Reversible Addition-fragmentation Transfer Polymerization Research Articles

Visible light-induced photo-radical ring-opening copolymerization of thionolactone and acrylates

Radical ring-opening (co)polymerization (RROP) provides an accessible method for synthesizing main chain degradable vinyl polymers. Although the applications of reversible deactivation radical polymerization (RDRP) into RROP have been reported, the use of photo-mediated RDRP methods has received less attention than the thermal process. Here, photo-RROP of the thionolactone dibenzo [c,e]-oxepine-5(7H)-thione (DOT) and methyl acrylate (MA) was studied using photo-iniferter (PI) reversible addition-fragmentation (chain) transfer (RAFT) polymerization at ambient temperature without external radical initiators or photocatalysts. Despite the occurrence of some side reactions including desulfurization-oxygenation and O–S isomerization of DOT promoted by photoexcited thiocarbonyl groups, polymers with thioester linkages in the backbone were prepared, which degraded in the presence of amines and bleach.

Synthesis of Poly(styrene)-g-Poly(oleic acid) Graft Copolymers via Reversible Addition/Fragmentation Transfer (RAFT) Polymerization Using a Poly Oleic Acid Macro-RAFT Agent

AbstractIn this study, a new polymeric oleic acid-derived macro addition/fragmentation transfer agent was utilized to produce a poly(styrene)-g-poly(oleic acid) graft copolymer. The double bond of oleic acid was initially saturated with bromine and the condensation polymerization between the carboxylic acid and the bromide resulted in polyoleic acid with pendant bromide groups. Xanthate groups were exchanged with the bromide groups to obtain the poly(oleic acid) macro RAFT agent (Pole-Xa). Poly(styrene)-g-poly(oleic acid) (PS-g-Pole) graft copolymers were synthesized via reversible addition fragmentation transfer (RAFT) polymerization of styrene and the reaction was evaluated in view of the polymerization kinetics. The effects of polymerization temperature and reaction time on graft copolymer yield, conversion and molecular weight were investigated. In the RAFT polymerization of styrene, the rate constant (k) was found to be 1.83 × 10–3 L/mol/dk and 7.27 × 10–4 L/mol/dk for the polymerization temperatures of 80 and 90 °C, respectively. The structural characteristics and thermal properties of the obtained products were characterized using FT-IR, 1H-NMR, GPC, TGA, DSC and SEM–EDX.

Statistical Copolymers that Mimic Aspects of Mussel Adhesive Proteins: Access to Robust Adhesive-Domains for Non-Covalent Surface PEGylation.

Reconstructing functional sequence motifs of proteins, using statistical copolymers greatly reduces the information content, but simplifies synthesis significantly. Key amino acid residues involved in the adhesion of mussel foot proteins are identified. The side-chain functionalities of Dopa, lysine, and arginine are abstracted and incorporated into acrylate monomers to allow controlled radical polymerization. The resulting Dopa-acrylate (Y*-acr), arginine-acrylate (R-acr), and lysine-acrylate (K-acr) monomers are polymerized in different monomer ratios and compositions by reversible addition fragmentation transfer polymerization with a poly(ethylene glycol) (PEG) macrochain transfer agent. This results in two sets of PEG-block-copolymers with statistical mixtures and different monomer ratios of catechol/primary amine and catechol/guanidine side-chain functionalities, both important pairs for mimicking π-cation interactions. The coating behavior of these PEG-block-copolymers is evaluated using quartz crystal microbalance with dissipation energy monitoring (QCM-D), leading to non-covalent PEGylation of the substrates with clear compositional optima in the coating stability and antifouling properties. The coatings prevent non-reversible albumin or serum adsorption, as well as reduce cellular adhesion and fungal spore attachment.

Sustainable Biomass Lignin-Based Hydrogels: A Review on Properties, Formulation, and Biomedical Applications.

