Search results for "ionic"
showing 10 items of 2016 documents
Concerning the reaction mechanism of the anionic polymerization of styrene in tetrahydrofuran
1969
1990
The effect of lithium tert-butoxide (t-BuOLi) on rate constants and equilibrium constants of reactions involved in the initial stage of the anionic polymerization of methyl methacrylate (MMA) in tetrahydrofuran, initiated by methyl α-lithioisobutyrate (P) was investigated at 23 ± 3°C. Addition of t-BuOLi decreases the rate constants of initiation and propagation by one order of magnitude; the rate constants of termination by cyclization decrease by two orders of magnitude. This leads to an overall tenfold higher preference of propagation with respect to termination and explains the favourable effect of alkoxide in the polymerization reported earlier. Within experimental error, the equilibri…
ISomerization of xylene: MINDO/3 study of the cyclization of benzenium cation into bicyclo[3.1.0]hexenyl cation
1989
Abstract A MINDO/3 study of thermal electrocyclic closing of the benzenium cation to form a bicyclo[3.1.0]hexenyl cation is presented. The calculated mechanism discusses the possibility of cyclization of xylenium cations on a silica catalyst or in superacid media. The structure and energy of the transition state, the enthalpies of isomerization and barriers of activation were calculated for the following processes: isomerization of 2,6-dimethylbenzenium cation into 2,6-dimethylbicyclo[3.1.0]hexenyl cation, isomerization of 2,4-dimethylbenzenium cation into 2,4-dimethylbicyclo[3.1.0]-hexenyl cation, and isomerization of benzenium cation into bicyclo[3.1.0]-hexenyl cation. Equilibrium and kin…
Anionische Polymerisation in Schwach Solvatisierenden Lösungsmitteln
2007
The anionic polymerization of styrene initiated by cumylsodium and carried out in cumyl methyl ether has been examined with use of conversion kinetics and molecular weight distribution. The solvent has a weaker solvation power than THF and THP, which have been studied with the same experimental technique. The polymerization rate is first order relative to monomer and the rate constant has a value of ca. 1 mole−1 1. sec.−1 at − 20.5°C. The constant is only slightly dependent on the initiator concentration, but the molecular weight distribution is broader than a Poisson function. Added electrolyte has little effect on the propagation constant but it greatly alters the molecular weight distrib…
Synthesis of chemisorbed imidazolium and phosphonium cations by reaction of ionic liquid precursors with silica.
2010
The reaction of four different basic ionic liquid precursors with Aerosil®300 is presented. Chemisorbed imidazolium and phosphonium cations, with silanolate anions as part of the silicatic support, were obtained and investigated with various solid state NMR techniques.
ChemInform Abstract: Green Conditions for the Suzuki Reaction Using Microwave Irradiation and a New HNT-Supported Ionic Liquid-Like Phase (HNT-SILLP)…
2014
Aryl iodides are coupled with conversions comparable to aryl bromides whereas conversions of aryl chlorides are significantly lower.
Selective Hydrogenation of 1,3-Butadiene to 1-Butene by Pd(0) Nanoparticles Embedded in Imidazolium Ionic Liquids
2005
The reduction of Pd(acac)2 (acac=acetylacetonate), dissolved in 1-n-butyl-3-methylimidazolium hexafluorophosphate (BMI⋅PF6) or tetrafluoroborate (BMI⋅BF4) ionic liquids, by molecular hydrogen (4 atm) at 75 °C affords stable, nanoscale Pd(0) particles with sizes of 4.9±0.8 nm. Inasmuch as 1,3-butadiene is at least four times more soluble in the BMI⋅BF4 than butenes, the selective partial hydrogenation could be performed by Pd(0) nanoparticles embedded in the ionic liquid. Thus, the isolated nanoparticles promote the hydrogenation of 1,3-butadiene to butenes under solventless or multiphase conditions. Selectivities up to 97% in butenes were observed in the hydrogenation of 1,3-butadiene by Pd…
1968
Über die darstellung von polyoxymethylenen mit thermisch stabilen endgruppen durch übertragung der kationischen polymerisation des trioxans. 24. Mitt…
1965
Die kationische Polymerisation von Trioxan wird durch Acetale, leicht spaltbare Ather sowie durch Ester und Anhydride ubertragen. Die entstehenden Polyoxymethylene tragen Ather- bzw. Ester-Endgruppen und sind daher bis uber 200°C thermisch stabil. Um in guten Ausbeuten hochmolekulare thermisch stabile Polyoxymethylene zu erhalten, mus der Polymerisationsansatz schr weitgehend wasserfrei sein; dies kann durch Trocknung des Trioxans mit Isocyanaten in einer speziellen Apparatur erreicht werden. Die relative Ubertragungskonstante von Dimethylformal bei 25°C betragt 1,2, die von Methylformiat ca. 0,03. Esters, anhydrides, acetals, and easily cleavable ethers transfer the cationic polymerization…
Anomalien bei der kationischen copolymerisation von trioxan. 32. Mitt. über polyoxymethylene
1967
Die kationische Copolymerisation von Trioxan mit Styrol, 1,3-Dioxolan und anderen Comonomeren last sich wegen folgender Nebenreaktionen nicht durch die ubliche MAYO-sche Copolymerisationskinetik erfassen: 1. Depolymerisation der Trioxymethylenbausteine zu Formaldehyd wahrend der Induktionszeit und daher Bildung sehr styrolreicher bzw. dioxolanreicher Prapolymerer. 2. Bildung und Polymerisation von Formaldehyd, welcher wahrend der gesamten Polymerisation in seiner ceiling-Gleichgewichtskonzentration zugegen ist. 3. Abspaltung oxacyclischer Verbindungen von den aktiven Kettenenden; Bildung von Tetroxan und 4-Phenyl-1,3-dioxan bei der Copolymerisation von Trioxan mit Styrol. 4. Ubertragung am …