‘Living’ radical polymerization of styrene mediated by spiro ring-substituted piperidinyl-N-oxyl radicals. The effect of the spiro rings on the control of polymerization

The bulk radical polymerizations of styrene (St) at 80-120 °C in the presence of 6-aza-7,7-dimethyl-9-hydroxyspiro[4.5]decane-6-yloxyl (1) and 1-aza-2,2-dimethyl-4-hydroxy[5.5]undecane-1-yloxyl (2) were studied. At 100 and 120 °C, the polymerizations were well controlled by those nitroxides to give poly(St)s with narrow polydispersities. On the other hand, the polymerization mediated by 2 at 80 °C showed a good ‘livingness’ of polymerization, but 1 had a poor ability to control the polymerization to give poly(St) with a broad polydispersity of 1.52. The rate constants (k_act) for the homolysis of the NO-C bond of the alkoxyamines prepared from 1 and 2 were measured at 333-373 K, and the A_acts and E_acts values were determined to be 2.8×10¹³ s⁻¹ and 128 kJ mol⁻¹ (1) and 4.0×10¹³ s⁻¹ and 125 kJ mol⁻¹ (2), respectively, from the Arrhenius plots. These results are compared with those for the structurally related piperidinyl-N-yloxyl radicals including TEMPO.     

A new fast methodology to measure total diene content in gasoline

The rate constants for the quenching of biacetyl phosphorescence by a series of conjugated dienes were measured. 1,3-cyclohexadiene (k_qP = 2.94 × 10⁹ s⁻¹ mol⁻¹ L), 2,5-dimethyl-2,4-hexadiene (k_qP = 1.91 × 10⁹ s⁻¹ mol⁻¹ L), 2,4-dimethyl-1,3-pentadiene (k_qP = 1.78 × 10⁸ s⁻¹ mol⁻¹ L), 3-methyl-1,3-pentadiene (k_qP = 1.22 × 10⁸ s⁻¹ mol⁻¹ L), 2,4-hexadiene (k_qP = 1.35 × 10⁸ s⁻¹ mol⁻¹ L) and trans-2-methyl-1,3-pentadiene (k_qP = 3.84 × 10⁸ s⁻¹ mol⁻¹ L). Cyclooctene also quenched biacetyl phosphorescence but with a lower rate (k_qP = 1.97 × 10⁷ s⁻¹ mol⁻¹ L). Quenching was not observed with 1-methylnaphthalene. Since conjugated dienes quench biacetyl phosphorescence preferentially, this method was studied using gasoline samples with known diene composition. A good correlation was found between the rate of quenching of biacetyl by the gasoline samples and the quantity of conjugated dienes present.     

Free-radical propagation and termination kinetics of the butyl acrylate dimer studied by pulsed laser polymerization techniques

The propagation and termination rate coefficients for bulk polymerization of the butyl acrylate dimer (BA dimer) are determined by pulsed laser techniques. The rate coefficient for propagation, k_p, is deduced for temperatures from 20 to 90 °C via the pulsed laser polymerization-size exclusion chromatography (PLP-SEC) method at pulse repetition rates between 1 and 10 Hz. The Arrhenius parameters were found to be: E_A(k_p) = (34.2 ± 1.0) kJ mol⁻¹ and A(k_p)/L mol⁻¹ s⁻¹ = (1.08 ± 0.49) × 10⁷ L mol⁻¹ s⁻¹. The termination rate coefficient, k_t, has been measured via SP-PLP-ESR, single pulse-pulsed laser polymerization in conjunction with time-resolved electron spin resonance detection of radical concentration. The resulting Arrhenius parameters as deduced from the temperature range −15 to +30 °C are: E_A(〈k_t〉) = (22.8 ± 3.7) kJ mol⁻¹ and log(A/L mol⁻¹ s⁻¹) = 10.6 ± 1. The chain-length dependence of k_t was studied at 30 °C. For short chains a significant dependence was found which may be represented by an exponent α = 0.79 in the power-law expression k_t(i) = k_t⁰i^−α.     

