1、BRITISH STANDARDBS EN 15136:2006Materials and articles in contact with foodstuffs Certain epoxy derivatives subject to limitation Determination of BADGE, BFDGE and their hydroxy and chlorinated derivatives in food simulants The European Standard EN 15136:2006 has the status of a British StandardICS
2、67.250g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 15136:2006This British Standard was published under the authority of the Standards Polic
3、y and Strategy Committee on 28 April 2006 BSI 2006ISBN 0 580 48173 5National forewordThis British Standard is the official English language version of EN 15136:2006.The UK participation in its preparation was entrusted by Technical Committee CW/47, Materials in contact with food, to Subcommittee CW/
4、47/1, Migration from 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
5、in the BSI Catalogue 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 responsi
6、ble for its correct 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 i
7、nterests informed; 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 31 and a back cover.The BSI copyright notice displayed in this document indicates when
8、the document was last issued.Amendments issued since publicationAmd. No. Date CommentsEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15136March 2006ICS 67.250English VersionMaterials and articles in contact with foodstuffs - Certain epoxyderivatives subject to limitation - Determination of BADGE,
9、BFDGE and their hydroxy and chlorinated derivatives in foodsimulantsMatriaux et objets en contact avec les denresalimentaires - Drivs poxy soumis des limitations -Dtermination du BADGE, du BFDGE et de leurs drivshydroxyls et chlors dans les simulants dalimentsWerkstoffe und Gegenstnde in Kontakt mit
10、 Lebensmitteln- Bestimmte Epoxyderivate, die Beschrnkungenunterliegen - Bestimmung von BADGE, BFDGE und derenHydroxy- und Chlorderivaten in PrflebensmittelnThis European Standard was approved by CEN on 23 January 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which st
11、ipulate 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 ex
12、ists 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 bodi
13、es 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 COMMITT
14、EE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement 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 15136:2006: EEN 15136:2006 (E) 2 Contents P
15、age Foreword3 Introduction .4 1 Scope.5 2 Normative references.5 3 Principle 5 4 Reagents .6 5 Apparatus9 6 Samples. 11 7 Procedure 13 8 Confirmation . 17 9 Precision . 17 10 Test report. 18 Annex A (informative) Structures of the main compounds cited in this standard 20 Annex B (informative) Princi
16、ple of the determination of BADGE, BFDGE and their hydroxyl and chlorinated derivatives in food simulants. 24 Annex C (informative) Typical chromatograms of BADGE, BFDGE and some of their derivatives. 25 Annex D (informative) Determination of BADGE and its hydrolysis and hydroxychlorinated products
17、in foodstuffs 29 Annex ZA (informative) Relationship between this European Standard and the Essential Requirements of EU Directives 30 Bibliography 31 EN 15136:2006 (E) 3 Foreword This document (EN 15136:2006) has been prepared by Technical Committee CEN/TC 194 “Utensils in contact with food”, the s
18、ecretariat of which is held by BSI. This European Standard shall be given the status of a national standard, either by publication 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 docu
19、ment has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association, and supports 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 s
20、hould be read in conjunction with EN 13130-1. WARNING: 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 whic
21、h 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
22、 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, Slov
23、enia, Spain, Sweden, Switzerland and United Kingdom. EN 15136:2006 (E) 4 Introduction 2,2-Bis(4-hydroxyphenyl)propane bis(2,3-epoxypropyl)ether (BADGE) and bis(hydroxyphenyl)methane bis(2,3-epoxypropyl)ether (BFDGE) are monomers used in the manufacture of certain polymeric food contact materials and
24、 articles. The main application of these monomers is in epoxy coatings for cans and ends. The substances may also be used in organosol coatings. After the manufacture, residues of the substances or the reaction products can remain in the finished product and might migrate into foodstuffs coming into
25、 contact with that product. The analytical method described allows for the determination of BADGE, BFDGE and their reaction products in aqueous and fatty food simulants. EN 15136:2006 (E) 5 1 Scope This European standard describes a method for the determination of BADGE, BFDGE and their reaction pro
26、ducts in food simulants: distilled water, 3 % w/v aqueous acetic acid, 10 % v/v aqueous ethanol solution and olive oil or sunflower oil. A high performance liquid chromatography (HPLC) method is employed based on reversed phase HPLC and fluorescence detection. The method is capable of determining BA
27、DGE and its derivatives at a minimum level of 0,05 g/ml food simulant. BFDGE and its derivatives can be determined at a minimum level of 0,1 g/ml food simulant. Direct HPLC analysis of the migration solutions may result in chromatograms difficult to interpret, due to interference from other componen
28、ts or the instability of the monomers 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 relevant substances is simplified and in addition the identities of the substances are indicat
29、ively confirmed. NOTE In this European standard the term “BADGE, BFDGE and their derivatives” refers to the substances listed in Directive 2002/16/EC 1 and its amendment, Directive 2004/13/EC 2. These substances are listed in 4.1. 2 Normative references The following referenced documents are indispe
