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Tuning Properties of Surfaces and Nanoscopic Objects using Dendronization and Controlled Polymerizations
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

In this study, dendronization and grafting via controlled polymerization techniques, atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP), have been explored. Modification of surfaces and cellulose using these techniques, which enable grafting of well-defined polymer architectures, has been investigated. The interest in using cellulose stems from its renewability, biocompatibility, high molecular weight, and versatile functionalization possibilities.

Dendronization was performed using disulfide-cored didendrons of 2,2-bis(methylol)propionic acid (bis-MPA) on gold surfaces, for the formation of self-assembled monolayers. It was found that the height of the monolayer increased with increasing dendron generation and that the end-group functionality controlled the wettability of the modified surface.

Superhydrophobic cellulose surfaces could be obtained when a ‘graft-on-graft’ architecture was obtained using ATRP from filter paper after subsequent post-functionalized using a perfluorinated compound. The low wettability could be explained by a combination of a high surface roughness and the chemical composition.

Biobased dendronized polymers were synthesized through the ‘attach to’ route employing dendronization of soluble cellulose, in the form of hydroxypropyl cellulose (HPC). The dendronized polymers were studied as nanosized objects using atomic force microscopy (AFM) and it was found that the dendron end-group functionality had a large effect on the molecular conformation on surfaces of spun cast molecules.

ATRP of vinyl monomers was conducted from an initiator-functionalized HPC and an initiator-functionalized first generation dendron, which was attached to HPC. The produced comb polymers showed high molecular weight and their sizes could be estimated via AFM of spun cast molecules on mica and from dynamic light scattering in solution, to around 100-200 nm. The comb polymers formed isoporous membranes, exhibiting pores of a few micrometers, when drop cast from a volatile solvent in a humid environment. HPC was also used to initiate ROP of ε-caprolactone, which was chain extended using ATRP to achieve amphiphilic comb block copolymers. These polymers could be suspended in water, cross-linked and were able to solubilize a hydrophobic compound.

Place, publisher, year, edition, pages
Stockholm: KTH , 2007. , 70 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2007:83
Keyword [en]
Dendrimers, dendronized polymers, cellulose, Atom Transfer Radical Polymerization, Ring-Opening Polymerization, surface modification, grafting, superhydrophobic, amphiphilic polymer, block copolymer, Atomic Force Microscopy
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4550ISBN: 978-91-7178-820-7 (print)OAI: oai:DiVA.org:kth-4550DiVA: diva2:12817
Public defence
2007-12-14, D3, Huvudbyggnaden, Lindstedtsvägen 5, Stockholm, 14:00
Opponent
Supervisors
Note
QC 20100826Available from: 2007-11-23 Created: 2007-11-23 Last updated: 2010-08-26Bibliographically approved
List of papers
1. Dendritic Structures Based on Bis(hydroxymethyl)propionic Acid as Platforms for Surface Reactions
Open this publication in new window or tab >>Dendritic Structures Based on Bis(hydroxymethyl)propionic Acid as Platforms for Surface Reactions
Show others...
2005 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 21, no 10, 4512-4519 p.Article in journal (Refereed) Published
Abstract [en]

In this paper we present results related to the self-assembly of different generations of disulfide-cored 2,2-bis(hydroxymethyl)propionic acid-based dendritic structures onto gold surfaces. These molecular architectures, ranging from generation 1 to generation 3, contain removable acetonide protecting groups at their periphery that are accessible for hydrolysis with subsequent formation of OH-terminated surface-attached dendrons. The deprotection has been investigated in detail as a versatile approach to accomplish reactive surface platforms. A special focus has been devoted to the comparison of the properties of the layers formed by hydrolysis of the acetonide moieties directly on the surface and in solution, prior to the layer formation.

