• Ab initio RAFT emulsion polymerization mediated by small cationic RAFT agents to form polymers with low molar mass dispersity

      Stace, Sarah J; Vanderspikken, Jochen; Howard, Shaun C; Li, Guoxin; Muir, Benjamin W; Fellows, Christopher M; Keddie, Daniel J; Moad, Graeme (Royal Society of Chemistry (RSC), 2019-07-29)
      We report on low molar mass cationic RAFT agents that provide predictable molar mass and low molar mass dispersities (Đm) 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 Đm 1.2–1.4 for Mn ∼ 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 Đm 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 Đm < 1.8 in ab initio emulsion polymerization of less activated monomers, specifically, the vinyl esters, vinyl acetate and vinyl benzoate.
    • Cu(0)-RDRP of methacrylates in DMSO: importance of the initiator

      Jones, Glen R.; Whitfield, Richard; Anastasaki, Athina; Risangud, Nuttapol; Simula, Alexandre; Keddie, Daniel J.; Haddleton, David M.; University of Warwick; University of Warwick; University of Warwick; et al. (RSC Publishing, 2017-08-17)
      The controlled radical polymerization of methacrylates via Cu(0)-mediated RDRP is challenging in comparison to acrylates with most reports illustrating higher dispersities, lower monomer conversions and poorer end group fidelity relative to the acrylic analogues. Herein, we present the successful synthesis of poly(methyl methacrylate) (PMMA) in DMSO by judicious selection of optimal reaction conditions. The effect of the initiator, ligand and temperature on the rate and control of the polymerization is investigated and discussed. Under carefully optimized conditions enhanced control over the molecular weight distributions is obtained furnishing methacrylic polymers with dispersities as low as 1.10, even at very high conversions. A range of methacrylates were found to be tolerant to the optimized polymerization conditions including hydrophobic, hydrophilic and functional methacrylates including methyl and benzyl methacrylate, ethylene glycol methyl ether methacrylate and glycidyl methacrylate. The control retained during the polymerization is further highlighted by in situ chain extensions yielding well-defined block polymethacrylates.
    • Functionalisation of MWCNTs with poly(lauryl acrylate) polymerised by Cu(0)-mediated and RAFT methods

      Gupta, Jaipal; Wan, Chaoying; Haddleton, David M.; McNally, Tony; Keddie, Daniel (Royal Society of Chemistry, 2016-05-12)
      Poly(lauryl acrylate) P[LA] of various molar masses were prepared via reversible addition–fragmentation chain transfer (RAFT) polymerisation and Cu(0)-mediated radical polymerisation, for the purpose of improving the dispersion and interfacial adhesion of MWCNTs with polymers such as isotactic poly(propylene) (iPP). Lauryl acrylate (LA) was polymerised via RAFT to high conversion (95%), furnished polymers in good agreement with theoretical Mn with dispersity increasing with increasing Mn. LA polymerised via the Cu(0)-mediated method to full conversion (>98%), gave polymers in good agreement with theoretical Mn and low dispersity (Đ ≈ 1.2) for lower molar mass polymers. Low molar mass tailing was also observed for P[LA] via Cu(0)-mediated polymerisation for higher molar mass polymers. Thermogravimetric analysis (TGA) of P[LA] via RAFT showed an onset of degradation occurred at ≈340–350 °C, however, this decreased to ≈250–260 °C for lower molar mass polymers. TGA of the RAFT agent revealed an onset of degradation of ≈200–250 °C. Free radicals generated from thermal degradation of end groups did not influence the thermal stability of the P[LA] backbone and ‘unzipping’ commonly seen with methacrylates was not observed. TGA analysis of P[LA] via the Cu(0)-mediated method revealed a similar degradation profile to that of P[LA] via RAFT. The thermal stability of P[LA] is sufficient to allow for melt processing with iPP. P[LA] via RAFT mixed with MWCNTs showed an adsorption of ≈10–25 wt% P[LA] on to the MWCNTs. The onset of thermal degradation of the P[LA] remained unchanged after adsorption on to the MWCNTs. P[LA] via the Cu(0)-mediated method adsorbed up to 85 wt% and an increase in thermal stability of ≈50 °C was recorded. Increasing P[LA] and MWCNT concentration independently also resulted in an increase in the level of adsorption, possibility due to increased CH–π interaction. The difference in thermal stability could possibly be due to heat transfer from the P[LA] to the MWCNTs, resulting in delayed pyrolysis of P[LA]. Size exclusion chromatography (SEC) and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF MS) of P[LA] after heating to 200 °C for 30 min in air showed loss of end groups but, the P[LA] backbone remained preserved for both polymer types. Evidence from transmission electron micrographs (TEM) shows the P[LA] adsorbing onto the MWCNT surface. Melt processing composites of P[LA] via Cu(0)-mediated with MWCNTs and iPP was possible as the P[LA] was thermally stable during the both extrusion and in the TGA when studied post melt mixing.
    • Influence of the tetraalkoxysilane crosslinker on the properties of polysiloxane-based elastomers prepared by the Lewis acid-catalysed Piers-Rubinsztajn reaction

      Hickman, Andrew M.; Chmel, Nikola; Cameron, Neil R.; Keddie, Daniel J.; Schiller, Tara L. (Royal Society of Chemistry, 2021-07-21)
      We investigate the preparation of polysiloxane-based networks under solvent-free, ambient conditions using the Lewis acid catalysed Piers-Rubinsztajn (PR) reaction of hydride-terminated siloxanes with various tetrafunctional alkoxysilanes (tetraethoxysilane, tetrapropoxysilane, tetra-n-buxoxysilane, tetra-s-butoxysilane, tetra-s-butoxysilane, and tetrakis(2- ethylbutoxy)silane) as crosslinkers. We explore the effects of polysiloxane chain length and crosslinker alkyl group on the rheological performance of the elastomers. By analysing the reaction progress by grazing angle Fourier-transform infrared spectroscopy (FTIR) and determining the rheological properties of the resulting materials, we show that the use of linear or branched alkoxysilanes strongly influences the morphology and properties of these network polymers. We have shown the PR process is can be tailored to reliably produce homogeneous, polysiloxane network materials. This work provides information on the relative rates of network formation under ambient conditions with an emphasis on the impact of crosslinker alkyl chain length. Our results show that electronics and s terics both play critical roles in influencing the the rate of the curing reaction. Crucially, we newly demonstrate the benefit of a having tertiary carbon α to the SiO reaction centre, as is the case for the tetra-s-butoxysilane crosslinker, for delivering exceptionally rapid network cure and a concomitant enhancement in storage modulus of the resultant materials.