ATRP of Silylated Glycerol Monomethacrylate in Organic Medium for Convenient Synthesis of Amphiphilic Copolymers

Abstract

A synthetic method with broad spectrum of application in the preparation of self‐organizing amphiphilic copolymers having poly(glycerol monomethacrylate) (PG2MA) as a hydrophilic part is herein reported. The approach relies on the facile preparation of silylated glycerol monomethacrylate (G2MA‐TMS) monomer, and its controlled atom transfer radical polymerization (ATRP) in organic media, which produced well‐defined (co)polymers with predictable molar mass and low dispersity, followed by desilylation. The wide scope of such a strategy was demonstrated by the successful synthesis of original polycaprolactone‐b‐poly(glycerol monomethacrylate) (PCL‐b‐PG2MA) diblock copolymers with the ability to self‐assemble into ordered structures (micelles and vesicles) in an aqueous medium.magnified image

Poly(ε‐caprolactone)‐graft‐poly(2‐(dimethylamino)ethyl methacrylate) Amphiphilic Copolymers Prepared via a Combination of ROP and ATRP: Synthesis, Characterization, and Self‐Assembly Behavior

“…Atom transfer radical polymerization (ATRP) is a successful method of controlled radical polymerization that allows the synthesis of well‐defined polymers with low polydispersities from a large variety of monomers 22–24. ATRP has many advantages over conventional living polymerization such as versatility of monomer types, tolerance of functional group, and mild reaction conditions 25–27. Using ATRP polymerization method, several PCL‐based graft copolymers has been synthesized by employing Poly(caprolactone‐ co ‐ γ ‐(2‐Bromo‐2‐methylpropionate)‐caprolactone) (P(CL‐ co ‐BMPCL)) as macroinitiator 28, 29.…”

Reversible Complexation of Iminophenylboronates with Mono- and Dihydroxy Methacrylate Monomers and Their Polymerization at Low Temperature by Photoinduced ATRP in One Pot

“…42 Accordingly, a higher catalytic activity of Cu I Br complexes with HMTETA versus dNbpy for the ATRP of methacrylates has been reported, with a 6-fold difference in the apparent rate constant of propagation, k Papp , for the ATRP of silylated GMA. 43 Thus, the observed total lack of catalytic activity with (+)-sparteine and dNbpy was rather unexpected, and the reasons behind are not really clear. It is known that the structures of the Cu I and Cu II complexes involved in the ATRP equilibrium play an important role in the overall activity of the catalyst.…”

“…Classical ATRP at room temperature, preferentially with a tetradentate tertiary amine ligand such as HMTETA, and photoinduced ATRP or photoinitiated free-radical polymerization (AIBN) at low temperatures down to 0 °C, are all suitable to carry out the polymerization without losing functionality. Great advantage would be gained by extending the presented strategy to the one-pot synthesis of block/graft copolymers of hydrophilic hydroxy-functionalized blocks (pHEMA, pGMA) with hydrophobic macroinitiators, e.g., biodegradable poly(εcaprolactone) or poly(lactic acid), 43 to the synthesis of random copolymers with cyclic ketene acetals which provides degradable ester linkages on the backbone, 20 or for the synthesis of amphiphilic graft copolymers. 64 Due in the first case to the low solubility of the hydrophobic blocks in aqueous/alcoholic media and to side reactions between the hydroxyl group and ketene acetals in the second case, such polymerizations are normally done in organic solvents in which HEMA/GMA or their polymers are not soluble.…”

Polylactide (PLA)-based amphiphilic block copolymers: synthesis, self-assembly, and biomedical applications

“…35,36 Several reports describe the successful ATRP of GlyMA in aqueous or protic solvents. 35,37 For the synthesis of PLA-b-PGlyMA, however, PLA was not dissolved in protic media; consequently, PGlyMA block was generated by the hydrolysis of pendent protected groups from the parent polymers, such as silyl groups from poly(2,3-bistrimethylsilyloxypropyl methacrylate) (P(GlyMA-TMS)) 38 and acetal groups from poly(2-phenyl-1,3-dioxan-5ylmethacrylate) (P(GlyMA-PhDO). 39 A zwitterionic block copolymer based on PLGA was synthesized by ATRP of 2-tert-butoxy-N-(2-(methacryloyloxy)ethyl)-N,N-dimethyl-2-oxoethanaminium (CB-tBu-MA) in the presence of 2-aminoethyl-2-bromoisobutyrate, followed by a carbodiimide coupling reaction with PLGA.…”