Designation: D 1652 – 97

AMERICAN SOCIETY FOR TESTING AND MATERIALS

100 Barr Harbor Dr., West Conshohocken, PA 19428
Reprinted from the Annual Book of ASTM Standards. Copyright ASTM

Standard Test Methods for

Epoxy Content of Epoxy Resins1
This standard is issued under the fixed designation D 1652; 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 (e) 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. Scope confirm the stated epoxy content of purchased epoxy resins.

1.1 These test methods cover the quantitative determination 5. Reagents
of the epoxy content of epoxy resins.
1.2 This standard does not purport to address all of the 5.1 Purity of Reagents—Reagent grade chemicals shall be
safety concerns, if any, associated with its use. It is the used in all tests. Unless otherwise indicated, it is intended that
responsibility of the user of this standard to establish appro- all reagents shall conform to the specifications of the Commit-
priate safety and health practices and determine the applica- tee on Analytical Reagents of the American Chemical Society,
bility of regulatory limitations prior to use. For specific hazard where such specifications are available.4 Other grades may be
statements, see Section 6. used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
2. Referenced Documents accuracy of the determination.
2.1 ASTM Standards: 5.2 Purity of Water—Unless otherwise indicated, references
D 1193 Specification for Reagent Water2 to water shall be understood to mean reagent water as defined
E 200 Practice for Preparation, Standardization, and Stor- by Type II of Specification D 1193.
age of Standard Solutions for Chemical Analysis3
6. Hazards
3. Summary of Test Method 6.1 Hydrogen bromide and glacial acetic acid are corrosive.
3.1 The resin is dissolved in a suitable solvent and the Chlorobenzene and chloroform are considered hazardous. In
resulting solution is titrated with hydrogen bromide either addition to other precautions, take care to avoid inhalation and
directly or in situ. The hydrogen bromide reacts stoichiometri- skin or eye contact with these chemicals. Use goggles or a face
cally with epoxy groups to form bromohydrins; therefore, the shield, or both. Protect skin by use of suitable protective
quantity of acid consumed is a measure of the epoxy content. clothing. All specimen preparations shall be done in a well
3.1.1 In Test Method A, the titration is direct with a standard ventilated area, such as a fume hood.
solution of hydrogen bromide in glacial acetic acid.
TEST METHOD A
3.1.2 In Test Method B, the titration is with standard
perchloric acid in the presence of an excess of tetraethylam- 7. Apparatus
monium bromide. Hydrogen bromide generated in situ by the 7.1 Buret, closed-reservoir type. The buret tip should be
addition of perchloric acid to the quaternary ammonium halide fitted with a rubber stopper of proper size to fit the neck of the
rapidly opens the oxirane ring. Erlenmeyer flask and the stopper should have an additional
4. Significance and Use small hole to permit escape of replaced air during titration.
7.2 Magnetic Stirrer, adjustable speed.
4.1 The epoxy content of epoxy resins is an important
7.3 Magnetic Stirring Bars, polytetrafluoroethylene (PTFE)
variable in determining their reactivity and the properties of
coated.
coatings made from them. These test methods may be used to
determine the epoxy content of manufactured epoxy resins and 8. Reagents and Materials
8.1 Chlorobenzene (Warning—See Section 6).
1
These test methods are under the jurisdiction of ASTM Committee D-1 on Paint
4
and Related Coatings, Materials, and Applications and are the direct responsibility Reagent Chemicals, American Chemical Society Specifications, American
of Subcommittee D01.33 on Polymers and Resins. Chemical Society, Washington, DC. For suggestions on the testing of reagents not
Current edition approved June 10, 1997. Published October 1997. Originally listed by the American Chemical Society, see Analar Standards for Laboratory
published as D 1652 – 59 T. Last previous edition D 1652 – 90 (1996). Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
2
Annual Book of ASTM Standards, Vol 11.01. and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
3
Annual Book of ASTM Standards, Vol 15.05. MD.

