Hyperbranched and Highly Branched Polymer Architectures—Synthetic Strategies and Major Characterization Aspects

“Life is branched” was the motto of a special issue of Macromolecular Chemistry and Physics1 on “Branched Polymers”, indicating that branching is of similar importance in the world of synthetic macromolecules as it is in nature. The significance of branched macromolecules has evolved over the last 30 years from just being considered as a side reaction in polymerization or as a precursor step in the formation of networks. Important to this change in perception of branching was the concept of “polymer architectures”, which formed on new starand graft-branched structures in the 1980s and then in the early 1990s on dendrimers and dendritic polymers. Today, clearly, controlled branching is considered to be a major aspect in the design of macromolecules and functional material. Hyperbranched (hb) polymers are a special type of dendritic polymers and have as a common feature a very high branching density with the potential of branching in each repeating unit. They are usually prepared in a one-pot synthesis, which limits the control on molar mass and branching accuracy and leads to “heterogeneous” products with a distribution in molar mass and branching. This distinguishes hyperbranched polymers from perfectly branched and monodisperse dendrimers. In the last 20 years, both classes of dendritic polymers, dendrimers as well as hb polymers, have attracted major attention because of their interesting properties resulting from the branched architecture as well as the high number of functional groups.2 The challenging synthesis of the dendrimers attracted especially scientists with a strong organic chemistry background and led to beautifully designed macromolecules, which allowed a deeper insight into the effect of branching and functionality. Dendrimers have been considered as perfect “nano-objects” where one can control perfectly size and functionality, which is of high interest in nanotechnology and biomedicine. hb polymers, however, were considered from the beginning as products suitable for larger-scale application in typical polymer fields like coatings and resins, where a perfect structure is sacrificed for an easy and affordable synthetic route. Thus, the first structures that were reported paralleled the chemistry used for linear polymers like typical polycondensation for polyester synthesis. More recently, unconventional synthetic methods have been adopted also for hb polymers and related structures. Presently, a vast variety of highly branched structures have been realized and studied regarding their properties and potential application fields. Excellent reviews appeared covering synthesis strategies, properties, and applications, like the very recent tutorial by Carlmark et al.,3 the comprehensive book on hyperbranched polymers covering extensively synthesis and application * E-mail: voit@ipfdd.de; lederer@ipfdd.de. Chem. Rev. 2009, 109, 5924–5973 5924