Theta Solvents H a n s G . E l i a s Mcihg ian Moelcualr n I stiute, 1910 West St. Ande rws Rd,. Md ialnd, Ml 48640, A. Introduction 1. Fundamentals 1.1. Thermodynamics 1.2. Unperturbed Dimensions 2. Methods to Determine Theta Solvents 2.1. Phase Equilibrium (PE) 2.2. Second Virial Coefficient (A) 2.3. Cloud Point Titration (CP) 2.4. Cloud Temperature Titration (CT) 2.5. Unperturbed Dimensions (RGM, VM, DM, SM) 2.6. Other Methods B. Tables of Theta Solvents for Polymers Table 1. Homochain Polymers 1.1. Poly(alkanes) 1.2. Poly(alkenes) 1.3. Poly(styrenes) 1.4. Poly(vinyls) 1.5. Poly(acrylics) and Related Compounds 1.6. Poly(methacrylics) and Related Compounds 1.7. Other Carbon Chains Table 2. Heterochain Polymers 2.1. Poly(acetals) and Poly(ethers) 2.2. Poly(esters) 2.3. Poly(amides) 2.4. Polyureas and Polyurethanes 2.5. Polysaccharides 2.6. Carbon-Sulfur Chains 2.7. Silicon-Oxygen Chains 2.8. Phosphorus-Oxygen Chains C. References A.

INTRODUCTION

1.

Fundamentals

VII-291 VII-291 VII-291 VII-292 VII-293 VII-293 VII-293 VII-294 VII-294 VII-294 VII-294 VII-295 VII-295 VII-295 VII-299 VII-300 VII-305 VII-307 Vll-308 VII-312 VII-313 VII-313 VII-315 VII-316 VII-316 VII-316 VII-317 VII-317 VII-318 VII-318

/ . / Thermodynamics The theta state is defined as that state of a polymer solution at which the excess chemical potential, and correspondingly, the excess Gibbs energy of

dilution is zero. For a given polymer-solvent system, this state is obtained at a certain characteristic temperature, the theta temperature 0. A solvent at this temperature is called a theta solvent. Since Flory (110) was the first to show the importance of the theta state for a better understanding of physical structures and properties of polymers, the theta temperature is sometimes also called "Flory temperature". The name "van't Hoff temperature" has also been suggested (127). However, neither "Flory temperature" nor "van't Hoff temperature" has gained acceptance. The exact definition of the theta state is given by chemical thermodynamics. The chemical potential of a solvent 1, A/i i, can be split into an ideal term and an excess term: (Al) where the excess chemical potential at the thermodynamic temperature T is given by the enthalpy of dilution, Ai/1, and the excess entropy of dilution, AS|XC: (A2) A zero excess chemical potential does not imply that both the enthalpy of solution and the excess entropy of solution are zero as in the case of true ideal solutions where AH\ = 0 and A5f c = 0. Rather, a theta state means only that the terms on the right side of Eq. (A2) compensate each other at the theta temperature 0°: (A8) where (M w ) app = apparent mass-average molar mass, Ko- optical constant at zero angle, and /?o = Rayleigh ratio at zero scattering angle. The virial coefficients B and C of light scattering average differently over interactions than those of colligative measurements; B and C of poly molecular ("polydisperse") polymers are numerically different for osmotic pressure and light scattering measurements. The theta temperature may also be phenomenologically defined as the critical miscibility temperature at the limit of infinite molar mass (110). Since a solution may exhibit two

