1、ENISO23649February2025EuropeanstandardNormeeuropeenneEuropaischenormICS59.140.30EnglishVersionChemicalsfortheleathertanningindustry-DeterminationofcyclosiloxanesISO23649:2025ProduitschimiquespourFindustriedutannageducuir-DeterminationdesCyclosiloxan(ISO23649:2025)ChemikalienfiirdieLedergerbereiindus
2、trie-BestimmungvonCyclosiloxaneninImpragnierfettungsmitteln(ISO23649:2025)ThisEuropeanStandardwasapprovedbyCENon24February2025.CENmembersareboundtocomplywiththeCEN/CENELECInternalRegulationswhichstipulatetheconditionsforgivingthisEuropeanStandardthestatusofanationalstandardwithoutanyalteration.Up-to
3、datelistsandbibliographicalreferencesconcerningsuchnationalstandardsmaybeobtainedonapplicationtotheCEN-CENELECManagementCentreortoanyCENmember.ThisEuropeanStandardexistsinthreeofficialversions(English,French,German).AversioninanyotherlanguagemadebytranslationundertheresponsibilityofaCENmemberintoit
4、sownlanguageandnotifiedtotheCEN-CENELECManagementCentrehasthesamestatusastheofficialversions.CENmembersarethenationalstandardsbodiesofAustria,Belgium,Bulgaria,Croatia,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,Malta,Ne
5、therlands,Norway,Poland,Portugal,RepublicofNorthMacedonia,Romania,Serbia,Slovakia,Slovenia,Spain,Sweden,Switzerland,TiirkiyeandUnitedKingdom.EUROPEANCOMMITTEEFORSTANDARDIZATIONCOMITEEUROPEENDENORMALISATIONEuropaischeskomiteefurnormungCEN-CENELECManagementCentre:RuedelaScience23,B-1040Brussels2025CEN
6、AllrightsofexploitationinanyformandbyanymeansreservedRef.No.ENISO23649:2025EworldwideforCENnationalMembers.ContentsPageEuropeanforeword3EuropeanforewordThisdocument(ENISO23649:2025)hasbeenpreparedbyTechnicalCommitteeISO/IULTCSInternationalUnionofLeatherTechnologistsandChemistsSocietiesincollaboratio
7、nwithTechnicalCommitteeCEN/TC289LeatherthesecretariatofwhichisheldbyUNLThisEuropeanStandardshallbegiventhestatusofanationalstandard,eitherbypublicationofanidenticaltextorbyendorsement,atthelatestbyAugust2025,andconflictingnationalstandardsshallbewithdrawnatthelatestbyAugust2025.Attentionisdrawntothe
8、possibilitythatsomeoftheelementsofthisdocumentmaybethesubjectofpatentrights.CENshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights.Anyfeedbackandquestionsonthisdocumentshouldbedirectedtotheusersnationalstandardsbody/nationalcommittee.AcompletelistingofthesebodiescanbefoundontheCENwebsite
9、AccordingtotheCEN-CENELECInternalRegulations,thenationalstandardsorganizationsofthefollowingcountriesareboundtoimplementthisEuropeanStandard:Austria,Belgium,Bulgaria,Croatia,Cyprus,CzechRepublic,Denmark,Estonia,Finland,France,Germany,Greece,Hungary,Iceland,Ireland,Italy,Latvia,Lithuania,Luxembourg,
10、Malta,Netherlands,Norway,Poland,Portugal,RepublicofNorthMacedonia,Romania,Serbia,Slovakia,Slovenia,Spain,Sweden,Switzerland,TiirkiyeandtheUnitedKingdom.EndorsementnoticeThetextofISO23649:2025hasbeenapprovedbyCENasENISO23649:2025withoutanymodification.InternationalStandardISO23649IULTCSIUC444Firstedi
11、tion2025-02ChemicalsfortheleathertanningindustryDeterminationofcyclosiloxanesProduitschimiquespourHndustriedutannageducuirDeterminationdescyclosiloxanesReferencenumbersISO23649:2025(en)IULTCS/IUC444:2025(en)COPYRIGHTPROTECTEDDOCUMENTISO2025Allrightsreserved.Unlessotherwisespecified,orrequiredintheco
12、ntextofitsimplementation,nopartofthispublicationmaybereproducedorutilizedotherwiseinanyformorbyanymeans,electronicormechanical,includingphotocopying,orpostingontheinternetoranintranet,withoutpriorwrittenpermission.PermissioncanberequestedfromeitherISOattheaddressbeloworISO,smemberbodyinthecountryoft
