Exploiting catalytic chain transfer polymerization for the synthesis of carboxylated latexes via sulfur‐free RAFT

Abstract

We present a systematic study of incorporating carboxyl groups into latex particles to enhance colloidal stability and the physical properties of the latex. Statistical copolymers of methacrylic acid and methyl methacrylate) were synthesized via catalytic chain transfer polymerization (CCTP) in emulsion. The vinyl‐terminated oligomers were in turn successfully utilized as chain transfer agents for the formation of diblock and pseudo triblock copolymers via sulfur‐free reversible addition–fragmentation chain transfer polymerization (SF‐RAFT). These copolymers were characterized using 1H NMR, size exclusion chromatography (SEC), dynamic light scattering (DLS), dynamic mechanical analysis (DMA), contact angle measurements and matrix‐assisted laser desorption/ionization time of flight mass spectroscopy (MALDI‐TOF‐MS) techniques. © 2019 The Authors. Journal of Polymer Science Part A: Polymer Chemistry published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, E1–E9

Rapidly self-deoxygenating controlled radical polymerization in water via in situ disproportionation of Cu(i)

“…Apart from the high concentration of dissolved O 2 in even puried water (>8 mg L À1 at ambient temperature), there is high potential of side reactions, such as hydrolysis or elimination of the R-X or P-X bond, dissociation of the deactivating Cu(II) species when Cu-RDRP is applied, 39,40 and hydrolysis of the (macro-)chain transfer agent (CTA or macro-CTA) [41][42][43] in the case of RAFT. 44,45 Consequently, oxygen tolerant polymerizations in aqueous media require the efficient removal of oxygen from the polymerization solution, and also necessitate rapid rates in order to avoid these chain termination events.…”

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.…”

Automatic peak assignment and visualisation of copolymer mass spectrometry data using the ‘genetic algorithm’

“…Copolymers represent a wide range of materials encompassing different chemical, mechanical, and thermal properties, which can be somewhat tuned by altering the structure and compositional make-up of the copolymer chain. [1][2][3][4][5][6] It is due to the relationship between synthetic methodology and tuneable properties that copolymers have found such diverse and essential applications. [7][8][9][10][11] Copolymers of vinyl monomers may be synthesised by a wide variety of polymerisation methods, including catalytic chain transfer polymerisation (CCTP), [12][13][14] atom transfer radical polymerisation (ATRP), [15][16][17] ionic polymerisation, 18,19 reversible addition-transfer chain-transfer polymerisation (RAFT), [20][21][22] and sulphur-free RAFT.…”