Polymerization Time Research Articles

Positively charged membranes for dye/salt separation based on a crossover combination of Mannich reaction and prebiotic chemistry

With the advent of increasingly loose nanofiltration membranes for dye desalination, synthesis methods based on interfacial polymerization and bio-inspired materials such as polydopamine (pDA) have been investigated. However, the long polymerization time of pDA greatly limits the synthesis and application of fast dye/salt separation membranes. In this work, prebiotic chemistry-inspired aminomalononitrile (AMN) was used as a binder to co-deposit the Mannich reaction of tetrakis(hydroxymethyl)phosphonium chloride (THPC) and polyethyleneimine (PEI) to form the positively charged selective layer rapidly. The optimum membrane had a water permeance of 30.7 LMH bar-1 and a rejection of positively charged Victoria blue B (VBB, 200 ppm) and Na2SO4 (1 g/L) of 99.5 % and 9.9 %, respectively. Moreover, the results of a practical application test showed that it had excellent separation performance towards various positively charged dyes and salts. In addition, the actual application test results show that the membrane has good long-term stability during application. In terms of antifouling and antibacterial, the membrane has excellent antibacterial and antifouling properties., Further antibacterial tests were carried out, and the inactivation effect of the membrane on E. coli was also confirmed. The preparation method proposed in this work provides technical support for developing new dye/salt separation membranes.

Effect of organosilicon resin containing disulfide bonds on elastic properties of cotton fabric

Cotton fabrics are popular for their excellent properties, but their property of creasing easily largely limits the wide application of cotton fabrics. In this paper, an organosilicon resin emulsion containing disulfide bonds was prepared with epoxy-terminated silicone oil and 4,4-diaminodiphenyl disulfide (AFD) as raw materials, and it was used as a finishing agent for the elastic finishing of cotton fabrics. The effects of raw material ratio on the elastic properties of organosilicon polymer film and the effects of emulsifier dosage and emulsification time of emulsion polymerization on the properties of organosilicon resin emulsion were studied. In addition, the effects of organosilicon finishing agent dosage, curing temperature, and curing time on the elastic properties of cotton fabric were also studied. The research results show that the average particle size of the prepared organosilicon resin emulsion is about 250 nm, the particle size distribution is concentrated and the emulsion is stable. The delayed elastic recovery angle of the cotton fabric treated with an organosilicon finishing agent can reach 185°, showing excellent high delayed elasticity. At the same time, it was found that the finished cotton fabric exhibited an excellent and special temperature-responsive shape memory function based on the existence of disulfide bonds in the organosilicon polymer network structure.

Polystyrene-Modulated Polypyrrole to Achieve Controllable Electromagnetic-Wave Absorption with Enhanced Environmental Stability.

The moderation of the dielectric properties of polymer composites and their environmental stability need to be considered comprehensively in the design of microwave-absorbing materials. In this work, polypyrrole/polystyrene (PPy/PS) composited particles were synthesized through a facile in situ bulk polymerization procedure. The PS component can be modulated conveniently by controlling the polymerization time. FTIR and Raman analyses disclosed that the PS component was immobilized in PPy via covalent bonds. The electromagnetic characterization results indicated that the dielectric properties and, thus, the microwave absorption could be controlled when the styrene polymerization was prolonged from 6 h (PPy-6) to 19 h (PPy-19). The composite PPy-19 displayed an optimal reflection loss of −51.7 dB with a matching thickness of 3.16 mm, and the effective absorption bandwidth (EAB) even reached 5.8 GHz at 2.4 mm. The PS component endowed PPy/PS composites with more robust environmental stability than homogeneous PPy. After being exposed to air for 365 days and hydrothermally treated at 100 °C for 12 h, PPy-19 still exhibited a reflection loss superior to −20 dB. The present work provides a new insight into the adjustment of the electromagnetic properties of PPy composites to fabricate high-performance microwave absorbers with superior environmental stability.

Properties of synthesized inorganic polymeric phosphate materials and possibilities for production of new environmentally friendly and economically viable supplies from local industrial waste

Properties of synthesized inorganic polymeric phosphate materials and possibilities for production of new environmentally friendly and economically viable supplies from local industrial waste. / M. Avaliani, V. Chagelishvili, E. Shapakidze, M. Gvelesiani, N. Barnovi, M. Vibliani, K. Chikovani. / Nano Studies. – 2020. – # 20. – pp. 65-70. – eng. In the paper, the data on obtaining and general properties of polymeric phosphates first time synthesized by the authors are considered. There are analyzed the possibilities of production of new geopolymeric binder materials by inclusion of small amounts of these condensed materials into industrial waste and using phosphoric acid. Ref. 34.

