Safety and Handling Practices for Sartomer Liquid Monomers and Oligomers 2 Skin and Eye Irritation Tests: determines the irritation potential of a material, following a single application of material to test-animals’ skin or eyes. Monomer irritation varies from non-irritating to corrosive. With respect to skin irritation, methacrylates are generally less irritating than acrylates with a similar chemical structure. Alkoxylated products are also generally less irritating than their non-alkoxylated counterparts. It is important that the potential health and safety hazards associated with chemicals be understood to ensure that they are used and handled safely in the workplace. The following information is intended to provide an overview of the toxicity of Sartomer liquid monomers and oligomers, along with guidelines to help ensure that good industrial hygiene practices are followed when using and handling these products. Consult the Material Safety Data Sheet (MSDS) for specific information on the health and safety hazards associated with the product(s) with which you will be working. Inhalation Toxicity Test: determines the median lethal concentration (LC50) of a gas, vapor or aerosol to test-animals. Available data indicate that monomers are not toxic to experimental animals when the ambient air is saturated with vapor. However, airborne mist could cause upper respiratory tract irritation if inhaled by employees. Direct health and safety questions concerning liquid monomers, oligomers, and photoinitiators to our Environmental, Health and Safety Department at 1-800SARTOMER. Mutagenicity Tests: There are several tests that have been developed to assess the mutagenic potential (i.e. the ability to cause genetic changes) of a substance. A mutagenicity screen, called the Ames test, is used to determine a material’s potential for producing mutations in bacteria. A positive test result indicates mutagenic potential; a negative result indicates no mutagenic potential. Monomers have a negative response in the Ames test. However, monomers are active in a second mutagenicity test, the mouse lymphoma forward mutation assay. The positive response seen in this assay is usually very weak and is only observed at relatively low cell survival rates. Therefore, there is reason to believe that the mouse lymphoma assay gives a false positive finding. It should be noted that this assay system produces a high incidence of false responses. Toxicology Toxicology refers to the branch of medical science devoted to the study of chemicals, including their mode of action, effects, detection, and counter- measures. To understand the role of chemicals in industry, the topic of toxicity must be discussed. Toxicity refers to the general capacity of a substance to cause injury to a living organism. This term must be defined in reference to exposure dose, the route and duration of exposure, the specific type and severity of the injury, and the time needed to produce the injury. Related to this concept is the term hazard, or the likelihood that a substance will cause injury in a given set of conditions of manufacturing, use or disposal. Carcinogenicity Tests: A limited number of monomers did show weak potential for carcinogenicity in lifetime mouse skin painting studies. The pathology and protocol of these studies were questioned by toxicologists. Subsequently, the Specialty Acrylate and Methacrylate Panel (SAM) worked in concert with the Environmental Protection Agency (EPA) to develop additional data to help characterize the carcinogenic potential of acrylate and methacrylate monomers. Based on a two-year bioassay (skin painting) study sponsored by SAM, involving triethylene glycol diacrylate and triethylene glycol dimethacrylate, acrylates and methacrylates as a class are not expected to be carcinogens. Animal Tests and Monomer Toxicity Acute and chronic animal tests are used to help assess the toxicity of chemicals. The types of tests typically conducted and test results for our monomer product line are summarized below: Acute Oral Toxicity Test: determines the single median lethal dose (LD50) of a material in test- animals following ingestion. Most monomers have low oral toxicity. In addition, ingestion is not a common route of exposure in an industrial setting. The monomers that Sartomer manufactures are not regulated by the Occupational Safety and Health Administration (OSHA) as carcinogens, or listed by the International Agency for Research on Cancer (IARC) or National Toxicology Program (NTP) as carcinogens or suspected carcinogens. Acute Dermal Toxicity Test: determines the single median lethal dose (LD50) of a material to test- animals following skin application. Available data indicate that monomers are low to moderate in dermal toxicity. 