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Surface-initiated ring-opening polymerization of ɛ-caprolactone from cellulose model surfaces monitored by quartz crystal microbalance
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology. KTH, School of Engineering Sciences (SCI), Centres, VinnExcellence Center BiMaC Innovation.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.ORCID iD: 0000-0001-8622-0386
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Fibre Technology.ORCID iD: 0000-0002-8348-2273
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2012 (English)Conference paper, Oral presentation with published abstract (Other academic)
Abstract [en]

In this work surface initiated ring-opening polymerization (SI-ROP) of ɛ-caprolactone on cellulose model surfaces was investigated using the quartz crystal microbalance (QCM). The polymerization was performed with the monomer, ɛ-caprolactone, in bulk with an organic catalyst, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), at room temperature with two different catalyst concentrations (0.5 mol% and 1 mol%). Initiation was done directly from the hydroxyl groups on the cellulose surface without any modification. A gold surface, which cannot initiate polymerization, was used as a reference surface which was connected in serial to the cellulose surface. This study shows that QCM is a viable technique to monitor SI-ROP of ɛ-caprolactone from cellulose surfaces. Grafting polymers from cellulose fibres/fibrils/whiskers has been an interesting way of increasing the compatibility between fibres/fibrils/whiskers and different matrices in biocomposites, and the QCM could therefore be an important tool to study and optimize the grafting of polymers, such as polycaprolactone (PCL), on cellulose surfaces.

Place, publisher, year, edition, pages
2012.
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-92616OAI: oai:DiVA.org:kth-92616DiVA: diva2:513957
Conference
ACS 243rd American Chemical Society National Meeting
Note

QC 20130531

Available from: 2012-04-04 Created: 2012-04-04 Last updated: 2014-02-03Bibliographically approved
In thesis
1. Surface Modification of Cellulose by Covalent Grafting and Physical Adsorption
Open this publication in new window or tab >>Surface Modification of Cellulose by Covalent Grafting and Physical Adsorption
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The interest in new environmentally friendly cellulose‐based productshas increased tremendously over the last years. At the same time theSwedish forest industry faces new challenges in its strive to increase the utilization of cellulose fibers in high‐value end‐products. The aim of this study was to expand the toolbox for surface modification of cellulose byemploying covalent surface‐initiated (SI) polymerizations or by physicaladsorption of polymers. SI‐ring‐opening polymerization (ROP) of ε‐caprolactone (ε‐CL) was performed from filter paper (FP) and high surface area nanopaper (NP).Larger amounts of polycaprolactone (PCL) were grafted from NP, compared to FP, owing to the higher amount of available initiating hydroxyl groups. Furthermore, the mechanical properties of PCL were improved by the grafting of FP and NP, as compared to pure PCL.It is challenging to characterize a polymer grafted from a surface. Hence, quartz crystal microbalance with dissipation (QCM‐D) was employed to investigate SI‐ROP in real time from a cellulose model surface. Furthermore, it was shown by colloidal probe AFM that increased lengthof grafted PCL, from cellulose microspheres, improved the interfacialadhesion to a pure PCL surface, suggesting that chain entanglements havea significant impact on the interfacial properties. Increased temperatureand time in contact also improved the adhesion.In order to investigate the degree of substitution (DS) and the degree of polymerization (DP), PCL‐grafted hydrolyzed cellulose cotton linters (HCCL) were studied by solid state NMR. It was found that despite a DS of only a few percent, the surface character changed considerably; furthermore, the DS was virtually independent of the DP. To increase theamount of grafted polymer, ring‐opening metathesis polymerization (ROMP) of norbornene was performed from FP. Short polymerizationtimes and low temperatures resulted in highly grafted surfaces. Alternatively, physical adsorption by electrostatic interactions was employed to modify a cellulose model surface in the QCM‐D. Cationic latex nanoparticles of poly(dimetylaminoethyl methacrylate‐co‐methacrylicacid)‐block‐poly(methyl methacrylate) were produced by reversible addition‐fragmentation chain‐transfer (RAFT)‐mediated surfactant‐freeemulsion polymerization by polymerization‐induced self‐assembly (PISA).This strategy does not require any organic solvents and could potentiallybe introduced in industrial processes.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2014. 77 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014-2
Keyword
Surface modification, cellulose, covalent modification, physical adsorption, polymer synthesis
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-140859 (URN)978-91-7501-987-1 (ISBN)
Public defence
2014-02-21, Kollegiesalen, Brinellvägen 8, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation, KFCE 8508Formas
Note

QC 20140203

Available from: 2014-02-03 Created: 2014-02-03 Last updated: 2014-02-03Bibliographically approved

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Wågberg, LarsMalmström, EvaCarlmark, Anna

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