13、herequester.ISOcopyrightofficeCP401Ch.deBlandonnet8CH-1214Vernier,GenevaPhone:+4122749Ol11Email:copyrightiso.orgWebsite:www.iso.orgPublishedinSwitzerlandContentsPageForewordivIntroductionv1 Scope12 Normativereferences13 Termsanddefinitions14 Principle15 Apparatus16 Reagents27 Samplingandsampleprepar
14、ation38 Procedure38.1 Samplesolutionpreparation38.2 Liquid-liquidextraction38.3 Instrumentalanalysis49 Expressionofresults410 Precision411 Testreport4Annex A (informative)ChromatographicanalysisoperatingparametersforGC-MS6Annex B (informative)Precision:reliabilityofthemethod7Annex C (normative)Sampl
15、epreparationfornon-water-solublechemicals8Bibliography9ForewordISO(theInternationalOrganizationforStandardization)isaworldwidefederationofnationalstandardsbodies(ISOmemberbodies).TheworkofpreparingInternationalStandardsisnormallycarriedoutthroughISOtechnicalcommittees.Eachmemberbodyinterestedinasubj
16、ectforwhichatechnicalcommitteehasbeenestablishedhastherighttoberepresentedonthatcommittee.Internationalorganizations,governmentalandnon-governmentabinliaisonwithISO1alsotakepartinthework.ISOcollaboratescloselywiththeInternationalElectrotechnicalCommission(IEC)onallmattersofelectrotechnicalstandardiz
17、ation.TheproceduresusedtodevelopthisdocumentandthoseintendedforitsfurthermaintenancearedescribedintheISO/IECDirectives,Part1.Inparticular,thedifferentapprovalcriterianeededforthedifferenttypesofISOdocumentsshouldbenoted.ThisdocumentwasdraftedinaccordancewiththeeditorialrulesoftheISO/IECDirectives,Pa
18、rt2(seeWWW.iso.org/directives).ISOdrawsattentiontothepossibilitythattheimplementationofthisdocumentmayinvolvetheuseof（八）patent(三).ISOtakesnopositionconcerningtheevidence,validityorapplicabilityofanyclaimedpatentrightsinrespectthereof.Asofthedateofpublicationofthisdocument,ISOhadnotreceivednoticeof（八
19、patent(三)whichmayberequiredtoimplementthisdocument.HoweverlImplementersarecautionedthatthismaynotrepresentthelatestinformation,whichmaybeobtainedfromthepatentdatabaseavailableatWWW.iso.org/patentsISOshallnotbeheldresponsibleforidentifyinganyorallsuchpatentrights.Anytradenameusedinthisdocumentisinfo
20、rmationgivenfortheconvenienceofusersanddoesnotconstituteanendorsement.Foranexplanationofthevoluntarynatureofstandards,themeaningofISOspecifictermsandexpressionsrelatedtoconformityassessment,aswellasinformationaboutISO,sadherencetotheWorldTradeOrganization(WTO)principlesintheTechnicalBarrierstoTrade(
21、TBT),seeWWW.iso.org/iso/foreword.htmLIULTCS,originallyformedin1897lisaworld-wideorganizationofprofessionalleathersocietiestofurthertheadvancementofleatherscienceandtechnology.IULTCShasthreeCommissions,whichareresponsibleforestablishinginternationalmethodsforthesamplingandtestingofleather.ISOrecogniz
22、esIULTCSasaninternationalstandardizingbodyforthepreparationoftestmethodsforleather.ThisdocumentwaspreparedbytheChemicalTestCommissionoftheInternationalUnionofLeatherTechnologistsandChemistsSocieties(IUCCommission,IULTCSJiincollaborationwiththeEuropeanCommitteeforStandardization(CEN)TechnicalCommitte
23、eCEN/TC289,Leather,inaccordancewiththeAgreementontechnicalcooperationbetweenISOandCEN(ViennaAgreement).Anyfeedbackorquestionsonthisdocumentshouldbedirectedtotheusersnationalstandardsbody.AcompletelistingofthesebodiescanbefoundatWWW.iso.org/membnrs.htmLIntroductionThisdocumentincludesaprocedureforana
24、lysingcertaincyclosiloxanesusinggaschromatography(GC)withmassspectrometer(MS)equipment.WiththisanalyticalmethodOctamethylcyclotetrasiloxane(D4),decamethylcyclopentasiloxane(D5)anddodecamethylcyclohexasiloxane(D6canbedetermined.Intheleatherindustrycyclosiloxanes(D4),(D5and(D6)areusedinthemanufactureo