critical miscibility temperatures, a polymer solution may display two theta temperatures. In the case of endothermic solutions, a lowering of temperature leads to less positive second virial coefficients and the theta temperature corresponds to an upper critical solution temperature (UCST) in the limit of infinite molar mass. The theta temperature corresponds to a lower critical solution temperature (LCST) in the case of exothermic solutions (see, e.g., (92)). 1.2. Unperturbed Dimensions The thermodynamic behavior described above results from the fact that longrange interactions between polymer segments are absent in the theta state. Long-range interactions are intramolecular interactions between segments or groups of one and the same polymer molecule that are separated by many chemical bonds along the chain; they are remote in sequence but adjacent in space. Short-range interactions are interactions between chain groups that are near to each other in sequence. They are determined by the length of chain bonds, the valence angles between chain atoms, and the hindrance to rotation around chain bonds (usually due to a pair (4 chain bonds) or two pairs (5 chain bonds) of conformers in the chain). In a thermodynamically good solvent (A2 > 0), polymer-solvent interactions are much larger than polymer-polymer and solvent-solvent interactions. The polymer chain expands in order to minimize polymer-polymer contacts; the dimensions of these chains are said to be perturbed. In such perturbed chains, the space occupied by one polymer segment is excluded for all other segments of the same polymer chain, i.e., even at infinite dilution. In a theta solvent (A2 = 0), polymer-solvent interactions are just balanced by polymer-polymer and solventsolvent interactions. Long-range interactions disappear and the polymer chain assumes its so-called unperturbed dimensions which manifest themselves for linear chains by a dependence of the root-mean square radii of gyration s, on the square root of molar masses: (A9) Intrinsic viscosities [rj] are also controlled by the space requirements of polymer molecules. For unperturbed coils of linear chains, one can write (see textbooks of polymer science) (AlO) where ^o is usually assumed to be a universal constant (but see Ref. 498). The dependence of the radius of gyration, (s2) ' ,or the intrinsic viscosity, [77], on the square-root of the molar mass is generally taken as a manifestation of unperturbed dimensions and thus also of the presence of the theta state of the polymer. The assumption that theta conditions lead to unperturbed dimensions is often fulfilled within limits of error for most of the investigated polymers but it is not true in the general

sense. The thermodynamic definition of the theta state refers to the global properties of polymer solutions whereas the definition of unperturbed dimensions relates to the local properties of the chain. Both definitions agree exactly only if infinitely thin chains are surrounded by a locally and globally homogeneous continuum of solvent molecules. The ability of a theta solvent to generate unperturbed dimensions thus depends on the constitution and configuration of the polymer, the solvent, and the temperature [83] since all these factors influence long-range interactions (excluded volume effects and interactions with the solvent). Small molar mass dependencies of theta temperatures are sometimes detectable for single solvents (230), especially at low molar masses when the effects of end groups or small helical segments (525) become noticeable. However, if the macromolecules have long side chains and if the main chain and the side chains are constitutionally different, then the theta state of a polymer solution may not be identical with the unperturbed state of polymer coils, even for single solvents. An example is the solution of poly(octadecyl methacrylate) in butyl acetate which is in the theta state at 10.50C (A2 = 0). At this temperature, the exponent ay of the intrinsic viscosity/molar mass relationship of Eq. (AlO) was found as av = 0.44 instead of 0.50, due to a contraction of the long side chains (406). A similar discrepancy between the theta state of the polymer-solvent system and the unperturbed dimensions of the polymer coils has been found for cyclic poly(styrene) in cyclohexane where 0 = 28.5°C according to thermodynamics but ay — 0.40 at the same temperature; aw = 1/2 was observed for the considerably higher temperature of T = 400C (366). In both cases, intrinsic viscosities were assumed to reflect unperturbed dimensions. This is not necessarily true, however, since atactic poly(methyl methacrylate) exhibited the same reduced mean-square radius of gyration, (s2)Q/Mw, in the two theta solvents acetonitrile (cp of the nonsolvent 3 at the cloud point is then plotted against the logarithm of the volume fraction 02,cP of the polymer at the cloud point (89,90,531) and extrapolated to pure polymer: (A13) where Bcv is the slope of the 03)Cp =/(ln02,cP)-curve and 03@ is the volume fraction of the nonsolvent in the theta mixture solvent-nonsolvent. At high molar masses (small # cp ) and polymer densities p2 « 1 g/ml, mass-concentrations ^2xp ~ P202,cp (in g/ml) can be used instead of volume fractions 02,cp (93); neglect of these conditions may lead to errors (58). This "Elias method" has been shown to have theoretical justification from the Flory-Huggins lattice model (532,533); a comprehensive review of this method is available (93).