2 Oligomer Toxicity Personal Protective Equipment Skin Contact As a result of their higher molecular weights, most epoxy, urethane, aromatic acid methacrylate and hydrophobic oligomers are low skin absorption, ingestion and inhalation hazards. These products also tend to be minimal irritants. However, these products are typically supplied as blends with monomers or solvents, so the toxicity and safety procedures pertaining to monomers and solvents may be applicable. Extensive protective measures are required to prevent skin contact and reduce the potential for contact dermatitis. Nitrile and butyl rubber have been shown to provide protection against some monomers in breakthrough studies.1 In addition, a RadTech Europe publication concludes that heavy (thick) nitrile gloves can be used to safely handle most acrylates.2 Disposable nitrile gloves are also adequate under certain conditions according to this publication.2 Industrial Hygiene You must also consider the compatibility with formulation solvents and additives when selecting gloves. Cotton lined gloves help to reduce perspiration, which has shown to increase the potential for dermatitis. In addition to gloves, use impervious clothing to protect exposed skin surfaces on the arms, legs and torso when there is potential for skin contact with monomers. Industrial hygiene is the science of protecting man’s health through control of the work environment. It involves the application of biological, chemical, physical and engineering sciences to recognize, evaluate and control potential, or existing in-plant environmental conditions and factors which may cause discomfort, inefficiency or impaired well-being among workers. The use of good industrial hygiene practices is critical in protecting the health and safety of employees working with monomers and oligomers. Contaminated work uniforms and clothing and protective equipment can create a dermatitis problem. Therefore, all Sartomer employees are provided with clean work clothes at the start of each work shift. Using a laundry service also reduces the possibility of workers removing contaminated clothing from the work place. In addition, contaminated protective equipment is removed immediately, discarded, or cleaned if appropriate, and clean protective equipment is donned for the next task or work activity. Potential Workplace Health Hazards Skin irritation is a major health hazard associated with the use of monomers in the workplace. Monomers can cause delayed, localized skin irritation, particularly if skin contact is prolonged. The severity of the skin irritation response depends on the conditions of exposure and the irritation potential of the monomer. An irritation response can include redness, swelling, and in severe cases, blister formation at the site of skin contact. This irritation response is commonly referred to as contact dermatitis. There are several skin care products on the market that are designed to effectively remove industrial chemicals and protect the skin. There are also products designed to control perspiration that are used under protective clothing. These perspiration control emulsions are especially effective during the summer months when chemical dermatitis can become more prevalent due to the high humidity. Barrier creams should never be used in place of the appropriate protective equipment — they should be used only in conjunction with protective clothing. Skin sensitization is an allergic skin reaction that can occur in susceptible individuals after repeated exposure to certain substances. While a skin sensitization response may resemble an irritation response, the mechanism that causes the response is immunologic in nature. There are animal data, and a limited number of worker case reports, which indicate that some monomers are skin sensitizers. If an employee becomes sensitized to one monomer, there is also the possibility of cross-sensitization with other monomers. Workers should wear chemically resistant safety shoes. Suede, canvas and soft leather shoes are not recommended. Wear an impervious overboot, made from nitrile or butyl rubber, if walking into an area where shoes can become saturated with product. Discard shoes contaminated with product to avoid blistering of the feet. Eye irritation is another important health hazard associated with the use of monomers in the work place. Eye contact with these products may cause tearing, redness and a burning sensation in the eyes some monomers are corrosive to the eye and may result in permanent eye damage with contact. Eye Contact Because eye contact is a primary route of exposure, personal protective equipment (PPE) should include safety glasses. Goggles are recommended when working with corrosive materials. Goggles or faceshields with safety glasses should also be worn when performing tasks with high splash potential. Goggles can present a potential problem if they become contaminated with monomer — this can cause skin irritation, particularly along the seal of the goggles. Contact lenses are not recommended. Because monomers and oligomers are typically nonvolatile and have high boiling points (> 150°C), they do not pose inhalation hazards at room temperature. However, aerosols or vapors generated from heating these materials may cause upper respiratory tract irritation if inhaled. 