Hyperbranched Polyols via Copolymerization of 1,2-Butylene Oxide and Glycidol: Comparison of Batch Synthesis and Slow Monomer Addition

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 Mn 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 …

Water-soluble and redox-responsive hyperbranched polyether copolymers based on ferrocenyl glycidyl ether

Water-soluble copolymers of ferrocenyl glycidyl ether (fcGE) and glycidol were prepared via anionic ring-opening multibranching polymerization (ROMBP). The resulting hyperbranched materials with molecular weights (Mn) of 3500 to 12 300 g mol−1 and relatively narrow molecular weight distributions (Mw/Mn = 1.40–1.69) exhibit both temperature- as well as redox-responsive behavior, which was studied via turbidity measurements. The cloud point temperatures (Tc) were adjusted between 45 and 60 °C through variation of the fcGE comonomer content. Additionally, these Tcs can be increased by the addition of an oxidizing agent. The extent of oxidation of the materials was quantified by Mosbauer spectr…

Synthesis and Solution Processing of Nylon‐5 Ferroelectric Thin Films: The Renaissance of Odd‐Nylons?

Multifunctional Fe(III)-Binding Polyethers from Hydroxamic Acid-Based Epoxide Monomers.

Multiple hydroxamic acids are introduced at poly(ethylene glycol) (PEG) via copolymerization of ethylene oxide with a novel epoxide monomer containing a 1,4,2-dioxazole-protected hydroxamic acid (HAAGE). AB- and ABA-type di- and triblock copolymers as well as statistical copolymers of HAAGE and ethylene oxide are prepared in a molecular weight range between 2600 and 12 000 g mol-1 with low dispersities (Ð < 1.2). Cleavage of the acetal protecting group after the polymerization is achieved by mild acidic treatment, releasing multiple free hydroxamic acids tethered to the polyether backbone. The chelation properties of different polymer architectures (statistical versus diblock and ABA triblo…

Chiroptical Induction and Molecular Recognition in Optically Active Hyperbranched Polyethers with Inherently Chiral Benzophenone Core

Solution-processed transparent ferroelectric nylon thin films

We have developed a method to solution process strongly hydrogen-bonded odd nylons into ferroelectric thin films.

Hyperbranched-linear-hyperbranched ABA-type block copolymers based on poly(ethylene oxide) and polyglycerol

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 lo…

Supramolecular Antioxidant Assemblies of Hyperbranched Polyglycerols and Phenols

Multi-olefin containing polyethers and triazolinediones: a powerful alliance

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). Specifically, two novel monomers (i) 2,4-hexadien-1-yl glycidyl ether (HDEGE) and (ii) citronellyl glycidyl ether (CitroGE), designed to undergo a Diels–Alder or Alder–Ene reaction with TADs, respectively, were synthesized and subsequently transformed into a variety of tailored polyethers, either via the monomer activated method or anionic ring opening polymerisation. Multi-functional copolymers of HDEGE with ethylene oxide, propylene oxide and ethoxy ethyl glycidyl ether as well as A…

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

Hyperbranched polyglycerol (PG) is established as one of the few hyperbranched polymers that offer the possibility to control molecular weight up to Mn = 6000 g/mol. This work introduces a facile 2-step strategy that relies on the use of a low molecular weight PG (Mn = 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 Mn = 24000 g/mol has been obtained under fully contr…