Zur kinetik der acrylnitril-polymerisation

The heterogeneous bulk polymerization of acrylonitrile initiated by AIBN has been studied by means of an improved dilatometric technique and a new method of analysis, where the initial reaction rate (v_w)₀ results from the intercept of a straight line in a \documentclass{article}\pagestyle{empty}\begin{document}$ \frac {\ln \left( 1 \hbox{---} {\rm U} \right)} {{\rm e}^{{- 0,5} {\rm k}_{\rm s}{\rm t} \hbox{---} 1}}$\end{document} versus t plot. It has been found that the initial reaction rate is proportional to the square root of the initial catalyst concentration S₀. The ratio of the rate coefficients of propagation and termination\documentclass{article}\pagestyle{empty}\begin{document}$\frac { {\rm k}_{\rm a} } { {\rm k}_{ {\rm w}^{2} } } $\end{document} could be calculated from the slope of a straight line passing through the origin in a plot of (v_w)₀ versus \documentclass{article}\pagestyle{empty}\begin{document}$\sqrt { {\rm S}_{0} }$\end{document} and yielded a value of 280 mol 1^?1.     

Identification of the state of palladium in various hydrogenation catalysts by XPS

Various commercial supported palladium hydrogenation catalysts were studied by XPS and treated at ambient pressure with hydrogen and air. Unused catalysts exhibit a significant fraction of divalent Pd (oxide) which is reduced by hydrogen treatment at room temperature. Exposure to air in systems with carbonate, alumina, silica or active carbon as support causes the formation of a solid solution of oxygen in Pd characterized by a Pd 3d chemical shift of ca. + 0.4 eV. The absolute binding energy of Pd depends strongly on the matrix, indicating a significant contribution of extra-atomic screening, which prevents a direct comparison of reference samples and supported catalysts. Using the oxidation of CO to CO₂ at 300 K as in situ chemical probe it was confirmed that Pd supported on carbonate, silica and alumina exists in the same metallic state which could be activated for the test reaction irrespective of the variation in XPS binding energies.     

Organic Nanoparticles with Polypropyleneoxide Chains as Support for Metallocene Catalysts: Ethylene Homopolymerization and Ethylene/α-olefin Copolymerization

Summary Novel organic nanoparticles functionalized with nucleophilic polypropyleneoxide (PPO) chains on their surfaces for supporting metallocene catalysts in heterogeneous olefin polymerization are presented. The nanoparticles (60–100 nm) were obtained by miniemulsion polymerization of styrene, divinylbenzene and PPO functionalized styrene. It is demonstrated that Me₂Si(2MeBenzlnd)₂ZrCl₂/MAO supported on these nanoparticles is suitable for the homopolymerization of ethylene, resulting in excellent product morphologies and high activities. lt is shown that by varying the MAO/Zr ratios and Zr concentrations the activities and productivities of the catalysts as well as the qualities of the polyethylene products can be tuned. These new supported catalysts are also suitable for the copolymerization of ethylene with several comonomers (1-hexene, 1-octene, 1-decene or norbornene). As the obtained product properties like crystallinity, melting temperature or bulk density match the results of silica supported systems, these organic nanoparticles can be considered as alternative carriers in comparison to the established inorganic ones.     

Closed‐Loop Identification for Control of Linear Parameter Varying Systems

This paper deals with system identification for control of linear parameter varying systems. In practical applications, it is often important to be able to identify small plant changes in an incremental manner without shutting down the system and/or disconnecting the controller; unfortunately, closed‐loop system identification is more difficult than open‐loop identification. In this paper we prove that the so‐called Hansen scheme, a technique known from linear time‐invariant systems theory for transforming closed‐loop system identification problems into open‐loop‐like problems, can be extended to accommodate linear parameter varying systems as well. We investigate the identified subsystem's parameter dependency and observe that, under mild assumptions, the identified subsystem is affine in the parameter vector. Various identification methods are compared in direct and Hansen Scheme setups in simulation studies, and the application of the Hansen Scheme is seen to improve the identification performance.     

A Unified Model for the Mixing of Non‐Newtonian Fluids in the Laminar,Transition, and Turbulent Region

Summary: Non‐Newtonian fluid behavior has significant influence on quantities in chemical engineering like power input, mixing time, heat transfer etc. In the laminar flow region, the concept of effective viscosity by Metzner and Otto is well established. In the transition region between laminar and turbulent flow, the existing concepts use three and even more empirical parameters to determine the specific power input. Here, a unified and general but simple approach is introduced to calculate the power input for shear thinning fluids over the whole flow region using just one empirical parameter. The Metzner‐Otto relation is obtained as a limiting case for the laminar region. The empirical parameter of the new approach is related to the Metzner‐Otto constant. The concept is validated for eight different stirrer systems. Mixing time and maximum shear rate and heat transfer can also be calculated using this approach. The new concept presented should also be applicable for other apparatuses, e.g., static mixers.

Comparison of experimental data and a curve calculated according to the new method (solid line).     

Structural control in radical polymerization with 1,1 diphenylethylene: 2. Behavior of MMA-DPE copolymer in radical polymerization

Copolymers of 1,1-diphenylethylene (DPE) behave in a very special way in radical polymerization. Particularly, the behavior of MMA-DPE copolymers in radical polymerization is investigated. The results reveal that the semiquinoid structure of the precursor polymer identified in a previous contribution is activated by the attack of free radicals and thus, in a second stage polymerization with a second monomer, block copolymers are formed. The block copolymer yield depends strongly on the ratio between the amount of DPE-containing precursor polymer and the initiator and monomer concentration used in the second stage. The mechanism proposed is able to explain at least qualitatively all experimental results including the restriction of this mode of control of radical polymerization to the formation of diblock copolymers only.