Transfer Living Radical Polymerization Research Articles

The Effect of Mixed Ligands on the Polymerization Rate of SET-LRP in Aqueous Solution

Abstract The mixed-ligand effect is investigated in single electron transfer-living radical polymerization (SET-LRP) of OEOMA in aqueous solution for the first time. Mediated by equimolar tris(2-aminoethyl)amine (TREN) and tris(dimethylaminoethyl)amine (Me6-TREN), SET-LRP exhibits the highest polymerization rate while maintaining living characteristics. The higher concentration of self-assembled micellar particles formed by amphiphilic initiator and monomer in aqueous solution under the influence of mixed ligands may be considered as one of factors for the mixed-ligand effect.

The Effect of mPEGA/EHA Ratio and Copolymer Composition on the Solution Behavior of Amphiphilic, Comb‐Shape Copolymers Synthesized via Cu(0)‐Mediated SET‐LRP for Potential Drug Delivery Applications

AbstractComb‐shape, block copolymers from hydrophilic poly(ethylenglycol) monomethyl ether acrylate (mPEGA, A) and hydrophobic 2‐ethylhexyl acrylate (EHA, B) are synthesized by copper(0)‐mediated single‐electron transfer living radical polymerization (SET‐LRP) via sequential addition of the two monomers, resulting in different compositions (AB, ABA, BAB, BA), molar masses, and mPEGA/EHA ratios. All polymers show narrow molar mass distributions and molecular weights of 7.7–25.50 kg mol−1, demonstrating precise control over the polymerization and molecular weights through the utilization of SET‐LRP. Kinetic experiments are conducted to investigate the polymerization behavior of mPEGA and EHA in N,N‐dimethylformamide as a rather uncommon solvent for SET‐LRP further underlining a living‐type polymerization. Amphiphilic properties are investigated by critical micelle concentration (CMC) measurements and formation of micelles in water. A reverse relation between mPEGA/EHA ratio and CMC values reveals that an increased hydrophobicity leads to decreased CMC values. The self‐assembly behavior of polymers in water confirms the formation of uniform and stable micelles in water with a size between 12 and 184 nm depending on the composition of the polymers. With increased hydrophilicity, micelle sizes increase as well. In vitro tests of the obtained polymers show excellent biocompatibility even at high concentrations further affirming their suitability for drug delivery applications.

Resolving the incompatibility between SET-LRP and non-disproportionating solvents

Cu(0)-catalyzed single-electron transfer-living radical polymerization (SET-LRP) has shown great potential for applications in which well-defined chain end-functionalized polymers are demanded as final products or as intermediates. However, the use of polar reaction media favoring the disproportionation of Cu(I)X species into Cu(0) and Cu(II)X2 was considered a limiting factor specially in the synthesis of complex hydrophobic polymers with functional chain ends. “Self-generated” biphasic systems, in which the polymer phase-separates from the homogeneous reaction mixture above a certain molecular weight, together with fundamental studies on the role of solvent, including catalytic solvent effect, and methodological developments such us the “mixed-ligand” concept served as inspiration, although sometimes in an unknown way, to solve this problem. Today, SET-LRP of both acrylic and methacrylic vinyl monomers is already feasible in both polar and non-polar non-disproportionating solvents using their corresponding bi(multi)phasic “programmed” mixtures with water. Under these conditions, SET-LRP is an interfacial process in which disproportionation and activation events occur independently in the aqueous and organic compartments, and the “self-controlled” reversible deactivation takes place at the interface. Consequently, this design entirely defeats the limiting requirement to exclusively use disproportionating solvents. After a brief discussion of the historical evolution of the field of LRP, starting with the landmark work of Otsu from 1950th, this feature article will describe the elaboration of “programmed” bi(multi)phasic SET-LRP systems starting from initial inspiration to development in laboratory large-scale experiments.

Stiffening Polymer Brush Membranes for Enhanced Organic Solvent Nanofiltration Selectivity.

Membrane-based separations allow energy-efficient purification of organic solvents which are typically carried out by energy-intensive distillation. Polymer membranes are inexpensive and have obtained widespread industrial acceptance for water and biotech applications but not organic solvent nanofiltration due to relatively low selectivities. In this work, a new class of polymer brush membranes was prepared with high selectivities for methanol-toluene separation. Stiffening the brush structure by cross-linking with aromatic trimesic acid and aliphatic itaconic acid resulted in an increase in selectivity from 1.4 to 6.5-11.5. This was achieved by graft polymerization of a primary amine monomer (aminoethyl methacrylate) using single electron transfer-living radical polymerization (SET-LRP) followed by cross-linking. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and captive bubble contact angle measurements were used to characterize these membranes. The stiffness of the brush membranes was measured using a quartz crystal microbalance-dissipation (QCM-D) and correlated positively with selectivity for separating organic feed mixtures. This new class of membranes offers a tunable and scalable method for purification of organics.

