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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Historical
Publication Date
31-Jul-2018
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ASTM D6099-18 - 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 − 18
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.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 3.2 Definitions of Terms Specific to This Standard:
3.2.1 acidity, n—the acid strength of a sample expressed in
1.1 This test method determines the acidity, expressed as
ppm HCl.
partspermillion(ppm)ofHCl,inaromaticisocyanatesamples
of greater than 100–ppm acidity.The test method is applicable
4. Summary of Test Method
to products derived from toluene diisocyanate and methylene-
4.1 Theisocyanateismixedwithanexcessofmethanoland
bis-(4–phenylisocyanate) (see Note 1).
a cosolvent.Additional acid is released into the solvent system
NOTE 1—This test method is equivalent to ISO 14898, Test MethodA.
during urethane formation. The acid is titrated potentiometri-
1.2 This international standard was developed in accor-
cally with methanolic KOH, and the acidity present in the
dance with internationally recognized principles on standard-
isocyanate sample is calculated from the titer.
ization established in the Decision on Principles for the
5. Significance and Use
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
5.1 This test method can be used for research or for quality
Barriers to Trade (TBT) Committee.
control to characterize aromatic isocyanates and prepolymers
of moderate to high acidity. Acidity correlates with perfor-
2. Referenced Documents
mance in some polyurethane systems.
2
2.1 ASTM Standards:
6. Apparatus
D883Terminology Relating to Plastics
E180Practice for Determining the Precision of ASTM
6.1 250-mL Beakers.
Methods for Analysis and Testing of Industrial and Spe-
6.2 50-mL Pipet or Repipet, Class A volumetric.
3
cialty Chemicals (Withdrawn 2009)
6.3 100-mL Pipet or Repipet, Class A volumetric.
E691Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
6.4 Automatic Titration Equipment, capable of inflection
2.2 ISO Standards:
detection and stirring the sample while, titrating, such as:
ISO 14898Plastics—Aromatic isocyanates for use in the
6.4.1 Commerically-available Automatic Titration
4
production of polyurethane—Determination of acidity
Apparatus,
6.4.2 Reference Electrode, with saturated LiCl/ethanol so-
3. Terminology
lution in both chambers.
3.1 Definitions—Terms used in this test method are in 6.4.3 pH Glass Electrode, (see Note 2).
accordance with Terminology D883.
NOTE 2—Acombination pH electrode with internal reference also may
be used.
1
ThistestmethodisunderthejurisdictionofASTMCommitteeD20onPlastics
6.5 Magnetic Stirrer.
and is the direct responsibility of Subcommittee D20.22 on Cellular Materials -
6.6 Stir Bars.
Plastics and Elastomers.
Current edition approved Aug. 1, 2018. Published August 2018. Originally
6.7 Watch Glasses.
approved in 1997. Last previous edition approved in 2013 as D6099-13. DOI:
10.1520/D6099-18.
6.8 Analytical Balance,capableofweighingtothenearest1
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
mg.
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
7. Reagents and Materials
the ASTM website.
3
The last approved version of this historical standard is referenced on
7.1 0.02 N KOH in Methanol—1.32 g KOH pellets (85%
www.astm.org.
4
KOH)/1000mLmethanol,standardizedwithpotassiumhydro-
Available fromAmerican National Standards Institute (ANSI), 25 W. 43rd St.,
4th Floor, New York, NY 10036, http://www.ansi.org. gen phthalate (KHP).
*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 − 18
TABLE 1 Round–Robin Acidity Data in Accordance With Practice
7.2 Tolueneor1,2,4–Trichlorobenzene(TCB),driedfor24h
E180
over molecular sieves.
Values, ppm HCl
7.3 Anhydrous Methanol. A B C D E F
Average S S r R n df
r R
Rubinate M 189 5.8 13.5 16.2 37.9 11 23
Mondur MR 414 3.4 27.5 9.5 76.9 11 20
8. Sampling
A
S = within-laboratory standard deviation of the replicates.
r
B
8.1 Since organic isocyanates react with atmospheric
S = between-labo
...

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 − 13 D6099 − 18
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)
E691 Practice for Conducting an Interlaboratory Study to Determine the Precision of a Test Method
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.
3.2 Definitions of Terms Specific to This Standard:
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.
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 Sept. 1, 2013Aug. 1, 2018. Published September 2013August 2018. Originally approved in 1997. Last previous edition approved in 20082013
as D6099 - 08.D6099 - 13. DOI: 10.1520/D6099-13.10.1520/D6099-18.
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 − 18
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-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—1.32 g KOH pellets (85 % KOH)/1000 mL methanol, standardized with potassium hydrogen
phthalate (KHP).
7.2 Toluene or 1,2,4–Trichlorobenzene (TCB), dried for 24 h over molecular sieves.
7.3 Anhydrous Methanol.
8. Sampling
8.1 Since organic isocyanates react with atmospheric moisture, take special precautions in
...