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 D 1652
8.2 Chloroform-Chlorobenzene Mixture (1+1) (Warning— B 5 HBr solution used for titration of the blank, mL, and
See Section 6). W 5 specimen used, g.
8.3 Crystal Violet Indicator Solution—Prepare a 0.1 % so- 10.3 Calculate the percent of oxirane oxygen, O, as follows:
lution of crystal violet in glacial acetic acid. O 5 1.6N~V – B!/W (3)
8.4 Glacial Acetic Acid (Warning—See Section 6).
8.5 Hydrogen Bromide (HBr), anhydrous (Warning—See 10.4 Calculate the weight per epoxy equivalent, WPE, that
Section 6). is, grams of resin containing 1 g equivalent of epoxy groups, as
8.6 Potassium Acid Phthalate (KHC8H4O4)—Primary Stan- follows:
dard grade. WPE 5 1000W/N~V– B! (4)
8.7 Hydrogen Bromide in Acetic Acid, Standard Solu- 11. Precision
tion (0.1 N) (Warning—See Section 6)—Prepare by bubbling
anhydrous HBr at a slow rate through glacial acetic acid until 11.1 Repeatability—The difference between two results ob-
the desired normality is attained (approximately 8 g of HBr/L). tained by the same analyst will approximate 0.7 % of the epoxy
Standardize each day used against 0.4 g of potassium acid content of the resin tested. Two such values should be
phthalate (KHC8H4O4) accurately weighed and dissolved by considered suspect if they differ by more than 2 % absolute.
gently heating in 10 mL of glacial acetic acid. 11.2 Reproducibility—The difference between two results,
each the mean of two determinations, obtained by analysts in
NOTE 1—Reagent of 0.1 N concentration has been specified. As different laboratories, will approximate 2 % of the epoxy
solutions exceed this concentration they became progressively less stable
content of the resin tested. Two such values should be
(for further information see Practice E 200).
considered suspect if they differ by more than 6 % absolute.
9. Procedure TEST METHOD B
9.1 Use a quantity of specimen that contains 0.001 to
0.002-g equivalents of epoxy groups. Weigh the appropriate 12. Apparatus
amount, to within 1 mg, into an Erlenmeyer flask. Use a 50-mL 12.1 Buret, closed-reservoir type, bottom filling, 25 mL with
1⁄10-mL division, or potentiometric automatic titrator.
flask for low-molecular-weight resins (liquid grades) and a
125-mL flask for high-molecular-weight resins (solid grades). 12.2 Erlenmeyer Flasks, 100-mL, 250-mL, and 500-mL.
9.2 Dissolve the specimen in a solvent at room temperature. 12.3 Magnetic Stirrer, adjustable speed.
Use 10 mL of chlorobenzene for liquid grade resins or 25 mL 12.4 Magnetic Stirring Bars, polytetrafluoroethylene
of a 1+1 mixture of chloroform and chlorobenzene for solid (PTFE) coated.
grade resins. Place a magnetic stirring bar into the flask and 12.5 Pipets:
mix on the magnetic stirrer to dissolve. 12.5.1 Measuring Pipet, 25-mL.
9.3 Add 4 to 6 drops of crystal violet indicator solution and 12.5.2 Volumetric Pipet, 50-mL.
attach the flask to the rubber stopper on the buret tip. Lower the 12.6 Volumetric Flask, 1 L.
buret tip to a point just above the solution and titrate with the 12.7 Bottle, 2 oz wide-mouth, or 100-mL disposable beaker,
hydrogen bromide in acetic acid solution to a blue-green end or equivalent.
point with the magnetic stirrer rotating at a moderate speed to 13. Reagents
avoid splashing. Slow down the titration near the end point to
allow ample time for the reaction to take place. Titrate, as 13.1 Glacial Acetic Acid (Warning—See Section 6).
nearly as possible, to the same color at the end point as that 13.2 Tetraethylammonium Bromide, anhydrous crystals.
obtained during standardization of the reagent. 13.3 Perchloric Acid (HClO4), 60 % (Warning—See Sec-
9.4 Make a blank determination on the reagents in an tion 6).
identical manner. 13.4 Acetic Anhydride (Warning—See Section 6).
13.5 Methylene Chloride (Warning—See Section 6).
10. Calculation 13.6 Crystal Violet Indicator, crystals.
13.7 Potassium Acid Phthalate—(KHC8H4O4) primary
10.1 Calculate the normality, N, of the HBr acetic acid as standard grade.
follows: 13.8 Diglycidyl Ether of Bisphenol-A.
N 5 ~W 3 1000!/~204.2 3 V! (1)
14. Reagent Preparation
where: 14.1 Perchloric Acid (0.1 N Solution in Glacial Acetic
W 5 KHC8H4O4 used, g, and Acid) (Warning—See Section 6)—Prepare in the following
V 5 HBr solution used, mL. manner and sequence in order to avoid an excessive rise in
10.2 Calculate the epoxy content, E, in gram equivalents of temperature.
epoxy groups per 100 g of resin as follows: 14.1.1 Place approximately 250 mL of glacial acetic acid
E 5 N~V – B!/10 3 W (2) into a 1 L volumetric flask. Add 13 mL of 60 % perchloric acid
and mix. Add 50 mL of acetic anhydride, dilute to the mark
where: with glacial acetic acid, and mix thoroughly.
N 5 normality of the HBr in acetic acid, 14.1.2 Allow to stand at least 8 h for completion of reaction
V 5 HBr solution used for titration of the specimen, mL,
between the acetic anhydride and water. A shorter time period

