Zur oligomerenbildung bei der thermischen polymerisation von styrol

It is shown that in thermal polymerization of styrene four dimers and six trimers are formed by parallel occurring oligomerization reactions. With increasing temperature the rate of oligomerization increases more rapidly than the rate of polymerization. The relativ yields of the different oligomers depend on temperature, too.     

Struktur und eigenschaften von ABS-polymeren. IX. Quantitative untersuchungen zur morphologie von ABS-polymerisaten

The technological properties of ABS polymers largely depend on the structure of the elastomer phase as well as on the elastomer/thermoplast interface. The morphological structure of such polymers can be determined from electron micrographs of ultramicrotome sections – after selective contrasting of the polybutadiene phase – or of replicas of fracture surfaces after selective chemical degradation. The various ABS polymers are classified by their manufacturing processes and their morphologies and characterized by electron micrographs. The degree and place of grafting are of particular importance. The quantitative determination of the surface- and internal grafting is achieved by combining the determination of the degree of grafting (extraction), the evaluation of the results obtained on particle counting, and a morphometric process. It is demonstrated that the morphometric process can in general be applied for the quantitative determination of the contrastable component in two-phase polymers.     

Effect of Zwitterionic Surfactants on Interparticle Forces, Rheology, and Particle Packing of Silicon Nitride Slurries

Phosphocholine (PC) zwitterionic surfactants, with different hydrocarbon chain lengths (C₆C₆PC to C₉C₉PC), were absorbed on the surface of silicon nitride near the isoelectric point (pH 6). Adsorption of the surfactants changed the lateral and normal surface forces, the rheology, and the consolidation behavior of the particles. The normal force between two silicon nitride surfaces as a function of separation and the lateral (friction) forces were measured using an atomic force microscope (AFM). These measurements indicated that surfactant adsorption reduced the magnitude of the long-range attractive van der Waals force and produced a repulsive short-range force. Although the adsorbed layers provided a barrier to particle contact, they could be ejected with a critical force that increased with the hydrocarbon chain length. The effect of an adsorbed layer on the viscosity and consolidation of slurries was also measured. The viscosity of all slurries decreased with increasing shear rate, indicative of attractive particle networks. The highest viscosity was observed for slurries formulated at the isoelectric point without added surfactant. Much lower viscosities were observed when the surfactant concentration was greater than the critical micelle concentration (cmc). A relative density of 0.46 was obtained via pressure filtration at 4 MPa without a surfactant, and between 0.46 to 0.59 (C₆C₆PC to C₉C₉PC, respectively) for surfactant concentrations greater than the cmc. Comparing force measurements with rheology and packing density provides a basis for discussing the role of interparticle forces in ceramic powder processing via colloidal routes.     

Das Verhalten organischer Pigmente in Polymeren

The importance of colouring matter is of prime importance in the plastics industry. The individual behaviour of organic pigments in the various polymer materials necessitates, however, on the part of the plastics manufacturer a precise knowledge of ?which pigment for which plastic”?. For example, a well known Thioindigo pigment behaves very differently in various polymer materials : In polystyrene, depending on the concentration used, it is monomolecularly dissolved, in associated solution or present as undissolved particles. In PVC, however, the good migration fastness is indicative of the insolubility of the pigment in this medium and so it is not surprising that PVC is the ideal plastic medium for this pigment. The behaviour of organic pigments in polymers is largely a function of molecular structure, e. g. intermolecular H-bonds can cause a decrease in solubility of a pigment in a polymer material, which in turn results in improved migration fastness. This is demonstrated by the improved migration fastness of variously substituted β-hydroxy naphthoic acid arylamide derivatives. Many phenomena exist however, which as yet can only be explained on the basis of the crystal structure of the pigment particles, i. e. the presence of aggregates or agglomerates. Such a phenomenon is, for example, the dispersibility of pigments in polymers. Here pigment surface, wettability by polymer and intermolecular forces are all of importance. In general, the dispersibility is better the smaller the specific surface area, as is shown for a typical quinacridone pigment. The influence of the rate of wetting on dispersibility is demonstrated using polyethylene wax. A further effect, which demonstrates the intermolecular forces between pigment and polymer, is the way in which certain pigments influence the rate of crystallization of partly crystalline polymers. This itself is connected with the shape and size of the pigment particles embedded in the polymer material. Such effects are demonstrated by measurements on various polyethylene objects. The pigment in this case was a naphthalene tetra carbonic acid derivative in both cis and trans form with widely varying specific surface areas.     

