Kinetics and mechanism of the radical copolymerization of 4-vinyl pyridine with methyl acrylate initiated by p-acetylbenzylidene triphenylarsonium ylide
✍ Scribed by S. P. Tiwari; C. L. Gehlot
- Publisher
- John Wiley and Sons
- Year
- 2009
- Tongue
- English
- Weight
- 137 KB
- Volume
- 113
- Category
- Article
- ISSN
- 0021-8995
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✦ Synopsis
Abstract
The free‐radical copolymerization of 4‐vinyl pyridine (4‐VP) with methyl acrylate (MA) initiated by p‐acetylbenzylidene triphenylarsonium ylide at 60 ± 0.1°C with dioxane as an inert solvent yielded random copolymers. The kinetic equation was R~p~ ∝ [Ylide]^0.83^[4‐VP]^0.33^ [MA]^0.40^ (where R~p~ is the rate of polymerization); in other words, the system followed nonideal kinetics. The values of the energy of activation and k~p~^2^/k~t~ (where k~p~ is the rate constant of propagation and k~t~ is the rate constant of termination) were 23.21 kJ/mol and 1.212 × 10^−5^ mol L^−1^ s^−1^, respectively. The reactivity ratios calculated with the Kelen–Tüdos method were 0.14 ± 0.0075 for 4‐VP and 0.56 ± 0.0078 for MA. The copolymers were characterized with Fourier transform infrared, proton nuclear magnetic resonance, differential scanning calorimetry, and electron spin resonance methods. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009