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Comb Polymers Prepared by ATRP from Hydroxypropyl Cellulose
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
Center for Materials Innovation, Department of Chemistry, Washington University in Saint Louis.
Center for Materials Innovation, Department of Chemistry, Washington University in Saint Louis.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-8348-2273
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.

Place, publisher, year, edition, pages
2007. Vol. 8, no 4, 1138-1148 p.
Keyword [en]
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: urn:nbn:se:kth:diva-7710DOI: 10.1021/bm061043wISI: 000245510100013Scopus ID: 2-s2.0-34247640609OAI: oai:DiVA.org:kth-7710DiVA: diva2:12815
Note
QC 20100826Available from: 2007-11-23 Created: 2007-11-23 Last updated: 2010-08-26Bibliographically approved
In thesis
1. Tuning Properties of Surfaces and Nanoscopic Objects using Dendronization and Controlled Polymerizations
Open this publication in new window or tab >>Tuning Properties of Surfaces and Nanoscopic Objects using Dendronization and Controlled Polymerizations
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
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:nbn:se:kth:diva-4550 (URN)978-91-7178-820-7 (ISBN)
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

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