Name: Vermeiren Toon.
Student number: r0809559
Exam Assignment Product safety
What are the CLP Hazards of Butyl Acrylate?
Butyl acrylate is the substance under investigation. This chemical's principal physical
risk is its flammability. It is categorized as a category 3 flammable liquid, or "H225:
“Flammable liquid and vapour." In terms of potential health risks, the skin and eyes are
harmed by butyl acrylate. It is categorized as a category 2 skin irritant, category 2 eye
irritant and a category 1 skin sensitization agent. "H315: Causes skin irritation", “H319:
causes serious eye irritation and "H317: May cause an allergic skin reaction" are the
related hazard statements respectively. The last thing that is included in the CLP is a single
target organ toxicity with single exposure, being “STOT SE 3: May cause respiratory
irritation. There are no environmental hazards formulated in the harmonized CLP, nor
acute toxicity hazards. [2, 1]
What are the intrinsic hazards?
Health Hazards
In several tests on rats held under the OECD Guidelines, it was found that butyl acrylate has a
median lethal dose (LD50) of ca. 3150 mg/kg bodyweight for oral toxicity, a LC50 of 41.3mg/ L air
(one hour of exposure) for inhalation toxicity and a LD50 of 2000 mg/ kg bodyweight for dermal
toxicity when being exposed for 24 hours. While this data is not sufficient for classification in the
harmonized CLP, the classification of acute toxicity, category 4: “H332 : Harmful if inhaled.” has
been included in REACH registration dossiers. The value corresponding to a median lethal dose for
humans is set to 10 300 mg/m³ air. Since such concentrations are extremely high, it is more useful to
look at the short term exposure limit (STEL). For 15 minute of exposure a maximum butyl acrylate
concentration of 10 ppm (53 mg/m³) is advised. This is in line with a Time weighted average (TWA)
of 11 mg/m³ over 8 hours.
Various in vitro tests and in vivo tests (on rats) were executed on genetic toxicity, which concluded
that butyl acrylate does not have the potential for genotoxic effects. In addition a reliable two year test
on rats held the same conclusion for carcinotoxicty.
As previously reported, butyl acrylate generally causes three types of irritation:
Skin irritation: Direct contact can cause redness, itching and burning of the skin.
Eye irritation: Direct contact causes redness and pain
Sensitivity: Some individuals may be allergic to butyl acrylate after repeated exposure. This condition
is known as sensitization and can cause symptoms ranging from mild dermatitis to severe skin
irritation. [16]
Butyl Acrylate can also cause respiratory irritation when inhaled.
Aquatic toxicity
Aquatic toxicity classifications are not included in the harmonized CLP. Nevertheless, the
classification of aquatic chronic cat. 3: H412: “harmful to aquatic life with longlasting effects”, is
included in a REACH registration dossier. Hence, for this process it is very important that, after
washing the vessel, the dirty water gets collected instead of being dumped into freshwater. This causes
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Name: Vermeiren Toon.
Student number: r0809559
acute toxicity to plants and fishes, living there. In a test executed by BASF on freshwater fish,
freshwater vertebrates and freshwater algae, that butyl acrylate has a median lethal dose of 5.2 mg/ L,
8.2 mg/L and 2.65 mg/L respectively. It was found that for the vertebrates, daphnia magna
specifically, butyl acrylate can cause long-term toxicity (hence the classification in the REACH
register)
Physical hazards
As mentioned above, butyl acrylate is reported as a category 3 in terms of flammability. This
means that the flash point is between: 23°C and 60°C. More specifically for butyl acrylate, the
flashpoint will be around 37°C. This is slightly above the room temperature of 20°C. However, a fast
increase in heat can cause the temperature of the premix to increase above the flash temperature.
Therefor the presence of heating equipment and electrical devices, close to the premix is considered a
serious hazard. Self-ignition occurs at a temperature of 273°C. This temperature will not be reached
under normal circumstances. Still, in the presence of fire or like in the case of the Dow Bristol Plant
[14] a lightning bolt could raise the temperature to the auto-ignition temperature. The lower explosion
limit (LEL) is 1.2 vol% and the upper explosion limit is 8%vol. Since the volume of the premixer is
quite small (25L) the design pressure may be at 4 barg(above ambient conditions) and the design
temperature at 100°C, A boiling liquid expanded vapor explosion (BLEVE) can occur when an
external heat source creates a rupture in the premix wall. [13,14] When the external heat source is a
fire this can also lead to ignition of butyl acrylate in the premix. However, since the recipe of the
different acrylates is known, it is possible to predict the pressure relieve systems accordingly.
Reactivity is another hazard associated with butyl acrylate. Since it is a monomer, contaminants might
cause it to polymerize. This process can be sped up using heat and light. It causes the temperature and
pressure to drastically increase. This can causes a runaway, which would be very dangerous for the
plant. Also the presence of strong oxidants can cause BA to polymerize quickly. [15] Due to their
uncontrolled temperature and pressure, polymerization should be avoided in the and the pipelines.
What is needed for protection to the instruction
workers?
