1、BS ISO 17735:2009ICS 13.040.30NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDWorkplace atmospheres Determination of total isocyanate groups in air using 1-(9-anthra-cenylmethyl)piperazine (MAP) reagent and liquid chromatographyThis British Standard was publishe
2、d under the authority of the Standards Policy and Strategy Committee on 30 June2009. BSI 2009ISBN 978 0 580 61753 9Amendments/corrigenda issued since publicationDate CommentsBS ISO 17735:2009National forewordThis British Standard is the UK implementation of ISO 17735:2009. The UK participation in it
3、s preparation was entrusted to TechnicalCommittee EH/2/2, Work place atmospheres.A list of organizations represented on this committee can be obtained onrequest to its secretary.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its corr
4、ect application. Compliance with a British Standard cannot confer immunityfrom legal obligations.BS ISO 17735:2009Reference numberISO 17735:2009(E)ISO 2009INTERNATIONAL STANDARD ISO17735First edition2009-03-15Workplace atmospheres Determination of total isocyanate groups in air using 1-(9-anthraceny
5、lmethyl)piperazine (MAP) reagent and liquid chromatography Air des lieux de travail Dosage des groupements isocyanates totaux dans lair par raction avec la 1-(9-anthracnylmthyl)piprazine (MAP) et par chromatographie en phase liquide BS ISO 17735:2009ISO 17735:2009(E) PDF disclaimer This PDF file may
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8、n parameters were optimized for printing. Every care has been taken to ensure that the file is suitable for use by ISO member bodies. In the unlikely event that a problem relating to it is found, please inform the Central Secretariat at the address given below. COPYRIGHT PROTECTED DOCUMENT ISO 2009
9、All 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 photocopying and microfilm, without permission in writing from either ISO at the address below or ISOs member body in the countr
10、y of the requester. ISO copyright office Case postale 56 CH-1211 Geneva 20 Tel. + 41 22 749 01 11 Fax + 41 22 749 09 47 E-mail copyrightiso.org Web www.iso.org Published in Switzerland ii ISO 2009 All rights reservedBS ISO 17735:2009ISO 17735:2009(E) ISO 2009 All rights reserved iiiContents Page For
11、eword iv Introduction v 1 Scope . 1 2 Normative references . 1 3 Principle. 1 4 Reagents and materials . 3 5 Apparatus 7 6 Air sampling 9 6.1 Pre-sampling laboratory preparation 9 6.2 Pre-sampling field preparation 10 6.3 Collection of air samples . 10 6.4 Blanks and negative controls 11 6.5 Bulk pr
12、oducts 11 6.6 Shipment of samples 11 6.7 Filter test samples 11 6.8 Impinger test samples 12 7 HPLC analysis . 12 7.1 Instrumental settings 12 7.2 HPLC programme . 12 8 Data handling 14 8.1 Monomer measurement . 14 8.2 Oligomer measurement (total detectable isocyanate) 14 9 Calibration and quality c
13、ontrol 14 9.1 Standard matching solutions 14 9.2 Calibration curves. 15 9.3 Blank tests. 15 9.4 Bulk products 15 9.5 Quality control spikes 15 10 Calculations. 15 10.1 Monomer 15 10.2 Oligomers (total detectable isocyanate). 16 11 Interferences . 16 12 Determination of performance characteristics 17
14、 12.1 Introduction . 17 12.2 Assessment of performance characteristics. 18 Annex A (informative) Performance characteristics. 25 Bibliography . 27 BS ISO 17735:2009ISO 17735:2009(E) iv ISO 2009 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federa
15、tion 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 technical committee has been established has the right to be represented on that committ
16、ee. 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 electrotechnical standardization. International Standards are drafted in accordance
17、 with the rules given in the ISO/IEC Directives, Part 2. The main task 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 ap
18、proval by at least 75 % of the member bodies casting a vote. 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 rights. ISO 17735 was prepared by Technical Comm
19、ittee ISO/TC 146, Air quality, Subcommittee SC 2, Workplace atmospheres. BS ISO 17735:2009ISO 17735:2009(E) ISO 2009 All rights reserved vIntroduction This International Standard specifies the use of 1-(9-anthracenylmethyl)piperazine (MAP) to measure monomeric and oligomeric isocyanate species in wo
