1、BRITISH STANDARD BS EN 13628-1:2002 Packaging Flexible packaging material Determination of residual solvents by static headspace gas chromatography Part 1: Absolute methods The European Standard EN 13628-1:2002 has the status of a British Standard ICS 55.040 BS EN 13628-1:2002 This British Standard,
2、 having been prepared under the direction of the Consumer Products and Services Sector Policy and Strategy Committee, was published under the authority of the Standards Policy and Strategy Committee on 21 October 2002 BSI 21 October 2002 ISBN 0 580 40627 X National foreword This British Standard is
3、the official English language version of EN 13628-1:2002. The UK participation in its preparation was entrusted by Technical Committee PKW/5, Primary and transport packaging, to Subcommittee PKW/5/26, Packaging made from flexible materials, which has the responsibility to: A list of organizations re
4、presented on this subcommittee can be obtained on request to its 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
5、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 correct application. Compliance with a British Standard does not of itself
6、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 the UK interests informed; monitor related international and European developments and prom
7、ulgate them in the UK. Summary of pages This document comprises a front cover, an inside front cover, the EN title page, pages 2 to 16, an inside back cover and a back cover. The BSI copyright date displayed in this document indicates when the document was last issued. Amendments issued since public
8、ation Amd. No. Date CommentsEUROPEANSTANDARD NORMEEUROPENNE EUROPISCHENORM EN136281 October2002 ICS55.040 Englishversion PackagingFlexiblepackagingmaterialDeterminationof residualsolventsbystaticheadspacegaschromatography Part1:Absolutemethods EmballageMatriauxdemballagessouples Dterminationdessolva
9、ntsrsiduelsparchromatographie enphasegazeuseetespacedettestatiquePartie1: Mthodesabsolues VerpackungFlexiblePackstoffeBestimmungder RestlsemitteldurchstatischeDampfraumanalysemittels GaschromatographieTeil1:AbsoluteVerfahren ThisEuropeanStandardwasapprovedbyCENon26August2002. CENmembersareboundtocom
10、plywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEurope an Standardthestatusofanationalstandardwithoutanyalteration.Uptodatelistsandbibliographicalreferencesconcernings uchnational standardsmaybeobtainedonapplicationtotheManagementCentreortoanyCENmember. ThisEuropeanSt
11、andardexistsinthreeofficialversions(English,French,German).Aversioninanyotherlanguagemadebytra nslation undertheresponsibilityofaCENmemberintoitsownlanguageandnotifiedtotheManagementCentrehasthesamestatusasthe official versions. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,
12、Denmark,Finland,France,Germany,Greece, Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain,Sweden,SwitzerlandandUnitedKingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2002CEN Allri
13、ghtsofexploitationinanyformandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.EN136281:2002EEN136281:2002(E) 2 Contents page Foreword3 1 Scope 4 2 Normativereferences 4 3 Principle4 4 Reagents.4 5 Apparatus .5 6 Sampling.8 7 Testspecimens 8 8 Incubationofthetestspecimens .8 9 Procedure .9
14、10 Precisiondata. 16 11 Testreport 16EN136281:2002(E) 3 Foreword ThisdocumentEN136281:2002hasbeenpreparedbyTechnicalCommitteeCEN/TC261“Packaging“,the secretariatofwhichisheldbyAFNOR. ThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextor byendorsement,att
15、helatestbyApril2003,andconflictingnationalstandardsshallbewithdrawnatthelatestby April2003. Thisstandardispartofastandardfordeterminationofresidualsolventsbystaticheadspacegaschromatography, whichispublishedintwoparts: Part1:Absolutemethods Part2:Industrialmethods AccordingtotheCEN/CENELECInternalRe
16、gulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,CzechRepublic,Denmark,Finland, France,Germany,Greece,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Spain, Sweden,SwitzerlandandtheUnitedKingdom.EN136281:200
