1、December 2008DEUTSCHE NORM English price group 8No part of this standard may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 83.080.20!$Tz“1498799w
2、ww.din.deDDIN EN ISO 6401Plastics Poly(vinyl chloride) Determination of residual vinyl chlorideEnglish version of DIN EN ISO 6401:2008-12Kunststoffe Polyvinylchlorid Bestimmung des Restgehaltes an Vinylchlorid-Monomer - GaschromatographischesVerfahren (ISO 6401:2008)Englische Fassung DIN EN ISO 6401
3、:2008-12SupersedesDIN EN ISO 6401:2005-02www.beuth.deDocument comprises 11 pagesmonomer Gas-chromatographic method (ISO 6401:2008)DIN EN ISO 6401:2008-12 2 National foreword This standard has been prepared by Technical Committee ISO/TC 61 “Plastics” in collaboration with Technical Committee CEN/TC 2
4、49 “Plastics”, (Secretariat: NBN, Belgium). The responsible German body involved in its preparation was the Normenausschuss Kunststoffe (Plastics Standards Committee), Technical Committee NA 054-01-03 AA Physikalische, rheologische und analytische Prfungen. The DIN Standard corresponding to the Inte
5、rnational Standard referred to in this document is as follows: ISO 472 DIN EN ISO 472 Amendments This standard differs from DIN EN ISO 6401:2005-02 as follows: a) The standard has been revised in form and substance. b) The table in Annex A (informative) has been revised. c) Annex B (informative) has
6、 been added. Previous editions DIN EN ISO 6401: 2005-02 National Annex NA (informative) Bibliography DIN EN ISO 472, Plastics Vocabulary EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 6401 September 2008 ICS 83.080.20 Supersedes EN ISO 6401:2004English Version Plastics - Poly(vinyl chlorid
7、e) - Determination of residual vinyl chloride monomer - Gas-chromatographic method (ISO 6401:2008) Plastiques - Poly(chlorure de vinyle) - Dtermination du chlorure de vinyle monomre rsiduel - Mthode par chromatographie en phase gazeuse (ISO 6401:2008) Kunststoffe - Polyvinylchlorid - Bestimmung des
8、Restgehaltes an Vinylchlorid-Monomer - Gaschromatographisches Verfahren (ISO 6401:2008) This European Standard was approved by CEN on 16 August 2008. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European Standard the status
9、of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national standards may be obtained on application to the CEN Management Centre or to any CEN member. This European Standard exists in three official versions (English, French, German). A ve
10、rsion in any other language made by translation under the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic,
11、Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMAL
12、ISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: rue de Stassart, 36 B-1050 Brussels 2008 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 6401:2008: EContents2 1 Scope 4 2 Normative references 4 3 Terms and definitions
13、 .4 4 Principle4 5 Sampling.4 6 Apparatus .5 7 Reagents and materials 5 8 Procedure .6 9 Calculation7 10 Precision.7 11 Test report 7 Annex A (informative) Suitable GC columns for the determination of vinyl chloride monomer 8 Annex B (informative) Typical responses for vinyl chloride monomer calibra
14、tion solutions.9 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) Foreword3 Page3 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) Foreword This document (EN ISO 6401:2008) has been prepared by Technical Committee ISO/TC 61 “Plastics“ in collaboration with Technical Committee CEN/TC 249 “Plastics” the secre
15、tariat of which is held by NBN. 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 March 2009, and conflicting national standards shall be withdrawn at the latest by March 2009. Attention is drawn to
16、 the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document supersedes EN ISO 6401:2004. According to the CEN/CENELEC Internal Regulations, the national
17、standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Polan
18、d, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 6401:2008 has been approved by CEN as a EN ISO 6401:2008 without any modification. SAFETY PRECAUTIONS Persons using this document should be familiar with normal laboratoryp
19、ractice, if applicable. This document does not purport to address all of the safety concerns, if any,associated with its use. It is the responsibility of the user to establish appropriate safety and healthpractices and to ensure compliance with any regulatory requirements.1ScopeThis International St
20、andard specifies a method for the determination of vinyl chloride monomer in homopolymerand copolymer resins of vinyl chloride and compounded materials. The method is based on sample dissolutionand headspace gas chromatography. Concentrations of vinyl chloride in the range to canbe determined.A “dry
