ASTM D5932-2008(2013) 9375 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

1、Designation: D5932 08 (Reapproved 2013)Standard 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 numb

2、er 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.1. Scope1

3、.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 performed with a segregat-ing device.2,3The gaseous fraction is collected

4、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 fluorescence detectors.1.4 The analysis of the aerosol fraction is perfo

5、rmed 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, which corresponds to concentrations of 0.002 to0.077 mg/m3of TDI based on a 1

6、5-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 The values stated in SI units are to be regarded as thestandard.1.8 Thi

7、s 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.2. Referenced Document

8、s2.1 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 Air Contaminants in the Workplace63. Terminology3.1 For definitions of te

9、rms 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.4.2 Gaseous and aerosol fraction are sampled simultane-ously with a two filter loaded cassette.2The aerosol is collected1This test method is under

10、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, 2013. Published April 2013. Originallyapproved in 1996. Last previous edition approved in 2008 as D5932 - 08. DOI:10.1520/D5932-08R13

11、.2The sampling device for isocyanates is covered 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 o

12、n Standards, ASTMInternational Headquarters, 100 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 O

13、mega SpecialtyDivision, Eighty-Four, PA.3The American 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

14、such patent rights, and the risk of infringement 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 Servi

15、ce at serviceastm.org. For Annual Book of ASTMStandards 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 AST

16、M International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1on the first filter made of polytetrafluoroethylene (PTFE), thegaseous counterpart being adsorbed on the second filter madeof glass fiber (GFF) impregnated with MAMA.4.3 The analysis of the monomer a

17、nd 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 to form a urea derivative (3,4), as shown below.4.5 Desorption is done wit

18、h 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 emission) (5).4.7 2,4- and 2,6-TDI urea derivatives are separated usingreverse

19、d 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 thesamples is calculated by using an external standard of theappropriate urea de

20、rivative.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 Diisocyanates and polyisocyanates are irritants to skin,eyes, and mucous membrane

21、s. 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 Limit Valu-eTime Weighted Average (TLVTWA) of 0.036 mg/m3witha Short-Term

22、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 and 0.005 ppm (V) or 0.036 mg/m3as atime-weighted average (11).5.5 Monito

23、ring 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 compatiblewith the duration of many industrial processes and its lowquantif

24、ication 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 both physical states to beobtained, thus helping in the selection of ventila

25、tion 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 reagentimpregnated on the GFF can affect the sampling efficiency.This includes

26、 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 to eliminate an interference.6.3 A field blank double-filter sampling sys

27、tem 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 Equipment:7.1.1 Personal Sampling Pump, capable of sampling 1.0L/min or less for

28、 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 pad.2Theglass fiber filter is impregnated with an amount of MAMA inthe ran

29、ge 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 254-nm excita-tion) and an automatic or manual sample injector.7.2.2 Liqui

30、d 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 anequivalent column.7.2.3 Electronic Integrator, an electronic integrator or anyother

31、 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 standards.An automaticpipet, or any equivalent method, is required for samplepre

32、paration.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.7.2.8 Magnetic Stirrer, a magnetic stirrer or any otherequivalent method.D5932 08

33、(2013)27.2.9 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, vacuum filtration systemwith 0.45-m porosity nylon filters or any equivalent m

34、ethod 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 for injection.7.2.14 Bottle, amber-colored bottle with cap and PTFE-coated se

35、ptum 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 the specificationsof the Committee on Analytical Reagents of the AmericanC

36、hemical 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 determination.8.2 Purity of WaterUnless otherwise indicated, water shallbe reagent

37、 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) to acidify to pH = 3.0. Filter the buffer undervacuum with a 0.45-m porosit

38、y 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 Helium (He)High purity, 99.999 %.8.9 9-(N-Methylaminomethyl) Anthracene (MAM

39、A), (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 2,4-Toluene Diisocyanate (2,4-TDI)(F.W. 174.2)97 % purity.8.13 2,6-Toluene

40、 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 in a volumetric flask.Place the 2,4-TDI solution in an additional flask.8.1

41、4.2 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 temperature of25C to the MAMA solution (8.14.2), stirring continuously for60 to 90 mi

42、n.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 recrystallize and filter as in 8.14.5.8.14.7 The compound has a melting point of 270C.

43、8.14.8 Confirm that the urea derivative with the massspectrum, the 2,4-TDI-MAMA has a molecular weight of610.8 g.8.14.9 The conversion factor for TDIU to TDI is 0.2823.8.15 2,6-Toluene Diisocyanate 9-(N-Methylaminomethyl)Anthracene Derivative (2,6-TDIU)Same preparation as 2,4-TDIU but use 2,6-TDI. T

44、he 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 MSD sheets for reagents.9.2 PrecautionAvoid exposure to diisocyanate standard

45、s.Sample and standard preparations should be done in anefficient operating hood. For remedial statement see Ref (13).9.3 PrecautionAvoid skin contact with all solvents andisocyanates.9.4 Wear safety glasses at all times and other laboratoryprotective equipment as necessary.10. Sampling10.1 Refer to

46、the Practices D1357 for general informationon sampling.10.2 This proposed test method recommends sampling inaccordance with the method described in Ref (12,14) of thistest method.10.3 Equip the worker, whose exposure is to be evaluated,with a filter holder connected to a belt-supported samplingpump.

47、 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 Specifications , AmericanChemical Society, Washington, DC. For suggestions on the t

48、esting 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 Convention, Inc. (USPC), Rockville,MD.8Whatman No. 40, ashless filter paper has bee

49、n found satisfactory for thispurpose.D5932 08 (2013)310.4 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, place it in a glass jar, and close the jar. Thisfilter is used to analyze the aero