Dataset Information

Synthesis of Highly Transparent Diblock Copolymer Vesicles via RAFT Dispersion Polymerization of 2,2,2-Trifluoroethyl Methacrylate in n-Alkanes.

ABSTRACT: RAFT dispersion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) is performed in n-dodecane at 90 °C using a relatively short poly(stearyl methacrylate) (PSMA) precursor and 2-cyano-2-propyl dithiobenzoate (CPDB). The growing insoluble poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) block results in the formation of PSMA-PTFEMA diblock copolymer nano-objects via polymerization-induced self-assembly (PISA). GPC analysis indicated narrow molecular weight distributions (M _w/M _n ? 1.34) for all copolymers, with ¹⁹F NMR studies indicating high TFEMA conversions (?95%) for all syntheses. A pseudo-phase diagram was constructed to enable reproducible targeting of pure spheres, worms, or vesicles by varying the target degree of polymerization of the PTFEMA block at 15-25% w/w solids. Nano-objects were characterized using dynamic light scattering, transmission electron microscopy, and small-angle X-ray scattering. Importantly, the near-identical refractive indices for PTFEMA (1.418) and n-dodecane (1.421) enable the first example of highly transparent vesicles to be prepared. The turbidity of such dispersions was examined between 20 and 90 °C. The highest transmittance (97% at 600 nm) was observed for PSMA₉-PTFEMA₂₉₄ vesicles (237 ± 24 nm diameter; prepared at 25% w/w solids) in n-dodecane at 20 °C. Interestingly, targeting the same diblock composition in n-hexadecane produced a vesicle dispersion with minimal turbidity at a synthesis temperature of 90 °C. This solvent enabled in situ visible absorption spectra to be recorded during the synthesis of PSMA₁₆-PTFEMA₈₆ spheres at 15% w/w solids, which allowed the relatively weak n??* band at 515 nm assigned to the dithiobenzoate chain-ends to be monitored. Unfortunately, the premature loss of this RAFT chain-end occurred during the RAFT dispersion polymerization of TFEMA at 90 °C, so meaningful kinetic data could not be obtained. Furthermore, the dithiobenzoate chain-ends exhibited a ?_max shift of 8 nm relative to that of the dithiobenzoate-capped PSMA₉ precursor. This solvatochromatic effect suggests that the problem of thermally labile dithiobenzoate chain-ends cannot be addressed by performing the TFEMA polymerization at lower temperatures.

SUBMITTER: Gyorgy C

PROVIDER: S-EPMC7879428 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Synthesis of Highly Transparent Diblock Copolymer Vesicles via RAFT Dispersion Polymerization of 2,2,2-Trifluoroethyl Methacrylate in n-Alkanes.

György Csilla C Derry Matthew J MJ Cornel Erik J EJ Armes Steven P SP

Macromolecules 20210122 3

RAFT dispersion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) is performed in n-dodecane at 90 °C using a relatively short poly(stearyl methacrylate) (PSMA) precursor and 2-cyano-2-propyl dithiobenzoate (CPDB). The growing insoluble poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) block results in the formation of PSMA-PTFEMA diblock copolymer nano-objects via polymerization-induced self-assembly (PISA). GPC analysis indicated narrow molecular weight distributions (M ...[more]

