Surface induced self-organization of comb-like macromolecules

Abstract

SummaryWe present a review of the theoretical and experimental evidence for the peculiar properties of comb copolymers, demonstrating the uniqueness of these materials among other polymer architectures. These special properties include an increase in stiffness upon increasing side-chain length, the spontaneous curvature of adsorbed combs, rod–globule transition, and specific intramolecular self-assembly. We also propose a theory of chemically heterogeneous surface nanopattern formation in ultrathin films of comblike macromolecules containing two different types (A and B) of incompatible side chains (so-called binary combs). Side chains of the binary combs are strongly adsorbed on a surface and segregated with respect to the backbone. The thickness of surface domains formed by the B side chains is controlled by the interaction with the substrate. We predict the stability of direct and inverse disc-, torus- and stripelike nanostructures. Phase diagrams of the film are constructed.

Adsorption of amphiphilic graft copolymers in solvents selective for the grafts on a lyophobic surface: a coarse-grained simulation study

“…Backbones with medium long grafts (N B ca. [20][21][22][23][24][25][26][27][28][29][30] for this solvent quality do not adsorb on the surface and their conformations are fairly stretched. In very poor solvents for the Fig.…”

“…It follows that the behavior of graft copolymers in combined SEC and IC chromatography is the result of an intricate interplay of a number of enthalpic forces and entropic effects. The conformations are affected by the interaction with the surface and can differ from those in bulk, which could modify the adsorption process [22][23][24][25][26][27][28] (feed-back effect).…”

Thermoresponsive Molecular Brushes with a Rigid-Chain Aromatic Polyester Backbone and Poly-2-alkyl-2-oxazoline Side Chains

“…Research on comb-like polymers, or more precisely, molecular brushes, intensified at the end of the 20th century, when new synthetic approaches were developed that allowed the controlled synthesis of high-molecular compounds of various architectures [24][25][26][27][28][29]. As a result, the main regularities of the behavior of graft copolymers in solutions were established; in particular, the influence of the size of the main and side chains, as well as the grafting density of the latter, on the hydrodynamic characteristics and conformation of comb-like macromolecules was revealed [23,[30][31][32][33][34][35][36][37][38][39]. In the formation of properties in solutions of amphiphilic comb-shaped macromolecules, in which the chemical nature of the main and side chains is very different, the affinity to the solvent of various blocks of the graft copolymer is of great importance [40][41][42][43][44][45].…”

Solution behavior of polyimide‐graft‐polystyrene copolymers in selective solvents

“…The solvent behavior of comb‐like polymers and, in particular, regular graft‐copolymers is controlled by the grafting density and the length of side chains since macromolecular conformations are affected by steric interactions between side chains . However, if the backbone and side chains are structurally strongly different, the thermodynamic quality of a solvent with respect to these components is an important factor, influencing solution properties of comb‐like macromolecules .…”