RAFT Dispersion Polymerization Research Articles

Preparation and Application of Nitrobenzene-Containing Copolymer Nanoparticles Obtained by RAFT Dispersion Polymerization

Preparation and Application of Nitrobenzene-Containing Copolymer Nanoparticles Obtained by RAFT Dispersion Polymerization

Amphiphilic pH-responsive ABC triblock copolymers via RAFT-mediated aqueous PISA and comparison with their A-b-(B-co-C) diblock copolymer counterparts

The influence of the macroRAFT agent architecture on the morphology of the self-assemblies obtained by aqueous RAFT dispersion polymerization in PISA is studied by comparing amphiphilic AC, A(B-co-C) diblocks and ABC triblock copolymers, constituted of N,N-dimethylacrylamide (DMAm = A), acrylic acid (AA = B) and N-cyanomethylacrylamide (CMAm = C) monomer units. The aim of this study is to better understand the impact of the presence of pH-sensitive acrylic acid units and their spatial distribution in block copolymers. Generally, the presence of a fully protonated intermediate block of PAA between the two blocks (based on PDMAm and PCMAm) favors the formation of higher-order morphologies. These ABC triblock copolymers assemblies are pH-responsive and can undergo morphological transitions through the controlled deprotonation or protonation of the PAA segment, but do not completely dissociate at high pH (i.e. when AA units are fully ionized) unlike their A(B-co-C) diblock counterparts, where the pH-responsive monomer unit is homogeneously distributed within the solvophobic block.

From RAFT emulsion polymerization to RAFT dispersion polymerization: a facile approach to tuning dispersities and behaviors of self-assembled block copolymers

We have demonstrated the successful transition from photoinitiated RAFT emulsion polymerization to photoinitiated RAFT dispersion polymerization by solely changing the solvent composition from water to water/ethanol.

Block copolymer synthesis in ionic liquid via polymerisation-induced self-assembly: a convenient route to gel electrolytes.

We report for the first time a reversible addition-fragmentation chain transfer polymerisation-induced self-assembly (RAFT-PISA) formulation in ionic liquid (IL) that yields worm gels. A series of poly(2-hydroxyethyl methacrylate)-b-poly(benzyl methacrylate) (PHEMA-b-PBzMA) block copolymer nanoparticles were synthesised via RAFT dispersion polymerisation of benzyl methacrylate in the hydrophilic IL 1-ethyl-3-methyl imidazolium dicyanamide, [EMIM][DCA]. This RAFT-PISA formulation can be controlled to afford spherical, worm-like and vesicular nano-objects, with free-standing gels being obtained over a broad range of PBzMA core-forming degrees of polymerisation (DPs). High monomer conversions (≥96%) were obtained within 2 hours for all PISA syntheses as determined by 1H NMR spectroscopy, and good control over molar mass was confirmed by gel permeation chromatography (GPC). Nanoparticle morphologies were identified using small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), and further detailed characterisation was conducted to monitor rheological, electrochemical and thermal characteristics of the nanoparticle dispersions to assess their potential in future electronic applications. Most importantly, this new PISA formulation in IL facilitates the in situ formation of worm ionogel electrolyte materials at copolymer concentrations >4% w/w via efficient and convenient synthesis routes without the need for organic co-solvents or post-polymerisation processing/purification. Moreover, we demonstrate that the worm ionogels developed in this work exhibit comparable electrochemical properties and thermal stability to that of the IL alone, showcasing their potential as gel electrolytes.

