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 Acetylene Acrylamide Acrylate esters Acrylic acid Acrylonitrile Alkyl vinyl ethers Amic acids Aryl sulfonates Butadiene -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
1

Solvents 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 80C: 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 80C: 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 (350C) 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

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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.

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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 (solvent), where 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 value, respectively. The same is provided for homopolymers in Table IV. As a guide, the solubility parameter difference, (polymer - solvent), 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 values.

Table II: Solubility Parameters for Plasticizers and Solvents (Alphabetical sequence)
Solvent (cal/cm3)F H-Bonding Strength 3 Solvent (cal/cm 3)F F H-Bonding Strength 3

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
2

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 9.5 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 p m s p m s m p p p p s s m m m m m p m s m m m m m m m m m m m p m m m

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

8.6 10.0 10.0 9.3 9.7 9.1 8.2 8.5 14.7 9.8 14.6 10.0 8.3 8.6 9.5 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 9.3 9.1 8.9 23.4

m m s m m m m m m p s m m m m m s s p m s m p m m m m s m s p p m p s

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

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Reference: Polymer Properties

Polymer Solutions: Solvents and Solubility Parameters (continued)
Table III: Solubility Parameters () for Plasticizers and Solvents (Increasing value sequence)
Solvent F (cal/cm 3) H-Bonding Strength 4 Solvent F (cal/cm 3) H-Bonding Strength 4

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

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 9.3 9.3 9.3 9.3 9.4 9.5

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 m p m m m m

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

9.5 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 10.2 10.3 10.5 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

m p p m p p m p m m s p m m m s s m 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.

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Reference: Polymer Properties

Polymer Solutions: Solvents and Solubility Parameters (continued)
Table IV: Solubility Parameters for Homopolymers5
Repeating Unit
(cal/cm 3)F F (Alphabetical Sequence)

Repeating Unit

(cal/cm 3)F F (Increasing Value 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
5

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

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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