1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS ISO 14382:2012W o r k p l a c e a t m o s p h e r e s Determination of toluene diisocyanate vapours using 1-(2-pyridyl) piperazine-coated glass fibre filters and analysis by h
2、igh performance liquid chromatography with ultraviolet and fluorescence detectorsBS ISO 14382:2012 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of ISO 14382:2012. The UK participation in its preparation was entrusted to T e c h n i c a l Committee EH/2/2, Work plac
3、e atmospheres.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2012. Publishe
4、d by BSI Standards Limited 2012.ISBN 978 0 580 69759 3 ICS 13.040.30 Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 December 2012.Amendments issued since pub
5、licationDate T e x t a f f e c t e dBS ISO 14382:2012 ISO 2012Workplace atmospheres Determination of toluene diisocyanate vapours using 1-(2-pyridyl)piperazine-coated glass fibre filters and analysis by high performance liquid chromatography with ultraviolet and fluorescence detectorsAir des lieux d
6、e travail Dtermination des vapeurs de tolune di-isocyanate laide de filtres en fibre de verre enduits de piprazine-1-(2-pyridyl) et par analyse par chromatographie liquide haute performance avec dtecteurs ultraviolets et fluorescenceINTERNATIONAL STANDARDISO14382First edition2012-12-01Reference numb
7、erISO 14382:2012(E)BS ISO 14382:2012ISO 14382:2012(E)ii ISO 2012 All rights reservedCOPYRIGHT PROTECTED DOCUMENT ISO 2012All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photoco
8、pying and microfilm, without permission in writing from either ISO at the address below or ISOs member body in the country of 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
9、 ISO 14382:2012ISO 14382:2012(E) ISO 2012 All rights reserved iiiContents PageForeword ivIntroduction v1 Scope . 12 Normative references 13 Principle 14 Reagents and materials . 25 Reagent solutions 25.1 Preparation of TDI urea derivatives . 25.2 Analytical standards . 25.3 Filter extraction solutio
10、n 35.4 1-2PP filter coating solution 35.5 HPLC mobile phase 36 Apparatus . 36.1 Air sampler . 36.2 Sampling pump . 46.3 Sampling pump calibration 46.4 Tubing . 46.5 Flowmeter . 46.6 Liquid chromatography system 47 Air sampling 57.1 Calibration of sampling pump . 57.2 Safety practices . 57.3 Preparat
11、ion of air sampler 57.4 Collection of air samples 57.5 Blanks 57.6 Sample shipment . 58 HPLC analysis . 68.1 Safety precautions 68.2 Sample preparation 68.3 Standards preparation . 68.4 HPLC conditions . 69 Analysis 79.1 Calibration 710 Quality control 711 Sample quantification . 711.1 Determination
12、 of TDI mass per sample . 711.2 Determination of TDI mass concentration in air . 811.3 Determination of TDI volume fraction in air. 812 Interferences 813 Determination of performance characteristics 913.1 Introduction 913.2 Relevant uncertainty contributions and criteria 1013.3 Assessment of perform
13、ance characteristics (ISO GUM approach) .10Annex A (informative) Performance characteristics 18Bibliography .20BS ISO 14382:2012ISO 14382:2012(E)ForewordISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of pr
14、eparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, i
15、n liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.The main task
16、of technical committees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote.Attention i
17、s 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 rights.ISO 14382 was prepared by Technical Committee ISO/TC 146, Air quality, Subcommittee SC 2, Workplace atmospheres.i
18、v ISO 2012 All rights reservedBS ISO 14382:2012ISO 14382:2012(E)IntroductionThe most common form of toluene diisocyanate (TDI) marketed commercially is a mixture containing 80 % 2,4-TDI and 20 % 2,6-TDI. It is also available as a mixture containing 65 % 2,4-TDI and 35 % 2,6-TDI, and as the pure 2,4-
19、TDI isomer. The main commercial use for TDI is the manufacture of polyurethane (PU) flexible foams used in upholstery, mattresses, shoe soles, and automotive seats. The PU foams are prepared by reacting the TDI with a polyol to produce the product. Depending on the components selected and how they a
20、re combined, end products with quite different properties can be achieved.The majority of flexible foams are produced by the slabstock foaming process, in which the mixture of polyurethane raw materials is dispensed onto paper linings in an open trough, where it gradually expands into a large bun of
