@article{StrehmelLaschewskyWetzel2006, author = {Strehmel, Veronika and Laschewsky, Andr{\´e} and Wetzel, Hendrik}, title = {Homopolymerization of a highly polar zwitterionic methacrylate in ionic liquids and its copolymerization with a non-polar methacrylate}, year = {2006}, abstract = {Free radical homo- and copolymerization of the highly polar 3-(N-[2-methacryloyloxyethyl]-N,N-dimethylammonio) propane sulfonate with the nonpolar n-butylmethacrylate was investigated in the ionic liquids 1-butyl-3-methyl imidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluoro phosphate, and compared to analogous polymerizations in standard solvents. Higher molar masses are obtained for the zwitterionic homopolymer when the polymerization is carried out in an ionic liquid compared to the classical reaction in water. Although homopolymerization of the sulfobetain monomer as well as of n-butylmethacrylate results in phase separation during the polymerization process, copolymerization of a stoichiometric ratio of the two monomers in the ionic liquids produced transparent gels indicating that no macrophase separation occurs. The use of ionic liquids as reaction medium improved the copolymerization behavior of the two methacrylates significantly. Whereas only minor amounts of n-butyl methacrylate were incorporated in the copolymer when synthesized in acetonitrile, the content of the non-polar monomer units in the zwitterionic copolymer approached increasingly its content in the polymerization mixture when ionic liquids were employed as solvents}, language = {en} } @article{StrehmelLaschewskyWetzeletal.2006, author = {Strehmel, Veronika and Laschewsky, Andr{\´e} and Wetzel, Hendrik and Gornitz, Eckhard}, title = {Free radical polymerization of n-butyl methacrylate in ionic liquids}, doi = {10.1021/Ma0516945}, year = {2006}, abstract = {Ionic liquids based on imidazolium, pyridinium, and alkylammonium salts were investigated as solvents in free radical polymerization of the model monomer n-butyl methacrylate. The properties of the ionic liquids were systematically varied by changing the length of the alkyl substituents on the cations, and by employing different anions such as tetrafluoroborate, hexafluorophosphate, tosylate, triflate, alkyl sulfates and dimethyl phosphate. Results were compared to analogous polymerizations in toluene and in bulk. The solvents have no detectable influence on polymer tacticity. However, the molar masses obtained and the degree of polymerization, respectively, are very sensitive to the choice of the solvent. The degrees of polymerization are significantly higher when polymerizations were carried out in ionic liquids compared to polymerization in toluene, and can even exceed the values obtained by bulk polymerization. Imidazolium salts unsubstituted at C-2 result in an increase in the degree of polymerization of the poly(butyl methacrylate) with increasing viscosity of these ionic liquids. Methyl substitution at C-2 of the imidazolium ion results in an increase in the viscosity of the ionic liquid and in a viscosity independent degree of polymerization of the poly(butyl methacrylate). Ionic liquids based on imidazolium salts seem preferable over pyridinium and alkylammonium salts because of the higher degree of polymerization of the poly(butyl methacrylate)s obtained in the imidazolium salts. The glass transition temperatures and thermal stabilities are higher for poly(butyl methacrylate)s synthesized in the ionic liquids compared to the polymer made in toluene}, language = {en} } @article{StrehmelLaschewskyStoesseretal.2006, author = {Strehmel, Veronika and Laschewsky, Andr{\´e} and Stoesser, Reinhard and Zehl, Andrea and Herrmann, Werner}, title = {Mobility of spin probes in ionic liquids}, doi = {10.1002/poc.1072}, year = {2006}, abstract = {The spin probes TEMPO, TEMPOL, and CAT-1 were used to investigate microviscosity and micropolarity of imidazolium based ionic liquids bearing either tetrafluoroborate or hexafluorophosphate as anions and a variation of the substitution at the imidazolium ion. The average rotational correlation times (r) obtained by complete simulation of the X-band ESR spectra of TEMPO, TEMPOL, and CAT-1 increase with increasing viscosity of the ionic liquid although no Stokes Einstein behavior is observed. This is caused by microviscosity effects of the ionic liquids shown by application of the Gierer-Wirtz theory. Interestingly, the jump of the probe molecule into the free volume of the ionic liquids is a nonactivated process. The hyperfine coupling constants (A(iso) (N-14)) of TEMPO and TEMPOL dissolved in the ionic liquids do not depend on the structure of the ionic liquids. The A(iso) (N-14) values show a micropolarity of the ionic liquids that is comparable with methylenchloride in case of TEMPO and with dimethylsulfoxide in case of TEMPOL. Micropolarity monitored by CAT-1 strongly depends on structural variation of the ionic liquid. CAT-1 dissolved in imidazolium salts substituted with shorter alkyl chains at the nitrogen atom exhibits a micropolarity comparable with dimethylsulfoxide. A significant lower micropolarity is found for imidazolium. salts bearing a longer alkyl substituent at the nitrogen atom or a methyl substituent at C-2. Copyright (c) 2006 John Wiley \& Sons, Ltd}, language = {en} } @article{StoesserHerrmannZehletal.2006, author = {Stoesser, Reinhard and Herrmann, Werner and Zehl, Andreas and Strehmel, Veronika and Laschewsky, Andr{\´e}}, title = {ESR spin probes in ionic liquids}, doi = {10.1002/cphc.200500651}, year = {2006}, abstract = {The spin probes 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), and 2,2,6,6-tetramethyl-4-trimethylammoniumpiperidine-1-oxyllodide (CAT-1) are examined in a number of ionic liquids based on substituted imidazolium cations and tetrafluoroborate and hexafluorophosphate anions, respectively. The reorientation correlation times tau(R) of the spin probes in these systems have been determined by complete spectra simulation and, for rapid reortientation, by analysis of the intensities of the hyperfine lines of the electron spin resonance (ESR) spectra. A comparison of the results with those from the model system glycerol/water and selected organic solvents is made. Additions of diamagnetic and paramagnetic ions allow the conclusion that salt effects and spin exchange are present, and that both are superimposed by motional effects. Specific interactions in the ionic liquids, as well as between the spin-probe molecules and the constituents of the ionic liquids are reflected in the spectra of the spin probes, depending on their molecular structure}, language = {en} }