Γ-type-invariants associated toPU(2)-bundles and the differentiable structure of Barlow's surface

Supported by a Heisenberg-scholarship of the DFG     

Lightly crosslinked,mesomorphic networks obtained through the reaction of dimeric,liquid‐crystalline epoxy–imine monomers and heptanedioic acid

We reacted various dimeric, liquid‐crystalline epoxy–imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid‐crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed‐frequency and frequency‐sweep modes in the shear sandwich configuration. The arrangement in the liquid‐crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid‐crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid‐crystalline phase with respect to side‐chain liquid‐crystalline elastomers and that the time–temperature superposition principle did not hold through the liquid‐crystalline‐to‐isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270–6286, 2006     

Vinyl‐terminated side‐chain liquid‐crystalline polyethers containing mesogenic benzylideneaniline moieties

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P₄ and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and ¹H and ¹³C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C₂ mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006     

Synthesis of poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) by the competitive single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization in water

The synthesis of a block copolymer poly(vinyl chloride)‐b‐poly(n‐butyl acrylate)‐b‐poly(vinyl chloride) is reported. This new material was synthesized by single‐electron‐transfer/degenerative‐chain‐transfer‐mediated living radical polymerization (SET‐DTLRP) in two steps. First, a bifunctional macroinitiator of α,ω‐di(iodo)poly (butyl acrylate) [α,ω‐di(iodo)PBA] was synthesized by SET‐DTLRP in water at 25 °C. The macroinitiator was further reinitiated by SET‐DTLRP, leading to the formation of the desired product. This ABA block copolymer was synthesized with high initiator efficiency. The kinetics of the copolymerization reaction was studied for two PBA macroinitiators with number–average molecular weight of 10 k and 20 k. The relationship between the conversion and the number–average molecular weight was found to be linear. The dynamic mechanical thermal analysis suggests just one phase, indicating that copolymer behaves as a single material with no phase separation. This methodology provides the access to several block copolymers and other complex architectures that result from combinations of thermoplastics (PVC) and elastomers (PBA). From industrial standpoint, this process is attractive, because of easy experimental setup and the environmental friendly reaction medium. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3001–3008, 2006     

Effect of excess halide on the palladium‐catalyzed insertion‐triggered radical copolymerization of methyl acrylate and 1‐hexene

[Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) is a very efficient initiator of the radical polymerization of methyl acrylate, but it is not active in the polymerization of methyl methacrylate or in the copolymerization with 1‐hexene. The addition of an excess of NBu₄Cl to solutions of [Pd₂(μ‐Cl)₂(C₆F₅)₂(tht)₂] ( 1 ) provides an initiator system that copolymerizes methyl acrylate and 1‐hexene by an insertion‐triggered radical mechanism. Random copolymers are obtained with 11% incorporation of 1‐hexene in moderate yields (about 35%). Studies of the decomposition products obtained after the first insertion of methyl acrylate in the Pd? C₆F₅ bond of 1 show that the addition of excess halide in the presence of monomer favors the homolytic cleavage of the Pd? C bond, and the generation of the radicals that are active species in the polymerization, versus alternative evolution pathways. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5682–5691, 2006     

Single electron transfer–degenerative chain transfer living radical polymerization of N‐butyl acrylate catalyzed by Na2S2O4 in water media

Living radical polymerization of n‐butyl acrylate was achieved by single electron transfer/degenerative‐chain transfer mediated living radical polymerization in water catalyzed by sodium dithionate. The plots of number–average molecular weight versus conversion and ln[M]₀/[M] versus time are linear, indicating a controlled polymerization. This methodology leads to the preparation of α,ω‐di(iodo) poly (butyl acrylate) (α,ω‐di(iodo)PBA) macroinitiators. The influence of polymerization degree ([monomer]/[initiator]), amount of catalyst, concentration of suspending agents and temperature were studied. The molecular weight distributions were determined using a combination of three detectors (TriSEC): right‐angle light scattering (RALLS), a differential viscometer (DV), and refractive index (RI). The methodology studied in this work represents a possible route to prepare well‐tailored macromolecules made of butyl acrylate in an environmental friendly reaction medium. Moreover, such materials can be subsequently functionalized leading to the formation of different block copolymers of composition ABA. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2809–2825, 2006     

N,N‐dimethylaminopyridine as initiator in the copolymerization of diglycidylether of bisphenol A with six‐membered cyclic carbonates

N,N‐Dimethylaminopyridine (DMAP) was used as initiator to cure mixtures of diglycidylether of bisphenol A (DGEBA) and 1,3‐dioxan‐2‐one (TMC) or 5,5‐dimethyl‐1,3‐dioxan‐2‐one (DMTMC). The curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated‐total‐reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the evolution of the groups involved in the curing. We observed the formation of five‐membered cyclic carbonates and anionic carbonate groups that remain unreacted at the chain ends. The formation of these groups was explained by the attack of the anionic propagation species on the methylene carbon of the carbonate group, which leads to an alkyl‐oxygen rupture. By performing the cure in the thermobalance we could evaluate the loss of CO₂ produced in the samples containing carbonates. The kinetics were studied by DSC and analyzed with isoconversional procedures. The addition of carbonates slows down the curing rate. Thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) experiments were used to evaluate the properties of the materials obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2873–2882, 2006     

Efficient Synthesis of Nitroflavones by Cyclodehydrogenation of 2′-Hydroxychalcones and by the Baker-Venkataraman Method

Summary. Several nitroflavone derivatives were synthesized by cyclodehydrogenation of 2′-hydroxychalcones and by the Baker-Venkataraman approach, starting from 2′-hydroxyacetophenones and benzoic acid derivatives. Nitroflavones synthesised by the first synthetic approach were obtained in better global yields than those obtained by the later method. The structures of all new compounds were elucidated by microanalyses, 1D and 2D NMR, IR, and mass spectroscopic measurements.     

Consequences of magnetic aging for iron losses in electrical steels

Electrical steels, when submitted to operation, present continuous decrease of their magnetic properties, depending on the carbon content. This effect is attributed to the increase of the size of carbides, a process also known as coarsening or Ostwald Ripening. Loss separation can offer a better understanding of this phenomenon. Experimental results show that all effect of aging is inside the hysteresis loss component, with the excess losses unaffected. The carbon content in electrical steels should be less than 25 ppm to avoid magnetic aging.