Pore engineering of MOFs through in-situ polymerization of dopamine into the cages to boost gas selective screening of mixed-matrix membranes

Reducing the effective pore size of MOFs is necessary to improve gas screening of mixed matrix membrane (MMMs). However, continuous and precise regulation on pore size of MOFs is still challenging. In this work, dopamine (DA) monomers are proposed to polymerize in situ into pore cages of UIO-66, achieving the tuning of effective pore size for CO2 screening. Meanwhile, the abundant hydroxyl and amino groups in polydopamine (PDA) offer high affinity with CO2 to improve the selective permeation of CO2. Furthermore, additional PDA existing outside UIO-66 at longer polymerization time can intensify the interface compatibility to promote CO2/N2 selectivity. Through increasing PDA content in the cage by prolonging polymerization time, the effective pore size and total pore volume of UIO-66 are decreased by 13.2% and 59.2%, respectively, compared with pure UIO-66. Correspondingly, PDA@UIO-66/Pebax MMM presents greatly improved CO2 separation performances, especially the CO2/N2 selectivity, compared with UIO-66/Pebax MMM. Specifically, both the permeability and selectivity of CO2 increase with the PDA content into the cages increasing, which is attributed to the synergy of reduced pore size and abundant CO2-philic groups in PDA. The PDA10.3@UIO-66/Pebax MMM shows the best CO2/N2 selectivity of 70.55 and CO2 permeability of 94.56 Barrer, 29.2% and 27.9% higher than those of UIO-66/Pebax MMM, respectively. The proposed PDA@UIO-66 based MMMs exhibit superior CO2 separation performance, especially high CO2/N2 selectivity compared with most reported UIO-66 based MMMs. Together with the good long-term stability, the proposed regulating strategy on effective pore engineering of MOFs is promising and competitive in CO2 screening of MOFs based MMM.

Enzymatic synthesis, post-polymerization modification and cross-linking of functionalized poly(β-thioether ester) with pendant vinyl group

Vinyl-functionalized poly(β-thioether ester) (PVTE) was synthesized by enzyme-catalyzed polymerization using immobilized lipase B from Candida antarctica (CALB) for the first time. Four different functionalized monomers were prepared and three polymerization strategies including polycondensation (PC), ring-opening polymerization (ROP), and ring-opening and condensation copolymerization (ROCCP) were investigated. The influences of reaction conditions such as polymerization temperature, time, and monomer ratio on the molecular weight of functionalized poly(β-thioether ester)s were also studied. Both the homopolymer and copolymers were characterized by NMR, SEC, TGA and DSC. Moreover, these poly(β-thioether ester)s containing pendant double bonds toward postfunctionalization were demonstrated by photoinitiated thiol-ene click chemistry and Michael addition reaction, providing a way to cross-linked polyester gels.

Fabrication of electrospun polyetherimide/polyaniline self-supporting microfiber membranes as electrodes for flexible supercapacitors via in-situ polymerization

The intrinsic properties and structural construction of active materials are crucial to improving the performance of electrodes. Herein, flexible and hydrophilic polyetherimide/polyaniline (PEI/PANI) conductive microfiber membranes with unique core-shell architecture were prepared via electrospinning followed by in-situ chemical oxidation polymerization of aniline doped with 2-acrylamido-2-methyl-1-propanesulfonic acid, and used to boost the properties through the combined action of the pseudocapacitive PANI and abundant porous PEI membranes. For achieving excellent PEI/PANI microfiber membranes as free-standing electrodes, the polymerization time was controlled to refrain from exceed PANI particles agglomeration and maintain the unique three-dimensional porous network structure. Optimized PEI/PANI microfiber membranes with the polymerization time of 7 h presented the best electrochemical properties with high specific capacitance of 249.5 F g−1 at 1 A g−1 and low charge-transfer resistance of 8.316 Ω. Ascribing to the combined effect between the unique pore structure of PEI microfiber membranes and pseudocapacitance of PANI, the flexible supercapacitor based on PEI/PANI-7 demonstrated exceptional capacitance (175.1 F g−1 at 1 A g−1), high energy density (43.4 Wh kg−1) and power density (34.0 kW kg−1), and outstanding flexibility while preserving the cyclic stability. Therefore, this free-standing PEI/PANI microfiber membranes could be deemed as a prospective electrode contender for flexible supercapacitor applications.

