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  • 1
    Electronic Resource
    Electronic Resource
    Model discrimination via designed experiments: discriminating between the terminal and penultimate models on the basis of composition data (1994)
    s.l. : American Chemical Society
    Macromolecules 27 (1994), S. 386-399 
    Details
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ma00080a011
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  • 2
    Electronic Resource
    Electronic Resource
    Adaptive control of conversion in a simulated solution polymerization continuous stirred tank reactor (1990)
    s.l. : American Chemical Society
    Industrial & engineering chemistry research 29 (1990), S. 82-89 
    Details
    ISSN: 1520-5045
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1021/ie00097a012
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  • 3
    Electronic Resource
    Electronic Resource
    On-line nonlinear model-based estimation and control of a polymer reactor (1997)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 43 (1997), S. 3042-3058 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Polymer reactor control problems often lack frequent measurements of polymer properties, while other reactor environment measurements, such as temperatures, are readily available. The experimental application of a new estimator for handling such multirate measurement systems is presented. The estimator, in conjunction with a detailed nonlinear model and all measurements at their respective sampling rates, is able to provide frequent predictions of the process variables related to the quality (weight-average molecular weight) and quantity (monomer conversion) of the polymer product. The experimental application of a multivariable, nonlinear model-based predictive controller using reactor temperature and initiator flow rate as the manipulated variables for controlling weight-average molecular weight and monomer conversion is presented. The control strategy is designed to handle control nonaffine systems (nonlinear in the manipulated variables), while allowing for the incorporation of rate and amplitude constraints on the manipulated variables. A continuous methyl methacrylate solution polymerization pilot plant was used for the experiment.
    Additional Material: 23 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690431116
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  • 4
    Electronic Resource
    Electronic Resource
    Hierarchical data analysis of a replicate experiment in emulsion terpolymerization (1996)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 42 (1996), S. 1985-1994 
    Details
    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 systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) was conducted. Complete replication of an emulsion terpolymerization experimental run was performed in a 5-L stainless-steel batch pilot-plant reactor. The polymers produced were characterized for conversion, terpolymer composition, molecular weight averages, and average particle size. A hierarchical (nested) data analysis was performed on the experimental data to ascertain various sources of error and to allow for comments to be made regarding the data quality.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690420719
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  • 5
    Electronic Resource
    Electronic Resource
    A systematic approach to the study of multicomponent polymerization kinetics: butyl acrylate/methyl methacrylate/vinyl acetate. III. Emulsion homopolymerization and copolymerization in a pilot plant reactor (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 37 (1995), S. 235-248 
    Details
    ISSN: 0959-8103
    Keywords: butyl acrylate ; methyl methacrylate ; vinyl acetate ; pilot plant reactor ; emulsion polymerization ; kinetics ; Chemistry ; Polymer and Materials Science
    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 systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) is being conducted. In this third stage of the study,Parts 1 and 2: Dubé, M. A. & Penlidis, A., Polymer, 36 (1995) 587. Dubé, M. A. & Penlidis, A., Macromol. Chem. Phys., 196 (1995) 1101. emulsion homopolymerizations and copolymerizations of the monomers comprising the BA/MMA/VAc system were performed in a 5 litre stainless steel pilot plant reactor, mainly for troubleshooting purposes and as a precursor to the detailed terpolymerization experiments to follow.First, a search for a stable emulsion recipe was conducted. At the same time, experimental procedures were established for the 5 litre pilot plant reactor along with product characterization techniques. Finally, selective emulsion homopolymerizations and copolymerizations were run for each of the three monomers and each combination of the three monomers, respectively. The polymers produced were characterized for conversion, composition, molecular weight and particle size.Although the emphasis of the experiments was to establish recipes, techniques, and procedures for emulsions terpolymerization, several useful observations were made regarding the kinetics even from these troubleshooting experiments.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pi.1995.210370401
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  • 6
    Electronic Resource
    Electronic Resource
    A systematic approach to the study of multicomponent polymerization kinetics: The butyl acrylate/methyl methacrylate/vinyl acetate example. IV. Optimal Bayesian design of emulsion terpolymerization experiments in a pilot plant reactor (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 811-831 
    Details
    ISSN: 0887-624X
    Keywords: butyl acrylate ; methyl methacrylate ; vinyl acetate ; Bayesian design of experiments ; terpolymerization kinetics ; emulsion polymerization ; pilot plant experiments ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) is being conducted. In this stage of the study, emulsion terpolymerizations were performed in a 5 L stainless steel pilot plant reactor. The experimental trials were of the two-level factorial type and were designed optimally using a Bayesian method. The design procedure allowed us to improve our knowledge about the process using our prior knowledge and our subjective judgement. The polymers produced were characterized for conversion, composition, molecular weight, and particle size. The Bayesian design of experiments is shown to have several advantages over conventional factorial designs. © 1996 John Wiley & Sons, Inc.
