Spherical hyperbranched polymers

Hyperbranched Polymers Grafted from Spherical Particles. 31... 

Dendrimers with terminal functional groups represent mode compact precursors that are spherical and almost monodisperse, with reactive groups placed on their periphery. Their synthesis, structure and properties have been reviewed in monographs and review articles often together with hyperbranched polymers (cf., e.g. [15-20]), as well as in this book. Application of dendrimers as precursors for conventional materials is limited at this time by their relatively high cost. 

Very recently, highly regular, highly controlled, dense branching has been developed. The resulting dendrimers often have a spherical shape with special interior and surface properties. The synthesis and properties of dendrimers has been reviewed (see e.g. G.R. Newkome et al. Dendritic Molecules , VCH, 1996). In this series, a chapter deals with the molecular dimensions of dendrimers and with dendrimer-polymer hybrids. One possible development of such materials may be in the fields of biochemistry and biomaterials. The less perfect hyper-branched polymers synthesized from A2B-type monomers offer a real hope for large scale commercialization. A review of the present status of research on hyperbranched polymers is included. 

In the search to develop new materials for immobilization of homogeneous transition metal catalyst to facilitate catalyst-product separation and catalyst recychng, the study of dendrimers and hyperbranched polymers for application in catalysis has become a subject of intense research in the last five years [68], because they have excellent solubility and a high number of easily accessible active sites. Moreover, the pseudo-spherical structure with nanometer dimensions opens the possibility of separation and recycling by nanofiltration methods. Although dendrimers allow for controlled incorporation of transition metal catalysts in the core [69] as well as at the surface [70], a serious drawback of this approach is the tedious preparation of functionalized dendrimers by multi-step synthesis. 

NLO effects in the thin films. Hyperbranched polymers should be ideal matrix materials as they offer three-dimensional spatial separation of the NLO chromophores in the spherical architecture, and their void-rich topological structure should help minimize optical loss in the NLO process. 

Our research interest in this field is based on the perception that these dendritic polymers could be useful as polymer-rheology control agents as well as spherical, multifunctional macromonomers. Hyperbranched polymers, which were not only thermally and chemically robust under the conditions used, but also could be economically obtained, were created to evaluate these concepts. The latter requirement led us to pursue the one-step polymerization of AB -type monomers. We will review mostly the synthesis of aromatic polymers with stable chemical linkages prepared by the single-step direct method, and we will briefly compare them with polymers made by more controlled multistep syntheses. 

Scanning electron microscopy (SEM) is one of the very useful microscopic methods for the morphological and structural analysis of materials. Larena et al. classified nanopolymers into three groups (1) self-assembled nanostructures (lamellar, lamellar-within-spherical, lamellar-within-cylinder, lamellar-within-lamellar, cylinder within-lamellar, spherical-within-lamellar, and colloidal particles with block copolymers), (2) non-self-assembled nanostructures (dendrimers, hyperbranched polymers, polymer brushes, nanofibers, nanotubes, nanoparticles, nanospheres, nanocapsules, porous materials, and nano-objects), and (3) number of nanoscale dimensions [uD 1 nD (thin films), 2 nD (nanofibers, nanotubes, nanostructures on polymeric surfaces), and 3 nD (nanospheres, nanocapsules, dendrimers, hyperbranched polymers, self-assembled structures, porous materials, nano-objects)] [153]. Most of the polymer blends are immiscible, thermodynamically incompatible, and exhibit multiphase structures depending on the composition and viscosity ratio. They have two types of phase morphology sea-island structure (one phase are dispersed in the matrix in the form of isolated droplets, rods, or platelets) and co-continuous structure (usually formed in dual blends). 

Dendritic architectures are highly branched polymers with tree like branching having an overall spherical or ellipsoidal shape and are known as additives having peripheral functional groups. These macromolecules consist of three subsets namely dendrimers, dendrigraft polymers and hyperbranched polymers (Figrrre 1). 

The spherical architectures of highly branched macromolecules, such as dendrimers, star-shaped polymers, and hyperbranched polymers, have attracted much attention from the viewpoint of nanotechnology, because their numerous terminal units can be converted into various functional groups leading to novel nanomaterials (Zeng and Zimmerman, 1997 Hirao etal., 2007 Satoh, 2009). Thus, various types of dendrimers, star polymers, and hyperbranched polymers have been synthesized and their properties were compared to the linear analogues (Stiriba et al., 2002 Hirao et al., 2005). 

The three-dimensional property was characterized based on a viscosity study. The [rj] value increased with the increasing M sls value and the a value of the Mark-Houwink-Sakurada equation was found to be 0.29, which was obtained from the slope of the logarithmic plots of [rj] versus Mw,sls- H is well known that the a value is less than 0.5 for the various hyperbranched polymers, so that Poly 13 had a spherical shape in solution (Jikei and Kakimoto, 2001). 

A carboxylate derivative of a fully aromatic, water-soluble, hyperbranched polyphenylene is considered as a unimolecular micelle due to its ability to complex and solubilize non-polar guest molecules [23]. The carboxylic acid derivative of hyperbranched polyphenylene polymer (HBP) (My,=5750-7077, Mn=3810-3910) consists of 40-60 phenyl units that branch outward from a central point forming a roughly spherical molecule with carboxylates on the outer surface. The free acid form of HBP was suspended in distilled water and dissolved by adding a minimum quantity of NaOH. The solution was adjusted to pH 6.2 with aqueous HCl. Calcium carbonate crystals were growth from supersaturated calcium hydrogencarbonate solution at room temperature. HBP gave... 

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