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  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 35 (1989), S. 1445-1456 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The kinetics of a semibatch melt transesterification of dimethyl terephthalate (DMT) with ethylene glycol (EG) is studied with zinc acetate as a catalyst. This paper quantifies the effect of various reactor operating conditions on the transesterification rate and the product composition distribution. Our experiments support the assumption that the methylesters in DMT and growing oligomer chains have the same reactivities for transesterification with EG and that the reactivity of hydroxyl groups in pure EG for esterification with DMT is twice that of the hydroxyl group in oligomers. With a molecular species model in which various oligomers are identified by the type of functional end groups, the progress of the transesterification and the oligomer concentration distribution were estimated and the agreement between the model predictions and the experimental data were excellent. It has also been shown that 30 wt. % of oligomers are produced for [EG]/[DMT] molar ratio of three, and up to 70 wt. % oligomers are produced at the [EG]/[DMT] molar ratio of one.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 26 (1986), S. 975-981 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The steady state structure of non-isothermal free radical solution polymerization in a continuous stirred tank reactor is analyzed. With mean residence time as a bifurcation parameter, five regions of steady states are identified. The effect of reactor operating conditions on the structure and the stability of steady state is discussed.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 33 (1987), S. 2067-2076 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A detailed kinetic model for the bulk styrene polymerization initiated by symmetrical diperoxyester bifunctional initiators is presented. When chain termination occurs via a combination termination mechanism, six distinct polymeric species are identified in accordance with the nature of the polymer end units. It is shown that the unequal thermal decomposition characteristics of the peroxides of the bifunctional initiator system lead to the formation of polymers having considerably higher molecular weight than those obtained by the monofunctional intiator systems. It has also been found that high monomer conversion, high molecular weight, and narrow molecular weight distribution can be obtained simultaneously by using the bifunctional initiators at high reaction temperatures. This is due to the reinitiation and propagation of inactive polymers carrying undecomposed peroxides. The molecular-weight-increasing effect of the bifunctional initiator is more pronounced at high reaction temperatures. The new possibilities of increasing the monomer conversion and controlling the polymer molecular weight properties more effectively through the use of bifunctional initiators are discussed.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 196-211 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Plausible stoichiometries for solvation and association complexes in binary mixtures of chloroform and one of six organic diluents (n-hexane, p-dioxane, acetone, diethyl ether, tri-n-butyl phosphate, or triethylamine) are examined parametrically. A range of stoichiometric assumptions based on hydrogen bonding are examined, but only a few such combinations yield statistically significant fits to the experimental vapor-liquid equilibria and NMR chemical shift data. Hydrogen bonding considerations and the “true” chemical species are much more important than nonspecific physical factors such as molecular sizes, shape differences, and regular solution terms. Thermodynamic equilibrium constants are presented for the most significant chloroform solvation complexes. Nonspecific dilution shift is important and more helpful in fitting NMR data than the assumption of a chloroform dimer. Physical effects and an orientation factor are used to predict excess enthalpy in chloroform/n-hexane mixtures where no solvation or association reactions occur. Model parameters are used to predict excess molar volumes and enthalpies. Commonly reported stability constants are concentration dependent.
    Additional Material: 19 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 27 (1987), S. 1703-1712 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A mathematical model of a semi batch reactor was developed to investigate the oligomerization reactions in the melt transesterification of dimethyl terephthalate with ethylene glycol catalyzed by metal acetate catalyst. The detailed kinetic scheme based on the molecular species model is used to estimate the conversion of methyl ester groups and the concentrations of various oligomeric species. The numerical simulation of the model shows that the oligomerization reactions lower the overall conversion of methyl ester end groups. Effects of ethylene glycol/dimethyl terephthalate mole ratios, reaction temperature and, catalyst concentration on the conversion, oligomer concentration, oligomer molecular weight, and molecular weight distribution were also analyzed.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 28 (1988), S. 81-89 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A method to obtain the tenacity and Young's modulus of nonwoven webs without direct measurement of web thickness is proposed. This has been tested with several series of samples with different basis weight. It was found that these properties were nearly Independent of the sample gage length, and both tenacity and modulus generally decreased with increase in the die temperature, the air pressure at the die, or the die to collector distance [DCD]. The web stiffness as measured by bending rigidity followed similar trends. The elongation Lo break also decreased as die temperature and air pressure at The die increased, but it increased with increasing DCD. The average filament diameter in the web decreased with increasing die temperature or air pressure at the die. The single filament strength was measured and compared with strength properties of web and of high-speed melt spun filament prepared from the same resins. The strength of single filaments in the web lie in between those of the web and high-speed spun filaments. The mechanical properties of melt blown web were interpreted in terms of the changes in Fiber diameter, the level of interfilament bonding, the molecular orientation developed in the filament, the diameter uniformity along the individual filaments in the web, and the presence of voids in the filament.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 31 (1991), S. 353-364 
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Optimal open loop control strategies are developed for a semibatch free radical copolymerization of methyl methacrylate and vinyl acetate using the multiobjective dynamic optimization method. A detailed kinetic model is validated through experimentation and used for the design of optimal controls. Both monomer feed rate and reactor temperature are varied to produce the copolymer of desired composition and molecular weight. The open loop control policies are implemented in a process control computer and tested on an experimental stirred tank polymerization system. Excellent agreement between the model predictions and the experimental data have been obtained.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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