PMID: 33583957

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Project description:A poly(2-(dimethylamino)ethyl methacrylate) (PDMA) chain transfer agent (CTA) is used for the reversible addition-fragmentation chain transfer (RAFT) alcoholic dispersion polymerization of benzyl methacrylate (BzMA) in ethanol at 70 °C. THF GPC analysis indicated a well-controlled polymerization with molecular weight increasing linearly with conversion. GPC traces also showed high blocking efficiency with no homopolymer contamination apparent and Mw/Mn values below 1.35 in all cases. 1H NMR studies confirmed greater than 98% BzMA conversion for a target PBzMA degree of polymerization (DP) of up to 600. The PBzMA block becomes insoluble as it grows, leading to the in situ formation of sterically stabilized diblock copolymer nanoparticles via polymerization-induced self-assembly (PISA). Fixing the mean DP of the PDMA stabilizer block at 94 units and systematically varying the DP of the PBzMA block enabled a series of spherical nanoparticles of tunable diameter to be obtained. These nanoparticles were characterized by TEM, DLS, MALLS, and SAXS, with mean diameters ranging from 35 to 100 nm. The latter technique was particularly informative: data fits to a spherical micelle model enabled calculation of the core diameter, surface area occupied per copolymer chain, and the mean aggregation number (Nagg). The scaling exponent derived from a double-logarithmic plot of core diameter vs PBzMA DP suggests that the conformation of the PBzMA chains is intermediate between the collapsed and fully extended state. This is in good agreement with 1H NMR studies, which suggest that only 5-13% of the BzMA residues of the core-forming chains are solvated. The Nagg values calculated from SAXS and MALLS are in good agreement and scale approximately linearly with PBzMA DP. This suggests that spherical micelles grow in size not only as a result of the increase in copolymer molecular weight during the PISA synthesis but also by exchange of individual copolymer chains between micelles and/or by sphere-sphere fusion events.

Project description:A near-monodisperse poly(stearyl methacrylate) macromolecular chain transfer agent (PSMA macro-CTA) was prepared via reversible addition-fragmentation chain transfer (RAFT) solution polymerisation in toluene. This PSMA macro-CTA was then utilised as a stabiliser block for the RAFT dispersion polymerisation of a highly polar monomer, N-2-(methacryloyloxy)ethyl pyrrolidone (NMEP), in n-dodecane at 90 °C. 1H NMR studies confirmed that the rate of NMEP polymerisation was significantly faster than that of a non-polar monomer (benzyl methacrylate, BzMA) under the same conditions. For example, when targeting a PSMA14-PNMEP100 diblock copolymer, more than 99% NMEP conversion was achieved within 30 min, whereas only 19% BzMA conversion was obtained on the same time scale for the corresponding PSMA14-PBzMA100 synthesis. The resulting PSMA-PNMEP diblock copolymer chains underwent polymerisation-induced self-assembly (PISA) during growth of the insoluble PNMEP block to form either spherical micelles, highly anisotropic worms or polydisperse vesicles, depending on the target DP of the PNMEP chains. Systematic variation of this latter parameter, along with the solids content, allowed the construction of a phase diagram which enabled pure morphologies to be reproducibly targeted. Syntheses conducted at 10% w/w solids led to the formation of kinetically-trapped spheres. A monotonic increase in particle diameter with PNMEP DP was observed for such PISA syntheses, with particle diameters of up to 462 nm being obtained for PSMA14-PNMEP960. Increasing the copolymer concentration to 15% w/w solids led to worm-like micelles, while vesicles were obtained at 27.5% w/w solids. High (≥95%) NMEP conversions were achieved in all cases and 3 : 1 chloroform/methanol GPC analysis indicated relatively high blocking efficiencies. However, relatively broad molecular weight distributions (Mw/Mn > 1.50) were observed when targeting PNMEP DPs greater than 150. This indicates light branching caused by the presence of a low level of dimethacrylate impurity. Finally, PSMA14-PNMEP49 spheres were evaluated as Pickering emulsifiers. Unexpectedly, it was found that either water-in-oil or oil-in-water Pickering emulsions could be obtained depending on the shear rate employed for homogenisation. Further investigation suggested that high shear rates lead to in situ inversion of the initial hydrophobic PSMA14-PNMEP49 spheres to form hydrophilic PNMEP49-PSMA14 spheres.

Dataset Information

Synthesis of Highly Transparent Diblock Copolymer Vesicles via RAFT Dispersion Polymerization of 2,2,2-Trifluoroethyl Methacrylate in n-Alkanes.

Publications

Synthesis of Highly Transparent Diblock Copolymer Vesicles via RAFT Dispersion Polymerization of 2,2,2-Trifluoroethyl Methacrylate in <i>n</i>-Alkanes.

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