Section: 13 | Upper Critical (UCST) and Lower Critical (LCST) Solution Temperatures of Binary Polymer Solutions |
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John R. Rumble, ed., CRC Handbook of Chemistry and Physics, 103rd Edition (Internet Version 2022), CRC Press/Taylor & Francis, Boca Raton, FL.
If a specific table is cited, use the format: "Physical Constants of Organic Compounds," in CRC Handbook of Chemistry and Physics, 103rd Edition (Internet Version 2022), John R. Rumble, ed., CRC Press/Taylor & Francis, Boca Raton, FL.


Christian Wohlfarth

Liquid–liquid demixing in solutions of polymers in low molar mass solvents is not a rare phenomenon. Demixing depends on concentration, temperature, pressure, molar mass and molar mass distribution function of the polymer, chain branching and end groups of the polymer, the chemical nature of the solvent, isotope substitution in solvents or polymers, chemical composition of copolymers and its distributions, and other variables. Phase diagrams of polymer solutions can therefore show quite complicated behavior when they have to be considered in detail (see Ref. 1a).

Polymer solutions can undergo demixing when cooling a homogeneous solution as well as when heating such a solution. The corresponding cloud-point curves show a maximum (UCST behavior) or a minimum (LCST behavior). For common polymer solutions, the LCST region is at higher temperatures (in many cases near the critical temperature of the solvent) than the UCST region. The temperature range between both extrema provides the essential information where the one-phase region of a polymer solution can be found. In the case of monodisperse polymers the extrema are equal to the critical points. However, in the case of polydisperse polymers with distribution functions, these extrema are threshold temperatures whereas the critical point shifts to higher concentrations on the shoulder of the cloud-point curve. Usually, the critical concentration is much more strongly influenced than the critical temperature. Thus, the table below does not distinguish between threshold and critical temperatures.

UCST and LCST values depend somewhat on pressure. LCST values in the table are usually given at the vapor pressure of the solvent at this temperature. UCST values are measured in most cases at normal pressure; data at higher pressures are neglected here. The interested reader can find such information, for example, in Refs. 76, 84, 104, 157, 165, 177, 185–187, or 192.

However, UCST and LCST values of a given polymer/solvent pair depend strongly on the molar mass of the polymer. In the case of monodisperse polymers, this dependency can be described in good approximation by the so-called Shultz-Flory plot (see Refs. 6 and 8):


where r denotes the number of segments of a polymer (being proportional to the degree of polymerization or to the molar mass or molar volume of the polymer). Extrapolation to r → ∞, i.e., to infinite molar mass, leads to the value of the θ-temperature. This θ-temperature is the highest temperature for UCST behavior or the lowest temperature for LCST behavior of a given polymer/solvent pair. In the case of polydisperse polymers, the segment number in equation (1) is to be replaced by its weight average, rw (related to Mw). The constant in equation (1) reflects further thermodynamic properties of the given polymer/solvent pair, but should not depend on molar mass. A detailed discussion can be found in Ref. 1b.

The table gives the UCST and LCST values for selected polymer/solvent pairs at specified values of the molar mass, as measured by the number average Mn, mass average Mw, or viscosity average Mη. Further information on the molar mass dependence of UCST and LCST can be found in the references.

Critical Solution Temperatures of Binary Polymer Solutions

PolymerMη/g mol–1Mw/g mol–1Mν/g mol–1SolventUCST/KLCST/KRef.
Continued on next page...
Acrylonitrile/butadiene copolymer
(18% Acrylonitrile)840000Ethyl acetate427220
(26% Acrylonitrile)1000000Ethyl acetate412220
Butadiene/α-methylstyrene copolymer (10% α-Methylstyrene)100000Ethyl acetate387393220
Carbon monoxide/ethylene copolymer (1:1, alternating)10000001,1,1,3,3,3-Hexafluoro-2-propanol453159
Cellulose diacetate120000Benzyl alcohol37286
Cellulose diacetate59900755002-Butanone279.7471.5111
Cellulose diacetate593002-Propanone216.2438.242
Cellulose diacetate/styrene graft copolymer (77.4 wt% grafted polystyrene)750000N,N-Dimethylformamide262399106
Cellulose diacetate/styrene graft copolymer (77.4 wt% grafted polystyrene)750000Tetrahydrofuran363106
Cellulose nitrate (13.3 wt% N)unknown2-Propanone328182148
Cellulose triacetate20000Benzyl alcohol32286
Cellulose triacetate1005002-Propanone290.0472.042
Cellulose tricaprylateinfiniteN,N-Dimethylformamide4135
Cellulose tricaprylateinfinite3-Phenyl-1-propanol3215
N,N-Dimethylacrylamide/2-butoxyethyl acrylate copolymer (50 wt% 2-butoxyethyl acrylate)Water<273.2164
N,N-Dimethylacrylamide/butyl acrylate copolymer
(15 wt% Butyl acrylate)Water346.2164
(20 wt% Butyl acrylate)Water323.2164
(30 wt% Butyl acrylate)Water294.2164

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