BS ISO 17734-2-2013 Determination of organonitrogen compounds in air using liquid chromatography and mass spectrometry Amines and aminoisocyanates using dibutylamine and ethyl chlo.pdf

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1、BSI Standards PublicationBS ISO 17734-2:2013Determination oforganonitrogen compoundsin air using liquidchromatography and massspectrometryPart 2: Amines and aminoisocyanates usingdibutylamine and ethyl chloroformatederivativesBS ISO 17734-2:2013 BRITISH STANDARDNational forewordThis British Standard

2、 is the UK implementation of ISO 17734-2:2013.It supersedes BS ISO 17734-2:2006 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee EH/2/2, Work place atmospheres.A list of organizations represented on this committee can beobtained on request to its secreta

3、ry.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2013. Published by BSI StandardsLimited 2013ISBN 978 0 580 77428 7ICS 13.040.30Compliance with a British Standard cannot conf

4、er immunity fromlegal obligations.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 December 2013.Amendments issued since publicationDate Text affectedBS ISO 17734-2:2013 ISO 2013Determination of organonitrogen compounds in air using liquid c

5、hromatography and mass spectrometry Part 2: Amines and aminoisocyanates using dibutylamine and ethyl chloroformate derivativesDtermination des composs organiques azots dans lair par chromatographie liquide et spectromtrie de masse Partie 2: Amines et aminoisocyanates par les drivs de la dibutylamine

6、 et du chloroformate dthyleINTERNATIONAL STANDARDISO17734-2Second edition2013-12-01Reference numberISO 17734-2:2013(E)BS ISO 17734-2:2013ISO 17734-2:2013(E)ii ISO 2013 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2013All rights reserved. Unless otherwise specified, no part of this publication

7、 may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs member body in the country of

8、the requester.ISO copyright officeCase postale 56 CH-1211 Geneva 20Tel. + 41 22 749 01 11Fax + 41 22 749 09 47E-mail copyrightiso.orgWeb www.iso.orgPublished in SwitzerlandBS ISO 17734-2:2013ISO 17734-2:2013(E) ISO 2013 All rights reserved iiiContents PageForeword ivIntroduction v1 Scope . 12 Normat

9、ive references 13 Principle 14 Reagents and materials . 25 Standard solutions 35.1 Reference compounds 35.2 Amine and deuterium-labelled amine derivatives . 35.3 Aminoisocyanate derivatives 45.4 Thermal decomposition products of polyurethane (PUR) 45.5 Stability of the amine and aminoisocyanate deri

10、vatives 46 Apparatus . 57 Air sampling 77.1 Pre-sampling laboratory preparation . 77.2 Pre-sampling field preparations 77.3 Collection of air samples 77.4 Blanks 87.5 Raw material . 87.6 Shipment of samples 88 Laboratory sample preparation . 98.1 Sample sequence . 98.2 Work-up procedure 109 Instrume

11、ntal settings .109.1 HPLC program (LC-MS) 109.2 HPLC program LC-chemiluminescent nitrogen detector (LC-CLND) .109.3 Mass spectrometer . 1010 Data handling 1110.1 Identification . 1110.2 Calibration curves . 1110.3 Quantification . 1111 Determination of performance characteristics.1111.1 General 1111

12、.2 Relevant uncertainty contributions and criteria 1211.3 Assessment of performance characteristics (following the detailed approach in Reference 12) . 12Annex A (informative) Performance characteristics 20Annex B (informative) Examples .22Bibliography .27BS ISO 17734-2:2013ISO 17734-2:2013(E)Forewo

13、rdISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technica

14、l committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of ele

15、ctrotechnical standardization.The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was

16、drafted in accordance with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives).Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent

17、 rights. Details of any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents).Any trade name used in this document is information given for the convenience of users and does not con

18、stitute an endorsement.For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary informationThe c

19、ommittee responsible for this document is ISO/TC 146, Air quality, Subcommittee SC 2, Workplace atmospheres.This second edition of ISO 17734-2 cancels and replaces ISO 17734-2:2006, which has been technically revised.ISO 17734 consists of the following parts, under the general title Determination of

20、 organonitrogen compounds in air using liquid chromatography and mass spectrometry: Part 1: Isocyanates using dibutylamine derivatives Part 2: Amines and aminoisocyanates using dibutylamine and ethyl chloroformate derivativesiv ISO 2013 All rights reservedBS ISO 17734-2:2013ISO 17734-2:2013(E)Introd

