Polymerisation von Vinylchlorid bei Atmosphärendruck. 2. Chemische und spektroskopische Methoden zur Charakterisierung von U-PVC

PVC, which was polymerized at atmospheric pressure (so called U-PVC) contains relatively high concentrations of defects contrary to normal PVC. The number of chain scissions in U-PVC determined by ozonolytic cleavage resulted in values between 0.026 and 0.058 per 100 monomer units (100 VC). The determination of allylic and tertiary chlorine was done by selective reaction of U-PVC with phenol and NMR-spectroscopic investigations of the phenolized polymers. The average ‘labile chlorine’ content amounts to 0.65/100 VC. Hydroxyl radicals formed during the decomposition of the initiator (K₂S₂O₈) resulted in alcoholic endgroups in U-PVC, which were detectable in the IR-spectrum at 3580 cm^?1. The termination with hydroxyradicals also led to structures at the chain ends changing into ß-chloraldehyde groups accompanied by HCl-elimination. The corresponding signal in the IR-spectrum appeared at 1720 cm^?1. U-PVC raw material contained about two branch points per 100 VC. The CCl₄ extracts of the same polymers revealed the ten-fold content of branching. The olefinic structures ? CH?CH? CHCl? and ? CHCl? CH?CH₂ were determined by NMR-spectroscopy. The concentrations of each ranged from 0.25 to 0.3/100 VC. A typical double bond for U-PVC at the chain ends represented the structure ? CH?CH? CH₂Cl, which was preferably present in the low molecular weight material.     

Herstellung von metallischen Nanopartikeln in einem asymmetrischen Dielectric Barrier Discharge‐Plasma bei Atmosphärendruck

This paper focuses on the production of metal nanoparticles in a dielectric barrier discharge (DBD) reactor at atmospheric pressure. In the developed reactor only one electrode is provided with a dielectric (alumina), while the point‐shaped counter electrode is not covered and is accessible to the filamentary discharges (asymmetrical DBD). The metallic particles are formed from the material of the open counter electrode, on which the filamentary discharges lead to the formation of craters. A high number of larger nanoparticles (with diameter of some tens of nanometers) are observed in the cold reactor at the beginning of the discharges. After the achievement of the thermal equilibrium in the reactor mainly very small metallic nanoparticles are produced with constant size and number concentration. The produced metallic particles in thermal equilibrium are crystalline and not agglomerated. The mean diameter of the produced particles is about 4 nm. For given operating conditions of the reactor (fixed electrode gap and gas flow rate) the electrode material has almost no influence on the size of the produced particles, but it determines the number concentration.     

Diskontinuierliche Polymerisation von Vinylchlorid in suspension mit Temperaturprogramm

The batch polymerization of vinyl chloride in suspension can be conducted with constant rate of polymerization up to very high degrees of conversion by means of a temperature programme. The temperature programme was determined from some conversion-time-curves of the batch polymerization of vinyl chloride at different temperatures. The molecular weight and the molecular weight distribution of the poly (vinyl chloride) produced with the temperature programme are in agreement with the calculated respectively expected values.     

Künstliche Atmosphären bei der Herstellung von Arznei- und Lebensmitteln,Farben und Lacken sowie anderen Produkten

Artificial Atmospheres in the Manufacture of Drugs, Foods, Colours, Paints and Others Products Application and construction of gas generators meant for producing artificial atmospheres, which prevent fire and explosion in factory plants and enable the processes to be carried out in the absence of air are reported.     

Der Einfluß von Sauerstoff auf die Polymerisation von Vinylchlorid am Beispiel der Suspensionspolymerisation

Under the conditions of suspension polymerization vinyl chloride reacts readily in the presence of radicals with oxygen to form vinyl chloride peroxide. This decomposes to the following products: formaldehyde, hydrogen chloride and carbon monoxide. This sideproducts have to be considered, when vinyl chloride is polymerized in the presence of oxygen. Thus the formation of PVC containing carbonyl groups can be explained. Furthermore oxygen can initiate the suspension polymerization of vinyl chloride under certain conditions.     

