Reference: Polymer Properties
Polymer Solutions: Solvents and Solubility Parameters
Various applications require the selection of a polymer-solvent or polymer-plasticizer system. Dissolving a polymer is
unlike dissolving low molecular weight compounds because
of the vastly different dimensions of solvent and polymer molecules. Dissolution is often a slow process. While some polymers dissolve readily in certain solvents resulting in a true
solution, others may require prolonged periods of heating at
temperatures near the melting point of the polymer. Network
polymers do not dissolve, but usually swell in the presence of
solvent. Table I is a quantitative guide1 for selecting solvents to
dissolve or swell polymers. The polymer is composed of the
stated Repeating Unit. Representative homopolymers from
each of the main polymer classes were selected. Since polymer solubility is a complex function of many variables including but not limited to molecular weight, degree of crystallinity,
extent of branching, and temperature, the solubility may vary
greatly within a given polymer class.
Table I: Solvents for Representative Homopolymers from Selected Polymer Classes
Repeating Unit
Solvents
Acetylene
Acrylamide
Acrylate esters
Acrylic acid
Acrylonitrile
Alkyl vinyl ethers
Amic acids
Aryl sulfonates
Butadiene
ε-Caprolactam (Nylon 6)
Cellulose
Cellulose ethers
Cellulose triacetate
Chloroprene
Ethylene
Ethylene phthalamide
Ethylene terephthalate
Ethylene oxide
Formaldehyde
Hexamethylene adipate (Nylon 6/6)
Isobutene
Isoprene
Lactic acid
Maleic anhydride
Methacrylate esters
Methacrylic acid
1,4-Phenylene ethylene
Phenylene sulfone
Phenyl glycidyl ether
Propylene
Propylene oxide
Pyromellitimides
Siloxanes
Styrene
Tetrafluoroethylene
Thiophenylene
Ureas
Urethanes
Vinyl acetal
Vinyl acetate
Vinyl alcohol
Vinyl butyryl
Vinyl chloride
Vinyl carbazole
Vinylidene chloride
Vinylidene fluoride
N-Vinyl pyrrolidone
Isopropylamine, aniline
Morpholine, water
Aromatic hydrocarbons, chlorinated hydrocarbons, THF, esters, ketones
Alcohols, water, dilute aqueous alkali
Phenylenediamines, ethylene carbonate, sulfuric acid
Benzene, halogenated hydrocarbons, methyl ethyl ketone
DMF, DMSO, tetramethylurea
DMF
Hydrocarbons, THF, higher ketones
m-Cresol, chlorophenol, formic acid
Trifluoroacetic acid, aqueous solutions of cupriethylenediamine
Aqueous alkali
Methylene chloride, THF, ethylene carbonate
Benzene, chlorinated hydrocarbons, pyridine
Above 80°C: halogenated hydrocarbons, higher aliphatic esters and ketones
Sulfuric acid
Trichloroacetaldehyde hydrate, phenol, chlorophenol
Chloroform, alcohols, esters
At elevated temperature: phenol, aniline, ethylene carbonate
Trichloroethanol, phenols, sulfuric acid
Chlorinated hydrocarbons, THF, aliphatic ethers
Hydrocarbons, THF, higher ketones
Chloroform, dioxane
Dioxane, ethers, ketones
Benzene, methylene chloride, methyl ethyl ketone
Alcohols, water, dilute aqueous sodium hydroxide
Biphenyl, phenyl ether
Methylene chloride, DMSO
Xylene (hot), 1,2-dichlorobenzene (hot)
Above 80°C: halogenated hydrocarbons, higher aliphatic esters and ketones
Benzene, chloroform, ethanol
m-Cresol, conc. sulfuric acid
Aromatic and chlorinated hydrocarbons, esters
Benzene, chlorinated aliphatic hydrocarbons, methyl ethyl ketone, ethyl acetate
Perfluorokerosene (350°C)
Biphenyl, dichlorobiphenyl
Phenol, m-cresol, formic acid
Phenol, m-cresol, formic acid
Benzene, chloroform, THF
Toluene, chloroform, methanol
Glycols (hot), water, piperazine
Methylene chloride, alcohols, ketones
THF, methyl ethyl ketone
Chloroform, chlorobenzene, dioxane
THF(hot), trichloroethane
Cyclohexanone, ethylene carbonate
Chloroform, ethanol, pyridine
1
A more extensive selection is found in “Polymer Handbook”, Eds. Brandrup, J.; Immergut, E.H.; Grulke, E.A., 4th Edition, John Wiley, New York, 1999,
VII /497-535. Aldrich Catalog Number Z41,247-3.
