On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics,kinetics, and mechanism |
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Authors: | Tom G T Jansen Jan Meuldijk Peter A Lovell Alex M van Herk |
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Institution: | 1. Eindhoven University of Technology, Department of Chemical Engineering and Chemistry, Laboratory of Chemical Reactor Engineering/Polymer Reaction Engineering, MB, Eindhoven, The Netherlands;2. Materials Science Centre, The University of Manchester, Manchester, United Kingdom;3. Institute of Chemical and Engineering Sciences, Jurong, Island, Singapore |
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Abstract: | Successful miniemulsion polymerizations of very hydrophobic monomers, such as lauryl methacrylate and 4‐tert‐butyl styrene, initiated by very hydrophobic (i.e., completely water‐insoluble) lauroyl peroxide, are reported. Conversion‐time histories, as well as final latex properties, for example, the particle size distribution, are different from similar miniemulsion polymerizations in the presence of water‐soluble initiators. The observed differences can be attributed to the average number of radicals inside a miniemulsion particle; the system obeys Smith‐Ewart case I rather than Case II kinetics. Albeit the pairwise generation of radicals in the monomer droplets, substantial polymerization rates are observed. Water, present in the droplet interfacial layer, is supposed to act as chain transfer agent. The product of a chain transfer event is a hydroxyl radical, exit of this hydroxyl radical allows for the presence of single radicals in particles. The proposed mechanisms allow for agreement between initial droplet and final particle size distributions in miniemulsion polymerization initiated by lauroyl peroxide. © 2016 The Authors Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2731–2745 |
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Keywords: | calorimetry lauroyl peroxide miniemulsion polymerization particle size distribution radical exit |
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