EN 15137:2006

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Materials and articles in contact with foodstuffs - Certain epoxy derivatives subject to limitation - Determination of NOGE and its hydroxy and chlorinated derivativesGHULYDWRYMatériaux et objets en contact avec des denrées alimentaires - Dérivés époxy soumis a des limitations - Détermination des NOGE et de leurs dérivés hydroxylés et chlorésWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Bestimmte Epoxyderivate, die Beschränkungen unterliegen - Bestimmung von NOGE und dessen Hydroxy- und ChlorderivatenTa slovenski standard je istoveten z:EN 15137:2006SIST EN 15137:2006en,fr,de67.250ICS:SLOVENSKI
STANDARDSIST EN 15137:200601-september-2006

EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15137March 2006ICS 67.250; 71.040.40 English VersionMaterials and articles in contact with foodstuffs - Certain epoxyderivatives subject to limitation - Determination of NOGE and itshydroxy and chlorinated derivativesMatériaux et objets en contact avec des denréesalimentaires - Dérivés époxy soumis à des limitations -Détermination des NOGE et de leurs dérivés hydroxylés etchlorésWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln- Bestimmte Epoxyderivate, die Beschränkungenunterliegen - Bestimmung von NOGE und dessen Hydroxy-und ChlorderivatenThis European Standard was approved by CEN on 23 January 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2006 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15137:2006: E

The 7 positional 3-ring NOGE isomers.16 Annex B (informative)
Substances that may occur in an HPLC chromatogram of a can coating.18 Annex C (informative)
Principle of the determination of the content of NOGE and its hydroxy and chlorinated derivatives in can coatings.20 Annex D (informative)
Typical chromatogram of NOGE standard, before and after hydrolysis.21 Annex ZA (informative)
Relationship between this
European
Standard and the Essential Requirements
of EU Directives.23 Bibliography.24

All chemicals are hazardous to health to a greater or lesser extent.
It is beyond the scope of this European standard to give instructions for the safe handling of all chemicals, that meet, in full, the legal obligations in all countries in which this European standard may be followed.
Therefore, specific warnings are not given and users of this European standard should ensure that they meet all the necessary safety requirements in their own country. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.

The main application of NOGE is in epoxy coatings for cans and ends. The substance may also be used in organosol coatings. After the manufacture, residues of NOGE or its reaction products can remain in the finished product and may migrate into foodstuffs coming into contact with that product.
The analytical method described allows for the determination NOGE and its reaction products in can coatings.

This European standard describes the determination of NOGE components with more than two aromatic rings (the two-ring NOGE is equal to BFDGE = Bis(2-hydroxyphenyl)methane bis(2,3-epoxypropyl)ether) and at least one epoxy group as well as their derivatives containing chlorohydrin functions and having a molecular mass less than 1000 Daltons in can coatings. A high performance liquid chromatography (HPLC) method is employed based on reversed phase HPLC and fluorescence detection.
The method is capable of determining NOGE and its derivatives at a minimum level of 1 µg/ml in solution. Direct HPLC analysis of the can coating extract may result in chromatograms difficult to interpret, due to interference from other components or the instability of the monomer resulting in a complex mixture of derivatives and/or reaction products. By forced hydrolysis of all epoxy groups and their reaction products, the quantification of the NOGE is simplified and the identities of the substances are indicatively confirmed.
NOTE In this European standard the term “NOGE and its derivatives” refers to the requirements of Directive 2002/16/EC [1] and its amendment, Directive 2004/13/EC [2]. This includes NOGE components with more than two aromatic rings and at least one epoxy group as well as their derivatives containing chlorohydrin functions and having a molecular mass less than 1000 Daltons. 2 Normative references The following referenced documents are indispensable for the application of this European standard. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 13130-1:2004, Materials and articles in contact with foodstuffs – Plastics substances subject to limitation – Part 1: Guide to the test methods for the specific migration of substances from plastics to foods and food simulants and the determination of substances in plastics and the selection of conditions of exposure to food simulants 3 Principle
3.1 Determination of NOGE and derivatives in a can coating Can coatings are extracted with acetonitrile for 24 h at room temperature. Then the extraction solvent is injected into a reverse phase HPLC column. The substances are separated using a gradient elution profile. Detection is performed by means of fluorescence detection. Identification is based on retention time and comparison with reference substances, fluorescence and UV detection response. For confirmation and quantification of NOGE and derivatives the epoxy and the chlorohydrin containing components are fully hydrolysed in alkaline medium at elevated temperature to form the diol components. The hydrolysed components (NOGE per H2O) are separated by HPLC using fluorescence detection. The NOGE per H2O components will appear early in the chromatogram due to the increased polarity of the hydrolysed components. Compared to the HPLC chromatogram prior to hydrolysis a simpler HPLC chromatogram is obtained after hydrolysis, containing fewer peaks because all epoxy components and chlorohydrin derivatives disappear; if a peak remains then this substance shall be considered an interfering substance originating from the matrix. To establish compliance with the restrictions set the total amount of diol substances is determined. If relevant, the total amount of NOGE per H2O derivatives is reduced with the amount of NOGE per H2O derivatives present initially, prior to hydrolysis.