Transitioning from Photoinitiation to Thermal Initiation in RAFT Dispersion Polymerization via a Small Modification of the Macro-RAFT Agent: A Scalable Approach for Monodisperse Surface-Functional Polymeric Microspheres

Transitioning from Photoinitiation to Thermal Initiation in RAFT Dispersion Polymerization via a Small Modification of the Macro-RAFT Agent: A Scalable Approach for Monodisperse Surface-Functional Polymeric Microspheres

RAFT Dispersion Polymerization of Nitrobenzene-based Monomer and Photo-response of its Polymer Nanoparticles

RAFT Dispersion Polymerization of Nitrobenzene-based Monomer and Photo-response of its Polymer Nanoparticles

Macromol. React. Eng. 2/2023

Macromolecular Reaction EngineeringVolume 17, Issue 2 2370003 Cover PictureFree Access Macromol. React. Eng. 2/2023 First published: 17 April 2023 https://doi.org/10.1002/mren.202370003AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract Front Cover: This study deals with the development of a reaction kinetic model describing the inhibition mechanism of RAFT dispersion polymerization by oxygen and its application to investigate the effect of re-initiation on the synthesized polymer quality. The experimental validation of the kinetic model creates a functional digital twin, establishing a valid method for diblock copolymer synthesis from a non-successful polymerization attempt. This is reported by Emil Pashayev, Felix Kandelhard, and Prokopios Georgopanos in article number 2200068. Volume17, Issue2April 20232370003 RelatedInformation

In Situ Synthesis of Branched Block Copolymer Assemblies via RAFT Dispersion Polymerization Using Branched Macro‐RAFT Agents†

Comprehensive SummaryHere, we demonstrate the use of branched macromolecular reversible addition‐fragmentation chain transfer (macro‐RAFT) agents in RAFT dispersion polymerization, to access branched block copolymers as well as well‐defined branched block copolymer assemblies. Two types of branched macro‐RAFT agents were first synthesized by using either a monofunctional chain transfer monomer or a difunctional chain transfer monomer in RAFT polymerization, and subsequently utilized in RAFT dispersion polymerization. It was found that only branched macro‐RAFT agents synthesized from the difunctional chain transfer monomer could lead to colloidally stable assemblies with well‐defined morphologies. Reaction conditions including monomer concentration, degree of polymerization (DP) of the core‐forming block, and DP of the solvophilic segment on morphologies of branched block copolymer assemblies were investigated in detail. Size exclusion chromatography (SEC) analysis further confirmed the successful formation of branched block copolymers by using branched macro‐RAFT agents. This work on the synthesis of branched block copolymer assemblies by RAFT dispersion polymerization offers new opportunities for the rational design of polymer assemblies with well‐defined structures.

Enhanced Adsorption of Epoxy‐Functional Nanoparticles onto Stainless Steel Significantly Reduces Friction in Tribological Studies

AbstractEpoxy‐functional sterically‐stabilized diblock copolymer nanoparticles (ca. 27 nm) are prepared via RAFT dispersion polymerization in mineral oil. Nanoparticle adsorption onto stainless steel is examined using a quartz crystal microbalance. Incorporating epoxy groups within the steric stabilizer chains results in a two‐fold increase in the adsorbed amount, Γ, at 20 °C (7.6 mg m−2) compared to epoxy‐core functional nanoparticles (3.7 mg m−2) or non‐functional nanoparticles (3.8 mg m−2). A larger difference in Γ is observed at 40 °C; this suggests chemical adsorption of the nanoparticles rather than merely physical adsorption. A remarkable near five‐fold increase in Γ is observed for ca. 50 nm epoxy‐functional nanoparticles compared to non‐functional nanoparticles (31.3 vs. 6.4 mg m−2, respectively). Tribological studies confirm that chemical adsorption of the latter epoxy‐functional nanoparticles leads to a significant reduction in friction between 60 °C and 120 °C.

Enhanced Adsorption of Epoxy-Functional Nanoparticles onto Stainless Steel Significantly Reduces Friction in Tribological Studies.