30、nsable 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
31、 subject to limitation Part 1: Guide to the test methods for the specific migration of substances from plastics to food and food simulants and the determination of substances in plastics and the selection of conditions of exposure to food simulants ISO 648, Laboratory glassware One-mark pipettes 3 P
32、rinciple 3.1 Determination of BADGE, BFDGE and their derivatives in food simulants Proper quantification of the sum of BADGE, BFDGE and/or their derivatives is obtained by analysing the simulants twice: a first analysis of the simulant as obtained from the migration is performed and, if necessary, t
33、he substances are fully hydrolysed and the hydrolysed substances are determined in a second HPLC analysis. This second analysis is used for confirmation and final quantification of the sum of BADGE or BFDGE and their derivatives as the bis(diol) derivatives. In the first instance, after the migratio
34、n period, samples from aqueous food simulants are directly injected into a reverse phase HPLC column and the substances are separated using a gradient elution profile. For fatty food simulants, the substances are extracted with acetonitrile followed by HPLC EN 15136:2006 (E) 6 analysis. Detection is
35、 performed by means of fluorescence detection. Identification is based on retention time and comparison with reference substances, fluorescence and UV detection. If it appears from this first analysis that the summed migration level of BADGE/BFDGE and/or their derivatives is 0.5 mg/kg, confirmation
36、and final quantification of BADGE, BFDGE and their derivatives is performed by forced hydrolysis of the epoxy components and the chlorinated components. If the substance of interest contains either an epoxy group or a HCl adduct, then this component will hydrolyse to the bis(diol) components. Compar
37、ed to the HPLC chromatogram prior to hydrolysis a simpler HPLC chromatogram is obtained after hydrolysis, containing fewer peaks because the peaks of BADGE, BFDGE and their adducts disappear; if the peak(s) remain(s) then this substance should be considered an interfering substance originating from
38、the matrix. Forced hydrolysis is obtained by mixing the sample solution with buffer and hydrolysis at 100 C. Then a second HPLC analysis is performed to determine the concentration of monomer.2H2O. 3.2 Hydrolysis BADGE, BFGDE and their partly hydrolysed adducts hydrolyse in aqueous neutral and acid
39、conditions. The chlorinated adducts are stable in acid conditions and hydrolyse only slowly in neutral aqueous media. However, in slightly alkaline conditions all adducts (excepting ether derivatives) hydrolyse to the bis(diol) component. To force complete hydrolysis of the epoxy and HCl adducts, th
40、e sample solutions are buffered at pH 8.5 and subsequently stored for a minimum of 20 h at 100 C. After that period the bis(diol) substances are determined. NOTE The structures of BADGE, BFDGE and their derivatives are included in Annex A as well as some derivatives that may be formed during contact
41、 with simulants. A flow chart showing the principle of the determination of BADGE, BFDGE and their derivatives in food simulants is given in Annex B. 4 Reagents 4.1 Analytes NOTE See Annex A for molecular structures. 4.1.1 BADGE CAS no. 1675-54-3 4.1.2 BADGE.2HCl CAS no. 4809-35-2 4.1.3 BADGE.2H2O C
42、AS no. 5581-32-8 4.1.4 BADGE.H2O CAS no. 76002-91-0 4.1.5 BADGE.HCl CAS no. 13836-48-1 4.1.6 BADGE.H2O.HCl CAS no. 227947-06-0 4.1.7 BFDGE CAS no. 2095-03-6 4.1.8 BFDGE.2HCl 4.1.9 BFDGE.2H2O CAS no. 72406-26-9 4.1.10 BFDGE.HCl, prepared as follows: Dissolve approximately 50 mg BFDGE (4.1.7) in 25 ml
43、 dioxane, add 10 l concentrated hydrochloric acid and reflux for 10 min. Using a rotavapor evaporate the dioxane and dissolve the residue in 25 ml acetonitrile. The mixture should contain the isomers of each of three substances BFDGE, BFDGE.HCl and BFDGE.2 HCl. This mixture is only used for referenc
44、e purposes. EN 15136:2006 (E) 7 4.1.11 BFDGE.H2O, prepared as follows: Dissolve 50 mg BFDGE in 25 ml dioxane, add 500 l water and reflux for 10 min. Using a rotavapor evaporate the dioxane and dissolve the residue in acetonitrile. The mixture should contain the isomers of each of three substances BF
45、DGE, BFDGE.H2O and BFDGE.2H2O. This mixture is only used for reference purposes. NOTE BFDGE and its derivatives consists of a mixture of isomers (see annex A). The ratio of the various isomers may differ depending on the supply source. 4.2 Reagents NOTE During the analysis, unless otherwise stated,
46、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 Ethanol 100 %, distilled 4.2.4 Methanol, HPLC grade 4.2.5 Sodium hydroxide 4.2.6 Water deionised, HPLC grade 4.3 Solutions 4.3.1 Borate buffer:
47、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. Top up the volume to 250 ml with water. 4.3.2 Stock solutions of pure reference substances of BADGE, BFDGE and their derivatives in acetonitrile (500 g/ml) NOTE If the derivatives of BADGE and
48、 BFDGE only are used for establishing their retention times before hydrolysis, qualitative solutions may be prepared. If the solutions are used to quantify each of the derivatives in order to avoid the hydrolysis procedure (see scheme in Annex B), quantitative solutions should be prepared of each of
49、 the derivatives. However, quantitative solutions containing only BADGE and BFDGE should always be prepared. Weigh to the nearest 0,1 mg approximately 50 mg of each of the relevant substances listed in 4.1 in a series of 100 ml volumetric flasks and add 80 ml acetonitrile (4.2.1). Place the flask for 5 min in an ultrasonic water-bath to dissolve the substances. Cool the solution to room temperature and fill the volumetric flask up to the mark with acetonitrile and mix carefully. Calculate the actual concentration of the substance in mic
