Safety and Handling Practices for Sartomer Liquid Monomers and

Safety and Handling Practices for Sartomer
Liquid Monomers and Oligomers
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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.
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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.
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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.
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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.
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