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Synthesis of Poly(3-vinylpyridine)-Block-Polystyrene Diblock Copolymers via Surfactant-Free RAFT Emulsion Polymerization.

ABSTRACT: In this work, we present a novel synthetic route to diblock copolymers based on styrene and 3-vinylpyridine monomers. Surfactant-free water-based reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of styrene in the presence of the macroRAFT agent poly(3-vinylpyridine) (P3VP) is used to synthesize diblock copolymers with molecular weights of around 60 kDa. The proposed mechanism for the poly(3-vinylpyridine)-block-poly(styrene) (P3VP-b-PS) synthesis is the polymerization-induced self-assembly (PISA) which involves the in situ formation of well-defined micellar nanoscale objects consisting of a PS core and a stabilizing P3VP macroRAFT agent corona. The presented approach shows a well-controlled RAFT polymerization, allowing for the synthesis of diblock copolymers with high monomer conversion. The obtained diblock copolymers display microphase-separated structures according to their composition.

SUBMITTER: Nieswandt K

PROVIDER: S-EPMC6803976 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Synthesis of Poly(methacrylic acid)-block-Polystyrene Diblock Copolymers at High Solid Contents via RAFT Emulsion Polymerization.

Project description:The combination of polymerization-induced self-assembly (PISA) and reversible-addition fragmentation chain transfer (RAFT) emulsion polymerization offers a powerful technique to synthesize diblock copolymers and polymeric nanoparticles in a controlled manner. The RAFT emulsion diblock copolymerization of styrene and methacrylic acid (MAA) by using a trithiocarbonate as surfactant and RAFT agent was investigated. The Z-group of the RAFT agent was modified with a propyl-, butyl- and dodecyl- sidechain, increasing the hydrophobicity of the RAFT agent to offer well-controlled polymerization of poly(methacrylic acid)-block-polystyrene (PMAA-b-PS) diblock copolymers at high solid contents between 30-50 wt% in water. The kinetic data of the PMAA homopolymerization with the three different RAFT agents for various solvents was investigated as well as the RAFT emulsion polymerization of the diblock copolymers in pure water. While the polymerization of PMAA-b-PS with a propyl terminus as a Z-group suffered from slow polymerization rates at solid contents above 30 wt%, the polymerization with a dodecyl sidechain as a Z-group led to full conversion within 2 h, narrow molar mass distributions and all that at a remarkable solid content of up to 50 wt%.

| S-EPMC8588034 | biostudies-literature

Surfactant-Free RAFT Emulsion Polymerization of Styrene Using Thermoresponsive macroRAFT Agents: Towards Smart Well-Defined Block Copolymers with High Molecular Weights.

Project description:The combination of reversible addition⁻fragmentation chain transfer (RAFT) and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX), increasing the phase transition temperature (PTT) of the used thermoresponsive poly(N-acryloylpyrrolidine) (PAPy) macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide)-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine) (PDMA-b-P(APi-co-APy)) as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy) block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS) block. In dynamic light scattering (DLS), as well as cryo-transmission electron microscopy (cryoTEM), moreover, all created latexes indeed reveal a high (temperature) stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability.

| S-EPMC6418535 | biostudies-literature

Immobilization of glucose oxidase to nanostructured films of polystyrene-block-poly(2-vinylpyridine).

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| S-EPMC4131735 | biostudies-literature

Electrochemically-Initiated RAFT Synthesis of Low Dispersity Multiblock Copolymers by Seeded Emulsion Polymerization.

Project description:We describe electrochemically initiated emulsion polymerization with reversible addition-fragmentation chain transfer (eRAFT) to form well-defined multiblock copolymers with low molar mass dispersity. We demonstrate the utility of our emulsion eRAFT process with the synthesis of low dispersity multiblock copolymers by seeded RAFT emulsion polymerization at ambient temperature (∼30 °C). Thus, a triblock, poly(butyl methacrylate)-block-polystyrene-block-poly(4-methylstyrene) [PBMA-b-PSt-b-PMS], and a tetrablock, poly(butyl methacrylate)-block-polystyrene-block-poly(styrene-stat-butyl acrylate)-block-polystyrene [PBMA-b-PSt-b-P(BA-stat-St)-b-PSt], were synthesized as free-flowing, colloidally stable latexes commencing with a surfactant-free poly(butyl methacrylate) macroRAFT agent seed latex. A straightforward sequential addition strategy with no intermediate purification steps was able to be employed due to the high monomer conversions achieved in each step. The method takes full advantage of compartmentalization phenomena and the nanoreactor concept described in previous work to achieve the predicted molar mass, low molar mass dispersity (Đ ∼ 1.1-1.2), incrementing particle size (Zav = 100-115 nm), and low particle size dispersity (PDI ∼ 0.02) for each generation of the multiblocks.

