Designation: D1652 − 11´1

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 Department of Defense.

´1 NOTE—Editorial corrections were made throughout in May 2012.

1. Scope* 3.1.1 In the Manual Titration Method, the titration is with

1.1 This test method covers the procedure for manual and standard perchloric acid in the presence of an excess of
automatic titration of epoxy resins for the quantitative deter- tetraethylammonium bromide. Hydrogen bromide generated in
mination of the percent epoxide content from 0.1 to 26 % situ by the addition of perchloric acid to the quaternary
epoxide. ammonium halide rapidly opens the oxirane ring.
3.1.2 In the Automatic Titration Method, the reaction is
1.2 The values stated in SI units are to be regarded as the measuring the millivolt (MV) potential as perchloric acid is
standard. The values given in parentheses are for information added, which combines with the bromide to form the hydro-
only. bromic acid, which reacts with the epoxide group. As the
1.3 This standard does not purport to address all of the reaction progresses, the potential will gradually increase until
safety concerns, if any, associated with its use. It is the the reaction nears completion at which point the potential
responsibility of the user of this standard to establish appro- increases very quickly. The titrator measures the rate of the
priate safety and health practices and determine the applica- reaction by calculating the change in potential between per-
bility of regulatory limitations prior to use. For specific hazard chloric acid addition increments. When the change in potential
statements, see Section 6. begins to decrease, the titrator determines that the titration is
complete. The epoxide content is calculated using the reagent
2. Referenced Documents factor entered by the user during standardization, the weight of
2.1 ASTM Standards:2 the sample, and the volume of perchloric acid added during
D1193 Specification for Reagent Water titration.
2.2 Other Documents:
OSHA Regulations, 29 CFR paragraphs 1910.1000 and 4. Significance and Use
1910.12003 4.1 The epoxy content of epoxy resins is an important
variable in determining their reactivity and the properties of
3. Summary of Test Method coatings made from them. These test methods may be used to
3.1 The resin is dissolved in a suitable solvent and the determine the epoxy content of manufactured epoxy resins and
resulting solution is titrated with hydrogen bromide either confirm the stated epoxy content of purchased epoxy resins.
directly or in situ. The hydrogen bromide reacts stoichiometri-
cally with epoxy groups to form bromohydrins; therefore, the 5. Reagents
quantity of acid consumed is a measure of the epoxy content. 5.1 Purity of Reagents—Reagent grade chemicals shall be
used in all tests. Unless otherwise indicated, it is intended that
1
all reagents shall conform to the specifications of the Commit-
This test method is under the jurisdiction of ASTM Committee D01 on Paint
and Related Coatings, Materials, and Applications and is the direct responsibility of tee on Analytical Reagents of the American Chemical Society,
Subcommittee D01.33 on Polymers and Resins. where such specifications are available.4 Other grades may be
Current edition approved Nov. 1, 2011. Published January 2012. Originally used, provided it is first ascertained that the reagent is of
approved in 1969. Last previous edition approved in 2004 as D1652 – 04. DOI:
10.1520/D1652-11E01.
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.

*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
 D1652 − 11´1
sufficiently high purity to permit its use without lessening the 10. Standardization of 0.1 N Perchloric Acid Reagent
accuracy of the determination.
10.1 Standardization with Potassium Hydrogen Phthalate:
5.2 Purity of Water—Unless otherwise indicated, references 10.1.1 Dissolve 0.4 g of potassium hydrogen phthalate,
to water shall be understood to mean reagent water as defined weighed accurately to the nearest milligram, in 50 mL of
by Type II of Specification D1193. glacial acetic acid, and add 6 to 8 drops of crystal violet
indicator solution. Insert a clean stirring bar into the sample,
6. Hazards and adjust the magnetic stirrer to effect solution. Continue
6.1 Hydrogen bromide and glacial acetic acid are corrosive. agitation throughout the titration procedure. Titrate with per-
Chlorobenzene and chloroform are considered hazardous. In chloric acid reagent solution to the end point, which is a sharp
addition to other precautions, take care to avoid inhalation and change in color from blue to green, stabilize for at least 2 min.
skin or eye contact with these chemicals. Use goggles or a face 10.1.2 Calculate and record the perchloric acid reagent
shield, or both. Protect skin by use of suitable protective normality as follows:
clothing. All specimen preparations shall be done in a well
N 5 ~ W 3 1000! / ~ 204.2 3 V ! (1)
ventilated area, such as a fume hood.
6.2 Consult current OSHA Regulations, Supplier’s Material where:
Safety Data Sheets, and local regulations for all materials used N = normality of perchloric acid reagent,
in this test method. W = potassium hydrogen phthalate used, g, and
V = volume of perchloric acid reagent required to titrate
Manual Titration for Epoxy Content of Epoxy Resins the standard, mL.

