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Title: | Ab initio RAFT emulsion polymerization mediated by small cationic RAFT agents to form polymers with low molar mass dispersity | Authors: | Stace, Sarah J. VANDERSPIKKEN, jochen Howard, Shaun C. Li, Guoxin Muir, Benjamin W. Fellows, Christopher M. Keddie, Daniel J. Moad, Graeme |
Issue Date: | 2019 | Publisher: | ROYAL SOC CHEMISTRY | Source: | POLYMER CHEMISTRY, 10(37), p. 5044-5051 | Abstract: | We report on low molar mass cationic RAFT agents that provide predictable molar mass and low molar mass dispersities (D-m) in ab initio emulsion polymerization. Thus RAFT emulsion polymerization of styrene in the presence of the protonated RAFT agent, ((((cyanomethyl) thio)carbonothioyl)(methyl)amino)pyridin-1-ium toluenesulfonate (4), and the analogous methyl-quaternized RAFT agents, 4-((((cyanomethyl)thio)carbonothioyl)(methyl)amino)-1-methylpyridin-1-ium dodecyl sulfate (6), provide low dispersity polystyrene with D-m 1.2-1.4 for M-n similar to 20 000. We postulate that the success of ab initio emulsion polymerization with 4 is due to the hydrophilicity of the pyridinium group, which is such that the water soluble RAFT agent partitions predominantly into the aqueous phase under the conditions of the experiment and that 4 provides little retardation. With 6, when the counterion is dodecyl sulfate, we can achieve "surfactant-free" RAFT emulsion polymerization to provide a low D-m polystyrene. However, the RAFT end-group is lost on isolation of the polymer. Preliminary results show that this class of RAFT agent is broadly applicable in ab initio emulsion polymerization of other more-activated monomers (e.g., butyl acrylate, butyl methacrylate). Furthermore, cyanomethyl(pyridin-4-yl)carbamodithioate (3, the RAFT agent in neutral form) provides molar mass control and D-m < 1.8 in ab initio emulsion polymerization of less activated monomers, specifically, the vinyl esters, vinyl acetate and vinyl benzoate. | Notes: | [Stace, Sarah J.; Fellows, Christopher M.; Keddie, Daniel J.] Univ New England, Sch Sci & Technol, Armidale, NSW 2351, Australia. [Stace, Sarah J.; Vanderspikken, Jochen; Howard, Shaun C.; Li, Guoxin; Muir, Benjamin W.; Moad, Graeme] CSIRO Mfg, Bag 10, Clayton, Vic 3169, Australia. [Vanderspikken, Jochen] Hasselt Univ, Inst Mat Res IMR, Agoralaan 1 Bldg, B-3590 Diepenbeek, Belgium. [Keddie, Daniel J.] Univ Wolverhampton, Sch Biol Chem & Forens Sci, Wulfruna St, Wolverhampton WV1 1LY, W Midlands, England. | Document URI: | http://hdl.handle.net/1942/29857 | ISSN: | 1759-9954 | e-ISSN: | 1759-9962 | DOI: | 10.1039/c9py00893d | ISI #: | 000487564000013 | Rights: | The Royal Society of Chemistry 2019 | Category: | A1 | Type: | Journal Contribution | Validations: | ecoom 2020 |
Appears in Collections: | Research publications |
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