3 Inhalation Inhalation Inhalation exposures are generally not common under normal conditions due to the low volatility of these materials. However, if monomers or oligomers are handled at elevated temperatures or under aerosol forming conditions, local exhaust ventilation is recommended. NIOSH-approved respiratory protection equipment may also be necessary. Monomers and oligomers generally do not pose an inhalation hazard at standard conditions due to their low volatility. However, if aerosols or vapors that may be generated at elevated temperatures are inhaled, the individual should be moved to fresh air. Trained personnel should administer oxygen or artificial respiration as needed. Obtain emergency medical attention. Personal Hygiene Sartomer recommends that all of our employees shower at the end of each work shift. When completing certain tasks involving the potential for increased exposure, a shower and a change of clothing are required. It is important that contaminated skin surfaces are washed promptly and thoroughly to remove material. Ingestion If ingestion occurs, dilute the material by drinking a pint of lukewarm water (do not administer to a person who is not completely conscious/alert). Do not induce vomiting unless directed to do so by medical personnel the risk of damage to the lungs usually exceeds the risk from poisoning. Obtain emergency medical attention if a large quantity of material is ingested, or if symptoms develop. Housekeeping Housekeeping is a very important aspect of eliminating dermatitis. When housekeeping practices are poor, dermatitis cases usually increase. In many instances, a person is not aware that they have had skin contact with a monomer or oligomer because irritation may not be immediate. By the time the skin reacts, the damage has started. By improving housekeeping practices, “unknown” causes of dermatitis can be minimized. Storage Store monomers and oligomers under conditions which will prevent polymerization and product degradation. Monomers and oligomers contain inhibitors such as hydroquinone (HQ) and methyl ether of hydroquinone (MEHQ), that have been added to provide stability. Take the following steps to prevent premature polymerization: First Aid Skin Contact Remove contaminated clothing and wash affected skin surfaces thoroughly with mild, non-abrasive soap and copious amounts of lukewarm or cool water. Consider a waterless cleaner if material is sticky. Next, flush skin with cool or lukewarm water for 15 minutes to ensure material is completely removed. Note: Cool water will prevent skin pores from opening. This will minimize the surface area of contact and reduce the chemical contact time. Mild soap will prevent abrading the skin or rubbing the chemical(s) into skin pores during cleansing. In addition, soap with aloe, vitamin E or other suitable skin oils can help prevent the skin from drying or cracking. This further protects the skin in the event of additional chemical exposure. • maintain a head space in storage containers to support the oxygen requirements of the inhibitor(s); • do not sparge or blanket with nitrogen or other oxygen-free gases; • avoid contact with contaminants such as iron and copper (which can initiate polymerization); • check inhibitor levels periodically. Store all Sartomer products indoors away from direct sunlight, oxidizing agents and materials which may generate free radicals. Appropriate storage containers are epoxy-phenolic lined carbon steel, stainless steel or polyethylene lined drums or glass. Store containers at temperatures above 50°F and below 100°F. If freezing occurs, warm the container as indicated on the product’s MSDS and mix thoroughly with low shear to disperse the inhibitor evenly throughout the solution. Never use a band heater or steam to heat product. These precautions listed above are necessary to standardize product properties and avoid premature polymerization. If product quality is in question, initiate the following quality checks: inhibitor concentration test, polymer test, and the acid test. Contact Sartomer for appropriate test methods. Sartomer employees have been fairly successful in preventing blister formation by applying an over- the-counter hydrocortisone cream to clean skin, immediately following a chemical splash. If the area is red and/or irritated after removing the monomer or oligomer, the cream is effective in reducing the blistering associated with chemical dermatitis. Once a blister forms, medical treatment is usually required to avoid infection and speed recovery. Eye Contact Immediately rinse eyes with copious amount of clean, lowpressure, lukewarm water for 20-30 minutes. Retract eyelids often. Obtain emergency medical attention. 4 Physical Hazards Disposal Procedure Persons handling empty product containers should wear protective equipment and handle containers in an area away from ignition sources because the containers may contain residual product. Recommended cleaning procedures for empty steel drums include washing the drums with a strong soap and water solution, followed by a thorough water rinse. If necessary, a 15% caustic solution followed by a water rinse can be used to further clean containers. All wash and rinse solutions must be disposed of in accordance with federal, state and local regulations. Uncontrolled Polymerization A polymerization is a chemical reaction in which a large number of relatively simple molecules combine to form a large, chain-like molecule. An uncontrolled polymerization poses an explosion hazard in a confined space such as a drum because the reaction results in heat generation and an increase in material volume. If it appears that uncontrolled polymerization is impending, the quality checks mentioned previously should be initiated to determine product condition if a sample of the product is already available. Do not attempt to sample product if a polymerization