20、rkplace atmospheres. MAP was designed to improve the reliability of identification of isocyanate species in sample chromatograms and to improve the accuracy of quantification of these species relative to established reagents. The high performance liquid chromatography (HPLC) analysis uses a pH gradi
21、ent to selectively accelerate the elution of MAP derivatives of oligomeric isocyanates that might be unobservable in an isocratic analysis. The performance of MAP has been compared to other reagents used for total isocyanate analysis (Reference 7). MAP has been found to react with phenyl isocyanate
22、(used as a model isocyanate) as fast or faster than other reagents commonly used for isocyanate analysis. The UV response of MAP derivatives is comparable to that of 9-(methylaminomethyl)anthracene (MAMA) derivatives and considerably greater than other commonly used reagents approximately three time
23、s greater than 1-(2-methoxyphenyl)piperazine (1-2MP) derivatives of aromatic isocyanates and 14 times greater than 1-2MP derivatives of aliphatic isocyanates. The compound-to-compound variability of UV response per isocyanate group for MAP derivatives is smaller than the variability of any other com
24、monly used reagent/detector combination (the coefficient of variation is 3,5 % for five model isocyanates). This results in accurate quantification of detectable non-monomeric isocyante species based on a calibration curve generated from analysing standards of monomeric species. The monomeric specie
25、s used for calibration is generally the one associated with the product being analysed, but others could be used due to the very small compound-to-compound response variability of the MAP derivatives. The intensity of fluorescence response of MAP derivatives is comparable to that of MAMA derivatives
26、 and considerably greater than other reagents (e.g. approximately 30 times more intense than that of tryptamine derivatives). The compound-to-compound variability in fluorescence response has been found to be smaller than that of MAMA derivatives but larger than that of tryptamine derivatives (MAMA
27、= 59 % coefficient of variation, MAP = 33 % coefficient of variation, and tryptamine = 16 % coefficient of variation for 5 model isocyanates). The compound-to-compound fluorescence variability of MAP derivatives is considered too great for accurate quantification of non-monomeric isocyanate species
28、based on calibration with monomer standards. However, the sensitivity of the fluorescence detection makes it especially suitable for quantification of low levels of monomer, and the selectivity is very useful to designate an unidentified HPLC peak as a MAP derivative. MAP derivatives also give a str
29、ong response by electrochemical detection. The pH gradient used in the HPLC analysis selectively accelerates the elution of amines (MAP derivatives are amines), and is very strong (it accelerates MDI more than 100-fold). Re-equilibration to initial conditions is almost immediate. Many oligomeric spe
30、cies can be measured in the 30 min MAP analysis that may be unobservable in a much longer isocratic analysis. MAP has been used in several studies comparing it side-by-side with other methods. Reference 8 found MAP impingers and NIOSH 5521 impingers (comparable to MDHS 25) to give comparable results
31、 in spray painting environments. Reference 8 used MAP reagent, but the pH gradient was not employed. Reference 9 compared MAP impingers with several other impinger methods (NIOSH 5521 and NIOSH 5522) and the double filter method. The average MAP oligomer value was substantially higher than the other
32、 impinger methods and slightly higher than the double filter method. The pH gradient was used in these MAP analyses. The MAP method is currently available as NIOSH Method 5525 (Reference 11). The performance characteristics of the method have been evaluated in Reference 12. BS ISO 17735:2009BS ISO 1
33、7735:2009INTERNATIONAL STANDARD ISO 17735:2009(E) ISO 2009 All rights reserved 1Workplace atmospheres Determination of total isocyanate groups in air using 1-(9-anthracenylmethyl)piperazine (MAP) reagent and liquid chromatography 1 Scope This International Standard gives general guidance for the sam
34、pling and analysis of airborne organic isocyanates in workplace air. This International Standard is appropriate for a wide range of organic compounds containing isocyanate groups, including monofunctional isocyanates (e.g. phenyl isocyanate), diisocyanate monomers (e.g. 1,6-hexamethylene diisocyanat
