Thermally induced polymerization of isobutylene in the presence of SnCl4: Kinetic study of the polymerization and NMR structural investigation of low molecular weight products

The polymerization reactivity of isobutylene/SnCl₄ mixtures in the absence of polar solvent, was investigated in a temperature interval from −78 to 60 °C. The mixture is nonreactive below −20 °C but slow polymerization proceeds from −20 to 20 °C with the initial rate r₀ of the order 10⁻⁵ mol · l⁻¹ · s⁻¹. The rate of the process increases with increasing temperature up to ∼10⁻² mol · l⁻¹ · s⁻¹ at 60 °C. Logarithmic plots of r₀ and M̄_n versus 1/T exhibit a break in the range from 20 to 35 °C. Activation energy is positive with values E = 21.7 ± 4.2 kJ/mol in the temperature interval from −20 to 35 °C and E = 159.5 ± 4.2 kJ/mol in the interval from 35 to 60 °C. The values of activation enthalpy difference of molecular weights in these temperature intervals are ΔH_Mn = −12.7 ± 4.2 kJ/mol and −38.3 ± 4.2 kJ/mol, respectively. The polymerization proceeds quantitatively, the molecular weights of products are relatively high, M̄_n = 1500–2500 at 35 °C and about 600 at 60 °C. It is assumed that initiation proceeds via [isobutylene · SnCl₄] charge transfer complex which is thermally excited and gives isobutylene radical‐cations. Oxygen inhibits the polymerization from −20 to 20 °C. Possible role of traces of water at temperatures above 20 °C is discussed. It was verified by NMR analysis that only low molecular weight polyisobutylenes are formed with high contents of exo‐ terminal unsaturated structures. In addition to standard unsaturated groups, new structures were detected in the products. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1568–1579, 2000     

Folding thermodynamics of PET-hydrolyzing enzyme Cut190 depending on Ca2+ concentration

The enzyme, cutinase from Saccharomonospora viridis AHK190 (Cut190), can hydrolyze the inner block of polyethylene terephthalate (PET). Cut190 has a unique feature that both its activity and thermal stability are increased upon Ca²⁺ binding. In consideration of the glass transition temperature of PET, which is between 60 and 65 °C, the increased activity and thermal stability are of great interest to apply for PET bio-recycling. Our previous mutational analysis showed that the S226P/R228S mutant (Cut190*) has a higher activity and thermal stability than those of the wild type. In this study, we analyzed the folding thermodynamics of the inactive mutant of Cut190*, Cut190*S176A, using circular dichroism and differential scanning calorimetry. The results show that the denaturation temperature increases from 54 to 71 °C due to the addition of 250 mM Ca²⁺, in a Ca²⁺ concentration-dependent manner. The increased thermal stability is mainly due to the increased enthalpy change, partially compensated by the increased entropy change. Based on the crystal structure of Cut190*S176A bound to Ca²⁺, molecular dynamics simulations were carried out to analyze the effects of Ca²⁺ on the structural dynamics, showing that the Ca²⁺-bound structure fluctuated less than the Ca²⁺-free structure. Structural analysis indicates that Ca²⁺ binding increases the intramolecular interactions of the enzyme, while decreasing its fluctuation, which are in good correlation with the experimental results of the folding thermodynamics.

     

Substituenteneffekte auf die C–C-Bindungsstärke, 8. Standardbildungsenthalpien und Spannungsenthalpien von 1,1,2,2-Tetraethylethylenglykol-dimethylether und D,L-1,2-Dimethyl-1,2-diphenylethylenglykol-dimethylether

Effects of Substituents on the Strength of C - C Bonds, 8¹. - Heats of Formation and Strain of 1,1,2,2-Tetraethylethylene Glycol Dimethyl Ether and D,L .-1,2-Dimethyl-l,2-diphenylethylene Glycol Dimethyl Ether The heats of combustion of the title compounds 1 and 2 were measured calorimetrically with the result (kcal mol ^-1, s. d. in parentheses) ΔH°_c = − 1880.1 (± 0.6) and − 2373.3 (± 1.4). The heat of vaporisation of 1 ΔH^v = 14.3 (± 0.3) and the heat of sublimation of 2 ΔH^sub = 27.2 (± 0.5) were derived from their temperature dependance of the vapor pressure. The latter were determined between 30 and 80°C using a flow method. The resulting standard heats of formation ΔH°_t(g) = −122.4 (± 0.7) and −43.8 (±1.5) for 1 and 2 correspond to a strain enthalpy (_s) of 15.9 and 8.0 kcal mol^-1, respectively. The steric strain of the dimethoxyethanes 1 and 2 is about one fourth lower than the strain of the corresponding dimethylethanes 3 and 4 bearing the same substituents. Thus, a methoxy group causes less steric stress than a methyl group.     

