ASTM D3132-84(1996)

Standard Test Method for Solubility Range of Resins and Polymers (Withdrawn 2005)

SCOPE
1.1 This test method covers determination of the solubility of resins and polymers in terms of the region of solubility parameter and hydrogen bonding of solvents in which complete solution occurs. In some cases dipole moment of the solvents may also be required to delineate more exactly the boundaries of solubility.  
1.2 This test method is applicable only if the test solutions are of sufficient clarity and freedom from color to allow accurate visual judgement of complete solubility and of low enough viscosity for solution to take place.  
1.3 This standard does not purport to address all of the safety problems 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 a specific hazard statement see Note in 6.2.
WITHDRAWN RATIONALE
This test method covers determination of the solubility of resins and polymers in terms of the region of solubility parameter and hydrogen bonding of solvents in which complete solution occurs. In some cases dipole moment of the solvents may also be required to delineate more exactly the boundaries of solubility.
Formerly under the jurisdiction of Committee D01 on Paint and Related Coatings, Materials, and Applications, this test method was withdrawn in June 2005 in accordance with section 10.5.3.1 of the Regulations Governing ASTM Technical Committees, which requires that standards shall be updated by the end of the eighth year since the last approval date.

General Information

• Status: Withdrawn
• Publication Date: 31-Dec-1995
• Withdrawal Date: 30-Jun-2005
• ICS: 83.080.10 - Thermosetting materials
• Technical Committee: D01 - Paint and Related Coatings, Materials, and Applications
• Drafting Committee: D01.33 - Polymers and Resins