| S-EPMC10035029 | biostudies-literature

Metallocene-Containing Homopolymers and Heterobimetallic Block Copolymers via Photoinduced RAFT Polymerization.

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| S-EPMC5739086 | biostudies-literature

Random and Diblock Thermoresponsive Oligo(ethylene glycol)-Based Copolymers Synthesized via Photo-Induced RAFT Polymerization.

Project description:Amphiphilic random and diblock thermoresponsive oligo(ethylene glycol)-based (co)polymers were synthesized via photoiniferter polymerization under visible light using trithiocarbonate as a chain transfer agent. The effect of solvent, light intensity and wavelength on the rate of the process was investigated. It was shown that blue and green LED light could initiate RAFT polymerization of macromonomers without an exogenous initiator at room temperature, giving bottlebrush polymers with low dispersity at sufficiently high conversions achieved in 1-2 h. The pseudo-living mechanism of polymerization and high chain-end fidelity were confirmed by successful chain extension. Thermoresponsive properties of the copolymers in aqueous solutions were studied via turbidimetry and laser light scattering. Random copolymers of methoxy- and alkoxy oligo(ethylene glycol) methacrylates of a specified length formed unimolecular micelles in water with a hydrophobic core consisting of a polymer backbone and alkyl groups and a hydrophilic oligo(ethylene glycol) shell. In contrast, the diblock copolymer formed huge multimolecular micelles.

| S-EPMC8747269 | biostudies-literature

Synthesis of High Molecular Weight Poly(glycerol monomethacrylate) via RAFT Emulsion Polymerization of Isopropylideneglycerol Methacrylate.

Project description:High molecular weight water-soluble polymers are widely used as flocculants or thickeners. However, synthesis of such polymers via solution polymerization invariably results in highly viscous fluids, which makes subsequent processing somewhat problematic. Alternatively, such polymers can be prepared as colloidal dispersions; in principle, this is advantageous because the particulate nature of the polymer chains ensures a much lower fluid viscosity. Herein we exemplify the latter approach by reporting the convenient one-pot synthesis of high molecular weight poly(glycerol monomethacrylate) (PGMA) via the reversible addition-fragmentation chain transfer (RAFT) aqueous emulsion polymerization of a water-immiscible protected monomer precursor, isopropylideneglycerol methacrylate (IPGMA) at 70 °C, using a water-soluble poly(glycerol monomethacrylate) (PGMA) chain transfer agent as a steric stabilizer. This formulation produces a low-viscosity aqueous dispersion of PGMA-PIPGMA diblock copolymer nanoparticles at 20% solids. Subsequent acid deprotection of the hydrophobic core-forming PIPGMA block leads to particle dissolution and affords a viscous aqueous solution comprising high molecular weight PGMA homopolymer chains with a relatively narrow molecular weight distribution. Moreover, it is shown that this latex precursor route offers an important advantage compared to the RAFT aqueous solution polymerization of glycerol monomethacrylate since it provides a significantly faster rate of polymerization (and hence higher monomer conversion) under comparable conditions.

| S-EPMC5959244 | biostudies-literature

Fructose-Based Acrylic Copolymers by Emulsion Polymerization.

