Reversible Addition-fragmentation Chain Transfer Polymerization Polymerization Research Articles

BaTiO3 Catalyzed Ultrasonic-Driven Piezoelectric-Induced Reversible Addition-Fragmentation Chain-Transfer Polymerization in Aqueous Media.

Compared with normal stimulus such as light and heat, ultrasonic possesses much deeper penetration into tissues and organs and has lower scattering in heterogeneous systems as a noninvasive stimulus. Reversible addition-fragmentation chain-transfer polymerization (RAFT) in aqueous media is performed in a commercial ultrasonic wash bath with 40kHz frequency ultrasonic, in the presence of piezoelectric tetragonal BaTiO3 (BTO) nanoparticles. Owing to the electron transfer from BTO under the ultrasonic action, the water can be decomposed to produce hydroxyl radical (HO•) and initiate the RAFT polymerization (piezo-RAFT). The piezo-RAFT polymerization exhibits features of controllable and livingness, such as linear increase of molar mass and narrow molar mass distributions (Mw/Mn < 1.20). Excellent temporal control of the polymerization and the chain fidelity of polymers are illustrated by "ON and OFF" experiment and chain extension, separately. Moreover, this ultrasonic-driven piezoelectric-induced RAFT polymerization in aqueous media can be directly used for the preparation of piezoelectric hydrogel which have potential application for stress sensor.

A new method for synthesis of modified cellulose‐graft‐poly(acrylic acid) copolymer using 4‐cyano‐4‐[(phenylcarbothioyl)solfanyl]pentanoic acid to serve as RAFT agent

AbstractIn this study, cellulose was first treated with 4‐cyano‐4‐((phenyl carbonothioyl)solfanyl) pentanoic acid to serve as the reversible addition‐fragmentation chain transfer polymerization (RAFT) agent, then the controlled grafting polymerization of acrylic acid was successfully performed. A well‐defined, cellulose‐graft‐acrylic acid copolymer (Cell‐g‐PAA), has been prepared by RAFT polymerization technique using three different approaches: RAFT agent was prepared by substitution of dithiobenzoate magnesium bromide with 4,4'‐azobis(4‐cyanopentanoic acid) in ethyl acetate as a solvent, mediated cellulose (Cell) block as the macromolecular Cell‐RAFT agent and (cellulose‐co‐acrylic acid) copolymer with alternating sequence. The resulting (Cell‐RAFT) for “living” free radical polymerization was then heated in the adjacent acrylic acid monomer for the development of the controlled graft copolymer onto cellulose. The structures of the intermediate, graft copolymer were investigated by FT‐IR, DSC, 1H NMR, scanning electron microscopy, and thermo gravimetric. The results demonstrate that the preparation of graft copolymers was successfully confirmed. This approach would provide an extensive classification of molecular designs to obtain modern types of tailored hybrid materials derived from natural polysaccharides and synthetic polymers. Also, using a macro‐initiator is an excellent method for synthesizing new materials.

Novel concrete superplasticizers with sterically hindered amines as stabilizing pendant side chains

In this work, a sterically hindered amine, 2,2,6,6-tetramethyl-4-piperidyl methacrylate (TMPMA), is introduced as a bulky pendant group to achieve steric hindrance, replacing the traditional poly(ethylene oxide) (PEO) side chains of traditional polycarboxylate ether (PCE) superplasticizers (SPs). Note that PCE is the common name for concrete superplasticizers having both carboxylic acid and PEO side-chains in which the bulky PEO pendant group exert large steric hindrance leading to good dispersion and stabilization of cement particles. In this work, the PEO side chains are replaced by a sterically hindered amine. Therefore, copolymers of methacrylic acid (MAA) and TMPMA with different molar ratios were prepared by Reversible-Addition Fragmentation Chain Transfer polymerization (RAFT). The prepared copolymers were characterized by proton nuclear magnetic resonance (1H NMR) and size exclusion chromatography (SEC) to elucidate the chemical structure and molecular weights. Rheological studies and fluidity measurements revealed that poly(MAA-co-TMPMA) SPs, which we introduce here as polycarboxylate amine (PCA) SPs, enhanced cement flowability, workability, and slump retention. Free radical polymerization (FRP) was also employed, as an industrially more relevant, more straightforward and more cost-effective synthesis technique, for the preparation of PCA SPs to reflect the possibility of scaling up these SPs via conventional polymerization methods. The resulting FRP PCA analog exhibited the same plasticizing efficacy as those prepared by RAFT polymerization, demonstrating that these polymers could have high potential in the concrete industry.

