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Surface Modification of Cellulose by Covalent Grafting and Physical Adsorption
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.
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 [en]
Surface modification, cellulose, covalent modification, physical adsorption, polymer synthesis
National Category
Polymer Technologies
Identifiers
URN: urn:nbn:se:kth:diva-140859ISBN: 978-91-7501-987-1 (print)OAI: oai:DiVA.org:kth-140859DiVA: diva2:692913
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
List of papers
1. Facile Preparation Route for Nanostructured Composites: Surface-Initiated Ring-Opening Polymerization of epsilon-Caprolactone from High-Surface-Area Nanopaper
Open this publication in new window or tab >>Facile Preparation Route for Nanostructured Composites: Surface-Initiated Ring-Opening Polymerization of epsilon-Caprolactone from High-Surface-Area Nanopaper
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2012 (English)In: ACS Applied Materials and Interfaces, ISSN 1944-8244, E-ISSN 1944-8252, Vol. 4, no 6, 3191-3198 p.Article in journal (Refereed) Published
Abstract [en]

In this work, highly porous nanopaper, i.e., sheets of papers made from non-aggregated nanofibrillated cellulose (NFC), have been surface-grafted with poly(epsilon-caprolactone) (PCL) by surface-initiated ring-opening polymerization (SI-ROP). The nanopaper has exceptionally high surface area (similar to 300 m(2)/g). The "grafting from" of the nanopapers was compared to "grafting from" of cellulose in the form of filter paper, and in both cases either titanium n-butoxide (Ti(On-Bu)(4)) or tin octoate (Sn(Oct)(2)) was utilized as a catalyst. It was found that a high surface area leads to significantly higher amount of grafted PCL in the substrates when Sn(Oct)2 was utilized as a catalyst. Up to 79 wt % PCL was successfully grafted onto the nanopapers as compared to filter paper where only 2-3 wt % PCL was grafted. However, utilizing Ti(On-Bu)4 this effect was not seen and the grafted amount was essentially similar, irrespectively of surface area. The mechanical properties of the grafted nanopaper proved to be superior to those of pure PCL films, especially at elevated temperatures. The present bottom-up preparation route of NFC-based composites allows high NFC content and provides excellent nanostructural control. This is an important advantage compared with some existing preparation routes where dispersion of the filler in the matrix is challenging.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2012
Keyword
ring-opening polymerization, nanofibrillated cellulose, nanopaper, surface grafting, high surface area
National Category
Nano Technology
Identifiers
urn:nbn:se:kth:diva-99242 (URN)10.1021/am300537h (DOI)000305716900052 ()2-s2.0-84863198035 (Scopus ID)
Note

QC 20160324

Available from: 2012-07-24 Created: 2012-07-23 Last updated: 2017-12-07Bibliographically approved
2. Surface-initiated ring-opening polymerization of ɛ-caprolactone from cellulose model surfaces monitored by quartz crystal microbalance
Open this publication in new window or tab >>Surface-initiated ring-opening polymerization of ɛ-caprolactone from cellulose model surfaces monitored by quartz crystal microbalance
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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.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-92616 (URN)
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
3. Nanobiocomposite Adhesion: Role of Graft Length and Temperature in a Hybrid Biomimetic Approach
Open this publication in new window or tab >>Nanobiocomposite Adhesion: Role of Graft Length and Temperature in a Hybrid Biomimetic Approach
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2013 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 14, no 4, 1003-1009 p.Article in journal (Refereed) Published
Abstract [en]

Cellulose microspheres bearing poly(e-caprolactone) grafts of different molecular weights were investigated to evaluate the effect of graft length on the interfacial properties. Surface force and friction measurements were performed using an atomic force microscope in colloidal probe mode. The maximum interaction distance and adhesion is dependent on the temperature and the time in contact via a diffusion controlled mechanism. The effects are highest for the longer grafts, and molecular weight thresholds were found to lie between 21 and 34 kDa at 25 degrees C and between 9 and 21 kDa at 40 degrees C. The interpenetration of the graft into a matrix leads to "hidden length contributions to adhesion, analogous to those in natural biocomposites. The nanotribology results display Amontonian behavior, and the friction force at zero applied load is higher at the graft graft interface than for a bare cellulose sphere interacting with the graft. These results clearly demonstrate the benefits of the grafted polymer layer on the adhesion, toughness, and resistance nanobiocomposites.

Keyword
Surface Force Measurements, Cellulose Surfaces, Sacrificial Bonds, Friction, Fibers, Xyloglucan, Microscope, Adsorption, Nanoscale, Polymers
National Category
Biochemistry and Molecular Biology Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-122333 (URN)10.1021/bm301790b (DOI)000317370500008 ()2-s2.0-84876008862 (Scopus ID)
Funder
Swedish Foundation for Strategic Research FormasSwedish Research CouncilKnut and Alice Wallenberg Foundation
Note

QC 20130522

Available from: 2013-05-22 Created: 2013-05-20 Last updated: 2017-12-06Bibliographically approved
4. Solid State CP/MAS 13C-NMR investigation of hydrolyzed cotton linters grafted by surface‐initiated ring‐opening polymerization of ε‐caprolactone
Open this publication in new window or tab >>Solid State CP/MAS 13C-NMR investigation of hydrolyzed cotton linters grafted by surface‐initiated ring‐opening polymerization of ε‐caprolactone
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(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-140861 (URN)
Note

QS 2014

Available from: 2014-02-03 Created: 2014-02-03 Last updated: 2015-05-26Bibliographically approved
5. Surface-initiated ring-opening metathesis polymerisation from cellulose fibres
Open this publication in new window or tab >>Surface-initiated ring-opening metathesis polymerisation from cellulose fibres
2012 (English)In: POLYM CHEM-UK, ISSN 1759-9954, Vol. 3, no 3, 727-733 p.Article in journal (Refereed) Published
Abstract [en]

In this study, cellulose fibres have been grafted utilizing surface-initiated ring-opening metathesis polymerisation (SI-ROMP). Initially, a Grubbs' type catalyst was immobilized onto filter paper whereafter SI-ROMP of norbornene was performed from the surface of the fibres at three different reaction temperatures, room temperature (RT), 0 degrees C and -18 degrees C, and for different reaction times. The evaluation of the grafted cellulose was performed by contact angle measurements, FT-Raman spectroscopy, FE-SEM and TGA. After the grafting, all samples were clearly hydrophobic with weight increases up to over 100%. The FT-Raman spectroscopy analysis showed significant structural changes after polymerization for cellulose substrates polymerized at 0 degrees C and RT, confirming that a polymer was grafted from the surface. FE-SEM images verified that these samples are covered by polynorbornene and that the fibrillar structure of the native cellulose disappeared. For the samples grafted at -18 degrees C, no significant changes were seen with these analysis methods. However, SI-ROMP appears to be a versatile method to modify cellulose fibres.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2012
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-90921 (URN)10.1039/c2py00554a (DOI)000300049900023 ()2-s2.0-84857335793 (Scopus ID)
Note
QC 20120305Available from: 2012-03-05 Created: 2012-03-05 Last updated: 2014-02-03Bibliographically approved
6. Modification of cellulose surfaces by cationic latex prepared by RAFT-mediated surfactant-free emulsion polymerization
Open this publication in new window or tab >>Modification of cellulose surfaces by cationic latex prepared by RAFT-mediated surfactant-free emulsion polymerization
Show others...
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-140863 (URN)
Note

QS 2014

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

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