Different techniques have been developed to overcome the recalcitrant nature of lignocellulosic biomass and extract lignin biopolymer. Lignin has gained considerable interest owing to its attractive properties. These properties may be more beneficial when including lignin in the preparation of highly desired value-added products, including hydrogels. Lignin biopolymer, as one of the three major components of lignocellulosic biomaterials, has attracted significant interest in the biomedical field due to its biocompatibility, biodegradability, and antioxidant and antimicrobial activities. Its valorization by developing new hydrogels has increased in recent years. Furthermore, lignin-based hydrogels have shown great potential for various biomedical applications, and their copolymerization with other polymers and biopolymers further expands their possibilities. In this regard, lignin-based hydrogels can be synthesized by a variety of methods, including but not limited to interpenetrating polymer networks and polymerization, crosslinking copolymerization, crosslinking grafted lignin and monomers, atom transfer radical polymerization, and reversible addition-fragmentation transfer polymerization. As an example, the crosslinking mechanism of lignin-chitosan-poly(vinyl alcohol) (PVA) hydrogel involves active groups of lignin such as hydroxyl, carboxyl, and sulfonic groups that can form hydrogen bonds (with groups in the chemical structures of chitosan and/or PVA) and ionic bonds (with groups in the chemical structures of chitosan and/or PVA). The aim of this review paper is to provide a comprehensive overview of lignin-based hydrogels and their applications, focusing on the preparation and properties of lignin-based hydrogels and the biomedical applications of these hydrogels. In addition, we explore their potential in wound healing, drug delivery systems, and 3D bioprinting, showcasing the unique properties of lignin-based hydrogels that enable their successful utilization in these areas. Finally, we discuss future trends in the field and draw conclusions based on the findings presented.

Improved Solid Electrolyte Conductivity via Macromolecular Self-Assembly: From Linear to Star Comb-like P(S-co-BzMA)-b-POEGA Block Copolymers.

Star block copolymer electrolytes with a lithium-ion conducting phase are investigated in the present work to assess the influence of this complex architecture compared to that of the linear one, on both, bulk morphology and ionic conductivity. For that purpose, the controlled synthesis of a series of poly(styrene-co-benzyl methacrylate)-b-poly[oligo(ethylene glycol) methyl ether acrylate] [P(S-co-BzMA)-b-POEGA] block copolymers (BCPs) by reversible addition-fragmentation transfer polymerization was performed from either a monofunctional or a tetrafunctional chain transfer agent containing trithiocarbonate groups. We emphasized how a small amount of styrene (6 mol %) drastically improved the control of the RAFT polymerization of benzyl methacrylate mediated by the tetrafunctional chain transfer agent. Transmission electron microscopy and small-angle X-ray scattering demonstrated a clear segregation of the BCPs in the presence of lithium salt. Interestingly, the star BCPs gave rise to highly ordered lamellar structures as compared to that of the linear analogues. Consequently, the reduced lamellae tortuosity of self-assembled star BCPs improved the lithium conductivity by more than 8 times at 30 °C for ∼30 wt % of the POEGA conductive phase.

RAFT polymerization of MMA in channels of different mesoporous materials

A series of mesoporous silica (MS) materials, including rod-like and spherical SBA-15, spherical MCM-41, and MCM-48, was successfully synthesized and modified by silane coupling agent γ-aminopropyltriethoxysilane. The modified MS was utilized as a microreactor for solution reversible addition–fragmentation transfer (RAFT) polymerization of methyl methacrylate (MMA) using xanthate as a chain transfer agent and azodiisobutyronitrile as an initiator. Notably, modified MS had a low specific surface area and pore volume while maintaining the original morphological structure. Given to the confinement effects, poly(methyl methacrylate) (PMMA) prepared from internal mesoporous channels had higher molecular weight and initial thermal decomposition temperature than those from conventional RAFT polymerization. Moreover, PMMA obtained from spherical SBA-15 and modified MCM-48 exhibited the highest molecular weight (Mn = 8.78 × 104 and Mn = 7.43 × 104, respectively). This work provided a novel approach in designing a polymer microstructure for a more comprehensive application, such as in drug release.Graphical abstract

Thermoresponsive Microgels with High Loading of Zwitterions Exhibiting Superior Performance: A Macromonomer Approach

AbstractIn this investigation, the synthesis of temperature‐responsive microgels containing high content of zwitterionic poly(phosphorylcholine) (PMPC) is reported. High loadings of polyzwitterionic chains are achieved by using PMPC‐based “macromonomers,” which are synthesized via a three‐step reaction process. The first step involves synthesis of PMPC homopolymers via reversible addition fragmentation transfer (RAFT) polymerization, followed by end‐group removal to generate reactive thiol groups, and last of all, introduction of polymerizable double bonds at the chain ends to provide PMPC‐based macromonomers. Macromonomers of three different molar masses (3000, 5000, and 10 000 g mol−1) are used in three different molar ratios (1, 3, and 5 mol%) to synthesize microgels using N‐vinylcaprolactam (NVCL) as the main co‐monomer in precipitation polymerization. It is observed that the extent of total incorporation of the zwitterionic moiety is a function of both the macromonomer molar mass as well as its molar fraction in the feed which has a direct effect on their solution properties such as hydrodynamic radii and volume phase transition temperature (VPTT). Interestingly, these microgels show unprecedented extent of protein‐repelling behavior owing to higher loading of zwitterionic moieties, what makes them interesting for the fabrication of protective coatings with anti‐fouling properties.