Operators should put on the proper personal protection gear. This comprises protective gloves (butyl
rubber with 0.7 mm coating thickness or nitrile rubber with 0.4 mm coating thickness), coveralls that
are flame resistant, and safety eyewear with side shields. Use explosion- and spark-proof tools when
performing maintenance. Also, since the BA is irritating the skin, face mask should be available when
doing jobs, close to the premix. It is necessary to cleanse and vent the equipment before opening
manholes or flange connections. In case of exposure, first aid supplies, emergency showers, and eye
showers should be positioned close to the process equipment. Workers should always wash their hands
before and especially after the shift for their own safety. To lower the risk of ingesting contaminants,
eating and drinking, regulations should be strictly followed at chemical plants.
Butyl acrylate should be maintained away from hot surfaces, ignition sources, and direct sunlight due
to its flammability and fast polymerisation. Therefore, it is suggested that electrical equipment for
instrumentation, lighting, and ventilation are spark and explosion proof. Action should also be taken to
prevent electrical discharge like lightning protection and grounding of electrical equipment present in
the area around the premix. The dissolved oxygen should also be of adequate amount. Other measures
are the fact that smoking and any form of fire starting should be prohibited. To alert you in the event
of a (possible) fire, fire detection system, such as smoke detectors, heat detectors, or flame detectors
should be installed. An integrated fire evacuation plan should, obviously, be integrated in the whole
plant.
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Name: Vermeiren Toon.
Student number: r0809559
Since butyl acrylate polymerizes easily, it is of crucial concern that certain chemicals (especially
oxidants) are avoided near the premix. Furthermore the premix should be kept away from direct
sunlight, other strong light sources and other radiation with high energy such as UV-light. since these
can cause polymerisation reactions. The use of a polymerisation inhibitor, like hydroquinone, could
possibly help to prevent polymerisation reactions. The headspace of the reactor should be made as
inert as possible with nitrogen gas (oxygen content less than 5%) and the atmosphere of the premix
should be monitored continuously. A minimum of two temperature sensors should also be included in
the design to alert when the temperature is rising and to make sure that the plant can be shut down and
evacuated timely if needed. The cooling water heat exchanger should be placed nearby the cooling
jacket to ensure a rapid emergency switch when needed.
In addition a working detector should be present in the room of the premix which measures the
amount of BA in the air and alarms the workers when the concentration is higher than the STEL over
15 minutes. This detector should also monitor other (flammable) gas mixtures. A efficient ventilation
system must be present in every closed space in the premix side of the plant to ensure good air quality.
Fire-extinguishers (CO2, Alcohol foam or dry chemical) must be ready to use in every room. Water
can also be used but mostly as a cooler to avoid polymerisation reactions.
Lastly, to protect the workers and the plant when an explosion occurs, all the walls and roofs of the
building where the premix is located, should be protected against large forces. In addition it should be
possible to isolate the premix from the whole plant safely. This can be obtained with fail-close valves.
What are the REACH Obligations for the supplier?
Registration
If you manufacture or import butyl acrylate in quantities of one ton or more per year, you must
register the substance with ECHA. The registration includes providing information about the
substance's properties, uses, potential hazards. The manufacturer needs to use this information to make
sure that all risks are controlled.
In particular the technical dossier is needed for general information about the substance and is required
for all registrations. It is described in annex VI and includes the identity of the manufacturer, the
chemical identity of the substance, information on the manufacture and use of the substance,
classification and labelling of the substance (according to the CLP legislation), a confidentiality
request, summaries on the intrinsic properties, an indication that indicates whether the information is
reviewed and guidance on safe use. Guidance on safe use includes information on first aid measures,
fire-fighting measures, accidental release measures and handling, storage and transport information.
Additionally, manufacturers must collect all freely available existing information on the substance,
regardless of tonnage [9]. Because the manufacturer produces over BA in a quantity over 1000 t/y1 ,
they must include data specified in Annexes VII and VIII, as well as testing proposals for information
in Annexes IX and X [8].
If the registrants imports more than 10 tonnes per annum, which is the case, than the manufacturer
needs to include a chemical safety report (CSR) which is the documentation of the manufacturers
chemical safety assessment. This chemical safety assessment comprises a human health hazard
assessment, a physicochemical assessment, a environmental assessment and a persistent, bio
accumulative and toxic (PBT) assessment. These assessments determine the derived no-effect levels
DNELs and the predicted no-effect concentrations PNECs of the substance but also gives the potential
effects to human health of the physicochemical hazards that belong to the substance. All these four
assessments are complemented with an exposure assessment. This assessment gives information about
the potential dose or concentration, humans or the environment could be exposed to. It gives an
exposure scenario for a given set of conditions. It gives advice on how to control the exposure on
human and the environment and it must include the risk assessment and operational conditions for
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Name: Vermeiren Toon.
Student number: r0809559
which the risks from the uses of the substance are controlled. At last the CSA must include a risk
characterisation which compares the DNELs and PNECS with the estimated the exposure
concentrations to humans and the environment.
Since more than one entity produces or imports butyl acrylate, all registrants are required to submit the
same joint application for that material. The registration dossier is thereafter put together in part with
assistance from other manufacturers, importers, and exclusively representatives of the same chemical.
