1、DRAFT FOR DEVELOPMENTDD CEN/TS 13130-20:2005Materials and articles in contact with foodstuffs Plastics substances subject to limitation Part 20: Determination of epichlorohydrin in plasticsICS 67.250g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g
2、59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58DD CEN/TS 13130-20:2005This Draft for Development was published under the authority of the Standards Policy and Strategy Committee on 16 September 2005 BSI 16 September 2005ISBN 0 580 46073 8National f
3、orewordThis Draft for Development is the official English language version of CEN/TS 13130-10:2005.This publication is not to be regarded as a British Standard.It is being issued in the Draft for Development series of publications and is of a provisional nature because the method was not evaluated u
4、sing recognized ring trial procedures. As a consequence there are no reproducibility data for the method. It should be applied on this provisional basis, so that information and experience of its practical application may be obtained.Comments arising from the use of this Draft for Development are re
5、quested so that UK experience can be reported to the European organization responsible for its conversion to a European standard. A review of this publication will be initiated 2 years after its publication by the European organization so that a decision can be taken on its status at the end of its
6、3-year life. Notification of the start of the review period will be made in an announcement in the appropriate issue of Update Standards.According to the replies received by the end of the review period, the responsible BSI Committee will decide whether to support the conversion into a European Stan
7、dard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent in writing to the Secretary of BSI Subcommittee CW/47/1 Migration from plastics, at British Standards House, 389 Chiswick High Road, London W4 4AL, giving the document reference and clause number and p
8、roposing, where possible, an appropriate revision of the text.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
9、 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 responsibl
10、e for its correct application.Summary of pagesThis document comprises a front cover, an inside front cover, the CEN/TS title page, pages 2 to 18, an inside back cover and a back cover.The BSI copyright notice displayed in this document indicates when the document was last issued.Amendments issued si
11、nce publicationAmd. No. Date CommentsTECHNICAL SPECIFICATIONSPCIFICATION TECHNIQUETECHNISCHE SPEZIFIKATIONCEN/TS 13130-20February 2005ICS 67.250English versionMaterials and articles in contact with foodstuffs - Plasticssubstances subject to limitation - Part 20: Determination ofepichlorohydrin in pl
12、asticsMatriaux et objets en contact avec les denresalimentaires - Substances dans les matires plastiquessoumises des limitations - Partie 20 : Dtermination delpichlorohydrine dans les matires plastiquesWerkstoffe und Gegenstnde in Kontakt mit Lebensmitteln- Substanzen in Kunststoffen, die Beschrnkun
13、genunterliegen - Teil 20: Bestimmung von Epichlorhydrin inKunststoffenThis Technical Specification (CEN/TS) was approved by CEN on 16 December 2004 for provisional application.The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be reques
14、ted to submit theircomments, particularly on the question whether the CEN/TS can be converted into a European Standard.CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS availablepromptly at national level in an appropriate form. It
15、is permissible to keep conflicting national standards in force (in parallel to the CEN/TS)until the final decision about the possible conversion of the CEN/TS into an EN is reached.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, F
16、rance,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia,Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGMan
17、agement Centre: rue de Stassart, 36 B-1050 Brussels 2005 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CEN/TS 13130-20:2005: E2 Contents page Foreword. 3 Introduction 5 1 Scope 6 2 Normative references . 6 3 Principle . 6 4 Reagents 6
18、 5 Apparatus 8 6 Samples . 9 7 Procedure 10 8 Precision 14 9 Confirmation 15 10 Test report . 16 Annex A (normative) Equipment for the micro-distillation of epichlorohydrin from dioxane extract 17 Bibliography . 18 DD CEN/TS 13130-20:20053 Foreword This document (CEN/TS 13130-20:2005) has been prepa