Effects of Polymerization Time towards Conductivity and Properties of Poly(methyl methacrylate)/Polyaniline (PMMA/PANi) Copolymer

The effects of various polymerization times on the properties and conductivity of poly(methyl methacrylate)/polyaniline (PMMA/PANi) copolymer has been investigated. Different polymerization times, such as 1 h, 2 h, and 3 h, have been employed during free radical copolymerization of PMMA/PANi copolymer. The properties of newly synthesized PMMA/PANi copolymer were discussed with the help of Fourier transform infrared (FTIR), 1H nuclear magnetic resonance (NMR) spectroscopies, UV-Vis spectroscopy, and transmission electron microscopy. All copolymers showed electrical conductivity of a semi-conductor material, compared with PMMA itself. It was found that the reaction played a significant role, especially at optimum polymerization time, where PANi formation and conductivity was at its highest. Our present work demonstrates that copolymer film could be a promising material to fabricate polymer conducting film in many electronics applications.

Reflectance-enhanced liquid crystal displays and thermochromic multi-color patterning

This paper presents a reflective liquid crystal display (LCD) combined with thermochromic liquid crystal microcapsules to enhance the electro-optical performance of the LCD and to empower new driving modes. The prepared reflectance-enhanced liquid crystal display (Re-LCD) possesses a bilayer structure, with the upper layer being a polymer-stabilized liquid crystal layer prepared by UV-induced phase separation and the lower layer being a thermochromic layer prepared by coating with thermochromic liquid crystal microcapsules. The effect of chiral compound content on the reflection wavelength of liquid crystal center was investigated. After that, the effects of monomer ratio, polymerization time and spin coating speed on the electro-optical properties and morphology of Re-LCD were investigated comprehensively by three sets of experiments. The results show that the combination of LCD and thermochromic materials has a synergistic effect in display, and the prepared Re-LCD shows more than 51% reflectance compared with typical LCD. The multi-field driving function allows the Re-LCD to rapidly switch optical states by force, electric, and temperature fields and obtain multi-color patterns during the driving process. This provides new application possibilities for LCD.

Polypyrrole and cotton fabric‐based flexible micro‐supercapacitors

AbstractWith the development of wearable electronic devices, there has been extensive research interest in portable energy supply systems. In this study, traditional cotton fabrics are finished with a water repellent coating and a single‐sided polyurethane (PU) coating to impart hydrophobicity. The hydrophobic lightweight cotton fabric can float on the surface of the pyrrole polymerization system solution. With increasing polymerization time, the pyrrole continues to polymerize and deposit on the side in contact with the fabric, resulting in a one‐sided conductive fabric. The highest doping level was obtained for the polypyrrole (PPy) coating for polymerization time of 12 h. For PPy coating thickness of 18 μm, the square resistance was as low as 220 Ω/sq. The PPy‐12 fabric electrode showed excellent electrochemical performance and cycling stability. An interdigitated pattern was etched on the surface of the one‐sided conductive fabric (PPy‐12) using a N, N‐dimethylformamide solution. Fabric micro‐supercapacitors were obtained by assembling with a H2SO4/PVA gel electrolyte. The fabric micro‐supercapacitor exhibited good flexibility and electrochemical energy storage properties. For current density of 0.08 mA/cm2 and power density of 19.1 μW/cm2, the energy density of the device was 0.09 μWh/cm2. After 3000 cycles, the micro‐supercapacitor retained approximately 85% of the capacitance. Thus, fabric‐based flexible micro‐supercapacitors have excellent application potential in the field of energy storage.

Structural characteristics and opto-electrical properties of in-situ synthesized polyaniline films

In the present study, polyaniline (PAni) thin films have been deposited on glass substrates by in-situ chemical polymerization method using simple dip-coating technique and their opto-electrical properties have been studied. The structure of deposited films have been analysed with Fourier transform infrared (FTIR) and Raman spectroscopic techniques to investigate the effect of deposition times on the conjugation length, polaron/bipolaron concentrations and other molecular structure conformations. FTIR and Raman spectroscopy studies reveal increase in both the conjugation length and the polaron/bipolaron carrier concentration with increasing deposition time of the prepared PAni films. The optical properties and optical band-gap of the deposited films have been estimated through UV–visible spectroscopy. The optical band-gap of the deposited films has been found to decrease from 3.31 eV to 3.13 eV with increase in deposition time from 1.5 h to 2.5 h, and further it has been increased slightly to 3.19 eV for the PAni film deposited for 3 h. The electrical conductivity of the deposited films has been found to increase with decrease in optical band gap. The parameters estimated from FTIR, Raman, UV–visible spectroscopy and electrical measurements are in good agreement with each other. It has been observed that the optical and electrical properties of the deposited films depend on the conjugation length of PAni. The polymerization time of 2.5 h has been found to be optimum for obtaining PAni thin films with good electrical conductivity and low optical band gap.