46
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Polymer Products from Aldrich
a
Reference: Polymer Properties
Polymer Solutions: Solvents and Solubility Parameters (continued)
Detailed studies of polymer solubilities using thermodynamic
principles have led to semi-empirical relationships for predicting solubility. A comparison of the solubility parameters of the
polymer (dpolymer) and solvent (δsolvent), where δ is a measure of
the attractive strength between molecules of the material, allows prediction of miscibility. Solubility parameters for solvents
and plasticizers are provided in Table II and Table III in alphabetical order and in order of increasing δ value, respectively.
The same is provided for homopolymers in Table IV. As a guide,
the solubility parameter difference, (δpolymer - δsolvent), must be
small for good miscibility.
Solubility parameter values are based on heats of vaporization.
The values obtained with this method give estimates of solution behavior. It is recommended that the reader consult the
reference given below2 or other references for a more detailed
explanation of δ values.
Table II: Solubility Parameters for Plasticizers and Solvents (Alphabetical sequence)
Solvent
Acetone
Acetonitrile
Amyl acetate
Aniline
Benzene
Butyl acetate
Butyl alcohol
Butyl butyrate
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
Cresol
Cyclohexanol
Diamyl ether
Diamyl phthalate
Dibenzyl ether
Dibutyl phthalate
Dibutyl sebacate
1,2-Dichlorobenzene
Diethyl carbonate
Di(ethylene glycol)
Di(ethylene glycol) monobutyl
ether (Butyl Carbitol®)
Di(ethylene glycol) monoethyl
ether (Carbitol®)
Diethyl ether
Diethyl ketone
Diethyl phthalate
Di-n-hexyl phthalate
Diisodecyl phthalate
N,N-Dimethylacetamide
Dimethyl ether
N,N-Dimethylformamide
Dimethyl phthalate
Dimethylsiloxanes
Dimethyl sulfoxide
Dioctyl adipate
Dioctyl phthalate
δ
(cal/cm3)F
H-Bonding
Strength 3
9.9
11.9
8.5
10.3
9.2
8.3
11.4
8.1
10.0
8.6
9.5
9.3
10.2
11.4
7.3
9.1
9.4
9.3
9.2
10.0
8.8
12.1
m
p
m
s
p
m
s
m
p
p
p
p
s
s
m
m
m
m
m
p
m
s
9.5
m
10.2
7.4
8.8
10.0
8.9
7.2
10.8
8.8
12.1
10.7
4.9-5.9
12.0
8.7
7.9
m
m
m
m
m
m
m
m
m
m
p
m
m
m
Solvent
Dioctyl sebacate
1,4-Dioxane
Di(propylene glycol)
Di(propylene glycol)
monomethyl ether
Dipropyl phthalate
Ethyl acetate
Ethyl amyl ketone
Ethyl n-butyrate
Ethylene carbonate
Ethylene dichloride
Ethylene glycol
Ethylene glycol diacetate
Ethylene glycol diethyl ether
Ethylene glycol dimethyl ether
Ethylene glycol monobutyl ether
(Butyl Cellosolve®)
Ethylene glycol monoethyl ether
(Cellosolve®)
Furfuryl alcohol
Glycerol
Hexane
Isopropyl alcohol
Methanol
Methyl amyl ketone
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Propyl acetate
1,2-Propylenecarbonate
Propylene glycol
Propylene glycol methyl ether
Pyridine
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
(perchloroethylene)
Tetrahydrofuran
Toluene
Water
δ
F
(cal/cm 3)F
H-Bonding
Strength 3
8.6
10.0
10.0
m
m
s
9.3
9.7
9.1
8.2
8.5
14.7
9.8
14.6
10.0
8.3
8.6
m
m
m
m
m
m
p
s
m
m
m
9.5
m
10.5
12.5
16.5
7.3
8.8
14.5
8.5
9.7
9.3
8.4
8.8
13.3
12.6
10.1
10.7
9.7
m
s
s
p
m
s
m
p
m
m
m
m
s
m
s
p
9.3
9.1
8.9
23.4
p
m
p
s
2
”Polymer Handbook”, Eds. Brandrup, J.; Immergut, E.H.; Grulke, E.A., 4th Edition, John Wiley, New York, 1999, VII /675-711. Aldrich Catalog Number
Z41,247-3.
