Designation: D 5629 – 99

Standard Test Method for

Polyurethane Raw Materials: Determination of Acidity in
Low-Acidity Aromatic Isocyanates and Polyurethane
Prepolymers1
This standard is issued under the fixed designation D 5629; 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.

1. Scope * and the difference in titer is used to calculate the acidity present
1.1 This test method covers the acidity, expressed as ppm of in the isocyanate sample.
hydrochloric acid, in aromatic isocyanate or polyurethane 5. Significance and Use
prepolymer samples of below 100 ppm acidity. The test method
is applicable to products derived from toluene diisocyanate and 5.1 This test method can be used for research or for quality
methylene-bis-(4-phenylisocyanate) (see Note 1). control to characterize aromatic isocyanates and low-acidity
prepolymers. Acidity correlates with performance in some
NOTE 1—There are no equivalent ISO standards. polyurethane systems.
1.2 The values stated in SI units are to be regarded as the
standard. 6. Apparatus
1.3 This standard does not purport to address all of the 6.1 Disposable Beakers, 250 mL.
safety concerns, if any, associated with its use. It is the 6.2 Repipet, 50 mL.
responsibility of the user of this standard to establish appro- 6.3 Pipet, 100 mL, class A volumetric; or a 50-mL buret
priate safety and health practices and determine the applica- dosimat unit, and a dosimat; or a 100-mL repipet, class A
bility of regulatory limitations prior to use. volumetric.
6.4 Automatic Titration Equipment, such as the following:
2. Referenced Documents 6.4.1 Titroprocessor.4
2.1 ASTM Standards: 6.4.2 Dosimat, with magnetic stirrer.4
D 883 Terminology Relating to Plastics2 6.4.3 Reference Electrode (Brinkman Catalogue No. 020-
E 180 Practice for Determining the Precision of ASTM 94-400-5 or equivalent: bridge electrolyte (double junction),
Methods for Analysis and Testing of Industrial Chemicals3 sleeve-type diaphragm), having saturated LiCl/ethanol solution
in both chambers.
3. Terminology 6.4.4 pH Glass Electrode (Brinkman Catalogue No. 020-
3.1 Definitions—The terminology in this test method fol- 91-012-7 or equivalent) (see Note 2).
lows the standard terminology defined in Terminology D 883. NOTE 2—A combination pH electrode with internal reference may also
3.2 Definitions of Terms Specific to This Standard: be used.
3.2.1 acidity, n—the acid strength of a sample expressed in
ppm HCl. 6.5 Magnetic Stirrer.
6.6 Polytetrafluoroethylene-Coated Stir Bars.
4. Summary of Test Method 6.7 Watch Glasses.
4.1 The isocyanate is mixed with an excess of n-propanol, a 6.8 Analytical Balance, capable of weighing to the nearest
cosolvent, and a known amount of HCl. Additional acid is 0.1 mg.
released into the solvent system during urethane formation. 7. Reagents and Materials
The acid is then titrated potentiometrically with methanolic
KOH. The same procedure is performed with a blank solution, 7.1 KOH in Methanol, 0.01 N: 0.66 g 87.7 % KOH/1000
mL methanol, standardized with potassium hydrogen phthalate
(KHP).
1
This test method is under the jurisdiction of ASTM Committee D-20 on Plastics
and is the direct responsibility of Subcommittee D20.22 on Cellular Plastics.
4
Current edition approved Nov. 10, 1999. Published February 2000. Originally Instruments similar to and including the Metrohn 686 Titroprocessor with a
published as D 5629 – 94. Last previous edition D 5629 – 94. Metrohn 665 Dosimat/magnetic stirrer as supplied by Brinkman Instruments
2
Annual Book of ASTM Standards, Vol 08.01. Company, Division of Sybron Corporation, Cantiague Road, Westbury, NY 11590-
3
Annual Book of ASTM Standards, Vol 15.05. 9974, have been found to be satisfactory for this analysis.

*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
 D 5629
7.2 Toluene or THF (dried for 24 h over 5 A sieves). 12. Calculation
7.3 n-Propanol, acidified with 120 µL concentrated hydro- 12.1 Calculate the acidity, as ppm HCl, as follows:
chloric acid per 4-L bottle. This solution should be allowed to
~Vsam 2 Vblank! 3 ~KOHnormality! 3 F
stand for at least 24 h before use to allow equilibration. The acidity 5 (1)
sample weight ~g!
solution should be mixed well before dispensing.
where:
8. Sampling Vsam = volume of titrant needed for the sample,
8.1 Since organic isocyanates react with atmospheric mois- mL,
ture, take special precautions in sampling (Warning—Organic Vblank = volume of titrant needed for the blank,
isocyanates are toxic when they are absorbed through the skin mL,
or when the vapors are breathed. Provide adequate ventilation, KOHnormality = normality of the titrant solution, and
and wear protective gloves and eye glasses.). Usual sampling F = 36465 = 36.456 (mol weight of HCl) 3
methods (for example, sampling an open drum thief), even 1000 (factor to change mg/g to µg/g, that
when conducted rapidly, can cause contamination of the is, ppm).
sample with insoluble urea. Therefore, blanket the sample with NOTE 8—Acidity is typically calculated as meq/Kg for prepolymers.
dry air or nitrogen at all times. For this calculation, F = 1000.