Tumor-Targeting Polymer–Drug Conjugate for Liver Cancer Treatment In Vitro

Bufalin (buf) has poor solubility in aqueous solution, poor tumor targeting, and many non-specific toxic and side effects. The advantages of high-molecular-weight polymer conjugates are that they can improve the water solubility of buf, prolong plasma half-life, and reduce non-specific toxicity. A novel water-soluble polymer-drug conjugate with buf and fluorescein pendants was prepared by the combination of reversible addition-fragmentation transfer (RAFT) polymerization and click chemistry. Its anticancer performance and cellular uptake behavior against liver cancer were investigated in vitro. The polymer-buf conjugates exhibit controlled release and tumor-targeting capabilities, showing promise for clinical applications.

Impact of RAFT chain transfer agents on the polymeric shell density of magneto-fluorescent nanoparticles and their cellular uptake.

The impact of nanoparticle surface chemistry on cell interactions and especially cell uptake has become evident over the last few years in nanomedicine. Since PEG polymers have proved to be ideal tools for attaining stealthiness and favor escape from the in vivo mononuclear phagocytotic system, the accurate control of their geometry is of primary importance and can be achieved through reversible addition-fragmentation transfer (RAFT) polymerization. In this study, we demonstrate that the residual groups of the chain transfer agents (CTAs) introduced in the main chain exert a significant impact on the cellular internalization of functionalized nanoparticles. High-resolution magic angle spinning 1H NMR spectroscopy and fluorescence spectroscopy permitted by the magneto-fluorescence properties of nanoassemblies (NAs) revealed the compaction of the PEG comb-like shell incorporating CTAs with a long alkyl chain, without changing the overall surface potential. As a consequence of the capability of alkyl units to self-assemble at the NA surface while hardly contributing more than 0.5% to the total polyelectrolyte weight, denser PEGylated NAs showed notably less internalization in all cells of the tumor microenvironment (tumor cells, macrophages and healthy cells). Interestingly, such differentiated uptake is also observed between pro-inflammatory M1-like and immunosuppressive M2-like macrophages, with the latter more efficiently phagocytizing NAs coated with a less compact PEGylated shell. In contrast, the NA diffusion inside multicellular spheroids, used to mimic solid tumors, appeared to be independent of the NA coating. These results provide a novel effort-saving approach where the sole variation of the chemical nature of CTAs in RAFT PEGylated polymers strikingly modulate the cell uptake of nanoparticles upon the organization of their surface coating and open the pathway toward selectively addressing macrophage populations for cancer immunotherapy.

Dispersion Polymerization versus Emulsifier-Free Emulsion Polymerization for Nano-Object Fabrication: A Comprehensive Comparison.

Although the preparation of nano-objects by emulsifier-free controlled/living radical emulsion polymerization has drawn much attention, the morphologies of these formed objects are difficult to predict and to reproduce because of the much more complex nucleation mechanisms of emulsion polymerization compared to only one self-assembling nucleation mechanism of controlled radical dispersion polymerization. The present study compares dispersion polymerization with emulsifier-free emulsion polymerization in terms of nucleation mechanism, polymerization kinetics, and disappearance behavior of the macrochain transfer agent, gel permeation chromatograms curves of the obtained block copolymer as well as the structural and morphological differences between the produced nano-objects on the basis of published data. Moreover, the effects of the inherently heterogeneous nature of emulsion polymerization on the mechanism of reversible addition-fragmentation transfer polymerization and the nano-object morphology are examined, and efficient agitation and adequate solubility of the core-forming monomer in water are identified as the most crucial factors for the fabrication of nonspherical nano-objects.