21、 foam. These buns are cut into blocks or slices, which are then processed into the final desired products.In the majority of workplace atmospheres, TDI is present as a vapour and the 2,6-isomer may be predominant. In those rare instances where TDI is emitted into workplace environments as an aerosol
22、, the aerosols are collected efficiently by the glass fibre filter. The TDI in the aerosol readily evaporates during sampling and is captured by the liquid reagent 1-(2-pyridyl)piperazine coated on the filter. This International Standard provides a simple, well-tested and reliable method for the sam
23、pling and analysis of TDI using instrumentation readily available in most commercial laboratories. This International Standard is based on the United States Occupational Safety and Health Administration (OSHA) Method 429for diisocyanates, ASTM D58368(which is based on the OSHA Method 429) and on mod
24、ifications to OSHA Method 429recommended by Bayer MaterialScience Environmental Analytics Laboratory10. The Bayer modifications include the use of 2 mg of reagent to coat the sampling filter and the use of cellulose spacer rings in the air sampling cassette.OSHA Method 42 is widely used throughout t
25、he world. In an interlaboratory evaluation of the ASTM D58368with 13 participating laboratories, the average recovery from spiked media for 2,4-TDI was (106 5,6) % and (104 5,7) % for 2,6-TDI. Laboratory precision, measured as a repeatability coefficient of variation, was 6,2 % for 2,4-TDI and 5,7 %
26、 for 2,6-TDI. ISO 2012 All rights reserved vBS ISO 14382:2012BS ISO 14382:2012Workplace atmospheres Determination of toluene diisocyanate vapours using 1-(2-pyridyl)piperazine-coated glass fibre filters and analysis by high performance liquid chromatography with ultraviolet and fluorescence detector
27、sWARNING This document does not purport to address all safety concerns, if any, associated with its use. It is the responsibility of the user of this document to establish appropriate health and safety practices and to determine the application of regulatory limitations prior to use.1 ScopeThis Inte
28、rnational Standard gives general guidance for the sampling and analysis of airborne toluene diisocyanate (TDI) in workplace atmospheres. The procedure specified in this International Standard is especially suitable for short (15 min) and long-term (4 h) sampling and analysis of 2,4- and 2,6-TDI vapo
29、urs.The upper limit for this method is approximately 85 g of TDI per sample. This is a conservative upper limit based on the requirement of maintaining a sufficient amount of reagent on the coated glass fibre filter while permitting a 4 h sample to be collected at 1 l/min from an atmosphere containi
30、ng 50 nl/l of TDI.The quantitation limits for this method are 0,039 g for 2,4-TDI and 0,034 g for 2,6-TDI using a fluorescence detector. These limits, for a 15-min sample collected at 1 l/min, are equivalent to 0,36 nl/l for 2,4-TDI, and 0,32 nl/l for 2,6-TDI. For a 4 h sample collected at 1 l/min,
31、the limits are equivalent to 0,022 nl/l for 2,4-TDI and 0,020 nl/l for 2,6-TDI.The commercial availability of the specified reagents, the use of common analytical instrumentation, and the current widespread use of the method make this standard method ideally suited for the determination of TDI in wo
32、rkplace environments.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 references, the latest edition of the referenced document
33、(including any amendments) applies.ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement methodISO 16200-1, Workplace air quality Sampling and analysis of volatile org
34、anic compounds by solvent desorption/gas chromatography Part 1: Pumped sampling method3 PrincipleSamples are collected by drawing a known volume of workplace air through glass fibre filters coated with 2 mg of 1-(2-pyridyl)piperazine (1-2PP) which are contained in open-face cassettes. Samples are co
35、llected at 1 l/min for 15 min; up to a maximum sampling time of 4 h. Bayer10has methods that use both 13 mm and 37 mm filters (both sizes are coated with 2 mg of 1-2PP), but OSHA Method 429uses only 37 mm filters. The Bayer 13 mm filters are coated with 5 l of diethylphthalate per filter in addition
