ASTM D3876-96(2007)

Standard Test Method for Methoxyl and Hydroxypropyl Substitution in Cellulose Ether Products by Gas Chromatography

SIGNIFICANCE AND USE
This test method determines the methoxyl and hydroxypropoxyl content of cellulose ethers by a Zeisel-gas chromatographic technique.
Substitution levels affect solution properties, rheology, viscosity, and many other properties of the polymer.
SCOPE
1.1 This test method is applicable to the determination of methoxyl and hydroxypropyl substitution content in cellulose ether products by a Zeisel-gas chromatographic technique.
1.2 This test method is not suitable for use for the analysis of hydroxypropyl-cellulose due to its very high substitution level.
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. For specific hazard statements, see Section 2, 11.1.4, and 11.1.7.

General Information

• Status: Historical
• Publication Date: 31-May-2007
• ICS: 85.040 - Pulps
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.36 - Cellulose and Cellulose Derivatives

Relations

• Replaces: ASTM D3876-96(2001) - Standard Test Method for Methoxyl and Hydroxypropyl Substitution in Cellulose Ether Products by Gas Chromatography
• Effective Date: 01-Jun-2007
• Referred By: ASTM D5400-15(2021) - Standard Test Methods for Hydroxypropylcellulose
• Effective Date: 01-Jun-2007

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: D3876 − 96 (Reapproved2007)
Standard Test Method for
Methoxyl and Hydroxypropyl Substitution in Cellulose Ether
Products by Gas Chromatography
This standard is issued under the fixed designation D3876; 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.
1. Scope 4.2 Electronic Integrator.
1.1 This test method is applicable to the determination of 4.3 Stainless Steel Tubing, 9.5 mm in outside diameter and
methoxyl and hydroxypropyl substitution content in cellulose 1981 mm in length, packed with reagent in 5.8.
ether products by a Zeisel-gas chromatographic technique.
4.4 Syringes, 10 and 100 µL.
1.2 This test method is not suitable for use for the analysis 5
4.5 Reaction Vials, Caps, and Heating Block.
of hydroxypropyl-cellulose due to its very high substitution
level.
5. Reagents
1.3 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 onAnalytical Reagents of theAmerican Chemical Society,
bility of regulatory limitations prior to use. For specific hazard
where such specifications are available. Other grades may be
statements, see Section 2, 11.1.4, and 11.1.7.
used, provided it is first ascertained that the reagent is of
sufficiently high purity to permit its use without lessening the
2. Summary of Test Method
accuracy of the determination.
2.1 When methyl cellulose or hydroxypropyl methyl cellu-
5.2 o-Xylene, ACS.
lose is reacted with hydriodic acid, 1 mol of methyl iodide and
5.3 Toluene, ACS.
1 mol of isopropyl iodide are liberated for each mole of
methoxyl and hydroxypropoxyl that is substituted on the
5.4 Iodomethane, 99 % min.
cellulose chain. The methyl iodide and isopropyl iodide are
5.5 2-Iodopropane, 97 % min.
extracted in situ with o-xylene and quantitated by gas chroma-
5.6 Hydriodic Acid (sp. gr. 1.69 to 1.70)57%.
tography using an internal standard technique.
5.7 Acetone.
3. Significance and Use
5.8 Packing Material.
3.1 This test method determines the methoxyl and hydroxy-
propoxyl content of cellulose ethers by a Zeisel-gas chromato-
6. Hazards
graphic technique.
6.1 Safety precautions must be taken for handling of hydri-
3.2 Substitution levels affect solution properties, rheology,
odic acid.
viscosity, and many other properties of the polymer.
4. Apparatus
Hewlett-Packard Model 3380 has been found satisfactory for this purpose.
Tubing from Supelco, Inc., Supelco Park, Bellefonte, PA16823 has been found
4.1 Gas Chromatograph, with thermal conductivity detec-
satisfactory for this purpose.
tor and heated injection port.
Reacti-therm Heating module, Reacti-Block Reacti-vials and Mininert valve
tops from Pierce Chemical Co., Box 117, Rockford, IL 61105 have been found
satisfactory for this purpose.
1 6
This test method is under the jurisdiction of ASTM Committee D01 on Paint Reagent Chemicals, American Chemical Society Specifications, American
and Related Coatings, Materials, andApplications and is the direct responsibility of Chemical Society, Washington, DC. For Suggestions on the testing of reagents not
Subcommittee D01.36 on Cellulose and Cellulose Derivatives. listed by the American Chemical Society, see Analar Standards for Laboratory
Current edition approved June 1, 2007. Published August 2007. Originally Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
approved in 1979. Last previous edition approved in 2001 as D3876 – 96 (2001). and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,
DOI: 10.1520/D3876-96R07. MD.
2 7
Hewlett-Packard Model 5700, available from Hewlett-Packard, Route 41, Starr Columnspackedwith10 %SP2100on100/120Supelcoport®havebeenfound
Rd,P.O.Box900,Avondale,PA19311,hasbeenfoundsatisfactoryforthispurpose. satisfactory for this purpose.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
D3876 − 96 (2007)
6.2 During the reaction, the glass vials are under pressure. 31 31000
mg methoxyl 5 g methyl iodide 3 (1)
S D
Exercise caution in handling the hot vials. 142
75 31000
7. Sampling mg hydroxy propoxyl 5 g propyliodide 3 (2)
S D
7.1 A specific sampling method is currently under study by
mg toluene 5 internal standard solution concentrated 34 ml (3)
the subcommittee.
10. Calibration of Electronic Integrator
8. Apparatus Preparation and Conditioning
10.1 Inject 1 µL of the upper layer of the prepared standard
8.1 Install prepackaged columns in the chromatograph and
solution (9.2) into the gas chromatograph and start the elec-
condition them by heating to 150°C over 1 h and then holding
tronic integrator.
at temperature for 16 h. Then set the chromatograph as
10.1.1 Calibrate in accordance with the manufacturer’s
follows:
instructions.
Oven temperature 130°C isothermal
Injection port temperature 200°C 10.2 In the event an electronic integrator is not available the
Detector temperature 250°C
peak areas can be measured manually and a factor determined
Detector current 170 mA
for each component can be obtained using the following
Attenuation 1
Carrier gas helium equation:
Column A 20 mL/min
A 3 B
Column B 20 mL/min
F 5 (4)
C 3 D
NOTE 1—The conditions used here were determined to be optimum for
...