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: D1652 − 11 (Reapproved 2019)

Standard Test Method for

Epoxy Content of Epoxy Resins1
This standard is issued under the fixed designation D1652; 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.
This standard has been approved for use by agencies of the U.S. Department of Defense.

1. Scope directly or in situ. The hydrogen bromide reacts stoichiometri-

1.1 This test method covers the procedure for manual and cally with epoxy groups to form bromohydrins; therefore, the
automatic titration of epoxy resins for the quantitative deter- quantity of acid consumed is a measure of the epoxy content.
mination of the percent epoxide content from 0.1 to 26 % 3.1.1 In the Manual Titration Method, the titration is with
epoxide. standard perchloric acid in the presence of an excess of
tetraethylammonium bromide. Hydrogen bromide generated in
1.2 The values stated in SI units are to be regarded as the situ by the addition of perchloric acid to the quaternary
standard. The values given in parentheses are for information ammonium halide rapidly opens the oxirane ring.
only. 3.1.2 In the Automatic Titration Method, the reaction is
1.3 This standard does not purport to address all of the measuring the millivolt (MV) potential as perchloric acid is
safety concerns, if any, associated with its use. It is the added, which combines with the bromide to form the hydro-
responsibility of the user of this standard to establish appro- bromic acid, which reacts with the epoxide group. As the
priate safety, health, and environmental practices and deter- reaction progresses, the potential will gradually increase until
mine the applicability of regulatory limitations prior to use. the reaction nears completion at which point the potential
For specific hazard statements, see Section 6. increases very quickly. The titrator measures the rate of the
1.4 This international standard was developed in accor- reaction by calculating the change in potential between per-
dance with internationally recognized principles on standard- chloric acid addition increments. When the change in potential
ization established in the Decision on Principles for the begins to decrease, the titrator determines that the titration is
Development of International Standards, Guides and Recom- complete. The epoxide content is calculated using the reagent
mendations issued by the World Trade Organization Technical factor entered by the user during standardization, the weight of
Barriers to Trade (TBT) Committee. the sample, and the volume of perchloric acid added during
titration.
2. Referenced Documents
2.1 ASTM Standards:2 4. Significance and Use
D1193 Specification for Reagent Water 4.1 The epoxy content of epoxy resins is an important
2.2 Other Documents: variable in determining their reactivity and the properties of
OSHA Regulations, 29 CFR paragraphs 1910.1000 and coatings made from them. These test methods may be used to
1910.12003 determine the epoxy content of manufactured epoxy resins and
3. Summary of Test Method confirm the stated epoxy content of purchased epoxy resins.
3.1 The resin is dissolved in a suitable solvent and the 5. Reagents
resulting solution is titrated with hydrogen bromide either
5.1 Purity of Reagents—Reagent grade chemicals shall be
1
This test method is under the jurisdiction of ASTM Committee D01 on Paint used in all tests. Unless otherwise indicated, it is intended that
and Related Coatings, Materials, and Applications and is the direct responsibility of all reagents shall conform to the specifications of the Commit-
Subcommittee D01.33 on Polymers and Resins. tee on Analytical Reagents of the American Chemical Society,
Current edition approved June 1, 2019. Published June 2019. Originally
approved in 1969. Last previous edition approved in 2011 as D1652 – 11ɛ1. DOI:
where such specifications are available.4 Other grades may be
10.1520/D1652-11R19.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
4
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM Reagent Chemicals, American Chemical Society Specifications, American
Standards volume information, refer to the standard’s Document Summary page on Chemical Society, Washington, DC. For suggestions on the testing of reagents not
the ASTM website. listed by the American Chemical Society, see Analar Standards for Laboratory
3
Available from U.S. Government Printing Office Superintendent of Documents, Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
732 N. Capitol St., NW, Mail Stop: SDE, Washington, DC 20401, http:// and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
www.access.gpo.gov. MD.

Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States

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 D1652 − 11 (2019)
used, provided it is first ascertained that the reagent is of 10. Standardization of 0.1 N Perchloric Acid Reagent
sufficiently high purity to permit its use without lessening the 10.1 Standardization with Potassium Hydrogen Phthalate:
accuracy of the determination. 10.1.1 Dissolve 0.4 g of potassium hydrogen phthalate,
5.2 Purity of Water—Unless otherwise indicated, references weighed accurately to the nearest milligram, in 50 mL of
to water shall be understood to mean reagent water as defined glacial acetic acid, and add 6 to 8 drops of crystal violet
by Type II of Specification D1193. indicator solution. Insert a clean stirring bar into the sample,
and adjust the magnetic stirrer to effect solution. Continue
6. Hazards agitation throughout the titration procedure. Titrate with per-
6.1 Hydrogen bromide and glacial acetic acid are corrosive. chloric acid reagent solution to the end point, which is a sharp
Chlorobenzene and chloroform are considered hazardous. In change in color from blue to green, stabilize for at least 2 min.
addition to other precautions, take care to avoid inhalation and 10.1.2 Calculate and record the perchloric acid reagent
skin or eye contact with these chemicals. Use goggles or a face normality as follows:
shield, or both. Protect skin by use of suitable protective N 5 ~ W 3 1000! / ~ 204.2 3 V ! (1)
clothing. All specimen preparations shall be done in a well
ventilated area, such as a fume hood. where:
6.2 Consult current OSHA Regulations, Supplier’s Material N = normality of perchloric acid reagent,
Safety Data Sheets, and local regulations for all materials used W = potassium hydrogen phthalate used, g, and
V = volume of perchloric acid reagent required to titrate
in this test method.
the standard, mL.
Manual Titration for Epoxy Content of Epoxy Resins 10.2 Standardization with Potassium Hydrogen Phthalate:
10.2.1 Dissolve 0.25 to 0.40 g of the potassium hydrogen
7. Apparatus
phthalate accurately weighed to the nearest milligram into a 2
7.1 Buret, closed-reservoir type, bottom filling, 25-mL with oz wide-mouth bottle or 100 mL disposable beaker. Add 40 to
⁄ -mL division, or potentiometric automatic titrator.
1 10
50 mL of glacial acetic acid. Insert a clean stirring bar into the
7.2 Erlenmeyer Flasks, 100-mL, 250-mL, and 500-mL. sample and adjust the magnetic stirrer to effect solution.
Continue agitation throughout the titration procedure.
7.3 Magnetic Stirrer, adjustable speed.
10.2.2 Add 10 mL of tetraethylammonium bromide reagent
7.4 Magnetic Stirring Bars, polytetrafluoroethylene (PTFE) and 6 to 8 drops of crystal violet indicator solution and titrate
coated. to a sharp blue-to-green end point with the perchloric acid
7.5 Pipets: reagent solution. The end point should be stable for at least 30
7.5.1 Measuring Pipet, 25-mL. s.
7.5.2 Volumetric Pipet, 50-mL. 10.2.3 Calculate and record the perchloric acid reagent
factor, F, as follows:
7.6 Volumetric Flask, 1 L.
F 5 ~ W d 3 E ! /V (2)
7.7 Bottle, 2 oz wide-mouth, or 100-mL disposable beaker,
or equivalent. where:
Wd = potassium hydrogen phthalate standard used, g and
8. Reagents E = epoxide of the potassium hydrogen phthalate standard
8.1 Glacial Acetic Acid (Warning—See Section 6). used (normally 21.05), weight %.
8.2 Tetraethylammonium Bromide, anhydrous crystals.
11. Procedure
8.3 Perchloric Acid (HClO4), 0.1 N in Glacial Acetic Acid (
Warning—See Section 6). 11.1 Weigh the required amount of specimen into a 2-oz
disposable glass bottle or plastic beaker. The amount of
8.4 Acetic Anhydride (Warning—See Section 6). specimen weight used is dependent on the expected epoxide
8.5 Methylene Chloride (Warning—See Section 6). equivalent weight (EEW) as follows:
8.6 Crystal Violet Indicator, crystals. EEW Approximate Specimen Size, g
170–375 0.4
8.7 Potassium Hydrogen Phthalate—(KHC8H4O4) primary 375–600 0.6
standard grade. 600–1000 0.8
1000–1500 1.3
1500–2000 1.8
9. Reagent Preparation 2000–2500 2.3
9.1 Tetraethylammonium Bromide Solution in Glacial Ace- 2500–5000 2.8
tic Acid (Warning—See Section 6): 11.2 Add 10 to 15 mL of methylene chloride to the
9.1.1 Dissolve, with agitation at room temperature, 100 g of specimen. Insert a clean stirring bar and adjust the magnetic
tetraethylammonium bromide in 400 mL of glacial acetic acid. stirrer to effect solution. Continue agitation through the titra-
9.2 Crystal Violet Indicator Solution—Prepare 0.1 % solu- tion procedure.
tion of crystal violet indicator in glacial acetic acid 11.3 Add 10 mL of tetraethylammonium bromide reagent
(Warnings—See Section 6). and 6 to 8 drops of crystal violet indicator solution. Titrate with