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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:D3132–84 (Reapproved 1996)
Standard Test Method for
Solubility Range of Resins and Polymers
This standard is issued under the fixed designation D 3132; 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.
3 4
1. Scope nique, and values range from 0 to about 25.Another method,
which limits values of g to the range of 2.2 to 10, defines g by
1.1 This test method covers determination of the solubility
the following equation:
of resins and polymers in terms of the region of solubility
parameter and hydrogen bonding of solvents in which com-
g5 ~0.03593Dn! 1 2.2 (2)
plete solution occurs. In some cases dipole moment of the
where n is the wavenumber shift as determined by Gordy’s
solvents may also be required to delineate more exactly the
method. Hydrocarbons, halogenated hydrocarbons and nitro-
boundaries of solubility.
hydrocarbons have low values of g; esters, ethers, ether-
1.2 This test method is applicable only if the test solutions
alcohols, and ketones are intermediate; and alcohols, amines,
are of sufficient clarity and freedom from color to allow
and acids have high values.
accurate visual judgement of complete solubility and of low
2.1.3 The solubility parameter d , of a mixture of solvents
m
enough viscosity for solution to take place.
having parameters, d , d , etc., is a function of the molar
1 2
1.3 This standard does not purport to address all of the
fraction and molar volume of the components:
safety concerns, if any, associated with its use. It is the
~d x V 1d x V !/ ~x V 1 x V ! (3)
1 1 1 2 2 2 1 1 2 2
responsibility of the user of this standard to establish appro-
in which x and V,x and V , etc., are the corresponding
priate safety and health practices and determine the applica-
1 1 2 2
molar fractions and volumes, respectively. If the components
bility of regulatory limitations prior to use. For a specific
have the same molar volumes (V 5 V ),
hazard statement see Note 1 in 6.2.
1 2
d 5 x d 1 x d (4)
m 1 1 2 2
2. Terminology
Thus, in a mixture of two components A and B having the
2.1 Definitions:
same molar volumes and solubility parameter values of d and
A
2.1.1 The solubility parameter d of a substance is defined as
d
B
the square root of the “cohesive energy density,” or energy of
~volume percent A3d !1~volume percent B3d !
vaporization per unit volume: A B
d 5 (5)
m
1/2
d5 DE / V! (1)
~
2.1.4 Similarly, the hydrogen bonding value, g,ofa
m
where: mixture is determined by:
DE 5 energy of vaporization, and
~volume percent A3g !1~volume percent B3g !
A B
g 5 (6)
V 5 molar volume.
m
The value of d for a volatile liquid can be calculated
and dipole moment by:
accurately from the latent heat of vaporization, or approxi-
~volume percent A 3 µ !1~volume percent B 3 µ !
mately from its boiling point. Solubility parameter values for
A B
µ 5 (7)
m
large number of solvents are available in Table 1.
2.1.2 Solvents are also classified according to their hydro-
3. Summary of Test Method
gen bonding power, g. Numerical values for g may be derived
3.1 Solubility of resinous and polymeric materials is depen-
from spectroscopic analysis. In one method, g is defined as
dent upon the solubility parameter, hydrogen bonding, and
one-tenth the wavenumber shift observed by Gordy’s tech-
dipolemomentofthesolvents.Solubilityparameteristhemost
importantpropertyofthethree,followedbyhydrogenbonding.
Consequently, the solubility of most materials is sufficiently
This test method is under the jurisdiction of ASTM Committee D-1 on Paint
and Related Coatings, Materials, andApplications and is the direct responsibility of
Subcommittee D01.33 on Polymers and Resins.
Current edition approved Aug. 31, 1984. Published January 1985. Originally
published as D 3132 – 72. Last previous edition D 3132 – 72 (1984). Gordy,W.,“SpectroscopicEvidenceofHydrogenBonds,” Journal of Chemical
Crowley, J. D., et al, “A Three Dimensional Approach to Solubility,” Journal Physics, JCPSA, February 1939, February 1940, March, 1941.
of Paint Technology, JPIRA, Vol 38, No. 496, 1966, p. 269; Vol 39, No. 504, 1967, E. I. du Pont de Nemours & Co., Bulletin PA 12-770, “Solvent Formulating
p. 19. Maps for Elvacite Acrylic Resins, Serial A-70562, July 1970.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D3132
