Synthesis, characterisation and Pickering emulsifier performance of poly(stearyl methacrylate)–poly(N-2-(methacryloyloxy)ethyl pyrrolidone) diblock copolymer nano-objects via RAFT dispersion polymerisation in n-dodecane

Abstract

Block copolymer spheres, worms or vesicles can be prepared via RAFT dispersion polymerisation of N-(methacryloyloxy)ethyl pyrrolidone in n-dodecane using a poly(stearyl methacrylate) chain transfer agent.

End-group ionisation enables the use of poly(N-(2-methacryloyloxy)ethyl pyrrolidone) as an electrosteric stabiliser block for polymerisation-induced self-assembly in aqueous media

“…16 Alternatively, PNMEP can be utilised as a core-forming block for RAFT dispersion polymerisation formulations conducted in n-dodecane. 17 Turbidimetry studies confirm that PNMEP exhibits inverse temperature solubility in aqueous solution. 15,26 Such behaviour has been used to prepare sterically-stabilised block copolymer nanoparticles with weakly hydrophobic PNMEP cores in water at 70 °C that subsequently dissolve to afford molecularlydissolved copolymer chains on cooling to ambient temperature.…”

Poly( N -2-(methacryloyloxy)ethyl pyrrolidone)-poly(benzyl methacrylate) diblock copolymer nano-objects via RAFT alcoholic dispersion polymerisation in ethanol

“…solution polymerisation [45][46][47][48]. For example, Deng et al prepared three PNMEP-based diblock copolymers by chain-extending a PNMEP macro-CTA with either glycidyl methacrylate, oligo(ethylene glycol) monomethacrylate or 2-(dimethylamino)ethyl methacrylate in methanol at 30 °C using visible light-mediated RAFT polymerisation.…”

“…NMEP conversions of 56 to 63 % were reported and post-polymerisation processing via a solvent switch led to the formation of PLMA-PNMEP diblock copolymer spheres in THF. We recently reported the first example of utilising NMEP in a PISA formulation [48]. A range of poly(stearyl methacrylate)-poly(N-(2-(methacryloyloxy)ethyl pyrrolidone) (PSMA-PNMEP) diblock copolymer nano-objects were prepared via RAFT dispersion polymerisation of NMEP using a PSMA macro-CTA in n-dodecane at 90 °C [48].…”

“…We recently reported the first example of utilising NMEP in a PISA formulation [48]. A range of poly(stearyl methacrylate)-poly(N-(2-(methacryloyloxy)ethyl pyrrolidone) (PSMA-PNMEP) diblock copolymer nano-objects were prepared via RAFT dispersion polymerisation of NMEP using a PSMA macro-CTA in n-dodecane at 90 °C [48]. Relatively high conversions (> 95 %) were achieved and the construction of a suitable phase diagram enabled the reproducible targeting of either spheres, worms or vesicles.…”

“…Compared to related pyrrolidone-functional monomers such as N-vinyl pyrrolidone, [49][50][51][52][53][54] there are rather few literature reports describing the RAFT polymerisation of NMEP [45][46][47][48]. Thus, a detailed study of the kinetics of the RAFT solution homopolymerisation of PNMEP in ethanol at 70 °C was conducted.…”