1、DRAFT FOR DEVELOPMENT DD CEN/TS 14577:2003 Materials and articles in contact with foodstuffs Plastics Polymeric additives Test method for the determination of the mass fraction of a polymeric additive that lies below 1 000 Daltons ICS 67.250, 83.040.30 DD CEN/TS 14577:2003 This Draft for Development
2、 was published under the authority of the Standards Policy and Strategy Committee on 16 January 2004 BSI 16 January 2004 ISBN 0 580 43260 2 National foreword This Draft for Development is the official English language version of CEN/TS 14577:2003. This publication is not to be regarded as a British
3、Standard. It is being issued in the Draft for Development series of publications and is of a provisional nature because of the need to develop a reliable method of test for the determination of molecular weight fractions below 1 000 Daltons in polymeric additives. It should be applied on this provis
4、ional basis, so that information and experience of its practical application may be obtained. Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the European organization responsible for its conversion to a European standard. A review o
5、f 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 3-year life. Notification of the start of the review period will be made in an announcement in the appropriate issue of Update Standards. Ac
6、cording 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 standard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent in writing to the Secretary of BSI Subco
7、mmittee 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 proposing, where possible, an appropriate revision of the text. A list of organizations represented on this committee can be obtained on re
8、quest 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 Index”, or by using the “Search” facility of the BSI
9、 Electronic Catalogue or of British Standards Online. Summary of pages This document comprises a front cover, an inside front cover, the CEN/TS title page, pages 2 to 14, an inside back cover and a back cover. The BSI copyright notice displayed in this document indicates when the document was last i
10、ssued. Amendments issued since publication Amd. No. Date CommentsTECHNICALSPECIFICATION SPCIFICATIONTECHNIQUE TECHNISCHESPEZIFIKATION CEN/TS14577 December2003 ICS67.250,83.040.30 Englishversion MaterialsandarticlesincontactwithfoodstuffsPlastics PolymericadditivesTestmethodforthedeterminationofthe m
11、assfractionofapolymericadditivethatliesbelow1000 Daltons WerkstoffeundGegenstndeinKontaktmit LebensmittelnKunststoffePolymereZusatzstoffe PrfverfahrenzurBestimmungdesMasseanteilseines polymerenZusatzstoffesunter1000Dalton ThisTechnicalSpecification(CEN/TS)wasapprovedbyCENon17 th March2003forprovisio
12、nalapplication. TheperiodofvalidityofthisCEN/TSislimitedinitiallytothreeyears.AftertwoyearsthemembersofCENwillberequested tosubmittheir comments,particularlyonthequestionwhethertheCEN/TScanbeconvertedintoaEuropeanStandard. CENmembersarerequiredtoannouncetheexistenceofthisCEN/TSinthesamewayasforanENa
13、ndtomaketheCEN/TSavailable .It ispermissibletokeepconflictingnationalstandardsinforce(inparalleltotheCEN/TS)untilthefinaldecisionaboutthep ossible conversionoftheCEN/TSintoanENisreached. CENmembersarethenationalstandardsbodiesofAustria,Belgium,CzechRepublic,Denmark,Finland,France,Germany,Greece, Hun
14、gary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway,Portugal,Slovakia,Spain,Sweden,SwitzerlandandUn ited Kingdom. EUROPEANCOMMITTEEFORSTANDARDIZATION COMITEUROPENDENORMALISATION EUROPISCHESKOMITEEFRNORMUNG ManagementCentre:ruedeStassart,36B1050Brussels 2003CEN Allrightsofexploitationinany
15、formandbyanymeansreserved worldwideforCENnationalMembers. Ref.No.CEN/TS14577:2003CEN/TS14577:2003(E) 2 Contents page Foreword3 1 Scope 5 2 Principle5 3 Reagents.5 4 Apparatus .6 5 Preparationofstandardsandsamples .8 6 SECanalysis .8 7 Expressionofresults . .10 8 Testreport . .11 AnnexA (informative)
16、 Couplingofliquidchromatographicpolymerseparationswithmass spectrometry 12 AnnexZA (informative) ClausesofthisTechnicalSpecificationaddressingessentialrequirementsor otherprovisionsofEUDirectives. . 13 Bibliography 14CEN/TS14577:2003(E) 3 Foreword Thisdocument(CEN/TS14577:2003)hasbeenpreparedbyTechn
