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.     

Impacts of new technologies on media usage and social behaviour in domestic environments

Technological infrastructure at home is changing continuously and is becoming increasingly interconnected. Media devices, including the TV set, provide access to the Internet and offer manifold opportunities to consume media on demand. Additionally, personal devices, such as smartphones, also enable flexible consumption and sharing of media. Questions about how these technologies change the user's media usage and how these changes affect the social structure of a household, however, remain largely unanswered. In order to gain insight into the adoption of new technologies into daily routines, we explored these changes in respect of people's media usage in a qualitative long-term Living Lab study. We will present findings regarding personal routines, flexible integration of new devices into existing practices, influences on households as social systems and related issues in device access and collective use. We will highlight potentials and conflicts regarding device shifts and roles; restrictions in device access; social influences in the living room; and individual changes in media consumption.     

Microenvironmental engineering: An effective strategy for tailoring enzymatic activities

Rationally, engineering a favorable physicochemical microenvironment for enzymes has recently emerged as an effective strategy to improve their catalytic performance. In this review, we discuss four microenvironmental effects according to the mechanism of action: localizing and excluding reactants and regulators, regulating microenvironmental pH, creating a water-like microenvironment, and increasing the local temperature. These mechanisms are enzyme-independent and can in principle be used in combination to tailor enzyme behaviors, offering new approaches to enabling, enhancing, and regulating enzyme catalysis in diverse applications without the need for genetic engineering.     

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.