Polymer solutions critical solution temperatures

Figure 2 illustrates the temperature dependence of the swelling degree as a function of precursor polymer type. Methylcellulose (MC), hydroxypropyl-methylcellulose, type E (HPMC-E) and hydroxypropylmethylcellulose, type K (HPMC-K) gels have comparable effective crosslink densities of about 2 x 10 5 mol/cm3 (as determined from uniaxial compression testing), while the crosslink density of the hydroxypropylcellulose (HPC) gel is about half this [52]. The transition temperature for each gel is within several degrees of the precursor polymer lower critical solution temperature (LCST), except for the MC gel, which has a transition temperature 9 °C higher than the LCST. The sharpness of the transition was about 3%/°C, except for the HPC gel transition, which was much sharper - about 8%/°C. 

Key words smart material, responsive polymer, lower critical solution temperature (LCST), upper critical solution temperature (UCST),phase transition. 

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. 

Second, Schneider s article reviews recent work (notably by Rowlinson, Kohn and co-workers) on phase relations in binary liquid systems where one of the components is much more volatile than the other (D1, D2, E3, M8, R9). Such systems may have lower critical solution temperatures for these systems, an increase in temperature (and, indirectly, pressure) causes precipitation of the heavy component, thereby providing a possible separation technique, e.g., for the fractionation of polymers. 

The critical point (Ij of the two-phase region encountered at reduced temperatures is called an upper critical solution temperature (UCST), and that of the two-phase region found at elevated temperatures is called, perversely, a lower critical solution temperature (LCST). Figure 2 is drawn assuming that the polymer in solution is monodisperse. However, if the polymer in solution is polydisperse, generally similar, but more vaguely defined, regions of phase separation occur. These are known as "cloud-point" curves. The term "cloud point" results from the visual observation of phase separation - a cloudiness in the mixture. 

The hydrophobic interaction results in the existence of a lower critical solution temperature and in the striking result that raising the temperature reduces the solubility, as can be seen in liquid-liquid phase diagrams (see Figure 5.2a). In general, the solution behaviour of water-soluble polymers... 

Figure 8 Schematic for the transition of lower critical solution temperature polymer. (From Ref. 29.)...

Fig. 51 Phase diagram for PS-PI diblock copolymer (Mn = 33 kg/mol, 31vol% PS) as function of temperature, T, and polymer volume fraction, cp, for solutions in dioctyl ph-thalate (DOP), di-n-butyl phthalate (DBP), diethyl phthalate (DEP) and M-tetradecane (C14). ( ) ODT (o) OOT ( ) dilute solution critical micelle temperature, cmt. Subscript 1 identifies phase as normal (PS chains reside in minor domains) subscript 2 indicates inverted phases (PS chains located in major domains). Phase boundaries are drawn as guide to eye, except for DOP in which OOT and ODT phase boundaries (solid lines) show previously determined scaling of PS-PI interaction parameter (xodt

A3 AIBN c Cp DLS DLVO DSC EO GMA HS-DSC KPS LCST Osmotic third virial coefficient 2,2 -Azobis(isobutyronitrile) Polymer concentration Partial heat capacity Dynamic light scattering Derjaguin-Landau-Verwey-Overbeek Differential scanning calorimetry Ethylene oxide Glycidylmethacrylate High-sensitivity differential scanning calorimetry Potassium persulphate Lower critical solution temperature... 

Polymer Adsorption at the Lower Critical Solution Temperature and Its Effect on Colloid Stability... 

Adsorption behavior and the effect on colloid stability of water soluble polymers with a lower critical solution temperature(LCST) have been studied using polystyrene latices plus hydroxy propyl cellulose(HPC). Saturated adsorption(As) of HPC depended significantly on the adsorption temperature and the As obtained at the LCST was 1.5 times as large as the value at room temperature. The high As value obtained at the LCST remained for a long time at room temperature, and the dense adsorption layer formed on the latex particles showed strong protective action against salt and temperature. Furthermore, the dense adsorption layer of HPC on silica particles was very effective in the encapsulation process with polystyrene via emulsion polymerization in which the HPC-coated silica particles were used as seed. 

In this study, adsorption behavior of water soluble polymers and their effect on colloid stability have been studied using polystyrene latices plus cellulose derivatives. As the aqueous solution of hydroxy propyl cellulose(HPC) has a lower critical solution temperature(LCST), near 50 °C(6 ), an increased adsorption and strong protection can be expected by treating the latices with HPC at the LCST. 

UOP FCC unit, 11 700-702 UOP/HYDRO MTO process, 18 568 UOP Olex olefin separation process, 17 724 Up-and-Down Method, 25 217 U/Pb decay schemes, 25 393-394 Updraft sintering, 26 565 Upflow anaerobic sludge blanket (UASB) in biological waste treatment, 25 902 Upgraded slag (UGS), 25 12, 33 Upland Cotton, U.S., 8 13 U-Polymer, 20 189 Upper critical solution temperature (UCST), 20 320, 322 Upper explosive limit (UEL), 22 840 Upper flammability limit, 23 115 Upper flammable limit (UFL), 22 840 Upper Freeport (MVB) coal... 

The preparation of monoliths with polyNIPAAm chains grafted to the internal pore surface was discussed previously. The extended solvated polyNIPAAm-chains that are present below the lower critical solution temperature of this particular polymer are more hydrophilic, while the collapsed chains that prevail above the lower critical solution temperature are more hydrophobic. In contrast to isothermal separations in which the surface polarity remains constant throughout the run [ 136], HIC separation of proteins can be achieved at constant salt concentrations (isocratically) while utilizing the hydrophobic-hydrophilic... 

Poly(A-isopropyl acrylamide) (PNIPAAm) is the most extensively studied temperature-sensitive polymer [10-20]. Crosslinked PNIPAAm exhibits drastic swelling transition at its lower critical solution temperature... 

LOST. We determined the lower critical solution temperature (LCST) of the polymer at various concentrations by visual observation of the temperature at which turbidity first appeared in a solution immersed in a silicone oil bath with the temperature raised at the rate of 3 C/hour. 

High polymers of N-isopropyl acrylamide (NIPAAM) exhibit a lower critical solution temperature (LCST) in phosphate buffered saline above 31 C precipitation occurs, with minimal concentration dependence. 

Lower Critical Solution Temperatures LCSTs were determined from plots of optical density at 600 nm versus temperature for 0.03% solutions of each polymer in PBS and were defined as the temperature at which Asoo = 0.1. Temperatures were raised at less than 0.3 C per minute and were measured with a thermometer that had been calibrated against an NBS primary standard thermometer. LCSTs for Figure 6 were determined from the cloud points of 0.01% solutions. 

The lower critical solution temperature is another crucial polymer property, which, together with the Upper Critical Solution Temperature (UCST), defines fhe fwo solubility boundaries of polymers in solution. Typically, systems are completely miscible below the LCST but only partially miscible above the LCST and completely immiscible above the UCST. 

Liu H, Zhong C (2005) Modeling of the theta (lower critical solution temperature) in polymer solutions using molecular connectivity indices. Eur Polym J 41 139-147... 

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