The doctoral dissertations of the former Helsinki University of Technology (TKK) and Aalto University Schools of Technology (CHEM, ELEC, ENG, SCI) published in electronic format are available in the electronic publications archive of Aalto University - Aaltodoc.
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Amphiphilic Cationic Polymethacrylates: Synthesis, Characterization and Interactions with Cellulose

Arja-Helena Vesterinen

Doctoral dissertation for the degree of Doctor of Science in Technology to be presented with due permission of the School of Chemical Technology for public examination and debate in Auditorium KE2 (Komppa Auditorium) at the Aalto University School of Chemical Technology (Espoo, Finland) on the 21st of October 2011 at 12 noon.

Overview in PDF format (ISBN 978-952-60-4274-9)   [3074 KB]
Dissertation is also available in print (ISBN 978-952-60-4273-2)

Abstract

Amphiphilic cationic co-polymers, containing poly([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide) (polyMETAI) or poly[2-(dimethylamino) ethyl methacrylate] (PDM) segment, were synthesized through two different main routes. Block co-polymers containing poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO) were synthesized with oxyanionic polymerization, whereas radical polymerization was used to obtain statistical co-polymers with stearyl methacrylate (SMA) and fluorodecyl methacrylate (FMA).

The melt and thermal transition properties of the polymers were studied with dynamic scanning calorimetry and rheometry. PDM decreased crystallinity of the polymer and increased the melt strength of the polymers. The solution properties were studied with a surface tension measurement, with dynamic light scattering equipment, and with rheometry. Polymers containing highly hydrophobic segments, such as stearyl, formed charge stabilized aggregates in a water solution, whereas polymers with a less hydrophobic block, such as PEO, formed a micellar structure.

The suitability of the prepared polymers, as well as a set of commercial polymers, on cellulose fiber systems was studied. The polymers containing a cationic segment formed permanent adhesion on the anionic surface, and strong bonding with the cellulose fibers. The mechanical strength of the cellulose fiber sheets was increased more with polymers containing cationic segments than the ones with corresponding nonionic segments. Strain hardening behaviour was introduced into the fiber-polymer sheets that did not contain cationic segments and the bonding between the fiber and the polymer was weak enough. A mechanically strong cellulose fiber network could also be prepared with a hydrophobic cationic polymer, but the strength was decreased with the high density of the hydrophobic side group in the polymer.

The polymers containing a highly hydrophobic segment formed a thin layer coating on the paper surface and a small amount of polymer was enough for a complete thin layer coverage of the surface. Additionally, the higher amount of the polymer did not change the chemical or physical properties of the surface, which supported the assumption of a nanolayer formation.

This thesis consists of an overview and of the following 7 publications:

  1. Arja-Helena Vesterinen, Petri Myllytie, Janne Laine, and Jukka Seppälä. 2010. The effect of water-soluble polymers on rheology of microfibrillar cellulose suspension and dynamic mechanical properties of paper sheet. Journal of Applied Polymer Science, volume 116, number 5, pages 2990-2997.
  2. Arja-Helena Vesterinen, Jaana Rich, Petri Myllytie, Janne Laine, and Jukka Seppälä. 2010. Poly(ethylene oxide)-block-poly[2-(dimethylamino)ethyl methacrylate] as strengthening agent in paper: dynamic mechanical characterization. Macromolecular Materials and Engineering, volume 295, number 3, pages 269-275.
  3. Arja-Helena Vesterinen, Jaana Rich, and Jukka Seppälä. 2010. Synthesis and solution rheology of poly[(stearyl methacrylate)-stat-([2-(methacryloyloxy)ethyl] trimethyl ammonium iodide)]. Journal of Colloid and Interface Science, volume 351, number 2, pages 478-484. © 2010 Elsevier. By permission.
  4. A. Vesterinen, S. Lipponen, J. Rich, and J. Seppälä. 2011. Effect of block composition on thermal properties and melt viscosity of poly[2-(dimethylamino)ethyl methacrylate], poly(ethylene oxide) and poly(propylene oxide) block co-polymers. eXPRESS Polymer Letters, volume 5, number 9, pages 754-765. © 2011 Budapest University of Technology and Economics. By permission.
  5. Arja-Helena Vesterinen, Mika Anttila, Kuisma Littunen, Jaana Rich, and Jukka Seppälä. 2011. Chemical modification of fine paper base with amphiphilic copolymer. Nordic Pulp and Paper Research Journal, volume 26, number 4, pages 476-484. © 2011 by authors.
  6. Maria S. Peresin, Youssef Habibi, Arja-Helena Vesterinen, Orlando J. Rojas, Joel J. Pawlak, and Jukka V. Seppälä. 2010. Effect of moisture on electrospun nanofiber composites of poly(vinyl alcohol) and cellulose nanocrystals. Biomacromolecules, volume 11, number 9, pages 2471-2477. © 2010 American Chemical Society (ACS). By permission.
  7. Xiaomeng Liu, Arja-Helena Vesterinen, Jan Genzer, Jukka V. Seppälä, and Orlando J. Rojas. 2011. Adsorption of PEO–PPO–PEO triblock copolymers with end-capped cationic chains of poly(2-dimethylaminoethyl methacrylate). Langmuir, volume 27, number 16, pages 9769-9780. © 2011 American Chemical Society (ACS). By permission.

Keywords: polyelectrolyte, cellulose, strength additive, surface modification, rheology, DMA

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Last update 2012-07-19