Synthesis of well‐defined macromonomers by the combination of atom transfer radical polymerization and a click reaction

Abstract

This article presents a new strategy for synthesizing a series of welldefined macromonomers. Bromine-terminated polystyrene and poly(t-butyl acrylate) with predetermined molecular weights and narrow distributions were prepared through the atom transfer radical polymerization of styrene and t-butyl acrylate initiated with ethyl 2-bromoisobutyrate. Then, azido-terminated polymers were obtained through the bromine substitution reaction with sodium azide. Catalyzed by CuBr/ N,N,N 0 ,N 00 ,N 00 -pentamethyldiethylenetriamine, the azido end group reacted with propargyl methacrylate via a 1,3-dipolar cycloaddition reaction, and x-methacryloylfunctionalized macromonomers were thus obtained. The end-group transformation yields were rather high, as characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectra and 1 H NMR analysis. By this effective and facile approach, some novel macromonomers that otherwise are difficult to achieve, such as poly(ethylene oxide)-block-polystyrene, were easily prepared. Radical homopolymerizations of these macromonomers were performed, and a series of comb polymers were prepared. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: [6103][6104][6105][6106][6107][6108][6109][6110][6111][6112][6113] 2006

Intramolecular Cross-linking of Polymers Using Difunctional Acetylenes via Click Chemistry

“…The Diels-Alder cycloaddition reac-tion [24][25][26] and thiol-ene chemistry [27,28] have recently been introduced as alternative click routes for providing new materials. Click reactions have been widely used for the synthesis of polymers with different compositions and topologies, ranging from linear (telechelic [29], macromonomer [30,31], macrophotoinitiator [32,33] and block co-polymer [34][35][36]) to nonlinear macromolecular structures (graft [37][38][39], star [40,41], miktoarm star [42,43], H-type [44], dendrimer [45][46][47], dendronized linear polymers [48,49], macrocyclic polymers [50,51], self-curable polymers [52][53][54], network systems [55,56] and polymeric nanoparticles [14,57]). Recently, the development and application of click chemistry in polymer and material science has been extensively reviewed [58][59][60][61][62][63].…”

One‐pot preparation of 3‐miktoarm star terpolymers via “click chemistry” and atom transfer nitroxide radical coupling reaction

“…The key precursors PS-alkyne/Br, 25 PtBA-N 3 , 26 and TEMPO-PEO 27,28 or TEMPO-PCL 29 were prepared according to previous literatures, and characterized fully by GPC, 1 H NMR, MALDI-TOF, and FT-IR (see Supp. Info.).…”

Polymer “Clicking” by CuAAC Reactions

“…[91] Polymerization of this kind of macromonomer provided large comb-type of block copolymers (24) containing PEG, polystyrene and polymethacrylates. [103] Polymerization from a central dimethyl 2,6-dibromoheptanedioate as an initiator allowed Gao et al [89] to prepare a polystyrene that carried bromine in both ends. After conversion to bis-azide the polymer was reacted with propargylalcohol or polymerized as described below.…”