13. Report
9. Calibration
13.1 Report the result as the average of duplicates, ex-
9.1 Calibrate the electrodes using pH 4 and 7 aqueous
pressed as ppm HCl, to the nearest 1 ppm. See also Note 8.
buffers.
14. Precision and Bias 5
10. Test Conditions
14.1 Precision—Table 1 is based on a round robin con-
10.1 Since isocyanates react with moisture, keep the labo-
ducted in 1993 per Practice E 180, involving six materials
ratory humidity low, preferably at approximately 50 % relative
tested by nine laboratories. All of the samples for each material
humidity.
were prepared at one source, but the individual specimens were
prepared at the laboratories that tested them. Each test result
11. Procedure was the average of two individual determinations. Each labo-
11.1 Make a blank determination in conjunction with each ratory obtained two test results for each material on each of two
series of samples. Prepare the blank in the same manner as a days. (Warning—The following explanations of r and R
sample, only omitting the sample. All samples and blanks (14.1-14.1.3) are intended only to present a meaningful way of
should be made in duplicate. considering the approximate precision of this test method. The
11.2 Accurately weigh, to the nearest 0.1 mg, 20 g of data in Table 1 should not be applied rigorously to the
sample into a 250-mL beaker. acceptance or rejection of material, as those data are specific to
11.3 Add 50 mL of dried toluene (dried over 5-A molecular the round robin and may not be representative of other lots,
sieves). conditions, materials, or laboratories. Users of this test method
NOTE 3—Substitute THF for toluene for prepolymers. should apply the principles outlined in Practice E 180 to
NOTE 4—If a sample is difficult to get into solution, it may be gently generate data specific to their laboratory and materials or
heated and stirred for a longer period of time to affect homogeneity. between specific laboratories. The principles of 14.1.1-14.1.3
would then be valid for such data.)
11.4 Pipet 100 mL of acidified n-propanol into the solution
so that the volume can be reproduced to 0.05 mL.
11.5 Add a stir bar, cover with a watch glass, and stir and
cool for 20 min.
5
Supporting data are available from ASTM Headquarters. Request RR:
NOTE 5—Samples must be at room temperature before titration. D20–1186.

11.6 Titrate the mixture with 0.01 N methanolic KOH

TABLE 1 Round Robin Acidity Data According to Practice E 180
through the titration endpoint as determined potentiometrically.
Continue the titration through an apparent pH of 8. Values in ppm HCl
Average SrA SRB rC RD nE
NOTE 6—If the results indicate a drift in the data or a slow electrode
response, the pH electrode should be cleaned by soaking in 2:1 sulfuric- TD-80 Grade B 73.81 3.14 7.80 8.79 21.84 8
TD-80 Grade A 39.47 1.44 4.28 4.03 11.98 8
:nitric acids for 10 min, followed by soaking in water for 20 min and then Adiprene L-100 23.56 0.99 4.00 2.77 11.20 8
rinsing with acetone. Vibrathane B836 3.37 0.82 2.27 2.30 6.36 7
Isonate 143L 1.12 1.53 2.41 4.28 6.75 7
11.7 Record the titrant volume for the potentiometric end- Mondur M 1.07 0.74 2.53 2.07 7.08 7
point. If more than one potentiometric endpoint is found, A
Sr = within-laboratory standard deviation of the replicates.
record the one at the highest apparent pH below 7. B
SR = between-laboratory standard deviation of the average.
C
r = within-laboratory repeatability limit = 2.8 3 Sr.
NOTE 7—The inflection point is typically at an apparent pH between 4 D
R = between-laboratory reproducibility limit = 2.8 3 SR.
E
and 5. n = number of laboratories contributing valid data for this material.

2
 D 5629
14.1.1 Repeatability, (r)—(Comparing two replicates for the 14.1.3 Any judgement per 14.1.1 and 14.1.2 would have an
same material, obtained by the same operator using the same approximate 95 % (0.95) probability of being correct.
equipment on the same day.) The two replicate results should 14.2 Bias—There are no recognized standards by which to
be judged not equivalent if they differ by more than the r value estimate the bias of this test method.
for that material.
14.1.2 Reproducibility, (R)—(Comparing two results for the 15. Keywords
same material, obtained by different operators using different
equipment on different days.) The two test results should be 15.1 acidity; aromatic isocyanates; isocyanates; methylene
judged not equivalent if they differ by more than the R value diphenyldiisocyanate; MDI; prepolymer; polyurethane; raw
for that material. materials; test method; TDI; titration; toluene diisocyanate

SUMMARY OF CHANGES

This section identifies the location of selected changes to this test method. For the convenience of the user,
Committee D-20 has highlighted those changes that may impact the use of this test method. This section may
include descriptions of the changes or the reasons for the changes, or both.

D 5629 – 99: review of the protocol used to generate the round-robin data, it
(1) In 6.6, added “-Coated.” is believed that Practice E 180 best describes the methodology.
(2) In 7.1, added “87.7 %” for clarification of KOH. PURMAC uses an E 180-based program to calculate the
(3) In 11.5, added “and cool” to ensure sample is at room precision and bias.
temperature before testing. (5) In 14.1, corrected reference to 14.1.1.
(4) In 14.1, replaced Practice E 691 with Practice E 180. Upon (6) In 15.1, added TDI as a keyword.

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