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Selective cleavage of polymer grafts from solid surfaces: assessment of initiator content and polymer characteristics
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Nuclear Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-8348-2273
2011 (English)In: POLYM CHEM, ISSN 1759-9954, Vol. 2, no 3, 556-558 p.Article in journal (Refereed) Published
Abstract [en]

A novel initiator for atom transfer radical polymerization, also allowing for selective cleavage of polymer grafts, was designed and immobilized on a solid substrate. After cleavage, the initiator content was determined by utilizing Ellman's reagent and the cleaved polymer grafts were isolated and characterized by size exclusion chromatography.

Place, publisher, year, edition, pages
2011. Vol. 2, no 3, 556-558 p.
Keyword [en]
National Category
Polymer Chemistry
URN: urn:nbn:se:kth:diva-31852DOI: 10.1039/c0py00388cISI: 000287378000009ScopusID: 2-s2.0-79951655921OAI: diva2:409111
Swedish Research Council
QC 20110407Available from: 2011-04-07 Created: 2011-03-28 Last updated: 2012-11-26Bibliographically approved
In thesis
1. ARGET ATRP as a Tool for Cellulose Modification
Open this publication in new window or tab >>ARGET ATRP as a Tool for Cellulose Modification
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The importance of finding new applications for cellulose‐based products has increased, especially to meet the demand for new environmentally friendly materials, but also since the digitalization of our society will eventually decrease the need for paper. To expand the application area of cellulose, modification to improve and/or introduce new properties can be a requisite. Thus, the focus of this study has been to achieve fundamental knowledge about polymer grafting of cellulose via well‐controlled radical polymerization.

Cellulose, in the form of filter paper, has successfully been grafted via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) of the monomers: methyl methacrylate, styrene, and glycidyl methacrylate. The advantages of ARGET ATRP are that only a small amount of a copper catalyst is required and the reaction can be performed in limited amount of air; yet, providing for relatively well‐controlled reactions. These benefits can render ARGET ATRP an attractive method for industrial utilization.

The contact‐angle measurements of the grafted filter papers confirmed that the hydrophobicity of cellulose was significantly increased, even for shorter graft lengths. FT‐IR spectroscopy established that the amount of polymer successively increased with monomer conversion. High‐resolution FT‐IR microscopy (FT‐IRM) was proven to be a very useful technique for the analysis of cellulose substrates, displaying the spatial distribution of polymer content on cellulose fibers. The polymer was shown to be fairly homogenously distributed on the fiber.

An initiator with a reducible disulfide bond rendered cleavage of the polymer grafts possible, employing mild reaction conditions. The cleaved grafts and the free polymers – formed from a sacrificial initiator in parallel to the grafting – were shown to have similar molar masses and dispersities, confirming that the grafts can be tailored by utilizing a sacrificial initiator. Moreover, the initiator content on filter paper and microcrystalline cellulose was assessed.

A comparison between the two grafting techniques, grafting‐from cellulose via ARGET ATRP and grafting‐to cellulose via copper(I)‐catalyzed alkyne‐azide cycloaddition, was performed. To achieve a trustworthy comparison, the free polymer formed in parallel to the grafting‐from reaction was employed as the prepolymer in the grafting‐to approach, resulting in nearly identical graft length on the substrates for the two grafting methods. FT‐IRM analyses verified that under the selected conditions, the grafting‐from technique is superior to the grafting‐to approach with respect to controlling the distribution of the polymer content on the surface. The results were corroborated with X‐ray photoelectron spectroscopy.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 62 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:60
National Category
Polymer Technologies
urn:nbn:se:kth:diva-105762 (URN)978-91-7501-544-6 (ISBN)
Public defence
2012-12-14, K2, Teknikringen 28, KTH, Stockholm, 10:00 (English)

QC 20121126

Available from: 2012-11-26 Created: 2012-11-26 Last updated: 2012-11-26Bibliographically approved

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Hansson, SusanneAntoni, PerBergenudd, HelenaMalmström, Eva
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