Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous–organic, and aqueous media via RAFT polymerization

Serkhacheva, N. S.; Smirnov, O. I.; Tolkachev, A. V.; Prokopov, N. I.; Plutalova, A. V.; Черникова, Е. В.; Kozhunova, Elena Yu.; Хохлов, А. Р.

doi:10.1039/c7ra03203j

Cited by 21 publications

(23 citation statements)

References 57 publications

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“…In addition, we note here that the case with p s = 0.1 and p t = 1.0 is probably close to the RAFT‐mediated micellar polymerization with the living/dormant probability of surfactant‐based RAFT agent about 10%. This set of parameters could be the basic choice to study influence of initiator concentration and surfactant/precursor architecture on the RAFT‐mediated emulsion polymerization, similar to …”

Section: Resultsmentioning

confidence: 99%

“…The combination of recombination process and surface termination, described by p t and p s parameters, determine all side reactions during our micellar polymerization. We have to note here, that several recent experimental studies operate RAFT‐mediated emulsion polymerization, when RAFT‐agent could be a surfactant/precursor itself . In this connection, the surface termination probability p s could be interpreted as a living/dormant ratio in such RAFT polymerization mechanism.…”

Section: Methodsmentioning

confidence: 93%

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Micellar polymerization: Computer simulations by dissipative particle dynamics

2018

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Nowadays, micellar polymerization is widely used in different fields of industry and research, including modern living polymerization technique. However, this process has many variables and there is no comprehensive model to describe all features. This research presents simulation methodology which describes key properties of such reactions to take a guide through a variety of their modifications. Dissipative particle dynamics is used in addition to Monte Carlo scheme to simulate initiation, propagation, and termination events. Influence of initiation probability and different termination processes on final conversion and molecular-weight distribution are presented. We demonstrate that prolonged initiation leads to increasing in polymer average molecular weight, and surface termination events play major role in conversion limitation, in comparison with recombination. © 2018 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 93%

Micellar polymerization: Computer simulations by dissipative particle dynamics

2018

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“…symmetrical trithiocarbonates that enable the synthesis of ABA triblock copolymers, have attracted much less attention. In our previous studies of emulsion homopolymerization and copolymerization of n ‐butyl acrylate (BA) in the presence of poly(acrylic acid) (PAA) based macroRAFT agents containing the trithiocarbonate group within the chain, we have analyzed the influence of monomer(s) to the medium volume ratio, the polymerization degree and the chemical nature of the co‐monomer in the macroRAFT agent on polymerization kinetics, particle size and morphology, and the molecular weight distribution (MWD) of the polymerization products …”

Section: Introductionmentioning

confidence: 99%

“…In these systems, independently of the polymerization conditions, i.e. the monomer to solvent ratio and the concentrations of macroRAFT agent and initiator (the former determines the ratio of A and B block lengths), particles of spherical morphology are formed …”

Section: Introductionmentioning

confidence: 99%

“…In contrast, emulsifier‐free emulsion polymerization of acrylates mediated by the same macroRAFT agents A–S–C(=S)–S–A, based on for example PAA trithiocarbonate, leads to different results . In contrast to products of solution or dispersion polymerization, the products of emulsion polymerization are typically characterized by a bimodal MWD in a wide range of monomer conversion.…”

Section: Introductionmentioning

confidence: 99%

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Emulsifier‐free reversible addition–fragmentation chain transfer emulsion polymerization of alkyl acrylates mediated by symmetrical trithiocarbonates based on poly(acrylic acid)

Serkhacheva

Prokopov

Черникова

et al. 2019

Polymer International

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Emulsifier-free batch emulsion polymerization of n-butyl acrylate and its semi-batch copolymerization with 2,2,3,3,4,4,5,5-octafluoropentyl acrylate and 2,2,3,4,4,4-hexafluorobutyl acrylate both mediated by poly(acrylic acid) containing the trithiocarbonate group in the chain was employed to produce amphiphilic triblock copolymers. The polymerization-induced self-assembly of these copolymers in aqueous media gave rise to spherical core-shell particles. Irrespective of the experimental conditions, the polymeric product was characterized by a bimodal molecular weight distribution. The apparent violation of the reversible addition-fragmentation chain transfer polymerization mechanism may be attributed to restricted accessibility of the trithiocarbonate group in the self-assembled block copolymers for propagating radicals that enter into the particle. Mean-field theoretical arguments were employed to explain the exclusively spherical morphology of the particles observed in the experiment.

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Polymerization‐Induced Self‐Assembly: From Macromolecular Engineering Toward Applications

Coumes¹,

Stoffelbach²,

Rieger³

2022

Macromolecular Engineering

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Polymerization‐induced self‐assembly (PISA) is nowadays a well‐established technology that is gaining more and more attention from academics and in the industry. It relies on the extension of a solvophilic reactive chain in heterogeneous polymerization conditions. An amphiphilic block copolymer is generated and concomitantly to the growth of the solvophobic block, self‐assembly occurs. PISA was initially developed to achieve radical emulsion polymerizations in the absence of low molecular weight surfactants in order to produce surfactant‐free latexes. Shortly after, it became clear that this technology had also great potential to synthesize well‐defined amphiphilic block copolymers. Finally, researchers became more and more interested in the formed particles themselves (mainly spheres, but also worm and vesicles) and tried to functionalize them for a large variety of applications. In this article, we will start with reviewing the different PISA polymerization techniques, and highlight the possibility to use PISA as a tool to synthesize well‐defined, functional, and complex macromolecular architectures. We will then discuss the main parameters that control the particle morphology, before presenting applications of PISA‐derived particles and dispersions. The article cites more than 400 references, and presents for each polymerization technique a great number of the existing systems in tabular format.

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Synthesis of amphiphilic copolymers based on acrylic acid, fluoroalkyl acrylates and n-butyl acrylate in organic, aqueous–organic, and aqueous media via RAFT polymerization

Abstract: Hydrophilic and amphiphilic polymeric trithiocarbonates based on polyacrylic acid are able to provide polymerization-induced self-assembly in copolymerization of butyl and fluoroalkyl acrylates.

Cited by 21 publications

References 57 publications

Micellar polymerization: Computer simulations by dissipative particle dynamics

Micellar polymerization: Computer simulations by dissipative particle dynamics

Emulsifier‐free reversible addition–fragmentation chain transfer emulsion polymerization of alkyl acrylates mediated by symmetrical trithiocarbonates based on poly(acrylic acid)

Polymerization‐Induced Self‐Assembly: From Macromolecular Engineering Toward Applications

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