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 D 1652
may be used if completion of the reaction is analytically 16. Procedure
verified. 16.1 Weigh the required amount of specimen into a 2-oz
14.2 Tetraethylammonium Bromide Solution in Glacial Ace- disposable glass bottle or plastic beaker. The amount ofspeci-
tic Acid (Warning—See Section 6): men weight used is dependent on the expected epoxide
14.2.1 Dissolve, with agitation at room temperature, 100 g equivalent weight (EEW) as follows:
of tetraethylammonium bromide in 400 mL of glacial acetic EEW Approximate Specimen Size, g
acid. 170–375 0.4
375–600 0.6
14.3 Crystal Violet Indicator Solution—Prepare 0.1 % solu-
600–1000 0.8
tion of crystal violet indicator in glacial acetic acid 1000–1500 1.3
(Warnings—See Section 6). 1500–2000 1.8
2000–2500 2.3
2500–5000 2.8
15. Standardization of 0.1 N Perchloric Acid Reagent
16.2 Add 10 to 15 mL of methylene chloride to the
15.1 Procedure A—Standardization with Potassium Acid
specimen. Insert a clean stirring bar and adjust the magnetic
Phthalate:
stirrer to effect solution. Continue agitation through the titra-
15.1.1 Dissolve, by gentle heating, 0.4 g of potassium acid
tion procedure.
phthalate, weighed accurately to the nearest milligram, in 50
16.3 Add 10 mL of tetraethylammonium bromide reagent
mL of glacial acetic acid, and add 6 to 8 drops of crystal violet
and 6 to 8 drops of crystal violet indicator solution. Titrate with
indicator solution. Insert a clean stirring bar into the sample,
0.1 N perchloric acid reagent to a sharp blue to green end point
and adjust the magnetic stirrer to effect solution. Continue
which is stable for at least 30 s. Record the volume of
agitation throughout the titration procedure. Titrate with per-
perchloric acid reagent used to titrate the specimen.
chloric acid reagent solution to the end point which is a sharp
change in color from blue to green, stablilize for at least 2 min. 17. Calculation
15.1.2 Calculate and record the perchloric acid reagent
17.1 If 15.1 is used for standardization, calculate weight
normality as follows:
percent epoxide, E, as follows:
N 5 ~W 3 1000!/~204.23 V! (5)
E 5 4.3 3 V 3 N/W (7)
where: 17.2 If 15.2 is used for standardization, calculate weight
N 5 normality of perchloric acid reagent, percent epoxide, E, as follows:
W 5 potassium acid phthalate used, g, and
E 5 F 3 V/We (8)
V 5 volume of perchloric acid reagent required to titrate
the standard, mL. where:
15.2 Procedure B—Standardization with Diglycidyl Ether of We 5 weight of epoxy resin specimen used, g.
Bisphenol-A (DGEBA): 17.3 Calculate the epoxy equivalent weight, WEEW, as
15.2.1 Dissolve 0.25 to 0.40 g of the DGEBA accurately follows:
weighed to the nearest milligram into a 2 oz wide-mouth bottle WEEW 5 43 3 100/E (9)
or 100 mL disposable beaker. Add 10 to 15 mL of methylene
chloride. Insert a clean stirring bar into the sample and adjust where 43 5 mol weight of the epoxy ring.
the magnetic stirrer to effect solution. Continue agitation 17.4 Calculate weight percent of oxirane oxygen, O, as
throughout the titration procedure. follows:
15.2.2 Add 10 mL of tetraethylammonium bromide reagent O 5 16/43 3 E 5 1.6 3 V 3 N/W (10)
and 6 to 8 drops of crystal violet indicator solution and titrate
18. Precision
to a sharp blue-to-green end point with the perchloric acid
reagent solution. The end point should be stable for at least 30 18.1 A liquid epoxy resin sample with approximately
s. 24.1 % epoxide was tested by seven laboratories where ten
15.2.3 Calculate and record the perchloric acid reagent analysts obtained the following results:
factor, F, as follows: 18.1.1 Repeatability—The difference between two results
obtained by the same analyst should not vary by more than
F 5 ~Wd 3 E!/V (6)
1.22 % relative.
where: 18.1.2 Reproducibility—The difference between two re-
Wd 5 diglycidyl ether of bisphenol-A standard used, g, sults, each the mean of two determinations obtained by
E 5 epoxide of the standard used (normally 25.19), analysts in different laboratories should not vary by more than
weight % 2.97 % relative.
The perchloric acid should be standardized initially by
Procedure A and thereafter at least twice per week by Proce- 19. Keywords
dure A or B. Temperature of the reagent solution must be kept 19.1 epoxide equivalent weight (EEW); liquid epoxy resin;
at 25 6 2°C (77 6 3°F). (For further information see Practice oxirane; weight percent epoxide; weight per epoxy equivalent
E 200.) (WPE)

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 D 1652
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