Dimethyl itaconate

Flammability

Description of key information

Experimentally no ignition achieved

Key value for chemical safety assessment

Flammability:

non flammable

Additional information

The flammability of the submission item Dimethyl itaconate (CAS 617-52-7) was investigated in a GLP-compliant study (Walker 2014, Harlan Laboratories Report no. 41400265) using the EU A.10 (Commission Regulation (EC) No 440/2008) protocol. The experiment can be considered relevant and adequate for the endpoint. Therefore it is deemed conclusive and was rated „reliable without restrictions“, i.e. “Klimisch 1” according to the scale of Klimisch et al. (1997).

In the preliminary screening test, a mould (250 mm long · 20 mm wide · 10 mm high) was loosely filled with the submission item. A non-combustible, non-porous board was placed onto the mould which was then inverted. The mould was removed and an air-rich Bunsen burner flame applied to one end of the pile for two minutes.

The pile melted and failed to ignite during the 2 minutes that the Bunsen flame was applied. The result of the preliminary screening test obviated the need to perform the main test.

According to EU standards the submission item is non-flammable (“not highly flammable”).

• Klimisch HJ, Andreae M, Tillmann U (1997). A Systematic Approach for Evaluating the Quality of Experimental Toxicological and Ecotoxicological Data. DOI 10.1006/rtph.1996.1076 PMID 9056496 Regul Toxicol Pharmacol 25:1-5.

Justification for classification or non-classification

Method A.10 was to be used according to Council Regulation (EC) No 440/2008 of 30 May 2008 laying down test methods pursuant to Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH).

It was not possible to initiate burning of the submission item in the pre-test procedure according to the EU A.10 (Commission Regulation (EC) No 440/2008) protocol (Walker 2014, Harlan Laboratories Report no. 41400265).

DSD

Under EU legislation (Commission Directive 2001/59/EC of 6 August 2001, 28th ATP of Council Directive 67/548/EEC, p L 225/269), called thereafter DSD, substances and preparations are classified in accordance with the results of a test following the protocol of the EU Method A.10.

First the criteria given in section 2.1.4. DSD, page L 225/270, for classification of highly flammable substances (labelling F and R11 or R15 or R17) were checked, where the criteria are as follows.

Classification as R11 “Highly flammable” should be assigned to:

• Solid substances which may readily catch fire after brief contact with a source of ignition and which continue to burn or to be consumed after removal of the source of ignition

Classification as R15 “Contact with water liberates extremely flammable gases” should be assigned to:

• Substances which, in contact with water or damp air, evolve extremely flammable gases in dangerous quantities, at a minimum rate of 1 litre per kilogram per hour.

Classification as R17 “Spontaneously flammable in air” should be assigned to:

• Substances which may become hot and finally catch fire in contact with air at ambient temperature without any input of energy.

Then the criteria given in section 2.2.5 DSD, page L 225/270, for classification as “Flammable” were checked. Labelling R10 should be assigned to:

• Liquid substances and preparations having a flash point equal to or greater than 21 °C, and less than or equal to 55 °C.

Finally the criteria given in section 2.2.6 DSD, page L 225/270, concerning other physico-chemical properties, for which additional risk phrases shall be assigned to substances, which have been classified by virtue of sections 2.2.1 to 2.2.5 (“Explosive”, “Oxidising”, “Extremely flammable”, “Highly flammable” and “Flammable” ), in accordance with the following criteria.