where r is the ratio of molecular volumes of polymer and solvent. 2.5. Unperturbed Dimensions (RGM, VISA, DM, SM) Root-mean-square radii of gyration, (s2)1^2, depend on the as power of the molar mass M (110): (A16) The exponent becomes a s — 1/2 for the unperturbed state where (s2) = (s2}0. The temperature dependence of the function (s2) =f(M) can thus be used to determine the temperature T0 at which as = 1/2 (RGM method). This method is cumbersome; more often used is the temperature dependence of the intrinsic viscosity/molar mass relationship (A17)

because av = 1/2 at the unperturbed state (at TQ) (VM method). Less often used are the corresponding relationships between molar masses and other hydrodynamic properties such as sedimentation coefficients (SM method) or diffusion coefficients (DM method). Unperturbed radii of gyration (from scattering experi2.4. Cloud Temperature Titration (CT) In a variation ments) always seem to indicate theta conditions (cf. Ref. of the cloud point titration method, cloud temperatures may 512) but the database is too small to allow definite proof. be determined by cooling or heating of dilute polymer Unperturbed dimensions from hydrodynamic measuresolutions of various concentrations until cloudiness appears ments in single solvents sometimes do not coincide with (58). The inverse cloud point temperature Tct is then plotted the theta state (cf. Refs. 366,466,512); see also Section 1.2. against the logarithm of the volume fraction 2,ct of the Hydrodynamic measurements in mixed solvents very often polymer 2 at the cloud point and extrapolated to pure deliver different unperturbed dimensions for theta condipolymer: tions (cf. Refs. 31,83,95,154). (A14) This method is also based on the Flory-Huggins lattice model (522,533). In a modification of the method, inverse cloud temperatures are plotted against 1/r06 (530), again based on the Flory-Huggins theory: (A15)

Method Abbreviation A CP CT PE VM

Name Second virial coefficient Cloud point titration Cloud point temperature Phase equilibria (critical solution temperature) Intrinsic viscosity/molar mass

2.6. Other Methods (IG, PL, R) The theta state and/or unperturbed dimensions have occasionally been determined by various other methods: refractometry (R) (7,24), dielectric measurements (E) (5), polarized luminescence (PL) (399), inverse gas chromatography (IG) (412), and dynamic light scattering (LS) (376). Common methods for the determination of theta temperatures 0, theta compositions ^1-, © of mixed solvents, and/or unperturbed dimensions are compared in the following table:

Required for the application Minimum number Knowledge of l>pe of of polymers molar mass solvent 3 1 1 3 3

Yes No No Yes Yes

Preferably single Mixed Preferably single Preferably single Single or mixed

Determined parameter O 03,e

B. TABLES OF THETA SOLVENTS FOR POLYMERS In the following tables, theta solvents and theta temperatures have been compiled for various polymers from the literature. The polymers are subdivided into groups of chemically similar compounds (see beginning of chapter for Contents). Within each group, polymers are arranged alphabetically, mostly according to the polymer names used in the original reference; no attempt has been made to use either IUPAC names (systematic names) or poly(monomer) names exclusively. Monomer units in alternating and random copolymers are listed alphabetically, regardless of their proportions; their relative amounts are given in parentheses on a mole/mole basis. Segments of block and graft copolymers are usually noted in the sequence reported by authors. The following abbreviations are used: alt (alternating), block (self-explanatory), co (statistical or random (or unspecified)), graft (self-explanatory). Polymers are further characterized by their tacticity (if any), provided it has been reported in the literature. Polymers by free radical polymerizations are usually assumed by authors to be "atactic". Tacticities are usually given as mole fractions of isotactic diads (JCJ), syndiotactic diads (jt5), isotactic triads (xa), syndiotactic triads (x ss ), heterotactic triads (^i8), ds-configurations (jtCis)» trans-

configurations (x trans)- If no quantitative characterization was reported, tacticities are described as it (predominantly isotactic), st (predominantly syndiotactic), at (neither predominantly iso- nor syndiotactic), cis (predominantly cis-tactic), or trans (predominantly trans-tactic). For each polymer, theta solvents are given in alphabetical order; no attempt was made to convert commonly used solvent names into systematic names (e.g. dioxane = 1,4dioxane). In mixed solvents, the liquid listed first may thus be a solvent or a nonsolvent. Compositions of mixed solvents are given in vol./vol. unless otherwise noted (ex: w/w indicates weight per weight). A recent (smaller) list (496) of "Theta Temperatures" is mainly concerned with unperturbed dimensions. Since these dimensions are often evaluated from measurements at nontheta temperatures using various theories of intrinsic viscosity/molar mass, or (far less frequent) radius of gyration/molar mass relationships, reported "theta temperatures" are often not theta temperatures per se but the temperatures at which measurements in thermodynamically good solvents have been performed. A comprehensive list of unperturbed dimensions of various polymers can be found in Section VII/1 of this Handbook and a list of characteristic ratios of polymethacrylates in (497).

