The controlled radical polymerization of N, N-dimethylamino-2-ethyl methacrylate on polyimide multicenter macroinitiators under the action of the activating complex of Cu(I) with nitrogen-containing...

Aqueous solutions of the graft copolymer with a polyimide backbone and poly(N,N-dimethylamino-2-ethyl methacrylate) side chains with a molecular mass of M = 4.7 × 10⁵ and a grafting density of side chains of 0.44 are investigated by light scattering and turbidimetry. Solutions are studied in a wide concentration range of 0.0008–0.0250 g/cm³ at рН values varying from 2 to 12 for each concentration. The temperature dependences of optical transmission, scattered light intensity, and hydrodynamic radii of scattering objects are obtained. It is shown that the copolymer is thermosensitive only at pH > 8.0. A decrease in acidity of the medium at a fixed concentration of the copolymer is accompanied by a decline in temperatures corresponding to the onset and end of phase separation Т₁ and Т₂, leading to the narrowing of this interval. At constant рН values, temperatures Т₁ and Т₂ rise with solution dilution, while the phase transition interval becomes wider.

The adsorption of a single $\mathit{AB}$ random copolymer (RC) chain onto an inhomogeneous $ab$ surface with a regular periodic pattern is studied theoretically. The problem is considered within the simplest model of a partially directed random walk in two dimensions by using the method of generating functions and the annealed approximation for the averaging over disorder in the RC sequence. The existence of the “optimal” RC composition and the degree of correlation in the monomer sequence, at which the inverse transition temperature has a local minimum, is shown. This is characteristic for symmetric and weakly asymmetric surfaces, whereas for surfaces with pronounced asymmetry there is no such local minimum. The best adsorbate for a strongly asymmetric surface is the homopolymer composed of monomer units that are complimentary to the majority sites on the surface. The results for the adsorption transition point obtained in the annealed approximation are compared with the numerical results for random-periodic $AB$-copolymers with a long period being a quenched random sequence of $A$ and $B$ units. The comparison shows that the annealed approximation provides a very good quantitative estimate of the adsorption transition point.

We propose a novel class of responsive polymer brushes, where the effective grafting density can be controlled by external stimuli. This is achieved by using end-grafted polymer chains that have an affinity to the substrate. For sufficiently strong surface interactions, a fraction of chains condenses into a near-surface layer, while the remaining ones form the outer brush. The dense layer and the more tenuous outer brush can be seen as coexisting microphases. The effective grafting density of the outer brush is controlled by the adsorption strength and can be changed reversibly and in a controlled way as a response to changes in environmental parameters. The effect is demonstrated by numerical self-consistent field calculations and analyzed by scaling arguments. Since the thickness of the denser layer is about a few monomer sizes, its capacity to form a microphase is limited by the product of the brush chain length and the grafting density. We explore the range of chain lengths and grafting densities where the effect is most pronounced. In this range, the SCF studies suggest that individual chains inside the brush show large rapid fluctuations between two states that are separated by only a small free energy barrier. The behavior of the brush as a whole, however, does not reflect these large fluctuations, and the effective grafting density varies smoothly as a function of the control parameters.