Standard Test Method for Polyurethane Raw Materials: Determination of Acidity in Moderate to High Acidity Aromatic Isocyanates

SIGNIFICANCE AND USE
5.1 This test method can be used for research or for quality control to characterize aromatic isocyanates and prepolymers of moderate to high acidity. Acidity correlates with performance in some polyurethane systems.
SCOPE
1.1 This test method determines the acidity, expressed as parts per million (ppm) of HCl, in aromatic isocyanate samples of greater than 100–ppm acidity. The test method is applicable to products derived from toluene diisocyanate and methylene-bis-(4–phenylisocyanate) (see Note 1).
Note 1: This test method is equivalent to ISO 14898, Test Method A.  
1.2 This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.

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31-Jan-2024
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ASTM D6099-24 - Standard Test Method for Polyurethane Raw Materials: Determination of Acidity in Moderate to High Acidity Aromatic Isocyanates
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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: D6099 − 24
Standard Test Method for
Polyurethane Raw Materials: Determination of Acidity in
1
Moderate to High Acidity Aromatic Isocyanates
This standard is issued under the fixed designation D6099; 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* 3. Terminology
1.1 This test method determines the acidity, expressed as 3.1 Definitions—Terms used in this test method are in
parts per million (ppm) of HCl, in aromatic isocyanate samples accordance with Terminology D883, unless otherwise speci-
of greater than 100–ppm acidity. The test method is applicable fied. For terms relating to precision and bias and associated
to products derived from toluene diisocyanate and methylene- issues, the terms used in this standard are defined in accordance
bis-(4–phenylisocyanate) (see Note 1). with Terminology E456.
3.2 Definitions of Terms Specific to This Standard:
NOTE 1—This test method is equivalent to ISO 14898, Test Method A.
3.2.1 acidity, n—the acid strength of a sample expressed in
1.2 This international standard was developed in accor-
ppm HCl.
dance with internationally recognized principles on standard-
ization established in the Decision on Principles for the
4. Summary of Test Method
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
4.1 The isocyanate is mixed with an excess of methanol and
Barriers to Trade (TBT) Committee. a cosolvent. Additional acid is released into the solvent system
during urethane formation. The acid is titrated potentiometri-
2. Referenced Documents
cally with methanolic KOH, and the acidity present in the
2
isocyanate sample is calculated from the titer.
2.1 ASTM Standards:
D883 Terminology Relating to Plastics
5. Significance and Use
E180 Practice for Determining the Precision of ASTM
Methods for Analysis and Testing of Industrial and Spe-
5.1 This test method can be used for research or for quality
3
cialty Chemicals (Withdrawn 2009) control to characterize aromatic isocyanates and prepolymers
E456 Terminology Relating to Quality and Statistics
of moderate to high acidity. Acidity correlates with perfor-
E691 Practice for Conducting an Interlaboratory Study to mance in some polyurethane systems.
Determine the Precision of a Test Method
E2935 Practice for Evaluating Equivalence of Two Testing 6. Apparatus
Processes
6.1 250-mL Beakers.
2.2 ISO Standards:
6.2 50-mL Pipet or Repipet, Class A volumetric.
ISO 14898 Plastics—Aromatic isocyanates for use in the
4
6.3 100-mL Pipet or Repipet, Class A volumetric.
production of polyurethane—Determination of acidity
6.4 Automatic Titration Equipment, capable of inflection
detection and stirring the sample while, titrating, such as:
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics 6.4.1 Commercially-available Automatic Titration
and is the direct responsibility of Subcommittee D20.22 on Cellular Materials -
Apparatus,
Plastics and Elastomers.
6.4.2 Reference Electrode, with saturated LiCl/ethanol so-
Current edition approved Feb. 1, 2024. Published February 2024. Originally
lution in both chambers.
approved in 1997. Last previous edition approved in 2018 as D6099 - 18. DOI:
10.1520/D6099-24.
6.4.3 pH Glass Electrode, (see Note 2).
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
NOTE 2—A combination pH electrode with internal reference also may
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on be used.
the ASTM website.
6.5 Magnetic Stirrer.
3