TABLE 1. HOMOCHAIN POLYMERS Polymer (mol/mol)

Theta solvent (v/v)

Theta temp. (0C)

Method

Refs.

35 30 20 23 83 83 86.2 141 61 61 - 46 89.1 89 35.0 148 64.5

A, VM A, VM PE, VM PE, VM VM PE, VM PE PE, VM VM PE, VM PE, VM PE PE, VM VM PE 5 VM PE, VM

238 237 16 245,246 245 246 190 246 245 246 246 190 246 304 246 246

1.1. POLY(ALKANES) Poly(acenaphthylene)

Ethylene dichloride (1,2-dichloro ethane)

PoIy(I-butene), atactic

i-Amyl acetate Anisole Diphenyl ether Phenetole

-,isotactic

Toluene Anisole Cyclohexane/n-propanol (69/31) Diphenyl ether Phenetole

Poly(butene-c0-ethylene), 40 branches per 100 backbone carbon atoms Poly(ethylene)

3-Octanol 2-Octanol 1-Octanol f-Amyl alcohol Anisole Benzyl phenyl ether Bis(2-ethylhexyl) adipate Bis(2-ethylhexyl sebacate) Carbon disulfide n-Decanol Dibutyl phthalate Dioctyl adipate Diphenyl

5.0 29.0 59.0 199.2 153.5 191.5 170 145 145 150 -73 153.3 >200 145 128

VM VM VM PE PE PE PE VM PE PE PE PE PE VM PE

514 514 514 251 251 251 324 351 240 324 510 251 324 508 353

References page VII - 318

TABLE 1. cont'd Polymer (mol/mol)

Theta solvent (v/v)

Diphenyl ether Diphenyl methane Diphenylene oxide n-Dodecanol n-Heptane n-Hexane *-Hexanol//?-xylene (70/30) «-Hexanol/xylene (70/30) Nitrobenzene /?-Nonyl phenol «-Octane /i-Octanol p-Octyl phenol rc-Pentane 3,5,5-Trimethylhexyl acetate Poly(ethylene-a/f-propylene)

Poly(ethylene-co-propylene) Poly(ethyl ethylene) Poly(l-hexene)

Benzene n-Decyl acetate n-Heptyl acetate n-Hexyl acetate n-Octyl acetate Methanol/toluene (50/50) 2-Octanol Phenetole Butanone/n-hexane (29.8/70.2) Butanone//-propanol (37/63) (41.5/58.5) Dioxane/n-hexane (40/60) n-Hexyl chloride

Poly(isobutene)

/-Amyl benzyl ether i-Amyl butyrate i-Amyl /-valerate

i-Amyl n-valerate n-Amyl butyrate Anisole Benzene

n-Butanol/n-hexane (23.6/76.4) n-ButanoI/methyicyclohexane (29.2/70.8) (42.1/57.9) Butanone/carbon tetrachloride (33.7/66.3) Butanone/cyclohexane (36.8/63.2) Butanone/n-hexane (36.6/63.4) n-Butyl n-butyrate

Theta temp. (0C)

Method

Refs.

127.5 127.5 125 118 118 165 163.9 161.4 142.2 118 143.4 138 137.3 173.9 133.3 133 155 170 >200 162.4 210 180.1 174.5 85 80.0 126 121 19-21.4 5.0 38.0 60.9 27.0

PE, VM VM PE CT PE A PE, VM PE PE, VM PE PE PE, VM PE PE PE PE PE CT PE PE PE PE PE PE PE A PE CP CP CP CP CP

485 492 324 355 462 177 251,485 46 251,485 324 353 324 251 132 132 252 8 136 324 251 132 251 251 252 132 353 353 453 453 453 453 453 346 458 514 210 18 18 154 154 19 154 18 339 339 183 427 517 499 221 339 339 113 517 44 113 320 339 100 100 100 100 100 100 339

23.5 23.5 61.3 8 24 23.5 4 20.5 13 13 23.7 28 22.1 25.0 25.0 27 22.1 21.0 22.0 105.5 25.0 25 24.0 24 22.8 25.0 25.0 49.0 25.0 25.0 25.0 46.2

A, VM VM VM PE PE A, PE A, PE VM A, PE A A, VM A, VM A DM, VM A A SM, VM A A PE 5 VM A PE, VM VM A, VM CP CP CP CP CP CP A