17、2(E) 4 1Scope ThispartofthisEuropeanStandardspecifiesmethodsforthequantitativedeterminationofresidualsolventsin flexiblepackagingbystaticheadspacechromatographywherethechemicalidentitiesoftheresidualsolventstobe determinedareknownbeforecommencingtheanalysis.Residuesfromthermaldecompositionproductsar
18、enot withinthescopeofthisstandard. Themethodisapplicabletoflexiblepackagingmaterialsthatmayconsistofmonoormultilayerplasticfilms,paper orboard,foilorcombinationsthereof. Thismethoddoesnotapplytoresidualsolventswithamountslowerthan0,5mg/m. 2 Normativereferences ThisEuropeanStandardincorporatesbydated
19、orundatedreference,provisionsfromotherpublications.These normativereferencesarecitedattheappropriateplacesinthetext,andthepublicationsarelistedhereafter.For datedreferences,subsequentamendmentstoorrevisionsofanyofthesepublicationsapplytothisEuropean Standardonlywhenincorporatedinitbyamendmentorrevis
20、ion.Forundatedreferencesthelatesteditionofthe publicationreferredtoapplies(includingamendments). ISO57252, Accuracy(truenessandprecision)ofmeasurementmethodsandresultsPart2:Basicmethodforthe determinationofrepeatabilityandreproducibilityofastandardmeasurementmethod . 3Principle Specimensoftheflexibl
21、epackagingmaterialareplacedinahermeticallyclosedvialandheatedunderclosely controlledconditionsoftimeandtemperaturetovaporizesolventsintotheheadspace.Theamountofsolvent releasedintotheheadspaceisdeterminedbytransferringanaliquotoftheheadspaceintoagaschromatograph foranalysis.Thetransfermaybeperformed
22、: a)byspecificsemiautomaticorautomaticsystemswhichallowpressurizationoftheheatedvials.Quantification isachievedbythemultipleheadspaceextraction(MHE)procedureusingexternalorinternalstandards; b)manuallyorautomaticallybyusingaheatedgastightsyringeoraloopwithoutpressurizationoftheheated vials.Quantific
23、ationisachievedbythestandardadditionmethod. NOTE Aprerequisiteforaquantitativedeterminationofresidualsolventsbyheadspacegaschromatographyisthata partitionequilibriumforthesolventbetweenthegasphaseandthesolidphasehasbeenreachedbeforeanaliquotofthe headspaceiswithdrawnandtransferredintothegaschromatog
24、raph. Duringtheanalysis,theremaybeinterferencesfrompossibleproductsofthermaldecomposition.Additionalpeaks duetotheseproductsshallnotbeconsideredforevaluationofresidualsolvents. 4Reagents 4.1General Allreagentsshallbeofarecognizedanalyticalreagentgrade. NOTE Gradesstatedasbeingsuitableforchromatograp
25、hyarecommerciallyavailableandarerecommendedforuseas referenceforstandardcalibrationsolutions.Appropriatesafetyprecautionsshouldbeusedwhenhandlingtoxicand/or flammablesolvents.EN136281:2002(E) 5 4.2 Referencesolvents, forthepreparationofstandardcalibrationsolutions . 4.3 Dilutionsolvent, witharetenti
26、ontimedifferentfromthoseofresidualsolventsinthesample. NOTE Solventssuchashexane,cyclohexanone,acidamidesandglyceroltriacetate(triacetin)areappropriate. 5Apparatus 5.1Glassvials, ofcapacity6ml,8ml,20ml,50mlor100mldependinguponthespecificrequirementsof accessoryequipment,forexample,theheadspacesample
27、r,fittedwithaninertseptumsealandaluminiumcrimp tops.Theseptumsealshallneitherabsorbnorreleasevolatilecomponents,shallbegastightduringincubation andshallpermitsamplesoftheheadspacegastobewithdrawnbysyringeforsubsequentanalysis. NOTE Elastomerslinedwithpolytetrafluoroethylene(PTFE)aresuitablematerials
28、forseptumseals. 5.2Crimpingtool, forsealingthevialswiththealuminiumcrimptops . 5.3Sealremovingtool. 5.4Analyticalbalance, capableofweighingtothenearest0,1mg . 5.5Template, forcuttingsamples.Thedimensionsofthistemplateshallbematchedtothevialvolumeused . 5.6Scalpelorsharpknife. 5.7Syringes (e.g.1l,10l
29、). 5.8Gaschromatograph, havingaflameionizationdetectororequivalentforthesolventstobedetermined. 5.9Gaschromatographiccolumn, eitherpackedorcapillary,thatwillgivegoodresolutionofthesolventsto bedeterminedfromanyothercomponentsthatmightbeinjectedwiththespecimenoftheheadspace.Examples forsuitablecolumn
30、sandoperationconditionsare: a)Packedcolumn: length:3m; internaldiameter:3,2mm; columnfilling:80/120meshgraphitisedcarbon,deactivatedwithpolyethyleneglycol; carriergas:N 2 ,20ml/min; injectortemperature:220C; temperatureprogramme:80C;raisedto160Cat6C/min;raisedto225Cat1,5C/min;heldfor16min; NOTE1 Aco
