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

Cunningham, Victoria J.; Ning, Yin; Armes, Steven P.; Musa, Osama M.

doi:10.1016/j.polymer.2016.07.072

Cited by 23 publications

(17 citation statements)

References 70 publications

(99 reference statements)

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“…Results showed that the k app value was reduced to 2/3 of that of the reaction with CTA-Me in DMF and that the reaction had an induction period t i ¼ 4.3 h. This result might derive from the slow chain transfer reaction of more stable 3 cyanopropyl radicals generated from CTA-Pr in the active/dormant equilibrium. 35,36 Nevertheless, this reaction affords controlled radical polymerization with narrow molecular weight distribution. In the case of polymerization of acrylamide monomers with shortbranched side chain (ptPA), the k app value was higher than that for pDDA (k app ¼ 6.4 Â 10 À5 s À1 in toluene, Fig.…”

Section: Resultsmentioning

confidence: 99%

Amphiphilic acrylamide block copolymer: RAFT block copolymerization and monolayer behaviour

2017

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Section: Resultsmentioning

confidence: 99%

Amphiphilic acrylamide block copolymer: RAFT block copolymerization and monolayer behaviour

2017

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“…[55][56][57] Thus it seems likely that the few cases where the onset of micellization has apparently coincided with the presence of higher order morphologies (rather than the formation of spheres) are actually artifacts caused by the ingress of hot solvent at elevated temperature into the nanoparticle cores. 21,[58][59][60] Each aliquot removed for these kinetic studies was also analyzed via GPC to assess the evolution of Mn and Mw/Mn during the DMA polymerization (see Figure 3b). A linear evolution of Mn with conversion was observed, as expected for a RAFT polymerization.…”

Section: Inspection Ofmentioning

confidence: 99%

RAFT Dispersion Polymerization in Silicone Oil

et al. 2019

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A near-monodisperse monohydroxy-terminated polydimethylsiloxane (PDMS; mean degree of polymerization = 66) was esterified using a carboxylic acid-functionalized trithiocarbonate to yield a PDMS66 precursor with a mean degree of functionality of 92 ± 5 % as determined by 1 H NMR spectroscopy. This PDMS66 precursor was then chain-extended in turn using nine different methacrylic monomers in a low-viscosity silicone oil (decamethylcyclopentasiloxane, D5). Depending on the monomer type, such PISA syntheses proceeded via either RAFT dispersion polymerization or RAFT emulsion polymerization. In each case the target DP of the core-forming block was fixed at 200 and the copolymer concentration was 25 % w/w. Transmission electron microscopy studies indicated that kinetically-trapped spheres were obtained in almost all cases. The only exception was 2-(dimethylamino)ethyl methacrylate (DMA), which enabled access to spheres, worm or vesicles. This striking difference is attributed to the relatively low glass transition temperature for this latter block. A phase diagram was constructed for a series of PDMS66-PDMAx nano-objects by systematically increasing the PDMA target DP from 20 to 220 and varying the copolymer concentration between 10 and 30 % w/w. Higher copolymer concentrations were required to access a pure worm phase, whereas only spheres, vesicles or mixed phases were accessible at lower copolymer concentrations. Gel permeation chromatography studies indicated a linear evolution of number-average molecular weight (Mn) with PDMA DP while dispersities remained below 1.39, suggesting relatively well-controlled RAFT polymerizations. Small angle x-ray scattering (SAXS) was used to characterize selected examples of spheres, worms and vesicles. PDMS66-PDMA100-112 worms synthesized at 25-30 % w/w formed freestanding gels at 20 °C. Oscillatory rheology studies performed on a 30 % w/w PDMS-PDMA105 worm dispersion indicated a storage modulus (gel strength) of 1057 Pa and a critical gelation concentration (CGC) of 12 % w/w. Finally, PDMS66-PDMAx worms could also be prepared in n-dodecane, hexamethyldisiloxane or octamethylcyclosiloxane. Rotational rheometry studies indicate that such worms are efficient viscosity modifiers for these non-polar oils.

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“…For example, Cunningham and co-workers reported the RAFT dispersion polymerisation of benzyl methacrylate in ethanol using PNMEP as a steric stabiliser block. 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.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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

Cited by 23 publications

References 70 publications

Amphiphilic acrylamide block copolymer: RAFT block copolymerization and monolayer behaviour

Amphiphilic acrylamide block copolymer: RAFT block copolymerization and monolayer behaviour

RAFT Dispersion Polymerization in Silicone Oil

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

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