A quantitative LC/MSMS method for determination of edoxaban,a Xa inhibitor and its pharmacokinetic application in patients after total knee arthroplasty

Edoxaban was extracted from human plasma by simple protein precipitation with acetonitrile, followed by quantitative determination using a liquid chromatography–mass spectrometry method. The recoveries of edoxaban and the internal standard (ticlopidine) from human plasma were >85%, and the within‐ and between‐day coefficients of variation were within 15%. The limit of quantification in human plasma was 1 ng/mL. The concentration of edoxaban in blood decreased at room temperature, but remained unchanged for 1 week at 4°C. On the other hand, the concentration in plasma at both −20 and −80°C remained unchanged for 5 months. These results indicated that blood samples should be centrifuged immediately or stored at 4°C, and that plasma samples should be stored below −20°C until analysis. This method was applied to human plasma obtained from four patients after total knee arthroplasty. Analysis of edoxaban pharmacokinetics demonstrated an absorption time lag of 4h, a maximum concentration of 110 ± 26 ng/mL and an oral clearance of 37 ± 16 L/h. The analytical methods established in this study will be suitable for determining the concentrations of edoxaban in human plasma.     

Thermal and electrical properties of Ca5Mg4−xZnx(VO4)6 (0 ≤ x ≤ 4)

Calcium vanadates Ca₅Mg_4−xZn_x(VO₄)₆ (0 ≤ x ≤ 4) have been studied for the first time using a set of high-temperature methods of analysis. The onset of melting process determined from differential scanning calorimetry decreases from 1158 to 881 °C (± 1.5 °C) with increasing of x (dopant’s content). CTE temperature dependence is found to show a hysteresis. Electrical transport properties measured by impedance spectroscopy in air of different humidity are also discussed. The value of electrical conductivity does not depend on air humidity. It is found to equal to 1.5 × 10⁻⁶ S cm⁻¹ at 720 °C for Ca₅Mg₄(VO₄)₆ which is specific for garnet-related crystals.

     

Ethylbenzene solubility,diffusivity, and permeability in poly(dimethylsiloxane)

The pure‐gas sorption, diffusion, and permeation properties of ethylbenzene in poly(dimethylsiloxane) (PDMS) are reported at 35, 45, and 55 °C and at pressures ranging from 0 to 4.4 cmHg. Additionally, mixed‐gas ethylbenzene/N₂ permeability properties at 35 °C, a total feed pressure of 10 atm, and a permeate pressure of 1 atm are reported. Ethylbenzene solubility increases with increasing penetrant relative pressure and can be described by the Flory–Rehner model with an interaction parameter of 0.24 ± 0.02. At a fixed relative pressure, ethylbenzene solubility decreases with increasing temperature, and the enthalpy of sorption is −41.4 ± 0.3 kJ/mol, which is independent of ethylbenzene concentration and essentially equal to the enthalpy of condensation of pure ethylbenzene. Ethylbenzene diffusion coefficients decrease with increasing concentration at 35 °C. The activation energy of ethylbenzene diffusion in PDMS at infinite dilution is 49 ± 6 kJ/mol. The ethylbenzene activation energies of permeation decrease from near 0 to −34 ± 7 kJ/mol as concentration increases, whereas the activation energy of permeation for pure N₂ is 8 ± 2 kJ/mol. At 35 °C, ethylbenzene and N₂ permeability coefficients determined from pure‐gas permeation experiments are similar to those obtained from mixed‐gas permeation experiments, and ethylbenzene/N₂ selectivity values as high as 800 were observed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1461–1473, 2000     

Asymmetric Solvents Regulated Crystallization-Limited Electrolytes for All-Climate Lithium Metal Batteries

