Multiblock copolymer synthesis<i>via</i>RAFT emulsion polymerization

Clothier, Glenn K. K.; Guimarães, Thiago R.; Thompson, Steven W; Rho, Julia Y.; Perrier, Sébastien; Moad, Graeme; Zetterlund, Per B.

doi:10.1039/d2cs00115b

Cited by 33 publications

(16 citation statements)

References 278 publications

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“…PISA syntheses of diblock copolymer nanoparticles in aqueous media involve reversible addition–fragmentation chain transfer (RAFT) dispersion or emulsion polymerization. − However, there are relatively few examples of the synthesis of multiblock copolymer nanoparticles using this approach. − In 2013, Gody et al reported the one-pot multistep sequential RAFT solution polymerization of various acrylamides and acrylates to prepare a wide range of relatively well-defined multiblock copolymers ( M w / M n < 1.40) on a multigram scale . This pioneering study utilized a relatively low initiator concentration to minimize the formation of dead chains.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization

Deane,

Mandrelier,

Musa

et al. 2024

Chem. Mater.

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Reversible addition−fragmentation chain transfer (RAFT) aqueous emulsion polymerization is used to prepare well-defined ABCB tetrablock copolymer nanoparticles via sequential monomer addition at 30 °C. The A block comprises water-soluble poly(2-(N-acryloyloxy)ethyl pyrrolidone) (PNAEP), while the B and C blocks comprise poly(t-butyl acrylate) (PtBA) and poly(n-butyl acrylate) (PnBA), respectively. High conversions are achieved at each stage, and the final sterically stabilized spherical nanoparticles can be obtained at 20% w/w solids at pH 3 and at up to 40% w/w solids at pH 7. A relatively long PnBA block is targeted to ensure that the final tetrablock copolymer nanoparticles form highly transparent films on drying such aqueous dispersions at ambient temperature. The kinetics of polymerization and particle growth are studied using 1 H nuclear magnetic resonance spectroscopy, dynamic light scattering, and transmission electron microscopy, while gel permeation chromatography analysis confirmed a high blocking efficiency for each stage of the polymerization. Differential scanning calorimetry and small-angle X-ray scattering studies confirm microphase separation between the hard PtBA and soft PnBA blocks, and preliminary mechanical property measurements indicate that such tetrablock copolymer films exhibit promising thermoplastic elastomeric behavior. Finally, it is emphasized that targeting an overall degree of polymerization of more than 1000 for such tetrablock copolymers mitigates the cost, color, and malodor conferred by the RAFT agent.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization

Deane,

Mandrelier,

Musa

et al. 2024

Chem. Mater.

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“…The versatility of RAFT polymerization makes it appropriate for controlled radical polymerization with a wide range of functional monomers. , Its applicability to perform in water and alcohols as well as their mixtures, enabling polymerizations in emulsion − and dispersion, − makes the RAFT method attractive and environmentally sustainable. These heterogeneous polymerization systems provide efficient heat transfer while simultaneously keeping the viscosity low throughout the polymerization .…”

Section: Introductionmentioning

confidence: 99%

Amphiphilic Block Copolymers via Blue-Light-Induced Iniferter RAFT Ab Initio Emulsion Polymerization in Water–Alcoholic Media

Hub,

Koll,

Held

et al. 2024

Macromolecules

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Amphiphilic block copolymers comprise a fascinating class of smart materials due to their unique ability to selforganize, making them attractive candidates for a wide range of applications in materials engineering and medical sciences. The synthesis of these copolymers commonly involves harmful solvents, especially in classical living anionic polymerization. With the development of reversible addition−fragmentation chain transfer (RAFT) and polymerization−induced self-assembly (PISA), an environmentally more friendly and versatile method has been established for the synthesis of such amphiphilic block copolymers. Through the utilization of visible light to initiate polymerization through the so-called photoiniferter process, we emphasize the adaptability of this photopolymerization in different scales although the incident light illuminates only the surface area of the reaction vessels. We describe an easily adjustable, blue-lightinitiated RAFT PISA approach to synthesize a series of amphiphilic poly(N,N-dimethylacrylamide)−block−polystyrene (PDMA−b− PS) and poly(4-vinylpyridine)−block−polystyrene (P4VP−b−PS) diblock copolymers with low molecular weight dispersities. The polymerizations were conducted as both two-step and semibatch processes. Furthermore, the effect of scalability on the polymerization kinetics was investigated, proving the light-induced RAFT polymerization as a scalable polymerization method in a batch process with a reaction volume of up to 500 mL. The bulk morphology of both resulting diblock copolymers having different weight fractions of the minor and major blocks was analyzed. While a cylindrical PDMA microdomain in a PS matrix can be observed at 20−25% by weight of PDMA, the equivalent composition reveals a spherical morphology of P4VP domains in a PS matrix. In essence, the scalable, rather eco-friendly photoinduced synthesis of tailored, nanostructured block copolymers without harmful solvents significantly increases their suitability for applications.

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“…1–9 A particularly exciting aspect of controlled radical polymerization explored over the last decade is the possibility of synthesizing sequence-controlled multiblock copolymers. 10–13 On one hand, such synthesis offers a unique approach to explore the effect of sequence on polymer properties including self-assembly, antimicrobial activity, folding and microphase separation. 14–22 On the other hand, the preparation of multiblock copolymers consists of a unique strategy to indirectly evaluate the livingness of a given polymerization system.…”

Section: Introductionmentioning

confidence: 99%

Enhanced synthesis of multiblock copolymers via acid-triggered RAFT polymerization

Antonopoulou,

Truong,

Anastasaki

2024

Chem. Sci.

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Multiblock copolymer synthesisviaRAFT emulsion polymerization

Abstract: Emulsion polymerization mediated by RAFT confers a plenty of advantages for the synthesis of multiblock copolymers, including but not limited to control over particle morphology, molecular weight, livingness, composition, and time.

Cited by 33 publications

References 278 publications

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization

Synthesis and Characterization of All-Acrylic Tetrablock Copolymer Nanoparticles: Waterborne Thermoplastic Elastomers via One-Pot RAFT Aqueous Emulsion Polymerization

Amphiphilic Block Copolymers via Blue-Light-Induced Iniferter RAFT Ab Initio Emulsion Polymerization in Water–Alcoholic Media

Enhanced synthesis of multiblock copolymers via acid-triggered RAFT polymerization

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