Search results for "Allyl glycidyl ether"
showing 8 items of 8 documents
From an epoxide monomer toolkit to functional PEG copolymers with adjustable LCST behavior.
2011
The lower critical solution temperature (LCST) behavior of novel poly(ethylene glycol) (PEG)-based copolymers bearing multiple functional groups, obtained by anionic ring-opening (co)polymerization (AROP), has been investigated. Variable comonomer ratios of ethylene oxide (EO) and the corresponding oxiranes isopropylidene glyceryl glycidyl ether (IGG), ethoxyl vinyl glycidyl ether (EVGE), allyl glycidyl ether (AGE), or N,N-dibenzyl amino glycidyl (DBAG), particularly designed to implement functional groups at the PEG backbone, were found to influence the LCST behavior. Sharp transitions from translucent to opaque solutions, comparable to other well-established stimuli-responsive polymers, w…
Poly(ethylene glycol-co-allyl glycidyl ether)s: a PEG-based modular synthetic platform for multiple bioconjugation.
2011
A series of random copolymers comprising ethylene oxide (EO) and 0-100% allyl glycidyl ether (AGE) has been prepared by anionic ring-opening polymerization with molecular weights between 5000 and 13,600 g/mol and polydispersity indices in the range of 1.04-1.19. As key for the homogeneity of the PEG conjugates, real-time ¹H NMR polymerization kinetics, ¹³C NMR analysis of triad sequence distribution, and analysis of the thermal behavior by differential scanning calorimetry (DSC) revealed a distinctive random copolymer structure. Via thiol-ene coupling (TEC), showing mainly "click" characteristics and nearly quantitative yields, PEG derivatives with multiple amino, carboxy, or hydroxy functi…
Thioether-Bearing Hyperbranched Polyether Polyols with Methionine-Like Side-Chains: A Versatile Platform for Orthogonal Functionalization
2016
The synthesis of thioether-bearing hyperbranched polyether polyols based on an AB/AB2 type copolymerization (cyclic latent monomers) is introduced. The polymers are prepared by anionic ring-opening multibranching copolymerization of glycidol and 2-(methylthio)ethyl glycidyl ether (MTEGE), which is conveniently accessible in a single etherification step. Slow monomer addition provides control over molecular weights. Moderate dispersities (Đ = 1.48–1.85) are obtained, given the hyperbranched structure. In situ 1H NMR copolymerization kinetics reveal reactivity ratios of rG = 3.7 and rMTEGE = 0.27. Using slow monomer addition, copolymer composition can be systematically varied, allowing for th…
Biodegradable hyperbranched polyether-lipids with in-chain pH-sensitive linkages
2016
Hyperbranched polyether-based lipids with cleavable acetal units were obtained via copolymerization of the epoxide inimer 1-(glycidyloxy)ethyl ethylene glycol ether (GEGE) and glycidol, using anionic ring-opening polymerization. Cholesterol-linear polyglycerol (Ch-linPG) was used as a macroinitiator, resulting in branched polyethers with an adjustable amount of acid-cleavable units. Random copolymerization led to Ch-P(GEGEx-co-Gy) copolymers, whereas sequential copolymerization provided access to Ch-P(GEGEx-b-Gy) amphiphiles. The amount of GEGE was varied between 8–49 mol% of the total amount of monomer units. In addition, hyperbranched polyethers with a single acetal unit were prepared usi…
Polyvinylferrocene-Based Amphiphilic Block Copolymers Featuring Functional Junction Points for Cross-Linked Micelles
2016
The synthesis of high-molecular-weight, well-defined poly(vinylferrocene)-block-poly(ethylene glycol) (PVFc-b-PEG) diblock copolymers (Mn = 13 000–44 000 g mol–1; Đ = 1.29–1.34) with precisely one allyl group at the junction point is introduced. Allyl glycidyl ether (AGE) was used to end-functionalize PVFc, resulting in hydroxyl functional macroinitiators for the oxyanionic polymerization of ethylene oxide. The self-assembly behavior of the amphiphilic PVFc-b-PEG copolymers in water has been investigated in a detailed manner, using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The redox activity of the PVFc block was confirmed by UV/vis spectroscopy, while cyclo…
Amphiphilic Linear-Hyperbranched Block Copolymers with Linear Poly(ethylene oxide) and Hyperbranched Poly(carbosilane) Block
2008
The synthesis of amphiphilic linear-hyperbranched block copolymers with a linear poly(ethylene oxide) (PEO) segment and a hyperbranched poly(carbosilane)s (PCS) block in a rapid three-step strategy is described, combining oxyanionic polymerization with carbosilane chemistry. A linear precursor block copolymer was synthesized via anionic polymerization of allyl glycidyl ether onto a commercial hydroxyl-terminated PEO, using its cesium alkoxide as macro-initiator. The resulting linear AB or ABA-type di- or triblock copolymers serve as polymer cores for the subsequent hydrosilylation polyaddition of an AB2-type carbosilane monomer. Di(allyl)methylsilane or methyldi(undec-10-enylsilane) were em…
Ferrocene-Containing Multifunctional Polyethers: Monomer Sequence Monitoring via Quantitative 13C NMR Spectroscopy in Bulk
2014
Ferrocenyl glycidyl ether (fcGE) and allyl glycidyl ether (AGE) are copolymerized via living anionic ring-opening polymerization to generate polyfunctional copolymers with molecular weights up to 40 300 g/mol and low molecular weight dispersities (Mw/Mn < 1.18). Copolymerizations were carried out in bulk at 100 °C and unexpectedly found to proceed without any isomerization of the allyl double bonds. The copolymerization behavior of fcGE and AGE was monitored by in situ quantitative 13C NMR kinetic measurements in bulk, evidencing the formation of random copolymers under these conditions, showing no gradient of comonomer incorporation. The redox-active behavior of the copolymers and homopoly…
Enlarging the Toolbox: Epoxide Termination of Polyferrocenylsilane (PFS) as a Key Step for the Synthesis of Amphiphilic PFS-Polyether Block Copolymer…
2022
Epoxide termination and functionalization of living poly(ferrocenyldimethylsilane) (PFDMS) is introduced by precapping the living PFDMS with a 4/2 molar mixture of 1,1-diphenylethylene and 1,1-dimethylsilacyclobutane acting as a “carbanion pump” system. Subsequent addition of allyl glycidyl ether (AGE) leads to quantitatively functionalized PFDMS–AGE polymers with molecular weights between 1500 and 15 400 g mol–1 and polydispersity indices ≤1.10, carrying one hydroxyl group and an additional allylic double bond. PFDMS–AGE was then applied as a macroinitiator for the living anionic ring-opening polymerization of ethylene oxide (EO) to generate amphiphilic and water-soluble poly(ferrocenyldim…