Anionic Polymerization of para-(1-Ethoxy ethoxy)styrene: Rapid Access to Poly(p-hydroxystyrene) Copolymer Architectures.

Living anionic polymerization of para-(1-ethoxy ethoxy)styrene (pEES) resulting in molecular weights between 2700 and 69 000 g mol-1 and polydispersity indices ≤1.09 is introduced. PpEES can be used as a precursor for the synthesis of well-defined poly(p-hydroxystyrene) (PHS) architectures, enabling facile and rapid acidic deprotection at room temperature within a few minutes. In addition, a series of block copolymers containing pEES and 2-vinylpyridine (2VP) have been synthesized by anionic block copolymerization, with varied block ratios (X2VP) between 0.13 and 0.83. Characterization by 1H NMR spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) was carried out, and all polymers have been deprotected, leading to the respective PHS-b-P2VP block copolymers. Furthermore, PHS-b-P2VP has been used as a macroinitiator for the anionic ring-opening polymerization of ethylene oxide (EO) to generate ((PHS-g-PEO51)13-b-P2VP40) graft-block copolymers.

Introducing an amine functionality at the block junction of amphiphilic block copolymers by anionic polymerization strategies.

A series of block copolymers bearing a single amino in-chain functionality was synthesized via anionic polymerization of styrene and ethylene oxide. By means of both a conventional and a continuous setup, living polystyrene was quantitatively end functionalized with an oxirane (DBAG) prior to the polymerization of the poly(ethylene oxide) segment. The in-chain amine was conjugated with a fluorescent dye.

A road less traveled to functional polymers: epoxide termination in living carbanionic polymer synthesis.

Functional polymers possess tremendous potential both in academia and in industry. In particular, oxiranes offer manifold possibilities for the introduction of single hydroxyl or multiple orthogonal functionalities in carbanionic polymerization. Here, we present a brief overview of the fascinating possibilities arising from the employment of common as well as individually designed epoxide derivatives for the synthesis of end-functional polymers. Continuous flow techniques can be utilized for the rapid generation and screening of precisely defined hydroxyl-modified polymers. The utilization of functionalized polymers as precursors for the formation of complex macromolecular architectures (e.g., miktoarm star polymers) is summarized and potential applications as well as future perspectives are discussed.

Entanglement transition in hyperbranched polyether-polyols.

Are hyperbranched polymers capable of forming entanglements? This is the central issue of this contribution. Hyperbranched polyglycerol (hbPG) samples with different molecular weights (600-106 000 g · mol(-1) ), narrow polydispersities (1.2-1.8) and high degrees of branching (≈0.6) were prepared by anionic ring-opening polymerization. The viscoelastic properties of these polymers with respect to molecular architecture and molar mass were investigated. At low molecular weights "classical" scaling behavior between zero shear viscosity and molecular weight can be observed, whereas between 3 000 and 10 000 g · mol(-1) a plateau-like area is found. The results indicate entanglement dynamics when exceeding a critical molar mass ($\overline {M} _{{\rm c}}^{*} $ ≈ 20 000 g · mol(-1) ) due to entangled hyperbranched polyglycerols.