S o l v e n t s

a n d

N o n

S o l v e n t s

f o r

P o l y m e r s

D a n i e l R. B l o c h Lakeshore Research, 5536 W. Branch Trail Racine, Wl, USA 53402

A. Introduction VII-498 B. Abbreviations VII-498 C. Tables of Solvents and Nonsolvents VII-499 Table 1. Main-Chain Acyclic Carbon Polymers VII-499 1.1. Poly(dienes), Poly(acetylenes) VII-499 1.2. Poly(alkenes) VII-500 1.3. Poly(acrylics), Poly(methacrylics) VII-501 1.3.1. Poly(acrylic acids) VII-501 1.3.2. Poly(acrylates) VII-501 1.3.3. Poly(methacrylates) VII-501 1.3.4. Poly(disubstituted esters) VII-502 1.3.5. Poly(acrylamides), Poly(methacrylamides) VII-503 1.4. Poly(vinyl ethers) VII-503 1.5. Poly(vinyl alcohols), Poly(acetals), Poly(vinyl ketones) ' VII-504 1.6. Poly(vinyl halides) VII-505 1.7. Poly(vinyl nitrites) VII-506 1.8. Poly(vinyl esters) VII-506 1.9. Poly(styrenes) VII-507 1.10. Other Compounds VII-508 Table 2. Main-Chain Carbocyclic Polymers VII-509 2.1. Poly(phenylenes) VII-509 2.2. Other Compounds VII-510 Table 3. Main-Chain Carbonyl Polymers VII-510 Table 4. Main-Chain Acyclic Heteroatom Polymers VII-511 4.1. Main-Chain - C - O - C Polymers VII-511 4.1.1. Poly(oxides) VII-511 4.1.2. Poly(carbonates) VII-513 4.1.3. Poly(esters) VII-513 4.1.4. Poly(anhydrides) VII-515 4.1.5. Poly(urethanes) VII-515 4.2. Main-Chain - O - Heteroatom Polymers VII-515 4.2.1. Poly(sulfonates) VII-515 4.2.2. Poly(siloxanes) VII-516

4.3.

Table 5.

Table 6. Table 7.

Main-Chain - C - S - C - and - C - S - N - Polymers 4.3.1. Poly(sulfides) 4.3.2. Poly(sulfones) 4.3.3. Others 4.4. Main-Chain - C - N - C Polymers 4.4.1. Poly(amides) 4.4.2. Poly(hydrazides) 4.4.3. Poly(ureas) 4.4.4. Poly(carbodiimides) 4.4.5. Other Compounds 4.5. Poly(phosphazenes) and Related Compounds 4.6. Poly(silanes), Poly(silazanes) Main-Chain Heterocyclic Polymers 5.1. Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) 5.2. Poly(dithiazoles), Poly(benzothiazoles) 5.3. Poly(imides) 5.3.1. Poly(benzimides) 5.3.2. Poly(pyromellitides) 5.3.3. Others 5.4. Poly(quinoxalines) 5.5. Poly(benzimidazoles) 5.6. Poly(piperazines) 5.7. Poly(anhydrides) 5.8. Poly(thiophenes) 5.9. Others Formaldehyde Resins Natural Polymers and Modified Natural Polymers 7.1. Natural Rubber and Derivatives 7.2. Cutta Percha 7.3. Cellulose and Derivatives 7.3.1. Cellulose 7.3.2. Cellulose Ethers

VII-516 VII-516 VII-517 VII-518 VII-518 VII-518 VII-520 VII-521 VII-521 VII-521 VII-522 VII-522 VII-523 VII-523 VII-524 VII-524 VII-524 VII-525 VII-525 VII-526 VII-526 VII-526 VII-527 VII-527 VII-527 VII-528 VII-528 VII-528 VII-529 VII-529 VII-529 VII-529

7.3.3. Cellulose Esters VII-530 7.3.4. Cellulose Nitrate and Sulfate VII-531 7.4. Starch and Derivatives VII-531 7.5. Other Poly(saccharides) VII-531 7.6. Natural Resins VII-532 Table 8. Inorganic Polymers VII-532 Table 9. Poly(electrolytes) VII-533 Table 10. Block Polymers VIJ-533 Table 11. Dendrimers VII-534 D. References VII-536

A.