7. Apparatus
10.2 Standardization with Potassium Hydrogen Phthalate:
7.1 Buret, closed-reservoir type, bottom filling, 25-mL with
1⁄10-mL division, or potentiometric automatic titrator.
10.2.1 Dissolve 0.25 to 0.40 g of the potassium hydrogen
phthalate accurately weighed to the nearest milligram into a 2
7.2 Erlenmeyer Flasks, 100-mL, 250-mL, and 500-mL. oz wide-mouth bottle or 100 mL disposable beaker. Add 40 to
7.3 Magnetic Stirrer, adjustable speed. 50 mL of glacial acetic acid. Insert a clean stirring bar into the
sample and adjust the magnetic stirrer to effect solution.
7.4 Magnetic Stirring Bars, polytetrafluoroethylene (PTFE) Continue agitation throughout the titration procedure.
coated.
10.2.2 Add 10 mL of tetraethylammonium bromide reagent
7.5 Pipets: and 6 to 8 drops of crystal violet indicator solution and titrate
7.5.1 Measuring Pipet, 25-mL. to a sharp blue-to-green end point with the perchloric acid
7.5.2 Volumetric Pipet, 50-mL. reagent solution. The end point should be stable for at least 30
7.6 Volumetric Flask, 1 L. s.
7.7 Bottle, 2 oz wide-mouth, or 100-mL disposable beaker, 10.2.3 Calculate and record the perchloric acid reagent
or equivalent. factor, F, as follows:
F 5 ~ W d 3 E ! /V (2)
8. Reagents
where:
8.1 Glacial Acetic Acid (Warning—See Section 6). Wd = potassium hydrogen phthalate standard used, g and
8.2 Tetraethylammonium Bromide, anhydrous crystals. E = epoxide of the potassium hydrogen phthalate stan-
8.3 Perchloric Acid (HClO4), 0.1 N in Glacial Acetic Acid dard used (normally 21.05), weight %.
(Warning—See Section 6).
11. Procedure
8.4 Acetic Anhydride (Warning—See Section 6).
11.1 Weigh the required amount of specimen into a 2-oz
8.5 Methylene Chloride (Warning—See Section 6).
disposable glass bottle or plastic beaker. The amount of
8.6 Crystal Violet Indicator, crystals. specimen weight used is dependent on the expected epoxide
8.7 Potassium Hydrogen Phthalate—(KHC8H4O4) primary equivalent weight (EEW) as follows:
standard grade. EEW Approximate Specimen Size, g
170–375 0.4
375–600 0.6
9. Reagent Preparation 600–1000 0.8
9.1 Tetraethylammonium Bromide Solution in Glacial Ace- 1000–1500 1.3
1500–2000 1.8
tic Acid (Warning—See Section 6): 2000–2500 2.3
9.1.1 Dissolve, with agitation at room temperature, 100 g of 2500–5000 2.8
tetraethylammonium bromide in 400 mL of glacial acetic acid. 11.2 Add 10 to 15 mL of methylene chloride to the
9.2 Crystal Violet Indicator Solution—Prepare 0.1 % solu- specimen. Insert a clean stirring bar and adjust the magnetic
tion of crystal violet indicator in glacial acetic acid stirrer to effect solution. Continue agitation through the titra-
(Warnings—See Section 6). tion procedure.