Project description:The exploration of a renewable resource for the preparation of waterborne copolymers was conducted. Low molar mass sugar resources were selected for their wide availability. A fructose-based monomer (MF) bearing a methacrylate radically polymerizable group was successfully synthesized. The latter was shown to be able to homopolymerize in emulsion. The high Tg of the resulting polymer (about 115 °C) makes it of particular interest for adhesive and coating applications where hard materials are necessary to ensure valuable properties. As a result, its incorporation in waterborne acrylic containing formulations as an equivalent to petrochemical-based methyl methacrylate was investigated. It was found that the bio-based monomer exhibited similar behavior to that of common methacrylates, as shown by polymerization kinetics and particle size evolution. Furthermore, the homogeneous incorporation of the sugar units into the acrylate chains was confirmed by a unique glass transition temperature in differential scanning calorimeter (DSC). The potential of MF for the production of waterborne copolymers was greatly valued by the successful increase of formulation solids content up to 45 wt %. Interestingly, polymer insolubility in tetrahydrofurane increased with time due to further reactions occurring in storage. Most likely, the partial deprotection of sugar units was the reason for the creation of hydrogen bonding and, thus, physically insoluble entangled chains. This behavior highlights opportunities to make use of hydroxyl groups either for further functionalization or, eventually, for achieving enhanced adhesion on casted substrates.

| S-EPMC6415512 | biostudies-literature

RAFT aqueous dispersion polymerization yields poly(ethylene glycol)-based diblock copolymer nano-objects with predictable single phase morphologies.

Project description:A poly(ethylene glycol) (PEG) macromolecular chain transfer agent (macro-CTA) is prepared in high yield (>95%) with 97% dithiobenzoate chain-end functionality in a three-step synthesis starting from a monohydroxy PEG113 precursor. This PEG113-dithiobenzoate is then used for the reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA). Polymerizations conducted under optimized conditions at 50 °C led to high conversions as judged by (1)H NMR spectroscopy and relatively low diblock copolymer polydispersities (M(w)/M(n) < 1.25) as judged by GPC. The latter technique also indicated good blocking efficiencies, since there was minimal PEG113 macro-CTA contamination. Systematic variation of the mean degree of polymerization of the core-forming PHPMA block allowed PEG113-PHPMA(x) diblock copolymer spheres, worms, or vesicles to be prepared at up to 17.5% w/w solids, as judged by dynamic light scattering and transmission electron microscopy studies. Small-angle X-ray scattering (SAXS) analysis revealed that more exotic oligolamellar vesicles were observed at 20% w/w solids when targeting highly asymmetric diblock compositions. Detailed analysis of SAXS curves indicated that the mean number of membranes per oligolamellar vesicle is approximately three. A PEG113-PHPMA(x) phase diagram was constructed to enable the reproducible targeting of pure phases, as opposed to mixed morphologies (e.g., spheres plus worms or worms plus vesicles). This new RAFT PISA formulation is expected to be important for the rational and efficient synthesis of a wide range of biocompatible, thermo-responsive PEGylated diblock copolymer nano-objects for various biomedical applications.

| S-EPMC3920722 | biostudies-literature

Hybrid Poly(<i>β</i>-amino ester) Triblock Copolymers Utilizing a RAFT Polymerization Grafting-From Methodology.

Project description:The biocompatibility, biodegradability, and responsiveness of poly(β-amino esters) (PBAEs) has led to their widespread use as biomaterials for drug and gene delivery. Nonetheless, the step-growth polymerization mechanism that yields PBAEs limits the scope for their structural optimization toward specific applications because of limited monomer choice and end-group modifications. Moreover, to date the post-synthetic functionalization of PBAEs has relied on grafting-to approaches, challenged by the need for efficient polymer-polymer coupling and potentially difficult post-conjugation purification. Here a novel grafting-from approach to grow reversible addition-fragmentation chain transfer (RAFT) polymers from a PBAE scaffold is described. This is achieved through PBAE conversion into a macromolecular chain transfer agent through a multistep capping procedure, followed by RAFT polymerization with a range of monomers to produce PBAE-RAFT hybrid triblock copolymers. Following successful synthesis, the potential biological applications of these ABA triblock copolymers are illustrated through assembly into polymeric micelles and encapsulation of a model hydrophobic drug, followed by successful nanoparticle (NP) uptake in breast cancer cells. The findings demonstrate this novel synthetic methodology can expand the scope of PBAEs as biomaterials.

| S-EPMC10941699 | biostudies-literature

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