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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of organic chemistry 50 (1985), S. 185-189 
    ISSN: 1520-6904
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Polymer bulletin 25 (1991), S. 583-590 
    ISSN: 1436-2449
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Summary A liquid Chromatographic method for the oligocarbonates and chloroformate-containing oligomers at various stages in a typical tetrabromobisphenol-A polycarbonate phosgenation reaction has been developed. It has been discovered that triethyl amine, normally used as a catalyst for the polymerization, also acted as a chain terminator producing carbamate end-group oligomers. The characterization of the polymer and various types oligomers during phosgenation should allow a better understanding of polymerization mechanism and provide an important aid in defining the critical process parameters.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 208 (1993), S. 65-77 
    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 Umsetzung von 2,2′,6,6′-Tetrabrombisphenol A (TBBPA) mit Phosgen in einer mit Trialkylamin katalysierten Grenzflächenpolykondensation liefert nur Polymere mit niedrigem Molekulargewicht. Die geringe Reaktivität von TBBPA wird auf dessen sterisch anspruchsvolle Struktur und den elektronenziehenden Charakter der o-Bromsubstituenten zurückgeführt. Aus der Bildung von Carbamaten bei der Reaktion einer Modellverbindung (2,4,6-Tribromophenylchlorformat, TBPC) mit Trialkylaminen geht hervor, daß durch Zerfall des Katalysator-TBPC-Komplexes die Polymerisation abgebrochen wird. Das Carbamat wird durch Zersetzung des Acylammoniumsalzes gebildet, wobei eine nucleophile Substitution durch das Chloridion an dem an das positiv geladene Stickstoffatom gebundenen Kohlenstoffatom stattfindet.
    Notes: 2,2′,6,6′-Tetrabromobisphenol-A (TBBPA), a sterically hindered bisphenol, is known to give only low-molecular-weight polymers using the interfacial phosgenation process. The low reactivity is attributed to the bulkiness and electron-withdrawing character of bromine substituents at the ortho positions. From the formation of carbamate products in model compound (2,4,6-tribromophenyl chloroformate, TBPC) reactions with trialkylamines, the trialkylamine catalyst was found to act as a terminator by the degradation of the chloroformate-trialkylamine complex. The generation of carbamate occurs through the decomposition of the acyl ammonium salt proceeding via nucleophilic displacement by Cl- at the carbon attached to the positive nitrogen center. The relative catalytic abilities of trialkylamines and pyridine derivatives were determined in the homogeneous (dichloromethane) and interfacial (dichloromethane/water) systems. From the results of model reactions with TBPC and sodium tribromophenolate, 4-dimethylaminopyridine (DMAP) was found to be the best catalyst.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 44 (1992), S. 849-857 
    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: Polycarbonate is prepared by the interfacial phosgenation and polycondensation of bisphenol A (BPA) in methylene chloride with caustic using triethylamine as a catalyst. In a typical batch reactor, where phosgenation and oligomerization proceed simultaneously, the critical process parameters are intermingled and are difficult to determine. Therefore, a semicontinuous process consisting of a series of static mixers for continuous phosgenation, followed by a batch reactor for oligomerization and polycondensation, was developed for better understanding of the reaction mechanisms. Phosgene hydrolysis was reduced greatly going from a batch to a continuous reactor (excess phosgene was reduced from 30 to 5%). Variables which influence the composition of intermediates are linear velocity, organic to aqueous volume ratio, PH (BPA to NaOH ratio), and phosgene to BPA ratio. These variables also affect BPA conversion, amount of phosgene hydrolysis, terminator capping efficiency, molecular weight, and molecular weight distribution of the resulted polycarbonate. Oligomerization takes place at the interface, and monochloroformates (HO-Bn-OCOCI) which contain both hydrophilic and lipophilic end groups, stay at the interface and, hence, react preferentially. Oligomers are analyzed by a newly developed HPLC technique.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 40 (1990), S. 555-567 
    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: A liquid chromatographic method for the oligocarbonates and chloroformate-containing oligomers at various stages in a typical polycarbonate phosgenation reaction has been developed. The accurate measurement of various types oligomers during phosgenation should allow for a better understanding of polymerization mechanism and provide great aid in defining the critical process parameters. Comparison of the total choloroformate concentration by accumulating every individual chlorofor-mate-containing componenent and the standard colorimetric method shows close agreement.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 50 (1993), S. 149-157 
    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: Tetrabromobisphenol-A (TBBPA), a sterically hindered bisphenol, is known to give only low molecular weight polymers using the interfacial process. The low reactivity is attributed to the bulkiness and electron-withdrawing bromine substituents at the ortho positions. The optimum reaction conditions for the interfacial polymerization of TBBPA using pyridine derivatives as a catalyst have been developed. From the two-phase concentration distribution constant (Ke) and pK's values of triethylamine, 4-dimethylaminopyridine (DMAP), and TBBPA, the critical process parameters were obtained. Because of its high nucleophilicity and facile leaving character, the DMAP catalyst system produces a high molecular weight TBBPA-polycarbonate (PC) successfully. The profile of the process was followed to obtain a better understanding of the reaction mechanism. © 1993 John Wiley & Sons, Inc.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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