17、icalCommitteeCEN/TC194,“Utensilsin contactwithfood“,thesecretariatofwhichisheldbyBSI. ThisdocumenthasbeenpreparedunderamandategiventoCENbytheEuropeanCommissionandtheEuropean FreeTradeAssociation. ForrelationshipwithEUDirective(s),seeinformativeannexZA,whichisanintegralpartofthisdocument. AnnexAisinf
18、ormative. AccordingtotheCEN/CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowing countriesareboundtoannouncethisEuropeanSpecification:Austria,Belgium,CzechRepublic,Denmark, Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Luxembourg,Malta,Netherlands,Norway, Portugal
19、Slovakia,Spain,Sweden,SwitzerlandandtheUnitedKingdom.CEN/TS14577:2003(E) 4 Introduction Someadditivesusedtomakeplasticsintendedtocomeintocontactwithfoodstuffsareknownaspolymeric additives1.Theyareaddedtoplasticsinordertoachieveatechnicaleffectbuttheydonotinisolationhavethe physicalpropertiesrequire
20、dofusableplasticsmaterialsandarticles.Inthisrespecttheydifferfromthehigh polymersthatareusedtomakeplastics.Thesepolymericadditivesdonotgenerallyhaveasinglemolecular weightbuttheyhaveamolecularweightdistributionasaresultofsynthesis.Theymayalsoshowfurther complexitywithdifferentendgroupchemistry(becau
21、seofdifferentinitiationandterminationprocesses),different repeatunits(becauseoftwoormoremonomersusedtomakerandomorblockcopolymers)anddifferentchain shapes(becauseoftheformationoflinear,branchedandcyclicstructureswithinthechains). Theseadditivesmaymigrateintofoodstuffsplacedincontactwiththeplasticsan
22、dsotheirsafetymustbe evaluated.Onlythefractionoftheadditivewithmolecularmassbelow1000Daltons(D)isregardedasbeing toxicologicallyrelevantandsoadistinctionhasbeenmadebytheScientificCommitteeforFood(SCF)between polymericadditiveswithaweightaveragedmolecularmass(MW)below1000DandthosewithMWabove1000D 2.F
23、orthosepolymericadditiveswithaMWabove1000D,onlyareducedsetofdatamayberequiredtoallow anevaluationoftheirsafety. TherequirementsoftheSCFandthepracticalimplicationshavebeendescribedanddiscussedinaCommission document3.Indecidingwhichtoxicologicalinformationisneeded,theSCFconsidersthedataavailableonthe
24、monomersusedtomakethepolymericadditive,thesizeoftheadditivefractionwithMWbelow1000D,andthe formulationleveloftheadditiveusedintheplastic2.Itispossiblethatapolymericadditiveconsideredbythe SCFisgivenapprovaltobeusedinplasticsintendedforfoodcontact,butwithspecificationsincludingalimiton themassfractio
25、noftheadditivebelowMW1000.Forthesereasons,forpetitionsandfortestingforcompliance,a methodoftestisrequiredtodeterminethemassfractionofapolymericadditivethatfallsbelowtheMW1000cut offsetbytheSCF.CEN/TS14577:2003(E) 5 1Scope ThisTechnicalSpecificationspecifiesatestmethodtodeterminethemassfractionofapol
26、ymericadditivethatfalls belowaMWof1000.Themethodisapplicabletopolymericadditives persei.e.suppliedintheirusableform, beforeformulationintoaplastic.Themethodisalsoapplicabletopolymericadditivesextractedfromfinished plasticmaterialsandarticles,providedthatprecautionsaretakentoensuretheabsenceofanyinte
27、rferencefrom anyothercoextractivesderivedfromtheplastic. 2Principle Thepolymericadditiveisfractionatedusingsizeexclusionchromatography(SEC)andthemassfractionbelowMW 1000Disdeterminedeithergravimetrically,offline,orbyusingchromatographicdetectorssuchasrefractive index,infrared,ultraviolet,orlightscat
28、teringdetectors,online. Thechromatogramiscalibratedformolecularweighteitherbyusingcalibrationstandards,wherethesesubstances areavailable,orbyusingmassselectivedetectorssuchasmassspectroscopy.Underidealconditionswhere thereisnointeractionwiththestationaryphase,intheSECseparationofoligoorpolymericmult
29、icomponent systemsthecomponentsareseparatedwithrespecttotheirhydrodynamicvolumes.Consequently,retentiontimes (elutionvolumes)indicatethemolecularsizeandcanbeconvertedintomolecularweightbyuseofcalibration standardsrunconcurrentlyorbyusingmolecularweightsensitivedetectors(onlineoroffline). Thepolymeri
30、cadditivesubmittedtothetestshouldbethesameasthatusedtoformulatethefinishedplastic materialorarticle.Iftheadditiveisnotavailableassuch,thenitmaybeextractedfromthefinishedplasticand thensubmittedtothistestprocedureprovidedthatcareistakentoensurethatnosignificantinterferenceoccurs fromanyothercoextract
