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  • Physics  (2)
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  • 1
    Electronic Resource
    Electronic Resource
    Polymerization of methyl methacrylate initiated by tri-n-butylborane-organic halide systems (1973)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3115-3124 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The polymerization of methyl methacrylate (MMA) initiated by tri-n-butylborane (TBB) was studied in the presence of various organic halides (R′X). It was found that R′X accelerated the polymerization of MMA. Aliphatic halides were more effective than aromatic halides. Cocatalytic effects of butyl halides decreased in the order: n-BuI 〉 n-BuBr 〉 n-BuCl; n-BuBr ⋍ sec-BuBr 〉 i-BuBr 〉 tert-BuBr. In the polymerization of MMA by TBB-n-BuI, the initial rate of polymerization was found to be proportional to the concentration of MMA and to the square root of the concentration of TBB-n-BuI. The apparent activation energy was 5.3 kcal/mole. From this and other results, it was assumed that the polymerization of MMA by this initiator system proceeds by a radical mechanism via a weak complex between TBB and R′X; alkyl radicals are formed by the interaction of R′X with TBB. The TBB-R′X system can initiate the polymerization of MMA and AN, but is ineffective in the polymerization of styrene.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1973.170111207
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  • 2
    Electronic Resource
    Electronic Resource
    Vinylhydroquinone. III. Copolymerization of vinylhydroquinone and vinyl monomers by tri-n-butylboraneDedicated to Professor Yoshio Iwakura on the occasion of his 60th birthday. (1974)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2801-2808 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The copolymerization of vinylhydroquinone (VHQ) and vinyl monomers, e.g., methyl methacrylate (MMA), 4-vinyl-pyridine (4VP), acrylamide (AA), and vinyl acetate (VAc), by tri-n-butylborane (TBB) was investigated in cyclohexanone at 30°C under nitrogen. VHQ is assumed to copolymerize with MMA, 4VP, and AA by vinyl polymerization. The following monomer reactivity ratios were obtained (VHQ = M2): for MMA/VHQ/TBB, r1 = 0.62, r2 = 0.17; for 4VP/VHQ/TBB, r1 = 0.57, r2 = 0.05; for AA/VHQ/TBB, r1 = 0.35, r2 = 0.08. The Q and e values of VHQ were estimated on the basis of these reactivity ratios as Q = 1.4 and e = -;1.1, which are similar to those of styrene. This suggests that VHQ behaves like styrene rather than as an inhibitor in the TBB-initiated copolymerization. No homopolymerization was observed either under nitrogen or in the presence of oxygen. The reaction mechanism is discussed.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1974.170121209
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