Highly tunable structure-by-design polymer brush membranes for organic solvent nanofiltration

Synthetic polymeric nanofiltration membrane processes offer an alternate low-energy option to energy-intensive distillation to fractionate similar size organic solvents for chemical, petroleum, food and biotechnology industries. Here, we synthesize and test a new class of structure-by-design hydrophilic polymeric brush membranes, that address the limitations of commercial polymer membranes, are tunable and exhibit commercially relevant filtration performance. Because these brush membranes are grafted by Single Electron Transfer-Living Radical Polymerization (SET-LRP) and replace statistically random phase inversion or interfacial polymerization used for synthesizing commercial polymer membranes, their porous structure can be remodeled by varying their morphology and chemistry. We graft hydroxyethyl methacrylate (HEMA) brush structures with short and long crosslinkers, demonstrate two competing phenomena - pore stiffening and opening - and obtain high selectivity at reasonable permeability for commercially relevant methanol/toluene separation. This new class of stable, tunable, and scalable membranes offers exciting opportunities to reduce energy for separation of organic solvents.

Redox-Responsive Comparison of Diselenide and Disulfide Core-Cross-Linked Micelles for Drug Delivery Application.

In this study, diselenide (Se-Se) and disulfide (S-S) redox-responsive core-cross-linked (CCL) micelles were synthesized using poly(ethylene oxide)2k-b-poly(furfuryl methacrylate)1.5k (PEO2k-b-PFMA1.5k), and their redox sensitivity was compared. A single electron transfer-living radical polymerization technique was used to prepare PEO2k-b-PFMA1.5k from FMA monomers and PEO2k-Br initiators. An anti-cancer drug, doxorubicin (DOX), was incorporated into PFMA hydrophobic parts of the polymeric micelles, which were then cross-linked with maleimide cross-linkers, 1,6-bis(maleimide) hexane, dithiobis(maleimido) ethane and diselenobis(maleimido) ethane via Diels-Alder reaction. Under physiological conditions, the structural stability of both S-S and Se-Se CCL micelles was maintained; however, treatments with 10 mM GSH induced redox-responsive de-cross-linking of S-S and Se-Se bonds. In contrast, the S-S bond was intact in the presence of 100 mM H2O2, while the Se-Se bond underwent de-crosslinking upon the treatment. DLS studies revealed that the size and PDI of (PEO2k-b-PFMA1.5k-Se)2 micelles varied more significantly in response to changes in the redox environment than (PEO2k-b-PFMA1.5k-S)2 micelles. In vitro release studies showed that the developed micelles had a lower drug release rate at pH 7.4, whereas a higher release was observed at pH 5.0 (tumor environment). The micelles were non-toxic against HEK-293 normal cells, which revealed that they could be safe for use. Nevertheless, DOX-loaded S-S/Se-Se CCL micelles exhibited potent cytotoxicity against BT-20 cancer cells. Based on these results, the (PEO2k-b-PFMA1.5k-Se)2 micelles can be more sensitive drug carriers than (PEO2k-b-PFMA1.5k-S)2 micelles.

Grafting of poly(stearyl acrylate) on cellulose fibers as 3D-printable HDPE composites

This paper aimed to produce a bio-based filament, suitable for 3D printing (fused deposition modeling), made of surface modified cellulose fiber and high density polyethylene. The cellulose fibers (CF) were first surface modified and transformed into a CF-based macroinitiator through an esterification reaction with the 2-bromoisobutyric acid. We finally studied the ability of this CF-based macroinitiator to initiate a single electron transfer-living radical polymerization (SET-LRP) with an hydrophobic monomer: the stearyl acrylate. The grafting of poly(stearly acrylate) onto the cellulose fibers did strongly increased the adhesion, compatibility of the modified fibers with the hydrophobic host matrix (HDPE). Finally, the resulting hydrophobic fibers were extruded with the high density polyethylene (HDPE) through a counter-rotating twin-screw extruder, yielding a bio-based filament suitable for FDM 3d printing. The successful surface modification, such as the correct incorporation of the modified fibers into the thermoplastic matrix, were characterized through ATR-FTIR, 13C CP-MAS NMR, FE-SEM, and mechanical testing. Throughout those characterization techniques, it was concluded that the fiber surface modification significantly improved the compatibility of the fibers with HDPE. Finally, the 3D printing properties of the composite were tested and compared to those of pure HDPE through the 3d printing of simple objects. It was concluded that the printability of the composite made with poly(stearyl acrylate)-grafted cellulose overcomes the problem (shrinkage, warpage, print fidelity) encountered with the printing of pure HDPE.Graphical abstract