3
H-Bonding: p= poor; m = moderate; s = strong
a
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Reference: Polymer Properties
Polymer Solutions: Solvents and Solubility Parameters (continued)
δ) for Plasticizers and Solvents (Increasing δ value sequence)
Table III: Solubility Parameters (δ
Solvent
Dimethylsiloxanes
Diisodecyl phthalate
Hexane
Diamyl ether
Diethyl ether
Dioctyl phthalate
Butyl butyrate
Ethyl amyl ketone
Ethylene glycol diethyl ether
Butyl acetate
Methyl isobutyl ketone
Methyl amyl ketone
Amyl acetate
Ethyl n-butyrate
Ethylene glycol dimethyl ether
Carbon tetrachloride
Dioctyl sebacate
Dioctyl adipate
Isopropyl alcohol
Diethyl carbonate
Propyl acetate
Diethyl ketone
Dimethyl ether
Toluene
Di-n-hexyl phthalate
Ethyl acetate
Diamyl phthalate
Tetrahydrofuran
Dibutyl sebacate
Benzene
Tetrachloroethylene
(perchloroethylene)
Di(propylene glycol)
monomethyl ether
Chloroform
Dibutyl phthalate
Methyl ethyl ketone
Dibenzyl ether
Ethylene glycol monobutyl ether
(Butyl Cellosolve®)
4
δ
F
(cal/cm 3)
H-Bonding
Strength 4
4.9-5.9
7.2
7.3
7.3
7.4
7.9
8.1
8.2
8.3
8.3
8.4
8.5
8.5
8.5
8.6
8.6
8.6
8.7
8.8
8.8
8.8
8.8
8.8
8.9
8.9
9.1
9.1
9.1
9.2
9.2
9.3
p
m
p
m
m
m
m
m
m
m
m
m
m
m
m
p
m
m
m
m
m
m
m
p
m
m
m
m
m
p
p
9.3
m
9.3
9.3
9.3
9.4
9.5
p
m
m
m
m
Solvent
Di(ethylene glycol) monobutyl
ether (Butyl Carbitol®)
Chlorobenzene
Methylene chloride
Dipropyl phthalate
1,1,2,2-Tetrachloroethane
Ethylene dichloride
Acetone
1,2-Dichlorobenzene
Diethyl phthalate
Ethylene glycol diacetate
Di(propylene glycol)
Carbon disulfide
1,4-Dioxane
Propylene glycol methyl ether
Di(ethylene glycol) monoethyl
ether (Carbitol®)
Cresol
Aniline
Ethylene glycol monoethyl
ether (Cellosolve®)
Pyridine
Dimethyl phthalate
N,N-Dimethylacetamide
Cyclohexanol
Butyl alcohol
Acetonitrile
Dimethyl sulfoxide
Di(ethylene glycol)
N,N-Dimethylformamide
Furfuryl alcohol
Propylene glycol
1,2-Propylenecarbonate
Methanol
Ethylene glycol
Ethylene carbonate
Glycerol
Water
δ
F
(cal/cm 3)
H-Bonding
Strength 4
9.5
m
9.5
9.7
9.7
9.7
9.8
9.9
10.0
10.0
10.0
10.0
10.0
10.0
10.1
10.2
p
p
m
p
p
m
p
m
m
s
p
m
m
m
10.2
10.3
10.5
s
s
m
10.7
10.7
10.8
11.4
11.4
11.9
12.0
12.1
12.1
12.5
12.6
13.3
14.5
14.6
14.7
16.5
23.4
s
m
m
s
s
p
m
s
m
s
s
m
s
s
m
s
s
H-Bonding: p = poor; m = moderate; s = strong
Carbitol and Cellosolve are registered trademarks of Union Carbide Corp.