Keyword
Carboxylic acids; Dendrimers; Fourier transform infrared spectroscopy; Gold; Hydrolysis; Molecular structure; Self assembly; Absorbates; Acetonide moieties; Dendritic structures; Supramolecular reactions; Surface reactions
National Category
Polymer Chemistry Physical Chemistry
Identifiers
urn:nbn:se:kth:diva-7707 (URN)10.1021/la047077b (DOI)000228983700040 ()2-s2.0-18844439420 (Scopus ID)
Note
QC 20100826Available from: 2007-11-23 Created: 2007-11-23 Last updated: 2012-03-20Bibliographically approved
2. Superhydrophobic Bio-fibre Surfaces via Tailored Grafting Architecture
Open this publication in new window or tab >>Superhydrophobic Bio-fibre Surfaces via Tailored Grafting Architecture
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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: 2010-10-25Bibliographically approved
3. Dendronized Hydroxypropyl Cellulose: Synthesis and Characterization of Biobased Nanoobjects
Open this publication in new window or tab >>Dendronized Hydroxypropyl Cellulose: Synthesis and Characterization of Biobased Nanoobjects
2007 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 8, no 12, 3815-3822 p.Article in journal (Refereed) Published
Abstract [en]

Dendronized polymers containing a cellulose backbone have been synthesized with the aim of producing complex molecules with versatile functionalization possibilites and high molecular weight from biobased starting materials. The dendronized polymers were built by attaching premade acetonide-protected 2,2-bis(methylol)propionic acid functional dendrons of generation one to three to a hydroxypropyl cellulose backbone. Deprotection or functionalization of the end groups of the first generation dendronized polymer to hydroxyl groups and long alkyl chains was performed, respectively. The chemical structures of the dendronized polymers were confirmed through analysis using H-1 NMR and FT-IR spectroscopies. From SEC analysis, the dendronized polymers were found to have an increasing polystyrene-equivalent molecular weight up to the second generation (M-n = 50 kg mol(-1)), whereas the polystyrene-equivalent molecular weight for the third generation was lower than for the second, although the same grafting density was obtained from H-1 NMR spectroscopy for the second and third generations. Tapping-mode atomic force microscopy was used to characterize the properties of the dendronized polymers in the dry state, exploring both the effect of the polar substrate mica and the less polar substrate highly oriented pyrolytic graphite (HOPG). It was found that the molecules were in the size range of tens of nanometers and that they were apt to undertake a more elongated conformation on the HOPG surfaces when long alkyl chains were attached as the dendron end-groups.

Keyword
Characterization; Molecular weight; Molecules; Structure (composition); Synthesis (chemical); Cellulose backbone; Dendronized polymers; Nanoobjects; alkyl group; graphite; hydroxyl group; hydroxypropylcellulose; nanoparticle; polystyrene; propionic acid derivative; article; atomic force microscopy; carbon nuclear magnetic resonance; chemical modification; chemical structure; complex formation; conformational transition; controlled study; dendronization; gel permeation chromatography; infrared spectroscopy; molecular weight; priority journal; proton nuclear magnetic resonance; synthesis; Biocompatible Materials; Cellulose; Nanostructures; Hydroxypropyl Cellulose; Molecular Weight; Synthesis
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-7709 (URN)10.1021/bm7007394 (DOI)000251547600019 ()2-s2.0-38049034907 (Scopus ID)
Note
QC 20100826Available from: 2007-11-23 Created: 2007-11-23 Last updated: 2010-08-26Bibliographically approved
4. Comb Polymers Prepared by ATRP from Hydroxypropyl Cellulose
Open this publication in new window or tab >>Comb Polymers Prepared by ATRP from Hydroxypropyl Cellulose
2007 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 8, no 4, 1138-1148 p.Article in journal (Refereed) Published
Abstract [en]

Hydroxypropyl cellulose (HPC) was used as a core molecule for controlled grafting of monomers by ATRP, the aim being to produce densely grafted comb polymers. HPC was either allowed to react with an ATRP initiator or the first generation initiator-functionalized 2,2-bis(methylol)propionic acid dendron to create macroinitiators having high degrees of functionality. The macroinitiators were then "grafted from" using ATRP of methyl methacrylate (MMA) or hexadecyl methacrylate. Block copolymers were obtained by chain extending PMMA-grafted HPCs via the ATRP of tert-butyl acrylate. Subsequent selective acidolysis of the tert-butyl ester moieties was performed to form a block of poly(acrylic acid) resulting in amphiphilic block copolymer grafts. The graft copolymers were characterized by H-1 NMR and FT-IR spectroscopies, DSC, TGA, rheological measurements, DLS, and tapping mode AFM on samples spin coated upon mica. It was found that the comb (co)polymers were in the nanometer size range and that the dendronization had an interesting effect on the rheological properties.

