In an effort to gain insight into the origin of the effects of end groups on the cloud point temperature (Tcp) as a function of the polymer molar mass of thermoresponsive polymers with lower critical solution behavior in dilute aqueous solutions, we use the Flory-Huggins (FH) theory amended for end groups. The theory was applied to available experimental data sets of poly(N-isopropylacrylamide) (PNIPAM), poly(4-vinylbenzyl methoxytris(oxyethylene) ether) (PTEGSt), and poly(α-hydro-ω-(4-vinylbenzyl)tetrakis(oxyethylene) ether) (PHTrEGSt). The theory relates the variations in TcpM,ϕcp for different end groups to the effective FH χ parameter of the end groups and explains the qualitative notion that the influence of the end groups is related to the hydrophobicity/hydrophilicity of the end groups relative to that of the so called intrinsic TcpM,ϕcp response of a polymer without end groups. The limits to the applicability of the FH theory are established, and a set of possible theoretical improvements is considered. The ultimate scrutiny of the simple FH theory and suggested improved theories must await the measurement of truly thermodynamic cloud points; the available cloud points are merely estimations of the thermodynamic cloud point, for which the deviation to the true cloud point cannot be established with sufficient accuracy.
Keywords: FH theory for end-functionalized homopolymers; cloud point temperature; dilute solution regime; end groups; lower critical solution behavior; thermoresponsive polymers.