31、ivesfromtheplastic. NOTE Fortheseparationofpolarsubstancesinaqueoussystems,SECissometimesreferredtoasgelfiltration chromatography(GFC).Fortheseparationoforganicsubstancesinnonaqueoussystemsitissometimescalledgel permeationchromatography(GPC).ThetermandabbreviationSECisusedheretodescribeallthesetypes
32、of chromatography. 3Reagents 3.1General Allreagentsshallbeofrecognisedanalyticalquality,unlessotherwisespecified. 3.2 Molecularweightstandards 3.2.1General Avarietyofmolecularweightstandardsareavailablecommercially.Someareavailableinpureform,andothers asmixtureswithtwoormorespeciespresent.Sincetheai
33、mofMWcalibrationistosetthe1000Dcutoffpointin theSECchromatogram,itispreferablytohaveoneMWstandardcloseto1000Dwithtwootherseachside(i.e. aboveandbelow1000D)sothatthecutoffpointcanbedeterminedbyinterpolation. 3.2.2 Forpolarpolymericadditives Examplesofpolarpolymericadditivesincludepolyethyleneglycols(
34、PEGs),lignosulfonates,polyacrylamidesand polyacrylates.PEGoligomersarecommonlyusedforSECcalibrationinbothaqueousandpolarorganicsolvents. PEGcalibrantsareavailablecommerciallyfromthedimer(MW106)upwards.Polyethyleneoxide(PEO) standardsarealsoavailablecommercially.CEN/TS14577:2003(E) 6 3.2.3 Fornonpola
35、rpolymericadditives Examplesofnonpolarpolymericadditivesarehydrocarbonoilsandwaxes,hydrogenatedhydrocarbonresins,and polyesterplasticisers.Polystyreneoligomersandindividualnalkanesarethemostwidelyusedstandardsfor calibratingSECinorganicsolvents.Polystyreneoligomersareavailablecommerciallyfromthedime
36、r(MW162) upwards.Averylargenumberofnalkanesareavailableinpureform. 4Apparatus 4.1General Aninstrumentorpieceofapparatusismentionedonlyifitisspecial,ormadetoparticularspecifications.Usual laboratoryequipmentisassumedtobeavailable. 4.2 SECequipment Highperformanceliquidchromatograph,equippedwithadetec
37、torsuitableforthepolymericadditiveundertest, andfittedwithafractioncollectorifitisintendedtocollectfractions.Theliquidchromatographshouldbecapable ofmaintainingaconstantflowrateofmobilephase. NOTE Underconditionsofconstantflow,theretentiontimeofacomponentisrelateddirectlytoitselutionvolumewhich, ont
38、heparticularSECcolumnemployed,isacharacteristicofitsmolecularsize. 4.3 SECcolumn Thecolumnhastopermittheseparationofthepolymericadditiveaccordingtoitsmolecularweightdistribution. ThecolumnshouldbecapableofseparatingtheadditiveespeciallyattheMW1000boundaryandtheporesize shouldbeselectedtogiveoptimums
39、eparationinthisregion. NOTE1 Thechoiceoftheappropriatecolumntype(stationaryphase)dependsonthemolecularsizeandthechemical propertiesofthepolymericadditivestobecharacterised.MostSECcolumnswillfractionatewithinaparticularmolecularwei ght range,determinedbytheporesizeofthestationaryphase.Largemoleculesa
40、retotallyexcludedfromthestationaryphaseand areelutedwiththevoidvolume.Smallmoleculesbelowthefractionationrangeareelutedatanelutionvolumeapproximately equaltothetotalbedvolume.Acolumnshouldbechosensothatthecriticalcutoffpointforthistest1000Doccursno tlater thanmidwaythroughtheseparationwindowbetweent
41、hetotallyexcludedvolumeandthetotallyincludedvolume. NOTE2 Foronlinedetection,thecolumnshouldbeananalyticalcolumn,withtypicalinternaldiameterof3to7mm.The columnlengthrequireddependsontheefficiencyofthepackingmaterialemployed.Atypicalcolumnlengthwouldbe100to 300mm.Columnscanbelinkedinseriesifneededtoi
42、ncreasetheseparation. NOTE3 Forofflinedetection,itisdesirabletouseawidercolumnboretoincreasethesamplecapacityandsoincreasethe massoffractioncollectedforsubsequentanalysisoffline.Thecolumnshouldbeapreparativeorsemipreparativecolumn, withtypicalinternaldiameterof7to20mm.Thecolumnlengthrequireddependso
43、ntheefficiencyofthepackingmaterial employed.Atypicalcolumnlengthwouldbe200to300mm.Columnscanbelinkedinseriesifneededtoincreasethe separation. NOTE4 Thefollowingcombinationsofcolumnandmobilephase(Table1)havebeenfoundtobesuitableforthetypesof polymericadditivesindicated.CEN/TS14577:2003(E) 7 Table1SECphasesandcalibrantsfoundtobesuitableforsometypicalpolymericadditives Chemicalcharacteristic ofthepolymericadditive SECstationaryphase(s) foundtobesuitable SECmobilephase(s) foundtobesuitable Molecularweight standardsfoundtobe suitableforcalibration purposes No
