1、Designation: D6561 06 (Reapproved 2011)Standard Test Method forDetermination of Aerosol Monomeric and OligomericHexamethylene Diisocyanate (HDl) in Air with (Methoxy-2phenyl-1) Piperazine (MOPIP) in the Workplace1This standard is issued under the fixed designation D6561; the number immediately follo
2、wing the designation indicates the 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
3、covers the determination of aerosolhexamethylene 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
4、 not known at the present timewhether 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 g
5、ive a single total value. Thereason 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
6、different, and are provided in separate, 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 vapor fraction is performed separately,as describe
7、d in Test Method D6562.1.2 Differential air sampling is performed with a segregat-ing device.2The aerosol fraction is collected on a polytetra-fluoroethylene (PTFE) filter.1.3 Immediately after sampling, the PTFE filter is trans-ferred into a jar containing a (methoxy-2 phenyl-1) piperazine(MOPIP) s
8、olution in toluene.1.4 The analysis of the aerosol fraction is performed byusing a high performance liquid chromatograph (HPLC)equipped with an ultraviolet (UV) detector. The range ofapplication of the test method has been validated from 0.052 to1.04 g of monomeric HDI/mL, which corresponds, based o
9、na 15 Lair sample, to concentrations from 0.004 to 0.070 mg/m3of HDI. Those concentrations correspond to a range of aerosolphase concentrations from 0.5 ppb (V) to 10 ppb (V) and coverthe established threshold limit valve (TLV) value of 5 ppb (V).1.5 The quantification limit for the monomeric HDI is
10、 0.041g per mL, which corresponds to 0.003 mg/m3fora15Lsampled air volume. This value is equivalent to ten times thestandard deviation obtained from ten measurements carried outon a standard solution in contact with the PTFE filter whoseconcentration of 0.1 g/mL is close to the expected detectionlim
11、it.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 establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. See Section
12、 9 foradditional hazards.2. Referenced Documents2.1 ASTM Standards:3D1193 Specification for Reagent WaterD1356 Terminology Relating to Sampling and Analysis ofAtmospheresD1357 Practice for Planning the Sampling of the AmbientAtmosphereD5337 Practice for Flow Rate Calibration of PersonalSampling Pump
13、sD6562 Test Method for Determination of Gaseous Hexam-ethylene Diisocyanate (HDI) in Air with 9-(N-methylaminomethyl) Anthracene Method (MAMA) in theWorkplace1This test method is under the jurisdiction of ASTM Committee D22 on AirQuality and is the direct responsibility of Subcommittee D22.04 on Wor
14、kplace AirQuality.Current edition approved Oct. 1, 2011. Published October 2011. Originallyapproved in 2000. Last previous edition approved in 2006 as D6561 - 06. DOI:10.1520/D6561-06R11.2The sampling device for isocyanates is covered by a patent held by JacquesLesage et al, IRSST, 505 De Maisonneuv
15、e Blvd. West, Montreal, Quebec, Canada.If you are aware of an alternative to this patented item, please provide thisinformation to ASTM Headquarters. Your comments will receive careful consider-ation at a meeting of the responsible technical committee,1which you may attend.3For referenced ASTM stand
16、ards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, P
17、A 19428-2959, United States.2.2 Other Standard:4Sampling Guide for Air Contaminants in the Workplace3. Terminology3.1 For definitions of terms used in this test method, refer toTerminology D13564. Summary of Test Method4.1 Vapor and aerosol fractions are sampled simultaneouslyby using a segregating
18、sampling device. The aerosols arecollected on PTFE filter while the gaseous fraction is beingadsorbed on a second filter made of glass fiber, impregnatedwith a 9-(N-methylaminomethyl) anthracene (MAMA).4.2 The analysis of the monomer in the gaseous fraction isperformed separately in accordance with
19、the procedure de-scribed in Test Method D6562.4.3 Diisocyanates present as aerosols are collected on thePTFE filter and derivatized in a MOPIP solution (1, 2).5SeeFig. 1.4.3.1 The solution is then evaporated to dryness and redis-solved, using the acetic anhydride solution (see 8.11). Mono-meric and
20、oligomeric HDI are separated by using a reversedphase HPLC column, and detection is made by using an HPLCequipped with UV detection.4.4 Concentration of monomeric and oligomeric diisocya-nates contained in a sample is calculated by using an externalstandard of the monomeric HDI.5. Significance and U
21、se5.1 HDI is mostly used in the preparation of paints. For thelast 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 sensiti
22、zation, asthmatic bronchitis, andacute respiratory intoxication (3-6).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/m3for monomeric HDI (7). The Occupational Safety dual filt
23、er sampling system; hexameth-ylene diisocyanate; high-performance liquid chromatography;(methoxy-2phenyl-1) piperazine; sampling and analysis;workplace atmospheresREFERENCES(1) Lesage, J., and Perrault, G., A Charactrisation physique et chimiquede l=exposition des travailleurs aux isocyanates. Rappo
24、rt de recher-che, Institut de recherche en sant et en scurit du travail du Qubec.1989, Montral. Qubec.(2) Lesage, J., Goyer, N., Desjardins, F., Vincent, J.-Y., and Perrault, G.,“Workers Exposure to Isocyanates” American Industrial HygieneAssociation Journal, Vol 53, No. 2, (1992), pp. 146-153.(3) A
25、 Criteria for a Recommended Standard “Occupational Exposure toToluene Diisocyanate,” Department of Health, Education and Welfare,National Institute for Occupational Safety and Health, Cincinnati, OH,No. DHEW (NIOSH) 73-11022, 1973.(4) Woolrich, P.F., “Toxicology, Industrial Hygiene and Medical Contr
26、olof TDI, MDI and PMPPI,” American Industrial Hygiene AssociationJournal, Vol 43, 1981, pp. 8997.(5) Moller, D.R., et al, “Chronic Asthma Due to Toluene Diisocyanate,”Chest, Vol 90, No. 4, 1986, pp. 494-499.(6) Butcher, B.T., et al,“ Polyisocyanates and Their Prepolymers,”Asthma in the Workplace, Ch
27、ap. 20, edited by I. Leonard Bernstein,Moira Chan-Yeung, Jean-Luc Malo, and David I. Bernstein, Cincin-nati, Ohio, 1994, pp. 415-436.(7) Threshold Limit Values for Chemical Substances and Physical Agentsand Biological Exposure Indices, ACGIH, Cincinnati, Ohio, 1993.(8) Occupational Safety and Health
28、 Administration (OSHA):OSHAMethod 42: Diisocyanates, OSHA Analytical Laboratory, OrganicMethods Development Branch, Salt Lake City, Utah, 1989.(9) Lesage, J., and Perrault, G., “Sampling Device for Isocyanates,” U.S.Patent No. 4 961 916.(10) Occupational Safety and Health Administration (OSHA):Evalu
29、a-tion scheme methods that use filters as the collection medium,OSHA Technical Center, OSHA Analytical Methods Manuals, 2ndEd., Part 2, Salt Lake City, Utah, 1991.(11) Guide d8chantillonnage des contaminants de lair en milieu detravail, Institut de recherche en sant et en scurit du travail duQubec,
30、Montral (1999)FIG. 2 Means of the Z-Scores Obtained by Ten Laboratories After n$3 Participations to an Interlaboratory EvaluationTest MethodD6561D6561 06 (2011)5ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this sta
31、ndard. Users of this standard are expressly advised that determination of the validity 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 revi
32、ewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsib
33、le technical committee, which you may attend. If you feel that your comments have not 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 Co
34、nshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) 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/).D6561 06 (2011)6