Synthesis of Biobased Block Copolymers Using A Novel Methacrylated Methyl Salicylate and Poly(3‐Hydroxybutyrate)

AbstractA novel biobased vinyl monomer was synthesized by the reaction of methyl salicylate with methacrylic anhydride. The resulting salicylate based monomer was polymerized by reversible addition fragmentation transfer (RAFT) polymerizations using two or three trithiocarbonate functionalized poly(3‐hydroxybutyrate) macro agents. The molecular structures of the obtained polymers were confirmed by NMR spectroscopy and GPC analysis. The resulting block copolymers showed glass transition temperature (Tg) at 5 °C and melting temperature (Tm) at 160 °C according to DSC results. Compared to PHB, the obtained block copolymers displayed enhanced thermal stability according to TGA results. The overall rate constants of the RAFT polymerization using tri‐functionalized PHB macro agent were determined as 2.58 ×10−4, 1.17×10−4, and 0.50×10−4 L mol−1s−1 for 70, 80 and 90 °C, respectively. The activation energy was found to be 18.6 kcal K−1mol−1. The overall rate constant of the homopolymerization of the obtained monomer was determined as 1.14×10−4 Lmol−1s−1.

Growth of two-layer copolymer as the stationary phase with very high separation efficiency for separating peptides in capillary electrochromatography.

Open tubular CEC (OT-CEC) column with a very high separation efficiency was prepared for peptides separation. A pretreated silica-fused capillary was reacted with 3-(methacryloxy) propyltrimethoxysilane followed by vinylbenzyl chloride and divinylbenzene to produce first thin monolithic monolayer. The second copolymer layer was formed on thin monolithic monolayer of the capillary by reversible addition-fragmentation transfer polymerization of N-phenylacrylamide and styrene. The key parameters including buffer pH value and organic modifier were systematically evaluated to provide the optimal chromatographic condition. The resultant OT-CEC columns were validated by separating a synthetic mixture of peptides and cytochrome C tryptic digest in capillary electrochromatography. The number of theoretical plates as high as 2.4 million per column was achieved for synthetic mixture peptides. In addition, the fabricated OT-CEC column also resolved more than 18 high-efficiency digestion peptides from a mixture containing tryptic digest of cytochrome C. The column to column and inter- to intraday repeatabilities of OT-CEC column through RSD% were found better than 3.0%, exhibiting satisfactory stability and repeatability of the two-layer deposited OT-CEC column. The results reveal that the open tubular capillary column modified with two-layer copolymer shows the great prospect for the separation of proteins in capillary electrochromatography.

Controlled Radical Polymerization: from Oxygen Inhibition and Tolerance to Oxygen Initiation

Molecular oxygen is a radical scavenger in both conventional and controlled radical polymerization (CRP), resulting in many time-consuming methods for physically removing oxygen before the polymerization. Different approaches have been developed to have oxygen tolerance by chemically consuming or converting molecular oxygen into non-initiating species to address this issue. Recently, we propose another approach called oxygen initiation that directly transforms molecular oxygen into the initiating carbon radical in CRP. This Feature Article summarizes our recent developments in this direction. Oxygen-initiated reversible addition-fragmentation transfer (RAFT) polymerization has been successfully conducted using oxygen and trialkylborane as co-initiators under the ambient conditions and atmosphere without any prior degassed procedures. This gas-trigger initiation provides the opportunity for spatiotemporal control of the polymerization by molecular oxygen or air. Rationally synthesized alkylborane compounds could derive the predesigned structure of the initiating alkyl radical to minimize the side reactions and free polymer chains, achieving the synthesis of ultra-high molecular weight polymers. The challenges and perspectives are also discussed at the end.

History of nitroxide mediated polymerization in Canada

AbstractNitroxide mediated polymerization (NMP), sometimes known as stable free radical polymerization (SFRP), is considered one of the main types of reversible deactivation radical polymerization (RDRP) that have emerged as a major advance in polymer synthesis in the past 30 years. This review examines NMP's development from a uniquely Canadian perspective. Inspired by reports of a reversible equilibrium between the TEMPO persistent radical and a growing polymeric radical chain, researchers at the Xerox Research Centre of Canada (XRCC) reported radical polymerizations of styrene with hallmarks typically associated with living polymerizations: linear degree of polymerization of with conversion, narrow molecular weight distributions, and ability to re‐initiate the chain end with additional monomer. This effort expanded to polymerizations in dispersed aqueous media (eg, miniemulsion) and to polymerizations directed for various architectures (block, graft, star), but NMP was ultimately generally limited to styrenic monomers. Consequently, NMP trailed other RDRP methods, such as atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer polymerization (RAFT), due to its limited monomer choice. With the advent of second‐generation alkoxyamine initiators, however, the range of monomers polymerizable in a controlled manner greatly expanded to include acrylates, acrylamides, and eventually methacrylates (under certain conditions), providing renewed impetus towards using NMP. Consequently, Canadian researchers applied these new alkoxyamines for more versatile polymers, resulting in products such as stimuli‐responsive polymers, CO2‐switchable latexes, bio‐hybrid composites, organic photovoltaic materials, and photolithographic materials. The chronological progression of the developments in NMP from various Canadian laboratories highlights these achievements in new polymeric materials.

