1、BRITISH STANDARDBS EN 15137:2006Materials and articles in contact with foodstuffs Certain epoxy derivatives subject to limitation Determination of NOGE and its hydroxy and chlorinated derivativesThe European Standard EN 15137:2006 has the status of a British StandardICS 67.250; 71.040.40g49g50g3g38g
2、50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 15137:2006This British Standard was published under the authority of the Standards Policy and Strategy Com
3、mittee on 31 March 2006 BSI 2006ISBN 0 580 48074 7National forewordThis British Standard is the official English language version of EN 15137:2006.The UK participation in its preparation was entrusted by Technical Committee CW/47, Materials in contact with food, to Subcommittee CW/47/1, Migration fr
4、om plastics, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to its secretary.Cross-referencesThe British Standards which implement international or European publications referred to in this document may be found in the BSI Catalog
5、ue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electronic Catalogue or of British Standards Online.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correc
6、t application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed;
7、 monitor related international and European developments and promulgate them in the UK.Summary of pagesThis document comprises a front cover, an inside front cover, the EN title page, pages 2 to 24, an inside back cover and a back cover.The BSI copyright notice displayed in this document indicates w
8、hen the document was last issued.Amendments issued since publicationAmd. No. Date CommentsEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15137March 2006ICS 67.250; 71.040.40English VersionMaterials and articles in contact with foodstuffs - Certain epoxyderivatives subject to limitation - Determin
9、ation of NOGE and itshydroxy and chlorinated derivativesMatriaux et objets en contact avec des denresalimentaires - Drivs poxy soumis des limitations -Dtermination des NOGE et de leurs drivs hydroxyls etchlorsWerkstoffe und Gegenstnde in Kontakt mit Lebensmitteln- Bestimmte Epoxyderivate, die Beschr
10、nkungenunterliegen - 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 nation
11、al 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 ot
12、her 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, Fra
13、nce,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 STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NOR
14、MUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15137:2006: EEN 15137:2006 (E) 2 Contents Page Foreword .3 Introduction.4 1 Scope5 2 Normative references5 3 Principle .5
15、 4 Reagents 6 5 Apparatus.8 6 Samples9 7 Procedure.11 8 Precision 14 9 Confirmation 14 10 Test report15 Annex A (informative) 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 de
16、termination of the content of NOGE and its hydroxy and chlorinated derivatives in can coatings20 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 Directi
17、ves.23 Bibliography24 EN 15137:2006 (E) 3 Foreword This document (EN 15137:2006) has been prepared by Technical Committee CEN/TC 194 “Utensils in contact with food”, the secretariat of which is held by BSI. This European Standard shall be given the status of a national standard, either by publicatio
18、n of an identical text or by endorsement, at the latest by September 2006, and conflicting national standards shall be withdrawn at the latest by September 2006. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and suppo
19、rts essential requirements of EU Directive(s). For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this document. This document should be read in conjunction with EN 13130-1. WARNING: All chemicals are hazardous to health to a greater or lesser extent. It is
20、 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 e
21、nsure 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, Estoni
22、a, 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. EN 15137:2006 (E) 4 Introduction NOGE (Novolac glycidyl ethers) is used as a
23、 monomer in the manufacture of certain polymeric food contact materials and articles. 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
24、 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. EN 15137:2006 (E) 5 1 Scope This European standard describes the determination of NOGE components with more tha
25、n 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
26、 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 g/ml in solution. Direct HPLC analysis of the can coating extract may result in chromatograms difficult to interpre
27、t, 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 substanc
28、es 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 th
29、eir 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 reference
30、s, 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
31、 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 in
32、jected 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 confirmat
33、ion 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 H
34、2O 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 derivat
35、ives 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 wi
36、th the amount of NOGE per H2O derivatives present initially, prior to hydrolysis. EN 15137:2006 (E) 6 3.2 Hydrolysis NOGE and its partly hydrolysed adducts hydrolyse in aqueous neutral and acid conditions. The chlorinated adducts are stable in acid conditions and hydrolyse only slowly in neutral aqu
37、eous media. However, in slightly alkaline conditions all adducts (excepting ether derivatives) hydrolyse to the NOGE per H2O components. To force complete hydrolysis of the epoxy and HCl adducts, the sample solutions are buffered at pH 8.5 and subsequently stored for a minimum of 20 h at 100 C. Afte
38、r that period the NOGE per H2O substances are determined. NOTE 1 Some structures of NOGE and derivatives are shown in Annex A and B. 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 g
39、lycidyl 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
40、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 i
41、nterest 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 gr
42、ade 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
43、 hydroxide solution to a pH of 8,5. Fill the volume to 250 ml with water. EN 15137:2006 (E) 7 4.3.2 Reference solutions of NOGE in acetonitrile (4 mg/ml) Weigh to the nearest 0,1 mg approximately 100 mg of NOGE (4.1) in a 25 ml volumetric flask. Fill the volumetric flask up to the mark with acetonit
44、rile and mix carefully. Calculate the concentration of the substance in milligrams per millilitre solution. 4.3.3 Intermediate reference solution of NOGE in acetonitrile (160 g/ml) 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 aceto
45、nitrile to give a solution containing approximately 160 g/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 C and 10
46、C. 4.3.4 Standard stock solutions of BFDGE in acetonitrile (500 g/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
47、 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 d
48、ivided by concentration of analyte solution, of the two primary standard solutions (or dilutions of that) does not differ by more than 5 %. If there is agreement within 5 %, make subsequent diluted standard solutions from only one of the primary standard solutions. If the levels of the two independe
49、ntly prepared stock solutions do not correspond to within 5 %, discard both stock solutions and prepare new solutions. 4.3.5 Intermediate standard solution of BFDGE in acetonitrile (10 g/ml) Into a 50 ml volumetric flask pipette 1,0 ml of the BFDGE stock solution (4.3.4) and fill the volumetric flask up to the mark with acetonitrile and mix carefully. Calculate the actual concentration of BFDGE in g/ml solution. NOTE The solutions may be stored for up to 6 months in a refrigerator at a temperature between 4 C and 10 C. 4.3.6 Sodium hydrox
