1、BRITISH STANDARDBS EN 14479:2004Packaging Flexible packaging material Determination of residual solvents by dynamic headspace gas chromatography Absolute methodThe European Standard EN 14479:2004 has the status of a British StandardICS 55.040g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g
2、54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58BS EN 14479:2004This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 March 2006 BSI 2006ISBN 0 580 480
3、62 3National forewordThis British Standard is the official English language version of EN 14479:2004.The UK participation in its preparation was entrusted to Technical Committee PKW/0, Packaging, which has the responsibility to: A list of organizations represented on this committee can be obtained o
4、n request to its secretary.Cross-referencesThe 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 B
5、SI 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 confer immunity from legal obligations. aid enquire
6、rs to understand the text; present to the responsible international/European committee any enquiries on the interpretation, or proposals for change, and keep UK interests informed; monitor related international and European developments and promulgate them in the UK.Summary of pagesThis document com
7、prises a front cover, an inside front cover, the EN title page, pages 2 to 13 and a back cover.The BSI copyright notice displayed in this document indicates when the document was last issued.Amendments issued since publicationAmd. No. Date CommentsEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 14
8、479April 2004ICS 55.040English versionPackaging - Flexible packaging material - Determination ofresidual solvents by dynamic headspace gas chromatography-Absolute methodEmballage - Matriaux demballage souples -Dtermination des solvants rsiduels par chromatographieen phase gazeuse et espace de tte dy
9、namique - MthodeabsolueVerpackung, Flexible Packstoffe - Bestimmung derRestlsemittel durch dynamische Dampfraumanalysemittels Gaschromatographie - Absolutes VerfahrenThis European Standard was approved by CEN on 2 February 2004.CEN members are bound to comply with the CEN/CENELEC Internal Regulation
10、s which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European S
11、tandard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national stan
12、dards bodies of 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, Switzerland and United Kingdom.EUROPEAN COMMIT
13、TEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2004 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 14479:2004: EEN 14479:2004 (E)2Contents Pa
14、geForeword. 31 Scope . 42 Principle. 43 Reagents 44 Apparatus 55 Sampling 86 Test specimens. 97 Analysis . 98 Procedure 109 Preparation of standard solutions 1010 Chromatographic parameters 1011 Number of test specimens . 1012 Incubation of the test specimens 1113 Determination with an external stan
15、dard . 1114 Results . 1115 Precision Data . 1116 Detection limits . 1117 Test report 11Bibliography . 13EN 14479:2004 (E)3ForewordThis document (EN 14479:2004) has been prepared by Technical Committee CEN/TC 261 “Packaging”, thesecretariat of which is held by AFNOR.This European Standard shall be gi
16、ven the status of a national standard, either by publication of an identicaltext or by endorsement, at the latest by October 2004, and conflicting national standards shall be withdrawn atthe latest by October 2004.According to the CEN/CENELEC Internal Regulations, the national standards organization
17、s of the followingcountries are bound to implement this European Standard: 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, Sp
18、ain, Sweden, Switzerlandand United Kingdom.EN 14479:2004 (E)41 ScopeThis standard describes methods for the quantitative determination of residual solvents in flexible packagingby dynamic headspace chromatography where the chemical identities of the residual solvents to bedetermined are known before
19、 commencing the analysis. Residues from thermal decomposition products arenot within the scope of this standard.The method is applicable to flexible packaging materials that may consist of mono- or multiplayer plastic films,paper or board, foil or combinations thereof.This method does not apply to r
20、esidual solvents with amounts lower than 0,5 mg/m.2 PrincipleDynamic extraction of the vapour phase of a sample is carried out using an inert gas for continuous strippingof the solvent. In this way thermodynamic equilibrium between the sample and its vapour phase is neverreached.The gas is fed in di
