1、BRITISH STANDARD BS EN 13130-4:2004 Materials and articles in contact with foodstuffs Plastics substances subject to limitation Part 4: Determination of 1,3-butadiene in plastics The European Standard EN 13130-4:2004 has the status of a British Standard ICS 67.250 BS EN 13130-4:2004 This British Sta
2、ndard was published under the authority of the Standards Policy and Strategy Committee on 17 June 2004 BSI 17 June 2004 ISBN 0 580 43947 X National foreword This British Standard is the official English language version of EN 13130-4:2004. It supersedes DD ENV 13130-4:1999 which is withdrawn. The UK
3、 participation in its preparation was entrusted by Technical Committee CW/47, Materials and articles in contact with foodstuffs, to Subcommittee CW/47/1, Migration from plastics, which has the responsibility to: A list of organizations represented on this subcommittee can be obtained on request to i
4、ts secretary. Cross-references The British Standards which implement international or European publications referred to in this document may be found in the BSI Catalogue under the section entitled “International Standards Correspondence Index”, or by using the “Search” facility of the BSI Electroni
5、c 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 correct application. Compliance with a British Standard does not of itself confer immunity from legal obligations. aid enquirers to under
6、stand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep the UK interests informed; monitor related international and European developments and promulgate them in the UK. Summary of pages This document comprise
7、s a front cover, an inside front cover, the EN title page, pages 2 to 17 and a back cover. The BSI copyright notice displayed in this document indicates when the document was last issued. Amendments issued since publication Amd. No. Date CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN13130
8、4 May2004 ICS67.250 Englishversion MaterialsandarticlesincontactwithfoodstuffsPlastics substancessubjecttolimitationPart4:Determinationof1,3 butadieneinplastics Matriauxetobjetsencontactaveclesdenres alimentairesSubstancesdanslesmatiresplastiques soumisesdeslimitationsPartie4:Dterminationdu 1,3butad
9、inedanslesmatiresplastiques WerkstoffeundGegenstndeinKontaktmitLebensmitteln SubstanzeninKunststoffen,dieBeschrnkungen unterliegenTeil4:Bestimmungvon1,3Butadienin Kunststoffen ThisEuropeanStandardwasapprovedbyCENon24March2004. CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipu
10、latetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheCentralSecretariatortoanyCENmember. ThisEuropeanStandardexistsinthreeofficialversions(English,Fren
11、ch,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheCentralSecretariathasthesamestatusast heofficial versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France, Germany
12、,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Netherlands,Norway,Poland,Portugal, Slovakia, Slovenia,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050B
13、russels 2004CEN Allrightsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN131304:2004:EEN 13130-4:2004 (E) 2 Contents page Foreword3 1 Scope 6 2 Normative references 6 3 Principle6 4 Reagents.6 5 Apparatus .7 6 Samples 8 6.1 General8 6.2 Sample preparation for ga
14、s chromatography.8 6.2.1 Test samples 8 6.2.2 Calibration samples for the standard addition method.8 6.2.3 Blank samples8 7 Procedure .9 7.1 GC preparation.9 7.2 Performance of GC measurements9 8 Expression of results 9 8.1 Method of calculation9 8.1.1 GC interferences10 8.1.2 Determination of the 1
15、,3-butadiene concentration in the polymer.10 8.2 Repeatability and reproducibility.11 8.2.1 Validation11 8.2.2 Repeatability and reproducibility.11 8.2.3 Detection limit 11 9 Confirmation.12 9.1 Requirements for confirmation 12 9.2 Confirmation by combined gas chromatography/mass spectrometry 12 10
16、Test report 12 Annex A (normative) Calibration via external standardization .13 A.1 General13 A.2 Construction of the calibration graph .13 A.3 Graphical determination .14 A.4 Calculation from the regression parameters 14 Annex B (normative) Manual sample injection.16 Bibliography 17 EN 13130-4:2004
17、 (E) 3 Foreword This document (EN 13130-4:2004) has been prepared by Technical Committee CEN/TC 194 “Utensils in contact with food”, the secretariat of which is held by BSI. This document was prepared by Subcommittee SC1 of TC 194 as one of a series of analytical test methods for plastics materials
18、and articles in contact with foodstuffs. 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 November 2004, and conflicting national standards shall be withdrawn at the latest by November 2004. This d
19、ocument has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. 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 85/572/EEC 6. At the time of preparati
20、on 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 change the legislative requirements wh
21、ich 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 EN 13130-4 should be read in conjunction with EN 13130-1 Further parts of EN 13130, under
22、 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 foodstuffs and food simulants and the determination
23、 of specific monomers and additives in plastics. The other 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 the selection of conditions of exposure to
24、 food simulants Part 2: Determination of terephthalic acid in food simulants Part 3: Determination of acrylonitrile in food and food simulants Part 5: Determination of vinylidene chloride in food simulants Part 6: Determination of vinylidene chloride in plastics Part 7: Determination of monoethylene
25、 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 food simulants Part 11: Determination of 11-aminoundecanoic acid in food simulants Part 12: Det
26、ermination of 1,3-benzenedimethanamine in food simulants Part 13: Determination of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A) in food simulants Part 14: Determination of 3,3-bis(3-methyl-4-hydroxyphenyl)-2-indoline in food simulants EN 13130-4:2004 (E) 4 Part 15: Determination of 1,3-butadiene in
