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Organic peroxides & polymerization...

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Support and Safety Measures...

Introduction   |   Explosion & Fire Hazards   |   Contamination   |   Health Hazards   |   Precautions

Storage   |   Handling   |   Supervision & Maintenance   |   Fire Protection  |  Working of OP  |  FAQ


Comply with Federal, State and Local requirements. Primary storage of organic peroxides should be separated from manufacturing areas, such as by a specially protected room or a separate storage facility. Opened containers should not be returned to primary storage. A separate case or room should be provided. Further storage safeguards can be attained through separation by distance or prescribed fire protection. The quantity of organic peroxides in the processing area should be limited to the minimum daily processing requirements. Adequately trained personnel and planned emergency procedures are essential for a safe operation.

  1. The local insurance inspection bureau and fire authorities should be consulted on all plans concerning the location and construction of organic peroxide storage facilities or buildings. The storage facilities should be so located that the organic peroxides are in the least vulnerable position to fire exposure. Vent panels or other mechanisms for relieving pressure of decomposition should be incorporated into the building design.
  2. Reinforced polyester plastics fabricators handling organic peroxides, depending on the quantity stored, should provide either a storage room separated by a fire-resistant wall or a detached storage building. All storage areas should have a sprinkler system. If not adequately protected by a fast-acting, deluge or automatic sprinkler system, the storage building or facility should be located an adequate distance from (a) flammable liquid storage, (b) combustible material in the open and (c) any other building or highway.
  3. Large quantity storage in highly populated areas should be avoided. The quantity of organic peroxide in storage should be held to the minimum that operating conditions and safety considerations permit.
  4. The storage building or facility should be constructed in accordance with the recommendations of the peroxide manufacturers and insurance authorities.
  5. Storage buildings should not, as a rule, be heated, but if heating is required, the recommendations of the manufacturer should be followed. It may be necessary, however, to cool some buildings or facilities in hot weather to prevent decomposition of the peroxides.
  6. Organic peroxides should be stored away from all sources of heat and ignition such as open flames, electrical devices and heating equipment. Care should be taken to prevent the exposure of these materials to prolonged storage in the direct rays of the sun. Truck motors should be turned off during a loading or unloading operation.
  7. Containers of organic peroxides should be stacked in such a way that water from the sprinkler system will reach and wet them in case of fire. (See Fire Protection.) Provisions should be made to contain the fire water runoff in a catch basin or equivalent.
  8. Organic peroxides should be stored in the same containers used by the manufacturers for shipping the material.
  9. Various organic peroxides should be separated from each other in the storage building or facility to prevent accidental misuse of materials. No other materials should be stored in the organic peroxide storage building or facility.
  10. Organic peroxides should not be stored in a refrigerator that also contains food or water.


More Information:

Organic peroxides are relatively unstable compounds which can decompose spontaneously and sometimes explosively.

Such decomposition can be caused:

 by heat or fire: organic peroxides are thermally unstable. They are sensitive to heat; above the SADT (Self Accelerating Decomposition Temperature) the reaction becomes uncontrolled and violent.
Organic peroxides are generally flammable and burn vigorously.
Decomposition can also be caused by hot material being added to an organic peroxide, or by the peroxide being put into a hot recipient.

 by mechanical effect: some organic peroxides are able to decompose as result of mechanical shock (impact and friction).
Thermal sensitivity and shock sensitivity are evaluated by standardized European test

 by contamination: organic peroxides can show hazardous reactions in contact with other chemicals because of contamination. Contamination can be caused by a large number of chemicals.
Particularly oxidizing and reducing agents, and polymerization accelerators such as cobalt octoate or dimethyl aniline may cause instantaneous decomposition which can be violent and accompanied by fire, depending on the product.
In addition to chemicals, peroxides can be contaminated by contact with metals, such as mild steel, brass or copper, particularly in divided form, and with rust, ash or even dust.

Organic peroxides show decomposition reactions, the rate of which depends on temperature and concentration of the product, grade of confinement, type of diluent and kind of molecular structure.

Therefore, organic peroxide transportation, storage and handling conditions must always respect the Self Accelerating Decomposition temperature (see figure 1).


Because of these fast decomposition reactions, handling, storing and transport conditions of organic peroxides must always be in compliance with the level of the Self Accelerating Decomposition Temperature (SADT).

Maximum Storage Temperature (see figure 1)
The maximum storage temperature is the temperature below which the product can be stored safely, but at which it may lose assay if stored for long periods.

Minimum Storage Temperature
A minimum temperature is only listed for those products which will exhibit lumping or crystallization or phase separation at low temperatures.


Recommended Storage Temperature
The recommended storage temperature is the safest for long term storage without deterioration of the product's quality.

Even when stored at the recommended temperature in their original containers, organic peroxides have a limited shelf life. All containers should be dated on receipt and either used or disposed of within the time recommended.

The "Control Temperature" and "Emergency Temperature" concern transportation conditions.
They are derived from the Self Accelerating Decomposition Temperature.

Control Temperature
Transportation regulations indicate a control temperature for those products which have to be transported under controlled temperature.

Emergency Temperature
Where a transportation temperature is defined in the transportation regulations, the emergency temperature is mentioned in addition. If this emergency temperature is reached, immediate actions must be taken such as disposing safely the peroxides (emergency procedures have to be implemented).


The decomposition of a peroxide is exothermic, releasing energy. When this energy can't be dissipated fast enough, it leads to a rise in the temperature, which increases the rate of the decomposition reaction: the reaction becomes self-accelerating.
The maximum temperature under which the self accelerating decomposition does not occur is called SADT (Self Accelerating Decomposition Temperature). It is specific of each peroxide formulation and of the packaging size and shape.
Strict control of the temperature must always be applied to avoid rise up to the SADT.
The required data are given in the Safety Data Sheet of each commercial product.



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