TABLE 1. cont'd Polymer (mol/mol)

Theta solvent (v/v) Carbon tetrachloride/dioxane (63.8/36.2) Chlorobenzene/n-propanol (67.5/37.5) (76.0./24.0) (79.7/20.3) Chloroform/n-propanol (57.9/42.1) (77.1/22.9) (79.5/20.5) Cyclohexane/dioxane (45.1/54.9) Cyclohexane/n-propanol Cyclohexanol/toluene (29.3/70.7) Cyclopentane n-Decanol/n-hexane (41.1/58.9) n-Decanol/methylcyclohexane (47.5/52.5) Dibuty ether Dioxane/n-hexane (48.2/51.8) Dioxane/methylcyclohexane (51.0/49.0) Diphenyl ether Diphenyl ether/ethylbenzene (50/50) (25/75) Ethylbenzene Ethyl caproate Ethyl caprylate Ethyl heptanoate

Poly [ 1 -(4-methylpentyl)-1 -buty lene-a?1 -(1,5-dimethylhexy l)ethylene ( = hydrogenated poly(myrcene) Poly(2-methylpentene-l-sulfone) PoIy(I-octene)

CP CP CP CP CP CP CP CP VM CP

Refs.

PE, VM PE, VM

100 100 100 100 100 100 100 100 305 100 536 100 100 76 100 100 113 113 113 113 113 263 44 113 44 44 536 100 100 100 100 100 100 100 536 536 183 183 100 100 100 536 183 339 183 536 76 44 113 113

n-Hexyl acetate 2-Octanol 0-Chloronaphthalene o-Dichlorobenzene Diphenyl Diphenyl ether Diphenylmethane

60.9 37.6 165 133 194.6 210.0 176.6

A VM VM VM PE, VM PE 1 VM PE, VM

363 454 262 262 334 334 334

2-Octanol Butanone/fl-hexane (35.4/64.6) Butanone//-propanol n-Pentane Phenetole

51.0 11.5 22.5 162.5 50.4

VM PE PE PE PE

514 18 18 169 170

Toluene

Poly(4-methyl-l-pentene, 0.90 < Xx < 0.94

Method

25.0 49.0 25.0 14.0 49.0 25.0 14.0 25.0 35 25.0 188 25.0 25.0 204 25.0 25.0 148 76.0 26.8 -24.0 57 22 33 33 57 22 185 25.0 25.0 25.0 25.0 25.0 25.0 25.0 52 ± 2 45 72.7 24.0 25.0 25.0 25.0 153 47.7 55.5 5.9 103 76.0 87 86.0 -13.0

Ethyl hexanoate Ethyl octanoate 3-Ethylpentane n-Heptanol/n-hexane (37.4/62.6) H-Heptanol/methylcyclohexane (39.5/60.5) rt-Hexane//i-hexanol (68.3/31.7) n-Hexane/3-methylbutanone (57.6/43.4) n-Hexane/n-octanol (63.7/36.3) n-Hexane/n-pentanol (71.7/28.3) n-Hexane/n-propanol (80.3/19.7) 2-Methylbutane (M = 23000, 150000) - , (M = 760000) Methyl capronate Methyl caprylate Methylcycohexane/n-octanol (56.0/44.0) Methylcyclohexane/n-pentanol (65.2/34.8) Methylcyciohexane/w-propanol (74.2/25.8) 2-Methylhexane Methyl heptanoate 3-Methylheptanone-5 Methyl pelargonate 2-Methylpentane Pentane Phenetole Poly(2-methyl-2-butylene) ( = hydrogenated l,4-poly(isoprene)) Poly(methylethylene) Poly([S]-4-methyl-l-hexene), X1 > 0.95

Theta temp. (0C)

CP CP A, RGM, VM CP CP PE PE PE PE PE PE PE

CP CP CP CP CP CP CP A A CP CP CP A A 1 VM A A, RGM, VM

References page VII - 318

TABLE 1. cont'd Polymer (mol/mol)

Theta solvent (v/v)

Poly(l-pentene), atactic

Anisole i-Butyl acetate Diphenylmethane Phenetole Phenetole Phenyl ether i-Amyl acetate Anisole i-Butyl acetate Diphenylmethane 2-Pentanol Phenetole

