Peroxidizable Organic Chemical Handout

Classes of peroxidizable organic chemical
Class A: Form explosive levels of peroxide without concentration
Butadienea Divinylacetylene Tetrafluoroethylenea
Vinylidene chloridea Chloroprene Isopropyl ether
Class B: Form explosive levels of peroxide upon concentration
Acetal Diacetylene 2-Hexanol 2-Phenylethanol
Acetaldehyde Dicyclopentadiene Methylacetylene 2-Propanol
Benzyl alcohol Diethyl ether 3-Methyl-1-butanol Tetrahydrofuran
2-Butanol Diethylene glycol dimethyl ether (diglyme) Methylcyclopentane Tetrahydronapthalene
Cumene Methyl isobutyl ketone Vinyl ethers
Cyclohexanol Dioxanes 4-Methyl-2-pentanol Other secondary alcohols
2-Cyclohexen-1-ol Ethylene glycol dimethyl ether (glyme) 2-Penten-1-ol
Cyclohexene 4-Penten-1-ol
Decahydronapthalene 4-Heptanol 1-Phenylethanol
Class C: May autopolymerize due to peroxide accumulation
Acrylic acidb Chlorotrifluoroethylene Vinyl acetate Vinylidiene chloride
Acrylonitrileb Methyl methacrylateb Vinylacetylene
Butadienec Styrene Vinyl chloride
Chloroprenec Tetrafluoroethylenec Vinylpyridine
Class D: Forms peroxides; insufficient information to classify
Acrolein tert-Butyl methyl ether Di(1-propynyl) etherf 4-Methyl-2-pentanone
Allyl etherd n-Butyl phenyl ether Di(2-propynyl) ether n-Methylphenatole
Allyl ethyl ether n-Butyl vinyl ether Di-n-propoxymethaned 2-Methyltetrahydrofuran
Allyl phenyl ether Chloroacetaldehyde diethylacetald 1,2-Epoxy-3-isopropoxypropaned 3-Methoxy-1-butyl acetate
p-(n-Amyloxy)benxoyl chloride 2-Chlorobutadiene 1,2-Epoxy-3-phenoxypropane 2-Methoxyethanol

(methyl Cellosolve)
n-Amyl ether 1-(2-Chloroethoxy)-2-phenoxyethane Ethoxyacetophenone 3-Methoxyethyl acetate
Benzyl n-butyl etherd 1-(2-Ethoxyethoxy)ethyl acetate 2-Methoxyethyl vinyl ether
Benzyl etherd Chloroethylene 2-Ethoxyethyl acetate Methoxy-1,3,5,7-cyclooctatetraene
Benzyl ethyl etherd Chloromethyl methyl ethere (2-Ethoxyethyl)-o-benzoyl benzoate
Benzyl methyl ether ß-Chlorophenatole ß-Methoxypropionitrile
Benzyl 1-napthyl etherd o-Chlorophenatole 1-Ethoxynapthalene m-Nitrophenatole
1,2-Bis(chloroethoxy)ethane p-Chlorophenatole o,p-Ethoxyphenyl isocyanate 1-Octene
Bis(2-ethoxyethyl) ether Cyclooctened 1-Ethoxy-2-propyne Oxybis(2-ethyl acetate)
Bis(2-methoxyethoxy)ethyl) ether Cyclopropyl methyl ether 3-Ethoxyopropionitrile Oxybis(2-ethyl benzoate)
Diallyl etherd 2-Ethylacrylaldehyde oxime ß,ß-Oxydipropionitrile
Bis(2-chloroethyl) ether p-Di-n-butoxybenzene 2-Ethylbutanol 1-Pentene
Bis(2-ethoxyethyl) adipate 1,2-Dibenzyloxyethaned Ethyl ß-ethoxypropionate Phenoxyacetyl chloride
Bis(ethoxyethyl) phthalate p-Dibenzyloxybenzened 2-Ethylhexanal Phenoxypropionyl chloride
Bis(methoxyethyl) carbonate 1,2-Dichloroethyl ethyl ether Ethyl vinyl ether Phenyl o-propyl ether
Bis(methoxyethyl) ether 2,4-Dichlorophenatole Furan p-Phenylphenetone
Bis(methoxyethyl) phthalate Diethoxymethaned 2,5-Hexadiyn-1-ol n-Propyl ether
Bis(2-methoxymethyl) adipate 2,2-Diethoxypropane 4,5-Hexadien-2-yn-1-ol n-Propyl isopropyl ether
Bis(2-n-butoxyethyl) phthalate Diethyl ethoxymethylenemalonate n-Hexyl ether Sodium 8,11,14-eicosatetraenoate
Bis(2-phenoxyethyl) ether Diethyl fumarated o,p-Iodophenatole
Bis(4-chlorobutyl) ether Diethyl acetald Isoamyl benzyl etherd Sodium ethoxyacetylidef
Bis(chloromethyl) ethere Diethylketenef Isoamyl etherd Tetrahydropyran
2-Bromomethyl ethyl ether m,o,p-Diethoxybenzene Isobutyl vinyl ether Tetraethylene glycol diacetate
ß-Bromophenetole 1,2-Diethoxyethane Isophoroned Triethylene glycol dipropionate
o-Bromophenetole Dimethoxymethaned p-Isopropoxypropionitriled 1,3,3-Trimethoxypropened
p-Bromophenetole 1,1-Dimethoxyethaned Isopropyl 2,4,5-trichlorophenoxyacetate 1,1,2,3-Tetrachloro-1,3,-butadiene
3-Bromopropyl phenyl ether Dimethylketenef
1,3-Butadiyne 3,3-Dimethoxypropene Limonene 4-Vinyl cyclohexene
Buten-3-yne 2,4-Dinitrophenatole 1,5-p-Methadiene Vinylene carbonate
tert-Butyl ethyl ether 1,3-Dioxepaned Methyl p-(n-amyloxy)benzoate Vinylidene chlorided

 

Notes on Peroxidizable Organic Compounds

Risk factors for peroxidization

  • Heat
  • Light
  • Air/oxygen
  • Volatility/ability to be concentrated
  • Low molecular weight
  • Long storage time
  • Catalyzing contaminants (e.g. heavy metals, alkali)

Peroxidizable organic compound classes

  1. Form explosive levels without concentration
  2. Form explosive levels with concentration
  3. Autopolymerize explosively
  4. Unknown/uncharacterized hazard

Detection
Kelly, R.J., A critical review of peroxide determination methods, Chem. Health & Safety, 1996, 3(5), 28.

Managing peroxidizable organic compounds

  • Purchase limited quantities/small containers/no stockpiling
  • Use in receipt order
  • Label as peroxide former
  • Periodically test (3 mo or more frequently if necessary)
  • Test inhibitor levels if used
  • Treat or dispose if >100ppm

Storing peroxidizable organic compounds

  • Inert blanket (except where inhibitors require oxygen to work)
  • Tight-fitting cap (no ground-glass stoppers)
  • No plastic (metal preferred)
  • Store away from heat and light
  • Advisable storage times: (JHU rules: 1 yr after receipt, 6 mo after opening)
    • Unopened containers: 18 months
    • Opened:
      • Class A: 3 months
      • Class B or D: 24 months (with testing every three or fewer months)
      • Class C
        • Uninhibited: 24 hours
        • Inhibited: 12 months (testing both peroxide and inhibitor every three or fewer months)

Another helpful resource: https://www.coleparmer.com/chemical-resistance