Synthesis of well‐defined glycidyl methacrylate based block copolymers with self‐activation and self‐initiation behaviors via ambient temperature atom transfer radical polymerization

Abstract

Well‐defined glycidyl methacrylate (GMA) based di‐ and triblock copolymers, with self‐activation and self‐initiation behaviors by incorporation of 2‐(diethylamino) ethyl methacrylate (DEA) blocks, were synthesized via ambient temperature atom transfer radical polymerization (ATRP). The stability of the GMA pendant oxirane rings in tertiary amine environments at ambient temperature was investigated. More importantly, both self‐activation behavior in oxirane ring opening addition reaction and self‐initiation behavior in post‐cure oxirane ring opening crosslinking of these block copolymers were evidenced by 1H NMR studies. The results demonstrated that the reactivity of pendent oxirane rings was strongly dependant on the nucleophilicity and steric hindrance of tertiary amine moieties and temperature. This facilitated the synthesis of well‐defined block copolymers of GMA and DEA via sequential monomer addition ATRP, particularly for polymerization of GMA monomer at ambient temperature. Moreover, these one‐component GMA based block polymers have novel self‐activation and self‐initiation properties, rendering some potential applications in both enzyme immobilization and GMA‐based thermosetting materials. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2947–2958, 2007

Synthesis of defined polyhedral oligosilsesquioxane‐containing diblock and triblock methacrylate copolymers by atom transfer radical polymerization

“…It is known that the GMA oxirane ring can undergo a nucleophilic attack by tertiary amine ligands 47–49. To avoid these unwanted side reactions, we performed all polymerizations in nonpolar solvent at moderate temperatures.…”

Aerosol Process for theIn SituCoating of Nanoparticles with a Polymer Shell

“…It was suggested that the reaction of GMA with ammonia can produce tertiary amine, hence the small amounts of tertiary amines can function as Lewis base initiators for anionic polymerization of oxirane ring opening according to the following mechanism: First, the tertiary amines attack oxirane rings via nucleophilic addition reaction to generate zwitterions; these zwitterions further attack other oxirane rings to induce anionic ring opening polymerization and produce polymer (Rozenberg 1986;Li et al 1996;Odian 2004;Dell'Erba and Williams 2006;Jiang et al 2007;Brocas et al 2013).…”

Synthesis and self-assembly behavior of amphiphilic methyl α-D-glucopyranoside-centered copolymers

“…According to the literature, the rings in linear PGMA were gradually attenuated, and finally, the reaction at a feed molar ratio of [epoxy group] 0 :[DEA] 0 = 1:1.5 in dioxane was essentially complete Table 1 at 30°C within 72 h [30]. However, the efficiency of transformation via aminolysis of the copolymer V as the representative for the resulting sugar-centered structures was not satisfied even at more stringent conditions (larger excess of amine and higher temperature), because only 20 % of the opened rings within 72 h were observed at a feed molar ratio of [epoxy group] 0 :[DEA] 0 = 1:3 in DMF at 50°C (Table 2).…”

“…Unfortunately, the copolymer XVII turned out to be unstable and the formation of gel occurred within less than 24 h of storage after completion of the ring-opening reaction. A crosslinking process has been previously reported for the modification of GMA units in linear polymers, as a concurrent reaction of the anionic oxirane ring-opening polymerization occurring between the unreacted epoxy groups initiated by tertiary amines that originated from the reaction of diethylamine with the epoxy groups at 80°C [31], or by the self-initiated crosslinking of oxirane rings in block copolymers of PGMA and poly(diethylamine-functionalized methacrylate) by thermal treatment [30]. However, in the studied star-shape copolymer, the branched topology is an additional factor supporting intermolecular side reactions, which can occur even at lower temperatures when the level of incorporated amine groups is properly high.…”