Polymerization of Methyl Acrylate Initiated by V(V)-Cyclohexanone Redox System in Micellar Phase MANABENDRA PATRA, 1 BIJOY K. SINHA 2 1 Department of Chemistry, Sambalpur University, Jyoti Vihar, Burla 768 019, Orissa, India 2 Department of Environmental Sciences, Sambalpur University, Jyoti Vihar, Burla 768 019, Orissa, India Received 5 December 1996; accepted 28 April 1997 ABSTRACT: The kinetics of methyl acrylate (MA) polymerization initiated by a V(V)- Cyclohexanone redox system, in the presence of surfactant, over a temperature range of 30–50°C in acidic medium are analyzed. The anionic surfactant (SDS) enhances the rate of polymerization ( R p ) as well as the rate of V ( V ) consumption ( 0 R v ) . The cationic surfactant, cetyl trimethylammonium bromide ( CTAB ) , decreases both the rates. The effect of variation of the concentration of surfactant, monomer, substrate, and acid have been examined. A suitable free radical mechanistic scheme has been proposed for the above process.  1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2081 – 2088, 1997 Key words: kinetics; methyl acrylate; micellar; polymerization; critical micelle con- centration INTRODUCTION tilled in an atmosphere of nitrogen under reduced The important role of surfactant on the polymer- pressure, respectively, before use. Sodium dodecyl ization process has been studied since the early sulphate and cetyltrimethylammonium bromide 1940s. 1–7 Many workers have used surfactant to ( Merck, India ) were purified by standard meth- study the vinyl polymerization in different forms, ods. Ammonium meta vanadate ( Fluka, Switzer- such as emulsions, 8–12 microemulsions, 13–23 mi- land ) , sulphuric acid, and sodium bisulphite were celles, 24–34 inverse micelle, 35–38 and adsolubiliza- of reagent grade and used as such. tion. 39 Lot of work has been done on the kinetic studies of vinyl polymerization using V ( V ) – or- ganic substrates as redox systems. 40–44 The pres- Method ent piece of work deals mainly with polymeriza- tion of methyl acrylate (MA ) initiated by a V( V) - The experimental setup and kinetic procedure are cyclohexanone ( CH ) redox system in the presence similar to that of our earlier work published else- of sodium dodecyl sulphate ( SDS ) , an anionic sur- where. 25–30 factant. EXPERIMENTAL Test for the Presence of V(V) in the Polymer Materials Methyl acrylate ( Koch Light Lab., London ) and A little of polymer was dissolved in the concen- cyclohexanone ( Fluka, Switzerland ) were dis- trated of HNO 3 . An equal volume of amyl alcohol was added to it, followed by 1 mL of H 2 O 2 .A Correspondence to: B. K. Sinha. brownish red precipitate was obtained, indicating Journal of Applied Polymer Science, Vol. 66, 2081 – 2088 ( 1997 )  1997 John Wiley & Sons, Inc. CCC 0021-8995/97 / 112081-08 presence of V(V). 2081 8EF6 4651 / 8ef6$$4651 10-06-97 18:06:28 polaas W: Poly Applied