Preparation of Star‐Shaped ABC Copolymers of Polystyrene‐Poly(ethylene oxide)‐Polyglycidol Using Ethoxyethyl Glycidyl Ether as the Cap Molecule

Abstract

The 3‐miktoarm star‐shaped ABC copolymers of polystyrene–poly(ethylene oxide)–poly(ethoxyethyl glycidyl ether) (PS‐PEO‐PEEGE) and polystyrene–poly(ethylene oxide)–polyglycidol (PS‐PEO‐PG) with low polydispersity indices (PDI ≤ 1.12) and controlled molecular weight were synthesized by a combination of anionic polymerization with ring‐opening polymerization. The polystyryl lithium (PS−Li+) was capped by EEGE firstly to form the functionalized polystyrene (PSA) with both an active ω‐hydroxyl group and an ω′‐ethoxyethyl‐protected hydroxyl group, and then the PS‐b‐PEO block copolymers, star(PS‐PEO‐PEEGE) and star(PS‐PEO‐PG) copolymers were obtained by the ring‐opening polymerization of EO and EEGE respectively via the variation of the functional end group, and then the hydrolysis of the ethoxyethyl group on the PEEGE arm. The obtained star copolymers and intermediates were characterized by 1H NMR spectroscopy and SEC.

Synthesis and characterization of star graft copolymers with asymmetric mixed “V‐shaped” side chains via “click” chemistry on a hyperbranched polyglycerol core

“…In a previous work,34 the PS‐EEGE [( 1 ), M n (GPC) = 2300 g/mol, PDI = 1.04] with an active and a protected hydroxyl group at ω‐end was synthesized by capping the poly(styryl)lithium (PS − Li + ) with EEGE. The obtained PS‐EEGE was used as the starting material and modified by the following procedure.…”

Synthesis of multifunctional ABC stars with a reduction-labile arm by consecutive ROP, RAFT and ATRP processes

“…The first one (Scheme 1(d)) is based on an initial coupling reaction between two reactive polymers such as linking reaction between living anionic polymer and DPE-bearing polymer [21][22][23] and atom transfer radical addition between macroinitiator and macromonomer [24], and the mid-functionalized diblock copolymer can be in-situ formed or generated by a subsequent FGT process and further initiate polymerization of M 3 to form ABC star. The second one (Scheme 1(e)) involves the application of a heterotrifunctional chemical or their reactive precursors as the core agent, in which linear polymer with functionalities F 2 and F 3 in the same end is obtained after one C/P process, and ABC star is further obtained by two-step reactions [25][26][27][28][29][30][31][32][33][34][35][36]. The last one comprises tandem C and P processes with good compatibility (Scheme 1(f)).…”

Calixarene‐centered amphiphilic A2B2 miktoarm star copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol): Synthesis and self‐assembly behaviors in water

“…Meanwhile, the appearance of “click” reactions8 also provides a powerful method for the synthesis and functionalization of polymers with unique structures during the past few years due to their high specificity, quantitative yields, and near‐perfect fidelity in the presence of most functional groups 9, 10. Therefore, by the combination of CLP techniques and “click” reactions, various types of miktoarm star copolymers with varying chemical composition and molecular topology such as AB 2 ,11 A 2 B 2 ,12–15 A 3 B 3 ,16 ABC,17–19 and so forth have been synthesized.…”