25、fsilicone-basedwaterproofingfatliquorsandcanalsobeusedintheproductionofsilicone-basedfinishingchemicalsespeciallyashandlemodifiers.Atpresent,theofficialclassificationrecognisedintheEUisthefollowing. Octamethylcyclotetrasiloxane(D4)isclassifiedaspersistent,bioaccumulativeandtoxic“ Decamethylcyclopent
26、asiloxane(D5)isclassifiedaspersistent,bioaccumulativeandtoxic.Kl Dodecamethylcyclohexasiloxane(D6)isclassifiedaspersistent,bioaccumulativeandtoxic.InternationalStandardChemicalsfortheleathertanningindustryDeterminationofcyclosiloxanes1ScopeThisdocumentspecifiesamethodfordeterminingthetotalcontentoft
27、hefollowingcyclosiloxanesinchemicalsfortheleathertanningindustry: Octamethylcyclotetrasiloxane(D4); decamethylcyclopentasiloxane(D5); dodecamethylcyclohexasiloxane(D6);Thismethodrequirestheuseofgaschromatography(GC)equippedwithasinglequadrupolemassspectrometer(MS)toidentifyandquantifythecyclosiloxan
28、es.2 NormativereferencesThefollowingdocumentsarereferredtointhetextinsuchawaythatsomeoralloftheircontentconstitutesrequirementsofthisdocument.Fordatedreferences,onlytheeditioncitedapplies.Forundatedreferences,thelatesteditionofthereferenceddocument(includinganyamendments)applies.ISO3696,Waterforanal
29、yticallaboratoryuseSpecificationandtestmethods3 TermsanddefinitionsNotermsanddefinitionsarelistedinthisdocument.ISOandIECmaintainterminologydatabasesforuseinstandardizationatthefollowingaddresses: ISOOnlinebrowsingplatform:availableathttps:WWW.iso.org/obp IECElectropedia:availableathttps:WWWeleCtrOP
30、edia.org4 PrincipleAftersolubilizingthechemicalspecimeninwater,aliquid-liquidextractionwithahexane-ethylacetatemixtureisperformedandthenthecyclosiloxanesareanalysedbygas-chromatographywithsinglequadrupolemassspectrometry(GC-MS).Usinganexternalcalibration,quantificationisperformedtakingintoaccountthe
31、recoveryrateoftheinternalstandard.5 ApparatusTheusuallaboratoryapparatusand,inparticular,thefollowingshallbeused:5.1 Ultrasonicbath,capableofoperatingatastartingtemperatureof40to45.5.2 Horizontalshaker,capableofatleast300cyclesperminute.5.3 Glasscontainerwithascrewcap,e.g.volumeof20ml.IS023649:2025(
32、en)IULTCSIUC444:2025(en)5.4 Suitablesyringemembranefilters,e.g.polyamidewithporesize0,2m.5.5 Volumetricflasks,e.g.volumeof10mland100ml.5.6 Plastictesttubes,50ml,orsuitablevesselthatallowsseparationoforganicandaqueousphase,thatcanbesealedforvigorousshaking.5.7 GCvials,withcap,e.g.volumeof2ml.5.8 Anal
33、yticalbalance,witharesolutionof1mgorbetter.5.9 Pipettes,varioussizes,e.g.volumeof0,1mlto10ml.5.10 Centrifuge,capableofatleast4000rmin.5.11 Instrumentalequipment,GC-MS.6 ReagentsIfnototherwisespecified,analyticalreagentgradechemicalsshallbeused.6.1 n-hexane,CASRegistryNumber(CASRN)I)110-54-3,suitable
34、forGC-MSanalysis.6.2 Ethylacetate,CASRN141-78-6,suitableforGC-MSanalysis.6.3 Watergrade1,accordingtoISO3696.6.4 Sodiumchloride,CASRN7647-14-5lpurity99,0%(massfraction).6.5 Magnesiumsulphateanhydrous,CASRN7487-88-9,purity99,0%(massfraction).6.6 Octamethylcyclotetrasiloxane(D4),CASRN556-67-2,purity99,
35、0%(massfraction).6.7 Decamethylcyclopentasiloxane(D5),CASRN541-02-6,purity99,0%(massfraction).6.8 Dodecamethylcyclohexasiloxane(D6),CASRN540-97-6,purity99,0%(massfraction).6.9 n-hexane-ethylacetate50:50(volumefraction)mixture,preparedbymixingequalamountsbyvolumeofn-hexaneandethylacetate.6.10 Stockso
36、lutionsofamixofcyclosiloxanesD4,D5andD6,P=Img/1and20mg/LEXAMPLEIOmgofeachoftherespectiveOctamethylcyclotetrasiloxane(D4)(6.6),decamethylcyclopentasiloxane(D5)(6.7),anddodecamethylcyclohexasiloxane(D6)(6.8),aredissolvedtogetherina100mlvolumetricflask(5.5)andfilledupwithmixedsolutionofn-hexaneandethyl
