0000000000211223
AUTHOR
Patrick Verkoyen
“Dumb” pH-Independent and Biocompatible Hydrogels Formed by Copolymers of Long-Chain Alkyl Glycidyl Ethers and Ethylene Oxide
The formation and rheological properties of hydrogels based on amphiphilic ABA triblock polyether copolymers are described, relying solely on the hydrophobic interaction of long-chain alkyl glycidyl ether (AlkGE)- based A-blocks that are combined with a hydrophilic poly(ethylene glycol) (PEG) midblock. Via anionic ring-opening copolymerization (AROP), ethylene oxide (EO) and long-chain alkyl glycidyl ethers (AlkGEs) were copolymerized, using deprotonated poly(ethylene glycol) (PEG) macroinitiators (Mn of 10, 20 kg mol-1). The polymerization afforded amphiphilic ABA triblock copolymers with molar masses in the range of 21-32 kg mol-1 and dispersities (Đ) of Đ = 1.07-1.17. Kinetic studies rev…
Long-Chain Alkyl Epoxides and Glycidyl Ethers: An Underrated Class of Monomers.
Long-chain epoxides and specifically alkyl glycidyl ethers represent a class of highly hydrophobic monomers for anionic ring-opening polymerization (AROP), resulting in apolar aliphatic polyethers. In contrast, poly(ethylene glycol) is known for its high solubility in water. The combination of hydrophobic and hydrophilic monomers in block and statistical copolymerization reactions enables the synthesis of amphiphilic polyethers for a wide range of purposes, utilizing micellar interactions in aqueous solutions, e.g., viscosity enhancement of aqueous solutions, formation of supramolecular hydrogels, or for polymeric surfactants. Controlled polymerization of these highly hydrophobic long-chain…
Amino-functional polyethers: versatile, stimuli-responsive polymers
Due to the increasing demand for “smart” materials and systems e.g. for actuators, microvalves, but also for drug delivery, electrooptical devices and many other applications, multi-stimuli responsive materials such as amino-functional polymers are attracting increasing attention in recent years. The hydrophilic character and excellent biocompatibility of the polyether backbone, in combination with multi-stimuli responsive amine moieties, offer intriguing opportunities for a wide range of applications, such as bioconjugation, stimuli-responsive drug delivery and surface modification. Furthermore, the controlled introduction of amino-functionalities at the polyether backbone via copolymeriza…
Efficiency Boosting of Surfactants with Poly(ethylene oxide)-Poly(alkyl glycidyl ether)s: A New Class of Amphiphilic Polymers
Twenty years ago, it was found that adding small amounts of amphiphilic block copolymers like poly(ethylene propylene)-co-poly(ethylene oxide) (PEP-b-PEO) to microemulsion systems strongly increases the efficiency of medium-chain surfactants to solubilize water and oil. Although being predestined to serve as a milestone in microemulsion research, the effect has only scarcely found its way into applications. In this work, we propose new types of efficiency boosters, namely, poly(ethylene oxide)-poly(alkyl glycidyl ether carbonate)s (PEO-b-PAlkGE) and their "carbonated" poly(ethylene oxide)-poly(carbonate alkyl glycidyl ether) analogs. Their synthesis via anionic ring-opening polymerization (…
Polymerization of long chain alkyl glycidyl ethers: a platform for micellar gels with tailor-made melting points
Controlled polymerization of long-chain alkyl glycidyl ethers (AlkGE) under anionic ring opening polymerization conditions is enabled by the addition of a crown ether (18-crown-6, K+). Homopolymers with molecular weights in the range of 4000 to 9000 g mol−1 and side chain melting temperatures of 14 °C (C12-AlkGE) and 43 °C (C16-AlkGE), respectively were synthesized. Furthermore, a series of amphiphilic ABA polyether triblock copolymers with polyethylene glycol (PEG) as the hydrophilic central block (Mn = 6k, 10k, and 20k g mol−1) with total molecular weights in the range of 7000 to 28 000 g mol−1 and narrow dispersity (1.12 to 1.34) were prepared. Separate melting endotherms of the triblock…
Crystalline CO2 -Based Aliphatic Polycarbonates with Long Alkyl Chains
Carbon dioxide (CO2 ) is an easily available, renewable carbon source and can be utilized as a comonomer in the catalytic ring-opening polymerization of epoxides to generate aliphatic polycarbonates. Dodecyl glycidyl ether (DDGE) is copolymerized with CO2 and propylene oxide (PO) to obtain aliphatic poly(dodecyl glycidyl ether carbonate) and poly(propylene carbonate-co-dodecyl glycidyl ether carbonate) copolymers, respectively. The polymerization proceeds at 30 °C and high CO2 pressure utilizing the established binary catalytic system (R,R)-Co(salen)Cl/[PPN]Cl. The copolymers with varying DDGE:PO ratios are characterized via NMR, FT-IR spectroscopy, and SEC, exhibiting high molecular weight…