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 HOME > NOF Businesses > Functional Chemicals & Polymers > Product Information > Organic peroxides > Handling of organic peroxides
Functional Chemicals & Polymers

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Organic peroxides


Handling of organic peroxides

Organic peroxides are marketed under conditions with adequate care to avoid danger as described earlier but users must treat the products carefully. The handling instructions described below are principles to handle organic peroxides for safe use of the product. However, observance of the laws concerning organic peroxides is required, and the directions of the competent authorities must be followed. Please contact the NOF group about any question arising from the contents of this book.

Precautions in handling organic peroxides

(1) Thorough care is required to prevent contamination of organic peroxides during handling because contamination may promote decomposition of organic peroxides. When organic peroxides are subdivided to small volumes for use, glass, stainless steel (SUS304 or SUS316), or polyethylene containers must be used. Containers made of steel, copper alloys, lead, rubber, etc. are not useful. Moreover, the subdivided organic peroxide must not be returned to the original container. Containers and vessels containing subdivided organic peroxide must be clearly labeled.

(2) Organic peroxides must not be directly mixed with compounds containing iron, cobalt, manganese, etc., because these compounds cause redox reaction with organic peroxides, and promote the decomposition of organic peroxides. Direct mixing of organic peroxides with amine compounds must also be avoided. When these compounds are used, organic peroxides and these compounds must be separately diluted with resin monomer. After dilution, either may be mixed with the other.

(3) When organic peroxides are mixed with chemicals except for those described in (2), testing is required using a small volume to confirm safety. NOF is ready to give advice to users in advance.

(4) Use of rubber gloves and goggles is advised to avoid contact with organic peroxides which may cause damage the human skin and eyes.

(5) Empty organic peroxide containers must immediately be washed with water, and the cleansed container must be safely kept uncapped in a storehouse to shield the container from sunlight until disposal.

(6) Organic peroxides are very sensitive to fire and heat, and undergo ignition and decomposition, sometimes explosion, so must be used or handled in a room away from ignition source such as electric sparking and high temperatures and heat from radiators, boilers, and other heat sources.

(7) Equipment materials in contact with organic peroxides must be selected from stainless steel, glass lining, glass, and polyethylene. Gaskets made of chemical-resistant materials such as Teflon (polytetrafluoroethylene) are also allowed.

(8) When organic peroxide is treated in a closed container, a temperature monitoring device, safety valve, and a rupture disc must be provided. Residual organic peroxide in equipment and pipes must be thoroughly removed after ceasing machinery operation.

(9) Some types of organic peroxides are very sensitive to friction and shock, so friction or impact to the organic peroxide during handling must be avoided. Accordingly, ground glass is not suitable for use in containers.

(10) When an organic peroxide spills over the floor, etc., a small amount of spillage may be wiped off with a rag for burning disposal at a safe place. A large spillage requires sawdust, diatomite, vermiculite, or dry sand to absorb organic peroxide for appropriate disposal. When temporarily storing a flammable material absorbing organic peroxide, the material must be saturated with water.

(11) To handle organic peroxides requiring temperature control, the necessary amount of organic peroxide must be subdivided, and used immediately. The remaining organic peroxide must be returned to a temperature-controlled storehouse. Organic peroxide reaching room temperature during the period outside the storehouse must not be returned to the storehouse as it is. Organic peroxide reaching a temperature higher than the required storage temperature must be abandoned, or cooled in a water bath below 5°C for return to the storehouse.

Precautions for storage and storing facilities

(1) The storehouse must be cool and dark inside, and organic peroxide must be sheltered from sunlight and separated from radiators, steam pipes, and other heat sources. Organic peroxide inside the storehouse must be kept away from fire.

(2) Organic peroxide must not be stored together with other chemicals. In particular, acids such as sulfuric acid and nitric acid, amines, and metals promote extremely violent decomposition of organic peroxides. Therefore, organic peroxides must be stored separately from these materials.

(3) Organic peroxides must be stored to ensure that containers do not fall down or drop.

(4) Some liquid organic peroxides gradually decompose into gas at room temperature, so containers for such peroxides are provided with a gas ejector on the lid of the container to release gas pressure inside the container. Therefore, the container must be placed with the lid side up for preventing liquid leakage. When organic peroxide is separated into another container, a gas discharge opening must be provided for the container lid.

