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Synthesis, characterization, and bulk properties of amphiphilic copolymers containing fluorinated methacrylates from sequential copper-mediated radical polymerization

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Hansen, Natanya M. L., Gerstenberg, Michael, Haddleton, David M. and Hvilsted, Soren. (2008) Synthesis, characterization, and bulk properties of amphiphilic copolymers containing fluorinated methacrylates from sequential copper-mediated radical polymerization. Journal of Polymer Science. Part A, Polymer Chemistry, Vol.46 (No.24). pp. 8097-8111. ISSN 0887-624X

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Abstract

The partly fluorinated monomers, 2,2,2-trifluoroethyl methacrylate (3FM), 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate (8FM), and 1,1,2,2-tetrahydroperfluorodecyl methacrylate (17FM) have been used in the preparation of block copolymers with methyl methacrylate (MMA), 2-methoxyethyl acrylate (MEA), and poly(ethylene glycol) methyl ether methacrylate (PEGMA) by Atom Transfer Radical Polymerization. A kinetic study of the 3FM homopolymerization initiated with ethyl bromoisobutyrate and Cu(I)Br/N-(n-propyl)-2-pyridylmethanimine reveals a living/controlled polymerization in the range 80-110 degrees C, with apparent rate constants of 1.6 . 10(-4) s(-1) to 2.9 . 10(-4) s(-1). Various 3FM containing block copolymers with MMA are prepared by sequential monomer addition or from a PMMA macroinitiator in all cases with controlled characteristics. Block copolymers of 3FM and PEGMA resulted in block copolymers with PDI < 1.22, whereas block copolymers from 3FM and MEA have less controlled characteristics. The block copolymers based on MMA with 8FM and 17 FM have PDI's < 1.30. The glass transition temperatures of the block copolymers are dominated by the majority monomer, as the sequential monomer addition results in too short pure blocks to induce observable microphase separation. The thermal stability of the fluorinated poly((meth)acrylate)s in inert atmosphere is less than that of corresponding nonfluorinated poly((meth)acrylate)s. The presence of fluorinated blocks significantly increases the advancing water contact angle of thin films compared to films of the nonfluorinated poly((meth)acrylate)s. (C) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8097-8111, 2008

Item Type: Journal Article
Subjects: Q Science > QD Chemistry
Divisions: Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH): Amphiphiles, Polymerization, Block copolymers, Fluoropolymers, Monomers
Journal or Publication Title: Journal of Polymer Science. Part A, Polymer Chemistry
Publisher: John Wiley & Sons, Inc.
ISSN: 0887-624X
Date: 15 December 2008
Volume: Vol.46
Number: No.24
Number of Pages: 15
Page Range: pp. 8097-8111
Identification Number: 10.1002/pola.23107
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Restricted or Subscription Access
Funder: Novo Nordisk
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URI: http://wrap.warwick.ac.uk/id/eprint/28827

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