Electrolytes that can keep liquid state are one of the most important physical metrics to ensure the ions transfer with stable operation of rechargeable lithium-based batteries at a wide temperature window. It is generally accepted that strong polar solvents with high melting points favor the safe operation of batteries above room temperatures but are susceptible to crystallization at low temperatures (≤−40 °C). Here, a crystallization limitation strategy was proposed to handle this issue. We demonstrate that, although the high melting points of ethylene sulfite (ES, −17 °C) and fluoroethylene carbonate (FEC, ≈23 °C), their mixtures can avoid crystallization at low temperatures, which can be attributed to low intermolecular interactions and altered molecular motion dynamics. A suitable ES/FEC ratio (10 % FEC) can balance the bulk and interface transport of ions, enabling LiNi_0.8Mn_0.1Co_0.1O₂||lithium (NCM811||Li) full cells to deliver excellent temperature resilience and cycling stability over a wide temperature range from −50 °C to +70 °C. More than 66 % of the capacity retention was achieved at −50 °C compared to room temperature. The NCM811||Li pouch cells exhibit high cycling stability under realistic conditions (electrolyte weight to cathode capacity ratio (E/C)≤3.5 g Ah⁻¹, negative to positive electrode capacity ratio (N/P)≤1.09) at different temperatures.     

Fabrication of Multi-pore Structure Cu,N-codoped Porous Carbon-based Catalyst and its Oxygen Reduction Reaction Catalytic Performance for Microbial Fuel Cell

The development of a non-noble metal cathode ORR catalyst with low cost, high activity and high stability has become an inevitable trend in MFC. The purpose of this study is to develop an efficient and stable Cu, N-codoped porous carbons catalysts with multi-pore structure for MFC. Herein, Cu, N-codoped porous carbons materials (Cu−NC−T) with high N content and multi-pore structure were successfully developed by co-pyrolysis with MOF-199 and melamine. By contrast, Cu-doped porous carbon (Cu−C−T) without melamine was synthesized using MOF-199 as template. The results showed that Cu−NC−T possessed a rough octahedral crystal with a unique multi-mesopore structure with pore centers of 3.4 nm and 11.2 nm, respectively. Owing to high N content, abundantly exposed Cu−N_x active sites and the multi-pore structure, Cu−NC−800 had a pronounced electrochemical ORR activity in neutral solution (onset potential and limiting current density were 0.161 V and −6.256 mA ⋅ cm⁻²), which were slightly lower than 20 wt % Pt/C (0.189 V and −6.479 mA ⋅ cm⁻²). Moreover, the MFC with Cu−NC−800 showed a power density of 662.8±3.6 mW ⋅ m⁻², which was higher than that of Cu−C−800 (425.7±3.9 mW ⋅ m⁻²) and was slightly lower than that 20 wt % Pt/C (815.0±6.2 mW ⋅ m⁻²). The output voltage of MFC with Cu−NC−T had no obvious decreasing trend in 30 days, demonstrating that the Cu−NC−T had great stability.     

The thermal expansion and high temperature transformation of GeSe

The thermal expansion of GeSe has been studied above room temperature up to the melting point of 670 ± 5°C by X-ray diffraction techniques using a 190 mm Unicam high temperature camera. The thermal expansion of the crystallographic axes is linear with a distinct change of the expansion coeffients for all axes above 400°C. The relative changes of the axes indicate a rearrangement of the structure towards cubic symmetry with increasing temperature. The transformation of GeSe from the orthorhombic to a normal NaCl-type structure is observed at 651 ± 5°C. The lattice parameter of the cubic form of GeSe is a₀ = 5.730 ± 0.003 Å at 656°C. The GeSe lattice remains cubic up to the melting point.     

Effects of temperature during irradiation and spectrophotometry analysis on the dose response of aqueous dichromate dosimeters

The irradiation temperature dependence of the ⁶⁰Co gamma-ray dose response of a silver-dichromate dosimeter was studied to verify temperature coefficients over 5–60°C, using both low and high range standard-type dosimeters. The temperature coefficients in the temperature range 25–60°C are estimated to be −0.20 and −0.26%/°C respectively at doses 2–10 kGy and 10–50 kGy, although there is a slight tendency of dose dependence. The coefficients covering temperatures of 25–50°C estimated to low and high dose ranges are respectively −0.20 and −0.23%/°C which lead us to confirm the previous data including the ASTM Standards E1401-96, 1997. The effect of temperature during spectrophotometry analysis on molar extinction coefficients was not appreciably observed in the temperature range 5–50°C.     

