Controlled synthesis of poly[(butyl methacrylate)-co-(butyl acrylate)] via activator regenerated by electron transfer atom transfer radical polymerization: insights and improvement

• Published in: Polymer international Vol. 63; no. 5; pp. 848 - 857
• Main Authors: Payne, Kevin A, Van Steenberge, Paul HM, D'hooge, Dagmar R, Reyniers, Marie-Françoise, Marin, Guy B, Hutchinson, Robin A, Cunningham, Michael F
• Format: Journal Article
• Language: English
• Published: Chichester, UK John Wiley & Sons, Ltd 01.05.2014; Wiley; Wiley Subscription Services, Inc
• Subjects: Acrylates; Applied sciences; ARGET ATRP; Computer simulation; control; Copolymerization; Copper; Exact sciences and technology; Initiators; kinetic Monte Carlo; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Radicals; Reducing agents; semi-batch; Monte Carlo method; copolymerization; Computer simulation; Atom transfer polymerization; ARGET ATRP; Electron transfer; control; Experimental study; Reducing agent; Butyl acrylate copolymer; Copper Complexes; Modeling; Kinetic model; semi-batch; Tin II Compounds; Preparation; Concentration effect; kinetic Monte Carlo; Carboxylate; Reaction mechanism; Kinetics; Butyl methacrylate copolymer
• ISSN: 0959-8103; 1097-0126
• DOI: 10.1002/pi.4678

Copolymerization by ARGET ATRP is investigated to improve polymerization rate and initiator efficiency. Semi‐batch addition of reducing agent (Sn(EH)2) is shown to significantly increase the polymerization rate. The copolymerization of butyl methacrylate and butyl acrylate initiated by CuBr2/tris[(2‐pyridyl)methyl]amine/ethyl 2‐bromoisobutyrate, with tin(II) 2‐ethylhexanoate as reducing agent, is studied experimentally and using kinetic Monte Carlo simulations at 70 and 90 °C under batch activator regenerated by electron transfer atom transfer radical polymerization conditions in anisole at low Cu levels (down to 35 ppm Cu on a molar basis with respect to monomer). With increasing initial butyl acrylate content, the initiator efficiency is improved with an accompanying increase in polymer dispersity due to oligomer formation. The addition of reducing agent during the polymerization, i.e. a semi‐batch approach, allows an increase in polymerization rate and initiator efficiency, driving the polymerization towards full conversion and allowing for better initiator consumption. © 2013 Society of Chemical Industry