21、 method”, suitable for PVC resins but not compounded materials, is widely used within the industry forin-house determinations. A separate International Standard based on this methodology is under development.2 Normative referencesThe following referenced documents are indispensable for the applicati
22、on of this document. For datedreferences, only the edition cited applies. For undated references, the latest edition of the referenced document(including any amendments) applies.ISO 472, Plastics Vocabulary3 Terms and definitionsFor the purposes of this document, the terms and definitions given in I
23、SO 472 apply.4 PrincipleThe level of vinyl chloride monomer is determined by headspace gas chromatography of the polymer testsample dissolved/swollen in N,N-dimethylacetamide.5 SamplingA representative sample shall be taken.A concentration gradient may form in stored resin samples due to the volatil
24、ity of vinyl chloride. Cooling of thesample prior to sampling is advisable but condensation of humidity must be avoided. Sample preparation shallbe carried out as quickly as possible to minimize losses of residual monomer. When exchanging samplesbetween laboratories or when storage is necessary, sam
25、ples should be sealed in completely filled and sealedglass bottles or vials (e.g. 6.5, 6.6).0,1 mg/kg 3,0 mg/kg4 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) 6 ApparatusStandard laboratory apparatus and the following:6.1 Gas chromatograph (GC), fitted with an automatic static headspace sampler.6.2 F
26、lame ionization detector (FID).6.3 Gas-chromatographic column.The signal obtained with a solution containing of vinyl chloride per litre shall be at least three times thatof the baseline noise. The limit of detection of the method is vinyl chloride in test samples. Examplesof suitable columns are de
27、scribed in Annex A, Table A.1.6.4 Data-processing system, for data acquisition and evaluation of GC runs.6.5 Glass bottles, capacity , with polytetrafluoroethylene (PTFE) faced silicone septa and aluminiumcaps.6.6 Glass vials, capacity , with polytetrafluoroethylene (PTFE) faced silicone septa and a
28、luminiumcaps.6.7 Crimping and decapping tools, for sealing and uncapping the vials.6.8 Glass pipettes, capacity and .6.9 Microsyringes, capacity and .6.10 Gastight glass syringe, capacity , with lock valve.6.11 Analytical balance, capable of weighing to .7 Reagents and materialsAll reagents shall be
29、 of recognized analytical grade.WARNING Vinyl chloride is a hazardous substance which is a gas at ambient temperature. Thepreparation of solutions should therefore be carried out only under a well-ventilated fume hood.7.1 Vinyl chloride, of purity greater than . The vinyl chloride gas cylinder shall
30、 be fitted with a syringeadapter.7.2 N,N-dimethylacetamide, density . The solvent shall not contain any impurity with thesame chromatographic retention time as vinyl chloride under the conditions of the test.WARNING N,N-dimethylacetamide is also a hazardous substance.7.3 Detector gases and carrier g
31、as: High-purity gases shall be used to achieve the required low limits ofquantification.7.4 Vinyl chloride, standard solution, with a vinyl chloride concentration of approximately .To a glass bottle (6.5), add, using a glass pipette (6.8), of N,N-dimethylacetamide (7.2) and cap thebottle with a PTFE
32、-lined silicone septum. Weigh (to ) the bottle containing the N,N-dimethylacetamide.Introduce of vinyl chloride gas through the septum into the N,N-dimethylacetamide, using a pre-flushedgastight syringe (6.10) and holding the end of the syringe needle below the surface of the liquid. Avoid theconten
33、ts of the bottle becoming contaminated by air. Identify this solution as solution A.Repeat the procedure with a second glass bottle and identify the resultant solution as solution B.0,01 mg0,1 mg/kg30 ml22,5 ml25 ml 10 ml500l 100l10 ml0,1 mg99,5 % = 0,937 g/ml1 600 mg/l30 ml 25 ml0,1 mg10 ml10 ml30
34、ml5 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) Leave both bottles for at room temperature to allow complete adsorption of the vinyl chloride. Reweigh to thenearest to determine the mass of monomer which has been added. The mass of vinyl chloride in eachstandard solution will be about , depending o
35、n cylinder pressure. Record the concentration of vinylchloride in solutions A and B in milligrams per litre.Store the solutions in a refrigerator.7.5 Vinyl chloride, working calibrant stock solutions, with a vinyl chloride concentration of approximately.To a glass bottle, add, using a glass pipette,