In vitro anti-prostate adenocarcinoma and lung cancer studies of phenoxyaniline-block-poly(methyl methacrylate) based nanocomposites via controlled radical polymerization.

A phenoxyaniline-based macroinitiator is utilized for the first time in order to produce phenoxyaniline-block-poly(methyl methacrylate) composites through single electron transfer-living radical polymerization (SET-LRP) under mild conditions. A different weight percentage of Cloisite 93A is added into the polymer mixtures in order to increase their biochemical properties. The prepared block copolymer nanocomposites are characterized using ATR-IR, UV-vis-spectroscopy, XRD, Raman, TGA, DSC, a particle size analyzer, contact angle measurements and SEM in order to characterize their structural, thermal, surface and morphological properties. Further, the developed polymeric nanocomposites are successfully applied in two different cancer cell lines (prostate adenocarcinoma and lung cancer), which show excellent anticancer properties. Also, acridine orange/ethidium bromide (AO/EtBr) dual staining is performed, which causes drastic cell death by apoptosis in both A549 and PC-3 cell lines, which indicated that the prepared polymeric nanocomposites effectively inhibit the cell proliferation and induce the apoptosis in both the cancer cells. Here nanoclay is used for cancer treatment because of its complete water solubility, which essentially causes the formation of a cationic complex between the clay and drug through electrostatic interactions. Hence, the exchange of ions between the clay and other ions in the biological environment leads to inhibition of the proliferation of prostate adenocarcinoma and lung cancer cells in the system.

Polymer-Modified Cellulose Nanofibrils Cross-Linked with Cobalt Iron Oxide Nanoparticles as a Gel Ink for 3D Printing Objects with Magnetic and Electrochemical Properties

This paper presents a strategy to convert hydrophilic cellulose nanofibrils (CNF) into a highly cross-linked hydrophobic network with inorganic nanoparticles to develop a gel ink suitable for gel 3D printing. The CNF were chemically modified initially through a single-electron transfer-living radical polymerization (SET-LRP) of stearyl acrylate (SA) in the presence of the surface-modified cobalt iron oxide (CoFe2O4, CFO) nanoparticles. The modified CFO nanoparticles provide their multifunctional properties, such as magnetic and electrochemical, to the CNF hybrid network and, at the same time, act as cross-linking agents between the nanocellulose fibrils, while the grafted poly-stearyl acrylate (PSA) introduces a strong hydrophobicity in the network. A suitable gel ink form of this CNF–PSA–CFO material for gel 3D printing was achieved together with a certain solvent. Some test structure prints were directly obtained with the CNF–PSA–CFO gel and were used to evaluate the consolidation of such 3D objects through solvent exchange and freeze-drying while also keeping the magnetic and electrochemical properties of CFO in the CNF-based composite intact. The pristine CNF and CFO particles and the CNF–PSA–CFO were characterized by FTIR, SEM, XPS, TGA, VSM, and CV measurements.

Association Behavior of Amphiphilic ABA Triblock Copolymer Composed of Poly(2-methoxyethyl acrylate) (A) and Poly(ethylene oxide) (B) in Aqueous Solution.

