Branched polymer brushes

Figure 5.4 Schematic illustration of conformational changes of polymer brushes of (a) homopolymers and (b) mixed polymer brushes. Furthermore, the schematic structure of (c) block copolymers and (d) branched polymer brushes is shown.

Highly branched polymers, polymer adsorption and the mesophases of block copolymers may seem weakly connected subjects. However, in this review we bring out some important common features related to the tethering experienced by the polymer chains in all of these structures. Tethered polymer chains, in our parlance, are chains attached to a point, a line, a surface or an interface by their ends. In this view, one may think of the arms of a star polymer as chains tethered to a point [1], or of polymerized macromonomers as chains tethered to a line [2-4]. Adsorption or grafting of end-functionalized polymers to a surface exemplifies a tethered surface layer [5] (a polymer brush ), whereas block copolymers straddling phase boundaries give rise to chains tethered to an interface [6],... 

The chain architecture and chemical structure could be modified by SCVCP leading to a facile, one-pot synthesis of surface-grafted branched polymers. The copolymerization gave an intermediate surface topography and film thickness between the polymer protrusions obtained from SCVP of an AB inimer and the polymer brushes obtained by ATRP of a conventional monomer. The difference in the Br content at the surface between hyperbranched, branched, and linear polymers was confirmed by XPS, suggesting the feasibility to control the surface chemical functionality. The principal result of the works is a demonstration of utility of the surface-initiated SCVP via ATRP to prepare surface-grafted hyperbranched and branched polymers with characteristic architecture and topography. 

In this article I review some of the simulation work addressed specifically to branched polymers. The brushes will be described here in terms of their common characteristics with those of individual branched chains. Therefore, other aspects that do not correlate easily with these characteristics will be omitted. Explicitly, there will be no mention of adsorption kinetics, absorbing or laterally inhomogeneous surfaces, polyelectrolyte brushes, or brushes under the effect of a shear. With the purpose of giving a comprehensive description of these applications, Sect. 2 includes a summary of the theoretical background, including the approximations employed to treat the equifibrium structure of the chains as well as their hydrodynamic behavior in dilute solution and their dynamics. In Sect. 3, the different numerical simulation methods that are appHcable to branched polymer systems are specified, in relation to the problems sketched in Sect. 2. Finally, in Sect. 4, the appHcations of these methods to the different types of branched structures are given in detail. 

Many different simulations have been performed to test the different features of brushes in different situations. Here we will give only a summary of these results, in the context of the similarities and differences with the features observed in individual branched polymers. 

In a series of papers, Matsuda et al. [291-295] employed RAFT-SIP with immobilized benzyl N,N-diethyldithiocarbamate to form polymer brushes from styrene, methacrylamides, acrylamides and acrylates, NIPAM and N-vinyl-2-pyrrolidone on various surfaces. The SIP is initiated by UV irradiation of the surface-bonded dithiocarbamates. Thermoresponsive polymer brushes were prepared by the polymerization of NIPAM and investigated by XPS, wetting experiments and mainly SPM [294]. Patterned polymer brush layers were also prepared. When chloro-methyl styrene was used as a comonomer, RAFT-SIP resulted in branching. By control of the branching, spatio-resolved hyperbranching of a controllable stem/ branch design was realized (Fig. 9.32) [293, 295]. 

The interest in polymer brushes and defined polymer coatings prepared via SIP is not at all restricted to the polymer community or the surface science community. The demand for tailored, fimctionahzed and adaptive surfaces comes from a multitude of scientific branches and also from industry. Possible applications are already discussed in many of the contributions compiled here. Besides polymer science, surface chemistry and physics, they include catalysis, biomedical applications, microfluidics and nanotechnology. This creates a highly interdisciplinary, Hvely and fruitful environment. 