19、red by Technical Committee CEN/TC 194 “Utensils in contact with food”, the secretariat of which is held by BSI. This part of EN 13130 has been prepared within the Standards, Measurement and Testing project, MAT1-CT92-0006, “Development of Methods of Analysis for Monomers” and has been prepared by Su
20、bcommittee (SC 1) of TC 194 “Utensils in contact with food“ as one of a series of test methods for plastics materials and articles in contact with foodstuffs. This standard is intended to support Directives 2002/72/EC 1, 89/109/EEC 2, 82/711/EEC 3 and its amendments 93/8/EEC 4 and 97/48/EC 5, and 85
21、/572/EEC 6. At the time of preparation and publication of this part of EN 13130 the European Union legislation relating to plastics materials and articles intended to come into contact with foodstuffs is incomplete. Further Directives and amendments to existing Directives are expected which could ch
22、ange the legislative requirements which this standard supports. It is therefore strongly recommended that users of this standard refer to the latest relevant published Directive(s) before commencement of a test or tests described in this standard. This part of EN 13130 should be read in conjunction
23、with EN 13130-1. Further parts of EN 13130, under the general title Materials and articles in contact with foodstuffs - Plastics substances subject to limitation, have been prepared, and others are in preparation, concerned with the determination of specific migration from plastics materials into fo
24、odstuffs and food simulants and the determination of specific monomers and additives in plastics. The parts of EN 13130 are as follows. Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food simulants and the determination of substances in plastics and
25、 the selection of conditions of exposure to food simulants Part 2: Determination of terephthalic acid in food simulants Part 3: Determination of acrylonitrile in food and food simulants Part 4: Determination of 1,3-butadiene in plastics Part 5: Determination of vinylidene chloride in food simulants
26、Part 6: Determination of vinylidene chloride in plastics Part 7: Determination of monoethylene glycol and diethylene glycol in food simulants Part 8: Determination of isocyanates in plastics Part 9: Determination of acetic acid, vinyl ester in food simulants Part 10: Determination of acrylamide in f
27、ood simulants Part 11: Determination of 11-aminoundecanoic acid in food simulants Part 12: Determination of 1,3-benzenedimethanamine in food simulants DD CEN/TS 13130-20:20054 Part 13: Determination of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A) in food simulants Part 14: Determination of 3,3-bis(
28、3-methyl-4-hydroxyphenyl)-2-indoline in food simulants Part 15: Determination of 1,3-butadiene in food simulants Part 16: Determination of caprolactam and caprolactam salt in food simulants Part 17: Determination of carbonyl chloride in plastics Part 18: Determination of 1,2-dihydroxybenzene, 1,3-di
29、hydroxybenzene, 1,4-dihydroxybenzene, 4,4-dihydroxybenzophenone and 4,4dihydroxybiphenyl in food simulants Part 19: Determination of dimethylaminoethanol in food simulants Part 20: Determination of epichlorohydrin in plastics Part 21: Determination of ethylenediamine and hexamethylenediamine in food
30、 simulants Part 22: Determination of ethylene oxide and propylene oxide in plastics Part 23: Determination of formaldehyde and hexamethylenetetramine in food simulants Part 24: Determination of maleic acid and maleic anhydride in food simulants Part 25: Determination of 4-methyl-pentene in food simu
31、lants Part 26: Determination of 1-octene and tetrahydrofuran in food simulants Part 27: Determination of 2,4,6-triamino-1,3,5-triazine in food simulants Part 28: Determination of 1,1,1-trimethylolpropane in food simulants Parts 1 to 8 are European Standards. Parts 9 to 28 are Technical Specification
32、s. WARNING All chemicals are hazardous to health to a greater or lesser extent. It is beyond the scope of this Technical Specification to give instructions for the safe handling of all chemicals, that meet, in full, the legal obligations in all countries in which this Technical Specification may be
33、followed. Therefore, specific warnings are not given and users of this Technical Specification 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 a
34、re bound to announce this CEN Technical Specification: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switz