Poly(2-methoxyethyl acrylate) (PMEA) and poly(ethylene oxide) (PEO) have protein-antifouling properties and blood compatibility. ABA triblock copolymers (PMEAl-PEO11340-PMEAm (MEOMn; n is average value of l and m)) were prepared using single-electron transfer-living radical polymerization (SET-LRP) using a bifunctional PEO macroinitiator. Two types of MEOMn composed of PMEA blocks with degrees of polymerization (DP = n) of 85 and 777 were prepared using the same PEO macroinitiator. MEOMn formed flower micelles with a hydrophobic PMEA (A) core and hydrophilic PEO (B) loop shells in diluted water with a similar appearance to petals. The hydrodynamic radii of MEOM85 and MEOM777 were 151 and 108 nm, respectively. The PMEA block with a large DP formed a tightly packed core. The aggregation number (Nagg) of the PMEA block in a single flower micelle for MEOM85 and MEOM777 was 156 and 164, respectively, which were estimated using a light scattering technique. The critical micelle concentrations (CMCs) for MEOM85 and MEOM777 were 0.01 and 0.002 g/L, respectively, as determined by the light scattering intensity and fluorescence probe techniques. The size, Nagg, and CMC for MEOM85 and MEOM777 were almost the same independent of hydrophobic DP of the PMEA block.

Redox-responsive properties of core-cross-linked micelles of poly(ethylene oxide)-b-poly(furfuryl methacrylate) for anticancer drug delivery application

The design and fabrication of smart delivery systems that can efficiently deliver a payload to a targeted site in a controlled manner are immensely desirable in chemotherapy. We report the redox-responsive drug delivery property of core-cross-linked (CCL) micelles of poly(ethylene oxide)5k-b-poly(furfuryl methacrylate)2k (PEO5k-b-PFMA2k). The PEO5k-b-PFMA2k was prepared by using single electron transfer-living radical polymerization of furfuryl methacrylate (FMA) with a PEO-Br macro-initiator. Doxorubicin (DOX) was loaded into hydrophobic PFMA cores of the polymeric micelles, which were subsequently cross-linked with a diselenide-containing cross-linker, bis(maleimidoethyl) 3,3′-diselanediyldipropionoate via Diels-Alder reaction. Under physiological conditions, CCL micelles displayed increased structural stability, whereas the micelles showed a redox-responsive behavior when treated with 100 mM hydrogen peroxide (H2O2) and 10 mM glutathione (GSH). The CCL micelles were de-cross-linked due to the breaking of diselenide bonds present in the core-cross-linkages. DOX-loaded CCL micelles were stable at pH 7.4, while a higher DOX release was achieved at acidic pH 5.0 owing to the protonation of DOX. The DOX release was significantly enhanced in presence of 10 mM GSH or 100 mM H2O2 at pH 5.0 (which is a similar environment in tumor cells). The non-CCL and CCL micelles were found non-toxic to HFF-1 normal cells. However, DOX encapsulated CCL micelles showed remarkable cytotoxicity in HeLa cells. The confocal images showed that the DOX-loaded CCL micelles can quickly be internalized and efficiently deliver DOX into the HeLa cells.

Unraveling the Mechanism and Kinetics of Binding of an LCI-eGFP-Polymer for Antifouling Coatings.

The ability of proteins to adsorb irreversibly onto surfaces opens new possibilities to functionalize biological interfaces. Herein, the mechanism and kinetics of adsorption of protein-polymer macromolecules with the ability to equip surfaces with antifouling properties are investigated. These macromolecules consist of the liquid chromatography peak I peptide from which antifouling polymer brushes are grafted using single electron transfer-living radical polymerization. Surface plasmon resonance spectroscopy reveals an adsorption mechanism that follows a Langmuir-type of binding with a strong binding affinity to gold. X-ray reflectivity supports this by proving that the binding occurs exclusively by the peptide. However, the lateral organization at the surface is directed by the cylindrical eGFP. The antifouling functionality of the unimolecular coatings is confirmed by contact with blood plasma. All coatings reduce the fouling from blood plasma by 8894% with only minor effect of the degree of polymerization for the studied range (DP between 101 and 932). The excellent antifouling properties, combined with the ease of polymerization and the straightforward coating procedure make this a very promising antifouling concept for a multiplicity of applications.

Biocatalytic nanoparticles for the stabilization of degassed single electron transfer-living radical pickering emulsion polymerizations

Synthetic polymers are indispensable in many different applications, but there is a growing need for green processes and natural surfactants for emulsion polymerization. The use of solid particles to stabilize Pickering emulsions is a particularly attractive avenue, but oxygen sensitivity has remained a formidable challenge in controlled polymerization reactions. Here we show that lignin nanoparticles (LNPs) coated with chitosan and glucose oxidase (GOx) enable efficient stabilization of Pickering emulsion and in situ enzymatic degassing of single electron transfer-living radical polymerization (SET-LRP) without extraneous hydrogen peroxide scavengers. The resulting latex dispersions can be purified by aqueous extraction or used to obtain polymer nanocomposites containing uniformly dispersed LNPs. The polymers exhibit high chain-end fidelity that allows for production of a series of well-defined block copolymers as a viable route to more complex architectures.

