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Termination Reactions (termination + reaction)
Selected AbstractsNumerical study on flame structure in H2,O2/CO2 laminar flamesINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 7 2003Jeong Park Abstract Numerical study, aimed at the understanding of the flame structure in O2/CO2 recycling combustion system, has been conducted with detailed chemistry. Special concern is focused on addition effect of carbon dioxide on flame structure in H2,O2 counterflow diffusion flame as a simulating configuration. To clarify chemical and thermal effects on flame structure, the comparison between predicted results with a virtual species X to displace the real carbon dioxide and with added carbon dioxide in oxidizer stream is made according to strain rate and the concentration of added CO2. From the systematical comparison of a dominant radical producing reaction with a chain termination reaction the effects of strain rate and composition control of oxidizer stream on flame structure are estimated. It is found that the behaviours of C1 - and C2 -branch species are a direct outcome of that of produced CO due to the breakdown of added CO2. There exists a temperature dependency in the behaviour of produced CO and this competes for the behaviour of the produced CO with chemical effects due to the backward reaction of CO+OH=CO2+H. Copyright © 2003 John Wiley & Sons, Ltd. [source] Oxidation of small alkenes at high temperatureINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 12 2002Barbara Heyberger If the mechanism of formation of alkenes, the main primary products of the combustion of alkanes above 1000 K, is now well understood, their ways of degradation have been much less studied. Following a previous modeling of the oxidation of propene in a static and a jet-stirred reactors by using an automatically generated mechanism, the present paper shows new validations of the same mechanism for ignition delays in a shock tube. It also describes the extension of the rules used for the automatic generation to the case of 1-butene. The predictions of the mechanism produced for the oxidation of 1-butene are compared successfully with two sets of experimental results: the first obtained in a jet-stirred reactor between 900 and 1200 K; the second being new measurements of ignitions delays behind reflected shock waves for temperatures from 1200 up to 1670 K, pressures from 6.6 to 8.9 atm, equivalence ratios from 0.5 to 2, and with argon as bath gas. Flux and sensitivity analyses show that the role of termination reactions involving the very abundant allylic radicals is less important for 1-butene than for propene. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 666,677, 2002 [source] Preparation of high cis -1,4 polyisoprene with narrow molecular weight distribution via coordinative chain transfer polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2010Changliang Fan Abstract High cis -1,4 polyisoprene with narrow molecular weight distribution has been prepared via coordinative chain transfer polymerization (CCTP) using a homogeneous rare earth catalyst composed of neodymium versatate (Nd(vers)3), dimethyldichlorosilane (Me2SiCl2), and diisobutylaluminum hydride (Al(i -Bu)2H) which has strong chain transfer affinity is used as both cocatalyst and chain transfer agent (CTA). Differentiating from the typical chain shuttling polymerization where dual-catalysts/CSA system has been used, one catalyst/CTA system is used in this work, and the growing chain swapping between the identical active sites leads to the formation of high cis -1,4 polyisoprene with narrowly distributed molecular weight. Sequential polymerization proves that irreversible chain termination reactions are negligible. Much smaller molecular weight of polymer obtained than that of stoichiometrically calculated illuminates that, differentiating from the typical living polymerization, several polymer chains can be produced by one neodymium atom. The effectiveness of Al(i -Bu)2H as a CTA is further testified by much broad molecular weight distribution of polymer when triisobutylaluminum (Al(i -Bu)3), a much weaker chain transfer agent, is used as cocatalyst instead of Al(i -Bu)2H. Finally, CCTP polymerization mechanism is validated by continuously decreased Mw/Mn value of polymer when increasing concentration of Al(i -Bu)2H extra added in the Nd(ver)3/Me2SiCl2/Al(i -Bu)3 catalyst system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source] Direct measurements of the addition and recombination of acrylate radicals: Access to propagation and termination rate constants?JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2006J. Lalevée Abstract Acrylate radicals produced by the addition of an aminoalkyl radical to five acrylate monomers were directly observed by transient absorption spectroscopy, which allowed us to easily follow their chemical reactivity. It was possible (1) to characterize their absorption in the visible part of the spectrum, (2) to calculate their absorption properties, (3) to determine the energy barriers of the addition through quantum mechanical calculations, (4) to monitor the kinetics of the subsequent addition to another monomer unit, and (5) to follow the recombination of two acrylate radicals. These two latter points could mimic the propagation and termination reactions of polymerization-propagating acrylate radicals. Methacrylate and acrylonitrile radicals were also studied. The obtained results were in good agreement with the propagation rate constants determined by the well-established pulsed laser polymerization techniques. Our method could likely provide rapid access to both the propagation and termination rate constants in suitable systems and appears to be powerful and promising for studying and comparing the reactivities of different acrylate monomer structures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3577,3587, 2006 [source] Synthesis of proton-conducting membranes by the utilization of preirradiation grafting and atom transfer