defined by the area of solubility parameter and hydrogen 4. Significance and Use
bonding of true solvents. A material is insoluble or incom-
4.1 This test method is useful for an emperical determina-
pletely soluble in a solvent if its solubility parameter and
tion of the solvent(s) in which a resin or polymer may be
hydrogen bonding properties fall outside this region.
dissolved. This test method is also applicable to estimate the
3.2 In this test method, the material is tested separately in solvents that may be useful for further dilution of a polymer
solvents that cover the entire solubility diagram so that
or resin solution without formation of haze or without polymer
boundaries of complete solubility can be determined. or resin precipitation.
TABLE 1 Solvent or Solvent Mixtures
Hydrogen Bonding
Solvent or Solvent Mixture (Mixture Solubility Dipole
No.
A
Given in Volume Percent) Parameter, d B C Moment, µ
g g
1* Diisopropyl ether 6.9 11.7 6.6 1.3
2 n-Pentane 7.0 0 2.2 0
3* n-Heptane 7.3 0 2.2 0
4 50 % Diisobutyl ketone 7.4 10.1 5.9 2.0
50 % Diisopropyl ether
5* Diethyl ether 7.4 13.0 6.9 1.2
6* 50% n-Heptane 7.6 4.2 3.7 1.4
50 % Diisobutyl ketone
725% n-Heptane 7.7 6.3 4.5 2.0
75 % Diisobutyl ketone
8 Methyl cyclohexane 7.8 0 2.2 0
9 66.7 % n-Heptane 7.8 2.9 3.3 0.6
33.3 % n-Butyl Acetate
10* Diisobutyl ketone 7.8 8.4 5.2 2.7
11* 57 % Diethyl ether 7.9 11.2 6.3 1.5
43 % n-Butyl acetate
12 66.7 % Diethyl ether 8.1 14.9 7.6 1.4
33.3 % 2-Ethylhexanol
13* Cyclohexane 8.2 0 2.2 0
14 40 % n-Heptane 8.2 5.3 4.1 1.1
60 % n-Butyl acetate
15 71 % Cyclohexane 8.4 1.3 2.7 0.1
29 % Toluene
16* n-Butyl acetate 8.5 8.8 5.4 1.9
17* 40 % Cyclohexane 8.6 2.7 3.2 0.2
60 % Toluene
18 50 % Cyclohexane 8.7 0 2.2 0
50 % Benzene
19 50 % n-Butyl acetate 8.7 6.7 4.6 1.2
50 % Toluene
20 50 % EGMBE (See No. 23) 8.7 10.9 6.2 1.8
50 % n-Butyl acetate
21* 33.3 % Diethyl ether 8.8 16.8 8.2 1.5
66.7 % 2-Ethylhexanol
22* Toluene 8.9 4.5 3.8 0.4
23 2-Butoxyethanol 8.9 13.0 6.9 1.6
24* Benzene 9.2 0 2.2 0
25 Propylene oxide 9.2 10.0 5.8 1.8
26 56 % EGMBE 9.2 15.5 7.8 1.6
44 % 2-Ethylhexanol
27 50 % Methylene chloride 9.3 3.0 3.3 1.0
50 % Toluene
28* 50 % Toluene 9.4 7.1 4.8 0.4
50 % Dioxane
29* 2-Ethylhexanol 9.5 18.7 8.9 1.7
30 Methyl acetate 9.6 8.4 5.2 1.7
31* Methylene chloride 9.7 1.5 2.7 1.5
32 66.7 % Methylene chloride 9.8 4.2 3.7 1.1
33.3 % Dioxane
33 50 % Dioxane 9.8 5.6 4.2 1.0
50 % Methylene chloride
34* Dioxane 9.9 9.7 5.7 0.4
35 Cyclohexanone 9.9 11.7 6.4 2.7
36* 2-Ethoxyethanol 9.9 13.0 6.9 1.6
37 75 % EGMEE 9.9 14.4 7.4 1.6
25 % Methyl isobutyl carbinol
38* Carbon disulfide 10.0 0 2.2 0
39 30 % EGMEE 10.0 17.0 8.2 1.7
70 % Methyl isobutyl carbinol
40 Methyl isobutyl carbinol 10.0 18.7 8.8 1.7
41 66.7 % Methylene chloride 10.2 1.8 2.8 2.2
D3132
TABLE 1 Continued
Hydrogen Bonding
Solvent or Solvent Mixture (Mixture Solubility Dipole
No.
A
B C
Given in Volume Percent) Parameter, d Moment, µ
g g
33.3 % Nitroethane
42 66.7 % Dioxane 10.3 7.3 4.8 1.5
33.3 % Nitroethane
43* 50 % Toluene 10.4 5.4 4.2 2.2
50 % Acetonitrile
44* 50 % EGMEE 10.4 15.9 7.9 1.7
50 % n-Amyl alcohol
45* 2-Ethylbutanol 10.5 18.7 8.9 1.7
46 33.3 % Methylene chloride 10.6 2.2 3.0 2.9
66.7 % Nitroethane
47 75 % Nitroethane 10.8 4.3 3.8 2.8
25 % Dioxane
48 75 % Dioxane 10.8 8.5 5.3 1.6
25 % Propylene carbonate
49 Dimethylacetamide 10.8 12.3 6.6 3.8
50 80 % EGMEE 10.8 14.1 7.3 1.6
20 % Methanol
51 33.3 % EGMEE 10.9 16.8 8.2 1.7
66.7 % n-Butanol
52 n-Amyl alcohol (pentanol) 10.9 18.7 8.9 1.7
53 48 % Benzene 11.0 1.3 2.7 1.8
52 % Nitromethane
54 50 % Dioxane 11.0 10.7 5.6 2.1
50 % Dimethylformamide
55* Nitroethane 11.1 2.5 3.1 3.6
56 25 % n-Butyl acetate 11.1 6.9 4.5 3.4
75 % Acetonitrile
57* n-Butanol 11.4 18.7 8.9 1.7
58* 50 % Nitroethane 11.5 4.4 3.8 3.8
50 % Acetonitrile
59 65 % EGMEE 11.5 15.0 7.6 1.6
35 % Methanol
60* 66.7 % n-Butanol 11.6 16.4 8.2 2.4
33.3 % Dimethylformamide
61* 50 % Dioxane 11.7 8.7 5.4 2.2
50 % Dimethyl sulfoxide
62 50 % Nitroethane 11.9 2.5 3.1 3.5
50 % Nitromethane
63* Acetonitrile 11.9 6.3 4.5 3.9
64 30 % n-Butanol 11.9 13.8 7.2 3.2
70 % Dimethylformamide
65 n-Propanol 11.9 18.7 8.9 1.7
66 70 % Acetonitrile 12.0 8.0 5.1 3.9
30 % Dimethylformamide
67 68 % Dimethylformamide 12.0 10.0 5.8 3.8
32 % Acetonitrile
68* Dimethylformamide 12.1 11.7 6.4 3.8
69 50% n-Propanol 12.3 18.7 8.9 1.7
50 % Ethanol
70 60 % Nitromethane 12.4 4.0 3.7 3.6
40 % Acetonitrile
71* 50 %
...