21、rectly over the thermostatically controlled sample for a period of time sufficient to allowextraction of most of the solvent present.Concentration methods using adsorbant solids or cryogenic liquids are required before the GC analysisbecause of the large volume of gas extracted. The procedure can th
22、us be divided into two phases:a) extraction and entrapmentb) desorption and transfer to the GC column.3 Reagents3.1 GeneralAll reagents shall be of recognized analytical reagent grade.NOTE Grades stated as being suitable for chromatography are commercially available and are recommended for useas ref
23、erence for standard calibration solutions. Appropriate safety precautions should be used when handling toxic and/orflammable solvents.3.2 Reference solvents, for the preparation of standard calibration solutions.3.3 Dilution solvent, with a retention time different from those of residual solvents in
24、 the sample.NOTE Solvents such as hexane, cyclohexanone, acid amides and glycerol triacetate (triacetin) are appropriate.EN 14479:2004 (E)54 Apparatus4.1 Dynamic headspace device4.2 Analytical balance, capable of weighing to the nearest 0,1 mg.4.3 Template for cutting samples.4.4 Scalpel or sharp kn
25、ife4.5 Syringes (e.g. 1 l, 10 l).4.6 Gas chromatograph, having a flame ionization detector or a mass-spectrometer or an FTIRspectrometer or another detector suitable for the solvents to be determined.4.7 Gas chromatographic column, either packed or capillary, that will give good resolution of thesol
26、vents to be determined from any other components that might eventually be present in the headspace.Examples for suitable columns and operation conditions are:a) Packed column:length : 3m;internal diameter : 3,2 mm;column filling : 80/120 mesh graphitised carbon, deactivated with polyethylene glycol;
27、carrier gas : N2, 20 ml/min ;injector temperature : 220 C ;temperature programme: 80 C; raised to 160 C at 6 C/min; raised to 225 C at 1,5 C/min; held for 16min.NOTE A corresponding chromatogram obtained for a mixture of solvents is shown in Figure 1.EN 14479:2004 (E)6Key1 4,23 methanol2 6,67 ethano
28、l3 9,25 acetone4 17,06 ethyl acetate5 19,1 butanol6 23,34 trichloroethylene7 28,4 isobutyl acetate8 33,87 methyl isobutylketone9 41,86 toluene10 64,06 xyleneA Retention time (min)B Peak heightFigure 1 Example of chromatogram obtained with a packed columnorb) Capillary column (fused silica) :. length
29、 : 30 m ;. internal diameter : 0,32 mm ;. stationary phase : Poly(dimethylsiloxane), film thickness 3 m ;EN 14479:2004 (E)7. carrier gas : He, 1,7 ml/min ;. carrier gas split ratio : 1:20 ;. injector temperature : 230 C ;. detector (flame ionisation) temperature : 280 C ;. temperature programme : 50
30、 C held for 5 min; raised to 100 C at 5 C/min raised to 250 C at 10C/min.NOTE A corresponding chromatogram for a mixture of solvents is shown in Figure 2.EN 14479:2004 (E)8Key1 Methanol2 Ethanol3 Isopropanol4 Methylethyl ketone5 Ethyl acetate6 Isobutanol7 Isopropyl acetate8 n-propyl acetate9 Methyli
31、sobutyl ketone10 Etoxypropanol11 Toluene12 n-butyl acetate13 Xylene14 Butyl cellosolveA Retention time (min)B Peak heightFigure 2 - Example of chromatogram obtained with a capillary column5 SamplingSamples of packaging materials that are to be analysed shall be handled and stored so as to prevent ei
32、therloss of volatile solvents or contamination by absorption of volatile solvents that may be present in thesurrounding atmosphere. Sampling and analysis shall be done in a place where the air is solvent-free in orderEN 14479:2004 (E)9to reduce the problem of contamination of the samples from their
33、surroundings due to the low concentrationsof residual solvents in the samples.NOTE Samples should be in tightly packed roll form if possible. Sheet samples can be prepared from the roll by cutting outa square window (several layers of sheets) with a knife. At least the first five layers should be di
34、scarded. When in the formof sheets they should be stacked tightly together to form a compact “block“ and wrapped tightly in a barrier material,preferably aluminium foil with a thickness of 30 m to 40 m. For storage periods of more than one hour the wrappedsamples should be stored at temperatures bel
35、ow 5 C and in an atmosphere free of volatile contaminants.6 Test specimens6.1 Specimen areaThe specimen area to be cut out depends on the equipment and the level of residual solvents to bedetermined in the material.NOTE In order to optimize the solvents quantification and avoid pollution of the equi
