Synthesis of linear and starlike polymers from poly(propylene glycol) methacrylate using controlled radical polymerization

The copper‐catalyzed atom transfer radical polymerization (ATRP) of poly(propylene glycol) methacrylate (PPGM) in solution to produce linear and starlike polymers is reported, using methylethyl ketone as the solvent and a temperature of 80 °C. The ATRP system used was efficient for polymerization of the functionalized monomer without protecting hydroxyl end groups of monomer. The polymerizations were consistent with “living” or controlled processes, as revealed by the linear evolution of molecular weight with conversion. Increasing the [M]₀:[I]₀ ratio resulted in increasing molecular weights, whereas the polydispersity indices remained low (M_w/M_n < 1.4) even at high conversion. Decreasing the [CuBr]₀:[I]₀ ratio resulted in lower conversions, slightly larger polydispersities, and decreased molecular weights, likely resulting from a lower initiation efficiency. Polymers were characterized by ¹H and ¹³C NMR; molecular weights of polymers with low degrees of polymerization were estimated by end‐group analysis from ¹³C NMR spectra obtained using distortionless enhancement by polarization transfer and the gated decoupling techniques. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 334–343, 2002     

Photoelectron spectroscopy of fullerene dianions C76(2-), C78(2-), and C84(2-)

We report laser photoelectron spectra of the doubly negatively charged fullerenes C(76) (2-), C(78) (2-), and C(84) (2-) at 2.33, 3.49, and 4.66 eV photon energy. From these spectra, second electron affinities and vertical detachment energies, as well as estimates for the repulsive Coulomb barriers are obtained. These results are discussed in the context of electrostatic models. They reveal that fullerenes are similar to conducting spheres, with electronic properties scaling with their size. The experimental spectra are compared with the accessible excited states of the respective singly charged product ions calculated in the framework of time dependent density functional theory.     

Splitting‐characterizations of the Papangelou process

For point processes we establish a link between integration‐by‐parts‐ and splitting‐formulas which can also be considered as integration‐by‐parts‐formulas of a new type. First we characterize finite Papangelou processes in terms of their splitting kernels. The main part then consists in extending these results to the case of infinitely extended Papangelou and, in particular, Pólya and Gibbs processes.     

A Simple Strategy to Improve the Accuracy of the Injection Step in Batch Injection Analysis Systems with Amperometric Detection

In this study, we describe for the first time the application of an internal standard method to compensate for random errors associated with the injection procedure in batch injection analysis (BIA) systems with multiple pulse amperometric detection. A sequence of potential pulses was selected in such a way that the internal standard (IS) compound was detected individually at one potential pulse and both the IS and analyte, were detected at another potential pulse. The current ratio (I_IS+analyte/I_IS) was used in the construction of the calibration curve and then to compensate for random errors. The use of disposable syringes or manual pipettes in BIA systems increases the robustness of the method and dispenses with skilled operators.     

Reactions with Oleum under Harsh Conditions: Characterization of the Unique [M(S2O7)3]2− Ions (M=Si,Ge, Sn) in A2[M(S2O7)3] (A=NH4, Ag)

The reactions of group 14 tetrachlorides MCl₄ (M=Si, Ge, Sn) with oleum (65 % SO₃) at elevated temperatures lead to the unique complex ions [M(S₂O₇)₃]^2?, which show the central M atoms in coordination with three chelating S₂O₇^2? groups. The mean distances M? O within the anions increase from 175.6(2)–177.5(2) pm (M=Si) to 186.4(4)–187.7(4) pm (M=Ge) to 201.9(2)–203.5(2) pm (M=Sn). These distances are reproduced well by DFT calculations. The same calculations show an increasing positive charge for the central M atom in the row Si, Ge, Sn, which can be interpreted as the decreasing covalency of the M? O bonds. For the silicon compound (NH₄)₂[Si(S₂O₇)₃], ²⁹Si solid‐state NMR measurements have been performed, with the results showing a signal at ?215.5 ppm for (NH₄)₂[Si(S₂O₇)₃], which is in very good agreement with theoretical estimations. In addition, the vibrational modes within the [MO₆] skeleton have been monitored by Raman spectroscopy for selected examples, and are well reproduced by theory. The charge balance for the [M(S₂O₇)₃]^2? ions is achieved by monovalent A⁺ counter ions (A=NH₄, Ag), which are implemented in the syntheses in the form of their sulfates. The sizes of the A⁺ ions, that is, their coordination requirements, cause the crystallographic differences in the crystal structures, although the complex [M(S₂O₇)₃]^2? ions remain essentially unaffected with the different A⁺ ions. Furthermore, the nature of the A⁺ ions influences the thermal behavior of the compounds, which has been monitored for selected examples by thermogravimetric differential thermal analysis (DTA/TG) and XRD measurements.     

Reactivity of urethanes at high temperature: Transurethanization and side reactions

The reactivity of urethanes based on 1,6‐hexamethylene diisocyanate (HDI) and 4,4′‐methylene diphenyl diisocyanate (MDI) was investigated at temperatures between 190 °C and 235 °C. Diurethane model compounds end‐capped with either 1‐dodecanol (D‐core‐D) or 1‐hexadecanol (H‐core‐H) were mixed and annealed at high temperature. The core was either MDI or HDI. The transurethanization reaction was followed based on the formation of the compounds (H‐core‐D). The amount of H‐core‐D and of side products, which had formed after variable annealing times, were identified with ¹H NMR, FTIR, SEC, and MALDI‐TOF. Transurethanization was considerably faster for MDI‐based urethanes than for HDI‐based urethanes. Only traces of side products were formed during annealing of MDI‐based urethanes, whereas a significant amount of allophanates was formed from HDI‐based urethanes under the same conditions. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 621–629