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Abstract
Recent experimental measurements on the temperature variation of the second virial coefficients A2 in polymer solutions below the Θ point are analyzed theoretically. In contrast to the existent theories we incorporate the ternary collision integral between monomers into our theory in order to recover the stability of the system beyond the Θ region. A scaling law A2=f(τ(M)1/2)/(M)1/2 is derived for the virial coefficient, where τ ≡ T/Θ−1 is the temperature deviation and M is the molecular weight of the polymer. Based on this scaling law, observed molecular weight independence is explained. It is also pointed that the tendency of A2 to increase through a minimum is expected in connection with the coil–globule transition.
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