Controlled synthesis of methacrylate and acrylate diblock copolymers via end-capping using CCTP and FRP

Abstract

This work demonstrates a method for preparing acrylic-methacrylic diblock copolymers via end-capping.

Block Copolymers Based on Ethylene and Methacrylates Using a Combination of Catalytic Chain Transfer Polymerisation (CCTP) and Radical Polymerisation

“…Polymerisation of MMA and copolymerisation of MMA with methacrylic acid (MAA) were conducted in at hreeneck, 500 mL double jacketed reactor or in ar ound bottom flask at 75 8 8C, utilising either emulsion or solution CCTP methodology. [37,47,55] CCTP is ar eliable method to synthesise methacrylic oligomers bearing an w-vinyl double bond and is av ery efficient and scalable technique which has been used in ar ange of industrial applications for > 25 years. [37,38,47,56] In this current work, bis[(difluoroboryl) dimethylglyoximato] cobalt(II) (CoBF) was used as catalyst, as it has been proven to be av ery effective chain transfer agent for the CCTP of MMA and other alkyl methacrylates.…”

“…[28][29][30][31][32][33][34][35][36] Thepolymers/oligomers bearing avinyl w-end group have been used as precursors for various materials,s uch as multi-block copolymers,amphiphilic dispersants for industrial applications,block, graft and branched copolymers. [37][38][39][40][41] Copolymerisation of methacrylic type w-unsaturated methacrylic oligomers from CCTP with methacrylates,acrylates and styrenic monomers has been studied and is reported to result in different materials. [26,42] In the case of methacrylates,t he chain transfer mechanism involves addition-fragmentation chemistry.…”

“…[52][53][54] Recently,n ew insights were given on the copolymerisation with acrylates by the investigation of the methacrylic macromonomers molar mass and the comonomer effects. [37] Graft copolymers were obtained using low molar mass PMMA reactive oligomers and MA, whereas diblock copolymers were synthesised using higher molecular weight reactive oligomers (based on lauryl, butyl or benzyl methacrylate) or other acrylates (n-butyl acrylate,B A).…”

Branched macromonomers from catalytic chain transfer polymerisation (CCTP) as precursors for emulsion-templated porous polymers

“…Catalytic chain transfer polymerisation (CCTP) is a facile and interesting controlled polymerisation technique that has been employed for the preparation of low molecular weight functional polymethacrylates. [15][16][17][18] This technique relies on the catalytic activity of certain low spin cobalt(II) complexes which have very high chain transfer constants, typically several orders of magnitude higher than conventional thiol chain transfer agents. Much of our current knowledge of CCTP comes from investigations carried out by commercial organisations such as DuPont 19 and ICI/Zeneca, 20,21 complemented in academia by Gridnev, 22,23 Heuts, 24 Davis and Haddleton.…”

Bromoform-assisted aqueous free radical polymerisation: a simple, inexpensive route for the preparation of block copolymers

“…in the case of RAFT). Indeed, recent work by Haddleton et al 43 elegantly highlights one of the challenges in polymer chemistry; the need to produce block copolymers without the use of sulfur or transition metals. Their group utilised ω-unsaturated oligomers as chain transfer agents, similar to studies of Rizzardo and co-workers 44,45 who previously used this approach to prepare poly(butyl methacrylate)-b-poly(phenyl methacrylate) block copolymers with narrow molar mass distributions 46 .…”