1、Designation: D6562 12Standard Test Method forDetermination of Gaseous Hexamethylene Diisocyanate(HDI) in Air with 9-(N-methylaminomethyl) AnthraceneMethod (MAMA) in the Workplace1This standard is issued under the fixed designation D6562; the number immediately following the designation indicates the
2、 year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of gaseou
3、shexamethylene diisocyanate (HDI) in air samples collectedfrom workplace and ambient atmospheres. The method de-scribed in this test method collects separate fractions. Onefraction will be dominated by vapor, and the other fraction willbe dominated by aerosol. It is not known at the present timewhet
4、her this represents a perfect separation of vapor andaerosol, and in any case, there are not separate exposurestandards for vapor and aerosol. Therefore, in comparing theresults for isocyanate against a standard, results from the twofractions should be combined to give a single total value. Thereaso
5、n for splitting the sample into two fractions is to increaseanalytic sensitivity for the vapor fraction and also to give thehygienist or ventilation engineer some information concerningthe likely state of the isocyanate species. The analyses of thetwo fractions are different, and are provided in sep
6、arate, linked,standards to avoid confusion. This test method is principallyused to determine short term exposure (15 min) of HDI inworkplace environments for personal monitoring or in ambientair. The analysis of the aerosol fraction is performed separately,as described in Test Method D6561.1.2 Diffe
7、rential air sampling is performed with a segregat-ing device.2The vapor fraction is collected on a glass fiberfilter (GFF) impregnated with 9-(N-methylaminomethyl) an-thracene (MAMA).1.3 The analysis of the gaseous fraction is performed with ahigh performance liquid chromatograph (HPLC) equippedwith
8、 ultraviolet (UV) and fluorescence detectors.1.4 The range of application of this test method, using UVand fluorescence detectors both connected in serial, has beenvalidated from 0.006 to 1.12 g of monomeric HDI/2.0 mL ofdesorption solution, which corresponds to concentrationsequivalent to 0.0004 to
9、 0.075 mg/m3of HDI based on a 15-Lair sample. Those concentrations correspond to a range ofvapor phase concentrations from 0.06 ppb(V) to 11 ppb(V) andcover the established threshold limit value (TLV) value of 5ppb(V).1.5 The quantification limit for the monomeric HDI, usingthe UV detection, has bee
10、n established as 0.012 g/2 mL ofdesorption solution and as 0.008 g/2 mL, using the fluores-cence detector. These limits correspond to 0.0008 mg/m3and0.0005 mg/m3respectively for an air sampled volume of 15 L.These values are equal to ten times the standard deviation (SD)obtained from ten measurement
11、s carried out on a standardsolution in contact with the GFF, whose concentration of 0.02g/2 mL is close to the expected detection limit.1.6 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to es
12、tablish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. See Section 9 foradditional hazards.2. Referenced Documents2.1 ASTM Standards:3D1193 Specification for Reagent WaterD1356 Terminology Relating to Sampling and Analysis ofAtmosphe
13、resD1357 Practice for Planning the Sampling of the AmbientAtmosphereD5337 Practice for Flow Rate Adjustment of PersonalSampling PumpsD6561 Test Method for Determination of Aerosol Mono-meric and Oligomeric Hexamethylene Diisocyanate (HDl)in Air with (Methoxy-2phenyl-1) Piperazine (MOPIP) inthe Workp
14、lace2.2 Other Standard:1This test method is under the jurisdiction of ASTM Committee D22 on AirQuality and is the direct responsibility of Subcommittee D22.04 on Workplace AirQuality.Current edition approved April 1, 2012. Published May 2012. Originallyapproved in 2000. Last previous edition approve
15、d in 2011 as D6562 - 06(2011).DOI: 10.1520/D6562-12.2The sampling device for isocyanates is covered by a patent held by JacquesLesage et al, IRSST, 505 De Maisonneuve Blvd. West, Montreal, Quebec, Canada.If you are aware of an alternative to this patented item, please provide thisinformation to ASTM
16、 Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee,1which you may attend.3For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume
17、 information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.Sampling Guide for Air Contaminants in the Workplace43. Terminology3.1 For definitions of terms used in thi