Study of the effects of drinking water treatment sludge on the properties of Class F fly ash-based geopolymer.

Drinking water treatment sludge (DWTS) generated from water treatment plants is a global issue because of the environmental risks it imposes. Managing the abundance of DWTS in landfills remains an important issue. The reuse of these sludges as a construction material could contribute to the development of a geopolymer and mitigate the harmful effects of the excessive production of these sludges on the environment. This study aims to evaluate the effect of DWTS on the properties of Class F fly ash (FFA) geopolymers. Seven geopolymer blends were made with the addition of DWTS in the total fly ash weight of 0%, 5%, 10%, 15%, 20%, 30%, and 40%, and with an alkaline solution composed of 12M sodium hydroxide (NaOH) and sodium silicate (Na2SiO3) solution; the liquid/solid and (Na2SiO3)/NaOH weight ratios were set to 0.75 and 2.5 respectively. The polymerization temperature was set at 60°C and different polymerization times such as 3, 7, 14, and 28days were considered. The bulk density, apparent porosity, compressive strength, and microstructure of the geopolymer samples were tested. The experimental results revealed that the optimum percentage of DWTS incorporation is 20 wt%, which generates a dense and homogeneous microstructure. The addition of more than 20% DWTS decreased the compressive strength from 40.87 to 35.3MPa and bulk density from 2.134 to 2.087g/cm3 due to the retention of air bubbles and evaporation of water during the polymerization process forming voids in the matrix, which results in increased apparent porosity from 19 to 22%. This investigation confirmed the feasibility of incorporating DWTS into FFA-based geopolymers.

Statistical analysis of parameters involved in the synthesis of polar copolymers using a nickel (II) α-diimine complex

In this article, the copolymerization of 1-hexene and butyl acrylate in the presence of a nickel(II) complex (α-diimine nickel (II) catalyst consisting of bulky 2,6-di (isopropyl) phenyl groups as imine substituents and a planar acenaphthyl backbone) as catalyst and methylaluminoxane (MAO) or ethylaluminum sesquichloride (EASC) as activators has been investigated. The main aim of this article is to provide a deep investigation of the effect of the type of activator, polymerization time, temperature, and comonomer content in the reactor feed on activity, comonomer incorporation, and molecular weight of resulting copolymers. Then, a nonlinear regression method was used to fit analytical results to a numeric model, which is very useful for predicting the properties of the final copolymers only by having the polymerization parameters.

Dual Function of β-Hydroxy Dithiocinnamic Esters: RAFT Agent and Ligand for Metal Complexation.

The reversible addition-fragmentation chain-transfer (RAFT) process has become a versatile tool for the preparation of defined polymers tolerating a large variety of functional groups. Several dithioesters, trithiocarbonates, xanthates, or dithiocarbamates have been developed as effective chain transfer agents (CTAs), but only a few examples have been reported, where the resulting end groups are directly considered for a secondary use besides controlling the polymerization. Herein, it is demonstrated that β-hydroxy dithiocinnamic esters represent a hitherto overlooked class of materials, which are originally designed for the complexation of transition metals but may as well act as reversible CTAs. Modified with a suitable leaving group (R-group), these vinyl conjugated dithioesters indeed provide reasonable control over the polymerization of acrylates, acrylamides, or styrene via the RAFT process. Kinetic studies reveal linear evolutions of molar mass with conversion, while different substituents on the aromatic unit has only a minor influence. Block extensions prove the livingness of the polymer chains, although extended polymerization times may lead to side reactions. The resulting dithiocinnamic ester end groups are still able to form complexes with platinum, which verifies that the structural integrity of the end group is maintained. These findings open a versatile new route to tailor-made polymer-bound metal complexes.

Conductive Microneedle Patch with Electricity-Triggered Drug Release Performance for Atopic Dermatitis Treatment.