36、 of N,N-dimethylacetamide (7.2) and seal with aPTFE-lined silicone septum and cap. Transfer of solution A through the septum into the bottle using asuitable syringe.Repeat for solution B and label the two diluted calibrant solutions as solution C and solution D.Record the concentration of vinyl chlo
37、ride in the working calibrant stock solutions in milligrams per litre.7.6 Vinyl chloride calibration solutions, with vinyl chloride concentrations between andapproximately .Take seven headspace vials (6.6) and add, using a glass pipette, of N,N-dimethylacetamide (7.2)to each. Using a syringe, transf
38、er , , , , , and of solution C into theindividual vials and seal with silicone/PTFE septa and caps. Take two more headspace vials and addof N,N-dimethylacetamide. To these add of solution D (giving a final concentration of ) andseal with a septum and cap. These last two solutions are used as check s
39、olutions.8 Procedure8.1 Preparation of test solutionsWeigh of sample (to ) into a headspace vial (cut compounded materials into small pieces)and add of dimethylacetamide. Seal with a silicone/PTFE septum and then cap the vial. Repeat this toproduce triplicate test solutions for each sample.8.2 Gas c
40、hromatographyDepending on the type of gas chromatograph and column used for the determination, establish the appropriateGC and FID parameters.NOTE For guidance, the transfer line temperature and column oven temperature profile established for a GC equipped withcolumn 2 described in Annex A are:Trans
41、fer line temperature: .Column oven temperature profile: Isothermal at for , from to at , then from toat . Under these conditions, vinyl chloride elutes at .8.3 DeterminationTransfer the test solutions, calibrant solutions and two check solutions to the static headspace sampler.Equilibrate them at fo
42、r prior to analysis.Suggested operating parameters for the headspace sampler are:needle temperature: ;pressurizing time: ;2h0,1 mg40 mg32 mg/l30 ml 25 ml500l0 mg/l0,3 mg/l22,5 ml 10 ml100l 0l 20l 40l 50l 60l 80l 100l22,5 ml10 ml 20l 0,06 mg/l1g 0,1 mg 22,5 ml10 ml150C80C 2min 80C 170C 5C/min 170C230
43、C 20C/min 8,4 min70C 1h150C1,0 min6 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) injection time: ;withdrawal time: .8.4 Preparation of the calibration graphPlot a graph of the vinyl chloride contents of the calibration solutions, in milligrams per litre, against thecorresponding peak areas.9 Calcula
44、tionDetermine the vinyl chloride content, in milligrams per litre, of the three test solutions and two check solutionsfrom the calibration graph.The vinyl chloride content of the sample, expressed in milligrams per kilogram, is given by the formulawhereis the vinyl chloride content, in milligrams pe
45、r litre, of the test solution, determined from thecalibration graph;is the mass, in grams, of vinyl chloride in the test solution.Confirm that the data obtained on the check solutions gives the concentration expected (within the repeatabilitycriterion for the method to be determined). If this is the
46、 case, report the results for each of the three testsolutions individually, as well as their arithmetic mean and the standard deviation from the mean.10 PrecisionTo be determined by interlaboratory trial.11 Test reportThe test report shall include the following information:a) a reference to this Int
47、ernational Standard;b) all details necessary for complete identification of the material tested;c) the individual results for the test solutions, their arithmetic mean and the standard deviation;d) the expected and measured vinyl chloride monomer content of the two check solutions;e) any deviations
48、from this International Standard;f) the date of the test.0,1 min0,5 minc 10/mcm7 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) Annex A(informative)Suitable GC columns for the determination of vinyl chloride monomerThe PLOT (porous layer open tubular) columns described in Table A.1 have been found to
49、be suitable for thedetermination.Table A.1 Suitable columnsColumnLength DiameterColumn type1 15,00 0,53 Bonded polystyrene-divinylbenzene2 30,00 0,53 Porous divinylbenzene homopolymerm mm8 DIN EN ISO 6401:2008-12 EN ISO 6401:2008 (E) Annex B(informative)Typical responses for vinyl chloride monomer calibration solutionsKeyelution time (min)instrument response1 vinyl choride2 v c3 vinyl chorideFigure B.1 Typical responses for vinyl chloride monomer calibration solutionsin N,N-dimethylacetamide using column 2 described in