INTRODUCTION

The tables contain qualitative solubility data for a selected number of polymers. Since no standard definition for solvent-nonsolvent systems has been used in most of the original sources, the recognition of a certain compound as a solvent or nonsolvent is to some extent influenced by personal interpretation. No attempt has been made to edit the original information. Division into only two classes, solvents and nonsolvents, is dictated by the practical point of view. For more quantitative information, the user is referred to the tables of theta solvents and fractionation of polymers in this Handbook. The arrangement of polymers into classes is based on chemical structure. Since properties change gradually within a series of homologs, polymers are arranged according to increasing complexity, as regards the size of the monomer unit, and the kind and number of substituents. Only when this principle could not be applied was an alphabetical listing chosen. We believe that a typical solution behavior of similar polymers may be recognized more easily by this arrangement. When formulas are given, they refer to the main structures present in the polymers. Polymers are named in a manner thought to be most recognizable to the reader. IUPAC or common names (and sometimes both) are used. The table has nearly doubled in size since the last edition. New polymer categories include copolymers, mainchain carbonyl polymers, block copolymers and dendrimers, emphasizing recently developed materials. Copolymers are generally named with the dominant monomer given first, but the reader should check alternate names, since each polymer is listed only once. Solubility of copolymers generally resemble more or less the properties of the dominating monomer, although they often exhibit higher solubilities than the corresponding homopolymers. The solubility of block copolymers may reflect the solubilizing/dispersing power of one of the polymer segments rather than true solubility of all segments. Dendrimers are shown as the repeating monomer unit, with the terminal unit specified when known.

Solubility normally increases with rising temperature. However, negative temperature coefficients in some solvents are observed. This is particularly true for cellulose and poly(ethylene oxide)s. Increasing molecular weight generally reduces solubility. Increased branching increases the solubility compared to a linear polymer of the same molecular weight. Certain combinations of two or more solvents may become nonsolvents. Conversely, mixtures of two or more nonsolvents may sometimes become solvents. These possibilities should be considered if new solvent-nonsolvent combinations are to be examined. It is recommended that the reader consults the solubility parameter section in this Handbook. The classification of a certain compound as a nonsolvent does not necessarily imply its ability to act as a precipitant since this is also influenced by the nature of the particular solvent of a solvent-nonsolvent pair. However, most nonsolvents combine both properties. The list of solvents and nonsolvents for each polymer is arranged alphabetically. If class names are used, they refer to the most common compounds. Less common compounds, although falling into a class already mentioned, are additionally cited. Water is a nonsolvent for most polymers and is, therefore, often not mentioned or only mentioned if similar polymers or derivatives are water soluble. The data refer to room temperature unless otherwise stated. Homologs and closely related compounds generally have similar solubility properties. When specific solvents or nonsolvents are cited, it is done so with the understanding that homologs and compounds with similar structures can be expected to exhibit similar properties.

B.

ABBREVIATIONS

bzn. DMA DMF DMSO HMPT TMS THF W aqu. cone. DS degrad. dil. mol. wt. rt SC sw temp.

Benzene /V,/V-Dimethylacetamide Af,N~Dimethylformamide Dimethyl sulfoxide Hexamethylphosphoric triamide Tetramethylene sulfone Tetrahydrofuran Water Aqueous Concentrated Degree of substitution Degradation Diluted Molecular weight Room temperature Substituent content Swelling Temperature

C. TABLES OF SOLVENTS AND NONSOLVENTS TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS Polymer 1.1.

Solvents

Nonsolvents

Refs.

POLY(DIENES), POLY(ACETYLENES) (see also 6.1, 6.2)

Poly(dienes) unsubstituted Poly(allene) PoIy(1,2-butadiene) 57% 1,2PoIy(1,3-butadiene)

98% cis-, 2% 1,295% cis-, 1% trans100% cis97% trans-, 3% 1,2Poly(isoprene), cis-, with chlorosulfonylisocyanato groups Poly(dienes) substituted Poly(2-terf-butyl-l,3-butadiene) Poly(dicyclopentadiene) Poly(5,7-dimethyl-1,6-octadiene) PoIy(I-methoxybutadiene), crystalline

Bzn., halogenated hydrocarbons Toluene Chloroform Higher aliphatic ethers, hydrocarbons, higher ketones, THF Bzn., toluene Cyclohexane Bzn., heptane/hexane (1/1) Cyclohexane, toluene See PoIy(1,3-butadiene) Toluene Bzn., carbon disulfide, carbon tetrachloride, chloroform, diethyl ether, heptane Toluene See Poly(2-terf-butyl-1,3-butadiene)

Poly(2-chlorobutadiene), chloroprene

Bzn., carbon tetrachloride, chlorinated hydrocarbons, cyclohexane/toluene, cyclohexanone, dioxane, ethyl * acetate, pyridine 1,4-dsBzn., chloroform, ether, hexane, THF Poly[2-(chloromethyl)butadienej Dichloromethane, THF, toluene Poly(perfluoro-1,4-pentadiene) Hexafluorobenzene Poly(2,5-diheptyl~l,4-phenylenehexa-l,3,5-triene-l,6~diyl) Acetone, bzn., chloroform PoIy(1,5-pentamethyl-2-enediyl) Methylene chloride Poly(butadiene-c