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Interfacial Properties of Chitosan-PEO graft Oligomers: Surface Competition with Unmodified Chitosan Oligomers
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface Chemistry.ORCID iD: 0000-0002-2288-819X
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Surface Chemistry.
Department of Polymer Chemistry, Vilnius University.
Department of Polymer Chemistry, Vilnius University.
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2006 (English)In: Progress in Colloid and Polymer Science, ISSN 0340-255X, E-ISSN 1437-8027, Vol. 132, 124-130 p.Article in journal (Refereed) Published
Abstract [en]

Oligomers of chitosan carrying 45 units long poly(ethylene oxide), PEO, chains grafted to the C-6 position of the sugar units were prepared using a novel synthesis route. The graft density was high, close to one poly(ethylene oxide) chain grafted to each sugar unit of the chitosan oligomer but a small fraction of unreacted chitosan remained in the sample. The molecular weight distribution of the sample was determined using GPC. The interfacial properties of the chitosan-PEO graft oligomers were evaluated using X-ray photoelectron spectroscopy and surface force measurements. It was found that the small fraction of unreacted chitosan was significantly enriched at the solid-solution interface on negatively charged muscovite mica surfaces. The interactions between chitosan-PEO oligomer coated surfaces were found to be dominated by the extended PEO chains, and at high coverage the measured forces were consistent with those expected for polymer brushes. Addition of salt up to 10 mM did not result in any significant desorption of preadsorbed oligomer layers.

Place, publisher, year, edition, pages
2006. Vol. 132, 124-130 p.
Keyword [en]
chitosan; graft copolymers; poly(ethylene oxide); polymer brushes; surface forces
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-8145DOI: 10.1007/2882_027ISI: 000238029200016Scopus ID: 2-s2.0-33750941158OAI: oai:DiVA.org:kth-8145DiVA: diva2:13390
Note
QC 20100813Available from: 2008-03-27 Created: 2008-03-27 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Poly(Ethylene Oxide) Based Bottle-Brush Polymers and their Interaction with the Anionic Surfactant Sodium Dodecyl Sulphate: Solution and Interfacial Properties
Open this publication in new window or tab >>Poly(Ethylene Oxide) Based Bottle-Brush Polymers and their Interaction with the Anionic Surfactant Sodium Dodecyl Sulphate: Solution and Interfacial Properties
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The aim of this thesis work is to study the physico-chemical properties of poly(ethylene oxide), PEO, based brush polymers both in solution and at solid/aqueous interfaces. The importance of studying the surface properties of brush polymers can be related to a broad spectrum of interfacial-related applications such as colloidal stability, lubrication, detergency, protein repellency to name a few. In many applications it is desirable to form brush-like structures through simple physisorption. In this context the surface properties of PEO based brush polymers differing in molecular architecture were studied, using ellipsometry and surface force apparatus (SFA), to gain some understanding regarding the effect of molecular architecture on the formation of brush structures. The molecular architecture was varied by varying the charge/PEO ratio along the backbone. This study demonstrates that the formation of a brush structure at solid/aqueous interface is due to interplay between the attraction of the backbone to the surface and the repulsions between the PEO side chains. An optimal balance between the two antagonistic factors is required if one aims to build a well-defined brush structure at the interface. In this study the brush-like structures are formed when 25-50% of the backbone segments carry poly(ethylene oxide) side chains. Scattering techniques such as light and neutron reveal that these brush polymers are stiff-rods up to a charge to PEO ratio of 75:25. These stiff PEO brush polymer easily replace the more flexible linear PEO at the silica/water interface, the reason being that the entropy loss on adsorption is smaller for the brush polymer due to its stiff nature.  Polymer-surfactant systems play a ubiquitous role in many technical formulations. It is well known that linear PEO, which adopts random coil conformation in aqueous solution, interact strongly with the anionic surfactant, Sodium Dodecyl Sulphate (SDS). It is of interest to study the interaction between SDS and brush PEO owing to the fact that the PEO side chains have limited flexibility as compared to the linear PEO.  The interaction between brush PEO and the anionic surfactant SDS in solution are studied using different techniques such as NMR, tensiometry, SANS and light scattering. The main finding of this study is that the interaction is weaker compared to the linear PEO-SDS interactions which poses an interesting question regarding the role of chain flexibility in polymer-surfactant interactions.

Place, publisher, year, edition, pages
Stockholm: KTH, 2008. x, 68 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:17
Keyword
PEO brush polymers, brush polymers, PEO, poly(ethylene oxide), polymer-surfactant, sodium dodecyl sulphate (SDS), Ellipsomtery, PEO-SDS interactions
National Category
Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-4680 (URN)978-91-7178-900-6 (ISBN)
Public defence
2008-04-11, E2, KTH, Lindstedtsvägen 26, Stockholm, 09:00
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Supervisors
Note
QC 20100813Available from: 2008-03-27 Created: 2008-03-27 Last updated: 2010-08-13Bibliographically approved

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