Synthesis of amphiphilic polymers and their application as nanoscale surface wettability modifiers
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Aalto-yliopiston teknillinen korkeakoulu |
Doctoral thesis (article-based)
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Authors
Date
2010
Department
Biotekniikan ja kemian tekniikan laitos
Department of Biotechnology and Chemical Technology
Department of Biotechnology and Chemical Technology
Major/Subject
Mcode
Degree programme
Language
en
Pages
Verkkokirja (3024 KB, 61 s.)
Series
TKK dissertations,
242
Abstract
Amphiphilic polyelectrolytes with statistical or block copolymer structure were synthesized by atom transfer radical polymerization (ATRP). The copolymers contained 2-(dimethylamino) ethyl methacrylate (DMAEMA) or [2-(methacryloyloxy)ethyl] trimethyl ammonium iodide (METAI) as a hydrophilic monomer unit and methyl methacrylate (MMA), butyl methacrylate (BMA) or 2,2,2-trifluoroethyl methacrylate (TFEMA) as a hydrophobic monomer unit. Solution properties of the synthesized copolymers were studied in aqueous medium. The obtained solution conformations and structures were studied at varying conditions with e.g. dynamic light scattering, 1H NMR and 19F NMR spectroscopy and surface tension measurements. The obtained conformations ranged from extended to collapsed and the obtained solution structures ranged from unimers to kinetically trapped nanoparticles. The copolymers were adsorbed or spin-coated on hydrophilic substrates from aqueous medium as ultra-thin layers. The effect of the thin polymer layer on surface wettability was studied by contact angle measurements. The surface structures were studied with atomic force microscopy and were found to correlate with the wetting properties. The effect of e.g. surface preparation process and annealing at elevated temperatures was studied. A range of wettability levels were obtained, with advancing contact angles up to 100° on inherently flat surfaces (mica) and up to 160° on inherently rough surfaces (cellulose fiber substrate). The level of contact angle hysteresis varied. In addition, carbohydrate based polymers were studied for their potential in a similar wettability modification. The studied polymers were starch graft copolymers prepared by ATRP and glycopolymers with e.g. cellobiose side chains, prepared by a combination of catalytic chain transfer polymerization and Cu(I)-catalyzed azide-alkyne cycloaddition.Description
Supervising professor
Seppälä, Jukka, Prof.Thesis advisor
Seppälä, Jukka, Prof.Keywords
amphiphilic polymer, polyelectrolyte, ATRP, ultra-thin film, wetting
Other note
Parts
- [Publication 1]: Leena Nurmi, Susanna Holappa, Hannu Mikkonen, and Jukka Seppälä. 2007. Controlled grafting of acetylated starch by atom transfer radical polymerization of MMA. European Polymer Journal, volume 43, number 4, pages 1372-1382. © 2007 Elsevier Science. By permission.
- [Publication 2]: Leena Nurmi, Josefina Lindqvist, Rajan Randev, Jay Syrett, and David M. Haddleton. 2009. Glycopolymers via catalytic chain transfer polymerisation (CCTP), Huisgens cycloaddition and thiol–ene double click reactions. Chemical Communications, volume 2009, number 19, pages 2727-2729. © 2009 Royal Society of Chemistry (RSC). By permission.
- [Publication 3]: Leena Nurmi, Susanna Holappa, Antti Nykänen, Janne Laine, Janne Ruokolainen, and Jukka Seppälä. 2009. Ultra-thin films of cationic amphiphilic poly(2-(dimethylamino)ethyl methacrylate) based block copolymers as surface wettability modifiers. Polymer, volume 50, number 22, pages 5250-5261. © 2009 Elsevier Science. By permission.
- [Publication 4]: Leena Nurmi, Hui Peng, Jukka Seppälä, David M. Haddleton, Idriss Blakey, and Andrew K. Whittaker. 2010. Synthesis and evaluation of partly fluorinated polyelectrolytes as components in 19F MRI-detectable nanoparticles. Polymer Chemistry, volume 1, number 7, pages 1039-1047. © 2010 Royal Society of Chemistry (RSC). By permission.
- [Publication 5]: Leena Nurmi, Katri Kontturi, Nikolay Houbenov, Janne Laine, Janne Ruokolainen, and Jukka Seppälä. 2010. Modification of surface wettability through adsorption of partly fluorinated statistical and block polyelectrolytes from aqueous medium. Langmuir, volume 26, number 19, pages 15325-15332.