Standard Test Method for Determination of 2,4-Toluene Diisocyanate (2,4-TDI) and 2,6-Toluene Diisocyanate (2,6-TDI) in Workplace Atmospheres (1-2 PP Method)

SIGNIFICANCE AND USE
Diisocyanates are used in the production of polyurethane foams, plastics, elastomers, surface coatings, and adhesives  (5,6). It has been estimated that the production of TDI will steadily increase during the future years.  
Diisocyanates are irritants to eyes, skin, and mucous membrane and are respiratory sensitizers. Chronic exposure to low concentrations of diisocyanates produces an allergic sensitization which may progress into asthmatic bronchitis (7,8).
The Occupational Safety and Health Administration (OSHA) has a permissible exposure limit for 2,4-TDI of 0.02 ppm or 0.14 mg/m3 as a ceiling limit (9). The American Conference of Governmental Industrial Hygienists (ACGIH) has a Threshold Limit Value (TLV) of 0.005 ppm or 0.036 mg/m3 and a short-term exposure limit (STEL) of 0.02 ppm or 0.14 mg/m3 (10). No exposure limits have been established for 2,6-TDI.
This proposed test method has been found satisfactory for measuring 2,4 and 2,6-TDI levels in the workplace.
SCOPE
1.1 This test method describes the determination of 2,4-toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate (2,6-TDI) in air samples collected from workplace atmospheres in a cassette containing a glass-fiber filter impregnated with 1-(2-pyridyl)piperazine (1-2 PP). This procedure is very effective for determining the vapor content of atmospheres. Atmospheres containing aerosols may produce low results.  
1.2 This test method uses a high-performance liquid chromatograph (HPLC) equipped with a fluorescence or an ultraviolet (UV) detector (1-4).  
1.3 The validated range of the test method, as written, is from 1.4 to 5.6 [mu]g of 2,4-TDI and 2,6-TDI which is equivalent to approximately 9.8 to 39 ppb for 2,4-TDI and 2,6-TDI based on a 20-L air sample. The HPLC method using an UV detector is capable of detecting 0.078 [mu]g of 2,4-TDI and 0.068 [mu]g of 2,6-TDI in a 4.0-mL solvent volume, which is equivalent to 0.55 ppb for 2,4-TDI and 0.48 ppb for 2,6-TDI based on a 20-L air sample.  
1.4 The isomers of 2,4-TDI, and 2,6-TDI, can be separated utilizing a reversed phase column for the HPLC method. Because industrial applications employ an isomeric mixture of 2,4- and 2,6-TDI, the ability to achieve this separation is important.  
1.5 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. See Section 9 for specific precautions.

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ASTM D5836-03 - Standard Test Method for Determination of 2,4-Toluene Diisocyanate (2,4-TDI) and 2,6-Toluene Diisocyanate (2,6-TDI) in Workplace Atmospheres (1-2 PP Method)
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation:D5836–03
Standard Test Method for
Determination of 2,4-Toluene Diisocyanate (2,4-TDI) and 2,6-
Toluene Diisocyanate (2,6-TDI) in Workplace Atmospheres
1
(1-2 PP Method)
This standard is issued under the fixed designation D 5836; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. See Section 9 for
1.1 This test method describes the determination of 2,4-
specific precautions.
toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate
(2,6-TDI) in air samples collected from workplace atmo-
2. Referenced Documents
spheres in a cassette containing a glass-fiber filter impregnated
4
2.1 ASTM Standards:
with 1-(2-pyridyl)piperazine (1-2 PP). This procedure is very
D 1193 Specification for Reagent Water
effective for determining the vapor content of atmospheres.
D 1356 Terminology Relating to Sampling and Analysis of
Atmospheres containing aerosols may produce low results.
Atmospheres
1.2 This test method uses a high-performance liquid chro-
D 1357 Practice for Planning the Sampling of the Ambient
matograph (HPLC) equipped with a fluorescence or an ultra-
,
2 3 Atmosphere
violet (UV) detector (1-4).
D 3686 Practice for Sampling Atmospheres to Collect Or-
1.3 The validated range of the test method, as written, is
ganic Compound Vapors (Activated Charcoal Tube Ad-
from 1.4 to 5.6 µg of 2,4-TDI and 2,6-TDI which is equivalent
sorption Method)
to approximately 9.8 to 39 ppb for 2,4-TDI and 2,6-TDI based
E 691 Practice for Conducting an Interlaboratory Study to
on a 20-Lair sample. The HPLC method using an UV detector
Determine the Precision of a Test Method
is capable of detecting 0.078 µg of 2,4-TDI and 0.068 µg of
2,6-TDI in a 4.0-mL solvent volume, which is equivalent to
3. Terminology
0.55ppbfor2,4-TDIand0.48ppbfor2,6-TDIbasedona20-L
3.1 For definitions of terms used in this test method, refer to
air sample.
Terminology D 1356.
1.4 The isomers of 2,4-TDI, and 2,6-TDI, can be separated
utilizing a reversed phase column for the HPLC method.
4. Summary of Test Method
Because industrial applications employ an isomeric mixture of
4.1 A known volume of air is drawn through a cassette
2,4- and 2,6-TDI, the ability to achieve this separation is
containing a glass-fiber filter impregnated with 1-(2-
important.
pyridyl)piperazine. The diisocyanate reacts with the secondary
1.5 This standard does not purport to address all of the
amine to form a urea derivative.
safety concerns, if any, associated with its use. It is the
4.2 Thecoatedglass-fiberfilterisextractedwithacetonitrile
responsibility of the user of this standard to establish appro-
(ACN) containing 10 % dimethyl sulfoxide (DMSO) and the
extract is analyzed by HPLC. The eluent is monitored with a
1
fluorescence detector (240-nm excitation, 370-nm emission
This test method is under the jurisdiction of ASTM Committee D22 on
Sampling and Analysis of Atmospheres and is the direct responsibility of Subcom-
cutoff filter) or a UV detector (254 nm).
mittee D22.04 on Workplace Atmospheres.
CurrenteditionapprovedOctober1,2003.PublishedDecember2003.Originally
approved in 1995. Last previous edition approved in 1995 as D 5836 - 95.
2
Validationdataandapreliminarydraftofthistestmethodwereprovidedbythe
4
Salt Lake Technical Center of the U.S. Dept. of Labor, Occupational Safety and For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Health Administration, Salt Lake City, UT. contactASTM Customer Service at service@astm.org. ForAnnual Book ofASTM
3
The boldface numbers in parentheses refer to the references at the end of this Standards volume information, refer to the standard’s Document Summary page on
test method. the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
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D5836–03
4.3 The amount of the urea derivative collected is deter- 7.2 Analytical Equipment:
mined by comparison of sample response (peak area integra- 7.2.1 Liquid Chromatograph, a high-performance liquid
tions or peak heights) to a standard calibration curve for the chromatograph (HPLC) equipped with a fluorescence detector
urea derivative. capable of monitoring 240-nm excitation and 370-nm cutoff or
4.4 The amount of diisocyanate is calculated from the a UV detector capable of monitoring 254-nm wavelength and
amount of urea determined in the analysis. a manual or automatic sample injector.
7.2.2 Liquid Chromatographic Column, an HPLC
...

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