(5) Explosion-proof electric appliances and machinery must be used for the storehouse.

(6) A refrigerated storehouse must be provided with a thermometer which can be monitored from outside the storehouse.

(7) Refrigerated organic peroxide must be stored at the temperatures recommended in this book.

(8) When a storage facility for organic peroxides is installed, legal regulations are provided for facilities, i.e., the structure and materials used for facilities as well as siting of a facility are regulated. Equipment such as an automatic charging device are required to be safe in use.

Precautions for safe transportation

(1) Containers of liquid organic peroxide must be handled and transported with the top side indicated. Laying a container on its side or upside down is not permitted for safety assurance.

(2) During transportation, containers must be sheltered from direct sunlight with covering materials.

(3) Careful handling and transportation are required for organic peroxides, to avoid friction and vibration, or dropping and falling.

(4) Loading and unloading work for organic peroxides must be carried out at a place without fire. Smoking is prohibited during handling work.

(5) The temperature required for organic peroxide transportation must be maintained.

First aid

Organic peroxides have highly oxidative properties, and are injurious to the skin and mucous membranes. It is therefore necessary to protect eyes, mouth, and hands to avoid direct contact with organic peroxide.

(1) When organic peroxide contacts the skin
Repeated cleansing with soap will be sufficient. However, if itching and pain are felt after cleansing, apply an adrenocortical hormone ointment to the skin. For detailed treatment, consult a doctor.

(2) When organic peroxide enters the eyes
Eyes must be washed with flowing water for 20 to 30 minutes without any delay, and medical treatment from a physician is necessary. (For reference, when hydroperoxides and methylethylketone peroxides enter the eyes, 5% ascorbic acid sodium solution and 3% sodium bicarbonate solution are useful for cleansing)

(3) When organic peroxide is swallowed
The oral toxicity of organic peroxides is not exactly known. When someone has swallowed organic peroxide, it is advisable to induce vomiting after giving a large amount of milk (in the case of hydroperoxides and methylethylketone peroxides, 5% ascorbic acid sodium solution is useful) and immediately seek treatment from a physician. If the patient is unconscious, convulsed, or has a convulsive fit, vomiting should not be induced. Lay the patient on the side, maintain the mouth open for breathing and the head lower than the body, and seek immediate admission to a medical facility.

Fire fighting

If a fire involving organic peroxide starts, or there is a fear of igniting organic peroxide, the fire extinguishing method varies according to the surrounding environment at the fire place.

In case of very small fire
A foam fire extinguisher can be used. After extinguishing the fire, keep pouring water because the residual heat causes decomposition of organic peroxide generating white smoke. If water is poured on the fire at the outbreak of the fire, the fire cannot be extinguished.

In case of fire
As explosion can be anticipated in a fire, fire expansion must be prevented by pouring water over the surrounding area, and fire-fighting personnel should keep at a safe distance. Fire extinguishing agents: water jet, water spray, foams, and reinforcing liquid.

Disposal

Organic peroxides that can not be used due to contamination, the guarantee period has expired, or are no longer required, must be treated with utmost care. Disposal of organic peroxides requires extensive knowledge about the properties of the specific organic peroxide to avoid occurrence of an unexpected accident. Refer to Table 3 for disposal of each organic peroxide.

(1) Burning in incinerator
A boiler as an incinerator can be used for burning disposal of organic peroxide diluted below 10% concentration (or active oxygen 1%) with inert organic solvent. However, this method is not suitable for solid type organic peroxides.

(2) Hydrolysis
Hydrolytic disposal uses a solution consisting of 80 parts water, 20 parts sodium hydroxide, and 0.3 parts surfactant, and the required solution is 10 times the weight of organic peroxide to be treated. Organic peroxide must be poured slowly into the solution. During this process, the solution should be stirred to prevent local heat increase. The solution generates heat upon decomposition of organic peroxide but there is no need to cool down the solution. Hydrolytic decomposition proceeds very slowly so stirring for 12 to 24 hours is required, and then organic peroxide is neutralized. After neutralization, separated organic substances can be recovered for burning, and/or biodegradable substances can be decomposed by the activated-sludge process.

(3) Activated-sludge process
Biodegradable organic peroxides can be decomposed by the activated-sludge process.

Organic peroxides

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