Hyperbranched polyglycerol (PG) is established as one of the few hyperbranched polymers that offer the possibility to control molecular weight up to M n ) 6000 g/mol. This work introduces a facile 2-step strategy that relies on the use of a low molecular weight PG (M n ) 500 and 1000 g/mol) as a macroinitiator for the slow addition of glycidol, permitting to overcome previous limitations concerning molecular weights and molecular weight control. A systematic investigation of the effect of the degree of deprotonation on the control of the polymerization reaction has been carried out. A series of hyperbranched PGs with molecular weights up to M n ) 24000 g/mol has been obtained under fully controlled conditions. The polydispersities of the samples prepared were in the range of 1.3 to 1.8. In summary, we present the first example of a synthetic strategy for a hyperbranched polymer that is now accessible over a broad range of molecular weights (300-24000 g/mol) without the ubiquitous problem of large polydispersities or the necessity for solid supports. In addition, the samples permitted a systematic study of the degree of branching DB of the hyperbranched PGs of elevated molecular weight. Values of DB ) 0.60 to 0.63 were obtained, approximating the theoretical limit of 0.66 for slow monomer addition.

Ferroelectricity, a bistable ordering of electrical dipoles in a material, is widely used in sensors, actuators, nonlinear optics, and data storage. Traditional ferroelectrics are ceramic based. Ferroelectric polymers are inexpensive lead-free materials that offer unique features such as the freedom of design enabled by chemistry, the facile solution-based low-temperature processing, and mechanical flexibility. Among engineering polymers, odd nylons are ferroelectric. Since the discovery of ferroelectricity in polymers, nearly half a century ago, a solution-processed ferroelectric nylon thin film has not been demonstrated because of the strong tendency of nylon chains to form hydrogen bonds. We show the solution processing of transparent ferroelectric thin film capacitors of odd nylons. The demonstration of ferroelectricity, as well as the way to obtain thin films, makes odd nylons attractive for applications in flexible devices, soft robotics, biomedical devices, and electronic textiles.

Hyperbranched poly­(butylene oxide) polyols have been synthesized by multibranching anionic ring-opening copolymerization of 1,2-butylene oxide and glycidol. Systematic variation of the composition from 24 to 74% glycidol content resulted in a series of moderately distributed copolymers (Đ = 1.41–1.65, SEC), albeit with limited molecular weights in the solvent-free batch process in the range of 900–1300 g mol–1 (apparent M n determined by SEC with PEG standards). In situ monitoring of the copolymerization kinetics by 1H NMR showed a pronounced compositional drift with respect to the monomer feed, indicating a strongly tapered microstructure caused by the higher reactivity of glycidol. In the case of slow monomer addition considerably higher apparent molecular weights up to 8500 g mol–1 were obtained (SEC). By alteration of the comonomer ratio, aqueous solubility of the hyperbranched copolymers could be tailored, resulting in well-defined cloud points between 20 and 84 °C. Glass transition temperatures between −60 and −29 °C were observed for the resulting polyether polyols. High degrees of branching (DB) between 0.45 and 0.77 were calculated from inverse gated (IG) 13C NMR. Online viscosimetry and analytical ultracentrifugation (AUC) were employed to study hydrodynamic properties and to establish a universal calibration curve for the determination of absolute molecular weights. This resulted in M w values between 2100 and 35 000 g mol–1 that were generally 2–3 times higher than the apparent values determined by SEC with linear PEG standards.

BACKGROUND: Until recently, hyperbranched polymers were thought to be ill‐defined materials that were not useful as building blocks for well‐defined complex polymer architectures. It is a current challenge to develop strategies that offer rapid access to well‐defined hyperbranched block copolymers. RESULTS: A convenient three‐step protocol for the synthesis of double‐hydrophilic hyperbranched–linear–hyperbranched ABA‐type triblock copolymers based on poly(ethylene oxide) (PEO) and hyperbranched polyglycerol (hbPG) is presented. The Bola‐type polymers exhibiting an aliphatic polyether structure were prepared from a linear (lin) linPG‐b‐PEO‐b‐linPG precursor triblock. The materials exhibit low polydispersities (Mw/Mn) in the range 1.19–1.45. The molecular weights of the block copolymers range from 6300 to 26 200 g mol−1, varying in the length of both the linear PEO chain as well as the hbPG segments. Detailed characterization of the thermal properties using differential scanning calorimetry demonstrates nanophase segregation of the blocks. CONCLUSION: The first example of well‐defined ABA hyperbranched–linear–hyperbranched triblock copolymers with PEO middle block and hbPG A‐blocks is presented. The biocompatible nature of the aliphatic polyether blocks renders these materials interesting for biomedical purposes. These new materials are also intriguing with respect to their supramolecular order and biomineralization properties. Copyright © 2009 Society of Chemical Industry

Multi-functional polyethers with ene or diene moieties were prepared via the polymerisation of tailored functional glycidyl ether monomers to create a platform for click chemistry with triazolinediones (TADs).