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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 20 (1978), S. 1577-1594 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: By means of stimulus-response experiments with a Li+ tracer, a description of the fluid flow in a 30 m3 reactor, used for anaerobic treatment of wastewater, was derived. It appeared that of the three parts that could be distinguished in the reactor (the sludge bed. The sludge blanket, and the settler), the sludge bed could be described as a combination of two perfectly mixed regions with bypassing and return flows; the sludge blanket was perfectly mixed, while the fluid flow in the settler could be described as plug flow. From experiments performed under different conditions it was concluded that 60 m3 gas/day were sufficient to provide good mixing and also that the height of the sludge bed should be 2-3 m. From this last conclusion it follows, e.g., that scale-up of the 30 m3 reactor should be done by increasing the cross section of the reactor while homogeneously distributing the influent over the bottom.
    Additional Material: 14 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 24 (1982), S. 443-459 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Residence-time-distribution experiments for the fluid in a 30-m3 pilot plant and a 200-m3 prototype upflow reactor were performed by means of continuous injection of an LiCl solution as a tracer in the influent of the reactor and measurement of the response of this stimulus on several location in the reactor and in the effluent. In a similar way as described in an article published earlier, models have been developed by use of the measured data of the fluid flow pattern which consisted of region of ideal mixing, plug flow, dead space, and short circuiting. It appeared that the fluid flow patterns in the two reactors were to a large extent analogous. For the pilot plant, three-mixer models appeared to be appropriate while for the prototype reactor two-mixer models have been found. This differences was a result of the difference in the heights of the sludge beds in the reactors: 2-3 m in the pilot plant and only 0.4 m in the prototype reactor, a result of too small an amount of sludge. Another differences was that, due to large amount of mud in the prototype reactor, a region of dead space occurred in the models for the fluid flow pattern in this reactor. The dimension of the prototype reactor have been chosen according to several recommendations obtained from work with the pilot plant (e.g., scale-up should be done by increasing the cross section of the reactor; one influent point should be applied per 5 m2 bottom surface). The results presented here clearly show the value of these recommendations.
    Additional Material: 10 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 56 (1976), S. 27-36 
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Zusammensetzung von Copolymeren aus Vinylacetat (VAc) und Vinylbutyrat (VB) kann schnell und mit genügender Genauigkeit mittels dynamischer thermogravimetrischer Analyse (TGA) festgestellt werden, obgleich Essigsäure und Buttersäure zu gleicher Zeit und unvollständig aus den diesbezüglichen Segmenten abgespalten werden. Die TGA-Resultate werden mit aus gaschromatographischen Analysen erzielten Ergebnissen verglichen; sie liegen innerhalb der experimentellen Fehler. Die Ausweitung auf andere binäre Vinylester-Kombinationen ist wahrscheinlich möglich.
    Notes: The composition of copolymers of vinylacetate (VAc) and vinylbutyrate (VB) can be determined rapidly and satisfactorily by dynamic thermogravimetric analysis (TGA), in spite of the fact that both acetic and butyric acid are abstracted simultaneously and incompletely from their respective segments. The TGA results are compared with those obtained by gaschromatographic analysis of the reaction mixtures during copolymerization, and are within experimental error. Extension of this analysis method to other binary vinylester combinations seems to be possible.
    Additional Material: 1 Ill.
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The inhibitor and initiator action of 33 compounds on the bulk polymerization of pure isoprene has been studied. Picric acid was found to be the most powerful inhibitor at 100°C. The conclusion reached in Part I, that the initiator activity of diazoaminobenzene is superior to all other compounds has been found to be valid also between 100-150°C. The heat polymerization of isoprene between 100-150°C. in the presence of picric acid leads only to the formation of dimers. Three of the four possible isomers have been separated. The solid complex compound of diprene (I) with silver nitrate has been used to separate it from dipentene (II) and the hydrocarbon of Lebedew (III, IV) has been identified as a monochloride. The relative yields (I): (II): (III+IV) = 16:1:2 are in agreement with the relative availability and localization of π-electrons in isoprene. Observations on the properties of polyisoprene are in agreement with the more extensive work by d'Ianni. Some remarks on polymers from bulk polymerization are added. Isoprene acts as a powerful inhibitor on the polymerization of vinylidene chloride. This effect is independent of the method of polymerization.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2915-2930 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Existing methods of calculating monomer reactivity ratios in copolymerization are reviewed briefly, evaluated, and classified according to their mathematical and computational similarities. More attention is paid to procedures based on the integrated copolymer equation with which calculation of r values is performed most often by electronic computer. Unfortunately, until now all procedures have shown shortcomings because the real-error structure of the observations has not been taken into account. A new algorithm that does account correctly for measurement errors in both variables is described. A computational method is illustrated for copolymerization data obtained from quantitative gas chromatographic analysis of the monomer feed throughout the reaction. It is shown that the actual error structure of the variables corresponds to the assumed error structure. Reliability of the estimates is substantially increased, compared with the existing methods. Standard deviations of the monomer reactivity ratios are given and appear to be in good agreement with reality.