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PEROXIDE FORMING CHEMICALS
Many chemicals can form peroxides when exposed to air over a period of time. Opening a container can introduce enough air for peroxide formation to occur. Structural characteristics of organic compounds that form peroxides are listed below in approximate order of decreasing peroxide forming potential:
H
M
1. C-O/
Ethen and accul* with byfcofto itow, duaoprcpyfether
* *
N
M
9. C-xr /
Alkyiireocs that contain tertiary hydrogen atettu, t.|, OBCM
H V 1 1/ 2. c-c-c /\
X \1 3. c-c/
Olefins with illylit hydrogen ttaoit, c.g. d-vinyicydchexene
CNaooJrfos and flueroolefiDS, e.g. vmylidmechlortde
-H,C H M
9. C/
-H,C
Alkanes and cycloalkane* that contain tertiary hytkogeo atom*, c,g doeahydrooaphihalcDe
10.
\1 CC-C0,R
/
Acrylates and methacrylates, c.g methylmethacrylate
\/ 4. c**c
/\ H
Vinyl hilides, ottn, and ethers. vinyl chloride
\ 1 I, / 5. c-c-c-c Diene*, t.g. L3-buudiene
tV
11.
N VI
C-OH
/
12.
K v|
C-C-C
/1
Secondary alccfcolt, e.g, 2*f>ropaoot
Ketones tht eontain hydrogen items c.g. mcthylisobutylketooc
H V1
VinyJaeetyiaic* with
s. C-C-CbCM hydrogos items, e g.
/ 4vioylaeetytenc
13.
H 1
-C-O
Aldehydes, e.g acetaldehyde
H M 7. C-C-CH
/
AlkyUcetyimes with w hydrogai items, e g propyne
RcC: I. Os. Sint r> (1910) 1W: I. Q<J* Edac. tS (1W| J3&
14.
HH M1
C-H-C-O /1
ti Clumnl Nrwi l|M{IW|
Ureas, amtdea, and lactams that have i hydrogen item on * carbon iftiched to nitrogen e.g. caprolactam
Scope - Applications
The list above indicates that a lot of chemicals are susceptible to peroxide formation. Presence of peroxides can be verified by the use of peroxide test paper. Extreme care should be taken in such processes where the peroxide can concentrate due to distillation, precipitation, evaporation of solvent, etc.
Significant incidents
Toul number of Dow incidents in 1981-1990 : IS
DO A 030741
confidential
1984 Vinvlidenc plant: A small explosion occurred in the top part of a filter element. A deposit of shock sensitive vrnylidene chloride peroxide bad apparently built up in the filter.
1986
Research: During the removal of methylene chloride solvent under vacuum from an organic solution at 2530C an explosion took place most probably due to concentrating trace amounts of hydrogen peroxide left from the previous synthesis step.
Outside Dow: A serious explosion occurred during measurement of the oxidation stability (ASTM D525) of a sample rich it. ^njugated C5 dienes (45-60 %), probably caused by autoignition of polyperoxidcs iormed during the reflux step. The test was developed for gasoline containing low amounts of polymerizable components.
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