35、erland and United Kingdom. DD CEN/TS 13130-20:20055 Introduction Epichlorohydrin, 1-chloro-2,3-epoxypropane, C3H5OCl, PM/Ref. No 16750, is a monomer used in the manufacture of certain plastics materials and articles, but mainly coatings intended to come into contact with foodstuffs. After manufactur
36、e residual epichlorohydrin can remain in the finished product and may migrate into foodstuffs coming into contact with that product. This analytical method allows the determination of the residual content of epichlorohydrin in coatings. The method has been pre-validated by collaborative trial with t
37、wo laboratories. NOTE A limit on the residual quantity of 1 mg/kg polymer in final product has been set. However, epichlorohydrin is mainly used in coatings on non-plastics substrates. The amount of coating on a final article, e.g. coated cans, cannot be determined with an acceptable accuracy. There
38、fore, the residual content of epichlorohydrin in coatings cannot be determined. The area of a coating is easy to determine and so the amount of residual epichlorohydrin content can be determined in milligrams per square decimetre. DD CEN/TS 13130-20:20056 1 Scope This document, part of EN 13130, spe
39、cifies an analytical procedure for the determination of residual epichlorohydrin in coatings. The method is appropriate for the quantitative determination of epichlorohydrin in the analyte concentration range of 5 ng/ml to 80 ng/ml of extract. In general this allows for the detection of epichlorohyd
40、rin at the level of 1 mg/kg of polymer or in the case of coatings, where the amount of polymer cannot be determined, detection of 1 g epichlorohydrin per square decimetre of coating is feasible. In order to obtain reliable and reproducible results, it is essential that the method described in this p
41、art of EN 13130 is followed as closely as possible. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including
42、 any amendments) applies. EN 13130-1:2004, Materials and articles in contact with foodstuffs Plastics substances subject to limitation Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food simulants and the determination of substances in plastics and
43、the selection of conditions of exposure to food simulants. 3 Principle To determine the residual amount of epichlorohydrin in a coating, the sample material is extracted with dioxane for 6 h at room temperature. Subsequently, the extract is distilled by means of a micro-distillation. The concentrati
44、on of epichlorohydrin in the distilled fraction thus obtained is determined by derivatization of the epoxide with an aromatic sulfonic acid, i.e. 9,10-dimethoxyanthracene-2-sulfonic acid (DAS), followed by reversed phase high performance liquid chromatography (HPLC) with fluorescence detection. Depe
45、nding on the quality and type of the HPLC column, it is possible to separate the two isomers that are formed in the derivatization reaction of epichlorohydrin with DAS. Quantification is achieved by means of external standard calibration using dioxane solutions fortified with known amounts of epichl
46、orohydrin. Confirmation of epichlorohydrin is carried out by normal phase HPLC with fluorescence detection. 4 Reagents NOTE All reagents should be of recognized analytical quality unless otherwise stated. DD CEN/TS 13130-20:20057 4.1 Analyte 4.1.1 Epichlorohydrin (C3H5OCl), purity 99 %. 4.2 Chemical
47、s 4.2.1 Acetonitrile (HPLC grade). 4.2.2 9,10-Dimethoxyanthracene-2-sulfonic acid sodium salt, i.e. DAS-Na, C16H13NaO5S. 4.2.3 Dioxane 99,5 %, absolute; over molecular sieve (H2O 0,01 %). 4.2.4 Hexane 4.2.5 Cation exchange resin, strongly acid with sulfonic acids as functional groups, ion form H+. 4
48、.2.6 Isopropanol 4.2.7 Methanol 4.2.8 Water, deionized (HPLC quality). 4.3 Preparation of the DAS reagent Dissolve approximately 100 mg DAS-Na (4.2.2) in 20 ml methanol/water (80/20). Heat the solution slightly to obtain a clear solution. In a glass beaker, wash an amount of the ion exchange resin (
49、4.2.5) with methanol/water (80/20) and subsequently pour the slurry into a glass column with a diameter of 1 cm, until the resin has reached a height of 20 cm. Elute the DAS solution through the ion exchange resin and flush the column with a mixture of methanol/water (80/20). Start to collect the eluate at the moment the eluate has decreased to a pH of approximately pH 1 to pH 2. Continue collecting the eluate until the pH starts to increase. Evaporate the solution thus obtained to dryness by means of a nitrogen stream. NOTE The dry residue should be