2
 D1652 − 11´1
11.3 Add 10 mL of tetraethylammonium bromide reagent 16. Reagent Preparation
and 6 to 8 drops of crystal violet indicator solution. Titrate with 16.1 Perchloric Acid (0.1 N Solution in Glacial Acetic Acid)
0.1 N perchloric acid reagent to a sharp blue to green end point (Warning —See Section 6.)—Prepare in the following manner
which is stable for at least 30 s. Record the volume of and sequence in order to avoid an excessive rise in tempera-
perchloric acid reagent used to titrate the specimen. ture.
16.1.1 Place approximately 250 mL of glacial acetic acid
12. Calculation
into a 1 L volumetric flask. Add 13 mL of 60 % perchloric acid
12.1 If 10.1 (Standardization of Potassium Hydrogen Phtha- and mix. Add 50 mL of acetic anhydride, dilute to the mark
late) is used for standardization, calculate weight percent with glacial acetic acid, and mix thoroughly.
epoxide, E, as follows: 16.1.2 Allow to stand at least 8 h for completion of reaction
E 5 4.3 3 V 3 N/W (3) between the acetic anhydride and water. A shorter time period
may be used if completion of the reaction is analytically
12.2 If 10.2 (Standardization of Potassium Hydrogen Phtha- verified.
late) is used for standardization, calculate the weight percent 16.2 Tetraethylammonium Bromide Solution in Glacial Ace-
epoxide, E, as follows: tic Acid (Warning—See Section 6):
E 5 F 3 V/W e (4) 16.2.1 Dissolve, with agitation at room temperature, 100 g
of tetraethylammonium bromide in 400 mL of glacial acetic
where: acid.
We = weight of epoxy resin specimen used, g.
17. Standardization of 0.1 N Perchloric Acid Reagent
12.3 Calculate the epoxy equivalent weight, WEEW, as 17.1 Standardization with Potassium Hydrogen Phthalate:
follows: 17.1.1 Dissolve 0.25 g of potassium hydrogen phthalate,
W EEW 5 43 3 100/E (5) weighed accurately to the nearest milligram, in 50 mL of
glacial acetic acid, and 15 mL 20 % TEAB solution. Titrate
where 43 = mol weight of the epoxy ring. with perchloric acid reagent solution.
17.1.2 Calculate and record the perchloric acid reagent
12.4 Calculate weight percent of oxirane oxygen, O, as normality as follows:
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
V = volume of perchloric acid reagent required to titrate
13.1 A liquid epoxy resin sample with approximately
the standard, mL.
24.1 % epoxide was tested by seven laboratories where ten
analysts obtained the following results:
18. Procedure
13.1.1 Repeatability—The difference between two results
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 %
18.3 Add the appropriate amount of sample to a sample cup.
relative.
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
sample. The method should prompt when to enter the sample
14.1 Automatic Titrator, equipped with a 10 mL burette and weight.
a pH electrode.
18.6 The titrator will automatically print out the results
14.2 A Four Place Analytical Balance. 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-
R2 5 R 3 C 3 0.1000/M (8)
cial acetic acid.
15.3 Methylene Chloride (MECL). where:
R2 = epoxide content,
15.4 Potassium Hydrogen Phthalate (KHP).

3
 D1652 − 11´1

R = actual mL perchloric acid used to reach equivalence 20.1.1 Repeatability—The difference between two results
point, obtained by the same analyst should not vary by more than
C = constant of 4.3 (see Note 2), and 1.1 % relative.
M = weight of the sample used. 20.1.2 Reproducibility—The difference between laborato-
NOTE 1—0.1000 is the normality of the perchloric acid. ries should no vary by more than 0.8 % relative.
NOTE 2—4.3 is the theoretical molecular weight of the epoxide ring, 43,
and it is adjusted to 4.3 for the calculation to percent epoxide.
21. Keywords
20. Precision
21.1 epoxide equivalent weight (EEW); liquid epoxy resin;
20.1 An epoxy resin sample, with 5.74 % epoxide, was oxirane; weight percent epoxide; weight per epoxy equivalent
tested by six laboratories in five different countries for % (WPE)
epoxide content and the following results were obtained:

SUMMARY OF CHANGES

Committee D01 has identified the location of selected changes to this standard since the last issue (D1652 - 04)
that may impact the use of this standard. (Approved November 1, 2011.)

(1) Updated 8.3.

(2) Deleted 9.1, 9.1.1, and 9.1.2 and renumbered subsequent
sections.

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned
in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk
of infringement of such rights, are entirely their own responsibility.

This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and
if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards
and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the
responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should
make your views known to the ASTM Committee on Standards, at the address shown below.

This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,
United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above
address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website
(www.astm.org). Permission rights to photocopy the standard may also be secured from the ASTM website (www.astm.org/
COPYRIGHT/).