Kinetik der polykondensation von natriumsulfidhydrat und 1,4-dichlorbenzol zu poly(thio-1,4-phenylen)

The kinetics of the polycondensation of sodium sulfide hydrate and 1,4-dichlorobenzene to poly(thio-1,4-phenylene) in 1-methyl-2-pyrrolidone as solvent was studied in a differential scanning calorimeter at temperatures between 220 and 280°C. This polycondensation shows an autocatalytic behavior and the kinetics can be modelled by a first order reaction up to complete conversion. This is explained by the low solubility of sodium sulfide in l-methyl-2-pyrrolidone. The concentration of sodium sulfide is regarded as being constant during the whole course of the reaction. The autocatalytic effect can be explained by the increase of the condensation rate constant at the beginning of polycondensation due to the higher reactivity of the oligomers compared to the monomers. The number- and the weight-average molecular weight of the products formed during the course of the polycondensation can be modelled by means of stochastic methods. A simple model with only two different rate constants of the condensation process is assumed. The concentration of sodium sulfide in the reactive phase is found to be 2–5% of the value of dichlorobenzene at the beginning of the reaction and remains constant nearly until the end of polycondensation.     

A Study of Surface Deformation during Wire‐Rod Rolling of High Speed Steels using Experimental and Computational Techniques

The evolution of surface defects during shape rolling of high‐speed steel billets is studied using longitudinal surface defects prepared by machining and welding. The reduction of the defects during rolling in a production mill is compared to the total area reduction of the billets. Samples are collected after pass 4, 6, 8, 14, 19 and the final pass, 28, representing the finished 5.5mm wire. By inspecting the cross sections, the rotation of the billets from pass to pass is evaluated. Results from FE simulations on solid billets are compared to the experimental results. Generally, simulations predict less reduction than observed experimentally. In most cases cracks reduce most effectively followed by carbon steel welds and stainless steel welds.     

The effect of reaction conditions on montmorillonite-catalysed peptide formation

Oligomerization of glycine (gly) and diglycine (gly₂) on montmorillonite was performed as cyclic, drying-wetting process at temperatures below 100°C, under varying reaction conditions. The influence of substrate/clay ratio, temperature and pH was found to be different for amino acid (AA) dimerization, cyclic anhydride (CA) formation and peptide chain elongation. High temperatures and neutral pH favour CA formation over diglycine production. An AA/catalyst ratio of 0.2 mmol/g leads to optimal yields. This supports the assumption that amino acid dimerization and CA formation take place at the edges of clay particles. Peptide chain elongation, starting from gly₂, produces higher yields at higher temperatures and neutral pH.     

Ring hydrogenation of naphthalene and 1-naphthol over supported metal catalysts in supercritical carbon dioxide solvent

Catalytic ring hydrogenations of naphthalene and 1-naphthol were studied over several supported metal catalysts in supercritical carbon dioxide solvent at low temperature. Higher concentration of hydrogen in supercritical carbon dioxide and lower reaction temperature were responsible for higher catalyst activity and selectivities to the desired partial ring hydrogenated products as compared with those observed in organic solvent for the same catalyst.     

Matrix‐assisted laser desorption/ionization mass spectrometry of synthetic polymers. VI. Analysis of phenol–urea–formaldehyde cocondensates

Phenolic resoles can be regarded as copolymers of phenol and formaldehyde that are distributed in the chain length and the number of methylol groups per molecule. While other spectroscopic methods like FTIR and NMR only give average structures, MALDI–TOF mass spectrometry is able to resolve the oligomer distribution of phenolic resoles. Using 2,5‐dihydroxybenzoic acid or 2,4,6‐trihydroxyacetophenone as matrices, MALDI–TOF spectra are obtained where each oligomer peak can be assigned to a particular chemical structure. Thus, the degree of polymerization and the number of reactive methylol groups can be determined. For urea‐modified resoles, in addition to phenol–formaldehyde and urea–formaldehyde structures, for the first time, phenol–urea–formaldehyde cocondensate structures can be identified directly. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2540–2548, 2003     

Structure of resorcinol,phenol, and furan resins by MALDI‐TOF mass spectrometry and 13C NMR

The structure of traditional, linear phenol–resorcinol–formaldehyde (PRF) resins, urea‐branched PRF resins, and phenol–resorcinol–furfural (PRFuran) resins has been investigated in depth by both matrix‐assisted laser desorption/ionization time of flight (MALDI‐TOF) mass spectroscopy and ¹³C NMR. The structure of a variety of oligomers has been obtained, and the structures present in each of the three types of resins related to the very different percentages of resorcinol needed for their equal performance as adhesives. The oligomers type and species distribution appeared very different for each case. PRF resins performance is improved by maximizing either the proportion of resorcinol‐containing oligomers or methylol‐groups containing oligomers, even without any resorcinol, or both. It is equally obtained by the minimization of the relative proportion of the low reactivity Phenol (CH₂ Phenol) species in which resorcinol is not present, this being the most important parameter. This can be obtained by more effective use of the resorcinol by just modifying the resin manufacturing procedure. This parameter instead does not appear to be determinant in PRFuran resins. In these, it is the higher molecular weight of furfural in relation to formaldehyde that engenders for the same manufacturing procedure a correspondingly lower proportion of resorcinol in the resin. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2665–2674, 2004     

Aldol condensation of butanal over alkali metal zeolites

Alkali metal zeolites and metal oxides were used for the aldol condensation of n-butanal to 2-ethyl-2-hexenal. The order of activity at 150 °C and 1 atm. was: CsNaY > NaY > LiNaY > MgO >Al₂O₃. Selectivity to 2-ethyl-2-hexenal was 100% for both pure and mixed isomer feed. Infrared spectroscopic studies showed that stable catalysts were produced by propene pretreatments which blocked Lewis acid sites. Adsorption of ammonia and carbon dioxide on CsNaY during aldol condensation of n-butanal causes a decrease in rate. This result, along with the order of activity, suggests that the presence of both acid and basic sites produce higher activity than strongly basic MgO.Work performed at San Jose State University.     

Note: flowing ion population from a resonance cavity source

The experimental low energy plasma for hemispherical analyzers nominal testing thermal plasma facility of Dartmouth College uses a microwave plasma source which generates an ionosphere-like plasma through a two-step process. The plasma is initially generated inside a cylindrical, insulated, resonance cavity. This initial plasma must pass through a sheath in order to enter the main experimental region. This process imparts a significant flow velocity to the ions which has been neglected in previous analysis of this plasma source. We predict the flow energy of the ions to be between 12-15 eV depending on conservation laws and show agreement with experimental results.