    Additional Material: 15 Tab.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Emulsion terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate: Experimental results (1997)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1659-1672 
    Details
    ISSN: 0887-624X
    Keywords: butyl acrylate ; methyl methacrylate ; vinyl acetate ; terpolymerization kinetics ; emulsion polymerization ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) was conducted. In this stage of the study, batch emulsion terpolymerizations were performed in a 5 L stainless steel pilot plant reactor. The experiments were designed using a Bayesian (optimal) technique. The polymers produced were characterized for conversion, composition, molecular weight, and particle size. Conversion, terpolymer composition, number- and weight-average molecular weight, and average particle size results are discussed in light of the influence of seven factors and the interaction of these factors. The factors studied include monomer feed composition, initiator concentration, chain transfer agent concentration, impurity concentration, initiator type, emulsifier concentration, and temperature. A “two-stage rate” phenomenon, similar to that occurring in bulk co- and terpolymerization and emulsion copolymerization of acrylic/vinyl acetate systems was observed in the conversion, composition and molecular weight data. Furthermore, an interesting yet often ignored effect of impurities on emulsion polymerization kinetics was explained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1659-1672, 1997
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Controlling molecular weight distributions of polyethylene by combining soluble metallocene/MAO catalysts (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 831-840 
    Details
    ISSN: 0887-624X
    Keywords: molecular weight distribution ; polyethylene ; soluble metallocene/MAO catalysts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A critical look at the possibility of controlling the molecular weight distribution (MWD) of polyolefins by combining metallocene/methylalumoxane (MAO) catalysts is offered. Catalysts investigated were bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2), its titanium and hafnium analogues (Cp2TiCl2 and Cp2HfCl2), as well as rac-ethylenebis(indenyl)zirconium dichloride (Et(Ind)2ZrCl2). As observed by other researchers, the MWD of polyethylene can be manipulated by combining soluble catalysts, which on their own produce polymer with narrow MWD but with different average molecular weights. Combined in slurry polymerization reactors, the catalysts in consideration produce ethylene homopolymer just as they would independently. Unimodal or bimodal MWDs can be obtained. This effect can be mimicked by blending polymers produced by the individual catalysts. We demonstrate how a variability in catalyst activity translates into a variability in MWD when mixing soluble catalysts in polymerization. Such a variability in MWD must be considered when setting goals for MWD control. We introduce a more quantitative approach to controlling the MWD using this method. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 831-840, 1998
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Kinetic model-based experimental design of the polymerization conditions in suspension copolymerization of styrene/divinylbenzene (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 2081-2094 
    Details
    ISSN: 0887-624X
    Keywords: copolymerization ; crosslinking ; polystyrene-divinylbenzene ; experimental designs ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of a mechanistic model-based experimental design technique to determine the polymerization conditions and polymer properties in suspension copolymerization of styrene and divinylbenzene is reported. The technique consists of using a mathematical model to design the polymerization conditions of a copolymer with characteristics specified beforehand. The properties (conversion, gel content, molecular weight averages, and copolymer composition) of the copolymer synthesized using this approach agree very well with the calculated properties for the pregelation period, but accurate prediction of properties during the postgelation period is still uncertain. It is demonstrated that the use of mechanistic modeling for experimental design purposes can be more adequate (when the model is sound, yet simple to solve) than other design techniques (e.g., factorial designs). © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2081-2094, 1998
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Model discrimination via designed experiments: Discriminating between the terminal and penultimate models based on triad fraction data (1994)
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 3 (1994), S. 1005-1031 
    Details
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Computer simulations have been used to study the application of statistical model discrimination techniques to the modelling of copolymerization reactions based on triad fraction data. Since there are six triad fraction measurements, the problems of parameter estimation and model discrimination become multivariate problems. The multivariate forms of three model discrimination methods (exact entropy, Hsiang and Reilly, and Buzzi-Ferraris et al.) are presented. Programs have been developed to simulate the application of these techniques to the systems styrene-acrylonitrile, styrene-methyl methacrylate and styrene-butyl acrylate. The simulation programs are explained, including the method used to simulate triad fraction data. Evidence is presented that the simulation programs are capable of duplicating the type of measurements that would be obtained in the laboratory. The simulation results show that model discrimination methods are able to accurately and reliably discriminate between the terminal and penultimate models. The use of simulated model discrimination methods leads to reliable discrimination in fewer experiments than have been used in past work. Also, model discrimination methods are able to detect smaller penultimate effects than those found by Hill et al. for styrene-acrylonitrile. In addition, the results show that the use of four of the six triad fractions, versus one copolymer composition measurement, should lead to more precise reactivity ratio estimates and an increased ability to discriminate between the terminal and penultimate models. Our work suggests that use of model discrimination methods will indeed lead to improvements in the modelling of copolymerization reactions.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mats.1994.040030606
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