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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 192 (1991), S. 377-404 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Describing network formation during chainwise polymerization is more complex than for stepwise (condensation) systems. The kinetics of chain growth must be combined with probability laws for random linking between chains. This approach is used to derive molecular weight averages, gel point and sol fraction during living, anionic copolymerization of vinyl with divinyl monomers. Comparison of predicted molecular weight and gel point to experimental values from Worsfold (1970), Lutz, Beinert and Rempp (1982) and others indicate that a significant amount of intramolecular linking or cyclization occurs in this system.
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0021-8995
    Keywords: 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: Kinetic data are reported for the fast polymerization of a thermoplastic polyurethane under conditions similar to that of commercial reaction injection molding (RIM). The components were a 2000 molecular weight polyester polyol, butanediol and 4,4′-diphenylmethane diisocyanate. Three catalysts-dibutyltin dilaurate, phenyl mercuric propionate, and triethylenediamine-as well as uncatalyzed formulations were studied. Kinetic parameters were obtained by numerically fitting adiabatic temperature rise data with both second-order and hyperbolic models. The hyperbolic model gave consistently better fits and is supported by mechanistic studies in the literature. Activation energies compare well to literature values. The uncatalyzed rate was found to be significant. The kinetic parameters obtained by this method are useful measures of catalyst performance in the RIM systems. Moreover, the models provide a conveient way to predict the extent of reaction during the production of parts by the RIM process. The shape of the reaction pathway (extent of reaction time) may be important in the development of physical properties of polymers produced by the RIM process. Physical properties for these samples compare favorably to those for a conventionally produced (batch) polyurethane of the same formulation.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 34 (1987), S. 2409-2432 
    ISSN: 0021-8995
    Keywords: 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: Development of polyurea-urethane and polyurea reaction injection molding (RIM) systems has created a need for kinetics of polyurea formation. Adiabatic batch reactions in solution were used to determine heats of reaction and relative reactivity of several aromatic amines and n-butanol with phenyl isocyanate (PI). In addition to comparing times required to reach 25, 50 and 75% conversion for both catalyzed and uncatalyzed reactions, n-th order models with Arrhenius rate constants were used to fit some of the exotherms. The reaction of 3,5-diethyl toluene (2,4 and 2,6)-diamine and PI could not be modeled due to unequal reactivity of the two amine groups. This unequal reactivity was studied using high performance liquid chromatography (HPLC) separation of the reaction products. The reactions of primary aliphatic amines and aromatic isocyanates were too rapid to be monitored in the batch apparatus. With a flow apparatus the reaction half time was estimated to be ∼ 0.002 s.
    Additional Material: 12 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1957-1967 
    ISSN: 0887-624X
    Keywords: end-capping reactions ; oligo(styryl)lithium anions ; gas chromatography ; mass spectrometry ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anionic living polymerization methods, using organometallic initiators such as butyllithium reagents, have proven useful for, inter alia, styrene polymerization and are amenable to subsequent functionalization of poly(styryl)lithium in the termination step. In this study, general methods for the selective preparation of small styrene oligomers and termination of the intermediate oligo(styryl)lithium anions were investigated. The crude reaction mixtures were analyzed directly by tandem gas chromatography/mass spectrometry (GC/MS). Of the carbon- and silicon-based electrophiles tested, chloro(chloroalkyl)silanes, Cl-SiR2(CH2)nCl in particular, were shown by GC/MS to be regioselective end-capping reagents, thus allowing subsequent transformation to the primary amine. The combined GC/MS data allow not only an estimate of the degree of functionalization, but also the identification of by-products, thus providing insight into the end-capping process that otherwise might be difficult to access. © 1995 John Wiley & Sons, Inc.