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: D6099 − 18
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* 3.2 Definitions of Terms Specific to This Standard:
3.2.1 acidity, n—the acid strength of a sample expressed in
1.1 This test method determines the acidity, expressed as
ppm HCl.
parts per million (ppm) of HCl, in aromatic isocyanate samples
of greater than 100–ppm acidity. The test method is applicable
4. Summary of Test Method
to products derived from toluene diisocyanate and methylene-
4.1 The isocyanate is mixed with an excess of methanol and
bis-(4–phenylisocyanate) (see Note 1).
a cosolvent. Additional acid is released into the solvent system
NOTE 1—This test method is equivalent to ISO 14898, Test Method A.
during urethane formation. The acid is titrated potentiometri-
1.2 This international standard was developed in accor-
cally with methanolic KOH, and the acidity present in the
dance with internationally recognized principles on standard-
isocyanate sample is calculated from the titer.
ization established in the Decision on Principles for the
5. Significance and Use
Development of International Standards, Guides and Recom-
mendations issued by the World Trade Organization Technical
5.1 This test method can be used for research or for quality
Barriers to Trade (TBT) Committee.
control to characterize aromatic isocyanates and prepolymers
of moderate to high acidity. Acidity correlates with perfor-
2. Referenced Documents
mance in some polyurethane systems.
2
2.1 ASTM Standards:
6. Apparatus
D883 Terminology Relating to Plastics
E180 Practice for Determining the Precision of ASTM
6.1 250-mL Beakers.
Methods for Analysis and Testing of Industrial and Spe-
6.2 50-mL Pipet or Repipet, Class A volumetric.
3
cialty Chemicals (Withdrawn 2009)
6.3 100-mL Pipet or Repipet, Class A volumetric.
E691 Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
6.4 Automatic Titration Equipment, capable of inflection
2.2 ISO Standards:
detection and stirring the sample while, titrating, such as:
ISO 14898 Plastics—Aromatic isocyanates for use in the
6.4.1 Commerically-available Automatic Titration
4
production of polyurethane—Determination of acidity
Apparatus,
6.4.2 Reference Electrode, with saturated LiCl/ethanol so-
3. Terminology
lution in both chambers.
3.1 Definitions—Terms used in this test method are in
6.4.3 pH Glass Electrode, (see Note 2).
accordance with Terminology D883.
NOTE 2—A combination pH electrode with internal reference also may
be used.
1
This test method is under the jurisdiction of ASTM Committee D20 on Plastics 6.5 Magnetic Stirrer.
and is the direct responsibility of Subcommittee D20.22 on Cellular Materials -
6.6 Stir Bars.
Plastics and Elastomers.
Current edition approved Aug. 1, 2018. Published August 2018. Originally
6.7 Watch Glasses.
approved in 1997. Last previous edition approved in 2013 as D6099 - 13. DOI:
10.1520/D6099-18.
6.8 Analytical Balance, capable of weighing to the nearest 1
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
mg.
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
7. Reagents and Materials
the ASTM website.
3
The last approved version of this historical standard is referenced on
7.1 0.02 N KOH in Methanol—1.32 g KOH pellets (85 %
www.astm.org.
4 KOH)/1000 mL methanol, standardized with potassium hydro-
Available from American National Standards Institute (ANSI), 25 W. 43rd St.,
4th Floor, New York, NY 10036, http://www.ansi.org. gen phthalate (KHP).
*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 − 18
TABLE 1 Round–Robin Acidity Data in Accordance With Practice
7.2 Toluene or 1,2,4–Trichlorobenzene (TCB), dried for 24 h
E180
over molecular sieves.
Values, ppm HCl
7.3 Anhydrous Methanol. A B C D E F
Average S S r R n df
r R
Rubinate M 189 5.8 13.5 16.2 37.9 11 23
Mondur MR 414 3.4 27.5 9.5 76.9 11 20
8. Sampling
A
S = within-laboratory standard deviation of the replicates.
r
B
8.1 Since organic isocyanates react with atmospheric
S = between-laboratory standard deviation of the average.
R
C
r = within-laboratory repeatability limi
...

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