Living radical polymerization of styrene mediated by a piperidinyl-N-oxyl radical having very bulky substituents

A new cyclic nitroxide 1 and the corresponding alkoxyamines 9 and 10 were synthesized and the polymerization of styrene (St) initiated with 10 was investigated. The NO-C bond of 9 is very weak, cleaving at room temperature. On the other hand, alkoxyamine 10 is stable at room temperature and the A_act and E_act for the NO-C bond homolysis were determined to be 1.4 × 10¹⁵ s⁻¹ and 124.5 kJ mol⁻¹, respectively. When the polymerization of St was carried out at 70 °C, the resultant poly(St) showed narrow polydispersities below 1.25. In the polymerization at 90 °C, the resulting poly(St) showed narrow polydispersity until 60% conversion, but M_w/M_n was rapidly increased above 60% conversion. On the other hand, the polymerization at 120 °C gave poly(St) with broad polydispersities. The unusual polymerization behavior was discussed on the basis of the SEC and ESR results.     

Kinetics and selectivity of asphaltene hydrocracking

Thermal hydrocracking and catalytic hydrocracking over NiMo/γ-Al₂O₃ of a pentane-insoluble asphaltene were conducted in a microbatch reactor at 430 °C. The experimental data of asphaltene conversion fit second-order kinetics adequately, to give the apparent rate constants of 2.435 × 10⁻² and 9.360 × 10⁻² wt frac⁻¹ min⁻¹ for the two processes respectively. A three-lump kinetic model is proposed to evaluate rate constants of parallel reactions from asphaltenes to liquid oil (k₁) and to gas + coke (k₃), and consecutive reaction from liquid to gas + coke (k₂). The evaluated k₁ is 2.430 × 10⁻² and 9.355 × 10⁻² wt frac⁻¹ min⁻¹, k₂ is 2.426 × 10⁻² and 6.347 × 10⁻³ min⁻¹, and k₃ is 5.416 × 10⁻⁵ and 4.803 × 10⁻⁵ wt frac⁻¹ min⁻¹ for asphaltenes hydrocracking in the presence or absence of the catalyst, respectively. Analysis of selectivity shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.     

Kinetics of asphaltene thermal cracking and catalytic hydrocracking

A pentane-insoluble asphaltene was processed by thermal cracking and catalytic hydrocracking over NiMo/γ-Al₂O₃ in a microbatch reactor at 430 °C. Kinetic analysis shows that the first-order kinetics fits the data of conversion in reaction times ≤ 30 min approximately, but deviates from the data of times over 30 min significantly; whereas the second-order kinetics fits the data of the reaction times up to 60 min adequately, to give the apparent rate constants of 1.704 × 10⁻² and 9.360 × 10⁻² wt frac⁻¹min⁻¹ for the two cracking processes. Furthermore, a three-lump kinetic model is proposed to include parallel reactions of asphaltenes to produce liquid oil (k₁) and gas + coke (k₃), and consecutive reaction from liquid to gas + coke (k₂). The evaluated value of k₁ is 1.697 × 10⁻² and 9.355 × 10⁻² wt frac⁻¹min⁻¹, k₂ is 3.605 × 10⁻² and 6.347 × 10⁻³ min⁻¹ , and k₃ is 6.934 × 10⁻⁵ and 4.803 × 10⁻⁵ wt frac⁻¹min⁻¹ for asphaltenes thermal cracking and catalytic hydrocracking, respectively. Selectivity analysis shows that the catalytic hydrocracking process promotes liquid production and inhibits coke formation effectively.     

Living and block polymerization of α-olefins using a Ni(II)-α-diimine catalyst containing OSiPh2Bu groups

A new siloxy-substituted α-diimine compound and its corresponding Ni(II) complex, {bis[N,N′-(4-tert-butyl-diphenylsiloxy-2,6-dimethylphenyl)imino]acenaphthene}dibromonickel (6), were successfully synthesized and the molecular structure of 6 characterized by X-ray crystallography. The precatalyst 6 activated by methylaluminoxane (MAO) or diethylaluminum chloride (DEAC) was tested in the polymerization of ethylene, showed to be highly active (e.g. 2.2×10⁷ and 1.8×10⁷ g polymer (mol Ni.h.bar)⁻¹, respectively) and led to a branched polyethylene (ca. 35-55 branches/1000 C). The catalyst system 6/methylaluminoxane (MAO) catalyzes, at −11 °C, living polymerization of propylene, to a polypropylene showing a syndiotactic-rich microstructure (P_r=0.74). 1-Hexene was also successfully polymerized via a living process, both at −11 and +16 °C. The ¹³C NMR spectra of the poly(1-hexene)s obtained at room temperature show a microstructure almost exclusively composed by n-butyl and methyl branches, the latter being present in a much higher number. Diblock polypropylene-block-poly(1-hexene) and triblock poly(1-hexene)-block-poly(propylene-ran-1-hexene)-block-poly(1-hexene) copolymers have also been synthesized and characterized by GPC/SEC, DSC and NMR.     

