EN 13130-8:2004

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Substanzen in Kunststoffen, die Beschränkungen unterliegen - Teil 8: Bestimmung von Isocyanaten in KunststoffenMatériaux et objets en contact avec les denrées alimentaires - Substances dans les matieres plastiques soumises a des limitations - Partie 8 : Détermination des isocyanates dans les matieres plastiquesMaterials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 8: Determination of isocyanates in plastics67.250Materiali in predmeti v stiku z živiliMaterials and articles in contact with foodstuffsICS:Ta slovenski standard je istoveten z:EN 13130-8:2004SIST EN 13130-8:2004en,fr,de01-september-2004SIST EN 13130-8:2004SLOVENSKI
STANDARDSIST ENV 13130-8:20001DGRPHãþD

EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 13130-8May 2004ICS 67.250English versionMaterials and articles in contact with foodstuffs - Plasticssubstances subject to limitation - Part 8: Determination ofisocyanates in plasticsMatériaux et objets en contact avec les denréesalimentaires - Substances dans les matières plastiquessoumises à des limitations - Partie 8 : Détermination desisocyanates dans les matières plastiquesWerkstoffe und Gegenstände in Kontakt mit Lebensmitteln- Substanzen in Kunststoffen, die Beschränkungenunterliegen - Teil 8: Bestimmung von Isocyanaten inKunststoffenThis European Standard was approved by CEN on 24 March 2004.CEN members are bound to comply with the CEN/CENELEC Internal Regulations 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 Standard 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 standards 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 COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2004 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 13130-8:2004: ESIST EN 13130-8:2004

page Foreword.3 1 Scope.6 2 Normative references.6 3 Principle.6 4 Reagents.6 4.1 Analytes.7 4.2 Reagents.7 5 Apparatus.9 5.1 General.9 6 Samples.9 7 Procedure.10 7.1 Test sample screening.10 7.1.1 Test sample extraction and derivatization.10 7.1.2 Preparation of reagent blank sample.10 7.1.3 Preparation of internal standard check sample.10 7.1.4 Preparation of un-derivatized sample blank.10 7.1.5 Chromatographic determination.10 7.2 Quantification of isocyanates by standard addition.11 7.2.1 General.11 7.2.2 Preparation of standard solutions for quantification (0 µµµµg/ml to 5 µµµµg/ml).11 7.2.3 Procedure for standard addition.12 7.2.4 Control sample.12 7.2.5 Analysis.12 7.3 Evaluation of data.12 7.3.1 General.12 7.3.2 HPLC interferences.12 8 Expression of results.13 8.1 Calculation by least squares regression.13 8.2 Graphical determination using internal standard.14 8.3 Precision data and detection limit.15 8.3.1 General.15 8.3.2 Repeatability.15 8.3.3 Reproducibility.15 8.3.4 Detection limits.15 9 Confirmation.16 9.1 Requirement for confirmation.16 9.2 Confirmation by re-analysis on an HPLC column of different elution characteristics.16 10 Test report.16 Annex A (normative)
Calibration by standard addition omitting the internal standard.18 Annex B (informative).19 Annex C (informative)
Suggested gradient profile.20 Bibliography.21
EN 13130 are as follows. Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food simulants and the determination of substances in plastics and the selection of conditions of exposure to food simulants Part 2: Determination of terephthalic acid in food simulants Part 3: Determination of acrylonitrile in food and food simulants Part 4: Determination of 1,3-butadiene in plastics
Part 5: Determination of vinylidene chloride in food simulants Part 6: Determination of vinylidene chloride in plastics Part 7: Determination of monoethylene glycol and diethylene glycol in food simulants Part 9: Determination of acetic acid, vinyl ester in food simulants Part 10: Determination of acrylamide in food simulants
Part 11: Determination of 11-aminoundecanoic acid in food simulants
Part 12: Determination of 1,3-benzenedimethanamine in food simulants Part 13: Determination of 2,2-bis(4-hydroxyphenyl)propane (Bisphenol A) in food simulants Part 14:
Determination of 3,3-bis(3-methyl-4-hydroxyphenyl)-2-indoline in food simulants SIST EN 13130-8:2004

