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  • 1
    ISSN: 1572-879X
    Keywords: diphenyl carbonate ; Redox cocatalyst ; phenol ; oxidative carbonylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A catalyst system for direct synthesis of diphenyl carbonate by oxidative carbonylation of phenol was investigated with special emphasis on the inorganic redox cocatalyst component. Besides the inorganic redox cocatalyst, the catalyst system was composed of a Pd carbonylation catalyst, an organic redox cocatalyst, a base and a drying agent. Ce(OAc)3·H2O was found to be the most efficient inorganic redox cocatalyst giving DPC in 76% yield with a Pd turnover number of 250 and without producing any major side products.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-879X
    Keywords: oxidative carbonylation ; phenol ; carbon monoxide ; palladium ; diimine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pd complexes with diimine ligands were investigated as novel Pd catalysts for direct synthesis of diphenyl carbonate by oxidative carbonylation of phenol using carbon monoxide and air. Best efficiency was obtained by using a PdCl2(ArN=CH–)2 or PdCl2(ArN=CMe–)2/Mn(TMHD)3/(Ph3P=)2NBr system where TOF reached 8.08 and 8.00 mol-DPC/mol-Pd h, respectively. The efficiency was increased with increases in the CO pressure.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 23 (1985), S. 901-904 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 2581-2594 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By the use of various boron compounds methyl methacrylate and styrene were copolymerized under photoirradiations at -20°C. The alternately regulating activities of the boron compounds in the copolymerizations were in the following order: boron trichloride 〉 ethylboron dichloride 〉 boron trifluoride 〉 diethylboron chloride ≫ triethylboron (≃0). Boron trichloride and ethylboron dichloride exhibited such high regulating activities that their presence in 1 mol% in the charged methyl methacrylate was sufficient to complete equimolar alternating copolymerization. The alternating copolymerization proceeded in the steady state. The copolymerization rates decreased in the following order: boron trichloride ≫ ethylboron dichloride 〉 diethylboron chloride ≫ triethylboron (≃0). The cotacticities of methyl methacrylate-centered triads in the resulting copolymers were identical to those prepared with boron trichloride, ethylboron dichloride, and diethylboron chloride. The mechanism of the alternating copolymerization is discussed.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1339-1352 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By the use of various metal halides methyl methacrylate and styrene were copolymerized to produce equimolar alternating sequences and different cotacticities. The 13C-NMR spectra of these copolymers were simple in comparison to those of random copolymers because of the fixed monomer sequence which yielded sharply split triplets for carbonyl, methoxy, and quaternary carbons. The relative intensities in these split peaks varied according to the metal halide used. A comparison of the intensities made it possible to obtain clear-cut and quantitative information on the methyl methacrylate-centered triad cotacticity of the copolymers. The spectral assignment with respect to the methoxy carbon was definitely justified by the combined use of partly relaxed Fourier transform and selective decoupling techniques. The spectrum of aromatic C1 carbon in styrene units also split into three main peaks. From their relative intensities the splitting was attributed to styrene-centered triad cotacticity. The assignment of this carbon was compared with two other assignments made for random copolymers of methyl methacrylate with styrene; they were contradictory, however. Furthermore, an apparent discrepancy was observed between methyl methacrylate-and styrene-centered tactic triads of these alternating copolymers. The origin of this discrepancy suggests a close relationship with the copolymerization mechanism.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 159-172 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Alternating copolymerizations of methyl methacrylate with styrene in the presence of boron trichloride at 0°C in 1,2-dichloroethane were carried out by using benzoyl peroxide as an initiator. Conversion increased proportionally with polymerization time, whereas the degree of polymerization was constant irrespective of time. The rate depended linearly on the square root of the concentration of benzoyl peroxide. The equilibrium constants for the formation of the ternary molecular complex composed of methyl methacrylate, styrene, and boron trichloride in 1,2-dichloroethane at -20, -10, and +4°C were determined by 1H-NMR spectroscopy. The concentrations of the ternary molecular complex in the polymerization mixtures were evaluated from the equilibrium constant of the formation. The rate of the alternating copolymerization was proportional to the first order of the concentration of the ternary molecular complex. The distribution of methyl methacrylate-centered triads in the alternating copolymer was different from that of styrene-centered triads. These results can be explained by a mechanism involving the homopolymerization of a ternary molecular complex.
    Additional Material: 10 Ill.
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