Organic peroxide

Occurrence and use

Organic peroxides find numerous uses in various industries, as accelerators, activators, promoters.

acetone is discouraged. Polymerization initiators are usually supplied as dilute solutions, but even commercial products, especially the more concentrated ones, may form crystals around the lid when older, making the can shock-sensitive.

Pinane hydroperoxide is used in production of synthetic rubber.

gluten easier; the alternative is letting the flour slowly oxidize by air, which is too slow for the industrialized era.

Benzoyl peroxide is a highly effective topical medication for treating most forms of acne.

Cumene hydroperoxide is an intermediate in the phenol.

Acetone peroxide has became a favorite explosive of paramilitaries, because of its easy manufacture, despite its instability. It is notorious for its susceptibility to heat, friction, and shock.

Safety

Many diethyl ether peroxide. As they combine unstably bound oxygen together with hydrogen and carbon in the same molecule, organic peroxides catch fire easily and burn rapidly and intensely. The same applies to organic materials contaminated with organic peroxides.

Since peroxides can form spontaneously in some materials, some caution must be exercised with such "peroxide forming materials". In addition, many liquid ethylene glycol dimethyl ether form explosive peroxides is the reason why they tend to be avoided in industrial processes.

Caution must be executed with mixing peroxide-forming materials with oxidizing agents. acetone, is partially oxidized to peroxide on the second reaction step).

Accidental preparation of organic peroxides can occur by mixing ketone solvents (most commonly acetone) with waste materials containing hydrogen peroxide or other oxidizers and leaving the mixture standing for several hours.

Organic peroxides tend to react with metals. Glass, polyethylene or teflon containers are suggested for handling and storage; steel, copper alloys, rubber, lead, etc. should not be used. Empty containers must be washed with water immediately.

Organic peroxides must not be directly mixed with materials containing heavy metal ions like iron, cobalt or manganese, as these promote the decomposition of the peroxides. Direct mixing with amine compounds should be avoided as well. When mixing peroxides with amines (e.g., when making polyamides), both the peroxide and the amine have to be diluted separately with the monomer; the diluted chemicals can then be mixed.

Spillages of small amounts of organic peroxides can be wiped off with a rag, which then has to be disposed by burning at a safe place. Materials with absorbed organic peroxides must be saturated with water when stored.

Organic peroxides are sensitive to light and have to be stored in darkness. Some decompose at room temperature and release gaseous products; gas ejectors on the lids of the containers are required. Based on the Self Accelerating Decomposition Temperature, some peroxides have to be stored refrigerated.

In case of a fire, an explosion can be anticipated. A foam fire extinguisher can be used for small fires.

Small amounts of organic peroxides can be disposed of by careful burning of a substance diluted to under 10% or hydrolyzed. For hydrolysis, using a solution consisting of 80 parts water, 20 parts exothermic, but additional cooling is not required. The reaction is slow, and requires stirring for some 12 to 24 hours; the peroxide can then be considered decomposed.

Synthesis

Peroxides can be synthesized in the laboratory in a number of ways:

• peroxy acids by hydrogen peroxide
• peroxy acids by oxidation and hydrolysis of Grignard reagents
• peroxides by photooxidation of dienes
• peroxides by alkenes followed by reaction with a hydroperoxide
• peroxy acids by reaction of alkyl halides with hydrogen peroxide

Reactions

Some peroxide reactions are:

• phosphite esters
• cleavage to ketones and alcohols in the base catalyzed Kornblum–DeLaMare rearrangement

See also

• Peroxide
• Peroxyacid
• Peroxyacyl nitrates
• Ozonide

References

1. ^ See for example the 2006 transatlantic aircraft plot.