35、e (HDI), toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), and isophorone diisocyanate (IPDI), prepolymers (e.g. the biuret and isocyanurate of HDI), as well as intermediate products formed during production or thermal breakdown of polyurethane. In mixed systems of HDI and IPDI pro
36、ducts, it is impossible to identify and quantify low levels of IPDI monomer using this International Standard, due to coelution of IPDI monomer with HDI-uretidinedione. The useful range of the method, expressed in moles of isocyanate group per species per sample, is approximately 1 1010to 2 107. 2 N
37、ormative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 5725-2, Accuracy (truenes
38、s and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method ISO 16200-1, Workplace air quality Sampling and analysis of volatile organic compounds by solvent desorption/gas chromatography Part 1:
39、 Pumped sampling method 3 Principle A measured volume of air is drawn through either an impinger containing a solution of 1-(9-anthracenylmethyl)piperazine (MAP), a filter impregnated with MAP, or a sampling train consisting of an impinger followed by an impregnated filter. The choice of sampler dep
40、ends on the chemical and physical characteristics of the airborne isocyanate (Reference 13). If an impinger is used, the solution is subjected to solid-phase extraction (SPE) and the eluate is concentrated and analysed by reverse phase high performance liquid chromatography (HPLC) with ultraviolet (
41、UV) absorbance and fluorescence (FL) detection in series. If an impregnated filter is used for sampling, it is extracted with solvent either in the field after completion of sampling or in the laboratory. Waiting to extract the filter until after the sample has been received by the analytical labora
42、tory is acceptable only for analysis of isocyanates collected as vapour. This solution is filtered and analysed by HPLC/UV/FL. Isocyanate-derived peaks are identified based on their UV and FL responses and by comparison with the chromatogram of a derivatised bulk isocyanate product if available. Qua
43、ntification of compounds for which analytical standards are available (generally monomers) is achieved by comparison BS ISO 17735:2009ISO 17735:2009(E) 2 ISO 2009 All rights reservedof the FL peak height of the sample peak with the FL peak height of standard matching solutions. Quantification of com
44、pounds for which analytical standards are not available is achieved by comparison of the UV area of the sample peak with the UV area of the appropriate monomer standard (i.e. the monomer from which the isocyanate product is derived). Structures of some common diisocyanate monomers are shown in Figur
45、e 1. Key 1 methyl isocyanate 2 butyl isocyanate 3 phenyl isocyanate 4 4,4-MDI 5 2,6-TDI 6 HDI 7 2,4-TDI 8 IPDI 9 HMDI Figure 1 Structures of some common isocyanates BS ISO 17735:2009ISO 17735:2009(E) ISO 2009 All rights reserved 34 Reagents and materials CAUTION Observe appropriate safety precaution
46、s when preparing reagents. Carry out preparations under a fume hood to avoid exposure to solvents, isocyanates or other volatile reagents. Wear nitrile gloves when manipulating reagents and solvents. During the analysis, unless otherwise stated, use only reagents of HPLC grade or better, and water o
47、f HPLC grade. 4.1 MAP reagent MAP is prepared by the reaction of 9-(chloromethyl)anthracene with piperazine as shown in Figure 2. The procedure using HPLC grade solvents is as follows. Dissolve 10,8 mmol (2,47 g) of 9-(chloromethyl)anthracene (98 % mass fraction) in 25 ml methylene chloride. Place t
48、his solution in a dropping funnel. Dissolve 54,4 mmol (4,69 g) of piperazine (99 % mass fraction) and 21,8 mmol (3,04 ml) of triethylamine (99,5 % mass fraction) in 37 ml methylene chloride. Place this solution in a 250 ml 2-necked round-bottomed flask with a magnetic stirring bar. While stirring th
49、is solution, add the 9-(chloromethyl)anthracene solution dropwise over a 30 min period. Rinse down the dropping funnel with an additional 10 ml of methylene chloride. Allow the reaction to continue while stirring for at least 2 h. Using a separating funnel, wash the reaction mixture three times with 130 ml water by shaking vigorously for 1 min. Discard the emulsion that forms after the first wash, which contains primarily an impurity and not MAP. Discard the aqueous washings. Place the washed MAP solution in