37、acetate(6.9).Mixedstocksolutionsarepreparedtoobtainconcentrationsof1mg/1and20mg/1.6.11 Internalstandard,p=100mg/LTheuseofaninternalstandardisrequiredtoavoidmatrixeffects.1) ChemicalAbstractsService(CAS)RegistryNumberisatrademarkoftheAmericanChemicalSociety(ACS).Thisinformationisgivenfortheconvenienc
38、eofusersofthisdocumentanddoesnotconstituteanendorsementbyISOoftheproductnamed.Equivalentproductsmaybeusediftheycanbeshowntoleadtothesameresults.IS023649:2025(en)IULTCSIUC444:2025(en)Examplesofsuitableinternalstandards:Naphthalene-D8,CASRN1146-65-2;Tetrakis(trimethylsilyloxy)silane,CASRN3555-47-3.Pre
39、parea100mg/1solutionoftheinternalstandardbydilutingtheinternalstandardwithn-hexane-ethylacetate50:50(volumefraction)mixture(6.9).6.12 Calibrationsolutionsofcyclosiloxanes.Prepareatleastfourcalibrationsolutionsofp=0,1mg/1top=10mg/1ofthemixofcyclosiloxanesusingthestocksolutionsf6.10),seeTableLTable1Ex
40、ampleofcalibrationsolutionsConcentrationmg/1Volumeofn-hex-ane-ethylacetate50:50(volumefraction)mixture(6.9)iVolumeofmixofcyclosiloxanes1mg/1(6.10)iVolumeofmixofcyclosiloxanes20mg/1(60)iVolumeofinternalstandard100mg/1(6.111i0,18901000100,54905000101940050105740025010104900500107 Samplingandsampleprep
41、arationThespecimenshouldbethoroughlymixedtogetarepresentativetestportionforanalysis.Inthecaseofverydensechemical,manuallyormechanicallyshakethesampletohomogenizethecompositionofthetestspecimen.8 Procedure8.1 SamplesolutionpreparationWeigh(0,50,05)gofthetestspecimenwithananalyticalbalance(5.8)ina100m
42、lvolumetricflask(5.5)andmakeuptovolumewithgrade1water(6.3).Closetheflaskandplaceitfor(102)mininanultrasonicbath(5.1)atastartingtemperatureof40to45.Thisprocedureisonlyapplicabletowater-solublechemicals.Otherwise,usetheproceduredescribedinAnneXC.8.2 Liquid-liquidextractionPipette10mlofthesamplesolutio
43、n(8.1)intoaplastictesttube(5.6)andadd1gofsodiumchloride(6.4)and4gofmagnesiumsulphateanhydrousf6.5).Thenpipette10mlofn-hexane-ethylacetate50:50(volumefraction)mixture(6.9)and10lofinternalstandard(6.11)tothesamplesolution,closetheplastictesttubeandshakebyhandanddegas.ShakeforflO2)minonamechanicalhoriz
44、ontalshaker(5.2at300cycles/min.Forcompletephaseseparationaftershaking,themixtureshallbecentrifugedf5.10)for(51)minat(3000400)rmin,thenanaliquotofthesupernatantofextractionsolutionisfiltered(5.4)intoaGCsamplevial(5.7).ThealiquotisthenreadyfortheGC-MSanalysis.ISO2025-Allrightsreserved8.3 Instrumentala
45、nalysisThedetectionofthecyclosiloxanesismadeusingGC-MS.ExamplesofsuitablechromatographicconditionsaregiveninAmleXA(forGC-MS).Iftheconcentrationofthecyclosiloxanesisoutoftherangeofthecalibration,makeanappropriatedilutionandanalyseagain.9 ExpressionofresultsThecontentofeachcyclosiloxaneiscalculatedast
46、hemassfraction,w,inmilligramsperkilogram(mgkg)ofthechemicalspecimenaccordingtoFOITnUIa:口力IlQsampleW=44sample_JX卜am)whereAsisthepeakareaofeachcyclosiloxaneintheextractionsolution;isampeisthepeakareaofthecorrespondinginternalstandardintheextractionsolution;Cisampleistheconcentrationoftheinternalstanda
47、rdintheextractionsolutioninmicrogramsperlitre(gl);bistheinterceptofthecalibrationgraph;distheeventualdilutionfactor;Qistheslopeofthecalibrationgraph;Visthefinalvolumeused(0,011);misthemassofthechemicalspecimeningrams(g).10 PrecisionWiththismethoditisfeasibletoreachlimitsofquantification(LoQ)below50m
48、g/kgforeachcyclosiloxane.TheresultsofinterlaboratorytrialstodeterminethecontentofOctamethylcyclotetrasiloxane(D4),decamethylcyclopentasiloxane(D5)anddodecamethylcyclohexasiloxane(D6)inchemicalsarepresentedinAnnexB.11 TestreportThetestreportshallincludeatleastthefollowinginformation:a) areferencetothisdocument,i.e.ISO23649:2025;b) type,origi