Epoxy-functional sterically-stabilized diblock copolymer nanoparticles (ca. 27 nm) are prepared via RAFT dispersion polymerization in mineral oil. Nanoparticle adsorption onto stainless steel is examined using a quartz crystal microbalance. Incorporating epoxy groups within the steric stabilizer chains results in a two-fold increase in the adsorbed amount, Γ, at 20 °C (7.6 mg m-2 ) compared to epoxy-core functional nanoparticles (3.7 mg m-2 ) or non-functional nanoparticles (3.8 mg m-2 ). A larger difference in Γ is observed at 40 °C; this suggests chemical adsorption of the nanoparticles rather than merely physical adsorption. A remarkable near five-fold increase in Γ is observed for ca. 50 nm epoxy-functional nanoparticles compared to non-functional nanoparticles (31.3 vs. 6.4 mg m-2 , respectively). Tribological studies confirm that chemical adsorption of the latter epoxy-functional nanoparticles leads to a significant reduction in friction between 60 °C and 120 °C.

Efficient preparation of polyoxometalate-junctional cross-linking hybrid nanocomposites by polymerization-induced self-assembly.

We reported a facile method for the preparation of POM-polymer hybrids in one-pot via polymerization-induced self-assembly. Polyoxometalate macroanions were complexed with cations to prepare cross-linking agents. RAFT dispersion polymerization was conducted in the presence of the cross-linking agent. The hybrid nanoparticles can be used as nanoreactors for the photocatalytic synthesis of Au nanoparticles.

Continuous synthesis of block copolymer nanoparticlesviatelescoped RAFT solution and dispersion polymerisation in a miniature CSTR cascade

Miniaturised continuous-flow reactors offer an economical and scalable route to explore the synthesis of block copolymersviaRAFT mediated polymerisation-induced self-assembly (PISA).

In situ synthesis of the Fe3O4@poly(4-vinylpyridine)-block-polystyrene magnetic polymer nanocomposites via dispersion RAFT polymerization

This work presents a facile strategy for the generation of Fe3O4@poly(4-vinylpyridine)-block-polystyrene (Fe3O4@P4VP-b-PS) magnetic polymer nanocomposites. P4VP-b-PS nanoparticles prepared by dispersion RAFT polymerization of styrene in methanol/water in the presence of macro-P4VP chain transfer agent was employed as templates to grow Fe3O4 on polymeric network templates. With the following addition of FeCl3 into the above polymer colloids, pyridyl moieties in P4VP block of nanoparticles could further react with Fe3+ through a coordination reaction to generate Fe3+@P4VP-b-PS nanoparticles. After the subsequent addition of FeCl2 and NH3⋅H2O, the co-precipitation reaction occurred on the surface of the polymeric nanoparticle to form Fe3O4@P4VP-b-PS magnetic polymer nanocomposites. Herein, FT-IR, XRD, TGA, XPS, TEM and VSM were applied to characterize the morphology, structure and magnetism performance of the synthesized magnetic polymeric nanocomposites.

Thermoresponsive Modular Nano-Objects Via RAFT Dispersion Polymerization in a Non-Polar Solvent

Thermoresponsive Modular Nano-Objects Via RAFT Dispersion Polymerization in a Non-Polar Solvent

Combining Green Light-Activated Photoiniferter RAFT Polymerization and RAFT Dispersion Polymerization for Graft Copolymer Assemblies

Combining Green Light-Activated Photoiniferter RAFT Polymerization and RAFT Dispersion Polymerization for Graft Copolymer Assemblies

Linear and Star Block Copolymer Nanoparticles Prepared by Heterogeneous RAFT Polymerization Using an ω,ω-Heterodifunctional Macro-RAFT Agent.

Herein, an ω,ω-heterodifunctional macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agent containing two different RAFT end groups was synthesized and employed to mediate aqueous photoinitiated RAFT dispersion polymerization of a methacrylic monomer. Because of the different RAFT controllability of two RAFT end groups toward methacrylic monomers, the RAFT end group with good controllability dominated the polymerization while the other RAFT end group with poor controllability was unreacted, leading to the formation of linear block copolymers. Because of the unique structure of the linear block copolymers, a diverse set of block copolymer nanoparticles with rich RAFT groups at the interface of the hydrophilic corona/the hydrophobic core were successfully prepared. Finally, μ-A(BC)C miktoarm star block copolymer nanoparticles were prepared by RAFT seeded emulsion polymerization of an acrylic monomer, which enables the further morphological control over polymer nanoparticles. We believe that the utilization of an ω,ω-heterodifunctional macro-RAFT agent in heterogeneous RAFT polymerization will offer considerable opportunities for the rational synthesis of well-defined molecular architectures and polymer nanoparticles.