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1489-1498 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of the alkyl group on the relative reactivity of a homologous series of vinyl esters (2) has been studied with ethylene (1) as reference monomer, tert-butyl alcohol as solvent, at 62°C and 35 kg/cm2. The experimental method was based on frequent measurement of the monomer feed composition throughout the copolymerization reaction by means of quantitative gas-chromatographic analysis. Highly accurate monomer reactivity ratios were estimated in a statistically justified manner by a nonlinear least-squares method applied to the integrated copolymer equation. The reactivity of the vinyl ester monomers towards an ethylene radical increased with decreasing electron-with-drawing ability of the ester group. All vinyl ester radicals considered turned out to have the same preference for their own monomer over ethylene (constant r2 = 1.50). Reactivity ratios are discussed in terms of the Q-e scheme and the Taft relation. It appeared that chiefly polar factors contribute to the observed relative reactivity, while probably resonance stabilization only plays a minor part. Steric hindrance seems to impair monomer reactivity, only from vinyl pivalate on. Relative reactivities of the vinyl esters are compared with literature values, where other reference monomers have been used.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1765-1772 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A short review of the effect of pressure on copolymerization kinetics shows the necessity of simple models for a better understanding of activation volumes. Therefore, a simple concept, possibly generally valid for free-radical polymerization, is proposed, based on the assumption that molar volumes of activation can be expressed as an addition of a characteristic radical and a monomer contribution, regardless of the combination involved. The scheme may facilitate the visualization of the transition state and contribute to the understanding of reaction mechanisms of radical polymerizations. Ethylene-vinyl acetate copolymerization at 62°C with tert-butyl alcohol as solvent agrees with the proposed scheme, appearing from the pressure independence of the product of reactivity ratios at the different levels (35,600, and 1200 kg/cm2). Implicitly it can be shown that an ethylene monomer contributes about 2 cm3/mole more to the activation volumes of the propagation reactions than does the vinyl acetate monomer, whereas for the radicals the difference of the respective contributions to the activation volumes is opposite in sign.
    Additional Material: 2 Ill.
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  • 8
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 571-582 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two new techniques for the determination of monomer reactivity ratios in copolymerization under high-pressure conditions have been developed, viz., the “sandwich” and the “quenching” method. Both methods are based on repeated quantitative gas chromatographic analysis of the reaction mixture during the low-pressure stages preceding and succeeding the high-pressure stage, of which the kinetics is under investigation. Application of the “sandwich” method implies the occurrence of reaction during both low-pressure stages and consequently the low-pressure kinetic data are required to obtain the transition points of low to high pressure and vice versa. These points constitute the initial and final conditions of the relevant high-pressure reaction. On the contrary, in the “quenching” method no reaction occurs during the low-pressure stages, owing to the lower temperature and the high activation energy of the initiator decomposition. As a consequence, the initial and final conditions of the high-pressure stage can be determined by a simple averaging procedure. Both methods have been tested for the ethylene - vinyl acetate copolymerization at 62°C and 600 kg/cm2 with tert-butyl alcohol as solvent, and appear to lead to almost identical monomer reactivity ratios, although the “quenching” method is slightly preferred in case of copolymerization reactions. Both methods are particularly valuable when one of the reactants is gaseous or the reaction produces a gas. Further merits and drawbacks of both methods are discussed.
    Additional Material: 4 Ill.
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  • 10
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A generally applicable computational procedure, which permits the accurate evaluation of the kinetic parameters of intricate and extended copolymerization schemes to be made, is described. This method is based on a numerical integration of the differential equation, and, according to the (improved) curve-fitting I procedure, experimental errors in both measured variables are considered. Furthermore, a description is given of the F test, in which a statistical comparison between the resulting residual sums of squares of two different schemes offers a possibility of selecting the most probable kinetic scheme for a given copolymerization system. The capability and applicability of the methods developed is demonstrated for the free radical copolymerization kinetics of methyl acrylate (MA) (M1) and butadiene (BD) (M2) with toluene as solvent. Here, the simple copolymer equation is unsatisfactory because a significant penultimate unit effect in BD macroradical reactivity shows up: k222/k221 = 0.84, and k122/k121 = 0.53, and k11/k12 = 0.088. The microstructure of the copolymer samples, determined by infrared (IR) spectroscopy, shows a decreasing fraction of BD units in the vinyl configuration in favor of the fraction of BD units in the cis-vinylene and trans-vinylene configuration at increasing MA (m) content. Statistical considerations indicate a strongly diminished probability of finding BD (b) in the vinyl configuration in ∼mb∼ transitions. Steric hindrance or polar repulsion of the ester side group of the penultimate MA unit probably account for the increased preference for monomer addition to the C4 site over the C2 site of the BD macroradical.
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