Atopic dermatitis (AD) is a chronic inflammatory skin disease that seriously affects the life quality of patients. Topical administration of glucocorticoids is considered to be the most effective anti-inflammatory treatment. However, due to the barrier function of skin, only less than 20% of topical drug molecules could diffuse into the skin. Therefore, it is of great importance to develop an effective strategy to improve AD therapy. In this study, we reported a two-electrode microneedle patch (t-EMNP) composed of a polylactic acid-platinum (PLA-Pt) MN array and polylactic acid-platinum-polypyrrole (PLA-Pt-PPy) MN array for improving the transdermal drug delivery efficacy. The drug loading capability of MNs could be altered by employing different polymerization times and drug concentrations. The drug release rate of MNs could be changed by applying different voltages. We further developed a controlled transdermal drug delivery system (c-TDDS) based on this two-electrode microneedle patch (t-EMNP), exhibiting the remarkable performance of the electricity-triggered drug release profile. The drugs could be released with electrical stimulation, while there was almost no drug release without electrical stimulation. For AD treatment in vivo, this MN patch with electricity-triggered drug release performance could effectively deliver more drugs into the skin compared with other controls such as dexamethasone cream, which efficiently alleviate AD. In sum, this work not only developed a smart patch for improving AD treatment but also provided a promising approach of transdermal drug delivery on demand.

Barbier Hyperbranching Polymerization-Induced Emission from an AB-Type Monomer.

Luminescent polymer materials have gained considerable research efforts in the past decades and are generally molecular designed by extending the π system of the polymer main chain or by incorporating chromophores into the polymer chain, which suffer from poor solubility, difficult synthesis, or multi-step procedures. Meanwhile, according to the step-growth polymerization theory, synthesis of hyperbranched polymers from an AB-type monomer is still challenging. Herein, we report a one-pot synthesis of nonconjugated luminescent hyperbranched polymer material via Barbier hyperbranching polymerization-induced emission (PIE) from an AB-type monomer. The key step in the realization of the hyperbranched polymer is bi-functionalization of a mono-functional group. Through a Barbier reaction between an organohalide and an ester group in one pot, bi-functionalization of mono-functional ester is realized through two-step nucleophilic additions, resulting in hyperbranched polytriphenylmethanols (HPTPM). Attributed to through-space conjugation and inter- and intramolecular charge-transfer effects induced by polymer chain, nonconjugated HPTPMs are PIEgens, which are tunable by monomer structure and polymerization time. When all phenyl groups are rotatable, HPTPM is aggregation-induced emission type PIEgen. Whereas, it is aggregation-caused quenching type PIEgen if some phenyl groups are rotation forbidden. Further potential applications of PIEgen are in the fields of explosive detection and artificial light harvesting systems. This work, therefore, expands the monomer library and molecular design library of hyperbranched polymers through "bi-functionalization of mono-functional group" strategy, which eventually expands the preparation library of nonconjugated luminescent polymer materials through one-pot PIE from nonemissive monomer.

Surface Characteristics and Formation of Polyserotonin Thin Films for Bioelectrical and Biocompatible Interfaces.

In this study, we examined the fundamental surface characteristics of a polyserotonin (pST) film, which is attractive as a bioelectrical and biocompatible interface of biosensors. The pST film can easily be modified on electrode materials such as Au by self-polymerization and electropolymerization. By a simple cytotoxicity test using nonadhesive living cells, we found that the pST film is biocompatible for culturing cells on it. This finding is also supported by the fact that the surface tension of the pST film is moderate for protein adsorptions. The pST film is thinner and smoother than a poly-dopamine film, the chemical structure of which is similar to that of the pST film, depending on the polymerization time, cycle, and temperature; thus, ST as the main monomer can facilitate the precise control of the thickness and roughness of functional polymer membranes on the nanometer order. In addition, the pST film is useful as a relatively insulative interface for preventing interfering species from approaching electrode surfaces without their nonspecific adsorption, depending on the surface charges of the pST film in solutions of different pHs. The formation of the pST film self-polymerized on electrode materials is derived from the adsorption of pST nanoparticles formed by oxidative polymerization under basic conditions; therefore, the process of pST film formation should be considered in the functionalization of the pST film as a bioelectrical interface that allows biomolecular recognition (e.g., molecularly imprinted polymer membrane) for its application to wearable and biocompatible biosensors.

Role of Surface Enhancement in the Enzymatic Cross-Linking of Lignosulfonate Using Alternative Downstream Techniques.

