with cold water. The lab floor was littered with sand
sized glass particles, and one of the polymerization bottle guards was about 15 feet from the polymerization bath. After about a half hour of cooling,
I donned apron, long gloves and face mask, and took out all the remaining bottles, and emptied those that still were intact- not many. The force of
the explosion ripped the stainless caps off some of the bottle shields, and one of those shields remains on my desk to remind me I'm fallible.
This was the last day before my vacation was to start, so when I left after cleaning up, I was gone for at least a week. When I got back, I found that
there had been an inquiry. Gerd Lenke had been assigned top look into the matter, and he found an ancient Gmelian book set which showed details of the
formaldehyde/hydrogen peroxide products. The one I wanted (and probably got) was dimethylol peroxide, which melts about 60 degrees C, and is a
"brisant" explosive at 72 degrees. It would not have detonated at 70 degrees, but I was five degrees higher. I still think it would be a good
di-functional initiator, BUT...Handle With Care! |