Part 16 Determination of caprolactam and caprolactam salt in food simulants Part 17: Determination of carbonyl chloride in plastics
Part 18: Determination of 1,2-dihydroxybenzene, 1,3- dihydroxybenzene, 1,4- dihydroxybenzene, 4,4’-dihydroxybenzophenone and 4,4’dihydroxybiphenyl in food simulants Part 19:
Determination of dimethylaminoethanol in food simulants Part 20:
Determination of epichlorohydrin in plastics Part 21:
Determination of ethylenediamine and hexamethylenediamine in food simulants Part 22:
Determination of ethylene oxide and propylene oxide in plastics Part 23:
Determination of formaldehyde and hexamethylenetetramine in food simulants Part 24:
Determination of maleic acid and maleic anhydride in food simulants Part 25: Determination of 4-methyl-pentene in food simulants Part 26: Determination of 1-octene and tetrahydrofuran in food simulants Part 27:
Determination of 2,4,6-triamino-1,3,5-triazine in food simulants Part 28:
Determination of 1,1,1-trimethylopropane in food simulants
Parts 1 to 8 are European Standards.
Parts 9 to 28 are Technical Specifications, prepared within the Standards, Measurement and Testing project, MAT1-CT92-0006, “Development of Methods of Analysis for Monomers”. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries 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, Spain, Sweden, Switzerland and United Kingdom. SIST EN 13130-8:2004

During manufacture residual isocyanates can remain in the polymer and can migrate into food coming into contact with the polymer. SIST EN 13130-8:2004

1 Scope This part of this European Standard describes a method for the determination of individual and total levels of residual isocyanates in plastics materials and articles. This method is applicable to the analysis of polyurethane polymers.
The total level of isocyanate monomers in materials and articles determined according to the procedure described in this standard is given in milligrams of NCO per kilogram of material or article.
The method is capable of quantitative determination of individual isocyanates measured as NCO at 0,04 mg/kg and total isocyanates at 1,0 mg/kg. NOTE The method has been applied to the analysis of 9 isocyanate monomers listed in 3.1.
It has not been applied to the analysis of octadecyl isocyanate, diphenylether-4,4'-diisocyanate or 3,3'-dimethyl-4,4'-diisocyanatobiphenyl as samples of these monomers have not been obtained.
There is no reason to anticipate that the method may not be suitable for the analysis of these monomers also. 2 Normative references This European Standard incorporates by dated or undated reference, provisions from other publications.
These normative references are cited at the appropriate places in the text, and the publications are listed hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to this European Standard only when incorporated in it by amendment or revision.
For undated references the latest edition of the publication referred to applies (including amendments).
EN 13130-1:2004, Materials and articles in contact with foodstuffs - Plastics substances subject to limitation - Part 1: Guide to test methods for the specific migration of substances from plastics to foods and food simulants and the determination of substances in plastics and the selection of conditions of exposure to food simulants. 3 Principle The procedure consists of two parts: screening and, if necessary, quantitative determination.
Quantitative determination is applied only if isocyanates are detected by the screening procedure. Materials and articles are initially screened for residual isocyanates by solvent extraction with dichloromethane and concurrent derivatization with 9-(methylaminomethyl)anthracene.
1-Naphthyl isocyanate is used during the screening procedure to check that the derivatization procedure has been successful.
The resultant fluorescent derivatives are analysed by high performance liquid chromatography with fluorescence detection.
Materials found to contain residual isocyanates are quantified by standard addition to the material or article under test, using 1-naphthyl isocyanate as internal standard. If interferences are experienced with the internal standard then calibration is carried out by standard addition omitting the internal standard, as described in annex A. Confirmation of isocyanate levels is carried out by re-analysing the sample extracts on an HPLC column with different elution characteristics. 4 Reagents WARNING:
All chemicals are hazardous to health to a greater or lesser extent.
It is beyond the scope of this standard to give instructions for the safe handling of all chemicals, that meet, in full, the legal obligations in all countries in which this standard may be followed.
Therefore, specific warnings are SIST EN 13130-8:2004

Suitable precautions should be taken to ensure all glassware is dry.
All laboratory glassware should be rinsed with diethyl ether (4.2.2) and baked at 105 °C overnight before use.
After baking, vials should be placed in a desiccator and stored until required.
Isocyanate standards should be protected from moisture and stored under refrigeration at -20 °C. NOTE 2 All reagents should be of recognised analytical quality, unless otherwise specified. 4.1 Analytes 4.1.1 2,6-toluene diisocyanate CH3C6H3(NCO)2 4.1.2 diphenylmethane-4,4'-diisocyanate OCNC6H4CH2C6H4NCO 4.1.3 2,4-toluene diisocyanate CH3C6H3(NCO)2 4.1.4 hexamethylene diisocyanate OCNC6H12NCO 4.1.5 cyclohexyl isocyanate C6H11NCO 4.1.6 1,5-naphthalene diisocyanate C10H6(NCO)2 4.1.7 diphenylmethane-2,4'-diisocyanate OCNC6H4CH2C6H4NCO 4.1.8 2,4-toluene diisocyanate dimer 4.1.9 phenyl isocyanate C6H5NCO 4.1.10 1-naphthyl isocyanate (internal standard, C10H7NCO), which contains no impurity at > 1 % by area which will elute at the same retention time as any of the nine individual isocyanate derivatives. All standards should be of > 99 % purity. 4.2 Reagents 4.2.1 Dichloromethane (DCM, CH2Cl2), < 30 ppm H2O, containing no impurity at > 1 %, by area, which elutes at the same HPLC retention time as the isocyanate derivatives or internal standard derivative peaks.
DCM should be dried over a bed of molecular sieve (5 Å) for 24 h prior to use. 4.2.2 Diethylether ((C2H5)2O), at least 99 % purity. 4.2.3 9-(Methylaminomethyl)anthracene (MAMA, CH3NHCH2C14H9), containing no impurity at > 1 %, by area, which elutes at the same HPLC retention time as the isocyanate derivatives or internal standard derivative peaks. 4.2.4 N,N'-Dimethylformamide (HCON(CH3)2), containing no impurity at > 1 %, by area, which elutes at the same HPLC retention time as the isocyanate derivatives or internal standard derivative peaks. 4.2.5 Individual stock standard solutions (1000 µg/ml) Weigh 0,01 g of isocyanate standard (4.1), to an accuracy of 0,1 mg, in a 10 l volumetric flask.
Rapidly make-up to the mark with DCM (4.2.1) and shake thoroughly.
Ultrasonification may be used as an aid to dissolution.
Repeat the procedure to provide a second stock solution. 4.2.6 Individual intermediate standard solutions (100 ug/ml) SIST EN 13130-8:2004