27、 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- dihydroxybenzene, 1,4- dihydroxybenzene, 4,4- dihydroxybenzophenone and 4,4dihydroxybiphenyl in fo
28、od 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 simulants Part 22: Determination of ethylene oxide and propylene oxide in plastics Part 23: D
29、etermination 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 simulants Part 26: Determination of 1-octene and tetrahydrofuran in food simulants Part 27: Determ
30、ination of 2,4,6-triamino-1,3,5-triazine in food simulants Part 28: Determination of 1,1,1-trimethylopropane in food simulants Parts 1 to 8 are European Standards. Parts 9 to 28 are Technical Specifications, prepared within the Standards, Measurement and Testing project, MAT1-CT92-0006, “Development
31、 of Methods of Analysis for Monomers”. 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, Hunga
32、ry, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 13130-4:2004 (E) 5 Introduction 1,3-Butadiene, CH 2 =CH-CH=CH 2 , is a monomer used in the manufacture of certain plastics m
33、aterials and articles intended to come into contact with foodstuffs. During the manufacture of 1,3-butadiene copolymers, residual 1,3-butadiene monomer can remain in the polymer and can migrate into food coming into contact with the polymer. The method described in this part of this standard is to b
34、e used in conjunction with part 1 of this standard, which describes the procedure required prior to determination of 1,3-butadiene. The method has been validated by a collaborative trial using acrylonitrile-butadiene-styrene copolymer (ABS). EN 13130-4:2004 (E) 6 1 Scope This part of this European S
35、tandard specifies a method for the determination of butadiene monomer in polymers. The method is applicable to acrylonitrile-butadiene-styrene copolymer (ABS) and to high-impact polystyrene (HIPS) as well as to other 1,3-butadiene polymers and copolymers where these are soluble in N,N- dimethylaceta
36、mide or finely dispersed, swollen suspensions in N,N-dimethylacetamide. The level of 1,3- butadiene monomer determined is expressed as milligrams of 1,3-butadiene per kilogram of polymer. The method is appropriate for the quantitative determination of 1,3-butadiene at a level of 0,1 mg/kg in the pol
37、ymer. 2 Normative references This European Standard incorporates by dated or undated reference, provisions from other publications. These normative references are cited at the appropriate places in the text, and the publications are listed hereafter. For dated references, subsequent amendments to or
38、 revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision. For undated references the latest edition of the publication referred to applies (including amendments). EN 13130-1:2004; Materials and articles in contact with foodstuffs -
39、 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 the selection of conditions of exposure to food simulants 3 Principle The level of 1,3-but
40、adiene in a polymer is determined by headspace gas chromatography of the polymer sample dissolved in N,N-dimethylacetamide, applying automated sample injection and using flame ionization detection (FID). Quantification is achieved using n-pentane as an internal standard with calibration against poly
41、mer samples fortified with 1,3-butadiene according to the standard addition procedure. If interferences are experienced with the internal standard, n-pentane, calibration is carried out by the external standardization as described in annex A. If automated headspace sampling cannot be performed, manu
42、al injection as described in annex B shall be applied. Confirmation of 1,3-butadiene levels is carried out by combined gas chromatography/mass spectrometry (GC/MS). 4 Reagents WARNING: All chemicals are hazardous to health to a greater or lesser extent. It is beyond the scope of this standard to giv
43、e instructions for the safe handling of all chemicals, that meet, in full, the legal obligations in all countries in which this standard may be followed. Therefore, specific warnings are not given and users of this standard shall ensure that they meet all the necessary safety requirements in their o
44、wn country. 4.1 1,3-Butadiene, CH 2 =CH-CH=CH 2 , purity greater than 99,5 % (w/w). EN 13130-4:2004 (E) 7 4.2 n-Pentane, CH 3 -(CH 2 ) 3 -CH 3containing no impurity at 1 % by area which will elute at the same GC retention time as 1,3-butadiene. 4.3 N,N-Dimethylacetamide, CH 3 -CO-N(CH 3 ) 2 , d T= 0
45、,9600 - 0,00094 T where T is the temperature in C. The N,N-dimethylacetamide shall be free of any interferences ( 1 %) which elute at the same retention times as 1,3-butadiene and n-pentane peaks. 4.4 Prepare stock solutions of 1,3-butadiene in N,N-dimethylacetamide with defined concentrations in th
46、e range 5 mg/g to 10 mg/g as follows: a) Weigh a 50 ml sample vial (5.4) including septum and cap to an accuracy of 0,01 mg. Pipette 50 ml N,N- dimethylacetamide (4.3) into the vial (5.4), close and weigh again to 0,01 mg. Insert hollow needles for introducing 1,3-butadiene and venting air and weigh
47、 again to 0,01 mg. Introduce, under a fume hood, 0,3 g to 0,5 g 1,3-butadiene (4.1) by bubbling through the N,N-dimethylacetamide. Re-weigh the vial plus needles to an accuracy of 0,01 mg and remove then the needles. Calculate the concentration in milligrams of 1,3-butadiene per gram of solution. b)
48、 Repeat item a) to provide a second stock solution. NOTE The stock solutions can be stored at - 20 C up to eight weeks protected from light in septum capped glass vials with minimum headspace; storage at 4 C with the exclusion of light should not exceed one week. 4.5 Prepare standard solutions of 1,3-butadiene in N,N-dimethylacetamide with defined concentrations in the range of 0,01 mg/ml to 0,5 mg/ml corresponding to 0,2 g/20 l to 10 g/20 l (see the note in 6.2.2) as follows: a) Weigh a sample vial (5.