The kinetic evidence for the formation of multiple active species in a bis(phenoxy-imine) zirconium dichloride/MAO catalyst during ethylene polymerization

The effects of polymerization time and temperature on the molecular weight and molecular weight distribution of polyethylene, produced over homogeneous catalyst bis[N-(3-tert-butyl salicylidene)anilinato]zirconium(IV) dichloride ^tBu-L₂ZrCl₂/MAO have been studied. The data on the number of active centers (C_P) and propagation rate constants (k_P) at different polymerization time have been obtained as well. It was found that at a short polymerization time two types of active centers, producing low molecular weight PE (M_w = (4-10) × 10³ g mol⁻¹) are formed. The number of these centers was estimated to be 11% of total zirconium complex and their reactivity is very high (the k_P value was found to be 54 × 10³ L mol⁻¹ s⁻¹ at 35 °C). High initial activity of the catalyst fell with the increase in polymerization time, whereas the polydispersity values of the resulting PE increase due to formation of new centers, producing high molecular weight PE (M_w = (30-1300) × 10³ g mol⁻¹). It was found that the decrease in activity is caused by reducing the initial active centers number and lower reactivity of the new-formed centers (k_P = 17 × 10³ L mol⁻¹ s⁻¹).     

The ultrasonic electropolymerization of an 5-[o-(4-bromine amyloxy)phenyl]-10,15,20-triphenylporphrin (o-BrPETPP) film electrode and its electrocatalytic properties to dopamine oxidation in aqueous solution

5-[o-(4-Bromine amyloxy)phenyl]-10,15,20-triphenylporphrin (o-BrPETPP) was electropolymerized on a glassy carbon electrode (GCE), and the electrocatalytic properties of the prepared film electrode response to dopamine (DA) oxidation were investigated. A stable o-BrPETPP film was formed on the GCE under ultrasonic irradiation through a potentiodynamic process in 0.1 M H₂SO₄ between −1.1 V and 2.2 V versus a saturated calomel electrode (SCE) at a scan rate of 0.1 V s⁻¹. The film electrode showed high selectivity for DA in the presence of ascorbic acid (AA) and uric acid (UA), and a 6-fold greater sensitivity to DA than that of the bare GCE. In the 0.05 mol L⁻¹ phosphate buffer (pH 6.0), there was a linear relationship between the oxidation current and the concentration of DA solution in the range of 5 × 10⁻⁷ mol L⁻¹ to 3 × 10⁻⁵ mol L⁻¹. The electrode had a detection limit of 6.0 × 10⁻⁸ mol L⁻¹(S/N = 3) when the differential pulse voltammetric (DPV) method was used. In addition, the charge transfer rate constant k = 0.0703 cm s⁻¹, the transfer coefficient α = 0.709, the electron number involved in the rate determining step n_α = 0.952, and the diffusion coefficient D_o = 3.54  10⁻⁵ cm² s⁻¹ were determined. The o-BrPETPP film electrode provides high stability, sensitivity, and selectivity for DA oxidation.     

Effect of Zr/Ti ratio on piezoelectric properties of Pb(Ni1/3Sb2/3)O3-Pb(ZrTi)O3 ceramics

Piezoceramic compositions [Pb(Ni_1/3Sb_2/3)]_0.02-[Pb(Zr_1−yTi_y)]_0.98O₃ with y = 0.46-0.50 were synthesized by solid state route to study the effect of Zr/Ti ratio on crystal structure, microstructure, piezoelectric and dielectric properties. Calcination was performed at 1060 °C. The specimens were sintered at 1280 °C for 1 h. X-ray diffraction studies indicate the co-existence of tetragonal and rhombohedral perovskite phases in these compositions. Microstructural analysis showed the dense and uniform microstructure for [Pb(Ni_1/3Sb_2/3)]_0.02-[Pb(Zr_0.52Ti_0.48)]_0.98O₃. This composition was resulted in optimum values of properties viz. charge constant (d₃₃ = 301 × 10⁻¹² C/N), voltage constant (g₃₃ = 33.7 × 10⁻³ V m/N), product of piezoelectric charge constant and voltage constant (d₃₃ × g₃₃ = 10.12 × 10⁻¹² C V m/N²) and coupling factor (k_p = 0.63). Results indicated that this material composition could be suitable for power harvesting and sensor applications.     