Experimental &amp; Modelling Digital Twin Approach for Polymer Synthesis via Re‐initiated Oxygen inhibited RAFT Polymerization

AbstractControlled polymerization techniques like the reversible‐addition fragmentation chain transfer polymerization (RAFT) are sensitive to impurities such as oxygen. This work explores the application of re‐initiation as a tool to enhance monomer conversion. A kinetic model for the oxygen inhibited RAFT dispersion polymerization for the synthesis of poly(4‐vinylpyridine)‐b‐polystyrene (P4VP‐b‐PS) is developed. Thus, using the kinetic model, the re‐initiation of the inhibited RAFT polymerization is partially (monomer conversion ≤10%) predicted. By implementing the re‐initiation as a solution, the synthesis of P4VP‐b‐PS copolymers with the high conversion (&gt;96%) and a good dispersity (≤1.2) is enabled.

Observation and Modeling of a Sharp Oxygen Threshold in Aqueous Free Radical and RAFT Polymerization.

It is known that oxygen (O2) stops radical polymerization (RP). Here, it was found that the reaction turn-off occurs abruptly at a threshold concentration of O2, [O2]t, for both free RP and reversible addition-fragmentation chain-transfer polymerization (RAFT). In some reactions, there was a spontaneous re-start of conversion. Three cases were investigated: RP of (i) acrylamide (Am) and (ii) sodium styrene sulfonate (SS) and (iii) Am RAFT polymerization. A controlled flow of O2 into the reactor was employed. An abrupt turn-off was observed in all cases, where polymerization stops sharply at [O2]t and remains stopped when [O2] > [O2]t. In (i), Am acts as a catalytic radical-transfer agent during conversion plateau, eliminating excess [O2], and polymerization spontaneously resumes at [O2]t. In no reaction, the initiator alone was capable of eliminating O2. N2 purge was needed to re-start reactions (ii) and (iii). For (i) and (ii), while [O2] < [O2]t, O2 acts a chain termination agent, reducing the molecular weight (Mw) and reduced viscosity (RV). O2 acts as an inhibitor for [O2] > [O2]t in all cases. The radical-transfer rates from Am* and SS* to O2 are >10,000× higher than the initial chain propagation step rates for Am and SS, which causes [O2]t at very low [O2].

A Simple and Green Oxygen‐Tolerant RAFT Polymerization without Additional Catalyst and Initiator

AbstractOxygen‐tolerant reversible addition‐fragmentation chain transfer polymerization (RAFT) can be successfully achieved through the addition of organic and inorganic photoredox catalysts or other additives. Thus, developing a simple oxygen‐tolerant RAFT without additional catalyst and initiator will augment the development of this field. In this work, two‐component systems, 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and 4‐cyanopentanoic acid dithiobenzoate (CPADB), have been successfully applied to develop green and oxygen‐tolerant RAFT under aqueous conditions without any additional catalysts, where dithioester CPADB was employed as an iniferter agent (initiator‐transfer‐terminator) for polymerization control, as well as an intrinsic photoredox catalyst for deoxygenation. DMAEMA was utilized as monomer and electron donor. In the present work, dithioester‐assisted oxygen removal in aqueous RAFT photopolymerization is reported for the first time. This work provides a simple and green method for oxygen‐tolerant RAFT polymerization.

Reversible addition‐fragmentation chain transfer polymerization for fabrication of polymer cations‐adjustable porous materials with excellent antibacterial activity

AbstractThe reversible addition‐fragmentation chain transfer polymerization (RAFT) is an effective method to control chain growth and regulate active centers in functional materials. Herein, a novel antibacterial material, polymer cations‐adjustable porous materials (PCaPM), was successfully synthesized by RAFT and quaternization. First, using 2‐(dodecylsulfanylthiocarbonylsulfanyl)‐2‐methylpropionic acid as the chain transfer agent of RAFT, methyl methacrylate and 2‐(dimethylamino)ethyl methacrylate as comonomers, and ethylene dimethacrylate as crosslinking agent, the light‐yellow crosslinked block copolymer (PM‐PDE), was synthesized by RAFT polymerization. Second, a series of porous materials (PCaPM) were obtained by quaternization of PM‐PDE with alternative alkyl halide and swelling effects in water. The composition and structure of PM‐PDE and PCaPM were characterized by scanning electron microscope, energy dispersive spectrometer, Fourier transform infrared spectra, 1H‐NMR, Brunauer–Emmett–Teller, and X‐ray photoelectron spectroscopy. Their antibacterial properties were also evaluated against Staphylococcus aureus, Escherichia coli, and Valsa mali. Remarkably, PCaPM, containing tertiary amine and possessing high porosity and large specific surface area, presented excellent antibacterial activity. Hence, the resultant PCaPM exhibited excellent antibacterial activity due to the quaternary ammonium salts groups, which has great prospects in application in medical treatment, agricultural antibiotic, emulator, and sewage treatment.

