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Tailoring Surface Properties of Bio-Fibers via Atom Transfer Radical Polymerization
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

The potential use of renewable, bio-based polymers in high-technological applications has attracted great interest due to increased environmental concern. Cellulose is the most abundant biopolymer resource in the world, and it has great potential to be modified to suit new application areas. The development of controlled polymerization techniques, such as atom transfer radical polymerization (ATRP), has made it possible to graft well-defined polymers from cellulose surfaces. In this study, graft-modification of cellulose substrates by ATRP was explored as a tool for tailoring surface properties and for the fabrication of functional cellulose surfaces.

Various native and regenerated cellulose substrates were successfully graft-modified to investigate the effect of surface morphology on the grafting reactions. It was found that significantly denser polymer brushes were grafted from the native than from the regenerated cellulose substrates, most likely due to differences in surface area.

A method for detaching the grafted polymer from the substrate was developed, based on the selective cleavage of silyl ether bonds with tetrabutylammonium fluoride. The results from the performed kinetic study suggest that the surface-initiated polymerization of methyl methacrylate from cellulose proceeds faster than the concurrent solution polymerization at low monomer conversions, but slows down to match the kinetics of the solution polymerization at higher conversions.

Superhydrophobic and self-cleaning bio-fiber surfaces were obtained by grafting of glycidyl methacrylate using a branched graft-on-graft architecture, followed by post-functionalization to obtain fluorinated polymer brushes. AFM analysis showed that the surface had a micro-nano-binary structure. It was also found that superhydrophobic surfaces could be achieved by post-functionalization with an alkyl chain, with no use of fluorine.

Thermo-responsive cellulose surfaces have been prepared by graft-modification with the stimuli responsive polymer poly(N-isopropylacrylamide) (PNIPAAm). Brushes of poly(4-vinylpyridine) (P4VP) rendered a pH-responsive cellulose surface. Dual-responsive cellulose surfaces were achieved by grafting block-copolymers of PNIPAAm and P4VP.

Place, publisher, year, edition, pages
Stockholm: KTH , 2007. , 56 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2007:16
Keyword [en]
cellulose, bio-fiber, atom transfer radical polymerization, surface modification, grafting, polymer brushes, functional surfaces, superhydrophobic, stimuli-responsive
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4325ISBN: 978-91-7178-616-6 (print)OAI: oai:DiVA.org:kth-4325DiVA: diva2:11815
Public defence
2007-04-20, D3, Lindstedtsvägen 5, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100804Available from: 2007-04-10 Created: 2007-04-10 Last updated: 2010-08-05Bibliographically approved
List of papers
1. Surface Modification of Natural Substrates by Atom Transfer Radical Polymerization
Open this publication in new window or tab >>Surface Modification of Natural Substrates by Atom Transfer Radical Polymerization
2006 (English)In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 100, no 5, 4155-4162 p.Article in journal (Refereed) Published
Abstract [en]

Surface modification of various solid polysaccharide substrates was conducted by grafting methyl acrylate (NU,) and styrene via atom transfer radical polymerization (ATRP) to produce well-defined polymer grafts. The hydroxyl groups on the surfaces of the substrates were reacted with 2-bromoisobutyryl bromide followed by graft copolymerization under ATRP conditions. The studied substrates were filter paper, microcrystalline cellulose, Lyocell fibers, dialysis tubing, and chitosan films. The modified Substrates were analyzed by FT-IR, water contact angle measurements, TGA, and SEM. FT-IR characterization of the grafted substrates showed significant differences between the different substrates in the amount of grafted polymer. Higher amounts of polymer seem to be possible to graft from native cellulose substrates than from regenerated cellulose substrates. To investigate whether the grafted polymers were "living" after a longer time period, a second layer of polystyrene was grafted from a filter paper modified with PMA one year ago. FT-IR characterization of the filter paper showed a peak corresponding to styrene, indicating that a block copolymer had been formed on the surface. Graft copolymerization can be used to change and tailor the surface properties of the polysaccharide substrates.

