ASTM D5836-08

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 (PEL) for 2,4-TDI of 0.02 ppm or 0.14 mg/m3 as a ceiling limit. There is no OSHA PEL for 2,6–TDI (9). The American Conference of Governmental Industrial Hygienists (ACGIH) has a time–weighted average (TWA) 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 for either 2,4–TDI, or 2,6–TDI, or for a mixture of 2,4– and 2,6–TDI(10).
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 cause TDI results to be underestimated.
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 μg 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 μg of 2,4-TDI and 0.068 μg 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 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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.

General Information

• Status: Historical
• Publication Date: 31-Mar-2008
• Technical Committee: D22 - Air Quality
• Drafting Committee: D22.04 - Workplace Air Quality

Relations

• Replaces: 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)
• Effective Date: 01-Apr-2008
• Replaced By: ASTM D5836-08(2013) - 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)
• Effective Date: 01-Apr-2013

Standards Content (Sample)

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 − 08
StandardTest 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 D5836; 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 (´) indicates an editorial change since the last revision or reapproval.
1. Scope 1.6 This standard does not purport to address all of the
safety concerns, if any, associated with its use. It is the
1.1 This test method describes the determination of 2,4-
responsibility of the user of this standard to establish appro-
toluene diisocyanate (2,4-TDI) and 2,6-toluene diisocyanate
priate safety and health practices and determine the applica-
(2,6-TDI) in air samples collected from workplace atmo-
bility of regulatory limitations prior to use. See Section 9 for
spheres in a cassette containing a glass-fiber filter impregnated
specific precautions.
with 1-(2-pyridyl)piperazine (1-2 PP). This procedure is very
effective for determining the vapor content of atmospheres.
2. Referenced Documents
Atmospheres containing aerosols may cause TDI results to be
4
underestimated. 2.1 ASTM Standards:
D1193 Specification for Reagent Water
1.2 This test method uses a high-performance liquid chro-
D1356 Terminology Relating to Sampling and Analysis of
matograph (HPLC) equipped with a fluorescence or an ultra-
Atmospheres
2,3
violet (UV) detector (1-4).
D1357 Practice for Planning the Sampling of the Ambient
1.3 The validated range of the test method, as written, is Atmosphere
from 1.4 to 5.6 µg of 2,4-TDI and 2,6-TDI which is equivalent
D3686 Practice for Sampling Atmospheres to Collect Or-
to approximately 9.8 to 39 ppb for 2,4-TDI and 2,6-TDI based ganic Compound Vapors (Activated Charcoal Tube Ad-
on a 20-Lair sample.The HPLC method using an UVdetector
sorption Method)
is capable of detecting 0.078 µg of 2,4-TDI and 0.068 µg of E691 Practice for Conducting an Interlaboratory Study to
2,6-TDI in a 4.0-mL solvent volume, which is equivalent to
Determine the Precision of a Test Method
0.55ppbfor2,4-TDIand0.48ppbfor2,6-TDIbasedona20-L
air sample.
3. Terminology
1.4 The isomers of 2,4-TDI, and 2,6-TDI, can be separated 3.1 For definitions of terms used in this test method, refer to
utilizing a reversed phase column for the HPLC method.
Terminology D1356.
Because industrial applications employ an isomeric mixture of
2,4- and 2,6-TDI, the ability to achieve this separation is
4. Summary of Test Method
important.
4.1 A known volume of air is drawn through a cassette
1.5 The values stated in SI units are to be regarded as containing a glass-fiber filter impregnated with 1-(2-
standard. No other units of measurement are included in this
pyridyl)piperazine. The diisocyanate reacts with the secondary
standard.
amine to form a urea derivative.
4.2 Thecoatedglass-fiberfilterisextractedwithacetonitrile
(ACN) containing 10 % dimethyl sulfoxide (DMSO) and the
1
This test method is under the jurisdiction of ASTM Committee D22 on Air
extract is analyzed by HPLC. The eluent is monitored with a
Quality and is the direct responsibility of Subcommittee D22.04 on Workplace Air
fluorescence detector (240-nm excitation, 370-nm emission
Quality.
cutoff filter) or a UV detector (254 nm).
Current edition approved April 1, 2008. Published May 2008. Originally
approved in 1995. Last previous edition approved in 2003 as D5836 - 03. DOI:
10.1520/D5836-08.
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 [e-mail]. 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
1

---------------------- Page: 1 ----------------------
D5836 − 08
4.3 The amount of the urea derivative collected is deter- 7.1.3 Cassette, plastic holders of the three-piece personal
mined by comparison of sample response (peak area integra- monitor type, that accept filters of 37-mm diameter. Number
tions or peak heights) to a standard calibration curve for the the cassette for identification.
urea derivative. 7.1.4 Cellulose Backup Pad, sized to fit the cassette (7.1.3).
4.4 The amount of diisocyanate is calculated from the 7.2 Analytical Equipment:
amount of
...

This document is not anASTM standard and is intended only to provide the user of anASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation:D5836–03 Designation: D 5836 – 08
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
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. cause TDI results to be underestimated.
1.2 Thistestmethodusesahigh-performanceliquidchromatograph(HPLC)equippedwithafluorescenceoranultraviolet(UV)
2,3
detector (1-4).
1.3 The validated range of the test method, as written, is from 1.4 to 5.6 µg 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 µg of 2,4-TDI and 0.068 µg 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
1.5 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.6 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.
2. Referenced Documents
4
2.1 ASTM Standards:
D 1193 Specification for Reagent Water
D 1356 Terminology Relating to Sampling and Analysis of Atmospheres
D 1357 Practice for Planning the Sampling of the Ambient Atmosphere
D 3686 Practice for Sampling Atmospheres to Collect Organic Compound Vapors (Activated Charcoal Tube Adsorption
Method)
E 691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
3. Terminology
3.1 For definitions of terms used in this test method, refer to Terminology D 1356.
4. Summary of Test Method
4.1 Aknown volume of air is drawn through a cassette containing a glass-fiber filter impregnated with 1-(2-pyridyl)piperazine.
The diisocyanate reacts with the secondary amine to form a urea derivative.
4.2 The coated glass-fiber filter is extracted with acetonitrile (ACN) containing 10 % dimethyl sulfoxide (DMSO) and the
1
This test method is under the jurisdiction of ASTM Committee D22 on Sampling and Analysis of Atmospheres Air Quality and is the direct responsibility of
Subcommittee D22.04 on Workplace Atmospheres. Air Quality .
Current edition approved OctoberApril 1, 2003.2008. Published December 2003.May 2008. Originally approved in 1995. Last previous edition approved in 19952003 as
D5836-95.D 5836 - 03.
2
Validation data and a preliminary draft of this test method were provided by the Salt Lake Technical Center of the U.S. Dept. of Labor, Occupational Safety and Health
Administration, Salt Lake City, UT.
3
The boldface numbers in parentheses refer to the references at the end of this test method.
4
ForreferencedASTMstandards,visittheASTMwebsite,www.astm.org,[e-mail]ards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
1

---------------------- Page: 1 ----------------------
D5836–08
extract is analyzed by HPLC. The eluent is monitored with a fluorescence detector (240-nm excitation, 370-nm emission cutoff
filter) or a UV detector (254 nm).
4.3 Theamountoftheureaderivativecollectedisdeterminedbycomparisonofsampleresponse(peakareaintegrationsorpeak
heights
...