Photocrosslinking of thin polymer films – materials for sensors and actuators

Polymers with temperature dependent degrees of swelling, especially polymers which exhibit lower critical solution temperature (LCST) behaviour in aqueous solutions, are of interest for applications in microsystems. For these applications it is necessary to form and pattern thin films in the μm-range. This has been achieved through photocrosslinking of linear prepolymers. Copolymers based on N-isopropylacrylamide (NIPAAm) were modified with a stilbazolium salt chromophore to yield photocrosslinkable temperature sensitive polymers. The chromophore reacts via a [2+2]-cycloaddition under irradiation, this can be used to crosslink the polymer. The photocrosslinking properties were studied by UV irradiation of thin films and measuring the changes in UV absorption spectra. Through irradiation of thin films through a mask it was possible to obtain patterned networks in the μm-range (20 μm space width and > 50 μm line width). The polymers exhibited LCST behaviour, which was measured using DSC. The resulting patterned networks had temperature dependent swelling properties in aqueous media.     

Novel Amidoniobium Complexes with a Functional Relationship to the [Cp2ZrR]+ Ion*

Partial abstraction of apical methyl groups is observed in aminopyridinatoniobium alkyne complexes, as exemplified with the synthesis and characterization of 1 . This results in cationic complex fragments, which facilitate the polymerization of ethylene and in the presence of methylalumoxane the selective dimerization of 1-butene.     

New polymers by homogenous zirconocene/aluminoxane catalysts

With homogenous catalysts on the basis of chiral metallocenes and methylaluminoxane it has become possible to polymerize cyclic olefins like cyclobutene, cyclopentene or norbornene. No ring opening reaction occurs. The crystalline polycycloalkenes show extremly high melting points between 400 and 600°C. Copolymers of cyclopentene with propene are amorphous. They have a low molecular weight and glass transition point. On the other hand the glass transition temperature of norbornene/ethene copolymers exceeds 130°C. These copolymers could be used as materials for optical discs and fibers.     

Automatically and electronically controllable hydrogel based valves and microvalves – design and operating performance

This paper describes automatically and electronically controlled valves and microvalves based on smart hydrogels. The operating performance of such devices will be discussed in dependence on various design parameters. Furthermore, it will be shown that hydrogel based valves are showing an outstanding possibility of miniaturization, a leakage free switching behavior up to a pressure drop of 8.4 bar, and a pronounced particle tolerance.     

Reactions of Group 4 Metallocenes with Monosubstituted Acetonitriles: Keteniminate Formation versus CC Coupling

The reactions of the Group 4 metallocene dichlorides [Cp′₂MCl₂] ( 1 a : M=Ti, Cp′=Cp*=η⁵‐pentamethylcyclopentadienyl, 1 b : M=Zr, Cp′=Cp=η⁵‐cyclopentadienyl) with lithiated MesCH₂?C?N gave [Cp*₂TiCl(N=C=C(HMes))] ( 3 ; Mes=mesityl) in the case of 1 a . For compound 1 b , a nitrile–nitrile coupling resulted in a five‐membered bridge in 4 . The reaction of the metallocene alkyne complex [Cp*₂Zr(η²‐Me₃SiC₂SiMe₃)] ( 2 ) with PhCH₂?C?N led in the first step to the unstable product [Cp*₂Zr(η²‐Me₃SiC₂SiMe₃)(NC?CH₂Ph)] ( 5 ). After the elimination of the alkyne, a mixture of products was formed. By variation of the solvent and the reaction temperature, three compounds were isolated: a diazadiene complex 6 , a bis(keteniminate) complex 7 , and 8 with a keteniminate ligand and a five‐membered metallacycle. Subsequent variation of the Cp ligand and the metal center by using [Cp₂Zr] and [Cp*₂Ti] with Me₃SiC₂SiMe₃ in the reactions with PhCH₂?C?N gave complex mixtures.