21、uctionIn many applications, when considering isocyanates as a workplace contaminant, there is also a need to investigate the presence of aminoisocyanates and amines. During thermal decomposition of polyurethane (PUR), not only isocyanates, but also amines and aminoisocyanates, are formed.123456The d

22、etermination of isocyanates in the work environment using DBA as a reagent has been demonstrated to be a robust method (see ISO 17734-1). Using the DBA method and derivatization with ethyl chloroformate in the following work-up procedure makes simultaneous determination of amines, aminoisocyanates,

23、and isocyanates possible.67For quantification of amine and aminoisocyanate derivatives, reference compounds are necessary, but are only available for a few diamines. Aminoisocyanates cannot be analysed directly because they react with themselves. In this method, a nitrogen-specific detector has been

24、 used for quantification of amine and aminoisocyanate derivatives in reference solutions. This technique has been demonstrated to be a useful tool, together with MS characterization, in greatly facilitating the production of reference solutions.6 ISO 2013 All rights reserved vBS ISO 17734-2:2013BS I

25、SO 17734-2:2013Determination of organonitrogen compounds in air using liquid chromatography and mass spectrometry Part 2: Amines and aminoisocyanates using dibutylamine and ethyl chloroformate derivatives1 ScopeThis part of ISO 17734 gives general guidance for the sampling and analysis of airborne a

26、mines and aminoisocyanates in workplace air. It is strongly recommended that the determination of amines and aminoisocyanates is made together with the determination of isocyanates in air, using DBA as a reagent (see ISO 17734-1).The method can be used for simultaneous determinations of amines, such

27、 as 4,4-methylenediphenyldiamine (4,4-MDA), 2,4- and 2,6-toluenediamine (2,4- and 2,6-TDA), and 1,6-hexamethylenediamine (1,6-HDA), and compounds containing both isocyanate and amine groups, such as 4,4-methylenediphenyl aminoisocyanate (4,4-MAI), 2,4-, 4,2-, and 2,6-toluene aminoisocyanate (2,4-, 4

28、,2-, and 2,6-TAI), and 1,6-hexamethylene aminoisocyanate (1,6-HAI). The method is suitable for collecting amines and aminoisocyanates in both the gas and particle phases. The instrumental detection limit for the amines is about 5 nmol/sample and for the aminoisocyanate, it is about 0,3 nmol/sample.

29、For a 15 l air sample, this corresponds to 0,4 ngm3for TDA and 0,03 ngm3for TAI.2 Normative referencesThe following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated

30、 references, the latest edition of the referenced document (including any amendments) applies.ISO 16200-1, Workplace air quality Sampling and analysis of volatile organic compounds by solvent desorption/gas chromatography Part 1: Pumped sampling methodISO 5725-2, Accuracy (trueness and precision) of

31、 measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method3 PrincipleThe method permits the simultaneous sampling and analysis of amines, aminoisocyanates, and isocyanates. Only amines and aminoisocyanates are dis

32、cussed in this part of ISO 17734, because isocyanates are considered in ISO 17734-1.Samples are collected by drawing a known volume of air through a midget impinger flask followed by a filter. The impinger contains 10 ml of 0,01 moll1of di-n-butylamine (DBA) in toluene, and the filter is a glass fib

33、re filter with no binder. After sampling, deuterium-labelled amine-ethyl chloroformate (ET) and isocyanate-DBA derivatives (used as internal standard) are added to the sample solutions. The excess reagent and solvent are evaporated, and the samples are dissolved in acetonitrile. The samples are anal

34、ysed using reversed-phase liquid chromatography (LC) and electrospray (ESP) mass spectrometric (MS) detection, monitoring positive ions. Quantification is made by quantifying selected ions.Quantification and qualitative determinations can be performed using different LC-MS techniques. LC-CLND (chemi

35、luminescent nitrogen detection) or, for aromatic isocyanates, aminoisocyanates, and amines, LC-UV (ultraviolet detection) can be used for the determination of higher concentrations. Reference INTERNATIONAL STANDARD ISO 17734-2:2013(E) ISO 2013 All rights reserved 1BS ISO 17734-2:2013ISO 17734-2:2013

