Block copolymer physical structure

Block copolymers are widely used industrially. In the solid and rubbery states they are used as thermoplastic elastomers, with applications such as impact modification, compatibilization and pressure-sensitive adhesion. In solution, their surfactant properties are exploited in foams, oil additives, solubilizers, thickeners and dispersion agents to name a few. Particularly useful reviews of applications of block copolymers in the solid state are contained in the two books edited by Goodman (1982,1985) and the review article by Riess etal. (1985). The applications of block copolymers in solution have been summarized by Schmolka (1991) and Nace (1996). This book is concerned with the physics underlying the practical applications of block copolymers. Both structural and dynamical properties are considered for melts, solids, dilute solutions and concentrated solutions. The book is organized such that each of these states is considered in a separate chapter. 

A very special type of ABA block copolymer where A is a thermoplastic (e.g., styrene) and B an elastomer (e.g., butadiene) can have properties at ambient temperatures, such as a crosslinked rubber. Domain formations (which serves as a physical crosslinking and reinforcement sites) impart valuable features to block copolymers. They are thermoplastic, can be eaisly molded, and are soluble in common solvents. A domain structure can be shown as in Fig. 2. 

Block copolymers have become increasingly important in recent decades. This importance is due to the fact that their special chemical structure yields unusual physical properties, especially as far as solid-state properties are concerned. Block copolymers are applied in various fields, they are used as surfactants, adhesives, fibres, thermoplastics, and thermoplastic elastomers. 

Somewhat limited work has been reported over the last decade. There are several reports on the synthesis and physical and structural characterization of styrene-dimethylsiloxane 141 144) and methylmethacrylate-dimethylsiloxane145> diblock, triblock and multiblock copolymers. Several reports are also available on the thermal223), solution 224,2251 and surface196 2261 characterization of various styrene-dimethyl-siloxane block copolymers synthesized by anionic techniques. 

Mortensen, K Brown, W Norden, B, Inverse Melting Transition and Evidence of Three-Dimensional Cubatic Structure in a Block-Copolymer Micellar System, Physical Review Letters 68, 2340, 1992. 

Recent developments in polymer chemistry have allowed for the synthesis of a remarkable range of well-defined block copolymers with a high degree of molecular, compositional, and structural homogeneity. These developments are mainly due to the improvement of known polymerization techniques and their combination. Parallel advancements in characterization methods have been critical for the identification of optimum conditions for the synthesis of such materials. The availability of these well-defined block copolymers will facilitate studies in many fields of polymer physics and will provide the opportunity to better explore structure-property relationships which are of fundamental importance for hi-tech applications, such as high temperature separation membranes, drug delivery systems, photonics, multifunctional sensors, nanoreactors, nanopatterning, memory devices etc. 

Kim, J.M., Sakamoto, Y., Hwang, Y.K., Kwon, Y.U., Terasaki, O., Park, S.E. and Stucky, G.D. (2002) Structural design of mesoporous silica by micelle-packing control using blends of amphiphilic block copolymers. Journal of Physical Chemistry B, 106, 2552— 2558. 

Abstract This article is a review of the chemical and physical nature of patternable block copolymers and their use as templates for functional nanostructures. The patternability of block copolymers, that is, the ability to make complex, arbitrarily shaped submicron structures in block copolymer films, results from both their ability to self-assemble into microdomains, the bottom-up approach, and the manipulation of these patterns by a variety of physical and chemical means including top-down lithographic techniques. Procedures for achieving long-range control of microdomain pattern orientation as well... 

PIPAAm-PBMA block copolymers form a micellar structures by selfassociation of the hydrophobic PBMA segments in water, a good solvent for PlPAAm chains below the LCST but a nonsolvent for the PBMA chains. This amphiphilic system produces stable and monodispersed micelles from polymer/A-ethylacetamide (good solvent for the both polymer blocks) solutions dialyzed against water. Hydrophobic dmgs can be physically incorporated into the iimer micelle cores with PBMA chains by hydrophobic interactions between the hydrophobic segments and dmgs. 

Many combinations of diacids—diamines and amino acids are recognized as isomorphic pairs (184), for example, adipic acid and terephthalic acid or 6-aminohexanoic acid and 4-aminocyclohexylacetic acid. In the type AABB copolymers the effect is dependent on the structure of the other comonomer forming the polyamide that is, adipic and terephthalic acids form an isomorphic pair with any of the linear, aliphatic C-6—C-12 diamines but not with -xylylenediamine (185). It is also possible to form nonrandom combinations of two polymers, eg, physical mixtures or blends (Fig. 10), block copolymers, and strictly alternating (187—188) or sequentially ordered copolymers (189), which show a variation in properties with composition differing from those of the random copolymer. Such combinations require care in their preparation and processing to maintain their nonrandom structure, because transamidation introduces significant randomization in a short time above the melting point. 

The structure of block copolymer melts is usually trapped upon vitrification. The mechanisms underlying the glass transition are similar to those of the constituent homopolymers. Thus there is little distinct physics associated with the formation of solid phases by glassy block copolymers. 

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