Fabry-Perot spectra of depolarized Rayleigh wing in water: a new analysis of its temperature dependence

An extension to very low frequency shift is reported for the depolarized Raman spectra of liquid water between −25 and 60°C. The results exclude the presence of any spectral component narrower than 4 cm⁻¹ fwhm. Two almost fully depolarized lorentzian components are identified in the −150 to 150 cm⁻¹ range using a subtraction technique on pairs of spectra taken at different temperatures. A constant width component (γ = 3.85 ± 0.15 cm⁻¹) is found, the integrated intensity of which rapidly decreases above 20°C; this is assigned to a proton ice-like relaxation mode, by comparison with the central peak already observed in hexagonal ice single crystals. The second component results to be strongly temperature dependent in both width and intensity with a different behaviour above and below 0°C. Two activation energies are derived from its hwhm, i.e. 5.7 kcal/mol for T < 20°C and 2.1 kcal/mol for T > 20°C. The previously suggested assignment of this component to hydrogen-bond breaking is rejected on the basis of its polarization properties. A different assignment is attempted comparing its anomalous temperature dependence with that of some transport properties.     

Impedimetric sensing of humidity and temperature using CeO2–Co3O4 nanoparticles in polymer hosts

Humidity and temperature sensors were fabricated from a nanocomposite consisting of CeO₂-Co₃O₄ hybrid nanoparticle-silicone adhesive and CeO₂-Co₃O₄ hybrid nanoparticle-polymer adhesive, respectively, to fix the material on a glass supported copper electrode. The impedance of the sensor decreases by a factor of 960 at a working frequency of 100 Hz, and by a factor of 800 at 1 kHz, on increasing relative humidity (RH) from 30 to 90 %. In parallel, the capacitances increase by factors of 567 and 355, respectively, under the same experimental conditions. The effect of temperature in the range from 25 to 70 °C on impedance (again at 100 Hz and 1 kHz) was also studied and found to decrease with increasing temperature. On going from 25 to 70 °C, the impedance measured at 100 Hz and 1 kHz decreases 2.22 and 1.58 times, respectively, in surface type sensors, while in sandwich type sensors this decrease is 3.0 and 2.08 times. The calculated average sensitivity to temperature is −1.02 and −0.8 % °C⁻¹ for the surface type and −1.5 and −1.2 % °C⁻¹ for the sandwich type sensors at frequencies of 100 Hz and 1 kHz, respectively.

A highly sensitive sensor with dual functionality for humidity and temperature has been fabricated by using CeO₂-codoped Co₃O₄ nanoparticles with silicone and polymer adhesive.

     

Sorption,diffusion, and permeation of ethylbenzene in poly(1‐trimethylsilyl‐1‐propyne)

The solubility, diffusivity, and permeability of ethylbenzene in poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) at 35, 45 and 55 °C were determined using kinetic gravimetric sorption and pure gas permeation methods. Ethylbenzene solubility in PTMSP was well described by the generalized dual‐mode model with χ = 0.39 ± 0.02, b = 15 ± 1, and C^′_H = 45 ± 4 cm³ (STP)/cm³ PTMSP at 35 °C. Ethylbenzene solubility increased with decreasing temperature; the enthalpy of sorption at infinite dilution was −40 ± 7 kJ/mol and was essentially equal to the enthalpy change upon condensation of pure ethylbenzene. The diffusion coefficient of ethylbenzene in PTMSP decreased with increasing concentration and decreasing temperature. Activation energies of diffusion were very low at infinite dilution and increased with increasing concentration to a maximum value of 50 ± 10 kJ/mol at the highest concentration explored. PTMSP permeability to ethylbenzene decreased with increasing concentration. The permeability estimated from solubility and diffusivity data obtained by kinetic gravimetric sorption was in good agreement with permeability determined from direct permeation experiments. Permeability after exposure to a high ethylbenzene partial pressure was significantly higher than that observed before the sample was exposed to a higher partial pressure of ethylbenzene. Nitrogen permeability coefficients were also determined from pure gas experiments. Nitrogen and ethylbenzene permeability coefficients increased with decreasing temperature, and infinite dilution activation energies of permeation for N₂ and ethylbenzene were −5.5 ± 0.5 kJ/mol and −74 ± 11 kJ/mol, respectively. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1078–1089, 2000     

Raman imaging to quantify the thermal transformation degree of Pompeian yellow ochre caused by the 79 AD Mount Vesuvius eruption