Synthesis and application of PHEMA-b-PMPS copolymers using RAFT polymerization

Poly (2-hydroxyethyl methacrylate)-block-poly (3-(methacryloxy)propyl trimethoxysilane) (PHEMA-b-PMPS) was obtained through the reversible addition–fragmentation chain transfer polymerization (RAFT) and analyzed using 1H NMR, FTIR, GPC and DSC techniques. Under the polymerization condition, the Mw /Mn value of the well-defined block copolymers was around 1.1–1.2. These silicon-containing polymers possess many applications. First, this amphiphilic block copolymers shown good ability based on its surface tension control performance. Then, the self-assembly behaviors of block copolymer in the mixed solvents were studied. DLS results have shown that the aggregates could self-assemble into core–shell particles. These core–shell structure and resulting hybrid core–shell nanoparticles were analyzed by TEM. Finally, the biocompatibility of the copolymer hydrogels was verified by in vitro cell viability studies on fibroblasts L929.

Tunable Thermo-Responsive Copolymers from DEGMA and OEGMA Synthesized by RAFT Polymerization and the Effect of the Concentration and Saline Phosphate Buffer on its Phase Transition.

Thermo-responsive polymers and copolymers derivatives of oligo(ethylene glycol) methyl ether methacrylate (Mn = 300 g mol−1) (OEGMA) and di(ethylene glycol) methyl ether methacrylate (DEGMA) have been synthesized by reversible addition fragmentation chain transfer polymerization (RAFT) using 5-amino-4-methyl-4-(propylthiocarbonothioylthio)-5-oxopentanoic acid (APP) as chain transfer agent (CTA). The monomer conversion was evaluated by hydrogen nuclear magnetic resonance (1H-NMR); number average molecular weights (Mn), weight average molecular weight (Mw), and dispersity (Đ) were obtained by gel permeation chromatography (GPC); glass transition temperature (Tg) was evaluated by modulated differential scanning calorimetry (DSC), cloud point temperature (Tcp) was measured and compared by turbidimetry and dynamic light scattering (DLS). The effect of polymer composition and concentration on the Tcp, either in water or in phosphate buffer saline (PBS), was studied. The values of Tcp using PBS were between 3 and 4 °C lower than using water. Results showed an ideal copolymerization behavior; therefore, the Tcp could be tuned by an adequate monomers feed ratio obtaining polymers which may be used in drug delivery and other applications.

Efficient Heterodifunctional Unimolecular Ring‐Closure Method for Cyclic Polymers by Combining RAFT and SuFEx Click Reactions

A novel ring-closure strategy for cyclic polymers by combining reversible addition-fragmentation chain transfer polymerization (RAFT) and the sulfur(VI)-fluoride exchange (SuFEx) click reaction is presented. Herein, a new heterodifunctional trithiocarbonate RAFT agent, 2-((tert-butyldimethylsilyl)oxy)ethyl (4-(fluorosulfonyl)benzyl) carbonotrithioate (TBDMS-FSBCT), containing both tert-butyldimethylsilyl ether and sulfonyl fluoride moieties, is developed. The polymerization behavior of TBDMS-FSBCT is first demonstrated by a standard RAFT polymerization procedure for two types of vinyl monomers, N-isopropylacrylamide (NIPAAm) (conjugated vinyl monomer) and N-vinylpyrrolidone (NVP) (unconjugated vinyl monomer). The tert-butyldimethylsilyl ether and sulfonyl fluoride groups at the α and ω positions of the obtained linear polymer precursors (L-PNIPAAm and L-PVP) are verified by 1 H, 13 C, and 19 F NMR spectra. Subsequent intramolecular SuFEx click cyclization of the α,ω-heterofunctionalized linear precursors in air at room temperature conveniently yields the corresponding cyclic polymers (C-PNIPAAm and C-PVP). Overall, this is the first report on the preparation of cyclic polymers based on the SuFEx reaction under ambient conditions. It is envisioned that the approach may open an avenue for the formation of cyclic polymers.