Copper (0) Mediated Single Electron Transfer-Living Radical Polymerization of Methyl Methacrylate: Functionalized Graphene as a Convenient Tool for Radical Initiator.

Polymer nanocomposites have been synthesized by the covalent addition of bromide-functionalized graphene (Graphene-Br) through the single electron transfer-living radical polymerization technique (SET-LRP). Graphite functionalized with bromide for the first time via an efficient route using mild reagents has been designed to develop a graphene based radical initiator. The efficiency of sacrificial initiator (ethyl α-bromoisobutyrate) has also been compared with a graphene based initiator towards monitoring their Cu(0) mediated controlled molecular weight and morphological structures through mass spectroscopy (MOLDI-TOF) and field emission scanning electron microscopy (FE-SEM) analysis, respectively. The enhancement in thermal stability is observed for graphene-grafted-poly(methyl methacrylate) (G-g-PMMA) at 392 °C, which may be due to the influence ofthe covalent addition of graphene, whereas the sacrificial initiator used to synthesize G-graft-PMMA (S) has low thermal stability as analyzed by TGA. A significant difference is noticed on their glass transition and melting temperatures by DSC. The controlled formation and structural features of the polymer-functionalized-graphene is characterized by Raman, FT-IR, UV-Vis spectroscopy, NMR, and zeta potential measurements. The wettability measurements of the novel G-graft-PMMA on leather surface were found to be better in hydrophobic nature with a water contact angle of 109 ± 1°.

Synthesis of Magnetite-Based Polymers as Mercury and Anion Sensors Using Single Electron Transfer-Living Radical Polymerization.

In this work, hydrophilic polymers modified with iron oxide nanoparticles, such as iron oxide–poly(2-dimethylaminoethyl methacrylate) [P(DMAEMA)] magnetite-based and iron oxide–poly(acrylamide) [P(AAm)] magnetite-based polymers, were prepared via a single electron transfer-living radical polymerization approach. Bile acid and 2-bromo-2-methylpropionic acid were covalently attached onto the surface of Fe3O4 nanoparticles, and these immobilized magnetite nanoparticles were used as an initiator for the polymerization. The binding capabilities of different ions, such as Hg2+, CN–, Cl–, F–, and NO3–, were tested using these polymeric sensors monitored by UV–vis spectroscopy. Magnetite-based P(DMAEMA) showed enhanced binding capability due to the presence of tertiary amine groups. In addition, it was possible to easily separate the bound ions from aqueous media using an external magnetic field.

Me6-TREN/TREN Mixed-Ligand Effect During SET-LRP in the Catalytically Active DMSO Revitalizes TREN into an Excellent Ligand.

A mixed-ligand effect was observed for mixtures of tris(2-dimethylaminoethyl)amine (Me6-TREN) with tris(2-aminoethyl)amine (TREN) ligands during Cu(0) wire-catalyzed, single-electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) initiated with bis(2-bromopropionyl)ethane (BPE) in DMSO. The external order of reaction of SET-LRP both in the presence of Me6-TREN, TREN and of the mixed-ligand Me6-TREN/TREN, in DMSO, demonstrated a catalytic activity for DMSO similar to that reported in the presence of Cu(0) powder. The catalytic activity of DMSO, with close to 100% chain-end functionality, facilitates the much less expensive TREN to act as a very efficient ligand that is competitive with Me6-TREN and with the mixed-ligand and revitalizes TREN into an excellent ligand. The highest activity of the mixed-ligand at 1/1 ratio between ligands suggests that in addition to a fast exchange between these two ligands, a new single dynamic ligand stabilized by hydrogen-bonding, may generate these results.

Controlled synthesis of azobenzene-containing block copolymers both in the main- and side-chain from SET-LRP polymers via ADMET polymerization

Novel ABA triblock copolymer contained azobenzene (azo) chromophores both in the main- and side-chain was designed and synthesized via combination of single electron transfer-living radical polymerization (SET-LRP) and acyclic diene metathesis (ADMET) polymerization. The α-bromoester end group of side-chain azo-polymer prepared in SET-LRP system using acrylate bearing azo group as monomer was reacted with potassium acrylate to yield azo-polymer with the chain end of α-acrylate, which acted as a monofunctional macromolecular chain stopper for subsequent ADMET polymerization of azo-functionalized α,ω-diene monomer to finally controllable synthesize ABA triblock azo-copolymer. The diluted solutions of main-chain ADMET azo-homopolymer, side-chain SET-LRP azo-homopolymer, and main-side chains azo-copolymer exhibited different photoisomerization behaviors (maximum absorption and rate of photoisomerization) under the irradiation of UV and visible light. All these interesting results could provide a guide for the design of photosensitive materials.

