One-Pot Two-Step (First ROP, Then SET-LRP) Synthesis of Polycaprolactone-Polyacrylate Star Block Copolymers
Autor: | Cristiano Giacomelli, Suelen G. Trindade, Andrés Eduardo Ciolino, Tanize Bortolotto, Vanessa Schmidt |
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Jazyk: | angličtina |
Rok vydání: | 2017 |
Předmět: |
CAPROLACTONE
Polymers and Plastics Two step Radical polymerization 02 engineering and technology INGENIERÍAS Y TECNOLOGÍAS Star (graph theory) 010402 general chemistry 01 natural sciences Ring-opening polymerization chemistry.chemical_compound Polymer chemistry Materials Chemistry Copolymer Physical and Theoretical Chemistry STAR COPOLYMERS Chemistry Organic Chemistry 021001 nanoscience & nanotechnology Condensed Matter Physics ROP 0104 chemical sciences Ingeniería Química Star polymer Polycaprolactone Otras Ingeniería Química 0210 nano-technology SET-LRP |
Popis: | A one-pot, two-step method is applied to the controlled synthesis of polyacrylate-b-(polycaprolactone)2 three-arm AB2-type star block polymers. First, ring-opening polymerization (ROP) of ε-caprolactone is carried out in toluene using either stannous octoate (Sn(Oct)2) or diphenyl phosphate (DPP) as catalyst, and a multifunctional initiator featuring one bromoester and two alcohol groups. Then, single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate and isobornyl acrylate is conducted in the same reaction vessel after sequential addition of its typical reactants, apart from the (PCL)2-Br macroinitiator generated in the first step, in either toluene/toluene + phenol or toluene/dimethyl sulfoxide solvent systems. DPP (the ROP catalyst) from the first step is found to take part in an acid?base reaction with tris[2-(dimethylamino)ethyl]amine (the SET-LRP N-ligand) in the second part, but stoichiometry could be adjusted to avoid interference and keep the controlled nature of the polymerizations. Interestingly, the electrochemically active Sn(Oct)2 ROP catalyst does not interfere with the SET-LRP process. Well-defined poly(methyl acrylate)-b-(polycaprolactone)2 and poly(isobornyl acrylate)-b-(polycaprolactone)2 are thus synthesized through a simple and cost-effective experimental procedure. The technique also applies to the synthesis of linear block copolymers. Fil: Trindade, Suelen G.. Universidade Federal de Santa Maria; Brasil Fil: Bortolotto, Tanize. Universidade Federal de Santa Maria; Brasil Fil: Ciolino, Andrés Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; Argentina Fil: Schmidt, Vanessa. Universidade Federal de Santa Maria; Brasil Fil: Giacomelli, Cristiano. Universidade Federal de Santa Maria; Brasil |
Databáze: | OpenAIRE |
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