Dual pH-/thermo-responsive chitosan-based hydrogels prepared using "click" chemistry for colon-targeted drug delivery applications

A dual pH-/thermo-responsive hydrogel was designed based on a polyelectrolyte complex of polyacrylic acid (PAA) and norbornene-functionalized chitosan (CsNb), which was synergized with chemical crosslinking using bistetrazine-poly(N-isopropyl acrylamide) (bisTz-PNIPAM). The thermo-responsive polymeric crosslinker, bisTz-PNIPAM, was synthesized via reversible addition–fragmentation transfer polymerization of NIPAM. FTIR, XRD, rheological and morphological analyses demonstrated the successful formation of the polyelectrolyte network. The highly porous structure generated through the in-situ “click” reaction between Tz and Nb resulted in a higher drug loading (29.35 %). The hydrogel (COOH/NH2 mole ratio of 3:1) exhibited limited drug release (8.5 %) of 5-ASA at a pH of 2.2, but it provided an almost complete release (92 %) at pH 7.4 and 37 °C within 48 h due to the pH responsiveness of PAA, hydrogel porosity, and shrinkage behavior of PNIPAM. The hydrogels were biodegradable and non-toxic against human fibroblast cells, suggesting their considerable potential for a colon-targeted drug delivery system.

Preparation and Evaluation of 2 m Long Open Tubular Capillary Columns of 50 μm Internal Diameter for Separation of Peptides in Liquid Chromatography

A 2 m long open tubular column with a copolymer layer fabricated on the inner surface of silica capillary of 50 μm id has been prepared. A ligand with a terminal halogen was bound to the capillary inner surface via silanol-isocyanate reaction and an initiator moiety was introduced by reacting with the terminal halogen. Then a thick layer of linear copolymer chains was generated on the inner surface of capillary by reversible addition-fragmentation transfer polymerization of styrene and N-phenyl acrylamide. The resultant open tubular column exhibited a remarkably high separation efficiency for the separation of a synthetic mixture of five peptides in liquid capillary chromatography (in the pressure mode). The effect of monomer mixing ratio (styrene versus N-phenyl acrylamide) on the chromatographic separation efficiency has been studied. The column prepared with the optimum mixing ratio produced the number of theoretical plates (N) of 391,200 per column under the optimized elution pressure. The column to column repeatability estimated as relative standard deviation in plate count, retention factor, asymmetry factor, and resolution was found better than 3.0%.

Разветвлённые полимеры N-изопропилакриламида: обзор англоязычной литературы за 2005–2020 годы

The search and the analysis of English scientific literature from 2005 to 2020 devoted to the methods of obtaining branched polymers and copolymers of N-isopropylacrylamide were made in order to obtain novel materials with valuable properties. It was found that modern methods of controlled radical polymerization were mainly used for this purpose, namely, atom transfer radical polymerization (ATRP), polymerization with reversible addition-fragmentation chain transfer (RAFT) and group transfer polymerization (GTP). In most cases the original compounds were the chain transfer agents in RAFT. CuCl was commonly used as a catalyst in ATRP; while in some cases cores of a different chemical nature (β-cyclodextrin, zinc phthalocyanine or zinc porphyrin) were used. In a number of cases, click chemistry reactions were used for synthesis. Depending on the order of the synthesis, a distinction was made between the “corearms” and “arms-core” approaches. The prospects of using branched N-isopropylacrylamide polymers as thermoresponsive materials, membranes for controlled drug release, photocatalysts, and agents of targeted photodynamic therapy and photoelectric storage of information were estimated.