radical polymerization techniquesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2002Svante Holmberg Abstract The atom transfer radical polymerization (ATRP) of styrene onto poly(vinylidene fluoride)- graft -poly(vinylbenzyl chloride) (PVDF- g -PVBC) membranes was investigated. Novel membranes were designed for fuel-cell applications. The benzyl chloride groups in the PVDF- g -PVBC membranes functioned as initiators, and a Cu-based catalytic system with the general formula Cu(n)Xn/ligand [where X is Cl or Br and the ligand is 2,2,-bipyridyl (bpy)] was employed for the ATRP. In addition, 10 vol % dimethylformamide was added for increased solubility of the catalyst complex in styrene. The system was homogeneous, except for the membrane, when the initiator/copper halide/ligand/monomer molar ratio was 1/1/3/500. As anticipated, the fastest polymerization rate of styrene was observed with the copper bromide/bpy-based catalyst system. The reaction rate was strongly temperature-dependent within the studied temperature interval of 100,130 °C. The degree of grafting increased linearly with time, thereby indicating first-order kinetics, regardless of the polymerization temperature. Furthermore, 120 °C was the maximum polymerization temperature that could be used in practice because the membrane structure was destroyed at higher temperatures. The degree of styrene grafting reached 400% after 3 h at 120 °C. Such a high degree of grafting could not be reached with conventional uncontrolled radiation-induced grafting methods because of termination reactions. On the basis of an Arrhenius plot, the activation energy for the homogeneous ATRP of styrene was 217 kJ/mol. The prepared membranes became proton-conducting after sulfonation of the polystyrene grafts. The highest conductivity measured for the prepared membranes was 70 mS/cm, which is comparable to the values normally measured for commercial Nafion membranes. The scanning electron microscopy/energy-dispersive X-ray results showed that the membranes had to be grafted through the matrix with both PVBC and polystyrene to become proton-conducting after sulfonation. In addition, PVDF- g -[PVBC- g -(styrene- block - tert -butyl acrylate)] membranes were also synthesized by ATRP. © 2002 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 591,600, 2002; DOI 10.1002/pola.10146 [source] Application of Nitroxide-Terminated Polymers Prepared by Sonochemical Degradation in the Synthesis of Block CopolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 2 2006Martina Bartsch Abstract Summary: The ultrasonic irradiation of a polymer solution results in the breakage of macromolecular CC bonds. In the presence of radical scavengers the formed macroradicals are prevented from termination reactions as combination or disproportionation. Using nitroxides as trapping agents the polymer is transformed into a macroinitiator, which can be used in controlled free-radical polymerization to synthesize block copolymers. In this work several polymers were exposed to sonochemical degradation and terminated with various nitroxides, e.g. OH-TEMPO and TIPNO. In a second reaction step the prepared polymer-nitroxide-adducts were applied as macroinitiators in controlled free-radical polymerizations with styrene. The obtained products were mixtures of block copolymer and the corresponding homopolymers. The visco-elastic properties were investigated by rheological analysis. A special separation technique with selective solvents was applied to determine the content of block copolymer. Synthesis of block copolymers with sonochemically prepared macroinitiators. [source] Kevlar and glass fiber treatment for thermoplastic composites by step polycondensationPOLYMER COMPOSITES, Issue 3 2007H. Salehi-Mobarakeh Nylon-6,6 was grafted at the surface of glass and plasma-treated Kevlar fibers for use in nylon,Kevlar thermoplastic composites. Hydroxyl and, in the case of Kevlar, amine end-groups occur at the fibre surface, either as defects or due to the plasma treatment. These were used as anchor points for nylon-6,6 step polycondensation. Fibers were subjected to successive dipping in adipoyl chloride/CH2Cl2 and aqueous hexamethylenediamine solutions in order to attach and grow high molecular weight polymer on the fiber surface. Grafted nylon was characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance, differential scanning calorimetry and thermogravimetry. It was shown that no backbiting occurred during the first stage of the grafting process and that the polymer quantity increased linearly with number of passes, up to ,50 passes for plasma-treated Kevlar and 100 for glass fibers, after which polymer quantity remained constant, within experimental error, which was attributed to the onset of termination reactions. POLYM. COMPOS., 28:278,286, 2007. © 2007 Society of Plastics Engineers [source] Homolysis of N -alkoxyamines: A Computational StudyCHEMPHYSCHEM, Issue 2 2006Anouk Gaudel-Siri Dr. Abstract During nitroxide-mediated polymerization (NMP) in the presence of a nitroxide R2(R1)NO., the reversible formation of N -alkoxyamines [PON(R1)R2] reduces significantly the concentration of polymer radicals (P.) and their involvement in termination reactions. The control of the livingness and polydispersity of the resulting polymer depends strongly on the magnitude of the bond dissociation energy (BDE) of the CON(R1)R2bond. In this study, theoretical BDEs of a large series of model N -alkoxyamines are calculated with the PM3 method. In order to provide a predictive tool, correlations between the calculated BDEs and the cleavage temperature (Tc,), and the dissociation rate constant (kd,), of the N -alkoxyamines are established. The homolytic cleavage of the NOC bond is also investigated at the B3P86/6-311++G(d,p)//B3LYP/6-31G(d), level. Furthermore, a natural bond orbital analysis is carried out for some N -alkoxyamines with a OCON(R1)R2fragment, and the strengthening of their CON(R1)R2bond is interpreted in terms of stabilizing anomeric interactions. [source] | |||||||||||||