Poly(phenylacetylene) with bulky chiral germyl groups: synthesis and effects of measuring solvents and temperature on chiroptical properties

(+)-p-[{Methyl(1-naphthyl)phenyl}germyl]phenylacetylene, an acetylene with a bulky chiral germyl group, was polymerized with [(nbd)RhCl]₂-Et₃N to give a high-molecular-weight polymer in good yield. The CD spectrum of the polymer exhibited very large molar ellipticities [θ] in the UV region in non-aromatic solvents (e.g. THF and CHCl₃). In contrast, the CD signals of the polymer in aromatic solvents (e.g. toluene, tetralin, and benzene) became appreciably smaller: [θ]_max=6.4×10⁴ (330 nm) and −4.7×10⁴° cm² dmol⁻¹ (370 nm) in CHCl₃; [θ]_max=1.1×10⁴ (330 nm) and −0.7×10⁴° cm² dmol⁻¹ (370 nm) in toluene. The [θ]_max values of the polymer in aromatic solvents increased when the solutions were heated, which is attributed to decreased π-π interaction between the solvents and side groups.     

The effect of cytosine on the two-step electroreduction of Zn ions in acetic buffers

Cytosine plays an important role in many biological processes since it constitutes the buildings blocks of DNA and RNA. A two-step reduction of Zn²⁺ ions at the dropping mercury electrode in acetic buffers at pH 4 and 5 in the presence of cytosine was examined. The measurements were performed using an impedance method in a wide potential and frequency ranges.The values of the standard rate constants k_s in the both studied system decrease from 3.8 × 10⁻³ to 2 × 10⁻³ cm s⁻¹ at pH 4 and from 5.1 × 10⁻³ to 2.5 × 10⁻³ cm s⁻¹ at pH 5. The values of the standard rate constants k_s1 characterizing the stage of the first electron transfer decrease similarly. However, the values of the standard rate constants k_s2 characterizing the stage of the second electron exchange decrease more markedly in the buffer at pH 4 than in the buffer at pH 5.     

Electrochemical study of stable N-alkoxyarylaminyl radicals

The electrochemical study of N-tert-butoxy-2,4-diphenyl-6-tert-butylphenylaminyl (1a), N-tert-butoxy-2,4-bis(4-chlorophenyl)-6-tert-butylphenylaminyl (1b), N-[2-(methoxycarbonyl)-2-propyl]-2,4-diphenyl-6-tert-butylphenylaminyl (2), and N-tert-butoxy-2,4,6-tris(4-chlorophenyl)phenylaminyl radicals (3) was performed by cyclic voltammetry using acetonitrile as the solvent and Bu₄NPF₆ as the supporting electrolyte. On cathodic scan (100 mV/s), all the radicals gave chemically reversible cyclic voltammograms, and the were determined to be −1.405 V (1a), −1.310 V (2a), −1.282 V (2b), and −1.195 V (3) (versus Fc⁺/Fc), respectively. On anodic scan (100 mV/s), on the other hand, 1a, 1b and 2 showed chemically reversible cyclic voltammograms, but 3 exhibited a partially reversible couple even on a scan rate of 500 mV/s, indicating that the cation species of 3 was less stable. The determined for 1a, 1b, 2 and 3 were 0.220, 0.280, 0.318 and 0.294 V (versus Fc⁺/Fc), respectively. The electrochemical data were compared with those of thioaminyl radicals, the corresponding sulfur analogues of 1-3.     

Surface-initiated nitroxide-mediated radical polymerization of 2-(dimethylamino)ethyl acrylate on polymeric microspheres

2-(Dimethylamino)ethyl acrylate (DMAEA) was grafted from the surface of alkoxyamine-functionalized crosslinked poly(styrene-co-chloromethylstyrene) microspheres by nitroxide-mediated radical polymerization (NMRP). Latex particles (∼60 nm diameter) bearing chloromethyl groups were synthesized by emulsion polymerization. N-tert-butyl-N-(1-diethyl phosphono-2,2-dimethylpropyl)nitroxide (SG1) was then immobilized on the particle surface. Microspheres grafted with the homopolymer pDMAEA, as well as block copolymers poly(styrene-b-DMAEA) and poly(butyl acrylate-b-DMAEA) were prepared by surface-initiated NMRP in N,N-dimethylformamide at 112 °C, with the addition of free SG1 to ensure that control is maintained. Particle size increases with number average molecular weight (M_n) of untethered polymers. The polymerizations exhibit linear first order kinetic plots and slight curvature of evolution of M_n with conversion. The functional microspheres were analyzed by infrared spectroscopy, transmission electron microscopy and thermal analysis, as well as their dispersibility in water; the results support the formation of surface-grafted pDMAEA on the microspheres.     