Qualitätsmanagement bei der Herstellung von Chemieapparaten aus Sonderwerkstoffen

Quality Management during the Fabrication of Chemical Equipment Made of Special Materials Optimizing a material's resistance to corrosion by the addition of alloying elements up to their solubility limits will make it increasingly difficult to use these frequently unstable alloys for the manufacture of chemical plant. The requirements these materials have to meet in the manufacture of chemical plant in terms of manufacturing technology and quality management, are becoming increasingly stringent. The current situation, for example in the manufacture of domed heads of pressure vessels, forgings, heat exchangers, and filter screens with a high specific surface area as a constituent part of stirred suction filters using advanced metallic materials, is not very satisfactory. Results of fabrication tests necessary for pressure vessel manufacture as well as in-service failures frequently demonstrate insufficient expertise of workshops dealing with high-alloy stainless steels and nickel-based materials. That the in-service failure of compoents clearly leads to considerable costs due to maintenance, delays in supply, and production downtimes. The economic consequences can be substantial. The aim of this paper is to highlight sensitive areas by demonstrating the impact of unintentional and unnoticed fabrication-related changes in welding parameters and to provide information on easily applicable methods of monitoring techniques.     

Chemische und physikalische Vorgänge bei der Herstellung von Polyurethan-Weichschaumstoffen

The kinetics of foam formation are observed by IR-spectroscopy. The formation of polyurethane and polyurea occurs simultaneously, the transition from the dissolved to the crystalline urea being chronologically measurable. The difference between hotcure and cold-cure (HR) foam is explained. NCO-linking reactions cannot be detected by IR-spectroscopy. Using a foam with a density of 26 kg/m³, a quantitative study of foam formation was made, using chemical methods of analysis. Gas yield and time of curing are determined.     

Untersuchungen zur Gegenionenstruktur bei der Kationischen Polymerisation von Isobutylvinylether mit iodhaltigen Initiatoren

Investigations on the Counter Ion Structure of the Cationics Polymerization of Isobutylvinylether with Iodine Based Systems The structure of counter ions of iodine based initiators for the cationic polymerization of isobutylvinylether is elucidated by means of u.v.-spectroscopy using as model system: Increasing electrophilicity of the cation causes a decrease of the counter ion stability. High concentrations of iodine lead to the formation of polyiodides, as I and I, respectively. The influence on chain propagation by iodine and monomer concentration as well have been followed by GPC and u.v.-spectroscopy. Both influences, strongly affects the propagation reaction. Triphenylmethylbromide in conjunction with iodine is a convenient initiating system, realizing a long living and transfer suppressed propagation, when solvents of higher polarity are used. An activated carbon-halide bond is concluded to be the active species.     

Methoden zur Herstellung und Charakterisierung von Kunststoffen mit verbesserter Blutverträglichkeit

Tubings of different internal diameter (ID) were prepared from 10 different polymers (CPE, EPDM, ETFE, EVA, LDPE, PP, PTFE, PUR, PVC and Silicone):

• tubings of 4–5 mm ID for in vitro- and ex vivo-blood compatibility tests with human blood,
• tubings of 0.3–0.4 mm ID for ex vivo-evaluations for blood compatibility via measuring the bleeding time after introduction of the tubing into the ear vein of rabbits.

The tubings were surface modified by grafting with N-vinyl-N-methyl acetamide (VIMA). For both the original and the grafted tubing correlations were established between the physical characterization (degree of grafting, critical surface tension, ESCA, FT-ATR-IR, SEM) and the in vitro and the ex vivo blood compatibility tests. The in vitro blood compatibility tests consist of an incubation of 4–5 mm tubing with citrated human blood and subsequent determinations of clotting parameters. The human ex vivo blood compatibility tests were performed on human arm veins followed by investigation of the internal surface of the tubing. The results could be correlated with the in vitro tests with human blood. A comparison with conventional tubing on the market (PVC and Silicone) as a standard shows, that PTFE/VIMA, LDPE/VIMA, PUR and EVA have better blood compatibility properties than the standard whereas untreated PTFE and LDPE are ranked below the standard.