The present article is intended to discuss the state-of-the-art of the design and characterization of the branched polymers obtained by the macromonomer technique, with particular stress on the characterization and the properties of the brush polymers obtained by the homopolymerization of macromonomer. The synthetic aspects of the macromonomer technique, including preparation of various kinds of macromonomers, have been recently reviewed by one of the authors [1]. Therefore, we intend here to outline briefly the macromonomer technique and describe only the very recent important developments in syntheses. Preparation and characterization of the polymeric microspheres by use of macromonomers as reactive (copolymerizable) emulsifiers or dispersants will be described in some detail to represent one of their unique applications. 

A number of well-defined macromonomers differing in the types of the monomer and the end functionality have been made available in these two decades. Their polymerization and copolymerization have provided a relatively easy access to a variety of branched polymers and copolymers, including comb-, star-, brush-, and graft-structures. Progress will no doubt continue to disclose further different types of macromonomers and branched polymers. 

We emphasize at the outset that this article deals with flexible linear chains only, neither branched polymers [54,159] nor the packing of stiff chains near surfaces [52,53] will find much attention. However, we also shall not cover films formed by end-grafted chains ( polymer brushes [160-172]), although in brushes formed from two different types of chains A,B interesting phase separation behavior can occur [165,166] that is related to the phase separation in non-grafted films as treated here. Also films formed from strictly two-dimensional chains in a plane [173-175] are outside of our attention.,... 

Figure 1 Macromolecular architectures linear macromolecular chains (homopolymer, block-copolymer and statistical copolymer [14]), brushed-polymer (= linear chains attached to a polymer-chain brush-polymer, brush-copolymers [14]), star polymer [4], mikto-star-polymer [16], arborescent graft polymer (=repeated grafting of linear chains on a macromolecule [17,18]), dendrimer (= maximally branched, regular polymer [15])...

The first theories that implemented a proper balance of intramolecular interactions and conformational elasticity of the branches were developed by Daoud and Cotton [21] and by Zhulina and Birshtein [22-24]. These theories use scaling concepts (the blob model), originally developed by de Gennes and Alexander to describe the structure of semidilute polymer solutions [64] and planar polymer brushes [65, 66]. Here, the monomer-monomer interactions were incorporated on the level of binary or ternary contacts (corresponding to good and theta-solvent conditions, respectively), and both dilute and semidilute solutions of star polymers were considered. Depending on the solvent quality and the intrinsic stiffness of the arms, the branches of a star could be locally swollen, or exhibit Gaussian statistics [22-24]. 

In contrast to organosoluble polymers, for most known water-based nonionic polymers, the quaUty of water as a solvent decreases upon an increase in temperature. This is known as LCST (lower critical solution temperature) behavior [144], Experimental observations of LCST behavior (thermoinduced collapse) of neutral stars or spherical polymer brushes in water are rare [145, 146], and do not yet provide systematic relationships between the LCST and the degree of branching. 

Regularly branched polymers examples brushes and dendrimers... 

Some polymers are linear—a long chain of connected monomers. PE, PVC, Nylon 66, and polymethyl methacrylate (PMMA) are some linear commercial examples found in this book. Branched polymers can be visualized as a linear polymer with side chains of the same polymer attached to the main chain. While the branches may in turn be branched, they do not connect to another polymer chain. The ends of the branches are not connected to anything. Special types of branched polymers include star polymers, comb polymers, brush polymers, dendronized polymers [1], ladders, and dendrimers. A cross-linked polymer, sometimes called a network polymer, is one in which different chains are connected. Essentially the branches are connected to different polymer chains on the ends. These three polymer structures are shown in Figure 1.3. 

Some non-self-assembled nanopolymers These may be classified as dendrimers, hyper-branched polymers, polymer brushes, etc. 

Polymers are macromolecules based on a large number of repeating units (monomers) covalently bound in a chain-like molecular architecture with a variety of compositions, structures, and properties. A large diversity of synthetic strategies and monomer combinations can be used to generate linear or nonlinear polymers, such as star-shaped, comb (brush), or branched polymers, and dendrimers (Fig. 11.1). 

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