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Identifying the nature of the active species in the polymerization of methacrylates: Inhibition of methyl methacrylate homopolymerizations and reactivity ratios for copolymerization of methyl methacrylate n-butyl methacrylate in classical anionic, alkyllithium/trialkylaluminum-initiated, group transfer polymerization, atom transfer radical polymerization, catalytic chain transfer, and classical free radical polymerization
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UNSPECIFIED (1997) Identifying the nature of the active species in the polymerization of methacrylates: Inhibition of methyl methacrylate homopolymerizations and reactivity ratios for copolymerization of methyl methacrylate n-butyl methacrylate in classical anionic, alkyllithium/trialkylaluminum-initiated, group transfer polymerization, atom transfer radical polymerization, catalytic chain transfer, and classical free radical polymerization. MACROMOLECULES, 30 (14). pp. 3992-3998. ISSN 0024-9297.
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Abstract
Reactivity ratios have been determined for the monomer pair methyl methacrylate and n-butyl methacrylate under st range of polymerization conditions. The value of using reactivity ratios as a mechanistic probe is discussed. Reactivity ratios determined where M1 = MMA and M2 = n-BMA are 1.04, 0.81, classical anionic; 1.10, 0.72, alkyllithium/trialkylaluminium initiated; 1.76, 0.67, group transfer polymerization; 0.98, 1.26, atom transfer radical polymerization; 0.75, 0.98, catalytic chain transfer; and 0.93, 1.22, classical free radical polymerization. The data suggest ATRP and CCTP proceed via radical type propagation. Li/Al-initiated polymerization undergoes an anionic mechanism, while strong evidence is found for an associative, catalyst dependent mechanism for GTP. Galvinoxyl is demonstrated to inhibit GTP as well as free radical polymerization, and it is suggested that neither the use of inhibition nor polymer stereochemistry can be used to distinguish between anionic and radical processes.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | MACROMOLECULES | ||||
Publisher: | AMER CHEMICAL SOC | ||||
ISSN: | 0024-9297 | ||||
Official Date: | 14 July 1997 | ||||
Dates: |
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Volume: | 30 | ||||
Number: | 14 | ||||
Number of Pages: | 7 | ||||
Page Range: | pp. 3992-3998 | ||||
Publication Status: | Published |
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