ASTM D5932-2008(2013)e1 2049 Standard Test Method for Determination of 2 4-Toluene Diisocyanate (2 4-TDI) and 2 6-Toluene Diisocyanate (2 6-TDI) in Air (with 9-(N-Methylaminomethyl.pdf

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1、Designation: D5932 08 (Reapproved 2013)1Standard Test Method forDetermination of 2,4-Toluene Diisocyanate (2,4-TDI) and 2,6-Toluene Diisocyanate (2,6-TDI) in Air (with 9-(N-Methylaminomethyl) Anthracene Method) (MAMA) in theWorkplace1This standard is issued under the fixed designation D5932; the num

2、ber immediately following 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.1NOTEEdi

3、torial corrections were made to 8.14.8 and 11.2.1 in March 2015.1. Scope1.1 This test method covers the determination of gaseous2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocya-nate (2,6-TDI) in air samples collected from workplace andambient atmospheres.1.2 Differential air sampling is p

4、erformed with a segregat-ing device.2,3The gaseous 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 ultraviolet (UV) and

5、 fluorescence detectors.1.4 The analysis of the aerosol fraction is performed sepa-rately as described in Ref (1).41.5 The range of application of this test method, utilizingUV and a fluorescence detector, is validated for 0.029 to 1.16g of monomer 2,4- and 2,6-TDI/2.0 mL of desorptionsolution, whic

6、h corresponds to concentrations of 0.002 to0.077 mg/m3of TDI based on a 15-L air sample. Thiscorresponds to 0.28 to 11 ppb(V) and brackets the establishedTLV value of 5 ppb(v).1.6 A field blank sampling system is used to check thepossibility of contamination during the entire sampling andanalysis.1.

7、7 The values stated in SI units are to be regarded as thestandard.1.8 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 app

8、lica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:5D1193 Specification for Reagent WaterD1356 Terminology Relating to Sampling and Analysis ofAtmospheresD1357 Practice for Planning the Sampling of the AmbientAtmosphere2.2 Other Documents:Sampling Guide for

9、Air Contaminants in the Workplace63. Terminology3.1 For definitions of terms used in this test method, refer toTerminology D1356.4. Summary of Test Method4.1 A known volume of air is drawn through a segregatingsampling device.1This test method is under the jurisdiction of ASTM Committee D22 on AirQu

10、ality and is the direct responsibility of Subcommittee D22.04 on Workplace AirQuality.Current edition approved April 1, 2013. Published April 2013. Originallyapproved in 1996. Last previous edition approved in 2008 as D5932 08. DOI:10.1520/D5932-08R13E01.2The sampling device for isocyanates is cover

11、ed by a patent held by JacquesLesage et al, IRSST, 505 De Maisonneuve Blvd West, Montreal, Quebec, Canada.Interested parties are invited to submit information regarding the identification ofacceptable alternatives to this patented item to the Committee on Standards, ASTMInternational Headquarters, 1

12、00 Barr Harbor Dr., PO Box C700, WestConshohocken, PA 19428. Your comments will receive careful consideration at ameeting of the committee responsible, which you may attend. This sampling deviceis currently commercially available under license from SKC Omega SpecialtyDivision, Eighty-Four, PA.3The A

13、merican Society for Testing and Materials takes no position respectingthe validity of any patent rights asserted in connection with any item mentioned inthis standard. Users of this standard are expressly advised that determination of thevalidity of any such patent rights, and the risk of infringeme

14、nt of such rights, areentirely their own responsibility.4The boldface numbers in parentheses refer to the list of references at the end ofthis test method.5For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTM

15、Standards volume information, refer to the standards Document Summary page onthe ASTM website.6Available from Institut de Recherche en Sant et en Scurit du Travail duQubec, Laboratory Services and Expertise Department, Montreal, IRSST, 2005.Copyright ASTM International, 100 Barr Harbor Drive, PO Box

16、 C700, West Conshohocken, PA 19428-2959. United States14.2 Gaseous and aerosol fraction are sampled simultane-ously with a two filter loaded cassette.2The aerosol is collectedon the first filter made of polytetrafluoroethylene (PTFE), thegaseous counterpart being adsorbed on the second filter madeof

17、 glass fiber (GFF) impregnated with MAMA.4.3 The analysis of the monomer and oligomer in theaerosol fraction is performed separately in accordance with theprocedure described in Ref (1,2).4.4 The diisocyanate present as a gas reacts with thesecondary amine function of the MAMA impregnated on theGFF

18、to form a urea derivative (3,4), as shown below.4.5 Desorption is done with dimethylformamide 67 % con-taining 33 % mobile phase (70 % acetonitrile, 30 % buffer).4.6 The resulting solution is analyzed by HPLC with twodetectors in series: UV (254 nm) and fluorescence (254-nmexcitation and 412-nm emis

19、sion) (5).4.7 2,4- and 2,6-TDI urea derivatives are separated usingreversed phase HPLC column.4.8 A complete calibration curve, covering the range ofapplication of the test method, was obtained to determine thelinearity of the method (see 1.5).4.9 Concentration of urea derivative contained in thesam