• R1 Explosive when dry: For explosive substances and preparations put on the market in solution or in a wetted form, e.g. nitrocellulose with more than 12,6 % nitrogen.
• R4 Forms very sensitive explosive metallic compounds: For substances and preparations which may form sensitive explosive metallic derivatives, e.g. picric acid, styphnic acid.
• R5 Heating may cause an explosion: For thermally unstable substances and preparations not classified as explosive, e.g. perchloric acid > 50 %.
• R6 Explosive with or without contact with air: For substances and preparations which are unstable at ambient temperatures, e.g. acetylene.
• R7 May cause fire: For reactive substances and preparations, e.g. fluorine, sodium hydrosulphite.
• R14 Reacts violently with water: For substances and preparations which react violently with water, e.g. acetyl chloride, alkali metals, titanium tetrachloride.
• R16 Explosive when mixed with oxidising substances: For substances and preparations which react explosively with an oxidising agent, e.g. red phosphorus.
• R18 In use, may form flammable/explosive vapour-air mixture: For preparations not in themselves classified as flammable, which contain volatile components which are flammable in air.
• R19 May form explosive peroxides: For substances and preparations which may form explosive peroxides during storage, e.g. diethyl ether, 1,4-dioxan.
• R30 Can become highly flammable in use: For preparations not in themselves classified as flammable, which may become flammable due to the loss of non-flammable volatile components.
• R44 Risk of explosion if heated under confinement: For substances and preparations not in themselves classified as explosive in accordance with section 2.2.1 above but which may nevertheless display explosive properties in practice if heated under sufficient confinement. For example, certain substances which would decompose explosively if heated in a steel drum do not show this effect if heated in less-strong containers.

None of these criteria were met by the submission item, as it was not possible to initiate burning in the pre-test according to EU A.10, and which is thus:

not classified

CLP/GHS

The classification was made considering ECHA (2013) guidance and the 5th ATP of Regulation (EC) 1272/2008 of the European Parliament and of the Council) as implementation of UN-GHS in the EU.

Physical state definitions (Regulation (EC) No 1272/2008 on Classification, Labelling and Packaging of substances and mixtures of 14 May 2009, Annex I: Part 1, 1.0.):

Gas means a substance which:

(i) at 50 °C has a vapour pressure greater than 300 kPa (absolute); or

(ii) is completely gaseous at 20 °C at a standard pressure of 101.3 kPa;

Liquid means a substance or mixture which:

(i) at 50 °C has a vapour pressure of not more than 300 kPa (3 bar);

(ii) is not completely gaseous at 20 °C and at a standard pressure of 101,3 kPa; and

(iii) which has a melting point or initial melting point of 20 °C or less at a standard pressure of 101,3 kPa;

Solid means a substance or mixture which does not meet the definitions of liquid or gas. The vapour pressure of the submission item at 50 °C is 88 Pa, it is solid at 20 °C and at a standard pressure of 101,3 kPa and it has a melting point of 38 °C.

The submission item is thus a solid under the terms of CLP/GHS

Classification of flammable solids is based upon their burning behaviour and powdered, granular or pasty substances or mixtures may be tested using method N.1 (Test method for readily combustible solids) as described in the UN Recommendations on the Transport of Dangerous Goods, Manual of Tests and Criteria, Part III, sub-section 33.2.1.4. Depending on the burning rate, one of two categories will be assigned.

Essentially, the test methods EU A.10 and UN N.1 are nearly identical, but N.1 has an additional criterion, a wetted zone. Depending on the ability of the wetting zone to stop the fire or not, CLP classifies substances and mixtures other than metals into either category 1 or 2, respectively.

Additionally solids causing fire through friction shall be classified. CLP Annex I: 2.7.1.1., p 127, defines “A flammable solid means a solid which is readily combustible, or may cause or contribute to fire through friction. Readily combustible solids are powdered, granular, or pasty substances or mixtures which are dangerous if they can be easily ignited by brief contact with an ignition source, such as a burning match, and if the flame spreads rapidly.”

It is considered needless to perform another experimental approach employing Method UN N.1. The differences in the test designs are irrelevant, since all attempts to ignite of the submission item failed. Ignition of the submission item by friction is unlikely according to the above mentioned experiments and the experience of production and use. The submission item is thus

not classified

• ECHA European Chemicals Agency (2013). Guidance on the Application of the CLP Criteria. Guidance to Regulation (EC) No 1272/2008 on classification, labelling and packaging (CLP) of substances and mixtures. Version 4.0. Self-published, Helsinki, Finland in November, Reference ECHA-12 -G-06-EN. 662 p.