Amphiphilic block copolymers bearing strong push-pull azo chromophores: Synthesis, micelle formation and photoinduced shape deformation

In this work, a series of amphiphilic diblock copolymers bearing strong push-pull type azo chromophores was synthesized through post-polymerization azo-coupling reaction scheme. The copolymers (P(CNAZO_m-b-MAA_n)), composed of 2-(N-ethyl-N-(4-(4′-cyanophenylazo)-phenyl)amino)ethyl methacrylate (CNAZO) and methacrylic acid (MAA) blocks, were obtained through four-step reactions. Firstly, precursor diblock copolymers (P(EMA_m-b-tBMA_n)) were obtained through sequential two-stage ATRP reactions of 2-(N-ethyl-N-phenylamino)ethyl methacrylate (EMA) and tert-butyl methacrylate (tBMA). Then, 4-amino-4′-cyanoazobenzene chromophores were introduced by azo-coupling reaction of P(EMA_m-b-tBMA_n) with diazonium salt of 4-aminobenzonitrile. Finally, P(CNAZO_m-b-MAA_n) was obtained through selective hydrolysis of the tert-butyl ester linkages in the tBMA blocks. Three block copolymers with the same CNAZO block length (m = 100) and different MAA block lengths (n = 5, 13, 23) were prepared by this method. The polymer and copolymers prepared in the process were characterized by GPC, ¹H NMR, UV-vis, DSC and TGA measurements. Results show that P(CNAZO_m-b-MAA_n) forms spherical micellar aggregates by gradually increasing the water content in THF/H₂O mixtures. The diameters of the spherical aggregates are related to the composition of the block copolymers and the water-adding rate. The block copolymer with larger molecular weight of the hydrophilic MAA block forms the aggregates with the smaller average size. The increase of the water-adding rate also shows an effect to reduce the diameters. Upon irradiation with a linearly polarized Ar⁺ laser beam, the spherical aggregates can be elongated in the light polarization direction. The deformation degree shows an almost linear dependence on the light irradiation time in the testing period. The deformed aggregates can recover the original spherical shape after thermal annealing at a temperature above T_g of the block copolymer.     

Kinetic study of hydrogen sulfide absorption in aqueous chlorine solution

Hydrogen sulfide (H₂S) is currently removed from gaseous effluents by chemical scrubbing using water. Chlorine is a top-grade oxidant, reacting with H₂S with a fast kinetic rate and enhancing its mass transfer rate. To design, optimize and scale-up scrubbers, knowledge of the reaction kinetics and mechanism is requested. This study investigates the H₂S oxidation rate by reactive absorption in a mechanically agitated gas–liquid reactor. Mass transfer (gas and liquid sides mass transfer coefficients) and hydrodynamic (interfacial area) performances of the gas–liquid reactor were measured using appropriated physical or chemical absorption methods. The accuracy of these parameters was checked by modeling the H₂S absorption in water without oxidant. A sensitivity analysis confirmed the robustness of the model. Finally, reactive absorption of H₂S in chlorine solution for acidic or circumneutral pH allowed to investigate the kinetics of reaction. The overall oxidation mechanism could be described assuming that H₂S is oxidized irreversibly by both hypochlorite anion ClO⁻ (k = 6.75 × 10⁶ L mol⁻¹ s⁻¹) and hypochlorous acid ClOH (k = 1.62 × 10⁵ L mol⁻¹ s⁻¹).     

Detection of N-methyladenosine in urine samples by electrochemiluminescence using a heated ITO electrode

A sensitive and rapid electrochemiluminescence (ECL) method for the detection of N⁶-Methyladenosine (m6A) in urine samples on a heated indium-tin-oxide (ITO) electrode is presented. The ECL intensity of Tris(2,2′-bipyridyl) dichlororuthenium(II)hexahydrate (Ru(bpy)₃²⁺) can be enhanced by the presence of m6A. Experimental results showed that the change of ECL intensities (ΔI) of the Ru(bpy)₃²⁺ between before and after addition of m6A was affected by the working electrode surface temperature (T_e); the highest ΔI occurred at 31 °C. Under optimum conditions, the ΔI had a linear relationship with the m6A concentration in the range of 1.9 × 10⁻⁹-3.9 × 10⁻⁶ mol/L and a detection limit of 7.7 × 10⁻¹⁰ mol/L (S/N = 3) at T_e = 31 °C. The recovery of m6A standards added to urine samples verified the accuracy of the proposed method.     

