Synthesis of Methacrylate Derivatives Oligomers by Dithiobenzoate-RAFT-Mediated Polymerization

Hosseini Nejed, E, Castignolles, Patrice, Gilbert, Robert G. and Guillaneuf, Yohann (2008) Synthesis of Methacrylate Derivatives Oligomers by Dithiobenzoate-RAFT-Mediated Polymerization. Journal of Polymer Science Part A - Polymer Chemistry, 46 6: 2277-2289. doi:10.1002/pola.22563

Author Hosseini Nejed, E
Castignolles, Patrice
Gilbert, Robert G.
Guillaneuf, Yohann
Title Synthesis of Methacrylate Derivatives Oligomers by Dithiobenzoate-RAFT-Mediated Polymerization
Journal name Journal of Polymer Science Part A - Polymer Chemistry   Check publisher's open access policy
ISSN 0887-624X
Publication date 2008-03-15
Year available 2008
Sub-type Article (original research)
DOI 10.1002/pola.22563
Open Access Status
Volume 46
Issue 6
Start page 2277
End page 2289
Total pages 13
Editor Mitsuo Sawamoto
Place of publication United State of America
Publisher John Wiley & Sons Inc
Language eng
Subject C1
860199 Processed Food Products and Beverages (excl. Dairy Products) not elsewhere classified
030399 Macromolecular and Materials Chemistry not elsewhere classified
Abstract Reversible addition fragmentation chain transfer (RAFT) was used to synthesize methacrylic acid oligomers and oligo(methacrylic acid)-b-poly(methyl methacrylate) (PMAA-b-PMMA) with targeted degree of polymerization 10. Characterization is by size-exclusion chromatography (SEC) and electrospray mass-spectrometry. SEC data are presented as hydrodynamic volume distributions (HVDs), the only proper means to present comparative and meaningful SEC data when there is no unique relationship between size and molecular weight. The RAFT agent, (4-cyanopentanoic acid)-4-dithiobenzoate (CPADB), produced dithiobenzoic acid as a side product during the polymerization of methacrylate derivatives. Precipitation in diethyl ether proved to be an easy way to remove this impurity from the PMAA-RAFT oligomers. Both unpurified and purified macro-RAFT agent were used to prepare amphiphilic PMAA-b-PMMA copolymers. Diblock copolymer prepared from the purified PMAA homopolymer had a narrower HVD in comparison to those obtained from the equivalent unpurified macro-RAFT agent. This work shows that while cyanoisopropyl-dithiobenzoate or CPADB are good RAFT agents for methacrylate derivatives, they exhibit some instability under typical polymerization conditions, and thus when oligomers are targeted, optimal control requires checking for the degradation product and appropriate purification steps when necessary (the same effect is present for larger polymers but is unimportant). © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2277-2289, 2008
Keyword amphiphiles
block copolymers
dithiobenzoic acid (DTBA)
methacrylic acid (MAA
RAFT agent degradation
reversible addition fragmentation chain transfer (RAFT)
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

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Created: Tue, 14 Apr 2009, 23:49:11 EST by Emma Cushworth on behalf of School of Land, Crop and Food Sciences