20、ples is calculated by using an external standard of theappropriate urea derivative.5. Significance and Use5.1 TDI is used mostly in the preparation of rigid andsemi-rigid foams and adhesives.5.2 Isocyanate use has been growing for the last 20 yearsand the industrial need is still growing.5.3 Diisocy

21、anates and polyisocyanates are irritants to skin,eyes, and mucous membranes. They are recognized to causerespiratory allergic sensitization, asthmatic bronchitis, andacute respiratory intoxication (6-9).5.4 The American Conference of Governmental IndustrialHygienists (ACGIH) has adopted a Threshold

22、Limit Valu-eTime Weighted Average (TLVTWA) of 0.036 mg/m3witha Short-Term Exposure Limit (STEL) of 0.14 mg/m3for2,4-TDI (10). The Occupational Safety and Health Adminis-tration of the U.S. Department of Labor (OSHA) has apermissible exposure limit of 0.02 ppm(V) or 0.14 mg/m3ofTDI as a ceiling limit

23、 and 0.005 ppm (V) or 0.036 mg/m3as atime-weighted average (11).5.5 Monitoring of respiratory and other problems related todiisocyanates and polyisocyanates is aided through the utiliza-tion of this test method, due to its sensitivity and low volumerequirements (15 L). Its short sampling times are c

24、ompatiblewith the duration of many industrial processes and its lowquantification limit also suits the concentrations often found inthe working area.5.6 The segregating sampling device pertaining to thisproposed test method physically separates gas and aerosolallowing isocyanate concentrations in bo

25、th physical states to beobtained, thus helping in the selection of ventilation systemsand personal protection.5.7 This test method is used to measure gaseous concentra-tions of 2,4- and 2,6-TDI in air for workplace and ambientatmospheres.6. Interference6.1 Any substance that can react with MAMA reag

26、entimpregnated on the GFF can affect the sampling efficiency.This includes strong oxidizing agents.6.2 Any compound that has the same retention time as theTDIU derivative and gives the same UV/fluorescence detectorresponse factor ratio can cause interference. Chromatographicconditions can be changed

27、 to eliminate an interference.6.3 A field blank double-filter sampling system is used tocheck contamination during the combined sampling,transportation, and sample storage process. A laboratory blankis used to check contamination occurring during the analyticalprocess.7. Apparatus7.1 Sampling Equipm

28、ent:7.1.1 Personal Sampling Pump, capable of sampling 1.0L/min or less for 4 h.7.1.2 Double Filter Sampling Device, 37 mm in diameter,three-piece personal monitor, plastic holder loaded with aPTFE filter close to the mouth, followed by a glass fiber filterimpregnated with MAMA and a plastic back-up

29、pad.2Theglass fiber filter is impregnated with an amount of MAMA inthe range of 0.07 to 0.25 mg.7.1.3 Flow Measuring Device.7.2 Analytical Equipment:7.2.1 Liquid Chromatograph, a high-performance liquidchromatograph equipped with UV (254-nm wavelength) andfluorescence detectors (412-nm emission and

30、254-nm excita-tion) and an automatic or manual sample injector.7.2.2 Liquid Chromatographic Column, an HPLC stainlesssteel column, capable of separating the urea derivatives. Thisproposed method recommends a 150- by 4.6-mm internaldiameter stainless steel column packed with 0.5-m C18, or anequivalen

31、t column.7.2.3 Electronic Integrator, an electronic integrator or anyother effective method for determining peak areas.7.2.4 Analytical Balance, an analytical balance capable ofweighing to 0.001 g.7.2.5 Microsyringes and Pipets, microsyringes are used inthe preparation of urea derivatives and standa

32、rds.An automaticpipet, or any equivalent method, is required for samplepreparation.7.2.6 pH Meter, a pH meter or any equivalent devicecapable of assaying a pH range between 2.5 and 7.7.2.7 Specialized Flasks, three-necked flask and an addi-tional flask for the synthesis of the TDIU standard.D5932 08

33、 (2013)127.2.8 Magnetic Stirrer, a magnetic stirrer or any otherequivalent method.7.2.9 Glass Jars, 30 mL, and lid, capable of receiving37-mm filters, used for desorption of samples.7.2.10 Reciprocating Shaker, a reciprocating shaker or anyother equivalent device.7.2.11 Vacuum Filtration System, vac

34、uum filtration systemwith 0.45-m porosity nylon filters or any equivalent method todegas the mobile phase.7.2.12 Syringe Operated Filter Unit, syringes with polyvi-nylidene fluoride 0.22-m porosity filter unit, or any equivalentmethod.7.2.13 Injection Vials, 1.5-mL vials with PTFE-coated sep-tums fo

35、r injection.7.2.14 Bottle, amber-colored bottle with cap and PTFE-coated septum for conservation of stock and standard solutionsof 2,4- and 2,6-TDIU or any equivalent method.8. Reagents and Materials8.1 Purity of ReagentsReagent grade chemicals shall beused in all tests.All reagents shall conform to