Grafting polyisoprene onto surfaces of nanosilica via RAFT polymerization and modification of natural rubber

In this contribution, we reported the investigation of natural rubber (NR) reinforced by silicon dioxide‐graft‐polyisoprene (SiO2‐g‐PIP) core–shell nanoparticle. First, the hydroxyl on the surface of the SiO2 nanoparticles was reacted with 2‐methyl‐2‐[(dodecylsulfanylthiocarbonyl) sulfanyl] propanoic acid to produce trithioester‐capped SiO2 (denoted as SiO2‐CTA). SiO2‐CTA was used as a nanoparticle chain transfer agent, and SiO2‐g‐PIP core–shell nanoparticles were synthesized via reversible addition‐fragmentation chain transfer polymerization (RAFT). The results of FTIR spectroscopy and TGA showed that the grafting weight of the PIP block in SiO2‐g‐PIP was 2.1 wt%. SiO2‐g‐PIP and SiO2 were simultaneously incorporated into NR. The curing properties of the NR compounds showed that the vulcanization rates of the NR/SiO2‐g‐PIP compounds were much higher than those of NR/silica compounds. The results of scanning electron microscopy showed that SiO2 microdomains in the NR/SiO2‐g‐PIP vulcanizate were much better disperse and distribute than SiO2 microdomains in the NR/SiO2 composite. The filler–rubber interaction of the NR/SiO2‐g‐PIP composite endowed the composite with improved mechanical properties. POLYM. ENG. SCI., 59:1167–1174 2019. © 2019 Society of Plastics Engineers

Characterizing the structure of styrene-maleic acid copolymer-lipid nanoparticles (SMALPs) using RAFT polymerization for membrane protein spectroscopic studies.

Membrane proteins play an important role in maintaining the structure and physiology of an organism. Despite their significance, spectroscopic studies involving membrane proteins remain challenging due to the difficulties in mimicking their native lipid bilayer environment. Membrane mimetic systems such as detergent micelles, liposomes, bicelles, nanodiscs, lipodisqs have improved the solubility and folding properties of the membrane proteins for structural studies, however, each mimetic system suffers from its own limitations. In this study, using three different lipid environments, vesicles were titrated with styrene-maleic acid (StMA) copolymer leading to a homogeneous SMALP system (∼10 nm) at a weight ratio of 1:1.5 (vesicle: StMA solution). A combination of Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM) was used to characterize these SMALPs. We used a controlled synthesis mechanism to synthesize StMA based block copolymers called reversible addition-fragmentation chain transfer polymerization (RAFT) SMALPs. Incorporation of the Voltage Sensor Domain of KCNQ1 (Q1-VSD) into RAFT SMALPs indicates that this is a promising application of this system to study membrane proteins using different biophysical techniques. V165C in Q1-VSD corresponding to the hydrophobic region was incorporated into the SMALP system. Continuous Wave-Electron Paramagnetic Resonance (CW-EPR) line shape analysis showed line shape broadening, exposing a lower rigid component and a faster component of the spin label.

Controlled graft polymerization on the surface of filter paper via enzyme-initiated RAFT polymerization

This study reports on eco-friendly graft polymerization approach for the modification of a cellulosic material via combination between enzymatic catalysis and reversible addition-fragmentation chain transfer polymerization (RAFT). Polyacrylamide (PAM) was polymerized on a cellulosic filter paper via horseradish peroxidase (HRP)-initiated RAFT polymerization. The results of grafting ratio, conversion, and pseudo-first-order kinetics were proved that the PAM graft polymerization on the filter paper followed RAFT rules. The results of Attenuated total reflection (ATR-FTIR), elemental analysis, and X-ray photoelectron spectroscopy (XPS) confirmed the presence of PAM in PAM-grafted filter paper. The results of water contact angle and Thermogravimetric analysis (TG) evidenced the change in the wetting properties and thermal performance, respectively of the treated filter paper. This work provides a new environmentally approach to graft polymerization on cellulosic materials.