Simultaneous Synthesis and Self-Assembly of Bottlebrush Block Copolymers at Room Temperature via Photoinitiated RAFT Dispersion Polymerization.

Bottlebrush polymers exhibiting unique properties have attracted considerable attention for applications in many research areas. Herein, the first simultaneous synthesis and self-assembly of bottlebrush block copolymers at room temperature via photoinitiated polymerization-induced self-assembly (photo-PISA) using multifunctional macromolecular chain transfer agents (macro-CTAs) is reported. Comparing with linear block copolymers, the bottlebrush block copolymers can promote the formation of higher-order morphologies (e.g., vesicles) when targeting similar degrees of polymerization (DPs). Moreover, a higher polymerization rate is observed in the case of bottlebrush block copolymers. Gel permeation chromatography (GPC) analysis shows that good polymerization control is maintained when synthesizing bottlebrush block copolymers by photo-PISA. Finally, the obtained bottlebrush block copolymer vesicles are used as seeds for further chain extension and multicompartment nanoparticles with a sponge internal structure are formed. It is expected that this study will not only expand polymer architectures employed in PISA, but also provide a new strategy to synthesize polymer nanoparticles with unique structures.

Styrene–acrylic acid copolymers as new stabilizers of dispersion RAFT polymerization of butyl acrylate

The RAFT-based copolymers of acrylic acid and styrene may be successfully used as stabilizers of dispersion polymerization of butyl acrylate by providing the formation of stable block copolymer dispersion.

RAFT dispersion polymerization induced self-assembly (PISA) of boronic acid-substituted acrylamides

For the unprotected monomer, the boroxine core of nanoparticles allows transitions to higher order morphologies, while worms and vesicles are yielded directly from PISA of the pinacol ester-protected monomer.

Kinetically stable sub-50 nm fluorescent block copolymer nanoparticles via photomediated RAFT dispersion polymerization for cellular imaging.

Self-assembled block copolymer nanoparticles (NPs) have emerged as major potential nanoscale vehicles for fluorescence bioimaging. The preparation of NPs with high yields possessing high kinetic stability to prevent the leakage of fluorophore molecules is crucial to their practical implementation. Here, we report a photomediated RAFT polymerization-induced self-assembly (PISA) yielding uniform and nanosized poly((oligo(ethylene glycol) acrylate)-block-poly(benzyl acrylate) particles (POEGA-b-PBzA) with a concentration of 22 wt%, over 20 times more than with micellization and nanoprecipitation. The spherical diblock copolymer nanoparticles have an average size of 10-50 nm controllable through the degree of polymerization of the stabilizing POEGA block. Subsequent dialysis against water and swelling with Nile red solution led to highly stable fluorescent NPs able to withstand the changes in concentration, ionic strength, pH or temperature. A PBzA/water interfacial tension of 48.6 mN m-1 hinders the exchange between copolymer chains, resulting in the trapping of NPs in a "kinetically frozen" state responsible for high stability. A spectroscopic study combining fluorescence and UV-vis absorption agrees with a preferential distribution of fluorophores in the outer POEGEA shell despite its hydrophobic nature. Nile red-doped POEGA-b-PBzA micelles without initiator residues and unimers but with high structural stability turn out to be noncytotoxic, and can be used for the optical imaging of cells. Real-time confocal fluorescence microscopy shows a fast cellular uptake using C2C12 cell lines in minutes, and a preferential localization in the perinuclear region, in particular in the vesicles.