Epoxy-functional diblock copolymer spheres, worms and vesicles <i>via</i> polymerization-induced self-assembly in mineral oil

Docherty, Philip J.; Girou, Chloé; Derry, Matthew J.; Armes, Steven P.

doi:10.1039/d0py00380h

Cited by 22 publications

(43 citation statements)

References 56 publications

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“… 10 − 15 This enables very high conversions to be achieved within relatively short time scales, which makes PISA much more efficient than the equivalent solution polymerization. 13 , 16 Depending on the monomer solubility within the continuous phase, PISA formulations can be classified as examples of either dispersion (miscible monomer) 4 , 5 , 13 − 15 , 17 − 24 or emulsion (immiscible monomer) 8 , 25 − 31 polymerization.…”

Section: Introductionmentioning

confidence: 99%

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles

György

Neal

Smith³

et al. 2022

Macromolecules

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A series of poly(lauryl methacrylate)–poly(methyl methacrylate- stat -lauryl methacrylate) (PLMA x –P(MMA- stat -LMA) y ) diblock copolymer nanoparticles were synthesized via RAFT dispersion copolymerization of 90 mol % methyl methacrylate (MMA) with 10 mol % lauryl methacrylate (LMA) in mineral oil by using a poly(lauryl methacrylate) (PLMA) precursor with a mean degree of polymerization (DP) of either 22 or 41. In situ 1 H NMR studies of the copolymerization kinetics suggested an overall comonomer conversion of 94% within 2.5 h. GPC analysis confirmed a relatively narrow molecular weight distribution ( M w / M n ≤ 1.35) for each diblock copolymer. Recently, we reported an unexpected morphology constraint when targeting PLMA 22 –PMMA y nano-objects in mineral oil, with the formation of kinetically trapped spheres being attributed to the relatively high glass transition temperature ( T g ) of the PMMA block. Herein we demonstrate that this limitation can be overcome by (i) incorporating 10 mol % LMA into the core-forming block and (ii) performing such syntheses at 115 °C. This new strategy produced well-defined spheres, worms, or vesicles when using the same PLMA 22 precursor. Introducing the LMA comonomer not only enhances the mobility of the core-forming copolymer chains by increasing their solvent plasticization but also reduces their effective glass transition temperature to well below the reaction temperature. Copolymer morphologies were initially assigned via transmission electron microscopy (TEM) studies and subsequently confirmed via small-angle X-ray scattering analysis. The thermoresponsive behavior of PLMA 22 –P(0.9MMA- stat -0.1LMA) 113 worms and PLMA 22 –P(0.9MMA- stat -0.1LMA) 228 vesicles was also studied by using dynamic light scattering (DLS) and TEM. The former copolymer underwent a worm-to-sphere transition on heating from 20 to 170 °C while a vesicle-to-worm transition was observed for the latter. Such thermal transitions were irreversible at 0.1% w/w solids but proved to be reversible at 20% w/w solids.

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Section: Introductionmentioning

confidence: 99%

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles

György

Neal

Smith³

et al. 2022

Macromolecules

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“…PISA formulations have been developed for use in aqueous solution, ,− for polar solvents such as lower alcohols, − and for non-polar media. ,, In the latter case, the solvent can be mineral oil − or silicone oil − or an n -alkane. − The first two solvents are well-suited for certain potential applications. For example, highly anisotropic worm-like nanoparticles can serve as useful thickeners for silicone oils, particularly if they are rendered stiffer via core cross-linking .…”

Section: Introductionmentioning

confidence: 99%

“…A wide range of diblock copolymers have been prepared via PISA in non-polar media. The soluble precursor block is typically either poly(lauryl methacrylate) ,,, or poly(stearyl methacrylate). − ,− , However, alternative examples include poly(2-ethylhexyl acrylate), , poly(lauryl acrylate), poly(behenyl methacrylate), or 3-[tris(trimethylsilyloxy)silyl] propyl methacrylate . In addition, monohydroxy-capped precursors such as polydimethylsiloxane or hydrogenated polybutadiene , can be converted into suitable macromolecular RAFT agents via esterification using a suitable carboxylic acid-functionalized RAFT agent.…”

Section: Introductionmentioning

confidence: 99%

“…In addition, monohydroxy-capped precursors such as polydimethylsiloxane or hydrogenated polybutadiene , can be converted into suitable macromolecular RAFT agents via esterification using a suitable carboxylic acid-functionalized RAFT agent. Similarly, various types of structure-directing insoluble blocks have been studied, including poly(benzyl methacrylate), − ,,− poly(benzyl acrylate), poly(3-phenylpropyl methacrylate), − poly(glycidyl methacrylate), , poly(2-hydroxypropyl methacrylate), poly(2,2,2-trifluoroethyl methacrylate), ,, or poly(2-(dimethylamino)ethyl methacrylate) …”