-, isotactic

Poly(propylene), atactic

Phenyl ether i-Amyl acetate n-Amyl acetate n-Butanol/carbon tetrachloride (33/67) n-Butanol/n-hexane (32/68) n-Butanol/methylcyclohexane (34/66) /-Butyl acetate n-Butyl acetate Carbon tetrachloride/n-propanol (74/26) 1-Chloronaphthalene Cyclohexanone Diphenyl Diphenyl ether

-, isotactic

n-Hexane/fl-propanol Methylcyclohexane/n-propanol (69/31) 1-Octanol 2-OctanoI 3-Octanol n-Propyl acetate *-Amyl acetate i-Amyl benzylether p-t-Amyl phenol Benzyl phenyl ether Benzyl propionate rc-Butyl alcohol r-Butyl alcohol p-r-Butyl phenol 1-Chloronaphthalene /7-Cresol Dibenzyl ether Diphenyl Diphenyl ether

-, syndiotactic Poly(propylene), head-to-head

Diphenylmethane p-Ethyl phenol i-Octyl phenol /7-Octyl phenol i-Amyl acetate i-Amylacetate

Poly(vinyl ethylene), at

2-Octanol

Theta temp. (0C)

Method

Refs.

85 32.5 121.0 64.0 48.3 149 31.5 85 32.5 121.0 62.4 55.8 64.0 149 34 34 36.6 25.0 25.0 25.0 65.5 58.0 58.5 25.0 74 68 92 129 153.3 146 25 25 77 37 6 5.0 85.5 70 34 111 140.8 181.8 132 147.2 122 166.0 74 206 183.2 183.2 125.1 125.1 125.0 146.2 145 143 142.8 142.8 116.5 184 115 106 45 43 56.8 32.8

PE, VM PE, VM PE, VM PE, VM A PE, VM VM PE, VM PE, VM PE, VM PE A PE, VM PE, VM VM VM A CP CP CP A VM A CP PE A PE VM PE VM CP CP CP CP CP A A

472 472 472 472 192 472 243 472 472 472 219 192 472 472 69 244 333 78 78 78 333 244 332 78 171,521 314 171,521 244 172 244 78 78 453 453 453 333 152 69 448 448 448 448 448 448 448 521 448 255 448 255 448 244 172 171,521 244 255 448 448 448 448 448 152 471 514 458

PE PE PE PE PE PE PE A PE PE PE PE PE VM PE PE, VM VM PE PE PE PE PE PE A PE VM A, VM

TABLEI. cont'd Polymer (mol/mol) 1.2.

Theta solvent (v/v)

Theta temp. (0C)

Method

Refs.

POLY(ALKENES)

1,4-Poly(butadiene), 97.0% cis 95.0% cis 94.6% cis

94.0% cis 93.0% cis

^-Heptane /7-Propyl acetate Diethyl ketone 5-Methyl-2-hexanone/2-pentanone (1/3) (1/1) (3/1) 3-Pentanone 3-Pentanone/2-pentanone (3/2) Diethyl ketone Ethyl propyl ketone Propylene oxide Diethyl ketone Ethyl propyl ketone Propylene oxide

90.0% cis

-, 70% cis-1,4; 23% trans-1,4; 7% 3,4 -, 43% 1,2 units; trans/cis = 2.3/1 -, 36% cis; 57% trans; 7% 1,2-vinyl -, -, hydrogenated rc-Hexyl 1,4-Poly(butadiene), 9% cyclization 31% cyclization 46% cyclization 63% cyclization 81% cyclization Poly(butadiene-o>-styrene) (76.1/23.9) (75/25) (70/30) 1,4-Poly(chloroprene), cis

/-Butyl acetate n-Heptane/w-hexane (25/75) (50/50) 5-Methyl-2-hexanone 2-Pentanone 3-Pentanone Dioxane Dioxane Dioxane acetate Cyclohexanone/dioxane (12/88) Cyclohexanone/dioxane (17/83) Cyclohexanone/dioxane (21/79) Cyclohexanone/dioxane (30/70) Cyclohexanone/dioxane (39/61) Methyl /-butyl ketone 2-Pentanone /?-Octane /?-Octane Butanone Cyclohexane Cyclopentane Decalin, trans

1 ,4-Poly(2,3-dimethylbutadiene) >85% trans-1,4; 3% 1,2-vinyl 1,4-Poly(isoprene). Natural rubber 96% cis 94% cis trans (gutta percha) trans (other)