36、(E)materials can be characterized using LC-MS/CLND. For characterization of volatile compounds, a GC-thermoionic specific detector (TSD) can also be used.Sampling with impinger and filter Transfer of sample solution and filter to test tube Addition of IS Work-up procedure Analysis with LC-MS Evaluat

37、ion of data Calibration curve from standard solution Gas phase and large particles (1,5 m are collected in the impinger flask. Small particles (0,01 mto 1,5 m) are collected on the filter ) . . Standard solution : Isocyanate-DBA, amine-ET and aminoisocyanate-DBA-ET derivatives Internal standard, IS:

38、- Similar in retention time - Similar in molecular structure i.e. aromatic or aliphatic - Preferably deuterium-labelled derivative -Extraction of analytes on the filter -Derivatisation of the amine groups with ET in a two phase derivatisation procedure - Change of solution media - Enrichment of the

39、analytes - SIM of molecular ion MH of analytes and IS + - Calculation of the area ratio of the analyte and IS- Comparison between area ratio of the air sample and calibration plotFigure 1 Principle of the described method4 Reagents and materials4.1 DBA reagent.Analytical grade di-n-butylamine is com

40、mercially available.4.2 Ethyl chloroformate reagent.Analytical grade ethyl chloroformate is commercially available.2 ISO 2013 All rights reservedBS ISO 17734-2:2013ISO 17734-2:2013(E)4.3 Reagent solution.In a 1 l volumetric flask, dilute 1,69 ml of DBA in toluene and make up to the mark. The solutio

41、n is stable and no special care during storage is necessary.4.4 Sodium hydroxide, 5 moll1.Dissolve 200 g of NaOH in water in a beaker, then transfer the solution to a 1 l volumetric flask and make up to the mark.4.5 Pyridine, analytical grade.4.6 Solvents.The reagent solvent, typically toluene, and

42、other solvents, such as acetonitrile and methanol, should be of liquid chromatographic quality.4.7 Formic acid, concentrated formic acid, analytical grade.4.8 Ethanol, absolute, extra pure 99,5 %.4.9 HPLC mobile phases.4.9.1 LC-MS.The weak mobile phase (mobile phase A) consists of water/acetonitrile

43、 (95/5 volume fraction) and 0,05 % formic acid. The strong mobile phase (mobile phase B) consists of water/acetonitrile/methanol (5/70/25 volume fraction) and 0,05 % formic acid. The mobile phases are degassed prior to use.4.9.2 LC-CLND.The weak mobile phase (mobile phase C) consists of water/methan

44、ol (95/5 volume fraction) and 0,05 % formic acid. The strong mobile phase (mobile phase D) consists of water/methanol (5/95 volume fraction) and 0,05 % formic acid. The mobile phases are degassed prior to use.5 Standard solutions5.1 Reference compoundsReference compounds are necessary for LC-MS dete

45、rmination. For the commercially available amines, the ethyl chloroformate (ET) derivatives are easily prepared by direct derivatization with ET for use as calibration standards. The aminoisocyanate derivatives are prepared by reacting one of the isocyanate groups with DBA and the other group with et

46、hanol. The mixed derivatives formed shall be characterized before use as calibration standards. Isocyanate, aminoisocyanate, and amine derivatives for compounds that are not commercially available can be made from the bulk material or from the thermal decomposition of PUR. Alternatively, standard so

47、lutions can be purchased.5.2 Amine and deuterium-labelled amine derivativesCalibration standards are made by spiking accurately weighed amounts (ca 0,1 mmol) of amines in 100 ml of toluene. The solution is further diluted to ca 0,01 molml1. 5 ml toluene solutions are spiked with volumes of the amine

48、 solutions appropriate for the construction of a calibration curve. The work-up procedure is then performed; this is described in 8.2. ISO 2013 All rights reserved 3BS ISO 17734-2:2013ISO 17734-2:2013(E)The procedure for the synthesis of derivatives is as follows.1) Dissolve a 10 mmol aliquot of the

49、 amines and the deuterium-labelled amines in 20 ml of toluene. Thereafter, add 150 l pyridine and 40 ml of 5 moll1NaOH. Then add 1,5 ml of ET dropwise under continuous stirring.2) After 10 min, separate the toluene phase.3) Evaporate the reaction mixture to dryness in a rotating evaporator, and dry the residue under vacuum.5.3 Aminoisocyanate derivatives5.3.1 PreparationTwo procedures, A and B, are used to enrich different mixed aminoisocyanate derivatives. The isocyanate groups in, for example