NOTE 2 A flow chart showing the principle of the determination of NOGE and derivatives in can coatings is given in Annex C. 4 Reagents
4.1 Analytes 4.1.1 Poly(phenyl glycidyl ether)-co-formaldehyde CAS no 28064-14-4
The analyte substance contains approximately 40% of NOGE with 3 – 6 aromatic rings, but batch and supplier variations may occur. Average Mn approximately 345; Average epoxy groups per molecule, 2.2. 4.1.2 BFDGE.2H2O
CAS no 72406-26-9
4.1.3 BFDGE
CAS no 2095-03-6
NOTE 1 NOGE and its derivatives consist of a mixture of isomers (see Annexes A and D). The ratio of the various isomers may differ, depending on the supply source. Also the composition of the reference material may vary, depending on supply source and Lot number. NOTE 2 The substances of interest are those with more than two aromatic rings and at least one epoxy group as well as their derivatives containing chlorohydrin functions and having a molecular mass less than 1000 Dalton.
4.2 Reagents NOTE During the analysis, unless otherwise stated, only reagents of recognized analytical grade and distilled water of equivalent purity should be used. 4.2.1 Acetonitrile, HPLC grade 4.2.2 Boric acid 4.2.3 Methanol, HPLC grade 4.2.4 Sodium hydroxide 4.2.5 Water deionised, HPLC grade 4.3 Solutions 4.3.1 Borate buffer: 0,6 M
Dissolve 9,28 g of boric acid in 220 ml of water. Add 4,5 M sodium hydroxide solution to a pH of 8,5. Fill the volume to 250 ml with water.

Pipette 1,0 ml of the stock solution (4.3.2) into a 25 ml volumetric flask and fill the flask up to the mark with acetonitrile to give a solution containing approximately 160 µg/ml of NOGE. NOTE 1 The solutions prepared contain approximately 40 % of the components of interest (NOGE with 3 to 6 aromatic rings).
NOTE 2 The solutions may be stored for up to 6 months in a refrigerator at a temperature between 4 ºC and 10 ºC. 4.3.4 Standard stock solutions of BFDGE in acetonitrile (500 µg/ml) Weigh to the nearest 0,1 mg approximately 50 mg of BFGDE (4.1.3) in a 100 ml volumetric flask and add 80 ml acetonitrile (4.2.1), and mix thoroughly to dissolve the BFDGE. Fill the volumetric flask up to the mark with acetonitrile and mix carefully. Calculate the actual concentration of BFDGE in micrograms per millilitre of solution. Repeat the procedure to obtain a second standard stock solution. Check the two primary standard solutions of analyte against one another. Check that the response factor, i.e. detector response divided by concentration of analyte solution, of the two primary standard solutions (or dilutions of that) does not
...