Investigation of the intra-particle sintering kinetics of a mainly agglomerated alumina powder by using surface area reduction

An alumina precursor was prepared by the aluminium sulphate (0.20 M) and excess urea reaction in boiling aqueous solution. The precursor was calcined at 900 °C for 2 h and then δ-Al₂O₃ powder having volumetric agglomeration degree of 80% was obtained. Cylindrical compacts having diameter of 14 mm were prepared under 32 MPa by axial pressing using oleic acid as binder. Each compact was fired isothermally at various temperatures between 950 and 1400 °C. The firing time was changed from zero to 2 h. The fired compacts were examined by scanning electron microscopy (SEM) and nitrogen adsorption techniques. The specific surface areas (S/m² g^− 1) of the samples were calculated using the Brunauer, Emmett, and Teller (BET) procedure. The rate constant (k) and mechanism-characteristic parameter (n) were obtained for different temperatures between 950 °C and 1150 °C from the application of the neck-growth sintering rate (NGRM) model on the surface area reduction data. An Arrhenius equation and the parameter n for the sintering were found in the forms of k = (7.648 × 10⁶ h^− 1) exp (− 186,234 J mol^− 1 / RT) and n = 4.0 × 10^− 7 T³-1.7 × 10^− 3 T² + 2.3 T − 1030.8 respectively. The parameter n changes in the interval 0.61 <  n < 1.34 with rising temperature having maximum at about 1025 °C. Based on the SEM images and NGRM data, the intra-particle sintering was discussed.     

Modeling and design of transdermal drug delivery patches containing an external heating device

Process modeling and design concepts were implemented to aid in the manufacturing of heat-enhanced transdermal drug-delivery systems. The simulated prototype consists of a corticosterone-loaded polymer patch applied to the skin and connected to a heating device in which an exothermic reaction occurs. To achieve a desired transdermal flux of 1.2 × 10⁻⁵ mg/cm² h, this contribution focuses on the influences of the (1) initial reaction rate (−r_A0), (2) mass of filler material in the device (m), (3) initial concentration (C₀) of medicament in the patch and (4) overall heat transfer coefficient (U). A regression technique yielded the following results: −r_A0 = 3.000 × 10⁻² kg/m³ s, m = 1.251 × 10⁻⁸ kg, U = 6.124 × 10 J/m² K s and C₀ = 1.966 × 10⁻¹ kg/m³. When m was fixed at 12.5 g, the optimum design required the following specifications: r_A0 = 2.765 × 10⁻² kg/m³ s, U = 1.402 × 10³ J/m² K s and C₀ = 1.941 × 10⁻¹ kg/m³. The priority (S_i) of the input factors (i) in reaching the target delivery rate is: SC₀>S−rA0>Sm>SU.     

RAFT polymerization and self-assembly of thermoresponsive poly(N-decylacrylamide-b-N,N-diethylacrylamide) block copolymers bearing a phenanthrene fluorescent α-end group

Phenanthrene α-end-labeled poly(N-decylacrylamide-b-N,N-diethylacrylamide) (PDcA_n-b-PDEA_m) block copolymers consisting in a highly hydrophobic block (n = 11) and a thermoresponsive block with variable length (79 ≤ m ≤ 468) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization. A new phenanthrene-labeled chain transfer agent (CTA) was synthesized and used to control the RAFT polymerization of a hydrophobic acrylamide derivative, N-decylacrylamide (DcA). This first block was further used as macroCTA to polymerize N,N-diethylacrylamide (DEA) in order to prepare diblock copolymers with the same hydrophobic block of PDcA (number average molecular weight: M_n = 2720 g mol⁻¹, polydispersity index: M_w/M_n = 1.13) and various PDEA blocks of several lengths (M_n = 10,000-60,000 g mol⁻¹) with a very high blocking efficiency. The resulting copolymers self-assemble in water forming thermoresponsive micelles. The critical micelle concentration (CMC) was determined using Förster resonance energy transfer (FRET) between phenanthrene linked at the end of the PDcA block and anthracene added to the solution at a low concentration (10⁻⁵ M), based on the fact that energy transfer only occurs when phenanthrene and anthracene are located in the core of the micelle. The CMC (∼2 μM) was obtained at the polymer concentration where the anthracene fluorescence intensity starts to increase. The size of the polymer micelles decreases with temperature increase around the lower critical solution temperature of PDEA in water (LCST ∼ 32 °C) owing to the thermoresponsiveness of the PDEA shell.