36、 to 2 mg of 1-2PP. The samples are extracted with 90 + 10 parts by volume acetonitrile/dimethyl sulfoxide (90 + 10 parts by volume ACN + DMSO) and are analysed by high performance liquid chromatography (HPLC) using an ultraviolet (UV) or a fluorescence detector. Use of both detectors in series allow
37、s the analyst to have high confidence in HPLC peak identification and quantitation. Other mixture ratios of ACN + DMSO can be used, providing they are tested and their use is consistent throughout the analysis.INTERNATIONAL STANDARD ISO 14382:2012(E) ISO 2012 All rights reserved 1BS ISO 14382:2012IS
38、O 14382:2012(E)4 Reagents and materialsUse only reagents of recognized analytical grade, unless otherwise specified. Always evaluate the derivatization and/or chromatographic effects when a reagent is changed.4.1 Methylene chloride CAS 75-0-2, HPLC grade.4.2 Hexane CAS 110-54-3, HPLC grade.4.3 Aceto
39、nitrile (ACN) CAS 75-05-8, HPLC grade.4.4 Dimethyl sulfoxide (DMSO) CAS 67-68-5, HPLC grade.4.5 Water CAS 7732-18-5, HPLC grade.4.6 1-(2-Pyridyl)piperazine CAS 34803-66-2, 99,5 % (mass fraction) grade.4.7 2,4-TDI CAS 584-84-9.4.8 2,6-TDI CAS 91-08-7.4.9 Ammonium acetate CAS 631-61-8, HPLC grade.4.10
40、 Acetic acid, glacial CAS 64-19-7, HPLC grade.4.11 Acetone CAS 67-64-1, HPLC grade.5 Reagent solutions5.1 Preparation of TDI urea derivativesPrepare a solution containing 3,5 g of 2,4-TDI in 25 ml of methylene chloride and slowly add it to a stirred solution of 7,25 g of 1-2PP in 100 mL of methylene
41、 chloride. Slowly heat the solution to about 35C, stirring constantly for several minutes. Reduce the volume of methylene chloride to about 10 ml with a stream of dry nitrogen. Precipitate the product by slowly adding approximately 50 ml of hexane to the solution (precipitation may start without add
42、ing the hexane). Filter the precipitate and then redissolve it in a minimal volume of methylene chloride and reprecipitate. Filter the solution and wash the collected precipitate with hexane. The approximate yield is 9 g of the derivative after being dried by a vacuum. This preparation is a modifica
43、tion of the procedure reported by Goldberg et al.11 . The purity of the TDI urea shall be checked using the melting point, elemental analysis, and/or NMR spectroscopy. The solid urea, when stored in a well-sealed dark bottle, is stable for more than 10 years. The 1-2PP derivative of 2,6-TDI is prepa
44、red by a similar procedure.5.2 Analytical standards5.2.1 Preparation of analytical standards using TDI urea derivativesStock analytical standard solutions are prepared by accurately weighing (to three significant figures) the TDI urea derivatives (5.1) and then dissolving them in DMSO. To express th
45、e derivative as free TDI, 2 ISO 2012 All rights reservedBS ISO 14382:2012ISO 14382:2012(E)weigh the amount of 2,4-TDI and 2,6-TDI ureas and multiply by the conversion factor of 0,3479, the ratio of molecular masses.MMrTDIrTDIurea)()(,=174 6500 10 3479 All dilutions of the stock solutions are made to
46、 arrive at the working range in 90 + 10 parts by volume ACN + DMSO. For example, a stock standard prepared in DMSO can be diluted 110 with pure ACN to arrive at 90 + 10 parts by volume ACN + DMSO. Any further dilutions are made with 90 + 10 parts by volume ACN + DMSO.5.2.2 Preparation of analytical
47、standards using pure TDIAnalytical standard solutions can also be prepared by reacting TDI (either pure 2,4-TDI or pure 2,6-TDI isomer) with 1-2PP in solution. Prepare a solution containing 1 mg/ml (0,006 mmol/l) 1-2PP by diluting 100 mg of 1-2PP to the mark with 90 + 10 parts by volume ACN + DMSO i
48、n a 100 ml volumetric flask, ISO 1042,1class A. Prepare a separate solution of 1 mg/ml (0,006 mmol/l) pure TDI by carefully and accurately weighing 50 mg of TDI (to three significant figures) and diluting it to the mark with 90 + 10 parts by volume ACN + DMSO in a 50 ml volumetric flask. Pipette 1 m
49、l to 3 ml of the 1 mg/ml TDI solution into a 25 ml volumetric flask and dilute to the mark with the 1 mg/ml 1-2PP solution. Mix the solution well and allow it to react overnight. Do not use more than 3 ml of the TDI solution in order to ensure a proper excess of 1-2PP. Do not use the conversion factor in 5.2.1 to calculate the concentration of these standards. Use fresh solutions. The amount of pure TDI isomer shall be accurately known to prepare accurate standards.5.2.3 Commerci
