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Recently a novel class of responsive uncharged polymer brushes has beenproposed [Klushin et al, J. Chem. Phys. 154, 074904 (2021)] where thebrush-forming chains have an affinity to the substrate. For sufficiently strongsurface interactions, a fraction of chains condenses into a near-surface layer,while the remaining ones form the outer brush with a reduced grafting density.The dense layer and the more tenuous outer brush can be seen as coexistingmicrophases. The effective grafting density of the outer brush is controlled bythe adsorption strength and can be changed reversibly as a response to changesin environmental parameters.  In this paper we use numerical self-consistent field calculations andtheoretical considerations to study this phenomenon in polydisperse brushes.Our results reveal an unexpected effect: Although all chains are chemicallyidentical, shorter chains are adsorbed preferentially. Hence, with the increasein the surface affinity parameter, a reduction in the surface grafting densityof the residual brush is accompanied by a change in the shape of its molecularmass distribution. In particular, an originally bidisperse brush can beeffectively transformed into a nearly monodisperse one containing only thelonger chain fraction.

Adsorption-active polydisperse brush with tunable molecular mass distribution