Most of the wall paintings from Pompeii are decorated with red and yellow colors but the thermal impact of 79 AD Mount Vesuvius eruption promoted the partial transformation of some yellow-painted areas into red. The aim of this research is to develop a quantitative Raman imaging methodology to relate the transformation percentage of yellow ochre (goethite, α-FeOOH) into red color (hematite, α-Fe₂O₃) depending on the temperature, in order to apply it and estimate the temperature at which the pyroclastic flow impacted the walls of Pompeii. To model the thermal impact that took place in the year 79 AD, nine wall painting fragments recovered in the archeological site of Pompeii and which include yellow ochre pigment were subjected to thermal ageing experiments (exposition to temperatures from 200 to 400 °C every 25 °C). Before the experiments, elemental information of the fragments was obtained by micro-energy dispersive X-ray fluorescence (μ-ED-XRF). The fragments were characterized before and after the exposition using Raman microscopy to monitor the transformation degree from yellow to red. The quantitative Raman imaging methodology was developed and validated using synthetic pellets of goethite and hematite standards. The results showed almost no transformation (0.5% ± 0.4) at 200 °C. However, at 225 °C, some color transformation (26.9% ± 2.8) was observed. The most remarkable color change was detected at temperatures between 250 °C (transformation of 46.7% ± 1.7) and 275 °C (transformation of 101.1% ± 1.2). At this last temperature, the transformation is totally completed since from 275 to 400 °C the transformation percentage remained constant.

     

Low temperature aqueous electrospray ionization mass spectrometry of noncovalent complexes

In the present study we describe conditions that permit the characterization of noncovalent protein–substrate complexes in aqueous solution by microspray electrospray ionization-mass spectrometry (ESI-MS), using a heated transfer capillary at low temperature (45 °C). Specifically, we examined the binding of calmodulin to two polypeptides; the calmodulin-binding domain of calmodulin-dependent protein kinase II (CamK-II) and melittin. Calmodulin, a well known calcium-binding protein, binds to a number of small amphipathic peptides in a calcium-dependent manner. Our results directly show that both peptides form equimolar complexes with calmodulin only in the presence of calcium. The stoichiometry necessary for the formation of each complex was 1:1:4 for calmodulin:peptide (melittin or CamK-II):Ca²⁺, respectively. Furthermore, it is demonstrated that the detection of the complex in ESI-MS is source temperature dependent.     

Mercury selenide stoichiometry and phase relations in the mercury-selenium system

The phase relations in the 0–65 at% Hg portion of the condensed mercury-selenium system were determined from liquidus temperatures to 250°C by evacuated silica tube experiments in which vapor is always a phase. Stoichiometric HgSe melts at 795 ± 2°C whereas Hg_0.51Se_0.49 melts at 797 ± 2°C and Hg_0.49Se_0.51 melts at 793 ± 2°C. In the HgSeSe portion of the system a monotectic exists at 683 ± 3°C and 71.5 at% Se and a liquid immiscibility field at this temperature extends from 71.5 to 85.5 at% Se. The presence of HgSe depresses the melting temperature of Se by about 8°C. An eutectic exists between HgSe and Se at 208°C and a composition of more than 99.95 at% Se. In the HgHgSe portion of the system a monotectic exists at 708 ± 3°C and about 25 at% Se. The solubility of Hg in HgSe was found to exceed stoichiometry by 1.11 ± 0.25 at% at 650°C whereas the solubility of Se in HgSe exceeds stoichiometry by 0.75 ± 0.25 at% Se at the same temperature. All synthetic mercury selenides show the sphalerite type structure. The unit cell dimension of stoichiometric HgSe is a₀ = 6.080 ± 0.001 Å. Mercury selenide synthesized in equilibrium with liquid Se gives a₀ = 6.082 ± 0.001 Å and mercury selenide synthesized in equilibrium with Hg gives a₀ = 6.078 ± 0.001 Å.     

POLAROGRAPHIC INVESTIGATION OF THE SYSTEMS ARSENIC(III)-TARTARIC ACID AND ARSENIC(III)-1,2-DIAMINO-CYCLOHEXANE-N,N,N′,N′-TETRAACETIC ACID (DCTA)

Abstract

The reactions between As(III), tartaric acid (H₂T)and DCTA were investigated polarographically. The conditional stability constants of As(III)-complexes at a given pH-value and variable ligand concentration were calculated from the change of the limiting currents. The optimum conditions for calculating stability constants from the current were also discussed. It was found that DCTA (H₄L)formed the complex [As(OH)₂HL]^2- whose overall formation constant was lgβ111=(20.67 ±0.09)atμ=0.1 and t°- (25.0±0.2)°C, whereas the complex between As(III) and H₂T was [As(OH)₂T]^? with an overall stability constant 1gβ 101= 6.62 ±0.14 at μ=0.1 and t°= (25 ± 0.2)°C.     