-, 51% 1,4-units (mainly trans; 49% 3,4units, 1-2% 1,2-units -, - . hydrogenated -, 50.0 12.5 > 30 32.3 33.1 34.3 36.8 37.0 39 30 31 -10 139 80.0 20, 27 5.7, 10 43, 53 34.5 38 9.5 10.0 16.4 85.0 45 20

CT CT CT CT CT CT CT CT A A A A VM A, VM

CP

280 280 280 280 280 280 280 280 63 63 63 63 64 3 272 217 536 536 470 479 479 479 479 59 266 479 494 479 217 98

20 20 20 220 -49 249.8 35 25 35

CP CP CP PE PE PE A A, CP A

98 98 98 296 296 460 62 95 62

22.3 21.0 18.1 30.5 32.9 30.0 29.3 75.0 25 25 25 25 25 52.2 25 25 25 92.6 23.4

VM VM VM VM VM VM VM VM A, VM VM

References page VII - 318

TABLE 1. cont'd Polymer (mol/mol)

Theta solvent (v/v) Benzene/n-hexane (38/61) (34.7/65.3) Benzene/methanol (74.7/25.3) (74/26) (77.8/22.2) (78/22) (78/22) Benzene//-propanol (66/34) (64.2/35.8) (69/31) Bicyclohexyl Butanone Butanone/methanol (89/11) (89.7/11.3) (88.9/11.1) Butanone//-propanol (85.7/14.3) (82.6/17.4) (87/13) (87/13) /-Butyl acetate f-Butyl acetate Butylchioride n-Butyl formate Carbon tetrachloride/n-butanol (65/35) Carbon tetrachloride/heptane (53/47) Carbon tetrachloride/methanol (81.7/28.3) Chlorobenzene/di-z-propyl ether (32/68) 1-Chlorodecane l-Chlorodecane/3-methylcyclohexane (21.8/78.2) (25.0/75.0) (50.5/49.5) (90.0/10.0) 1-Chlorododecane Chloroform/methanol (74.7/25.3) (75.2/24.8) 1-Chloroundecane Cyclodecane Cycloheptane Cyclohexane

Theta temp. (0C)

Method

Refs.

20 25 35 34 25 23.5 21.5 20 25 35 61 148.8 25 25 30 23 34 67 67 - 46 - 34.7 109.3 35.6 - 9 -7.5 35 35 25 25 6 6.6 8.5

CP A, CP A VM A, CP A PE CP A, CP A PE PE A, VM A, CP PE A VM A A PE PE PE SM A CP A A A, CP A1 CP CT A VM

128 95 62 31 95 42 42 98 95 62 522 460 273 95 315 53 31 115 274 296 374 374 233 307 375 62 62 95 95 22 269 456

22.8 35.0 59.6 87.8 58.6 58.6 25 25 32.8 32.8 32.8 16 17 19.0 213 34.0 34.0 34.0 34.0 34.4 34.5 34.5 34.5 34.5 34.5 34.5 34.8 35.0 35.0 35.0 35.0 35.0

CT CT CT CT A VM A, VM A, CP A A VM PE PE VM PE VM PE A PE A, VM VM VM A VM DM, VM VM A A DM, SM DM A SM

22 22 22 22 269 456 273 95 269 270 456 445 445 456 371 31 189 307 439 188 2, 476 488 42 290 427 456 270 274 43,308 232 229 144

TABLE 1. cont'd Polymer (mol/mol)

Theta solvent (v/v)

Cyclohexane, deuterated Cyclohexane/methylcyclohexane (2/1) (1/1) (1/2) Cyclohexane/toluene (86.9/13.1) Cyclohexanol

Cyclopentane

Cyclooctane Decalin (wcis = 0) (wcis = 0) (Wc1S=O) (wcis=0) (wcis=0) (w c l s =0.20) (w c i s =0.23) (wcls = 0.50) (wcis = 0.54) (wcis =0.60) (w c i s =0.66) (w cis = 0.80) (wcis = 1.00) (Wcis = 1.00) (Wcis = 1.00) cis/trans cis/trans unknown unknown unknown Diethyl ether/dimethoxy ethane (0.7/0.3) Di(2-ethylhexyl) phthalate Diethyl malonate