36、 the specificationsof the Committee on Analytical Reagents of the AmericanChemical Society where such specifications are available.7Other grades may be used, provided it is first ascertained thatthe reagent is of sufficiently high purity to permit its usewithout lessening the accuracy of the determi

37、nation.8.2 Purity of WaterUnless otherwise indicated, water shallbe reagent water as defined by Type 2 of Specification D1193,HPLC grade.8.3 Acetonitrile (CH3CN)HPLC grade.8.4 BufferPlace 30 mL of triethylamine (8.16) in waterand dilute to 1 L in a volumetric flask. Add phosphoric acid(H3PO4)(8.11)

38、to acidify to pH = 3.0. Filter the buffer undervacuum with a 0.45-m porosity filter.8.5 Desorption SolutionA solvent mixture of dimethylfor-mamide (8.7) and mobile phase (8.10) in the percentage of 67and 33 (v/v), respectively.8.6 DichloromethaneReagent grade.8.7 DimethylformamideReagent grade.8.8 H

39、elium (He)High purity, 99.999 %.8.9 9-(N-Methylaminomethyl) Anthracene (MAMA), (F.W.221.31) 99 % purity.8.10 Mobile PhaseA solvent mixture of acetonitrile(CH3CN) (8.3) and buffer (8.4) in the percentage of 70 and 30(v/v), respectively, suitably degassed.8.11 Phosphoric Acid (H3PO4)Reagent grade.8.12

40、 2,4-Toluene Diisocyanate (2,4-TDI)(F.W. 174.2)97 % purity.8.13 2,6-Toluene Diisocyanate (2,6-TDI)(F.W. 174.2)97 % purity.8.14 2,4-Toluene Diisocyanate 9-(N-Methylaminomethyl)Anthracene Derivative (2,4-TDIU).8.14.1 Add 320 L of 2,4-TDI (8.13) (2 mmoles) to dichlo-romethane (8.6) and dilute to 25 mL

41、in a volumetric flask.Place the 2,4-TDI solution in an additional flask.8.14.2 Dilute approximately 1.3 g (6 mmoles) of 9-(N-methylaminomethyl) anthracene (MAMA) (8.9)in50mLofdichloromethane (8.6). Place the MAMA solution in a three-necked flask.8.14.3 Add the TDI (8.13) drop by drop at a temperatur

42、e of25C to the MAMA solution (8.14.2), stirring continuously for60 to 90 min.8.14.4 Cool the resulting solution on crushed ice.8.14.5 Filter on a medium speed ashless filter paper8or anyequivalent device.8.14.6 Dissolve the precipitate in hot dichloromethane (8.6).Place in an ice bath to recrystalli

43、ze and filter as in 8.14.5.8.14.7 The compound has a melting point of 270C.8.14.8 Confirm that the urea derivative with the massspectrum, the 2,4-TDI-MAMA has a molecular weight of616.75 g.8.14.9 The conversion factor for TDIU to TDI is 0.2823.8.15 2,6-Toluene Diisocyanate 9-(N-Methylaminomethyl)Ant

44、hracene Derivative (2,6-TDIU)Same preparation as 2,4-TDIU but use 2,6-TDI. The compound starts to show decom-position at 275C.8.16 TriethylaminePurity 98 % min.9. Hazards9.1 WarningDiisocyanates are potentially hazardouschemicals and extremely reactive. Warning on compressed gascylinders. Refer to M

45、SD sheets for reagents.9.2 PrecautionAvoid exposure to diisocyanate standards.Sample and standard preparations should be done in anefficient operating hood. For remedial statement see Ref (12).9.3 PrecautionAvoid skin contact with all solvents andisocyanates.9.4 Wear safety glasses at all times and

46、other laboratoryprotective equipment as necessary.10. Sampling10.1 Refer to the Practices D1357 for general informationon sampling.10.2 This proposed test method recommends sampling inaccordance with the method described in Ref (13,14) of thistest method.10.3 Equip the worker, whose exposure is to b

47、e evaluated,with a filter holder connected to a belt-supported samplingpump. Place the filter, holder pointing downward, in thebreathing zone of the worker. Draw air through the samplingdevice and collect 15 L at a rate of approximately 1.0 L/min.7Reagent Chemicals, American Chemical Society Specifi

48、cations, AmericanChemical Society, Washington, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Conventi

49、on, Inc. (USPC), Rockville,MD.8Whatman No. 40, ashless filter paper has been found satisfactory for thispurpose.D5932 08 (2013)1310.4 For stationary monitoring, use a tripod or any othersupport to locate the sampler in a general room area at a heightequivalent to the breathing zone.10.5 Open the field blanks in the environment to be sampledand immediately close them. Treat field blanks in the samemanner as samples. Submit at least one field blank with eachset of samples.10.6 Once the sampling is done, open the cassette, withdrawthe PTFE filter,