Lignosulfonate (LS), one of the byproducts of the paper and pulp industry, was mainly used as an energy source in the last decade until the valorization of lignin through different functionalization methods grew in importance. Polymerization using multicopper oxidase laccase (from the Myceliophthora thermophila fungus) is one of such methods, which not only enhances properties such as hydrophobicity, flame retardancy, and bonding properties but can also be used for food and possesses pharmaceutical-like antimicrobial properties and aesthetic features of materials. Appropriate downstream processing methods are needed to produce solids that allow the preservation of particle morphology, a vital factor for the valorization process. In this work, an optimization of the enzymatic polymerization via spray-drying of LS was investigated. The response surface methodology was used to optimize the drying process, reduce the polymerization time, and maximize the dried mass yield. Particles formed showed a concave morphology and enhanced solubility while the temperature sensitivity of spray-drying protected the phenol functionalities beneficial for polymerization. Using the optimized parameters, a yield of 65% in a polymerization time of only 13 min was obtained. The experimental values were found to be in agreement with the predicted values of the factors (R2: 95.2% and p-value: 0.0001), indicating the suitability of the model in predicting polymerization time and yield of the spray-drying process.

Synthesis and property of EPEG‐based polycarboxylate ether superplasticizers via RAFT polymerization

AbstractPolycarboxylate ether superplasticizers (PCEs) with comb‐shaped molecular structures have attracted considerable attention in the area of admixtures for construction engineering. However, there are some contradictions in studying the relationship between the molecular structure and property of PCE due to its random structure based on traditional free radical polymerization, which is confused for designing and developing novel PCEs. In this article, a series of reversible addition fragmentation chain transfer (RAFT) polymerization‐based polycarboxylate ether superplasticizers (RPCs) were prepared by the copolymerization of acrylic acid (AA) and ethylene‐glycol monovinyl polyethylene glycol (EPEG). The chemical structure and composition of RPCs were characterized and their adsorption behavior and dispersion properties were conducted. The results demonstrate that the molecular weights of RPCs do not vary significantly with prolonging reaction time, and the actual monomer ratio in RPCs displays a significant change to the feed one due to the monomer reactivity and conversion at higher reaction temperature, which is different from conventional free radical polymerization. The dispersion and adsorption properties of RPCs to cement were evaluated by slurry fluidity tests and total organic carbon (TOC) experiments. The effect of polymerization temperature and time on the dispersion ability has been systematically studied. The results indicate that the dispersion ability and adsorption capacity of RPCs are closely related to their molecular structures. The dispersion ability of RPCs were enhanced with increasing carboxyl group density in a certain range of monomer molar ratios (≤6:1). This study will provide a new platform for designing and developing high‐performance and rational cost‐effective superplasticizers with well‐defined structure and controlled molecular weight.

Synthesis and characterization of star-shaped block copolymers composed of poly(3-hydroxy octanoate) and styrene via RAFT polymerization

This study investigated a macro reversible addition fraction chain transfer (RAFT) agent based on three-arm hydroxylated star-shaped poly(3-hydroxy octanoate). The utilization of this star-shaped poly(3-hydroxy octanoate) macro-RAFT agent in the RAFT process resulted in efficient control in the preparation of star-shaped block styrene copolymers. Poly(3-hydroxy octanoate) (PHO) was reacted with diethanol amine (DEA) in order to obtain three-arm hydroxylated poly(3-hydroxy octanoate) (PHO-DEA). A carboxylic acid-functionalized RAFT agent (2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid) was reacted with the PHO-DEA in order to obtain a star-shaped PHO macro-RAFT agent (PHO-R2). A series of AB3 type PHO-polystyrene (PHO-PS) star-shaped block copolymers were obtained via the polymerization of styrene (S) using the PHO-R2 in toluene at 80 °C. The RAFT polymerization was seen to obey the polymerization kinetics of controlled free radical polymerization. The plasticizing effect of the PHO soft segments was influenced by the glass transition temperature (Tg) of polystyrene. This was clearly observed in the block copolymers. Moreover, it was clear that this plasticizing effect disappeared in the block copolymers as a result of the increase in polymerization time. The molar masses of the obtained copolymers increased in parallel with increases in the polymerization time. Structural, physiochemical, and thermal characterization of the obtained products was carried out using size-exclusion chromatography (SEC), proton nuclear magnetic resonance (1H NMR), differential scanning calorimetry (DSC), and thermal gravimetric analysis (TGA) techniques. The polymerization kinetics of the star-shaped block copolymers were also investigated in detail.