Zur Selbstdiffusion von Benzol und Azeton in Polymethylmethacrylat

The selfdiffusion coefficients of acetone and benzene are studied in the systems acetone/poly(methylmethacrylate) and benzene/poly(methylmethacrylate) by means of the spin echo technique as function of concentration and temperature. From the dependence of temperature, the activation energies are calculated as function of concentration. The dependence of concentration of the selfdiffusion coefficients is discussed using the theory of Free Volume according to FUJITA. The Free Volume of the poly(methylmethacrylate) is calculated as function of temperature.     

"Alumina" Surface Modification of Silicon Nitride for Colloidal Processing

Two different methods are used to coat silicon nitride particles with an alumina precursor to make Si₃N₄ behave like Al₂O₃ in aqueous slurries. The first method involves the precipitation of an aluminum hydroxycarbonate from dissolved Al(NO₃)₃ during the decomposition of urea. In the second method, dry silicon nitride powder is reacted with aluminum tri- sec -butoxide in hexane at room temperature. Both methods produce a coated powder in which the electrophoretic and rheological properties of aqueous slurries mimic those of alumina. When salt is added to slurries consisting of coated Si₃N₄ powder, all rheological evidence suggests the presence of a short-range repulsive potential that produces a weakly attractive particle network similar to that previously reported for Al₂O₃ powder. Although electrophoretic and rheological data showed that the coated powder behaved like Al₂O₃, consolidation data indicated that slurries of coated powder with added salt did not pack to high density. In addition, these bodies were not plastic as found for bodies consolidated from dispersed and salt-added Al₂O₃ slurries.     

Syntheses of female sex pheromone precursors of pine sawfly species and of some structurally related methyl-branched long-chain 2-alkanols

3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R,11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of -butyrolactones by using different alkyl lithiums as nucleophiles.     

Antioxidative effects of polyamines

The antioxidative effects of spermine, spermidine and putrescine were determined by measurement of primary and secondary oxidation products of polyunsaturated fatty acids, using gas and liquid chromatography as well as spectrophotometric recordings. It was demonstrated that polyamines inhibit the oxidation of polyunsaturated fatty acids,α-tocopherol and carotenoid pigments. Both linear and nonlinear dose/response relationships have been observed. The efficiency of a given polyamine was correlated with the number of amine groups in the molecule. Spermine was, thus, more efficient than spermidine, which in turn had a higher efficiency than putrescine. The relative antioxidative effect was as follows: spermine (100.0), spermidine (61.0), putrescine (23.0), ethoxyquin (27.6), ascorbyl palmitate (18.3), octyl gallate (7.9), tert butylhydroquinone (6.3), butylated hydroxyanisole (3.6) andα-tocopherol (3.4).     

Intercorrelations among plasma high density lipoprotein,obesity and triglycerides in a normal population

The interrelationships among fatness measures, plasma triglycerides and high density lipoproteins (HDL) were examined in 131 normal adult subjects: 38 men aged 27–46, 40 men aged 47–66, 29 women aged 27–46 and 24 women aged 47–66. None of the women were taking estrogens or oral contraceptive medication. The HDL concentration was subdivided into HDL_2b, HDL_2a and HDL₃ by a computerized fitting of the total schlieren pattern to reference schlieren patterns. Anthropometric measures employed included skinfolds at 3 sites, 2 weight/height indices and 2 girth measurements. A high correlation was found among the various fatness measures. These measures were negatively correlated with total HDL, reflecting the negative correlation between fatness measures and HDL₂ (as the sum of HDL_2a and_2b). Fatness measures showed no relationship to HDL₃. There was also an inverse correlation between triglyceride concentration and HDL₂. No particular fatness measure was better than any other for demonstrating the inverse correlation with HDL but multiple correlations using all of the measures of obesity improved the correlations. Partial correlations controlling for fatness did not reduce any of the significant correlations between triglycerides and HDL₂ to insignificance. The weak correlation between fatness and triglycerides was reduced to insignificance when controlled for HDL₂. Presented (in part) at the Annual Meeting of the Oil Chemists' Society in St. Louis, MO, May 1978.     

Sulfur deactivation and regeneration of Pt/BaO/Al2O3 and Pt/SrO/Al2O3 NO x storage catalysts

Transient experiments were performed to study sulfur deactivation and regeneration of Pt/BaO/Al₂O₃ and Pt/SrO/Al₂O₃ NO _x storage catalysts. It was found that the strontium-based catalysts are more easily regenerated than the barium-based catalysts and that a higher fraction of the NO _x storage sites are regenerated when H₂ is used in combination with CO₂ compared to H₂ only.