Recycling of poly(ethylene terephthalate) by chain extension during reactive extrusion using functionalized block copolymers synthesized by RAFT polymerization

ABSTRACTIn this study, a series of reactive block copolymers of glycidyl methacrylate (G), styrene (S), and maleic anhydride (MA) (GS–SMA–GS), with well‐defined properties and high number average functionalities, is presented. They were synthesized through reversible addition–fragmentation chain transfer polymerization (RAFT) and evaluated as chain extenders in reactive extrusion recycling of poly(ethylene terephthalate) (rPET). Modification of the process using GS–SMA–GS results in increased melt flow and intrinsic viscosities higher than those of conventional rPET. Results show that increasing epoxide content makes chain organization in rPET difficult and promotes lower crystallization rates and lower degrees of crystallinity, both of which are characteristics suited to produce preforms with the desired clarity. Chain‐extended rPET exhibits improved rheological characteristics with increasing glycidyl methacrylate content. Chain‐extended rPET using GS–SMA–GS shows enhanced complex viscosity; elastic and viscous modules, which are indicative of high melt elasticity, improved mechanical properties, and processability. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46771.

Perylene as a visible light photoredox catalyst for photoinduced electron transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization of MMA

The organic photocatalyst, perylene, was used to mediate photoinduced electron transfer (PET) reversible addition-fragmentation chain transfer polymerization (RAFT) of methyl methhacrylate (MMA) under light irradiation in N,N-dimethylformamide (DMF) at 25°C with 4-cyanopentanoic acid dithiobenzoate (CPADB) as chain transfer agent (CTA). Kinetic studies confirmed that the polymerization obeyed the first order kinetic m'odel. The production of PMMAs with a good control of molecular weights (Mn,GPC) and narrow polymer molecular weight distribution (Mw/Mn) were obtained. It is found that well-controlled PET RAFT polymerization of MMA can be manipulated even with the amount of perylene decreasing to ppm level. No polymer was obtained in the absence of light irradiation, implying that the model of PET RAFT polymerization of MMA is an ideal light “on”-“off” switchable system. Furthermore, the speed of PET RAFT polymerization of MMA was also finely tunable by the external light irradiation intensity. The resultant PMMA macro-CTA was characterized by 1H nuclear magnetic resonance spectrum (1H NMR) and gel permeation chromatography (GPC). The accessibility of the high end group fidelity was further demonstrated by chain extension experiments.

Grafting strategies for the synthesis of active DNase I polymer biohybrids

Protein polymer hybrids play an increasingly important role in therapeutics and biocatalysis. Synthesis of these biohybrids can be achieved by either the grafting-from or grafting-to strategy and are generally thought to be interchangeable. Therefore, when choosing between these two strategies the decision is usually based on polymer accessibility and purification preference. However, in this study, we demonstrated that the choice of the polymer ligation strategy played a significant role in the stability and bioactivity of the final hybrid. Our goal was to prepare a thermally stable DNase I polymer hybrid by utilizing either synthetic strategies. We found that the grafting-from strategy using reversible addition-fragmentation chain transfer polymerization (RAFT) or atom transfer radical polymerization (ATRP) yielded DNase I biohybrids with no activity. Control reactions were used to demonstrate inherent protein deactivation caused by the grafting-from conditions for either ATRP or RAFT polymerization. The grafting-to method yielded active and thermally stable DNase I biohybrids.

RAFT derived fatty acid based stimuli responsive fluorescent block copolymers as DNA sensor and cargo delivery agent

Novel capric acid-tryptophan based block copolymers with unique self-assembled feature and fluorescence property have been synthesized via reversible addition fragmentation chain transfer polymerization (RAFT) polymerization. For employing the copolymerization, at first the fatty acid based methacrylate monomer has been efficiently polymerized in presence of 4-cyano-4-(thiobenzylthio)pentanoic acid (CTP) as chain transfer agent (CTA) via RAFT polymerization. The polymerization has been preceded in a controlled fashion as confirmed by their narrow polydispersity and molecular weight determination from several methods. The capric acid based polymer then exploited as macro-CTA to synthesize the copolymers of poly(2-(methacryloyloxy)ethyl caprylate)-block-poly(tert-butyloxycarbonyl tryptophan methacryloyloxyethyl ester) (PCRMA-b-P(Boc-Trp-HEMA)) with variable block length of amino acid segment. Removal of Boc group from the amino acid block results in formation of pH responsive cationic polymers soluble in water depending on their block length. The amphiphilic polymer self-assemble in water forming higher ordered structure is then utilized as a scaffold to encapsulate and delivery of anticancer drug doxorubicin. Finally we provide a fatty acid based polymeric DNA sensor that can bind with DNA followed by significant fluorescence quenching.