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 D1652 − 11 (2019)
0.1 N perchloric acid reagent to a sharp blue to green end point 16.1.1 Place approximately 250 mL of glacial acetic acid
which is stable for at least 30 s. Record the volume of into a 1 L volumetric flask. Add 13 mL of 60 % perchloric acid
perchloric acid reagent used to titrate the specimen. and mix. Add 50 mL of acetic anhydride, dilute to the mark
with glacial acetic acid, and mix thoroughly.
12. Calculation 16.1.2 Allow to stand at least 8 h for completion of reaction
12.1 If 10.1 (Standardization of Potassium Hydrogen Phtha- between the acetic anhydride and water. A shorter time period
late) is used for standardization, calculate weight percent may be used if completion of the reaction is analytically
epoxide, E, as follows: verified.
E 5 4.3 3 V 3 N/W (3) 16.2 Tetraethylammonium Bromide Solution in Glacial Ace-
12.2 If 10.2 (Standardization of Potassium Hydrogen Phtha- tic Acid (Warning—See Section 6):
late) is used for standardization, calculate the weight percent 16.2.1 Dissolve, with agitation at room temperature, 100 g
epoxide, E, as follows: of tetraethylammonium bromide in 400 mL of glacial acetic
acid.
E 5 F 3 V/W e (4)

where: 17. Standardization of 0.1 N Perchloric Acid Reagent

We = weight of epoxy resin specimen used, g. 17.1 Standardization with Potassium Hydrogen Phthalate:
17.1.1 Dissolve 0.25 g of potassium hydrogen phthalate,
12.3 Calculate the epoxy equivalent weight, WEEW, as
weighed accurately to the nearest milligram, in 50 mL of
follows:
glacial acetic acid, and 15 mL 20 % TEAB solution. Titrate
W EEW 5 43 3 100/E (5) with perchloric acid reagent solution.
where 43 = mol weight of the epoxy ring. 17.1.2 Calculate and record the perchloric acid reagent
normality as follows:
12.4 Calculate weight percent of oxirane oxygen, O, as
follows: N 5 ~ W 3 1000! / ~ 204.2 3 V ! (7)

O 5 16/43 3 E 5 1.6 3 V 3 N/W (6) where:

N = normality of perchloric acid reagent,
13. Precision W = potassium hydrogen phthalate used, g, and
13.1 A liquid epoxy resin sample with approximately V = volume of perchloric acid reagent required to titrate
24.1 % epoxide was tested by seven laboratories where ten the standard, mL.
analysts obtained the following results:
13.1.1 Repeatability—The difference between two results 18. Procedure
obtained by the same analyst should not vary by more than 18.1 Fill burette with 0.1 N perchloric acid solution in
1.22 % relative. glacial acetic acid.
13.1.2 Reproducibility—The difference between two results, 18.2 Flush all titrator lines to assure no air bubbles are
each the mean of two determinations obtained by analysts in present.
different laboratories should not vary by more than 2.97 %
relative. 18.3 Add the appropriate amount of sample to a sample cup.
18.4 Add 30 mL of MECL and 15 mL of TEAB to the
Automatic Titration Method sample.
14. Apparatus 18.5 Select the correct method on the titrator and run the
14.1 Automatic Titrator, equipped with a 10 mL burette and sample. The method should prompt when to enter the sample
a pH electrode. weight.
14.2 A Four Place Analytical Balance. 18.6 The titrator will automatically print out the results
using the formula in Section 19.
15. Reagents and Materials
19. Calculation
15.1 Perchloric Acid, 0.1N in glacial acetic acid.
19.1 Calculate:
15.2 Tetraethylammonium Bromide (TEAB), solution in gla-
cial acetic acid. R2 5 R 3 C 3 0.1000/M (8)

15.3 Methylene Chloride (MECL). where:

15.4 Potassium Hydrogen Phthalate (KHP). R2 = epoxide content,
R = actual mL perchloric acid used to reach equivalence
16. Reagent Preparation point,
C = constant of 4.3 (see Note 2), and
16.1 Perchloric Acid (0.1 N Solution in Glacial Acetic Acid) M = weight of the sample used.
(Warning —See Section 6.)—Prepare in the following manner NOTE 1—0.1000 is the normality of the perchloric acid.
and sequence in order to avoid an excessive rise in tempera- NOTE 2—4.3 is the theoretical molecular weight of the epoxide ring, 43,
ture. and it is adjusted to 4.3 for the calculation to percent epoxide.

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 D1652 − 11 (2019)
20. Precision 20.1.2 Reproducibility—The difference between laborato-
20.1 An epoxy resin sample, with 5.74 % epoxide, was ries should no vary by more than 0.8 % relative.
tested by six laboratories in five different countries for %
epoxide content and the following results were obtained: 21. Keywords
20.1.1 Repeatability—The difference between two results 21.1 epoxide equivalent weight (EEW); liquid epoxy resin;
obtained by the same analyst should not vary by more than oxirane; weight percent epoxide; weight per epoxy equivalent
1.1 % relative. (WPE)

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