Untersuchung des einflusses molekularer parameter auf morphologie und eigenschaften von polyethylenen niedriger dichte

Based on the example of PE-LD grades and on model substances obtained by preparative fractionation (fractions in the molecular weight range M?_w = 1.2 ? 390·10⁴ g/mol), comprehensive investigations regarding the problems of structure/properties have been carried out. The correlations of M?_w with 15 physical and application technological perameters have been investigated taking into account the reaction mechanism during the manufacturing of PE-LD in the tubular and agitated autoclave reactor, resulting in the formation of so-called primary structure perameters M?_n, M?_w, molar mass distribution, short chain branching and long chain branching. For the interpretation of the results, among other factors, also the morphological conditions have been taken into consideration, which in connection with the molecular parameters reveal — for specific M?_w-ranges — strong changes and saturation ranges, resp., for the physical and application technological properties.     

Preparation and properties of high molecular weight poly(1-germa-) or poly(1-sila-cis-pent-3-enes)

High molecular weight poly(1,1-dimethyl-1-germa-cis-pent-3-ene), poly(1,1-diphenyl-1-germa-cis-pent-3-ene), poly(1,1-dimethyl-1-sila-cis-pent-3-ene), and poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene) have been prepared. The thermal stability of these polymers is found to increase with their molecular weight.     

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.     

In situ ellipsometric study of a palladium catalyst during the oxidation of methane

Ellipsometry is used to follow the growth of a PdO layer on the surface of a thick Pd-film catalyst during methane oxidation at 500°C. The oxide layer that develops under rich conditions (excess CH₄) is quite porous and roughens with time. Little CO is formed during this period, but the CO₂ formation rate increases until spontaneous oscillations develop, which correlate with changes in the ellipsometric data. These changes indicate that the porous oxide rapidly converts to a metal-rich state, which has decreased catalytic activity, and then slowly reoxidizes.     

Liquid spouting of pulp fibers in a conical vessel

Pulp fibers can be spouted in water in a conical vessel. The entities which are spouted are fiber flocs rather than individual fibers. Synthetic fibers, which do not flocculate, cannot be spouted. For comparison, rigid spherical particles were spouted with water in the same conical vessel. Liquid spouting of rigid particles was similar to gaseous spouting. For pulp spouting, the minimum spouting velocity is proportional to the mass of fibers in the bed and inversely proportional to the diameter of the inlet. For rigid particles, the minimum spouting velocity is proportional to the height of the bed and inversely proportional to the square of the diameter of the inlet. A model for the minimum spouting velocity was developed for pulp spouting.     

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.     

Synthesis of poly(1-methyl-1-phenyl-1-silapentane) by chemical reduction of poly)1-methyl-1-phenyl-1-sila-cis-pent-3-ene with diimide

Summary Poly(1-methyl-1-phenyl-1-silapentane) (I) has been prepared by the chemical reduction of the carbon-carbon double bonds of poly(1-methyl-1-phenyl-1-sila-cis-pent-3-ene (cis-II) with diimide, which was generatedin-situ by the thermal decomposition ofp-toluenesulfonhydrazide in refluxing toluene. At lower temperature (100°C),cis-II is isomerized byp-toluenesulfinic acid to lower molecular weight poly(1-methyl-1-phenyl-1-sila-cis andtrans-pent-3-ene) (cis/trans-II). Protodesilation of I with trifluoromethanesulfonic acid yields poly(1-methyl-1-trifluoromethanesulfonyl-1-silapentane) (III). The structures of I andcis/trans-II have been characterized by¹H,¹³C and²⁹Si NMR, GPC, TGA and elemental analysis. The structure of I has been characterized spectroscopically by¹H,¹³C,¹⁹F and²⁹Si NMR.     

A simple method for the objective characterisation of fabric softness. Part 1: Influence of bleaching,dyeing and crosslinking of wool*

A simple method for the characterisation of fabric softness using a conventional tensile tester and a special measurement device has been developed. The method is demonstrated to be especially useful in detecting changes in softness of a given substrate due to different treatments. The results obtained, particularly hysteresis at 75% of the maximum extension, provide a good correlation with subjective ranking for samples that are subjectively distinguishable; they also differentiate well between samples which seem subjectively indistinguishable. Screening tests were carried out, mainly on wool fabrics, to find the effect of different treatments such as oxidative (alkaline and acidic) and reductive (Blankit IN) bleaching, dyeing with acid and a 1:2 metal complex, chrome and (mono and bi)reactive dyes, the effect of the antisetting agent Basolan AS (BASF) and of crosslinking with Irgasol HTW (CGY) on fabric softness.     

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.