Diethyl malonate/diethyl oxalate (4/1) (1/1) (1/4) Diethyl oxalate

Dimethyl succinate Dioctylphthalate

Theta temp. (0C) 35.0 35.0 40.2 40.0 38 43 48 54 15 79 83.5 83.5 83.5 86 87 87.8 19.6 19.6 19.8 20 20.5 20.6 154 154.5 154.2 12 20.5 23.8 22.8 21.2 21.0 20.4 21.2 19.3 15.5 16.0 15.0 15.2 14.0 12.5 12.2 10.8 19.3 14.5 31 29.5 18.2 - 5 - 27 22 31 34.2 34.5 35.6 35.9 36.0 40 47 52.6 51.5 55.8 58.2 59.6 67.6 22

Method

A A PE VM VM VM PE CT A VM A PE PE CT PE A, VM PE VM PE A, VM PE PE VM A CT A DM 1 VM PE 5 VM A PE A A A A A A CP PE A A A DM A A A VM VM PE A VM VM VM VM A VM VM CT VM

Refs. 328 439 328 439 438 2 2 2 315 135 118 290 307 461 8 22 203 368 460 536 456 204 536 368 203 445 456 153 22 26 427 119 26 268 26 160 26 451 26 26 451 523 271 42 289 153 182 356 356 160 307 2 456 42 270 503 2 2 2 307 2 456 22 456 26

References page VII - 318

TABLE 1.

cont'd

Polymer (mol/mol)

Theta solvent (v/v) Dioxane/n-heptane (41.5/58.5) DioxaneM-hexane (38/62) Dioxane/methanol (71.4/28.6) (65.1/34.9) (66.5/33.5) (66.5/33.5) Dioxane/i-propanol (55/45) (51.5/48.5) Ethyl acetate

Ethyl acetoacetate Ethylcyclohexane Heptane/nitropropane (58/42) Heptane/toluene (52.4/47.6) Hexane/3-methylbutanone (48/52) Hexyl m-xylene Methanol/tetrahydrofuran (28.7/71.3) Methanol/toluene (20/80) (23/77) (23.1/76.6) (24.8/75.2) (27.2/72.8) Methyl acetate Methyl cyclohexane

3-Methyl cyclohexanol Methyl cyclopentane D,L-Menthol 1-Phenyldecane i-Propyl acetate n-Propyl acetate

Poly(styrene), deuterated

D,L-Terpineol Tetrahydrofuran/water (92.3/7.7) Toluene (estimated theta temperature) Cyclohexane Cyclohexane, deuterated

Poly(styrene), H-shaped Poly(styrene), head-to-head

Carbondisulfide Cyclohexane Cyclohexane

Poly(styrene), combs (theta temperatures depend strongly on number and length of branches)

Benzene/methanol (78/22) Cyclohexane

Theta temp. (0C)

Method

Refs.

35 20 25 34 35 35 20 35 - 44.3 -44 - 43.5 139 108.5 70 75.0 35 30 20 12.5 25 25 25.0 25.0 34 45.0 43 114 60 67.2 68 68.0 69.3 70.5 70.5 98.0 98.0 75 144 115 28.0 30.6 - 27 107 - 80 178 78.5 25 -154 30 30 36 36 35 36 34.8 19 16

A CP A, CP VM A A 1 VM CP A LS PE CP PE CP PE VM A PE CP A A, CP A, VM CP VM VM VM PE PE VM A A VM A VM VM CT VM PE PE VM A PE PE PE PE PE VM CP

62 128 95 31 62 82 98 62 376 296 375 296 147 114 456 62 315 99 307 95 273 505 490 31,490 490 296 296 290 184 307 456 438 2 85 22 296 440 440 290 124 124 296 296 296 296 290 322 375 328 439 328 439 439 60 372 329 369

16-24 16-24 18-33 18-33 20-36 28-33

A, PE A PE RGM VM A

PE A, VM PE A, VM A, CT A

42 502 42 502 75 294

TABLE 1. cont'd Polymer (mol/mol)

I beta solvent (v/v) Decalin (cis-trans) Diethyl malonate

Poly(styrene), Poly(styrene), Poly(styrene), Poly(styrene),

3-star 9.4-star (6-15.5) stars cyclic

Poly (1,4-divinylbenzene) (soluble; by anionic polymerization) 1.4. POLY(VINYLS) Poly(2,5-dimethyl-4-vinylethynylpiperidol-4) Poly(divinyl ether-c