Solvents polymers, critical solution temperatures

Supercritical fluids can be used to induce phase separation. Addition of a light SCF to a polymer solvent solution was found to decrease the lower critical solution temperature for phase separation, in some cases by mote than 100°C (1,94). The potential to fractionate polyethylene (95) or accomplish a fractional crystallization (21), both induced by the addition of a supercritical antisolvent, has been proposed. In the latter technique, existence of a pressure eutectic ridge was described, similar to a temperature eutectic trough in a temperature-cooled crystallization. 

Properties. Hydroxypropylcellulose [9004-64-2] (HPC) is a thermoplastic, nonionic cellulose ether that is soluble in water and in many organic solvents. HPC combines organic solvent solubiUty, thermoplasticity, and surface activity with the aqueous thickening and stabilising properties characteristic of other water-soluble ceUulosic polymers described herein. Like the methylceUuloses, HPC exhibits a low critical solution temperature in water. 

Considering the rather complicated processes that take place during dissolution it is not surprising that some systems show peculiar behavior. For example, while solubility generally increases with temperature, there are also polymers that exhibit a negative temperature coefficient of solubility in certain solvents. Thus, poly(ethylene oxide), poly(N-isopropylacrylamide), or poly(methyl vinyl ether) dissolve in water at room temperature but precipitate upon warming. This behavior is found for all polymer-solvent systems showing a lower critical solution temperature (LCST). It can be explained by the temperature-dependent... 

The instance we have considered here, that of a polymer in a poor solvent, results in an upper critical solution temperature (UCST) as shown in Figure 2.33. This occurs due to (a) decreased attractive forces between like molecules at higher temperatures and (b) increased solubility. For some systems, however, a decrease in solubility can occur, and the corresponding critical temperature is located at the minimum of the miscibility curve, resulting in a lower critical solution temperature (LCST). This situation is illustrated in Figure 2.34. 

Interactions between different distant parts of the molecule tend to expand it, so that in the absence of other effects a would be greater than unity, but in solution in poor solvents interactions with the solvent tend to contract it. According to Flory s theory (18) these two tendencies will just balance so that a — 1 at a particular temperature T—0 (the theta temperature ), and at this temperature A2 =0 and further this temperature is the limit as Mn- go of the upper critical solution temperature for the polymer-solvent system in question. Quantities relating to T=0 will be denoted by subscript 0. Flory s theory implies that ... 

At present, we believe that the jump transitions observed in many of the gels studied here represent first order phase transitions. If this is the case, then the gels studied here are among the first found so far in which a first order phase transition occurs near room temperature in pure aqueous solvent with substantial added salt. Early studies by Tanaka s group with poly(acrylamide) based gels required that hydrophobic solvents such as acetone be added for a discontinuous phase transition to be observed near room temperature [6-10]. The more recently studied gels based on poly(n-isopropylacrylamide) [11, 12] and other lower critical solution temperature polymers show discrete phase transitions in water with no salt [11], but the swelling transitions become continuous when moderate amounts of salt are added [12],... 

The phase behaviour of many polymer-solvent systems is similar to type IV and type HI phase behaviour in the classification of van Konynenburg and Scott [5]. In the first case, the most important feature is the presence of an Upper Critical Solution Temperature (UCST) and a Lower Critical Solution Temperature (LCST). The UCST is the temperature at which two liquid phases become identical (critical) if the temperature is isobarically increased. The LCST is the temperature at which two liquid phases critically merge if the system temperature is isobarically reduced. At temperatures between the UCST and the LCST a single-phase region is found, while at temperatures lower than the UCST and higher than the LCST a liquid-liquid equilibrium occurs. Both the UCST and the LCST loci end in a critical endpoint, the point of intersection of the critical curve and the liquid liquid vapour (hhg) equilibrium line. In the two intersection points the two liquid phases become critical in the presence of a... 

The Flory-temperature or theta-temperature (0F) is defined as the temperature where the partial molar free energy due to polymer-solvent interactions is zero, i.e. when y = 0, so that the polymer-solvent systems show ideal solution behaviour. If T = 0F, the molecules can interpenetrate one another freely with no net interactions. For systems with an upper critical solution temperature (UCST) the polymer molecules attract one another at temperatures T < 0F. If the temperature is much below 0F precipitation occurs. On the other hand for systems with a lower critical solution temperature (LOST) the polymer molecules attract one another at temperatures T > F. If the temperature is much above 0F precipitation occurs. Aqueous polymer solutions show this behaviour. Systems with both UCST and LCST are also known (see, e.g. Napper, 1983). 

In SAS, a compressed gas is added to a polymer solution. The upper critical solution temperature (UCST) and lower critical solution temperature (LCST) of that solution are shifted to higher and lower temperatures respectively until they finally merge to one region of immiscibilty over the whole temperature range. This process can be used for solvent recovery in solution polymerisation processes as well as for molecular weight fractionation of polymers. 

Irani, C. A. Cozewith, "Lower Critical Solution Temperature Behavior of Ethylene Propylene Copolymers in Multicomponent Solvents," J. Appl. Polym. Sci., 31, 1879 (1986). 

