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The use of a monoalkyltrichlorosilane in the Wurtz-type polymerization is reported to yield (RSi)n referred to as polyalkylsilyne [Bianconi et al., 1989]. The elemental composition and NMR spectra of the polymer suggest a three-dimensional crosslinked structure. 2-16 DENDRITIC (HIGHLY BRANCHED) POLYMERS
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There is an ongoing effort to synthesize different, well-de ned polymer architectures. A considerable thrust in this direction has been the synthesis of dendritic polymers [Bosman et al.,
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DENDRITIC (HIGHLY BRANCHED) POLYMERS
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1999; Fischer and Vogtle, 1999; Frechet and Tomalia, 2002; Kim, 1998; Newkome et al., 1999, 2001; Tomalia, 2001; Tomalia et al., 1990; Vogtle et al., 2000; Voit, 2000]. Dendritic polymers are highly branched polymers polymers with treelike branching, where there are branches on branches on branches, and so on. Dendritic polymers differ considerably from linear (and also from lightly branched) polymers in their molecular shapes. Dendritic polymers have globular shapes, whereas linear polymers have elongated shapes. The term globular shape indicates that the dimensions of the polymer molecule are about the same in all directions, whereas the term elongated shape indicates that the dimensions are much greater in one direction than the other directions. [In the extreme, the globular shape is illustrated by a sphere or ellipsoid (where no axis is much longer than the other axes) and the elongated shape, by a cylinder (where the length of the cylinder is much greater than the diameter)]. The difference in molecular shape leads to differences in the attractive secondary forces present in linear and dendritic polymer molecules. The attractive secondary forces are greater for linear (elongated) polymers because the molecules pack together and attract each other over a larger surface area than is possible for dendritic (globular) polymer molecules. Also, dendritic polymer molecules do not undergo chain entanglements as do linear polymers. Thus, unlike linear polymers, dendritic polymers rarely have suf cient strength to be useful as bers, rubbers, and plastics. However, because of their low secondary forces, dendritic polymers have higher solubility and miscibility with other materials, including other polymers. The globular shape of dendritic polymers also results in lower hydrodynamic volume and lower viscosity compared to linear polymers. Dendritic polymers have potential for use as additives to polymers and oils to modify their viscosity, melt behavior, and lubricating properties; and to aid in compatibilizing mixtures of different materials. The difference between linear and dendritic polymers has an analogy in nature. For example, there are globular and elongated (more often called brous) proteins. The brous proteins have strong secondary attractive forces and are used to construct such materials as bone, skin, and nails. Globular protein molecules do not attract each other strongly and are soluble in aqueous media, and this ts their biological functions. Globular proteins perform catalytic, transport, regulatory, hormonal, and other functions that require their solubility in blood and the other aqueous media of cells and tissures. Another (obvious) difference between linear and dendritic polymers is that dendritic polymers have a much larger number of chain ends. The interesting situation arises when the dendritic polymers are synthesized by methods that result in functional groups such as NH2, OH, or COOH at the chain ends. Such polymers carry a large number of derivitizable functional groups and hold promise as carrier molecules for drug delivery, gene therapy, catalysis, and sensors [Frechet and Tomalia, 2002; Stiriba et al., 2002]. Two types of dendritic polymers have been developed: hyperbranched polymers and dendrimers. 2-16a Random Hyperbranched Polymers
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Hyperbranched polymers are produced in a one-pot synthesis using a multifunctional monomer such as ABf where f is 2 or greater [Bolton and Wooley, 2002; Galina et al., 2002; Kim, 1998; Voit, 2000]. Hyperbranched polymers are more correctly called random hyperbranched polymers because the branching occurs in a random manner. For an AB2 multifunctional monomer such as a diamino or dihydroxy carboxylic acid, f 2 and the product has a structure described by LXII. With increasing conversion AB2 adds to LXII to produce higher X n polymer. The random hyperbranched polymer at every stage of its growth has a single
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