Non-ionic fluorinated amphiphilic block copolymer via RAFT polymerization and their application as surfactant in emulsion polymerization

This investigation reports the synthesis of block copolymer of poly(ethylene glycol) methyl ether methacrylate (PPEGMA) with poly(heptafluorobutyl acrylate) (PHFBA). The blockcopolymer was prepared via reversible addition-fragmentation chain transfer polymerization (RAFT). The RAFT end-capped poly[poly(ethylene glycol) methyl ether methacrylate] (PPEGMA) macro-chain transfer agent (CTA) was prepared using 2-cyano-2-propyl dithiobenzoate (CPBT) as RAFT agent. The synthesized PPEGMA was later used as macro-RAFT agent for the polymerization of 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) which yielded well-defined block copolymers of varied lengths. The PPEGMA-b-PHFBA block copolymer self-assembles in water produces spherical micelles with core-shell nano-structure where the core made of hydrophobic block (PHFBA) and shell is of hydrophilic block (PPEGMA). The synthesized block copolymers, PPEGMA−b−PHFBA, an amphiphilic block copolymers were used as surfactant in the surfactant free emulsion polymerization of styrene. Aqueous micellar solutions of the block copolymers were characterized by DLS and TEM analyses. The CMC value of polymeric surfactant was 0.046 mg. mL−1, determined by surface tension analysis. The block copolymers were characterized by GPC, 1H NMR, FT-IR, DSC analyses.

Styrenation of air blown linseed oil via RAFT–mediated miniemulsion polymerization

Abstract In this study styrenated oil products were prepared under miniemulsion conditions by reversible addition-fragmentation chain transfer polymerization (RAFT) technique using phenacyl morpholine dithiocarbamate (PMDC) as a RAFT agent. First, hydroperoxide groups were formed on the oil structure by air-blowing process. Then the prepared miniemulsion of air blown linseed oil (ABLO)-styrene mixture was subjected to styrenation in the presence of the RAFT agent. Miniemulsion was prepared by means of ultrasonication by using cetyl trimethyl ammonium bromide (CTAB) and hexadecane (HD) as surfactant and co-surfactant, respectively. The best miniemulsion conditions were determined by a new strategy based on the determination of the conditions ensuring not to change of droplet/particle size throughout the polymerization. In this way, the conditions for the elimination of monomer diffusion between droplets were established. The styrenated oil product obtained under optimum conditions was characterized by FT-IR, 1 H NMR and GPC measurements. In order to understand the effect of miniemulsion conditions on molecular weight and polydispersity index (PDI), styrenated oil samples were also prepared in solvent (dioxane) medium. Tests for film properties of product prepared by RAFT in miniemulsion medium were applied according to related standards. The styrenated oil obtained in this study exhibited molecular weight distribution values lower than styrenated oil products obtained by the classical RAFT polymerization in solvent medium. The film properties showed that these styrenated oil samples could be used as an oil based binder.

Synthesis and Nanoprecipitation of HEMA-CLn Based Polymers for the Production of Biodegradable Nanoparticles.

The control over the size distribution and stability of polymeric nanoparticles (NPs) is crucial in many of their applications, especially in the biomedical field. These characteristics are typically influenced by the production method and the nature of the starting material. To investigate these aspects, the controlled radical polymerization of functionalized methacrylates constituted by 2-hydroxyethyl methacrylate (HEMA) functionalized with a controlled number of ε-caprolactone (CL) units (HEMA-CLn), was carried out via reversible addition–fragmentation chain transfer polymerization (RAFT) in solution. The living reaction allows for good control over the molar mass of the final polymer with a low molar mass dispersity. The obtained polymer solutions were nanoprecipitated in order to produce NPs suitable for drug delivery applications with narrow particle size distribution and a wide size range (from 60 to 250 nm). The NP synthesis has been performed using a mixing device, in order to control the parameters involved in the nanoprecipitation process. As already seen for similar systems, the size of the produced NPs is a function of the polymer concentration during the nanoprecipitation process. Nevertheless, when the polymer concentration is kept constant, the NP size is influenced by the chemical structure of the polymer used, in terms of the presence of PEG (poly(ethylene glycol)), the degree of RAFT polymerization, and the length of the caprolactone side chain. These characteristics were also found to influence the stability and degradation properties of the produced NPs.