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The rubber and plastics industries heavily rely on organic peroxides in applications such as accelerators, activators, catalysts, and cross-linking agents. Due to their unstable nature, handling these substances requires meticulous care to ensure safety.

This post outlines hazards associated with organic peroxides and insights on how to treat these substances with better care to prevent contamination and maintain safety during handling and storage.

Hazardous Properties

Flammability

Any organic peroxide can pose a significant risk due to its highly combustible nature and powerful ignition. The violent reaction of some peroxides denote them as explosively combustible. When heated to a decomposition point, these substances generate heat and vapors, many of which are extremely flammable and can result in an explosion. Even without a fire, an explosion can occur if the auto-ignition temperature is reached.

Thermal (Heat) Sensitivity

When peroxide is heated to its decomposition point, the peroxide bond breaks, releasing heat that accelerates the breakdown of the remaining product. If the acceleration gets out of control, the product may catch fire or explode. If a decomposition occurred after the air has cleared, there may not be any evidence of fire but vapors may have been released. If exposed to ignition sources, such as lit cigarettes, matches, lighters, sparks or flames, they can combust and cause a fire.

Chemical Contamination

In addition to heat, chemical contamination can accelerate the decomposition of organic peroxides. Several chemicals, such as accelerators, acids, and bases, can trigger rapid decomposition at ambient temperatures. Heavy metals like copper, iron, and brass have a similar effect over time. Contaminants such as amines, metal salts, or even construction materials like iron and copper can lead to dangerous reactions. It’s vital to prevent contamination from occurring to avoid the same hazards associated with heat-induced decomposition.

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Organic peroxide is used in manufacturing a wide variety of products, including golf ball cores.

Safe Storage of Organic Peroxide

Proper storage of organic peroxides is critical for maintaining stability and minimizing risk. Below are some key safety measures to observe:

• Temperature Control: Most organic peroxides can be stored at temperatures below 90°F (30°C), but for long-term stability, they should be stored below 77°F (25°C). High-activity peroxides may even require refrigeration. Temperature monitoring systems are recommended to alert you if refrigeration fails.
• Avoid Direct Sunlight and Heat Sources: Ensure storage is in cool, shaded areas away from steam pipes, heaters, or any other sources of heat.
• Use Proper Packaging: Always store organic peroxides in their original packaging. Repackaging or using damaged containers can lead to dangerous consequences. Never return unused materials to their original container once opened.
• Venting Caps: If shipped with venting caps, ensure these are functioning correctly to prevent gas buildup. Vented containers should never be stacked to avoid accidental explosions.
• Storage Facilities: Large quantities of organic peroxides should be kept in specialized, isolated storage buildings designed with fire and explosion safety measures, in compliance with NFPA regulations.

• The self-accelerating decomposition temperature (SADT) is the lowest temperature at which a peroxide will undergo self-accelerating decomposition in a shipping package. Storage temperatures should be controlled to never exceed the SADT (the lowest temperature for self-accelerating decomposition in organic peroxides) to avoid thermal hazards during storage and transport. Temperature alarm systems are recommended for monitoring products requiring refrigeration to send an alarm if refrigeration fails.

• Exposure to heat or contamination by other chemicals can cause organic peroxide initiators to decompose rapidly. Proper temperature management and awareness of chemical compatibility are essential to avoid hazardous scenarios. Initiators that react with organic peroxides require a controlled temperature storage environment. High-activity initiators should be stored at refrigerated temperatures, while others may require storage at below 0 °F (-18 °C).

Safe Handling of Organic Peroxide

Handling organic peroxide requires strict adherence to safety protocols:

• Inspect Containers of Incoming Shipments:  Ensure they arrive undamaged and are properly labeled.  Reject those that are damaged.
• Wear Protective Gear: Always wear gloves, safety goggles, and protective clothing. Avoid skin contact and inhaling fumes or particles.  Seek medical attention if workers are exposed to organic peroxides.
• Use Clean Tools: Ensure all equipment used for weighing or transferring peroxides is free from any contaminants. Avoid mixing peroxides with incompatible chemicals like accelerators.
• Handle Gently: When moving or transferring peroxides, handle them gently to avoid friction or impact that could initiate a dangerous reaction.  When adding peroxides to resin batches, add material slowly to avoid splashing or spilling.
• Fire Safety: In the event of a fire, use water spray, dry chemicals, or carbon dioxide to extinguish it. Organic peroxide fires are explosive, so they must be contained with caution.
• Follow Fire Codes and Ordinances.  Not all organic peroxides are alike.  Follow specific manufacturer codes and local fire codes for handling and use of these materials.

Organic peroxide plays a critical role in various industrial applications, but their unstable nature requires meticulous care during handling, storage, and transportation.

Understanding the risks associated with flammability, heat sensitivity, and chemical contamination is essential for maintaining safety in the workplace. Always refer to the Safety Data Sheet (SDS) for product-specific guidelines and implement the safety measures outlined here to ensure a safe environment when working with organic peroxides.

Following these best practices will help you avoid dangerous incidents and ensure the stability of organic peroxides in your operations.

H.M. Royal carries a complete line of Nouryon peroxides.Learn more about Nouryon’s safety services for organic peroxides by watching this video.