ASTM D4875-05

Standard Test Methods of Polyurethane Raw Materials: Determination of the Polymerized Ethylene Oxide Content of Polyether Polyols

SIGNIFICANCE AND USE
Measurements of EO content correlate with polyol reactivity (as related to primary hydroxyl content), linearity of foam rise, and the hydrophilicity of the polyol and final product.
Statistical data suggest that the  13C NMR test method is the preferred method for measuring low levels (less than 10 %) of polymerized EO in polyols.
The  1H and  13C NMR test methods give different results which are highly correlated. The equation of the linear regression is:
The standard deviation of the regression is 0.49 and the multiple R-square is 0.9990.
SCOPE
1.1 Test Method A—Proton Nuclear Magnetic Resonance Spectroscopy (1H NMR) measures polymerized ethylene oxide (EO) in ethylene oxide-propylene oxide polyethers used in flexible urethane foams and nonfoams. It is suitable for diols made from the commonly used initators and containing EO percentages above five. For triols initiated with glycerin and trimethylol propane, an uncorrected EO value is obtained since both initiators have protons that contribute to the EO measurement.
1.2 Test Method B—Carbon-13 Nuclear Magnetic Resonance Spectroscopy (13C NMR) measures the polymerized EO content of ethylene oxide-propylene oxide polyethers used in flexible urethane foams and nonfoams. It is suitable for diols and triols made from the commonly used initiators and containing EO percentages above five.
Note 1—There are no equivalent ISO standards.
1.3 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.

General Information

• Status: Historical
• Publication Date: 30-Jun-2005
• ICS: 83.080.20 - Thermoplastic materials
• Technical Committee: D20 - Plastics
• Drafting Committee: D20.22 - Cellular Materials - Plastics and Elastomers

Relations

• Replaces: ASTM D4875-99 - Standard Test Methods of Polyurethane Raw Materials Determination of the Polymerized Ethylene Oxide Content of Polyether Polyols
• Effective Date: 01-Jul-2005
• Replaced By: ASTM D4875-11 - Standard Test Methods of Polyurethane Raw Materials: Determination of the Polymerized Ethylene Oxide Content of Polyether Polyols
• Effective Date: 01-Apr-2011

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:D4875–05
Standard Test Methods of
Polyurethane Raw Materials: Determination of the
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Polymerized Ethylene Oxide Content of Polyether Polyols
This standard is issued under the fixed designation D4875; 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. Terminology
1.1 Test Method A—Proton Nuclear Magnetic Resonance 3.1 Definitions—Terminology in these test methods follows
1
Spectroscopy( HNMR)measurespolymerizedethyleneoxide the standard terminology defined in Terminology D883 and
(EO) in ethylene oxide-propylene oxide polyethers used in Practice E386.
flexible urethane foams and nonfoams. It is suitable for diols 3.2 Definitions of Terms Specific to This Standard:
made from the commonly used initators and containing EO 3.2.1 heteric polyol, n—a polyether polyol in which ethyl-
percentages above five. For triols initiated with glycerin and ene oxide and propylene oxide units are randomly arranged.
trimethylolpropane,anuncorrectedEOvalueisobtainedsince 3.2.2 initiator, n—asubstancewithwhichethyleneoxideor
both initiators have protons that contribute to the EO measure- propylene oxide reacts to form a polyether polyol.
ment. 3.2.2.1 Discussion—One initiator unit is incorporated into
1.2 Test Method B—Carbon-13 Nuclear Magnetic Reso- each polymer or oligomer molecule.
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nance Spectroscopy ( C NMR) measures the polymerized EO
4. Summary of Test Methods
content of ethylene oxide-propylene oxide polyethers used in
1
flexible urethane foams and nonfoams. It is suitable for diols 4.1 Test Method A—The H NMR spectra of polyether
polyols show two groups of resonance peaks corresponding to
and triols made from the commonly used initiators and
containing EO percentages above five. the methyl protons of propylene oxide (PO) and to the
methylene and methine protons of EO and PO. The EO peak
NOTE 1—There are no equivalent ISO standards.
areaisobtainedbysubtractingtheareaofthePOmethylpeaks
1.3 This standard does not purport to address all of the
from the area of the methylene and methine peaks. Initiators
safety concerns, if any, associated with its use. It is the
other than glycols of EO and PO give systematic errors (see
responsibility of the user of this standard to establish appro-
Note 2).
priate safety and health practices and determine the applica-
NOTE 2—The initiator error can be estimated by calculating the
bility of regulatory limitations prior to use.
theoretical contribution of initiator protons to the EO and PO peak areas.
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2. Referenced Documents
4.2 Test Method B—The C NMR spectra of polyethers
2
contain multiple resonances arising from initiator, alkoxide,
2.1 ASTM Standards:
alkoxide sequencing, and end-group distribution. EO content
D883 Terminology Relating to Plastics
can be determined relative to PO or relative to PO and triol
E386 Practice for Data Presentation Relating to High-
initiator.Intheformer,theareaoftheEOpeaksisratioedtothe
ResolutionNuclearMagneticResonance(NMR)Spectros-
total area of alkoxide methylene and methine carbons. In the
copy
latter, the area of the EO peaks is ratioed to the total area of
E691 Practice for Conducting an Interlaboratory Study to
alkoxide methylene and methine carbons and two initiator
Determine the Precision of a Test Method
carbons. This test method describes the determination of EO
relative to PO only.
1
These test methods are under the jurisdiction of ASTM Committee D20 on
Plastics and is the direct responsibility of Subcommittee D20.22 on Cellular
5. Significance and Use
Plastics.
Current edition approved July 1, 2005. Published August 2005. Originally 5.1 Measurements of EO content correlate with polyol
approved in 1988. Last previous edition approved in 1999 as D4875-99. DOI:
reactivity (as related to primary hydroxyl content), linearity of
10.1520/D4875-05.
foam rise, and the hydrophilicity of the polyol and final
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
product.
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website.
*A Summary of Changes section appears at the end of this standard.
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D4875–05
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5.2 Statistical data suggest that the C NMR test method is
Spectral width 10 ppm
Acquisition time 4 s
thepreferredmethodformeasuringlowlevels(lessthan10%)
Data points 8K
of polymerized EO in polyols.
Number of transients 128
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