Section: Introductionmentioning

confidence: 99%

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RAFT Dispersion Polymerization of Methyl Methacrylate in Mineral Oil: High Glass Transition Temperature of the Core-Forming Block Constrains the Evolution of Copolymer Morphology

et al. 2021

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RAFT dispersion polymerization of a prototypical methacrylic monomer, methyl methacrylate (MMA), is performed in mineral oil using various poly(lauryl methacrylate) (PLMA) precursors prepared with a trithiocarbonate-based RAFT agent. GPC analysis indicated reasonably narrow molecular weight distributions (M w /M n ≤ 1.39) for all diblock copolymers, with 1 H NMR studies indicating high MMA conversions (≥95%) for all syntheses. An efficient one-pot synthesis protocol enabled high blocking efficiencies to be achieved when targeting higher PMMA DPs. However, the relatively high glass transition temperature (T g ) of the corresponding core-forming PMMA block unexpectedly constrains the evolution in copolymer morphology during polymerization-induced self-assembly (PISA). More specifically, well-defined PLMA 22 −PMMA x spheres (x = 19−39) and relatively short worms (x = 69−97) can be obtained at 90 °C when using a PLMA 22 precursor but targeting higher x values (x ≥ 108) invariably leads to colloidally unstable aggregates of spheres, rather than long worms or vesicles. Interestingly, similar constraints were observed when targeting higher solids, when using n-dodecane instead of mineral oil, or when employing an alternative steric stabilizer block. Raising the PISA synthesis temperature from 90 to 115 °C (i.e., from below to above the T g of the final PMMA block) does not alleviate this unexpected problem. Moreover, only spherical nanoparticles can be obtained at 115 °C when targeting PMMA DPs between 50 and 400 with the same PLMA 22 precursor. This suggests that nanoparticle formation may occur by a chain expulsion/insertion mechanism at this relatively high reaction temperature. PLMA 22 −PMMA x nanoparticles were characterized in terms of their particle size and morphology using dynamic light scattering (DLS), transmission electron microscopy (TEM), and small-angle X-ray scattering (SAXS). DLS and TEM studies of a 0.1% w/w dispersion of PLMA 22 −PMMA 69 short worms indicated an irreversible worm-to-sphere transition on heating from 20 to 150 °C. Oscillatory rheology and TEM studies indicated that this thermal transition was only partially reversible for a 20% w/w dispersion of PLMA 22 −PMMA 69 short worms.

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“…A reasonable error is expected since the GPC detector is calibrated against PMMA standards. 41 The same effect is seen in the final triblock terpolymer product (74.8 kg mol −1 ). Dispersity for these block copolymers is reasonably low and comparable to those of previous diblock copolymers synthesised in scCO 2 .…”

Section: Polymer Chemistry Papermentioning

confidence: 63%

Porous hollow TiO₂microparticles for photocatalysis: exploiting novel ABC triblock terpolymer templates synthesised in supercritical CO₂

et al. 2021

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Epoxy-functional diblock copolymer spheres, worms and vesicles via polymerization-induced self-assembly in mineral oil

Abstract: Epoxy-functional poly(stearyl methacrylate)-poly(glycidyl methacrylate) spheres, worms or vesicles can be prepared by RAFT dispersion polymerization of glycidyl methacrylate in mineral oil at 70 °C.

Cited by 22 publications

References 56 publications

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles

RAFT Dispersion Polymerization of Methyl Methacrylate in Mineral Oil: High Glass Transition Temperature of the Core-Forming Block Constrains the Evolution of Copolymer Morphology

Porous hollow TiO₂microparticles for photocatalysis: exploiting novel ABC triblock terpolymer templates synthesised in supercritical CO₂

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Epoxy-functional diblock copolymer spheres, worms and vesicles via polymerization-induced self-assembly in mineral oil

Abstract: Epoxy-functional poly(stearyl methacrylate)-poly(glycidyl methacrylate) spheres, worms or vesicles can be prepared by RAFT dispersion polymerization of glycidyl methacrylate in mineral oil at 70 °C.

Cited by 22 publications

References 56 publications

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles

Tuning the Glass Transition Temperature of a Core-Forming Block during Polymerization-Induced Self-Assembly: Statistical Copolymerization of Lauryl Methacrylate with Methyl Methacrylate Provides Access to Spheres, Worms, and Vesicles

RAFT Dispersion Polymerization of Methyl Methacrylate in Mineral Oil: High Glass Transition Temperature of the Core-Forming Block Constrains the Evolution of Copolymer Morphology

Porous hollow TiO2microparticles for photocatalysis: exploiting novel ABC triblock terpolymer templates synthesised in supercritical CO2

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Porous hollow TiO₂microparticles for photocatalysis: exploiting novel ABC triblock terpolymer templates synthesised in supercritical CO₂