Using a 1000 µl syringe, dispense 1000 µl of stock solution (4.2.5) into the flask, ensuring that the syringe needle tip is immersed into the DCM before dispensing.
Make-up to the mark with DCM and shake thoroughly.
Repeat the procedure using the second stock solution (4.2.5) to provide a second intermediate standard solution. 4.2.7 Individual dilute standard solutions (1 µg/ml) Put approximately 5 ml DCM (4.2.1) in a 10 ml volumetric flask.
Using a 100 µl syringe, dispense 100 µl of intermediate standard solution (4.2.6) into the flask, ensuring that the syringe needle tip is immersed into the DCM before dispensing.
Make-up to the mark with DCM and shake thoroughly. NOTE Individual dilute standard solutions should be prepared for each isocyanate (4.1). 4.2.8 Internal standard stock solution (1000 µg/ml) Weigh 0,01 g of 1-naphthyl isocyanate (4.1.10), to an accuracy of 0,1 mg, into a 10 ml volumetric flask.
Rapidly make-up to the mark with DCM (4.2.1) and shake thoroughly.
Ultrasonification may be used as an aid to dissolution. 4.2.9 Intermediate internal standard solution (100 µg/ml) Put approximately 5 ml DCM (4.2.1) in a 10 ml volumetric flask.
Using a 1000 µl syringe, dispense 1000 µl of internal standard stock solution (4.2.8) into the flask, ensuring that the syringe needle tip is immersed into the DCM before dispensing.
Make-up to the mark with DCM and shake thoroughly. 4.2.10 Dilute internal standard solution (1 µg/ml) Put approximately 5 ml DCM (4.2.1) in a 10 ml volumetric flask.
Using a 100 µl syringe, dispense 100 µl of intermediate internal standard solution (4.2.9) into the flask, ensuring that the syringe needle tip is immersed into the DCM before dispensing.
Make-up to the mark with DCM and shake thoroughly. NOTE Stock and standard solutions (4.2.5 to 4.2.10) should be stored with the exclusion of light and moisture at - 20 °C.
They are stable for up to 1 month under these conditions. 4.2.11 Derivatization reagent solution (0,26 mg/ml) Weigh 0,013 g of MAMA (4.2.3), to an accuracy of 0,1 mg, into a 50 ml volumetric flask.
Make-up to the mark with DCM (4.2.1) and shake thoroughly. NOTE Derivatization reagent should be prepared fresh daily, because of the photo-instability of MAMA, and stored with the exclusion of light. 4.2.12 Derivative dissolution solvent Using a measuring cylinder, dispense 50 ml N,N'-dimethylformamide (4.2.4) into a 100 ml volumetric flask, make-up to the mark with the requisite HPLC mobile phase (7.1.5.1) and mix thoroughly. 4.2.13 Preparation of individual isocyanate derivatives for HPLC peak assignment Using a 100 µl syringe, dispense 100 µl of dilute isocyanate standard solution (4.2.7) into a vial (5.4).
Using a 1 ml syringe dispense 1 ml of derivatization reagent solution (4.2.11) into the same vial.
Cap, gently agitate to mix the contents, and allow to stand for 60 min with the exclusion of light.
Evaporate the vial contents to dryness under a stream of nitrogen, add 10 ml derivative dissolution solvent (4.2.12) and mix thoroughly.
Ultrasonification may be used as an aid to dissolution.
Repeat for each isocyanate, using the individual dilute solutions (4.2.7).
NOTE Derivative solutions should be stored with the exclusion of light at ambient temperature.
They are stable for up to two weeks under these conditions. SIST EN 13130-8:2004
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