Kodama, Y. Swinton, F. L., "Lower Critical Solution Temperatures. Part II. Polymethylene in Binary n-Alkane Solvents," Brit. Polym. J., 10, 201 (1978). 

There is, however, a mass transfer problem of demixing at lower temperatures caused by high viscosities. Concentrated polymer solutions tend to take hours to form two distinct liquid phases. A solution to this problem is the use of the lower critical solution temperature. Because of their thermodynamic nature, all polymer-solvent mixtures tend to form two liquid phases ( LL ) with low viscosities, at higher temperatures (LCST) as depicted in Figure 3. 

SCF technology has spread quickly from molecules such as naphthalene to more complex substances such as polymers, biomolecules, and surfactants. Supercritical fluids can be used to reduce the lower critical solution temperature of polymer solutions in order to remove polymers from liquid solvents(6.26 The technology has been extended to induce crystallization of other substances besides polymers from liquids, and has been named gas recrystallization(4). In other important applications, SCF carbon dioxide has been used to accomplish challenging fractionations of poly(ethylene glycols) selectively based on molecular weight as discussed in this symposium, and of other polymers(. ... 

Upper and lower theta-temoeratures. Many polymers precipitate from solution when heated. This "lower critical solution temperature" [LCST] lies above the normal (1 atm) boiling temperature for the solvent. The phentmienon is observed for samples in sealed tubes. 

Figure 1.28. A phase diagram for a (hypothetical) polymer-solvent or pol5mier-polymer system showing both lower (LCST) and upper (UCST) critical solution temperatures. The boundary may be determined by locating the cloud point as a function of temperature for a fixed composition as the system moves from being a single-phase system to being a two-phase system and vice versa.

Particularly evident is the lack of systematic reports on polymer-mixed solvents data (VLE or LLE) in the open hterature, especially in form of full-phase equilibrium measurements. Most experimental studies for mixed solvent systans have been reported by Chinese and Japanese investigators - and only a few by other investigators. Data are often reported simply as soluble/nonsoluble or as theta temperatures (critical solution temperature at infinite polymer molecular weight). Several reported polymer-mixed solvent data concern supercritical fluid applications (e.g., polypropylene/pen-tane/C02, and PEG/C02/cosolvent ) and bioseparations, especially for systems related to the partitioning of biomolecules in aqueons two-phase systems, which contain PEG and dextran. A recent review for data on solnbihty of gases in glassy polymers is also available. ... 

Cloud-point curves or precipitation curves for different polymer-solvent systems have different shapes (Figs. 3.12 and 3.13). The maxima and minima on these curves indicate the upper critical solution temperature (UCST) and the lower critical solution temperature (LCST), respectively. As indicated in Figs. 3.12 and 3.13, the phase diagram of a polymer solution has two regions of limited miscibility (i) below UCST associated with the theta temperature (see Problem 3.16) and (ii) above LCST. 

The thermodynamic affinity of a solvent to a polymer changes with temperature, and this predetermines the type of critical solution temperature. If the positive values of the second virial coefficient A2 and the negative values of AGmix decrease as temperature drops, it may be predicted that the system will separate into two phases on cooling, i.e., UCST is observed (e.g., solution of polystyrene in cyclohexane). If the positive values of A2 and the negative values of AGmix decrease as temperature rises, the system will separate on heating, i.e., it possesses LCST (e.g., solution of polyisobutylene in pentane). 

Polymer-solvent mixtures can be separated and the polymer recovered from solution at the lower critical solution temperature (LCST). This is the temperature at which the miscible polymer-solvent mixture separates into a polymer-rich phase and a solvent-rich phase. LCST phenomena are related to the chemical nature of the mixture components, the molecular weight of the mixture components, especially the polymer, and the critical temperature and critical pressure of the solvent (Allen and Baker, 1965). As the single-phase polymer solution is isobarically heated to conditions near the critical point of the solvent, the polymer and solvent thermally expand at different rates. This means their free volumes change at different rates (Patterson, 1969). The thermal expansion of the solvent is much greater than that of the polymer. Near its critical point, the solvent has expanded so much that it is no longer able to solubilize the polymer. Hence, the polymer falls out of solution. If the molecular weight of the polymer is on the order of 10 a polymer-solvent LCST can occur within about 20-30°C of the solvent s critical temperature. If the molecular weight of the polymer is closer to 10, the LCST phase... 

It is claimed that although measurements of the lower limit are reproducible determination of the upper limit is quite a problem with errors of 2-3 nm in the calculations. Apparently above this limit solvent cast films appear to be immiscible whatever the polymer tacticity. It is suggested that changes in the donor/acceptor emissions with tacticity are simply due to an effect on the chain conformation of the probability of intermolecular interactions. As a final criticism it is shown that heating a monophase blend above the lower critical solution temperature does not actually result in a significant enough change in the donor/acceptor emission ratio to be able to detect phase separation. However, it should be pointed out that the studies of... 

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