48
_
Polymer Products from Aldrich
a
Reference: Polymer Properties
Polymer Solutions: Solvents and Solubility Parameters (continued)
Table IV: Solubility Parameters for Homopolymers5
δ (cal/cm 3)F
F
Repeating Unit
(Increasing δ Value Sequence)
(Alphabetical Sequence)
Acrylonitrile
Butyl acrylate
Butyl methacrylate
Cellulose
Cellulose acetate (56% Ac groups)
Cellulose nitrate (11.8% N)
Chloroprene
Dimethylsiloxane
Ethyl acrylate
Ethylene
Ethylene terephthalate
Ethyl methacrylate
Formaldehyde (Oxymethylene)
Hexamethylene adipamide (Nylon 6/6)
n-Hexyl methacrylate
Isobornyl acrylate
1,4-cis-Isoprene
Isoprene, natural rubber
Isobutylene
Isobornyl methacrylate
Isobutyl methacrylate
Lauryl methacrylate
Methacrylonitrile
Methyl acrylate
Methyl methacrylate
Octyl methacrylate
Propyl acrylate
Propylene
Propylene oxide
Propyl methacrylate
Stearyl methacrylate
Styrene
Tetrafluoroethylene
Tetrahydrofuran
Vinyl acetate
Vinyl alcohol
Vinyl chloride
Vinylidene chloride
δ (cal/cm 3)F
F
Repeating Unit
12.5
9.0
8.8
15.6
27.8
14.8
9.4
7.5
9.5
8.0
10.7
9.0
9.9
13.6
8.6
8.2
8.0
8.2
7.8
8.1
7.2
8.2
10.7
10.0
9.5
8.4
9.0
9.3
7.5
8.8
7.8
8.7
6.2
9.4
10.0
12.6
9.5
12.2
Tetrafluoroethylene
Isobutyl methacrylate
Dimethylsiloxane
Propylene oxide
Isobutylene
Stearyl methacrylate
Ethylene
1,4-cis-Isoprene
Isobornyl methacrylate
Isoprene, natural rubber
Lauryl methacrylate
Isobornyl acrylate
Octyl methacrylate
n-Hexyl methacrylate
Styrene
Propyl methacrylate
Butyl methacrylate
Ethyl methacrylate
Butyl acrylate
Propyl acrylate
Propylene
Chloroprene
Tetrahydrofuran
Methyl methacrylate
Ethyl acrylate
Vinyl chloride
Formaldehyde (Oxymethylene)
Methyl acrylate
Vinyl acetate
Methacrylonitrile
Ethylene terephthalate
Vinylidene chloride
Acrylonitrile
Vinyl alcohol
Hexamethylene adipamide(Nylon 6/6)
Cellulose nitrate (11.8% N)
Cellulose
Cellulose acetate (56% Ac groups)
6.2
7.2
7.5
7.5
7.8
7.8
8.0
8.0
8.1
8.2
8.2
8.2
8.4
8.6
8.7
8.8
8.8
9.0
9.0
9.0
9.3
9.4
9.4
9.5
9.5
9.5
9.9
10.0
10.0
10.7
10.7
12.2
12.5
12.6
13.6
14.8
15.6
27.8
5
Values reported are for homopolymers of the Repeating Unit. Reported d values vary with the method of determination and test conditions. Averaged
values are given in this table.
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