31、rrespondingchromatogramobtainedforamixtureofsolventsisshowninFigure1.EN136281:2002(E) 6 Key 1 4,23methanol 2 6,67ethanol 3 9,25acetone 4 17,06ethylacetate 5 19,1butanol 6 23,34trichloroethylene 7 28,4isobutylacetate 8 33,87methylisobutylketone 9 41,86toluene 10 64.06xylene A Retentiontime(min) B Pea
32、kheight Figure1Exampleofchromatogramobtainedwithapackedcolumn or b)Capillarycolumn(fusedsilica): length:30m; internaldiameter:0,32mm; stationaryphase:Poly(dimethylsiloxane),filmthickness3m; carriergas:He,1,7ml/min;EN136281:2002(E) 7 carriergassplitratio:1:20; injectortemperature:230C; detector(flame
33、ionization)temperature:280C; temperatureprogramme:50Cheldfor5min;raisedto100Cat5C/minraisedto250Cat10C/min. NOTE2 AcorrespondingchromatogramforamixtureofsolventsisshowninFigure2. Key 1 Methanol 2 Ethanol 3 Isopropanol 4 Methylethylketone 5 Ethylacetate 6 Isobutanol 7 Isopropylacetate 8 npropylacetat
34、e 9 Methylisobutylketone 10 Ethoxypropanol 11 Toluene 12 nbutylacetate 13 Xylene 14 Butylcellosolve A Retentiontime(min) B Peakheight Figure2ExampleofchromatogramobtainedwithacapillarycolumnEN136281:2002(E) 8 NOTE3 Otherapparatuswhichismorespecifictothealternativemethodsisidentifiedundertherelevantc
35、lauses. 6Sampling Samplesofpackagingmaterialsthataretobeanalysedshallbehandledandstoredsoastopreventeitherlossof volatilesolventsorcontaminationbyabsorptionofvolatilesolventsthatmaybepresentinthesurrounding atmosphere.Samplingandanalysisshallbedoneinaplacewheretheairissolventfreeinordertoreducethe p
36、roblemofcontaminationofthesamplesfromtheirsurroundingsduetothelowconcentrationsofresidualsolvents inthesamples. NOTE Samplesshouldbeintightlypackedrollformifpossible.Sheetsamplescanbepreparedfromtherollbycuttingout asquarewindow(severallayersofsheets)withaknife.Atleastthefirstfivelayersshouldbedisca
37、rded.Whenintheformo f sheetstheyshouldbestackedtightlytogethertoformacompact“block“andwrappedtightlyinabarriermaterial,preferably aluminiumfoilwithathicknessof30mto40m.Forstorageperiodsofmorethanonehourthewrappedsamplesshouldbe storedattemperaturesbelow5Candinanatmospherefreeofvolatilecontaminants.
38、7 Testspecimens 7.1Specimenareainrelationtovialvolume Thespecimenareatobecutoutshalldependonthevialvolumeandthelevelofresidualsolventstobe determinedinthematerial.Theratiobetweenthespecimenarea(incm)andthevialvolume(inml)shallbe betweenthreeandfive.Thespecimensshallbecutoutusinganappropriatetemplate
39、( 5.5). NOTE Asanexampleforavialwithavolumeof6mlto9mlaspecimenof30cm(2cm15cm)canbeusedor proportionaldimensionsforothervolumes. 7.2Testspecimensfromsheets Fromthetopofthesampletakeablockofabout15to20sheetsoutwithoutseparatingthem.Immediatelyput backtheremainingpartofthesampleinitspackagingundertheco
40、nditionsspecifiedinclause 6. Prepareafirstvial;afterwithdrawalofatleastonelayer(ormoredependingonthenumberofspecimenstobe preparedfromtheblock)fromthetopoftheblocktakethefollowingsheetandrapidlycutthefirstspecimenusinga template( 5.5).Coilthespecimenrapidlyandimmediatelyputitintothevial.Crimpthevial
41、immediatelytosealit. Preparefurtherspecimensinthesameway. Thefollowingprecautionsshallbetaken. Thedifferentstepsofthepreparationshallbedoneveryrapidlytoavoidevaporationofthesolvents. Thesamplesheetfromwhichthespecimeniscutshallbetakenoutoftheblockimmediatelybeforepreparation. Thespecimensshallalways
42、becutatadefinedplacee.g.onthesamedrawingprintedonthesameplaceinthe widthandthetemplateforcuttingshallalwaysbeplacedinthesamemanner. 8 Incubationofthetestspecimens 8.1General Incubationtimeandtemperatureshallbeoptimizedforeachindividualsysteminordertoachieveapartition equilibriumoftheresidualsolvents
43、betweenthesolidphaseandthegasphase.Withacertaintemperature selectedanoptimumheatingtimeshallbedetermined.EN136281:2002(E) 9 NOTE1 Thetimetakentoreachpartitionequilibriumwillvaryfordifferentsolventsdependingontheboilingpointandthe absorptivepropertiesofthematerialstobeanalysed. NOTE2 Asaninitialguidanceincubation,atemperatureof100Cfor60mincanbeappropriate.Howeverotherincubation conditionsdependingonthematerialsandsolventstobeanalysedarealsocommonlyused,e.g.temperaturebetween80C and150Candheatingtim