Replacing Cu(II)Br2 with Me6-TREN in Biphasic Cu(0)/TREN Catalyzed SET-LRP Reveals the Mixed-Ligand Effect.

The mixed-ligand system consisting of tris(2-aminoethyl)amine (TREN) and tris(2-dimethylaminoethyl)amine (Me6-TREN) during the Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) of methyl acrylate (MA) in "programmed" biphasic mixtures of the dipolar aprotic solvents NMP, DMF, and DMAc with H2O is reported. Kinetic and chain end analysis studies by NMR and MALDI-TOF before and after thio-bromo "click" reaction demonstrated that Me6-TREN complements and makes the less expensive TREN a very efficient ligand in the absence of externally added Cu(II)Br2. Statistical analysis of the kinetic data together with control experiments demonstrated that this mixed-ligand effect enhanced the apparent rate constant of propagation, monomer conversion, and molecular weight control. The most efficient effect was observed at a 1/1 molar ratio between these two ligands, suggesting that in addition to a fast exchange between the two ligands, a new single dynamic ligand generated by hydrogen bonding may be responsible for the mixed ligand observed.

Cu(0) Wire-mediated Single-electron Transfer-living Radical Polymerization of Oligo(ethylene oxide) Methyl Ether Acrylate by Selecting the Optimal Reaction Conditions

The efficient Cu(0) wire-catalyzed single-electron transfer-living radical polymerization (SET-LRP) in organic solvents and mixtures of the organic solvents with water has been thoroughly investigated. Oligo(ethylene oxide) methyl ether acrylate was used as an exemplar oligomer monomer to determine the optimum polymerization conditions for rapid, controlled, and quantitative production of well-defined polymers. The effects of Cu(0)-wire length (12.5 or 4.5 cm), ligand type (tris(dimethylaminoethyl)amine, Me6-TREN, or tris(2-aminoethyl)amine, TREN), and solvent type (dipolar aprotic solvents, cyclic ethers, alcohol, or acetone) on the polymerization have been evaluated. Kinetic experiments were performed for all polymerizations to assess the “living” behavior of each system employed. Importantly, TREN could be used as a replacement for Me6-TREN in Cu(0) wire-catalyzed SET-LRP of oligomer monomer, which probably provides the most economical and efficient methodology since TREN is 80 times less expensive than Me6-TREN. The high chain-end fidelity of resulting polymer was experimentally verified by thiol-Michael addition reaction at the α-Br chain end and subsequent chain extension with methyl acrylate.

Polyacrylates Derived from Biobased Ethyl Lactate Solvent via SET-LRP.

The precise synthesis of polymers derived from alkyl lactate ester acrylates is reported for the first time. Kinetic experiments were conducted to demonstrate that Cu(0) wire-catalyzed single electron transfer-living radical polymerization (SET-LRP) in alcohols at 25 °C provides a green methodology for the LRP of this forgotten class of biobased monomers. The acrylic derivative of ethyl lactate (EL) solvent and homologous structures with methyl and n-butyl ester were polymerized with excellent control over molecular weight, molecular weight distribution, and chain-end functionality. Kinetics plots in conventional alcohols such as ethanol and methanol were first order in the monomer, with molecular weight increasing linearly with conversion. However, aqueous EL mixtures were found to be more suitable than pure EL to mediate the SET-LRP process. The near-quantitative monomer conversion and high bromine chain-end functionality, demonstrated by matrix-assisted laser desorption ionization time-of-flight analysis, further allowed the preparation of innovative biobased block copolymers containing rubbery poly(ethyl lactate acrylate) poly(ELA) sequences. For instance, the poly(ELA)- b-poly(glycerol acrylate) block copolymer self-assembled in water to form stable micelles with chiral lactic acid-derived block-forming micellar core as confirmed by the pyrene-probe-based fluorescence technique. Dynamic light scattering and transmission electron microscopy measurements revealed the nanosize spherical morphology for these biobased aggregates.