Living Anionic Polymerization of N-Methacryloyl-2-methylaziridine

Anionic polymerization of N-methacryloyl-2-methylaziridine ( 1 ) proceeded with 1,1-diphenyl-3-methylpentyllithium (DMPLi) in the presence of LiCl or Et₂Zn to give the polymers possessing predicted molecular weights and narrow molecular weight distributions (M_w/M_n < 1.1) at −78 ∼ −40 °C in THF. In each polymerization initiated with DMPLi/LiCl at the various temperatures ranging from −40 to −60 °C, the linear relationship between polymerization time and conversion of monomer was obtained from the GLC analysis. The rate constant and the activation energy of the anionic polymerization for 1 were determined as follows: ln k = −5.85 × 10³/T + 23.3 L mol⁻¹ s⁻¹ and 49 ± 4 kJ mol⁻¹, respectively. Poly( 1 ) showed the glass transition temperature at 98 °C, and gave the insoluble product at higher temperature around 150 °C through the thermal cross-linking of highly strained N-acyl-aziridine moiety.     

Influence of monomer structure on chemo- and stereoselectivity of 1,3-diene polymerization

MAO/CpTiCl₃ is an active catalyst for the polymerization of various types of 1,3-dienes. Butadiene, (E) - and (Z) −1,3-pentadiene, (E) −2-methyl-1,3-pentadiene and 2,3-dimethylbutadiene yield, at room temperature, polymers with a cis-1,4 or a mixed cis/1,2 structure. 4-Methyl-1,3-pentadiene and (E,E) −2,4-hexadiene give, respectively, a 1,2 syndiotactic and a trans-1,4/1,2 polymer. MAO/CpTiCl₂·2THF and MAO/(CpTiCl₂)_n are less active than the CpTiCl₃ catalyst, but give the same type of polymers. A change of stereospecificity with temperature was observed in the polymerization of (Z)-1,3-pentadiene: a cis-1,4 isotactic polymer was obtained at +20°C, and a crystalline 1,2 syndiotactic polymer at −20°C. This effect was attributed to a different mode of coordination of the monomer, which is cis-η⁴ at +20°C and may be trans-η² at −20°C. Results obtained with catalysts from CpTi(OBu)₃ and Ti(OBu)₄ are reported for comparison. An interpretation is given of the formation of cis-1,4 isotactic poly(2-methylpentadiene) and of 1,2 syndiotactic poly(4-methylpentadiene), as well as of syndiotactic polystyrene.     

Direct observation and stability of active species in cationic polymerization: A reexamination of the polymerization of styrene initiated by triflic acid

Polymerization of styrene initiated by triflic acid in CH₂Cl₂ solution was reexamined, using a new stopped-flow device working in high purity conditions over a wide temperature range. Monomer and styryl cation were followed simultaneously through their respective absorbances at 290 and 340 nm. Initiation is very rapid, and cations concentration reaches a plateau the duration of which is depending on temperature. In our conditions (I₀ = 0.5 − 9.10⁻³M, M₀/I₀ = 1 to 20), cations concentration is so low at room temperature that it is almost unmeasurable. At −65°C, it is 100 times higher, remains constant for several seconds and complete termination takes place within a minute or more. Such a profile of cation evolution agrees with an equilibrium situation between initiation and a much more temperature-dependent backward deprotonation. Apparent initial rate of initiation is first order with respect to monomer, but the order with respect to initiator was found very high and variable with temperature (from 4.5 at −65°C to 3 at −20°C). This supports the presence, even if they are in low concentration, of acid high agregates, the reactivity of which increases with size. A first order monomer consumption is observed during the plateau, which leads to k_p values ranging from 10³ at −65°C to 9.10⁴ M⁻¹.s⁻¹ at −10°C (Ep^# = 43 kJ.mol⁻¹). The disappearance of cations, which follows the plateau, slows down and becomes unimolecular when monomer consumption is complete, and k_t values range from 6.10⁻²s⁻¹ at −65°C to 1.2s⁻¹ at −23°C (E_t^# = 33 kJ.mol⁻¹).