    Additional Material: 5 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 1293-1302 
    ISSN: 0887-624X
    Keywords: methylethoxysilanes ; hydrolysis ; polycondensation ; sol-gel ; modeling ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using 29Si NMR, we monitor the copolymerization of trimethylethoxysilane and dimethyldiethoxysilane (model compounds for more complex sol-gel copolymer systems) in a batch reactor. Under the chosen conditions, the extents of self- and cross-condensation reactions are readily determined. Using a nonideal polycondensation kinetic model, we show that the copolymerization rate coefficient for a pair of sites of differing functionality is bounded by their homopolymerization rate coefficients, lying closer to the larger one. This reactivity pattern generates a heterogeneous monomer distribution in the copolymerization products. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1293-1302, 1997
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2165-2174 
    ISSN: 0887-624X
    Keywords: amic acid ; cyclic anhydride ; imidization ; kinetics ; model compounds ; polymer bound functional groups ; polymer-polymer reactions ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The validity of extrapolating the reactivity of low molar mass compounds in solution to the polymer-analogous chemistry between polymer-bound functionality is investigated for the reaction of primary amines with cyclic anhydrides in the moderately polar solvents, anisole and tetraethyleneglycol dimethylether. The kinetics of amic-acid formation and imidization of polymeric and small molecule mixtures measured by Fourier-Transform Infrared Spectroscopy at near-ambient and elevated temperatures are compared. A Significant decrease in both reaction rates is observed upon changing the primary amine from aliphatic to benzylic, benzylic to 1,2-diphenylethylamine, and 1,2-diphenylethylamine to polystyrene-bound 1,2-diphenylethylamine. Reasons for the influence of polymer-bound chemical functionality on the reaction rates for these amines are discussed. The imidization step is found to be rate limiting in the reaction of phthalic anhydride with benzylamine at the functional group concentrations reported (0.14M or less). © 1995 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 7
    ISSN: 0935-9648
    Keywords: 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
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 1-54 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polymer chains are crosslinked to form a network. The chains are polydispersed, with an arbitrary distribution of weight and functionality. Crosslinks may form in three different ways: direct coupling (homopolymerization), direct coupling with propagation, and coupling through copolymerization with small monomers. Various network parameters are calculated. We give computational formulae for gel point, weight fraction soluble, weight fraction pendant, weight fraction effective, concentration of effective junctions, concentration of effective network strands, and the entanglement trapping factor. These formulae give exact values for systems that previously have only been solved using simplifying approximations. Examples show that such simplification may lead to sizable errors in the computation of network parameters.
    Additional Material: 7 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 691-709 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The goal of this study is to elucidate the relationship between the mechanism of bond formation, resulting structure, and the viscosity during the step polymerization of a thermoset. The system chosen for this work consists of a bifunctional epoxy, diglycidyl ether of bisphenol A, cured with a tetrafunctional amine, diaminodiphenyl sulfone. Steady shear and dynamic viscosity are measured as a function of extent of reaction throughout the epoxy-amine cure. Branching theory is used to relate the extent of reaction (i.e., conversion of epoxy groups) to certain structural parameters, including the weight-average molecular weight. The combination of the viscosity-conversion data with the branching theory enables the correlation between changes in rheological properties and network structure during polymerization. The steady shear viscosity rise is modeled as the product of a structure-dependent friction factor and weight-average molecular weight. The structural significance of the point in cure when the dynamic storage and loss modulus are equal (i.e., tan δ = 1) is also explored.
    Additional Material: 14 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 2585-2606 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A comparison between the entirely statistical and the combined kinetic and statistical model for amine-epoxy networks, both studied previously in the literature is made. The chemistry studied involves the generation of a secondary site which reacts in the network through chainwise addition rather than the stepwise addition mode of the primary reaction. It is shown that the combined model is exact and the naïve statistical models are approximate. The assumptions underlying the two models are delineated. It is shown, that under certain circumstances, the predictions of the two models can differ by several hundred percent. Further, the combined model is extended to predict the postgel properties of the network.
    Additional Material: 7 Ill.
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