Batch Emulsion Polymerization Mediated by Poly(methacrylic acid) MacroRAFT Agents: One-Pot Synthesis of Self-Stabilized Particles

Chaduc, Isabelle; Girod, Marion; Antoine, Rodolphe; Charleux, Bernadette; D’Agosto, Franck; Lansalot, Muriel

doi:10.1021/ma300875y

Cited by 143 publications

(208 citation statements)

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“…[15] Unexpectedly,some PISA systems (prepared in "onepot" or by sequential steps) invariably led to spherical morphologies,i rrespective of the degree of polymerization of the hydrophobic block. [16] We recently turned our attention to the effect of hydrophile on the PISA process.T argeting alginate-decorated polystyrene spherical nanoparticles,weintroduced one to two units of alginate macromonomer into poly(N-acryloylmorpholine) (PNAM) to serve as ah ydrophilic macroRAFT agent for styrene emulsion polymerization.…”

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The Effect of Hydrophile Topology in RAFT‐Mediated Polymerization‐Induced Self‐Assembly

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Polymerization-induced self-assembly (PISA) was employed to compare the self-assembly of different amphiphilic block copolymers. They were obtained by emulsion polymerization of styrene in water using hydrophilic poly(N-acryloylmorpholine) (PNAM)-based macromolecular RAFT agents with different structures. An average of three poly (ethylene glycol acrylate) (PEGA) units were introduced either at the beginning, statistically, or at the end of a PNAM backbone, resulting in formation of nanometric vesicles and spheres from the two former macroRAFT architectures, and large vesicles from the latter. Compared to the spheres obtained with a pure PNAM macroRAFT agent, composite macroRAFT architectures promoted a dramatic morphological change. The change was induced by the presence of PEGA hydrophilic side-chains close to the hydrophobic polystyrene segment.

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The Effect of Hydrophile Topology in RAFT‐Mediated Polymerization‐Induced Self‐Assembly

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“…However, to circumvent the need for an additional step, research groups have developed one-pot procedures in which the solvophilic block is synthesised in situ before the addition of hydrophobic monomer. 65,66,174,175,190,195,197,213,217,230 Dispersion CLRP synthesis of amphiphilic block copolymers is an attractive approach due to the initially homogeneous conditions, but the range of monomers applicable under aqueous conditions is limited. Dispersion polymerisation in non-aqueous solvents such as cyclohexane, 173 chloroform 191 and methanol.…”

Section: F Amphiphilic Block Copolymer Synthesis: Discussionmentioning

confidence: 99%

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

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Nanostructured soft materials open up new opportunities in material design and application, and block copolymer self-assembly is one particularly powerful phenomenon that can be exploited for their synthesis. The advent of controlled/living radical polymerisation (CLRP) has greatly simplified block copolymer synthesis, and versatility towards monomer types and polymer architectures across the different forms of CLRP has vastly expanded the range of functional materials accessible. CLRP-controlled synthesis of block copolymers has been applied in heterogeneous systems, motivated by the numerous process advantages and the position of emulsion polymerisation at the forefront of industrial latex synthesis. In addition to the inherent environmental advantages of heterogeneous routes, the incidence of block copolymer self-assembly within dispersed particles during polymerisation leads to novel nanostructured materials that offer enticing prospects for entirely new applications of block copolymers. Here, we review the range of block copolymers prepared by heterogeneous CLRP techniques, evaluate the methods applied to maximise purity of the products, and summarise the unique nanoscale morphologies resulting from in situ self-assembly, before discussing future opportunities within the field.2

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“…[4][5][6][7] Surfactant-free reversible addition-fragmentation chain transfer (RAFT) emulsion polymerisation technique is an advantageous method to synthesise latex particles for potential bioapplications, [8][9][10] since this approach does not required the use of particle-stabilising surfactants, which may desorb from particles overtime and hampered therapeutic applications. 11 To act as particle stabiliser in the preparation of latex particles by surfactantfree RAFT emulsion polymerisation, two strategies have already been employed: the use of surface-active amphiphilic RAFT-capped block copolymers, [12][13][14][15][16] or a one-pot polymerisation of a hydrophobic monomer from a low molar mass surface-active RAFT agent. 17 While the particles formation kinetics and their morphology control have been studied extensively, there are only a few scarce examples describing the use of this technique to engineer latex particles for the attachment of biomolecules or therapeutic agents.…”

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Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

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Permanent WRAP URL:http://wrap.warwick.ac.uk/83846 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. Publisher's statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Biomacromolecules, copyright © American Chemical Society after peer review and technical editing by the publisher.To access the final edited and published work see http://dx.doi.org/10.1021/acs.biomac.5b01633 A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. AbstractWe present the preparation of 11 nm polyacrylamide-stabilised polystyrene latex particles for conjugation to a microRNA model by surfactant-free RAFT emulsion polymerisation. Our synthetic strategy involved the preparation of amphiphilic polyacrylamide-block-polystyrene copolymers, which were able to self-assemble into polymeric micelles and 'grow' into polystyrene latex particles. The surface of these sterically stabilised particles was postmodified with a disulfide-bearing linker for the attachment of the microRNA model, which can be released from the latex particles under reducing conditions. These nanoparticles offer the advantage of ease of preparation via a scaleable process, and the versatility of their synthesis makes them adaptable to a range of applications.

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Batch Emulsion Polymerization Mediated by Poly(methacrylic acid) MacroRAFT Agents: One-Pot Synthesis of Self-Stabilized Particles

Cited by 143 publications

References 63 publications

The Effect of Hydrophile Topology in RAFT‐Mediated Polymerization‐Induced Self‐Assembly

The Effect of Hydrophile Topology in RAFT‐Mediated Polymerization‐Induced Self‐Assembly

Block copolymer synthesis by controlled/living radical polymerisation in heterogeneous systems

Preparation of Inert Polystyrene Latex Particles as MicroRNA Delivery Vectors by Surfactant-Free RAFT Emulsion Polymerization

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