36、pment it is recommended tomake preliminary trials with increasing area of the specimens.6.2 Test specimens from sheetsFrom the top of the sample take a block of about 15 to 20 sheets out without separating them. Immediately putback the remaining part of the sample in its packaging under the conditio
37、ns specified in clause 5.After withdrawal of at least one layer (or more depending on the number of specimens to be prepared from theblock) from the top of the block take the following sheet and rapidly cut the first specimen using a template(4.3). The specimen should be immediately put into the des
38、orption device.Further specimens are prepared accordingly.The following precautions shall be taken.The different steps of the preparation should be done very rapidly to avoid evaporation of the solvents.The sample sheet from which the specimen is cut shall be taken out of the block immediately befor
39、epreparation.The specimens shall always be cut at a defined place e.g. on the same drawing printed on the same place inthe width and the template for cutting is placed always in the same manner.7 Analysis7.1 ConditioningAs an initial guidance the sample conditioning can be carried out at a temperatu
40、re between 80 C and 150 Cfor a period of time necessary to guarantee that in a further analysis on the same specimen, the total solventextract should be less than 5% of the first one.If this % cannot be reached, revise the parameters of the method (temperature, conditioning time, strippingflow, amou
41、nt of specimen etc) and repeat the extractions.EN 14479:2004 (E)10NOTE In each laboratory the conditioning time can be ascertained by repeating the analysis several times withdifferent samples (packaging materials with different structure) and choosing the longest.7.2 PurgingThe purging time and the
42、 stripping flow shall be chosen according to the different available dynamic headspace equipment and the type of the sample in order to optimise the extraction. However the gas extractedmust be at least three times the volume of the desorption device. A periodic control of the stripping flow isneces
43、sary in order to maintain the analytical efficiency.7.3 ConcentrationThe choice of the concentration method depends on the available system. The methods most widely in useare based on the use of cryogenic systems and entrapment adsorbant materials. The temperature of theadsorbant material during sam
44、pling shall be controlled.Regardless of the trapping system the amount of each solvent shall be in the calibration range.8 Procedure8.1 Incubate the sample at time and temperature defined in 7.18.2 Carry the desorbed solvents in inert gas stream and send them in a gas trap containing one or moresoli
45、d absorbers or equipped with a cryogenic system.8.3 Thermally desorb the trap to transfer the solvents into gas chromatographic column.8.4 Second extraction: incubate the sample at time and temperature defined in 7.1.8.5 Repeat at least two more times the operations from 8.2 to 8.4 on the same vial,
46、 unless with the secondinjection the areas of all solvents are not increased by more than 5 % with respect to the areas obtained withthe first injection. If so it is not necessary to go any further and one can take the sum of the areas of the firsttwo injections as a reference value for the calculat
47、ions.8.6 Third extraction in accordance with the procedure as in 8.1.9 Preparation of standard solutionsA mix of standard solvents (3.2) of same quantities by weight is prepared. If necessary it can be diluted. Careshould be taken when weighing to avoid loss by evaporation.10 Chromatographic paramet
48、ersThese depend on the type of column and the specific equipment used for the determination. Examples aregiven in 4.7 as guidance.11 Number of test specimensFrom each sample at least 3 test specimens for analysis shall be prepared as in clause 6.EN 14479:2004 (E)1112 Incubation of the test specimens
49、Incubation time and temperature have to be optimised accordingly for each individual system (see 7.1).13 Determination with an external standardAnalysis of the standard solution- Incubate a vial containing 1,0 l of standard solution at time and temperature defined in 7.1.- Follow procedure as with the samples (8.2 to 8.6).14 ResultsCalculation of amount of one residual solvent in the sampleQ = Sepawhere :Q is the quantity of one residual solvent in mg/m of packaging material ;a is the area of peak on chromatogram for this solvent ;p i
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