For the first time, a 1000 Hz pulse laser has been applied to determine detailed kinetic rate coefficients from pulsed laser polymerization–size exclusion chromatography experiments. For the monomer tert‐butyl acrylate, apparent propagation rate coefficients kpapp have been determined in the temperature range of 0–80 °C. kpapp in the range of few hundreds to close to 50 000 L·mol–1·s–1 are determined for low and high pulse frequencies, respectively. The apparent propagation coefficients show a distinct pulse‐frequency dependency, which follows an S‐shape curve. From these curves, rate coefficients for secondary radial propagation (kpSPR), backbiting (kbb), midchain radical propagation (kptert), and the (residual) effective propagation rate (kpeff) can be deduced via a herein proposed simple Predici fitting procedure. For kpSPR, the activation energy is determined to be (17.9 ± 0.6) kJ·mol–1 in excellent agreement with literature data. For kbb, an activation energy of (25.9 ± 2.2) kJ·mol–1 is deduced.
The propagation kinetics of isoprene radical polymerizations in bulk and in solution are investigated via pulsed laser initiated polymerizations and subsequent polymer analyses via size‐exclusion chromatography, the PLP‐SEC method. Because of low polymerization rate and high volatility of isoprene, the polymerizations are carried out at elevated pressure ranging from 134 to 1320 bar. The temperatures are varied between 55 and 105 °C. PLP‐SEC yields activation parameters of kp (Arrhenius parameters and activation volume) over a wide temperature and pressure range that allow for the calculation of kp at technically relevant ambient pressure conditions. The kp values determined are very low, e.g., 99 L mol?1 s?1 at 50 °C, which is even lower than the corresponding value for styrene polymerizations. The presence of a polar solvent results in a slight increase of kp compared to the bulk system. The kp values reported are important for determining rate coefficients of other elemental reactions from coupled parameters as well as for modeling isoprene free‐radical polymerizations and reversible deactivation radical polymerization with respect to tailored polymer properties and optimizing the polymerization processes. 相似文献
The kinetic and mechanistic study of Ag(I)‐catalyzed chlorination of linezolid (LNZ) by free available chlorine (FAC) was investigated at environmentally relevant pH 4.0–9.0. Apparent second‐order rate constants decreased with an increase in pH of the reaction mixture. The apparent second‐order rate constant for uncatalyzed reaction, e.g., k″app = 8.15 dm3 mol−1 s−1 at pH 4.0 and k″app. = 0.076 dm3 mol−1 s−1 at pH 9.0 and 25 ± 0.2°C and for Ag(I) catalyzed reaction total apparent second‐order rate constant, e.g., k″app = 51.50 dm3 mol−1 s−1 at pH 4.0 and k″app. = 1.03 dm3 mol−1 s−1 at pH 9.0 and 25 ± 0.2°C. The Ag(I) catalyst accelerates the reaction of LNZ with FAC by 10‐fold. A mechanism involving electrophilic halogenation has been proposed based on the kinetic data and LC/ESI/MS spectra. The influence of temperature on the rate of reaction was studied; the rate constants were found to increase with an increase in temperature. The thermodynamic activation parameters Ea, ΔH#, ΔS#, and ΔG# were evaluated for the reaction and discussed. The influence of catalyst, initially added product, dielectric constant, and ionic strength on the rate of reaction was also investigated. The monochlorinated substituted product along with degraded one was formed by the reaction of LNZ with FAC. 相似文献
It is demonstrated by experiment and simulation that the commercially available thioketone 4,4‐bis(dimethylamino)thiobenzophenone is capable of controlling AIBN‐initiated bulk butyl acrylate polymerization at 80 °C. On the basis of molecular weight data and from monomer conversion versus time curves, the associated rate parameters are estimated. The addition rate coefficient, kad, for the reaction of a propagating chain with the thioketone is close to 106 L · mol−1 · s−1 and the fragmentation rate coefficient, kfrag, is around 10−2 s−1 giving rise to large equilibrium constants in the order of 108 L · mol−1. Furthermore, cross‐ and self‐termination of the dormant radical species are identified to be operational.
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 (Mw/Mn < 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. 相似文献
Two long-chain multidentate ligands: 2,9-di-(n-2',5',8'-triazanonyl)-1,10-phenanthroline (L^1) and 2,9-di- (n-4',7',10'-triazaundecyl)-1,10-phenanthroline (L^2) were synthesized. The hydrolytic kinetics of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) catalyzed by the complexes of L^1 or L^2 with La(Ⅲ) or Gd(Ⅲ) have been studied in aqueous solution at (298.2±0.1) K, I=0.10 mol·dm^-3 KNO3 in pH 7.5-9.1, respectively, finding that the catalytic effect of GdL^1 was the best among the four complexes for hydrolysis of HPNP. Its kLnLH-1, kLnLand pKa are 0.047 mol^-1·L·s^-1, 0.000074 mol^-1·L·s^-1 and 8.90, respectively. This paper expounded the studied result with the structure of the ligands and the properties of the metal ions, and deduced the catalysis mechanism. 相似文献
Chain‐length‐dependent termination rate coefficients of the bulk free‐radical polymerization of styrene at 80 °C are determined by combining online polymerization rate measurements (DSC) with living RAFT polymerizations. Full kt versus chain‐length plots were obtained indicating a high kt value for short chains (2 × 109 L · mol−1 · s−1) and a weak chain‐length dependence between 10 and 100 monomer units, quantified by an exponent of −0.14 in the corresponding power law 〈kti,i〉 = kt0 · P−b.
Double logarithmic plots of 〈kti,i〉 versus P, evaluated from experimental time‐resolved Rp data according to the procedure described in the text, for different CPDA and AIBN concentrations. The best linear fit for (10 < P < 100) is indicated as full line. 相似文献