This comprises the risks, testing ideas, classification, and labelling, as well as, optionally, the CSR,
instructions for safe use, and quality checks of the data that was supplied.[9] Each producer is given a
specific amount of information, including information on how butyl acrylate is produced, used, and
who the manufacturer is.
Authorisation and restriction
If butyl acrylate is listed as a Substance of Very High Concern (SVHC), authorization may be required
for certain uses. Suppliers must assess whether their use falls under the scope of authorization and take
necessary steps to obtain authorization if required. However, this is not the case. Therefor
authorisation and restriction obligations are not applicable to butyl acrylate
Communication
The supplier has a responsibility to communicate relevant information on the safe use of butyl acrylate
to downstream users, including distributors and customers. This includes sharing information on safe
handling practices, exposure controls, and any necessary risk management measures.
The supplier must prepare and provide a Safety Data Sheet for butyl acrylate. The format of the SDS
is defined by Annex II to REACH. The SDS contains information on the substance's properties,
hazards, safe handling instructions, and emergency measures. In general the supplier must provide
“sufficient information to enable the user to take all necessary measures as regards the protection of
human health, safety and the environment.” The SDS must be updated regularly and All information
in the SDS must be consistent with the information provided in the registration dossier.
References
1] BASF (2019). Safety Data Sheet - Butyl acrylate. Retrieved on 23/05/2023 at
https://download.basf.com/p1/000000000030041258_SDS_GEN_TH/en_TH/BUTYL_ACRYLATE_
000000000030041258_SDS_GEN_TH_en_5-0.pdf
[2] ECHA (2008). Registration Dossier - butyl acrylate. Retrieved on 04/06/2023 at
https://echa.europa.eu/nl/registration-dossier/-/registered-dossier/15779
[3] ECHA (2023). Substance Infocard – Butyl acrylate. Retrieved on 04/06/2023 at
https://echa.europa.eu/nl/substance-information//substanceinfo/100.004.983#:~:text=According%20to%20the%20harmonised%20classification,and%2
0may%20cause%20respiratory%20irritation.
[4] ECHA (2023). Candidate List of substances of very high concern for Authorisation. Retrieved on
27/05/2023 at https://echa.europa.eu/candidate-list-table
[5] ECHA (2023). Authorisation list. Retrieved on 04/06/2023 at https://echa.europa.eu/authorisationlist
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Name: Vermeiren Toon.
Student number: r0809559
[6] ECHA (2021). Assessment of Regulatory Needs - Acrylates and Methacrylates. Retrieved on
04/06/2023 at https://echa.europa.eu/documents/10162/e0893f32-99a8-ad5f-d481-55cd8362f7c6
[7] ECHA (2023). Substance Regulatory Obligations – Butyl methacrylate. Retrieved on 26/05/2023
at https://echa.europa.eu/legislation-obligation/-/obligations/100.001.180
[8] ECHA (2021). Guidance on registration. Retrieved on 02/06/2023 at
https://echa.europa.eu/documents/10162/2324906/registration_en.pdf/ de54853d-e19e-4528-9b348680944372f2?t=1629205524601
[9] ECHA (2015). Registration - Guidance in a nutshell. Retrieved on 27/05/2023 at
https://echa.europa.eu/documents/10162/2324906/nutshell_guidance_registration_en. pdf/9fda505f972d-4bbb-b22c-bd71b6941571?t=1499266032298
[10] ECHA (2023). Guidance for monomers and polymers. Retrieved on 24/05/2023 at
https://echa.europa.eu/documents/10162/2324906/polymers_en.pdf/ 9a74545f-05be-4e10-85554d7cf051bbed
[11] ECHA (2015). Compilation of safety data sheets - Guidance in a nutshell. Retrieved on
24/05/2023 at https://echa.europa.eu/documents/10162/2324906/sds_nutshell_guidance_en.pdf/
5d5eff4a-3596-4ba8-a4c8-3311ba4ad07b
[12] ECHA (2015). REACH Fee Regulation (Article 17). Retrieved on 24/05/2023 at https: //eurlex.europa.eu/legal-content/EN/TXT/HTML/?uri=CELEX:02008R0340-20150625#tocId1
[13] Manders, L. G. et al. (2011). Online Model-Based Process Safety Concepts in Polymerization. In
Macromolecular Symposia, issue 302, pages 289-296
[14] Kas, K., Morrison, D. T. (2021). It was a dark and stormy night - Investigation of acrylate storage
tank explosions.
[15] KULoket (s.d.). Gevaarlijke stoffen en etiketten – n-butylacrylaat. Retrieved on 23/05/2023 at
https://webwsp.aps.kuleuven.be/sap/bc/ui2/flp#zr_0097-display&/product/KUL_00001740/
SubNode/KUL_00001740%20SAP_EHS_1014/label/EE6BAC99350D1EDA93D3A66D2720520A
[16] International Chemical Safety Card, Butyl Acrylate reviewed on 04/06/2023 at
https://www.ilo.org/dyn/icsc/showcard.display?p_lang=en&p_card_id=0400
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