Keyword
Atom transfer radical polymerization (ATRP); Cellulose; Graft copolymers; Polysaccharides; Surface modification; Copolymerization; Free radical polymerization; Grafting (chemical); Scanning electron microscopy; Surface treatment; Thermogravimetric analysis; Polysaccharides; cellulose; polymerization; polysaccharide; substrate; surface modification
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-6953 (URN)10.1002/app.23457 (DOI)000237016200094 ()2-s2.0-33646380840 (Scopus ID)
Note
QC 20100804Available from: 2007-04-10 Created: 2007-04-10 Last updated: 2017-12-14Bibliographically approved
2. Kinetic Study of the Surface-Initiated Atom Transfer Radical Polymerization from Bio-Fiber Surfaces
Open this publication in new window or tab >>Kinetic Study of the Surface-Initiated Atom Transfer Radical Polymerization from Bio-Fiber Surfaces
(English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835Article in journal (Refereed) Submitted
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-6954 (URN)
Note
QS 20120327Available from: 2007-04-10 Created: 2007-04-10 Last updated: 2017-12-14Bibliographically approved
3. Superhydrophobic Bio-fibre Surfaces via Tailored Grafting Architecture
Open this publication in new window or tab >>Superhydrophobic Bio-fibre Surfaces via Tailored Grafting Architecture
Show others...
2006 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, no 34, 3594-3596 p.Article in journal (Refereed) Published
Abstract [en]

Superhydrophobic bio-fibre surfaces with a micro-nano-binary surface structure have been achieved via the surface-confined grafting of glycidyl methacrylate, using a branched "graft-on-graft'' architecture, followed by post-functionalisation to obtain fluorinated brushes.

Keyword
glycidylmethacrylate; methacrylic acid derivative; unclassified drug; article; chemical analysis; chemical structure; fiber; fluorination; hydrophobicity; nanotechnology; surface property; Cellulose; Fluorocarbon Polymers; Hydrophobicity; Molecular Structure; Polymethacrylic Acids; Surface Properties
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-8369 (URN)10.1039/b607411a (DOI)000239937600006 ()2-s2.0-33747616433 (Scopus ID)
Note
QC 20100805Available from: 2008-05-08 Created: 2008-05-08 Last updated: 2017-12-14Bibliographically approved
4. Superhydrophobic and self-cleaning bio-fiber surfaces via ATRP and subsequent postfunctionalization
Open this publication in new window or tab >>Superhydrophobic and self-cleaning bio-fiber surfaces via ATRP and subsequent postfunctionalization
Show others...
2009 (English)In: ACS applied materials & interfaces, ISSN 1944-8244, Vol. 1, no 4, 816-823 p.Article in journal (Refereed) Published
Abstract [en]

Superhydrophobic and self-cleaning cellulose surfaces have been obtained via surface-confined grafting of glycidyl methacrylate using atom transfer radical polymerization combined with postmodification reactions. Both linear and branched graft-on-graft architectures were used for the postmodification reactions to obtain highly hydrophobic bio-fiber surfaces by functionalization of the grafts with either poly(dimethylsiloxane), perfluorinated chains, or alkyl chains, respectively, Postfunctionalization using alkyl chains yielded results similar to those of surfaces modified by perfluorination, in terms of superhydrophobicity, self-cleaning properties, and the stability of these properties over time. in addition, highly oleophobic surfaces have been obtained when modification with perfluorinated chains was performed.

Keyword
biomaterial; biopolymer; epoxide; glycidyl methacrylate; methacrylic acid derivative; article; chemistry; crystallization; materials testing; methodology; surface property; Biocompatible Materials; Biopolymers; Crystallization; Epoxy Compounds; Materials Testing; Methacrylates; Surface Properties
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-6956 (URN)10.1021/am800235e (DOI)000267536100012 ()20356007 (PubMedID)2-s2.0-73249117937 (Scopus ID)
Note
QC 20100805. Uppdaterad från Submitted till Published 20100805.Available from: 2007-04-10 Created: 2007-04-10 Last updated: 2012-03-20Bibliographically approved
5. Dual-Responsive Bio-Fiber Surfaces via ATRP
Open this publication in new window or tab >>Dual-Responsive Bio-Fiber Surfaces via ATRP
Show others...
(English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835Article in journal (Refereed) Submitted
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-6957 (URN)
Note

QS 20120327

Available from: 2007-04-10 Created: 2007-04-10 Last updated: 2017-12-14Bibliographically approved

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