18、s test method, refer toTerminology D1356.4. Summary of Test Method4.1 Vapor and aerosol fractions are sampled simultaneouslyby using a segregating sampling device. The aerosols arecollected on a polyterafluoroethylene (PTFE) filter while thegaseous fraction is being adsorbed on the second filter mad
19、e ofglass fiber impregnated with MAMA.4.2 The analysis of the oligomer in the aerosol fraction isperformed separately in accordance with the procedure de-scribed in Test Method D6561.4.3 Diisocyanates present as vapors react with the second-ary amine function of the MAMA, impregnated on the GFF tofo
20、rm a urea derivative (1,2) as shown in Fig. 1.5Desorption of the GFF is done by using a solution mixture of67 % N,N-dimethylformamide and 33 % of a 30:70 buffer-acetonitrile mixture. Monomeric and oligomeric diisocyanatesare separated by using a reversed phase HPLC column,followed by UV (254 nm) and
21、 fluorescence detectors (254-nmexcitation and 412-nm emission) in series (3).4.4 Concentration of urea derivative contained in thesamples is calculated by using an external standard of theappropriate urea derivative.5. Significance and Use5.1 HDI is mostly used in the preparation of paints. For thel
22、ast ten years, the use of isocyanates and their industrial needshave been in constant growth.5.2 Diisocyanates and polyisocyanates are irritants to skin,eyes, and mucous membranes. They are recognized to causerespiratory allergic sensitization, asthmatic bronchitis, andacute respiratory intoxication
23、 (4-7).5.3 The American Conference of Governmental IndustrialHygienists (ACGIH) has adopted a threshold limit value - timeweighted average (TLV - TWA) of 0.005 ppm (V) or 0.034mg/m3(8). The Occupational Safety dual filter sampling system; hexameth-ylene diisocyanate; high-performance liquid chromato
24、graphy;9-(N-methylaminomethyl) anthracene; sampling and analysis;workplace atmospheresREFERENCES(1) Melcher, R.G., Langner, R.R., and Kagel, R.O., “Criteria for theevaluation of methods for the collection of organic pollutants in airusing solid sorbents,” American Industrial Hygiene AssociationJourn
25、al, Vol 39, No. 5, May 1983, pp. 349-361.(2) Dugehn,A., “Improved Chromatographic Procedure for Determinationof 9-(N-methylaminomethyl) anthracene Isocyanate Derivatives byHigh-Performance Liquid Chromatography,” Journal of Chromatog-raphy, No. 301, 1984, pp. 481-484.(3) Lesage, J., Goyer, N., Desja
26、rdins, F., Vincent, J.-Y., and Perrault, G.,“Workers Exposure to Isocyanates,” American Industrial HygieneAssociation Journal, Vol 53, No. 2, 1992, pp. 146-153.(4) Criteria for a Recommended Standard, Occupational Exposure toToluene Diisocyanate,“ Department of Health, Education and Welfare,National
27、 Institute for Occupational Safety and Health, Cincinnati, OH,No. DHEW (NIOSH) 73-11022, 1973.(5) Woolrich, P.F., “Toxicology, Industrial Hygiene and Medical Controlof TDI, MDI and PMPPI,” American Industrial Hygiene AssociationJournal, Vol 43, 1981, pp. 89-97.(6) Moller, D.R. et al, “Chronic Asthma
28、 Due to Toluene Diisocyanate,”Chest Vol 90, No. 4, 1986, pp. 494-499.(7) Butcher, B.T. et al, “Polyisocyanates and Their Prepolymers,”Asthma in the Workplace, edited by I. Leonard Bernstein, Moira Chan- Yeung, Jean- Luc Malo, and David I. Bernstein, Cincinnati, Ohio,Chap. 20, 1994, pp. 415-436.(8) T
29、hreshold Limit Values for Chemical Substances and Physical Agentsand Biological Exposure Indices, ACGIH, Cincinnati, Ohio, 1993.FIG. 2 Means of the Z-Scores Obtained by 13 Laboratories after n$3 Participations to an Interlaboratory EvaluationD6562 125(9) Occupational Safety and Health Administration
30、 (OSHA): OSHAMethod 42: Diisocyanates, OSHA Analytical Laboratory, OrganicMethods Development Branch, Salt Lake City, Utah, 1989.(10) Lesage, J., and Perrault, G., “Sampling Device for Isocyanates,” U.S.Patent No. 4 961 916.(11) Occupational Safety and Health Administration (OSHA): Evaluationscheme
31、methods that use filters as the collection medium, OSHATechnical Center, OSHAAnalytical Methods Manual, 2nd Ed., Part 2,Salt Lake City, Utah, 1991.(12) The Sigma-Aldrich Library of Chemical Safety Data, 1st Ed., RobertE. Lenga.(13) Guide dchantillonnage des contaminants de lair en milieu detravail,
32、Institut de recherche en sant et en scurit du travail duQubec, Montral, 1994.ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validi
33、ty of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your commen
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35、t received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple cop
36、ies) of this standard may be obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/COPYRIGHT/).D6562 126