event is suspected or occurring. Upon disposal, uncontaminated, properly inhibited monomers and oligomers are generally not RCRA hazardous wastes. However, it is the responsibility of the waste generator to determine if the material meets the criteria of a hazardous waste at the time of disposal (see 40 CFR 261). Disposal options include landfilling solids at permitted sites, and fuel blending or incinerating liquids. Disposal must comply with federal, state and local regulations. Heat evolution is the most characteristic feature of an uncontrolled polymerization. If the temperature of the material exceeds the recommended temperature range, any heating of the product should cease and the product should be cooled immediately if possible. If the temperature continues to rise in spite of cooling, a polymerization is probably occurring. Vapor evolution follows as product degradation occurs. 1. Renard,E.P.etal.”Permeation of Multifunctional Acrylates Through Selected Protective Glove Materials,” in American Industrial Hygiene Association Journal. 53. 2. (American Industrial Hygiene Association, February, 1992) pp. 117-123. 2. Zwanenburg, Rob. “Adequate Protective Gloves for Working with UV/EB-Curing Acrylates” (November 26, 1999 RadTech Europe Publication) Fire Hazard In the event of a fire, these materials can become inhalation hazards. Smoke, vapors and combustion products from burning materials may be extremely irritating. Heat from a fire may also initiate an uncontrolled polymerization, which can cause closed containers of these products to rupture, and the fire to spread. Emergency Response When responding to an uncontrolled polymerization or fire, equip trained emergency responders with proper protective equipment, including self-contained breathing apparatus, full coveralls or running gear, face shields, safety shoes and gloves. Evacuate nonemergency personnel and ventilate the area. If a polymerization is occurring in a 55 gallon container or less, cool the container with water. If possible, vent the container and move it to a remote location while continuing to cool. If a larger amount of material is polymerizing, vent and cool with large quantities of water. Vents may become clogged from material expansion. In the case of a fire, extinguish with dry chemical, foam, carbon dioxide or water fog and spray from a safe distance or protected location. Cool containers exposed to fire or heat with water fog or spray. 5 Arkema - a French "société anonyme" registered with the Commercial and Companies Register of Nanterre under number 319 632 790. 6000/03.2016 The statements, technical information and recommendations contained herein are believed to be accurate as of the date hereof. Since the conditions and methods of use of the product and of the information referred to herein are beyond our control, Arkema expressly disclaims any and all liability as to any results obtained or arising from any use of the product or reliance on such information; NO WARRANTY OF FITNESS FOR ANY PARTICULAR PURPOSE, WARRANTY OF MERCHANTABILITY OR ANY OTHER WARRANTY, EXPRESSED OR IMPLIED, IS MADE CONCERNING THE GOODS DESCRIBED OR THE INFORMATION PROVIDED HEREIN. The information provided herein relates only to the specific product designated and may not be applicable when such product is used in combination with other materials or in any process. The user should thoroughly test any application before commercialization. Nothing contained herein constitutes a license to practice under any patent and it should not be construed as an inducement to infringe any patent and the user is advised to take appropriate steps to be sure that any proposed use of the product will not result in patent infringement. See SDS for Health & Safety Considerations. Arkema has implemented a Medical Policy regarding the use of Arkema products in medical devices applications that are in contact with the body or circulating bodily fluids (http://www.arkema.com/en/socialresponsibility/responsible-product-management/medical-device-policy/index.html) Arkema has designated medical grades to be used for such medical device applications. Products that have not been designated as medical grades are not authorized by Arkema for use in medical device applications that are in contact with the body or circulating bodily fluids. In addition, Arkema strictly prohibits the use of any Arkema products in medical device applications that are implanted in the body or in contact with bodily fluids or tissues for greater than 30 days. The Arkema trademarks and the Arkema name shall not be used in conjunction with customers’ medical devices, including without limitation, permanent or temporary implantable devices, and customers shall not represent to anyone else, that Arkema allows, endorses or permits the use of Arkema products in such medical devices. It is the sole responsibility of the manufacturer of the medical device to determine the suitability (including biocompatibility) of all raw materials, products and components, including any medical grade Arkema products, in order to ensure that the final end-use product is safe for its end use; performs or functions as intended; and complies with all applicable legal and regulatory requirements (FDA or other national drug agencies). 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