Daniel Wilms

Hyperbranched Polyglycerols: From the Controlled Synthesis of Biocompatible Polyether Polyols to Multipurpose Applications

Dendritic macromolecules with random branch-on-branch topology, termed hyperbranched polymers in the late 1980s, have a decided advantage over symmetrical dendrimers by virtue of typically being accessible in a one-step synthesis. Saving this synthetic effort once had an unfortunate consequence, though: hyperbranching polymerization used to result in a broad distribution of molecular weights (that is, very high polydispersities, often M(w)/M(n) > 5). By contrast, a typical dendrimer synthesis yields a single molecule (in other words, M(w)/M(n) = 1.0), albeit by a labor-intensive, multistep process. But 10 years ago, Sunder and colleagues reported the controlled synthesis of well-defined hyperbranched polyglycerol (PG) via ring-opening multibranching polymerization (ROMBP) of glycidol. Since then, hyperbranched and polyfunctional polyethers with controlled molar mass and low polydispersities (M(w)/M(n) = 1.2-1.9) have been prepared, through various monomer addition protocols, by ROMBP. In this Account, we review the progress in the preparation and application of these uniquely versatile polyether polyols over the past decade. Hyperbranched PGs combine several remarkable features, including a highly flexible aliphatic polyether backbone, multiple hydrophilic groups, and excellent biocompatibility. Within the past decade, intense efforts have been directed at the optimization of synthetic procedures affording PG homo- and copolymers with different molecular weight characteristics and topology. Fundamental parameters of hyperbranched polymers include molar mass, polydispersity, degree of branching, and end-group functionality. Selected approaches for optimizing and tailoring these characteristics are presented and classified with respect to their application potential. Specific functionalization in the core and at the periphery of hyperbranched PG has been pursued to meet the growing demand for novel specialty materials in academia and industry. A variety of fascinating synthetic approaches now provide access to well-defined, complex macromolecular architectures based on polyether polyols with low polydispersity. For instance, a variety of linear-hyperbranched block copolymers has been reported. The inherent attributes of PG-based materials are useful for a number of individual implementation concepts, such as drug encapsulation or surface modification. The excellent biocompatibility of PG has also led to rapidly growing significance in biomedical applications, for example, bioconjugation with peptides, as well as surface attachment for the creation of protein-resistant surfaces.

Hyperbranched PEG by Random Copolymerization of Ethylene Oxide and Glycidol

The synthesis of hyperbranched poly(ethylene glycol) (hbPEG) in one step was realized by random copolymerization of ethylene oxide and glycidol, leading to a biocompatible, amorphous material with multiple hydroxyl functionalities. A series of copolymers with moderate polydispersity (

Nonlinear Macromolecules by Ring-Opening Polymerization

\overline {M} _{{\rm w}} /\overline {M} _{{\rm n}}

Hyperbranched Polyglycerols with Elevated Molecular Weights: A Facile Two-Step Synthesis Protocol Based on Polyglycerol Macroinitiators

 < 1.8) was obtained with varying glycidol content (3-40 mol-%) and molecular weights up to 49 800 g mol(-1) . The randomly branched structure of the copolymers was confirmed by (1) H and (13) C NMR spectroscopy and thermal analysis (differential scanning calorimetry). MTS assay demonstrated low cell toxicity of the hyperbranched PEG, comparable to the highly established linear PEG.

Microstructured Reactors for Polymer Synthesis: A Renaissance of Continuous Flow Processes for Tailor‐Made Macromolecules?

Ring-opening polymerization (ROP) is a well-established method for the controlled synthesis of linear polymers, which can be found in various everyday applications. However, during the past decades, there has been an increasing interest in the generation of nonlinear highly branched polymers, profiting from the fascination created by the structurally perfect dendrimers. The applicability of various heterocyclic monomers renders the ring-opening multibranching polymerization (ROMBP), a versatile tool for the generation of multifunctional hyperbranched polymers. First, the historical key steps leading to the development of ROMBP are described, which is the basis for the controlled synthesis of nonlinear macromolecules. Subsequently, specific concepts in ROMBP, namely cationic, anionic, and catalytic polymerizations, are detailed. In particular, anionic multibranching polymerizations are powerful tools for the controlled synthesis of hyperbranched polyether polyols, which are interesting candidates for applications ranging from the biomedical field to catalysis. In the last section, the recent trends in the generation of complex macromolecular architectures containing nonlinear polymers synthesized by ROMBP as building blocks, for example, linear-hyperbranched hybrid structures or conjugates with biologically relevant molecules, are discussed.