The last approved version of this historical standard is referenced on
www.astm.org.
6.6 Stir Bars.
4
Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
4th Floor, New York, NY 10036, http://www.ansi.org. 6.7 Watch Glasses.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D6099 − 24
TABLE 1 Round–Robin Acidity Data in Accordance With Practice
6.8 Analytical Balance, capable of weighing to the nearest 1
E180
mg.
Values, ppm HCl
A B C D E F
Average S S r R n df
7. Reagents and Materials r R
Rubinate M 189 5.8 13.5 16.2 37.9 11 23
7.1 0.02 N KOH in Methanol—1.32 g KOH pellets (85 %
Mondur MR 41
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM 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: D6099 − 18 D6099 − 24
Standard Test Method for
Polyurethane Raw Materials: Determination of Acidity in
1
Moderate to High Acidity Aromatic Isocyanates
This standard is issued under the fixed designation D6099; 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*
1.1 This test method determines the acidity, expressed as parts per million (ppm) of HCl, in aromatic isocyanate samples of greater
than 100–ppm acidity. The test method is applicable to products derived from toluene diisocyanate and methylene-bis-
(4–phenylisocyanate) (see Note 1).
NOTE 1—This test method is equivalent to ISO 14898, Test Method A.
1.2 This international standard was developed in accordance with internationally recognized principles on standardization
established in the Decision on Principles for the Development of International Standards, Guides and Recommendations issued
by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
2. Referenced Documents
2
2.1 ASTM Standards:
D883 Terminology Relating to Plastics
E180 Practice for Determining the Precision of ASTM Methods for Analysis and Testing of Industrial and Specialty Chemicals
3
(Withdrawn 2009)
E456 Terminology Relating to Quality and Statistics
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
E2935 Practice for Evaluating Equivalence of Two Testing Processes
2.2 ISO Standards:
4
ISO 14898 Plastics—Aromatic isocyanates for use in the production of polyurethane—Determination of acidity
3. Terminology
3.1 Definitions—Terms used in this test method are in accordance with Terminology D883, unless otherwise specified. For terms
relating to precision and bias and associated issues, the terms used in this standard are defined in accordance with Terminology
E456.
3.2 Definitions of Terms Specific to This Standard:
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics and is the direct responsibility of Subcommittee D20.22 on Cellular Materials - Plastics
and Elastomers.
Current edition approved Aug. 1, 2018Feb. 1, 2024. Published August 2018February 2024. Originally approved in 1997. Last previous edition approved in 20132018 as
D6099 - 13.D6099 - 18. DOI: 10.1520/D6099-18.10.1520/D6099-24.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
3
The last approved version of this historical standard is referenced on www.astm.org.
4
Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036, http://www.ansi.org.
*A Summary of Changes section appears at the end of this standard
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
D6099 − 24
3.2.1 acidity, n—the acid strength of a sample expressed in ppm HCl.
4. Summary of Test Method
4.1 The isocyanate is mixed with an excess of methanol and a cosolvent. Additional acid is released into the solvent system during
urethane formation. The acid is titrated potentiometrically with methanolic KOH, and the acidity present in the isocyanate sample
is calculated from the titer.
5. Significance and Use
5.1 This test method can be used for research or for quality control to characterize aromatic isocyanates and prepolymers of
moderate to high acidity. Acidity correlates with performance in some polyurethane systems.
6. Apparatus
6.1 250-mL Beakers.
6.2 50-mL Pipet or Repipet, Class A volumetric.
6.3 100-mL Pipet or Repipet, Class A volumetric.
6.4 Automatic Titration Equipment, capable of inflection detection and stirring the sample while, titrating, such as:
6.4.1 Commerically-availableCommercially-available Automatic Titration Apparatus,
6.4.2 Reference Electrode, with saturated LiCl/ethanol solution in both chambers.
6.4.3 pH Glass Electrode, (see Note 2).
NOTE 2—A combination pH electrode with internal reference also may be used.
6.5 Magnetic Stirrer.
6.6 Stir Bars.
6.7 Watch Glasses.
6.8 Analytical Balance, capable of weighing to the nearest 1 mg.
7. Reagents and Materials
7.1 0.02 N KOH in Methanol—1.
...

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