Keyword
Acrylic monomers; Block copolymers; Chain length; Ethers; Graft copolymers; Grafting (chemical); Initiators (chemical); Monomers; Polymethyl methacrylates; Rheology; Comb polymers; Hexadecyl methacrylate; Macroinitiators; Selective acidolysis; Cellulose derivatives; acrylic acid butyl ester; copolymer; hydroxypropylcellulose; methacrylic acid methyl ester; polyacrylic acid; polymer; propionic acid derivative; article; atom transfer radical polymerization; atomic force microscopy; chemical reaction; chemical structure; differential scanning calorimetry; gel permeation chromatography; infrared spectroscopy; light scattering; priority journal; proton nuclear magnetic resonance; synthesis; thermogravimetry; Carbohydrate Conformation; Carbohydrate Sequence; Cellulose; Molecular Sequence Data; Particle Size; Polymers; Rheology; Temperature; Acidolysis; Acrylates; Block Copolymers; Catalysts; Copolymerization; Degree Of Polymerization; Graft Copolymers; Hydroxypropyl Cellulose; Methyl Methacrylate; Monomers; Rheology
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-7710 (URN)10.1021/bm061043w (DOI)000245510100013 ()2-s2.0-34247640609 (Scopus ID)
Note
QC 20100826Available from: 2007-11-23 Created: 2007-11-23 Last updated: 2010-08-26Bibliographically approved
5. Unimolecular Nanocontainers Prepared by ROP and Subsequent ATRP from Hydroxypropylcellulose
Open this publication in new window or tab >>Unimolecular Nanocontainers Prepared by ROP and Subsequent ATRP from Hydroxypropylcellulose
2008 (English)In: Macromolecules, ISSN 0024-9297, E-ISSN 1520-5835, Vol. 41, no 12, 4405-4415 p.Article in journal (Refereed) Published
Abstract [en]

Hydroxypropylcellulose (HPC) is used as a macroinitiator for ring-opening polymerization of epsilon-caprolactone for the synthesis of a high molecular weight comb polymer consisting of a cellulose backbone and PCL grafts. The PCL end groups are converted into initiating sites for ATRP and chain extension of the PCL block is performed through grafting of tert-butyl acrylate to different lengths. The comb block copolymers are thereafter converted to amphiphilic polymers through deprotection of the tert-butyl group by acidic treatment, resulting in PCL-block-PAA grafts. These block copolymers are suspended in water and cross-linked using a water-soluble diamine to different attempted cross-link densities. Initial studies of the solubilization and encapsulation capacities of the amphiphilic polymers are performed using the hydrophobic model compound pyrene.

Keyword
Amines; Arsenic compounds; Atom transfer radical polymerization; Block copolymers; Chemical reactions; Complexation; Copolymerization; Copolymers; Crosslinking; Encapsulation; Monomers; Plastic products; Polymerization; Ring opening polymerization; Synthesis (chemical); Acidic treatment; American Chemical Society (ACS); Amphiphilic polymers; Butyl acrylate (BuA); Butyl group; Caprolactone (PCL); Chain extensions; Cross-link densities; De-protection; End groups; High-molecular weight (HMW); Hydrophobic model; Hydroxypropyl cellulose (HPC); Macro initiators; Nanocontainers; Ring opening polymerization (ROP); Unimolecular; Polymers
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-7711 (URN)10.1021/ma702681u (DOI)000256843100047 ()2-s2.0-47249111376 (Scopus ID)
Note
QC 20100826. Uppdaterad från Submitted till Published 20100826.Available from: 2007-11-23 Created: 2007-11-23 Last updated: 2010-08-26Bibliographically approved

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Output format
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