Poly(N,N-bis(2-methoxyethyl)acrylamide), a thermoresponsive non-ionic polymer combining the amide and the ethyleneglycolether motifs

Poly(N,N-bis(2-methoxyethyl)acrylamide) (PbMOEAm) featuring two classical chemical motifs from non-ionic water-soluble polymers, namely, the amide and ethyleneglycolether moieties, was synthesized by reversible addition fragmentation transfer (RAFT) polymerization. This tertiary polyacrylamide is thermoresponsive exhibiting a lower critical solution temperature (LCST)–type phase transition. A series of homo- and block copolymers with varying molar masses but low dispersities and different end groups were prepared. Their thermoresponsive behavior in aqueous solution was analyzed via turbidimetry and dynamic light scattering (DLS). The cloud points (CP) increased with increasing molar masses, converging to 46 °C for 1 wt% solutions. This rise is attributed to the polymers’ hydrophobic end groups incorporated via the RAFT agents. When a surfactant-like strongly hydrophobic end group was attached using a functional RAFT agent, CP was lowered to 42 °C, i.e., closer to human body temperature. Also, the effect of added salts, in particular, the role of the Hofmeister series, on the phase transition of PbMOEAm was investigated, exemplified for the kosmotropic fluoride, intermediate chloride, and chaotropic thiocyanate anions. A pronounced shift of the cloud point of about 10 °C to lower or higher temperatures was observed for 0.2 M fluoride and thiocyanate, respectively. When PbMOEAm was attached to a long hydrophilic block of poly(N,N-dimethylacrylamide) (PDMAm), the cloud points of these block copolymers were strongly shifted towards higher temperatures. While no phase transition was observed for PDMAm-b-pbMOEAm with short thermoresponsive blocks, block copolymers with about equally sized PbMOEAm and PDMAm blocks underwent the coil-to-globule transition around 60 °C.

Synthesis of water-based cationic polyacrylate copolymer emulsion by RAFT polymerization and its application as an inkjet printing agent

PurposeIn this work, the authors used reversible addition-fragmentation transfer (RAFT) polymerization to develop a new cationic acrylate modified epoxy resin emulsion for water-borne inkjet which have the advantages of both polyacrylate and epoxy resin. The emulsion was successfully used in the canvas coating for inkjet printing. This paper aims to contribute to the development of novel cationic emulsions for inkjet printing industry.Design/methodology/approachIn this work, the epoxy acrylate was synthesized from RAFT agent and epoxy resin firstly. Cationic macromolecular emulsifier was prepared by RAFT polymerization, using 2,2’-Azobisisobutyronitrile as initiator, 2-(dimethylamino)ethyl methacrylate and styrene as monomer, which was directly used to prepare the emulsion. The influences of the amount of 2-(dimethylamino)ethyl methacrylate on particle size, zeta potential and water contact angle were studied. Finally, the cationic emulsion was used to print images by inkjet printing.FindingsThe emulsion has the smallest particle size, the highest potential and the highest water contact angle when the DM content is 13 Wt.%. The transmission electron microscopy analysis reveals the latex particles is core-shell sphere with the diameters in the range 120–200 nm. The emulsion was successfully used in the canvas coating for inkjet printing. This work will contribute to the development of novel cationic emulsions for inkjet printing industry.Originality/valueThe emulsion was successfully used in the canvas coating for inkjet printing. This work will contribute to the development of novel cationic emulsions for inkjet printing industry.

Biobased Amphiphilic Block Copolymers by RAFT-Mediated PISA in Green Solvent.

Biobased amphiphilic diblock copolymers are prepared thanks to the combination of reversible addition-fragmentation transfer (RAFT) polymerization and polymerization-induced self-assembly (PISA) in an eco-friendly solvent mixture. First, the formation of a poly(acrylic acid) macroRAFT agent (PAA-TTC) is performed in water at 70 °C. Then, in a series of experiments, the PAA-TTC macroRAFT agent is used directly, without purification, as both chain transfer agent and stabilizing agent in the RAFT-PISA of menthyl acrylate (MnA) in dispersion in an ethanol/water mixture. The polymerizations of MnA are fast with high final conversions and well-controlled amphiphilic diblock copolymers are synthesized. Stable, sub-micrometric spherical particles composed of the diblock copolymers are formed. The influence of the monomer concentration and the length of the solvophobic block on the diameter of the self-assemblies is studied by means of dynamic light scattering and cryogenic transmission electron-microscopy.