Optimization of the RAFT polymerization conditions for the in situ formation of nano-objects via dispersion polymerization in alcoholic medium

Zhao, Wei; Gody, Guillaume; Dong, Siming; Zetterlund, Per B.; Perrier, Sébastien

doi:10.1039/c4py00855c

Cited by 103 publications

(154 citation statements)

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“…PISA has been implemented as both emulsion polymerization [15][16][17][18][19][20][21][22][23] and dispersion polymerization, [24][25][26][27][28][29] most commonly the latter in recent years. Various parameters influence the morphology of the nanoparticles formed during PISA: (i) the relative lengths of the hydrophilic and the hydrophobic blocks; 24,26,[29][30][31] (ii) the interactions between each block and the solvent; 26,32 (iii) the monomer concentration (in dispersion polymerization), 24,26,29,30 and (iv) in the case of aqueous formulations, the pH value and salt concentration. 15,16,23,25,28,33,34 In recent work, 35 we demonstrated how CO 2 can be used to tune the particle morphology in dispersion PISA.…”

Section: Introductionmentioning

confidence: 99%

Polymerization induced self-assembly: tuning of morphology using ionic strength and pH

et al. 2017

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(2017) Polymerization induced self-assembly : tuning of morphology using ionic strength and pH. Polymer Chemistry, 8 (20). pp. 3082-3089. Permanent WRAP URL:http://wrap.warwick.ac.uk/88640 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work of 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. 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. Investigations of RAFT dispersion polymerization-induced self-assembly (PISA) of 2-hydroxypropyl methacrylate (HPMA) in water/methanol at 60 o C using a cationically charged macroRAFT agent as stabilizer block, namely P(N,N-diethylaminoethyl methacrylate)-stat-poly((ethylene glycol) methyl ether methacrylate) (PDEAEMA-stat-PEGMA), have been conducted with a view to tune particle morphologies by manipulation of the pH and the ionic strength. Above the LCST (45 °C) of (PDEAEMA-stat-PEGMA), the system can only be conducted as a dispersion polymerization at sufficiently low pH such that the stabilizer block is sufficiently protonated to ensure solubility in the continuous phase. It is demonstrated (reported in the form of an extensive morphology diagram) that a range of morphologies including spherical particles, rods and vesicles can be accessed by adjustment of the pH (via addition of HCl) and the ionic strength (via the concentration of NaCl). A decrease in the charge density of the coronal stabilizer layer via an increase in pH (less protonation) shifts the system towards higher order morphologies. At a given pH, an increase in ionic strength leads to more extensive charge screening, thus allowing formation of higher order morphologies.

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Section: Introductionmentioning

confidence: 99%

Polymerization induced self-assembly: tuning of morphology using ionic strength and pH

et al. 2017

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“…[29][30][31][32][33][34][35][36] Pan and co-workers have made a number of notable contributions to the field of RAFT alcoholic dispersion polymerisation [37][38][39][40]. Their approach typically involves chain extension of a soluble macro-CTA such as poly(2-dimethylaminoethyl methacrylate) with styrene in methanol [37].…”

Section: Introductionmentioning

confidence: 99%

Poly( N -2-(methacryloyloxy)ethyl pyrrolidone)-poly(benzyl methacrylate) diblock copolymer nano-objects via RAFT alcoholic dispersion polymerisation in ethanol

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Armes

et al. 2016

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were produced by polymerisation-induced self-assembly (PISA). Finally, a PNMEP 47 -PBzMA 243 diblock copolymer was synthesised via a convenient -whereby a PNMEP 47 macro-CTA was first prepared at 97% conversion, followed by in situ RAFT dispersion polymerisation of BzMA to produce diblock copolymer nano-objects. TEM analysis of aliquots taken during the diblock copolymer synthesis indicated a gradual evolution in copolymer morphology from spherical micelles after 1 h to a pure vesicle phase after 8 h via intermediate mixed phases (including worms).

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“…Perrier and coworkers 198 employed cryo-TEM to demonstrate that the morphologies observed after St polymerisation using PEG-methyl ether acrylate or methacrylate (P(PEG454A) and P(PEG475MA), respectively) in water/dioxane at 44 C were indeed obtained during the polymerisation process itself, as opposed to being driven by selective solvent or solvent evaporation during TEM preparation. Aqueous dispersion systems require that the monomer is water-soluble and the corresponding homopolymer is water-insoluble under reaction conditions, criteria which only a limited number of vinyl monomers fulfil, including NIPAM, DEAA, 2-methoxyethyl acrylate (MEA), 2-hydroxypropyl methacrylate (HPMA), and di(ethylene glycol) methyl ether methacrylate (DEGMA).…”

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confidence: 99%

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

et al. 2016

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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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Optimization of the RAFT polymerization conditions for the in situ formation of nano-objects via dispersion polymerization in alcoholic medium

Cited by 103 publications

References 56 publications

Polymerization induced self-assembly: tuning of morphology using ionic strength and pH

Polymerization induced self-assembly: tuning of morphology using ionic strength and pH

Poly( N -2-(methacryloyloxy)ethyl pyrrolidone)-poly(benzyl methacrylate) diblock copolymer nano-objects via RAFT alcoholic dispersion polymerisation in ethanol

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

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